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I. INTRODUCTION
EARTHS COMPARTMENTS (Figure I.1). The earth can be divided into 4 distinct
compartments, three of them are physical compartments, i.e., atmosphere (the gaseous
envelope surrounding the earth), hydrosphere (the water belt around the earth, liquid
and frozen, fresh and salty), and lithosphere (the soil and rock of the earths crust). The
4th compartment that overlaps the three physical compartments is the biosphere, which
is the global sum of all ecosystems. The biosphere is the global ecological system that
integrates all living beings and their relationships, including their interactions with the
atmosphere, hydrosphere, and lithosphere.
Atmosphere (Figure I.2). Atmosphere is the gaseous envelope surrounding the
earth. The atmosphere is composed of a series of five concentric layers: troposphere,
stratosphere, mesosphere, thermosphere, and exosphere. The troposphere is the
atmosphere from the earths surface to the stratosphere which is characterized by the
presence of clouds, turbulent winds, and decreasing temperature with increasing altitude
(i.e., 6oC/km). The troposphere extends to a height of approximately 10 km. The
stratosphere extends from 10 to 45 km above the earths surface and contains a layer of
ozone (O3) critical to life because it absorbs much of the suns damaging ultraviolet (UV)
radiation. The absorption of UV radiation by the O3 layer heats the air and therefore,
temperature increases with increasing altitude in the stratosphere. There is a steady
wind but no turbulence in the stratosphere. There is little water, and the temperature
in the lower stratosphere, which commercial jets fly, remains largely uniform (i.e., 45oC
to 75oC). The mesosphere, the layer of atmosphere directly above the stratosphere,
extends from 45 to 80 km above the earths surface. Temperature drops steadily in the
mesosphere to the lowest in the atmosphere, i.e., as low as 138oC. The thermosphere
extends from 80 to 500 km above the earths surface and is very hot. Gases in the
thermosphere absorb X rays and short-wavelength UV radiations. This absorption
drives the few gas molecules present to great speeds, raising their temperature to
> 1,000oC. The aurora, a colorful display of lights in dark polar skies, is produced when
charged particles from the sun hit oxygen and nitrogen molecules in the thermosphere.
The thermosphere is important in long-distance communication because it reflects
outgoing radio waves back to the earth without the aid of satellites. The outmost layer
of the atmosphere, the exosphere, begins about 500 km above the earths surface. The
exosphere continues to thin out until it converges with interplanetary space. The
composition of atmosphere in ppmv (m3/106 m3 air) is: N2 (nitrogen), 780,840
(78.084%); O2 (oxygen), 209,460 (20.946%); Ar (argon), 9,340 (0.9340%); CO2 (carbon
dioxide), 383 (0.0383%); Ne (neon), 18.18 (0.001818%); He (helium), 5.24
(0.000524%); CH4 (methane), 1.745 (0.0001745%); Kr (krypton), 1.14 (0.000114%); and
H2 (hydrogen), 0.55 (0.000055%). Water vapor accounts for about 0.4% over full
atmosphere and 1 to 4% near the earths surface.
pA (patm) = Atmospheric Pressure = 101 kPa = 101 kN/m2 [1 N (Newton) = 1 kg-m/s2]
SE = Earths Surface Area = 4R2 = 5.11014 m2 (R = the earths radius = 6,371 km)
MA = Mass of Atmosphere =

p A S E (101 103 )(5.1 1014 )


= 5.251018 kg (g = 9.81 m/s2)

g
9.81

Mass in Troposphere (~ 10 km in elevation) = 78%

Atmosphere
Hydrosphere

Lithosphere

Biosphere

Figure I.1. Four compartments of the earth. Atmosphere, hydrosphere, and


lithosphere are physical compartments.

Figure I.2. Atmospheric structure.


Hydrosphere. A hydrosphere in physical geography describes the combined mass of
water found on, under, and over the surface of the earth. The total mass of the earth's
hydrosphere is about 1.41021 kg, which is about 0.023% of the earth's total mass. About
201015 kg of this is in the earths atmosphere (the volume of 1 kg of water is 1 liter).
Approximately 71% of the earths surface (3.61108 km2), is covered by oceans. The

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average salinity of the earth's oceans is about 35 g salt/kg sea water (3.5%). The global
ocean is a single, continuous body of water, which is divided into five sections separated
by the continents (Figure I.3): the Pacific (155,557,000 km2), Atlantic (76,762,000 km2),
Indian (68,556,000 km2), southern or Antarctica (20,327,000 km2) and Arctic
(14,056,000 km2) Oceans. The Pacific Ocean is the largest which covers one-third of the
earths surface and contains more than half of the earths water.
Ocean Mass ( MO) = SOdOO = (0.7)(5.11014 m2)(3,800 m)(1,030 kg/m3) = 1.401021 kg

where SO is oceans surface area, dO is oceans average depth, and O is oceans average
mass density.

Figure I.3. The worlds oceans.


Lithosphere (Figure I.4). The lithosphere is the solid part of the earth and it has two
parts: the crust and the upper mantle. The crust (rocks, minerals, and soil), which has a
thickness from 5 to 70 km, is the earths outermost layer. The rocks and minerals are
made of just 8 elements: oxygen (46.6%), silicon (27.72%), aluminum (8.13%), iron
(5.00%), calcium (3.63%), sodium (2.83%), potassium (2.70%), and magnesium
(2.09%). Soil is formed rock that is slowly broken down, or fragmented, into smaller and
smaller particles by biological, chemical, and physical weathering processes in nature.
The thickness of soil varies from a thin film on young lands, near North and South Poles

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and on slopes near the top of mountains, to more than 3 m on old lands, such as certain
forests. Soil is composed of 4 distinct parts: mineral particles, which make up about 45%
of a soil; organic matter (about 5 %); water (about 25%); and air (about 25%). The
average bulk density of soil is about 1,500 kg/m3.
Soil Mass (MS) = SSdSS = (0.255)(5.11014 m2)(2 m)(1,500 kg/m3) = 3.901017 kg

where SS is earths land mass surface area, dS is soils average depth, and S is soils bulk
density.

Figure I.4. The earths lithosphere.


Biosphere. The biosphere is the global sum of all ecosystems (i.e., the zone of life on
earth). From the broadest bio-physiological point of view, the biosphere is the global
ecological system that integrates all living beings and their relationships, including their
interactions with the atmosphere, hydrosphere, and lithosphere. The biosphere is
postulated to have evolved, beginning through a process of biogenesis or biopoesis, at
least some 3.5 billion years ago. Every part of the planet, from the polar ice caps to the
equator, support life of some kind. Recent advances in microbiology have demonstrated
that microbes live deep beneath the earths terrestrial surface, and that the total mass of
microbial life is so called uninhabitable zones, may exceed all animal and plant life on
the surface. The actual thickness of biosphere on earth is difficult to measure. Birds
typically fly at altitudes of 650 to 1,800 m, and fish that live deep underwater can be
found down to 8,372 m in the Puerto Rico Trench.
There are more extreme examples for life on the planet: Rppells vulture has been found
at altitudes of 11,300 m; bar-headed geese migrate at altitudes of at least 8,300 m (over
Mount Everest); yaks live at elevations from 3,200 to 5,400 m above the seas level;
mountain goats live up to 3,050 m. Herbivorous animals at these elevations depend on
lichens, grasses, and herbs. Microscopic organisms live at such extremes that, taking
them into consideration puts the thickness of the biosphere much greater. Culturable
microbes have been found in the earths upper atmosphere as high as 41 km. It is
unlikely, however, that microbes are active at such altitudes, where temperatures and air
pressures are extremely low and UV radiation is very high. These microbes are more
likely brought into the upper atmosphere by winds or possibly volcanic eruptions.
Barophilic marine microbes have been found at more than 10 km depth in the Marianas
Trench. Microbes are not limited to the air, water, or the earths surface. Culturable

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thermophilic microbes have been extracted from cores drilled more than 5 km into the
earths crust in Sweden, from rocks with temperatures ranging from 65 to 75oC.
Temperature increases rapidly with increasing depth into the earths crust. The rate at
which the temperature increases depends on many factors, including type of crust
(continental vs. oceanic), rock type, geographic location, etc. The upper known limit is
about 112oC (Methanopyruskandleri Strain 116), and it is likely that the limit of life in
the deep biosphere is controlled by temperature rather than absolute depth.
The earths biosphere is divided into a number of biomes, inhabited by broadly similar
flora and fauna. On land, biomes are separated primarily by latitude. Terrestrial biomes
lying ithin the Arctic and Antarctic Circles are relatively barren of plant and animal life,
while most of the more populous biomes lie near the equator.
INVENTORY OF WATER AT THE EARTHS SURFACE (Table I.1). Although
75% of the earths surface is covered with water, substantially less than 1% is available for
humans. Most water is salty, frozen, or inaccessible in the soil and atmosphere. The
definition of freshwater is water containing less than 1,000 mg/L of dissolved solids,
most often salt. The U. S. Geological Survey (USGS) reports that about 1.54109 m3 of
water per day were withdrawn for use in the U.S. during 2000.

Table I.1. Water Inventory at the Earths Surface.


Reservoir
Oceans
Ice Caps & Glaciers
Deep groundwater (750 4,000 m)
Shallow Groundwater (< 750 m)
Lakes
Soil Moisture
Atmosphere (measured as liquid water)
Rivers
Biosphere
TOTAL

Volume (106 km3)


1,370
29
5.3
4.2
0.125
0.065
0.013
0.0017
0.0006
1,408.7

% of the Total
97.25
2.05
0.38
0.30
0.01
0.005
0.001
0.0001
0.00004
100

Great Lakes (Figure I.5 & Table I.2). The total volume of water in Great Lakes is
about 24,260 km3 and the total water mass is therefore 2.461016 kg [i.e., (24,260 km3)
(109 m3/km3)(1,000 kg/m3)]. The Great Lakes contain about 95% of total freshwater
mass in the U.S. and 20% of worlds total freshwater mass. The effects the Great Lakes
have on weather in the region are known as the lake effects. In winter, the moisture
picked up by the prevailing winds from the west can produce very heavy snowfall,
especially along lakeshores to the east such as Michigan, Ohio, Pennsylvania, Ontario,
and New York.
The lakes also moderate seasonal temperatures somewhat, by absorbing
heat and cooling the air in summer, then slowly radiating that heat in autumn. This
temperature buffering produces areas known as "fruit belts", where fruit typically grown
farther south can commercially be produced. The eastern shore of Lake Michigan, the
southern shore of Lake Erie, and the Niagara Peninsula between Lake Erie and Lake
Ontario are homes to many wineries. Lake effects also cause the occurrence of fog over
medium-sized areas, particularly along the shorelines of the lakes. The Great Lakes have
also been observed to help strengthen storms, such as Hurricane Hazel in 1954, and a
frontal system in 2007 that spawned a few tornadoes in Michigan and Ohio.

Table I.2. Morphological Data of the Great Lakes.


Lake
Superior
Huron
Michigan
Erie
Ontario

Area (km2)
83,300
59,510
57,850
28,280
18,760

dmax1 (m)
397
223
265
60
225

dmean (m)
145
76
99
21
97

Volume (km3)
12,000
4,600
5,760
540
1,720

1d

max is the maximum depth and dmean is the mean depth.


2 is the mean residence time, which is the average amount

resides in the system. =

Shoreline (km)
3,000
2,700
2,210
1,200
1,380

2 (years)
190
40
37
3
8

of time that a water molecule

, where V is the volume of the surface water body and V is

V
the total water volumetric inflow to the surface water body.

Figure I.5. The Great Lakes.


The Worlds Largest Lakes (surface area).
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Caspian Sea (Asia), 371,000 km2. Some consider the Caspian Sea as a full-fledge
seas, but it is surrounded by land and thus meets the generally accepted
definition of a lake.
Lake Superior (North America), 82,100 km2.
Lake Victoria (Africa), 68,800 km2.
Lake Huron (North America), 59,600 km2.
Lake Michigan (North America), 57,800 km2.
Lake Tanganyika (Africa), 32,900 km2.
Baikal (Asia), 30,500 km2.
Great Bear Lake (North America), 31,328 km2.
Lake Malawi (Africa), 30,044 km2.
Great Slave Lake (North America), 28,568 km2.

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The Worlds Largest Lakes (volume).
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Baikal (Asia), 23,600 km3. Lake Baikal holds 20% of the world's freshwater.
Lake Tanganyika (Africa), 18,900 km3.
Lake Superior (North America), 11,600 km3.
Lake Malawi (Africa), 7,725 km3.
Lake Michigan (North America), 4,900 km3.
Lake Huron (North America), 3,540 km3.
Lake Victoria (Africa), 2,700 km3.
Great Bear Lake (North America), 2,236 km3.
Issyk-Kul (Asia), 1,730 km3.
Lake Ontario (North America), 1,710 km3.

The Worlds Deepest Lakes.


1.
2.
3.
4.
5.

Lake Baikal (Asia), 1,637 m.


Lake Tanganyika (Africa), 1,470 m.
Caspian Sea (Asia), 1,025 m.
O'Higgins Lake (South America), 836 m.
Lake Malawi (Africa), 706 m.

The Worlds 10 Longest Rivers.


1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Nile River (Africa), 6,693 km.


Amazon River (South America), 6,4,36 km.
Yangtze River (Asia), 5,463 km.
Yellow River (Asia), 5,463 km.
Ob-Irtysh River (Asia), 5,410 kim.
Amur River (Asia), 4,415 km.
Lena River (Asia), 4,399 km.
Congo River (Africa), 4,241 km.
MacKenzie River (North America), 4,241 km.
Mekong River (Asia), 4,183 km.

The Worlds Largest Aquifers. The Great Artesian Basin situated in Australia is
arguably the largest groundwater aquifer in the world (over 1.7106 km). It plays a
large part in water supplies for Queensland and remote parts of South Australia. The
Guarani Aquifer which has an area of 1.2 million km, a volume of about 40,000 km,
and a thickness of between 50 m and 800 m and a maximum depth of about 1,800 m, is
shared by Brazil, Argentina, Paraguay, and Uruguay. It is estimated to contain about
37,000 km of water. The water in the aquifer is replenished with a total recharge rate
of about 166 km/year from precipitation. It is said that this vast underground reservoir
could supply fresh drinking water to the world for 200 years.
The Ogallala Aquifer, also known as the High Plains Aquifer (Figure I.6), is a vast yet
shallow underground unconfined aquifer located beneath the Great Plains in the U.S. It
covers an area of approximately 450,000 km in portions of the eight states of South
Dakota, Nebraska, Wyoming, Colorado, Kansa, Oklahoma, New Mexico, and Texas.
About 27% of the irrigated land in the U.S. overlies this aquifer system, which yields
about 30% of the nation's ground water used for irrigation. In addition, the aquifer
system provides drinking water to 82% of the people who live within the aquifer

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boundary. The depth of the water below the surface of the land ranges from almost 122
m in parts of the north to between 30 to 61 m throughout much of the south. Presentday recharge of the aquifer with fresh water occurs at an exceedingly slow rate,
suggesting that much of the water in its pore spaces is paleowater, dating back to the
most recent ice age and probably earlier.

Figure I.6. The Ogallala Aquifer.

WATER POVERTY INDEX (WPI). A holistic water poverty index (WPI),


developed by Britains Center for Ecology and Hydrology and the World Water Council,
grades countries according to their water resource (R), access (A), use (U), capacity (C),
and environment (E), as shown in (I.1).

WPI wr R wa A wuU wcC we E


wr wa wu wc we 1

(I.1)

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WPI was created as an interdisciplinary indicator to assess water stress and scarcity,
linking physical estimates of water availability with the socioeconomic drivers of poverty.
WPI is the weighted sum of the above 5 components, each having a value ranging from 0
to 100. wr,, we are weighing factors assigned and each has a value that ranges from 0
to 1. Based on the WPI rankings summarized in Table I.3 Finland is rated as the top
scorer, with plenty of water wisely used; Haiti comes bottom. On the whole, poor
countries do worse than rich ones, with some exceptions: Guyanas score, for example,
is raised by good access to safe water, and Japan is marked down by problems with
pollution. U.S.s standing is lowered by inefficient use of water in fields, factories, and
homes (e.g., 3.4% of the rainfall is used for irrigational purposes and 3.6% of the rainfall
is used for industrial purposes).
Table I.3. WPI Rankings.
Country
Finland
Suriname
Iceland
Norway
Guyana
Austria
Ireland
Chile
Canada
Thailand
Sweden
Indonesia
Czech Republic
Pakistan
Japan
Russia

WPI
79.9
78.6
74.4
73.8
72.8
72.2
71.9
70.5
70.4
67.7
67.2
66.2
64.5
64.5
64.2
63.4

Country
Argentina
Poland
Mexico
Brazil
U.S.
India
Saudi Arabia
Singapore
China
South Africa
Israel
Morocco
Cambodia
Uganda
Niger
Haiti

WPI
62.8
61.3
59.2
58.8
58.5
58.2
58.0
57.2
56.6
55.7
55.6
52.3
44.9
43.3
36.0
32.7

HYDROLOGIC CYCLE (Figure I.7). The hydrologic cycle depicts the continuous
circulation of water from the ocean to the atmosphere, to the land, and back to the ocean.
Most of the freshwater formed by evaporation/evapotranspiration returns directly to the
sea (i.e., 75% of 389,500 km3/year globally). Small portion of the precipitation that falls
on the land is used in agriculture, in industry, and for municipal purposes. In the United
States only 0.6% of the rainfall is used for municipal purposes, and of that only 5% is
used for food preparation or drinking. By comparison, 3.4% of the rainfall is used for
irrigational purposes and 3.6% of the rainfall is used for industrial purposes. The
following are some useful terminologies that are widely used in the description of the
hydrologic cycle.
Precipitation: Any form of moisture condensing in the air and depositing on the
ground.
Evaporation: Molecules leaving the liquid state and entering the vapor or gaseous state
as, e.g., water evaporates to form water vapor.
Surface Runoff: The portion of precipitation which runs off the surface as opposed to
either percolating through the subsurface soil or soaking into the soil.
Groundwater Infiltration: The process of water percolating through the subsurface

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soil and entering the groundwater aquifers. An aquifer is an underground layer of
porous rock, sand, or other materials that allows the movement of water.

Figure I.7. The hydrologic cycle.


Some useful information on the global and U.S. hydrologic cycles is summarized as
follows:
I.

Global Hydrologic Cycle:

1.
2.
3.
4.
5.
6.
7.
8.
9.

Precipitation on the land: 110,000 km3/year.


Evaporation from soil/streams/rivers/lakes and evapotranspiration from
vegetation: 71,000 km3/year.
Precipitation to the ocean: 385,000 km3/year.
Evaporation from the ocean: 425,000 km3/year.
Runoff to the ocean: 40,000 km3/year.
Water in the atmosphere: 13,000 km3.
Water in the ocean: 1,350,000,000 km3;
Water in groundwater aquifers: 15,300,000 km3.
Movement of moist air in the atmosphere: 40,000 km3/year.

II.

U.S. Hydrologic Cycle:

1.
2.
3.
4.
5.

Precipitation (100%): 5.8671012 m3/year.


Evaporation (30%): 2.1391012 m3/year.
Evapotranspiration (Transpiration) (40%): 2.3471012 m3/year.
Surface Runoff (20%): 1.1731012 m3/year.
Groundwater Infiltration (10%): 0.5871012 m3/year.

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TIME AND SPACE SCALE OF AIR POLLUTION PROBLEMS.
Environment
Indoor Air
Industrial Plumes
Urban Air Basins
Regional
Global

Length Scale
10 m
1 km
100 km
1,000 km
20,000 km

Time Scale
1 hour
10 minutes
1 day
1 week
Decades

Examples
Radon/Environmental Tobacco Smoke (ETS).
Toxic Organics/Metals.
O3/CO/Particles.
Acid Deposition (dry and wet).
Climate Change/Stratospheric O3 Depletion.

CRITICAL AIR POLLUTANTS. Given the ongoing focus of the Clean Air Act,

most of the monitoring of emissions, concentrations, and effects of air pollution has been
directed toward the 6 criteria pollutants: ground level ozone (O3), carbon monoxide
(CO), sulfur dioxide (SO2), small particles (PM), nitrogen dioxide (NO2), and lead (Pb).
Carbon Monoxide (CO). CO is a primary pollutant which is produced via incomplete
combustion of carbonaceous fuel. CO binds reversibly with hemoglobin in red blood
cells, impairing the oxygen-carrying capacity of the blood. The affinity of hemoglobin for
CO is about 150 times as high as for O2. The presence of carboxyhemoglobin in the blood
makes the remaining O2 bind more tightly to the hemoglobin, reducing the effectiveness
of O2 delivery to tissues and organs. The atmospheric lifetime of CO, several weeks, is
much longer than the residence time in an urban air basin. As a result, CO is considered
as a non-reactive species in urban air. CO does not react rapidly with surfaces and has
low water solubility.
Nitrogen Dioxide (NO2). NO2 is a respiratory irritant that can lower resistance to
respiratory infections via inhalation exposure. Chronicle exposure to elevated NO2 levels
may cause increased incidence of acute respiratory disease in children. NO2 also causes
O3 formation, visibility impairment, and acid deposition. NO2 is primarily a secondary
pollutant which is formed by the oxidation of nitric oxide (NO) in the atmosphere. NO is
a combustion by-product. The sum of NO and NO2 is termed NOX.
Ozone (O3). O3 is a strong chemical oxidant. When inhaled, it damages lung tissue and
sensitizes the lung to other irritants. O3 exposure may cause chest pain, coughing, and
nausea. Chronicle exposure to O3 may cause permanent structural damage to the lungs
and may accelerate lung aging. O3 also causes damages to agricultural crops and forest
trees. O3 is strictly a secondary pollutant which is formed by photochemical reactions in
the atmosphere. It has a short atmospheric lifetime, especially in polluted air.
Sulfur Dioxide (SO2). SO2 is a respiratory irritant that can have adversary effects on
breathing, contribute to respiratory illness, alter the defense mechanisms of the lungs,
and aggravate existing pulmonary and cardiovascular disease (e.g., asthma). SO2 also
causes damages to agricultural crops and forest trees. SO2 is the most important
precursor for acid deposition. SO2 is produced by the combustion of fuels that contain
sulfur and by some industrial processes (e.g., coal and oil combustion, steel mills, oil
refineries, pulp and paper mills, and non-ferrous smelters). SO2 is a primary pollutant.
It may deposit to the earths surface either as a gaseous molecule or dissolved in rain or
fog droplets.
Particulate Matter (PM10/PM2.5). The primary health concern with particulate
matter is impairment of the respiratory system Particle exposure may have adversary
effects on breathing aggravate existing pulmonary and cardiovascular disease (e.g.,

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asthma). PM10 and PM2.5 refer to airborne particles with diameters < 10 and 2.5 m,
respectively (1 m = 10-6 m). Particulate matter is a mixed primary and secondary
pollutant. Coarse particles are mainly primary pollutants, with dominant sources that
include fugitive dust from roads, construction, and agricultural emissions. Wind
erosion, especially during dry seasons, is another important source. Industrial
emissions, transportation sources (e.g., diesel soot), and residential wood smoke are
major sources of fine particles.
Lead (Pb). Lead is regulated both as a criteria pollutant and as a hazardous air
pollutant. Lead is strictly a primary pollutant. In the atmosphere, lead is associated with
suspended particulate matter, mainly in the fine mode. Lead in fine particles has a long
atmospheric lifetime and deposits broadly over the globe. The removal of lead from
gasoline has largely eliminated atmospheric lead problems in urban areas of the U.S.

UNITS OF MEASUREMENTS. For most water pollution work, it is customary to


express pollutant concentrations in mg/L or mg/m3. Since the density of water is
roughly 1 kg/L under normal conditions, then 1 mg/L = 1 g/m3 = 1 mg pollutant/kg water
= 1 mg/106 mg = 1 parts per million (ppm). In addition, 1 g/L = 1 mg/m3 = 1 g
pollutant/kg water = 1 mg/109 mg = 1 parts per billion (ppb). For most air pollution
work, on the other hand, it is customary to express pollutant concentrations in
volumetric terms. For instance, the concentration of a gaseous pollutant in parts per
million is the volume of pollutant per million volumes of the air mixture (ppm or
ppmv). Concentrations are sometimes expressed as mass pollutant per air volume, such
as g/m3 or mg/m3.
The relationship between ppmv and mg pollutant/m3 air, which depends on the
pressure, temperature, and molecular weight (MW) of the pollutant, can be established
using the ideal gas law, i.e., PV = nRT, where P is the absolute pressure, atm; V is the
volume, m3; n is the moles gas, moles; R is the universal gas constant, 0.082056 Latm/mol-oK; and T is the absolute temperature, oK. Note that 1 atm = 101.325 kPa =
101,325 Pa = 101.325 bar.

Since the specific volume of an ideal gas (i.e., V

V
) at 1 atm and 273.15oK (0oC) is
n

22.410-3 m3/mole, then at P and T the specific volume of the same ideal gas is

PV
PV
PV T
(1)(22.414 103 )(T )
V S S .
calculated as
, m3/mole, i.e., S S R
TS
T
PTS
P(273.15)

If the gaseous pollutant behaves like an ideal gas, then its specific volume at P and T can

(1)(22.414 103 )(T )


be expressed as
, m3 pollutant/mg pollutant; or
( P)(273.15)(103 )(MW )
1

V ( P, T )

( P)(273.15)(MW )(106 )
, mg pollutant/m3 pollutant. Therefore,
(1)(22.414)(T )

1
yields mg pollutant/m3 air, i.e.,
( ppmv)(10 6 )
V ( P, T )

13

mg POLLUTANT ( ppmv)( P)(273.15)(MW )

m3AIR
(1)(22.414)(T )

(I.2)

SOLID WASTES. Solid wastes are wastes that are in either liquid or gaseous forms,
e.g., food scraps, packaging materials, yard trimmings, miscellaneous inorganic wastes.
Municipal solid wastes (MSW) are the solid wastes produced from residential,
commercial, institutional, and industrial sources, but they do not include such wastes as
construction wastes, automobile bodies, municipal wastewater sludge, combustion ash,
and serving food. Major sources of solid wastes in the U.S. are: mining, 75%; agriculture,
12%; industry, 9.0%; municipalities, 3.0%; and municipal wastewater sludge, 1.0%. U.S.
EPA estimates that the U.S. generated 246 million tons of MSW in 2005, which is about
2.2 kg/capita-day. Paper and paperboard products accounted for about 34.2% of total
MSW weight. Another 37% is roughly equally divided among yard trimmings (13.1%),
food scraps (11.9%), and plastics (11.8%).
Solid Waste Management Strategies. New concepts about the management of
solid wastes can be applies depending on the countries or regions. Some of the most
general, widely used concepts include:
Waste Hierarchy (Figure I.8). The waste hierarchy refers to the "3 Rs" (i.e., reduce,
reuse, and recycle), which classify waste management strategies according to their
desirability in terms of waste minimization. The waste hierarchy remains the
cornerstone of most waste minimization strategies. The aim of the waste hierarchy is to
extract the maximum practical benefits from products and to generate the minimum
amount of waste. 3 Rs along with composting and energy recovery are all examples of
resource conservation. Resource conservation reduces greenhouse gas (GHG) emissions
from common solid waste management pathways, including: (1) the incineration of solid
wastes (emissions of CO2 and nitrous oxide, a GHG that is 310 times as potent as CO2),
(2) the transportation of solid wastes to disposal sites (GHG emissions from the
combustion of the fuel used in the equipment), and (3) landfills (wastes in landfills
decompose anaerobically and produce CH4, a GHG that is 21 times as potent as CO2).
Recycling typically requires less energy than producing goods from virgin materials.
Energy savings from recycling translates into GHG savings because fewer fossil fuels are
combusted to produce energy. Source reduction and recycling can also increase carbon
storage in forests. By preventing or reducing harvests of raw materials, preserved trees
continue to remove CO2 from the atmosphere. Composting produces a useful product
from organic waste that otherwise would have been landfilled, therefore composting
helps prevent methane emissions from and leachate formulation in the landfills. Energy
recovery at incineration facilities and landfills can conserve resources by offsetting fossil
Recycling typically requires less energy than producing goods from virgin materials.
Energy savings from recycling translates into GHG savings because fewer fossil fuels are
combusted to produce energy. Source reduction and recycling can also increase carbon

14

Figure I.8. The solid waste management hierarchy.


storage in forests. By preventing or reducing harvests of raw materials, preserved trees
continue to remove CO2 from the atmosphere. Composting produces a useful product
from organic waste that otherwise would have been landfilled, therefore composting
helps prevent methane emissions from and leachate formulation in the landfills. Energy
recovery at incineration facilities and landfills can conserve resources by offsetting fossil
fuels used for energy. Energy recovery is often associated with electricity generation
such as landfill methane capture, although it can also offset fossil fuels used at industrial
sites, resulting in fewer GHG emissions. In terms of climate benefits, reducing and
reusing materials offers the best approaches to reduce GHGs. Because no wastes are
generated, source reduction and reuse avoid all emissions associated with recycling,
composting, combusting, or landfilling the materials.
Extended Producer Responsibility (EPR). EPR is a strategy designed to promote the
integration of all costs associated with products throughout their life cycle (including
end-of-life disposal costs) into the market price of the product. EPR is meant to impose
accountability over the entire lifecycle of products and packaging introduced to the
market. This means that firms which manufacture, import, and/or sell products are
required to be responsible for the products after their useful life as well as during
manufacture.
Polluter Pay Principle. This is the principle that requires the polluting party to pay for
the impacts caused to the environment. With respect to solid waste management, this
generally refers to the requirement for a waste generator to pay for appropriate disposal
of the wastes. Table I.4 summaries the net environmental impacts of recycling,
incineration, and landfilling of 1 kg MSW. Negative values results from displacement of
energy and processing of raw materials when incineration or recycling are used. MSW
landfills generate CH4 as a by-product because of the anaerobic biodegradation of
organic components in MSW.

15
Table I.3. Recycling, Incineration, and Landfilling of MSW.
Solid Waste (kg/kg)
CO2 (kg/kg)
CH4 (kg/kg)
CO (kg/kg)
NOX (kg/kg)
SO2 (kg/kg)

Recycling
0.416
1.247
0
0.013
4.710-3
5.510-3

Incineration
+0.233
+0.490
0
+410-4
110-4
2.910-3

Landfilling
+1.000
+0.159
+0.062
+510-4
+510-4
+110-4

Combustion of MSW in Various Countries (1996).


Country
Japan
Switzerland
Sweden
France
Germany
Netherlands
U.S.
Italy
U.K.
Spain

%
67.0
64.0
43.0
40.0
37.0
33.0
18.0
14.0
7.0
4.0

Example I.1. If the current recycling rate for aluminum can is 63%, find the primary
energy required to produce the aluminum in a 355 mL (12 oz) aluminum can having a
mass of 16 g. (1) How much energy is saved when a can is recycled instead of being
thrown away? (2) What is the equivalent amount of gasoline wasted when one can is
thrown away? Gasoline has an energy content of about 35,000 kJ/L.
Source

Electricity
(kWh/kg)1

Fossil Fuel
(kJ/kg)

Primary Energy
(kJ/kg)2

CO2 Emissions3
(kg/kg)

Bauxite

15

60,000

235,0004

13.1

Recycled
0.08
4,000
5,1505
0.48
1 1 kWh (kW-hr) = (1 kJ/s)(3,600) = 3,600 kJ. 2 The equivalent heat energy an average thermal
power plant (e.g., a 33-% efficient coal-burning power plant) would need to generate 1 kW-hr
(kWh) electricity (~ 11,700 kJ/kWh for the U.S.). 3 Half hydroelectric, half coal-fired power
plants. 4 1511,700 + 60,000. 5 0.0811,700 + 4,000.

1.1.
1.2.
2.1.
2.2.
3.

The primary energy needed for the 37% of the can made from bauxite is:
(0.016 kg/can)(0.37)(235,000 kJ/kg) = 1,391 kJ/can.
The primary energy needed to produce the rest from recycled aluminum is:
(0.016 kg/can)(0.63)(5,150 kJ/kg) = 52 kJ/can. Therefore, total primary energy
for an average can with 63% recycled aluminum is 1,391 + 52 = 1,443 kJ/can.
The primary energy needed to produce a new can from ore is:
(0.016 kg/can)(235,000 kJ/kg) = 3,760 kJ/can.
The primary energy needed to produce a new can from recycled aluminum is:
(0.016 kg/can)(5,150 kJ/kg) = 82 kJ/can. Therefore, the energy saved by
recycling is: 3,760 82 = 3,678 kJ/can.
The equivalent amount of gasoline thrown away when a can is not recycled is:

16

3,678
= 0.105 L = 105 mL.
35,000
Mineral Ore Requirements. The magnitude of the earth- and ore-moving tasks
needed to provide the minerals society demands is truly monumental. Digging holes,
removing the ores, and piling up the leftover residues create enormous aesthetic,
environmental, economic, and energy problems.
Mineral

Average Grade (%)

Ore (Residue) (kg/100 kg Product)

Aluminum

23.00

435 (335)

Copper

0.91

10,900 (10,890)

Iron

40.00

250 (150)

Lead

2.50

4,000 (3,900)

Nickel

2.50

4,000 (3,900)

Generation and Recovery of Materials in MSW in the U.S. (1993).


Material
Paper/Paperboard
Glass
Metals
Ferrous Metals
Aluminum
Non-Ferrous Metals
Plastics
Rubber & Leather
Textiles
Wood
Other Materials
Food Wastes
Yard Trimmings
Miscellaneous Inorganic
Wastes
Total MSW

Generated (million tones)


70.6
12.4

Recovered (million tones)


24.0
2.7

11.7
2.7
1.1
17.5
5.6
5.5
12.4
3.0
12.5
29.8
2.8

3.1
1.0
0.7
0.6
0.4
0.6
1.2
0.6
Nil
5.9
Nil

187.7

40.8

Figure I.9 illustrates the energy values of various constituents found in solid waste
streams. Figure I.10 illustrates plastics that can be recycled.

HAZARDOUS WASTES. A waste is hazardous if (1) it is, or contains, a listed


waste; or (2) it demonstrates any of the Following 4 characteristics: ignitability,
corrosivity, reactivity, and toxicity; or (3) it is otherwise capable of causing
environmental or health damage if disposed of improperly.
Ignitability. Ignitable wastes can create fires under certain conditions, are
spontaneously combustible, or have a flash point less than 60C (140F). Examples
include waste oils and used solvents.

17

Figure I.9. Energy values of various constituents in solid waste streams.

Figure I.10. Recyclable plastics chart.


Corrosivity. Corrosive wastes are acids or bases (pH < 2, or > 12.5) that are capable of
corroding metal containers, such as storage tanks, drums, and barrels. Battery acid is an
example.

18
Reactivity. Reactive wastes are unstable under "normal" conditions. They can cause
explosions, toxic fumes, gases, or vapors when heated, compressed, or mixed with water.
Examples include lithium-sulfur batteries and explosives.
Toxicity. Toxic wastes are those containing concentrations of certain substances in
excess of regulatory thresholds which are expected to cause injury or illness to human
health or the environment. There are generally three types of toxic entities; chemical,
biological, and physical. Chemical toxicants include inorganic substances such as lead;
mercury; hydrofluoric acid; and chlorine gas, organic compounds such as methyl
alcohol; most medications; and poisons from living things. Biological toxicants include
bacteria and viruses that can induce disease in living organisms. Biological toxicity can
be difficult to measure because the "threshold dose" may be a single organism.
Theoretically one virus, bacterium, or worm can reproduce to cause a serious infection.
However, in a host with an intact immune system the inherent toxicity of the organism is
balanced by the host's ability to fight back; the effective toxicity is then a combination of
both parts of the relationship. A similar situation is also present with other types of toxic
agents. Physical toxicants are substances that, due to their physical nature, interfere
with biological processes. Examples include coal dust and asbestos fibers, both of which
can ultimately be fatal if inhaled.
Examples of hazardous wastes include: (1) spent halogenated solvents used for
degreasing, e.g., trichloroethylene (TCE) and methylene chloride; (2) spent nonhalogenated solvents such as xylene, acetone, and ethylbenzene; (3) wastewater
treatment sludges from electroplating operations; (4) dewatered air pollution control
scrubber sludges from coke ovens and blast furnaces; (5) sludges generated during the
production of various chromium compounds; and (6) API (American Petroleum
Institute) separator sludges from petroleum refineries.
Cradle-to-Grave Hazardous Waste Management (Figure I.10). The EPAs
cradle-to-grave hazardous waste management system is an attempt to track hazardous
waste from its generation point (the cradle) to its ultimate disposal point (the grave).
The system requires generators to attach a manifest (itemized list describing the
contents) form to their hazardous waste shipments. This procedure is designed to
ensure that wastes are directed to, and actually reach, a permanent disposal site. Under
the cradle-to-grave concept, a generator of hazardous wastes can no longer avoid the
liability by contracting with a third party to dispose of the wastes. Even if it can be
shown that the wastes were mishandled through the actions of a third party, the original
generator will remain liable for improper disposal. This compels generators to exercise
care in the selection of the disposal companies they utilize.
Example I.2 (Site audit of hazardous waste inventories). The state agency has
accused your waste transfer facility of accidental PCB (polychlorinated biphenyl) spillage
over the past year that has contaminated the upper 5 cm of the soils in the facility (~ 140,000
kg of soil) with PCBs > the regulatory action level of 50 ppm. Since measurements of soil
samples for PCBs will cost $60,000, you instead decide to perform a waste audit on PCB
inventories at the facility over the past year. Can you refute the agencys claims? Because
PCBs have low volatility and water solubility, volatilization and leaching losses are negligible.
The facility generates a wastewater stream with a mean flow of 890,000 L/day and a mean
PCB concentration of 0.002 mg/L.

19

Generator (cradle)
U.S. EPA

Transporter

Treatment/Storage/Disposal Facility (grave)


Figure I.10. Hazardous waste management (the cradle-to-grave approach).
RCRA Disposal Manifests:

Manifest #

Volume (L)

PCB Concentration (mg/L)

Mass (kg)

0124

1,890

22,100

41.8

0125

1,890

18,400

34.8

0126

1,890

9,550

18.0

0127

1,890

6,420

12.1

Incoming Shipments of Transformer Oils:

Invoice #

Volume (L)

PCB Concentration (mg/L)

Mass (kg)

01137

208

42,000

8.75 (20842,00010-6)

01138

1,740

1,300

2.27

01139

795

22,000

17.5

01140

3,260

8,200

26.7

01141

1,440

38,000

54.6

1.
2.
2.1.
2.2.
3.
4.
5.

Mass of PCBs delivered to the waste transfer facility: 8.75 + 2.27 +17.5 + 26.7 +
54.6 = 109.8 kg.
Mass of PCBs leaving the waste transfer facility:
Industrial wastewater: (1,890,000 L/day)(0.002 mg/L)(365 days) = 1.38 kg.
RCRA manifests: 41.8 + 34.8 + 18.0 + 12.1 = 106.7 kg.
Total (Wastewater + RCRA): 108.1 kg.
Total mass unaccounted for: 109.8 108.1 = 1.7 kg.
Total mass that triggers regulatory action: (50 mg/kg)(140,000 kg) = 7.0 kg >
1.7 kg. Therefore, a case could be presented to the state regulatory agency that
the losses do not provide sufficient PCB concentrations in the soil to exceed the
regulatory action level.

20

PCBs

U.S. ENERGY USE. The U.S. is the largest energy consumer in terms of total use,
using 1.051017 kJ (1 kJ = 1,000 J) in 2005. This is three times the consumption by the
U.S. in 1950. The U.S. ranks 7th in energy consumption per-capita after Canada and a
number of small countries. The majority of this energy is derived from fossil fuels: in
2005, it was estimated that 40% of the nation's energy came from petroleum, 23% from
coal, and 23% from natural gas. Nuclear power supplied 8.4% and renewable energy
supplied 7.3%, which was mainly from the hydropower. Energy consumption has
increased at a faster rate than energy production over the last 50 years in the U.S., and
the difference is now largely met through imports. The per capita energy consumption in
the U.S. has been somewhat consistent from the 1970s to today (i.e., 3.27108 kJ/capitayear, from 1980 to 2006). Major reasons for this include the significant improvements
in manufacturing efficiencies, better energy conservation practices, and overseas
productions of many consumer goods purchased by the U.S. consumers. However, U.S.
"off-shoring" of manufacturing is sometimes exaggerated, because U.S. domestic

manufacturing has grown by 50% since 1980.


Industrial (37%)
Primary Metals (26.1%).
Chemicals (19.3%).
Petroleum and Coal (13.8%)
Paper (7.9%).
Stone and Glass (6.9%).
6. Other Industry (20.6%).
1.
2.
3.
4.
5.

1.
2.
3.
4.

Transportation (28%)
Highway Vehicles (74%).
Air (14%).
Marine (7%).
Rail (5%).

World Proven Conventional Natural Gas (NG) Reserves (can last ~ 60 years).
Former U.S.S.R.
Iran
U.S.A.
Saudi Arabia
Algeria
Other

44%
15%
6%
4%
3%
28%

Shale Gas (Figures I.11 and I.12). Shale gas is the natural gas that is being trapped
within shale formations. Shale gas has become an increasingly important source of
natural gas in the U.S. since the start of the 21th century. In 2000 shale gas provided
only 1% of U.S. natural gas production; by 2010 it was over 20% and the U.S.
government's Energy Information Administration predicts that by 2035 shale gas will
account for about 46% of the natural gas supply in the U.S. Shale gas is one of a number
of unconventional sources of natural gas; others include coal-bed methane, tight
sandstones, and methane hydrates.

21

Figure I.11. The location of shale gas.

(1) Marcellus (141 tcf), Haynesville (66 tcf), Eagle Ford (50 tcf), Barnett-Woodford (27 tcf),
and Woodford (24 tcf).
(2) Total for Continental U.S. Shale Gas Reserve: 542 tcf.
(3) Annual U.S. NG Consumption (2011): 2.43 tcf.
(4) 1 tcf = 11012 ft3 = 2.831010 m3.

Figure I.12. Shale gas deposits in the continental U.S.


Since shales have low permeability to allow significant fluid flow to a well bore, they are
not commercially viable sources of natural gas until the technology of hydraulic
fracturing (fracking) matures after nearly 20 years of development. In general, the
technology of fracking has two parts, vertical drilling and horizontal drilling. First, a well
is drilled down to the shale, and then the well is drilled horizontally up to 3,000 m within

22
the shale to create maximum borehole surface in contact with the shale. A fluid mix of
water, sand, and chemicals is pumped down the well at the high pressure, creating
fissures in the shale that permit gas flow to the well. Pathways may be created during the
whole drilling process that allow gas or chemicals to enter the streams and groundwater
aquifers. Contaminated water from fracking is often stored in surface ponds, which can
overflow or leak, polluting streams or groundwater. Wells are usually reinforced with
steel casing and sealed with concrete. But poor cementing can leave gaps that allow
methane or fracking chemicals to contaminate the groundwater aquifers. Fracking
fissures might connect to natural ones, allowing pollutants to migrate. Whether they
would be able to move hundred meters upwards to reach shallow aquifers is unclear.
World Proven Conventional Oil Reserves ( ~ 4 trillion barrels).
Saudi Arabia
Iraq
United Arab Emirates (UAE)
Iran
Kuwait
Former U.S.S.R.
Venezuela
Mexico
U.S.A.
Other

18.4%
11.0%
10.8%
10.6%
10.3%
6.5%
6.3%
6.2%
3.5%
16.4%

Oil Sands (Figure I.13). Oil sands, tar sands or, more technically, bituminous sands,
are unconventional oils. The oil sands are loose sand or partially consolidated
sandstone containing naturally occurring mixtures of sand, clay, and water that are
saturated with bitumen (or tar). Natural bitumen deposits are reported in many
countries, but in particular are found in extremely large quantities in Canada. Other
large reserves are located in Kazakhstan and Russia. The estimated deposits in the U.S.
could be as much as 2 trillion barrels. The estimates include deposits that have not yet
been discovered; proven reserves of bitumen contain approximately 100 billion barrels.
Total natural bitumen reserves are estimated at 249.67 billion barrels (39.7109 m3)
globally, of which 176.8 billion barrels (28.1109 m3), or 70.8%, are in Canada. U.S.
consumed roughly 6.9 billion barrels of oil (18.8 million barrels per day) in 2011.
Making liquid fuels from oil sands requires energy for steam injection and refining. This
process generates a 12 percent higher amount of greenhouse gases per barrel of final
product as the "production" of conventional oil. The oil sands must be extracted by strip
mining or the oil made to flow into wells by in-situ techniques, which reduce the
viscosity by injecting steam, solvents, solvents, and/or hot air into the sands. These
processes can use more water and require larger amounts of energy than conventional oil
extraction, although many conventional oil fields also require large amounts of water
and energy to achieve good rates of production. After excavation, hot water and caustic
soda (NaOH) is added to the sand, and the resulting slurry is piped to the extraction
plant where it is agitated and the oil skimmed from the top. Provided that the water
chemistry is appropriate to allow bitumen to separate from sand and clay, the
combination of hot water and agitation releases bitumen from the oil sands, and allows
small air bubbles to attach to the bitumen droplets. The bitumen froth floats to the top
of separation vessels, and is further treated to remove residual water and fine solids.

23
About 2,000 kg of oil sands are required to produce one barrel of oil. Originally, roughly
75% of the bitumen was recovered from the sand.

Figure I.13. Oil sands.


However, recent enhancements to this method include Tailings Oil Recovery (TOR) units
which recover oil from the tailings, Diluent Recovery Units to recover naptha from the
froth, Inclined Plate Settlers (IPS) and disc centrifuges. These allow the extraction
plants to recover well over 90% of the bitumen in the sand. After oil extraction, the
spent sand and other materials are then returned to the mine, which is eventually
reclaimed.
LAND USE. The United States has a total land area of nearly 2.3 billion acres. Major
uses in 2002 were forest-use land, 651 million acres (28.8 percent); grassland pasture
and range land, 587 million acres (25.9 percent); cropland, 442 million acres (19.5
percent); special uses (primarily parks and wildlife areas), 297 million acres (13.1
percent); miscellaneous other uses, 228 million acres (10.1 percent); and urban land, 60
million acres (2.6 percent). Soil, water, air, minerals, biota, and energy are resources
essential to human. These resources are fundamentally dependent on land.
1.
2.
3.
4.
5.
6.

Land contains water the largest reservoir of fresh water, both surface water and
groundwater.
Land supports all terrestrial biota, both natural and domesticated. This biota
provides over 90% of food, all timber, and natural fibers that human consumes.
By supporting natural biota and ecosystems, land provides natural services
affecting water and air quality.
Nearly all mineral resources are mined from the land.
Coal, oil, natural gas, and uranium mined from the land. In addition, land
provides space for hydroelectric reservoirs, power plants, wind mills, and solar
installations.
Land provides space for all human activities, homes, stores, schools, offices,
factories, roadways, parking lots, airports, landfills, and other facilities that make

24
up cities and towns and connections between them. Also, land is used for
recreational activities and aesthetic pleasure. Even water-based activities require
land facilities such as beaches and marinas.
Overview of Land Use in the U.S. The U.S. has 2.3 billion acres of land. However,
375 million acres are in Alaska and not suitable for agricultural production. The land
area of the lower 48 states is approximately 1.9 billion acres. To put things in
perspective, keep in mind that California is 103 million acres, Montana 94 million acres,
Oregon 60 million acres and Maine 20 million acres. Only 66 million acres in the U.S. (~
3%) are considered developed lands, which is home to 75% of the population in the
country. In general, urban lands are nearly useless for biodiversity preservation.
Moreover, urbanized lands, once converted, usually do not shift to another use.
Rural residential land comprises nearly all sprawl and subdivisions along with
farmhouses scattered across the country. The total acreage for rural residential is 73
million acres. Of this total, 44 million acres are lots of 10 or more acres.
About 349 million acres in the U.S. are planted for crops. This is about 4 times the size
of Montana. Four crops, namely, feeder corn (80 million acres), soybeans (75 million
acres), alfalfa hay (61 million acres), and wheat (62 million acres), make up 80% of total
crop acreage. All but wheat are primarily used to feed livestock. The amount of land
used to produce all vegetables in the U.S. is less than 3 million acres.
Some 788 million acres, or 41.4% of the U. S. excluding Alaska, are grazed by livestock.
This is an area the size of 8.3 times the size of Montana. Grazed lands include rangeland,
pasture, and cropland pasture. More than 309 million acres of federal, state, and other
public lands are grazed by domestic livestock. Another 140 million acres are forested
lands that are grazed. Forest lands comprise 747 million acres. Of these lands, some 501
million acres are primarily forest (minus lands used for grazed forest and other special
categories).
The USDA report concludes that urbanization and rural residences (subdivisions) "do
not threaten the U.S. cropland base or the level of agricultural production." This does
not mean sprawl doesn't have impacts where it occurs. But the notion that sprawl is the
greatest threat to biodiversity is false. Figure I.14 shows the urban sprawl in Las Vegas,
Nevada.

25

Figure I.14. Urban Sprawl (Las Vegas, NV).

26

II. PRINCIPLES OF MASS AND ENERGY BALANCES


Mass (material) and energy balances are key tools in understanding the fate of a
contaminant in the environmental compartments under a wide variety of conditions.
The law of conservation of mass states that mass can neither be produced nor
destroyed. This law means that if the amount of a chemical somewhere (e.g., in a lake)
increases, then that increase cannot be the result of some magical formation. The
chemical must have been either carried into the lakefrom elsewhere or produced via
chemical and/or biological reactions from other compounds that were already in the
lake. Similarly, if reactions produced the mass increase of this chemical, they must also
have caused a corresponding decrease in the mass of some other compound(s). In
addition to the utilization of materials for various purposes, modern society also depends
on the extensive uses of energy which require transformations in the form of energy and
control of energy flows. Energy takes many forms and the movement of energy and
changes in its forms can be tracked using energy balances, which are analogous to mass
balances. The 1st law of thermodynamics states that energy can neither be produced
nor destroyed. However, all energy balances are treated as conservative; as long as all
possible forms of energy are considered (in the absence of nuclear reactions), there is no
term in energy balances that is analogous to the chemical/biological reaction term in
mass balances.
CONTROL VOLUME (c.v.). Mass and energy balances are only meaningful in terms
of a specific region in the space, which has boundaries across which the terms of input(s)
output(s), heat flow(s), and work flow(s) (i.e., flow work and shaft work) can be defined,
determined, and quantified. Theoretically, any volume of any shape and location can be
used as a control volume (c.v.). Realistically, however, certain control volumes are more
useful than others. The system boundary defined can be real, imaginary, stationary, or
moving. Figure II.1 illustrates the schematic of a control volume along with the terms to
be included.

Input(s)

CONTROL VOLUME
Accumulation
Generation
Consumption

Output(s)

System Boundary
Figure II.1. Schematic of a control volume.
MASS BALANCES. The law of conservation of mass for a chemical species i can be
applied to the control volumes illustrated in Figure II.1 and written in the following
general way. However, the characteristics of the c.v. need to be clearly defined prior to

27
the formulation of the mass balance equations that will be useful for practical
applications.
Accumulation rate of species i in the c.v. (mass/time, or M/T) = Input(s) of species i to
the c.v. (M/T) Output(s) of species i from the c.v. (M/T) + Generation rate of species i
in the c.v. (M/T) - Consumption rate of species i in the c.v. (M/T).
A Completely Mixed Control Volume. In many cases large quantities of energy in
various forms can be transported, via artificial or natural means, across the system
boundary from the surroundings into the control volume. Such energy input(s) render
the contents in the control volume to be completely mixed and uniform. As a result, the
characteristics of the output(s) will be identical to those observed in the control volume.
A number of assumptions can be made to facilitate the mathematical derivation of mass
balance equations for a completely mixed control volume:
1.

Species i is being carried into and out of the c.v. by a single slow of a specific

2.

3.
4.

environmental medium (e.g., water or air) at a constant volumetric flow rate ( V ,


volume/time, or L3/T).
Species i is being consumed in the c.v. at a rate that is proportional to its mass m
according to the first-order rate expression km = kVC, where k is the firstorder degradation rate coefficient, T-1; V is the volume of the c.v., volume, or L3;
and C is the concentration of species i in the c.v., M/L3.
No generation of species i in the c.v.
The volume of the c.v. (V) is constant.

Therefore,

dm
dt

c .v .

m in m out km c.v.

d (VC )
dC
V
V Ci V C kVC
dt
dt

dC V
V
Ci
dt V
V

(II.1)

C kC

m m
C
V V

where m is the mass rate (or mass flux) of species i, M/T; and Ci is the input
concentration of species i, M/L3. The first-order rate expression for the consumption
term is commonly used to describe the rate at which a contaminant is removed in a
specific environmental compartment. A similar expression can also be used to define the
generation term. (II.1) is the mass balance equation for a control volume which is

28
referred to as the first-order CFSTR (continuous-flow, stirred-tank reactor) system. At
steady state (i.e.,

dC
0 ), then (II.1) is simplified to:
dt

Ci
V
1 k

V
V

Ci
1 k
(II.2)

V
where is the hydraulic retention time (HRT), T; which is the average detention time
of species i in the c.v. If k = 0, then species i is a conservative (or non-reactive) species.
Many anthropogenic chemicals are recalcitrant which are degraded very slowly in the

environment and therefore, they are often treated as conservative. If V 0 , then the c.v.
is defined as the batch system. If species i is carried into the c.v. by multiple streams,
then

V V

Ci

Cj V

(II.3)

where V j is the volumetric flow of the jth stream, L3/T; and C j is the input
concentration of species i in the jth stream, M/L3. Sometimes, the chemical species can
also be released directly inside the c.v. via internal emission sources (e.g., a smokestack
that emits flue gas containing SO2). Then, the input term in (II.1) should include such
sources in addition to those introduced by input streams. The internal emissions are
often expressed directly as the mass fluxes.
A Plug-Flow Control Volume. Unlike a CFSTR system, mixing is completely absent
in a plug-flow (PF) system. For instance, if water flows in a long channel with small
cross-sectional area, then the physical configuration of the channel hinders the
longitudinal mixing in the direction of flow. As a result, this channel can be modeled as a
PF system. A PFR system simply indicates that the reaction terms (generation or
consumption or both) should be included in the mass balance equation. The mass
balance equation for a PFR system can proceed by focusing on a differential volume with
a constant cross-sectional area A and a volume of Ax, where x is the differential
distance in the direction of flow. The concentration in the volume can be considered as
uniform because the volume is small.

x x

29

Ax

C
V C V C
kCAx
t
x
x x

C
V C x C
t
Ax
Ax

C V C x C

t A
x

x 0

x x

x x

kCAx

kC

(II.4)

C
C
u
kC
t
x

V
u
A
where u is the average velocity of the environmental medium that carries the pollutant in
the direction of flow, L/T.
At steady state, then
kx

*
dC
u
kC C ( x) Ci e u Ci e kt
dx
x
t*
u

(II.5)

where t * is the travel time which is the time required to cover a distance x at a constant
velocity of u, T.
Example II.1 (A Polluted Lake). A lake (V = 1107 m3) is fed by (1) a polluted stream
having a flow rate of 5.0 m3/s and a pollutant concentration of 10 g/m3 and (2) a
wastewater discharge having a flow rate of 0.5 m3/s and a pollutant concentration of 100
g/m3. The pollutant is degraded in the lake at a first-order rate of 0.2 day-1. Assuming
the lake is completely mixed with no evaporation or other water losses or gains, find the
steady-state pollutant concentration in the lake.
1.
2.
3.

At steady state, inputs = output + consumption (or degradation).


Inputs = (0.5 m3/s)(100 g/m3) + (5.0 m3/s)(10 g/m3) = 100 g/s.
Output = (0.5 m3/s + 5.0 m3/s)(C g/m3) = 5.5C g/s.

4.

Consumption = kCV = (0.2 day-1)(1107 m3)(C g/m3)(

5.

Therefore, 100 = 23.1C + 5.5C C = 3.5 g/m3.

1
s/day) = 23.1C g/s.
86,400

30
Example II.2 (A Smoking Bar). A bar (V = 500 m3) has 50 smokers in it, each
smoking 2 cigarettes per hour. An individual cigarette emits about 1.4 mg formaldehyde
(HCHO). HCHO converts to CO2 at a first-order rate of 0.4 hr-1. Fresh air enters the bar
at 1,000 m3/hr, and stale air leaves at the same rate. Assume complete mixing, estimate
the steady-state HCHO concentration in the air inside the bar. At 25oC and 1 atm, how
does the result compare with the threshold for eye irritation of about 0.5 ppmv?
1.
2.
3.
4.
5.

At steady state, input = output + consumption (or degradation).


Input = (50)(2)(1.4) = 140 mg/hr (note that this input is the internal emission
and that the incoming fresh air is free of HCHO).
Output = (1,000 m3/hr)(C mg/m3) = 1,000C mg/hr.
Consumption = kCV = (0.4 hr-1)(500 m3)(C mg/m3) = 200C mg/hr.
Therefore, 140 mg/hr = (1,000 + 200 m3/hr)(C mg/m3) C = 0.117 mg/m3.

6.

According to (I.2), C

(0.117)(273.15 25)(22.414)
= 0.095 ppmv > 0.05
(273.15)(30)

ppmv the steady-state HCHO concentration in the air inside the bar will cause
eye irritation.
Example II.3. The air in the bar of Example II.2 is clean when it opens at 5PM. If
formaldehyde is emitted from cigarette smoking at a constant rate of 140 mg HCHO/hr
starting at 5 PM, what would the concentration be at 6PM?
1.

This is a non-steady-state problem. Since formaldehyde is introduced directly via


cigarette smoking at a rate of 140 mg/hr, (II.1) should be modified to:

V
2.

dC
140 V C kVC
dt

(a)

(a) can be integrated with initial condition (C = 0 at t = 0), then

V kV t

140

1 e V 0.117 1 e 2.4t
C (t )

V kV

3.

(b)

If 5 PM is taken as t = 0, then 6 PM is t = 1 hr. Therefore, C = 0.106 mg/m3.


Note that

140

C ( ) C

V kV

steady state

Example II.4 (CFSTR vs PFR). Calculate the respective volumes of a CFSTR system and a
PFR system that are required to remove 95% of a pollutant. The first-order decay rate
coefficient is 0.2 day-1.
1.

For a CFSTR system,

C
1

0.05 95 days.
Ci 1 k

31

2.

For a PFR system,

*
C ( x)
e kt 0.05 t * = 15 days. Therefore, a first-order
Ci

PFR system is always more efficient than a first-order CFSTR system, i.e.,

VCFSTR 95

6.33.
VPFR
15
Example II.5 (Burning of Biogas). Biogas, which is about 70% CH4 and 30% CO2, is
produced from the anaerobic fermentation of organic sludge. The biogas can be used as a fuel
if the corrosive sulfur compounds (e.g., H2S) are in low concentrations or are removed.
Assuming that this is done, make the mass balance for combustion in the presence of 10%
excess O2 to insure complete combustion. The source of O2 is air, which is 79% by weight N2
and 21% by weight O2. Use 1,000 kg input of dry biogas as the basis for calculations. The
combustion reaction is: CH 4 2O2 CO2 2H 2O .
1.

(700)(64)
= 2,800 kg O2 Feed O2 = (2,800)(1.1) =
16
(3,080)(79)
3,080 kg O2 Feed N2 =
= 11,586 kg N2. CO2 produced =
21
(700)(44)
(700)(36)
= 1,925 kg CO2. H2O produced =
= 1,575 kg H2O.
16
16
700 kg CH4 will consume

Therefore,

4.

Inputs

Outputs

700 kg CH4

0 kg CH4

300 kg CO2

2,225 (1,925 + 300) kg CO2

3,080 kg O2

280 (3,080 2,800) kg O2

11,586 kg N2

11,586 kg N2

0 kg H2O

1,575 kg H2O

Total: 15,666 kg gas

Total: 15,666 kg gas

Inputs = Outputs.

ENERGY BALANCES. When dealing with the energy problems, two fundamental
thermodynamics laws must prevail:
1st Law of Thermodynamics: Although energy assumes many forms, the total
quantity of energy is constant, and when energy disappears in one form it appears
simultaneously in other forms.
2nd Law of Thermodynamics: The 2nd law of thermodynamics can be stated in
different manners. Two most cited statements are:
1.
No equipment can be designed and operated for the sole purpose of
converting all energy inputs it received into useful work.

32
2.

It is impossible to devise a machine that can convert the energy from one
form to another with 100% efficiency.

Energy Forms: Various forms of energy are summarized in Table II.1. u is the velocity
of the working fluid, z is the elevation of the working fluid measured against a reference
point, and U is the internal energy of the working fluid (or the energy content of the
working fluid). The absolute value of U is unknown and as a result, a reference state
must be defined at which U is arbitrarily set at zero. For instance, the reference state for
calculating U values for water at different conditions is liquid water [H2O(l)] @ 0oC and 1

atm. X is the time rate of X, e.g., W is referred to as power which has the unit of
energy/time. The terms of heat and work refer only to energy that is being transferred
(i.e., the amount of heat energy added to or extract from the c.v.). It is meaningless to
speak of the heat and work possessed by or contained within the c.v. Heat is the energy
that flows as a result of temperature difference between a c.v. and its surroundings.
Work is the energy that flows in response to any driving force other than a temperature
difference (e.g., a force, a torque, or a voltage). Heat is defined as positive when it is
transferred to the c.v. from the surroundings. Work is defined as positive when it is done
by the c.v. on the surroundings.
Table II.1. Energy Forms.
Kinetic Energy

Ek

mu 2
2

Potential Energy

E p mgz

Internal Energy

Heat

Work

mu2
Ek
2

E p m gz

Energy and Power Units:


1.
2.
3.
4.

1 Joule (J) = 1 N-m = 107 ergs = 107 dyne-cm = 0.23901 cal (cal: calories) =
9.48610-4 Btu (Btu: British thermal unit) (1 kJ = 103 J).
1 Watt (W) = 1J/s (1 kW = 103 W = 103 J/s).
1 kW-h (kWh) = (103 J/s)(3,600 s) = 3,600 kJ.
1 horsepower (hp) = 746 W = 746 J/s.

Table II.2 summaries power consumptions of common household appliances.


Energy Balances on Steady-State, Continuous-Flow Systems. It is convenient
to evaluate the rate of change of a specific energy form as the fluid streams (i.e., air or
water) flow across the c.v. from the inlet locations to the outlet locations. If = outlet
inlet, then
Table II.2. Power Consumptions of Household Appliances.
Appliance

Power (W)

Hours Used/Year (year 2000)

33
Clock
Clothes Dryer
Hair Dryer
Light Bulb
Compact Fluorescent Light Bulb
T.V.
Water Heater (150 L)
EnergyEfficient Water Heater (150 L)
Toaster
Washing Machine
Refrigerator
EnergyEfficient Refrigerator

2
mj uj
Ek
2
j

2
4,600
1,000
100
18
350
4,500
2,800
1,150
700
360
180

mj uj

j
out

17
1,049
60
108
19
504
4,698
2,900
552
1,008
2,160
1,100

in

E p m j gz j m j gz j
j
out j
in

U U
j

out j

W W fl W s Pj V
j

in

(II.5)

Pj V

out j

W s

in

where the subscript j represents the jth stream, W

fl

is the rate of flow work which is the

power required to move the fluid streams through the c.v., W s is the shaft work that
accounts for the work transferred across the boundary of the c.v. by devices with moving

parts located at the boundary of the c.v. (e.g., a pump or a turbine); and Q is the rate at

which heat is transferred across the system boundary. The definition of W fl is based on

V
Ax
x
the observation that P V P
P
F
Fu , where F is the force in the
t
t
t
direction of flow, A is the cross-sectional area which is perpendicular to F and across
which the fluid flows, x is the displacement in the direction of flow, and u is the fluid

velocity in the direction of flow. ( Pj V j ) in , which is the work done by the surroundings
on the jth fluid stream entering into the c.v., is negative (i.e., the fluid is being pushed

into the c.v. from the surroundings. ( Pj V j ) out is the work done by the c.v. on the jth
fluid stream exiting the c.v. and therefore, it is positive (i.e., the fluid is being pushed out

of the c.v.). By the same token, W s is positive if the devices with moving parts extract

the energy from the c.v., and W s is negative if the devices with moving parts deliver the
energy from the surroundings into the c.v. At steady state, the sum of the rates of change

34
in kinetic, potential, and internal energies between input and output locations is equal to
the sum of work and heat flows across the system boundary, or
Accumulation rate of energy in the c.v. = Input(s) of energy to the c.v. Output(s) of energy out of
the c.v. Input(s) = Output(s) (steady state).
Therefore,

Q W s [(U j Pj V j ) E kj E pj ]output [(U j Pj V j ) E kj E pj ]input

(II.6a)

( H j E kj E pj ) output ( H j E kj E pj ) input

(II.6)

H E k E p Q W s

where H = U + PV is termed as enthalpy that can be taken as the total energy value of the
working fluid at given P and T. Also,

H U PV

(II.7)

H H
where H
is the specific enthalpy which is an intensive property that is
m m

independent of the quantity of the substance present. The absolute values of H and

U U are not known, only and U can be determined by referring to a


U
H

m m

reference state that can be arbitrarily selected for convenience. V is the reciprocal of

density (i.e., V =

V
V
or ) (n is the number of moles of the species concerned). For
m
n

liquid water [H2O(l)] at low pressures (0100oC), H m C p T , where Cp is the


specific heat capacity of water at constant pressure (4.184 J/g-oK, or 75.4 J/mol-oK) and
T is the temperature difference between input and output locations.
Mechanical Energy Balances. In some flow processes the internal energy values of
the fluid streams remain constant as they enter into and exit from a c.v. As a result,
energy exchanges across a c.v. occur among kinetic, potential, and pressure energy terms
(e.g., water flow in a pipe, hydropower generations from reservoirs, etc.). In such cases,
(II.6) is modified to either (II.8) or (II.9) when a single fluid stream (j = 1) with a
constant mass density ( ) flows across a c.v. at a constant mass rate (i.e.,

m output m input m ):

35


W
u 2
Q

gz U s

2
m
m

Ws
P u 2
Q
U

z

g 2 g
g
m g
mg

(II.8)

(II.8a)

u 2
gz 0 (Bernoullis Equation)
2

Note that V

(II.9)

and U

is the friction loss. U is the amount of energy

exchanges that is caused by the viscous action between fluid particles.

is the amount

m
of energy dissipated from the system that is caused by the frictional resistances
encountered by the flowing fluid stream (e.g., water that flows in a conduit will
encountered the frictional resistances at the inner wall of the conduit). Each term in

u2
P
is the pressure head,
is the
2g
g

Q
U
velocity head, z is the potential head, and
is the head loss. The sum of
g
m g

(II.8a) has the unit of length and as a result,

pressure head, velocity head, and potential head is total head. The left side of (II.8a)
must be < 0 in order for the energy stored in the incoming fluid stream to be recovered
using the device such as a turbine. If the left side of (II.8a) is > 0, then the fluid stream
cannot flow from the inlet to outlet without using the device such as a pump to obtain
additional energy input. If (II.8a) = 0, then the fluid stream can flow from the inlet to
outlet by it self but no energy can be extracted from the fluid stream. (II.9) applies to
ideal flow conditions (i.e., no friction loss) and without moving parts located at the
boundary of a c.v.
Thermal Processes. Enthalpy changes for processes that involve phase changes (e.g.,
from liquid phase to vapor phase), chemical reactions (e.g., combustion of fuels), or large
temperature changes are usually very large as compared to kinetic and potential energy
changes. As a result, (II.6) can be modified to:

H Q W s

H m j H j m j H j
j
out j
in

(II.10)

If the c.v. is well insulated from the surroundings, then it is adiabatic and Q = 0. W s =
0 if there are no moving parts located at the boundary of the c.v. Note that the number
of incoming fluid streams may be different from that of outgoing fluid streams. Table
II.1 shows the specific enthalpy values of water and vapor at selected temperatures and

36
pressures. The P-T pair in Table II.3 represents the conditions at which liquid water
(saturated water) and water vapor (saturated vapor) can coexist in different
proportions according to:

mH 2O ( v ) saturated
mH 2O (l ) saturated mH 2O ( v ) saturated

(II.11)

m H 2O ( v ) saturated

m H 2O (l ) saturated m H 2O ( v ) saturated

where x is the quality of the water-vapor mixture, mH 2O ( v ) saturated [ m H 2O ( v ) saturated ] is the


mass (mass rate) of saturated water vapor in the mixture, and mH 2O (l ) saturated

[ m H 2O (l ) saturated ] is the mass (mass rate) of saturated liquid water in the mixture. x = 1
indicates that saturated liquid water is absent in the mixture whereas x = 0 indicates the
absence of saturated water vapor in the mixture. The reference state for Table II.1 is

liquid water at 0oC and 1 atm [i.e., H water(l )@ 0o C 0 kJ/kg (P = 1 atm)]. For instance,
at P = 100 kPa and T = 99.6oC water can exist as liquid water (saturated water) with a
specific enthalpy value of 417.5 kJ/kg, or as vapor (saturated vapor) with a specific
enthalpy value of 2,675.4 kJ/kg, or a mixture of water and vapor with a specific enthalpy
value calculated by (II.11) and (II.12). The specific enthalpy value of the mixture

[ H mixture (T , P) ] is:

H mixture (T , P) x H water(v ) (T , P) (1 x) H water(l ) (T , P)

(II.12)

Sensible and Latent Heats. The specific enthalpy changes ( H ) associated with
temperature changes for a single-phase system is referred to as the sensible heat of
the temperature change. The specific enthalpy changes associated with the
transition of a substance from one phase to another at constant temperature and
pressure is referred to as the latent heat of the phase change. Figure II.2 illustrates
the heat needed to convert 1 kg ice to steam at 1 atm. To change the temperature of 1 kg
of ice, 2.1 kJ/oC are needed (sensible heat requirement that change the temperature of
the ice which remains as a solid). To completely melt that ice requires another 333 kJ
(latent heat of melting, since the temperature remains constant at 0oC while the ice
changes from the solid state to liquid state). Raising the temperature of that liquid water
requires 4.184 kJ/oC (sensible heat), and converting it to steam requires another 2,257
kJ (latent heat of vaporization). To raise the temperature of 1 kg steam (at 1 atm)
requires another 2.0 kJ/oC. Table II.4 shows the latent heats of evaporation of water

[ H v ] at selected temperatures which are independent of P (low pressures). The

reference state for Table II.2 is liquid water at 0oC [i.e., H water(l )@ 0o C 0 kJ/kg (P = 1
atm)]. The latent heat of evaporation of water is calculated as:

37
Table II.3. Specific Enthalpy Values of Saturated Water [water(l)] and Vapor [water(v)].

P (kPa)
T (oC)
H water(l ) (kJ/kg)
H water(v ) (kJ/kg)
1
7.0
29.3
2,514.4
5
32.9
137.8
2,561.6
10
45.8
191.8
2,584.8
50
81.3
340.6
2,646.0
100
99.6
417.5
2,675.4
200
120.2
504.7
2,706.3
400
143.6
604.7
2,737.6
600
158.8
670.4
2,755.5
800
170.4
720.9
2,767.5
1,000
179.9
762.6
2,776.2
2,000
212.4
908.6
2,797.2
5,000
263.9
1,154.4
2,794.2
10,000
311.0
1,408.0
2,727.7
15,000
342.1
1,611.0
2,615.0
20,000
365.7
1,826.5
2,418.4

1 atm = 100kPa. 1 Pa = 1 N/m2. 1 atm = 1.01325105 Pa = 101.325 kPa = 1.01325 bar.

H water(v ) (T , P) H water( v ) (T , P) H water(l ) (0o C ) H water(v ) (T , P).

D
C
1

B
A

Heat Added
A: mixture of ice/water; B: liquid water (subcooled liquid); C: mixture of water/vapor (saturated
water/vapor); D: steam (superheated steam), 1: 100% saturated water (liquid), and 2: 100%
saturated steam (vapor).

Figure II.2. Heat needed to convert 1 kg ice to 1 kg steam.

H v (T , P) H water( v ) (T , P) H water(l ) (T , P)

(II.13)

For instance, at P = 100 kPa and T = 99.6oC, H water(l ) = 417.5 kJ/kg and H water(v ) =

38

2,675.4 kJ/kg (Table II.1). Therefore, H v = 2,675.4 417.5 = 2,258 kJ/kg, which is
the value in Table II.2 at T = 100oC.
Example II.6 (Power for the Hydrologic Cycle). Global rainfall has been
estimated to average about 1 m per year across the entire 5.101014 m2 of the earths
surface. Find the energy required to cause that much water to evaporate each year
(average global temperature is about 15oC). Compare this to the estimated 1987 world
energy consumption of 3.31017 kJ and compare it to the average rate at which sunlight
is absorbed at the surface of the earth, 168 W/m2.
1.
2.

T (oC)
0
2
4
6
8
10
12
14
16
18
20
22
24
25
26
28
30
32
34
36
38
40
42
44
46
48
50

The energy required to evaporate 1 kg of water at 15oC is 2,466.2 kJ (Table II.2,


the average of values @ 14 and 16oC).
The total energy requires to vaporize all of that water is: (1 m/yr)(5.101014
m2)(1,000 kg/m3) (2,466 kJ/kg) = 1.251021 kJ/yr, which is roughly 4,000
times of the energy consumed worldwide in 1987. Averaged over the globe, the
energy required to power the hydrologic cycle is: (1.251021 kJ/yr)(1 W/J/s)
(365 days/yr)-1(86,400 s/day)-1 = 78 W/m2 (~ 46% of the average rate at which
sunlight is absorbed at the earths surface).
Table II.4. Latent Heats of Evaporation of Water at Low Pressures.
Latent Heat of Evaporation (kJ/kg)
T (oC) Latent Heat of Evaporation (kJ/kg)
2,501.6
52
2,377
2,496.8
54
2,373
2,492.1
56
2,368
2,487.4
58
2,363
2,482.6
60
2,358
2,477.9
62
2,353
2,473.2
64
2,348
2,468.5
66
2,343
2,463.8
68
2,338
2,459.0
70
2,333
2,454.3
72
2,329
2,449.6
74
2,323
2,444.9
76
2,318
2,442.5
78
2,313
2,440.2
80
2,308
2,435.4
82
2,303
2,430.7
84
2,298
2,425.9
86
2,293
2,421.2
88
2,288
2,416.4
90
2,282
2,411.7
92
2,277
2,406.9
94
2,272
2,402.1
96
2,267
2,397.3
98
2,262
2,392.5
100
2,258
2,387.7
2,382.9

39

III. POWER GENERATION AND ENERGY EFFICIENCY


U.S. ENERGY CONSUMPTIONS (sources).
Source
Oil
Coal
Natural Gas (NG)
Nuclear
Hydropower
Others

%
40
23
23
8
2.7
3.3

THE COST OF A KILOWATT-HOUR (kW-h).


Source
Coal
NG
Wind
Nuclear
Solar

/kW-h
5.0
5.0
6.0
7.0
22.0

NEW YORK CITY WITHOUT FOSSIL FUELS (60% of NYCs electricity


is produced from coal and natural gas).
Solar
Wind
Nuclear

74 mi2 (145,225,714 6432 175W-panels)


10.6 mi2 (6,800 1.5MW-turbines)
2 mi2 (4 1,000-MW reactors)

ENERGY CONTENTS OF MSW (Table III.1) The energy content of MSW


depends on the materials that it contains as well as its moisture content. The standard
test used to determine the heating value of a material involves completely burning a
sample in a bomb calorimeter and then measure the rise in temperature of a surrounding
water bath.
Table III.1. MSW Energy Contents (without removing moisture).
Material
Paper & Paperboard
Yard Trimmings
Plastics
Food Wastes
Wood
Metals
Glass
Rubber & Leather
Textiles
Miscellaneous
TOTAL

kg
31.7
16.2
11.5
8.5
7.6
7.4
6.6
3.6
3.3
3.6
100

kJ/kg
15,800
6,300
32,800
5,500
16,000
--22,300
18,700
---

kJ
500,860
102,060
377,200
46,750
121,600
--80,280
61,710
-1,290,460

40
The following equations are useful in estimating the heating values of MSW:
HHV (kJ/kg) = 53.5(F + 3.6CP) + 372PLR
QL = 2,440(W + 9H)
LHV = HHV QL

(III.1)

(III.2)
(III.3)

where HHV is the higher heating value, kJ/kg; F is mass % of food, %; CP is the mass %
of cardboard and paper, %; PLR is the mass % of plastics, rubber, and leather, %; QL is
the latent heat of vaporization of water, kJ; W is the amount of moisture in the waste, kg;
H is the amount of hydrogen in the dry waste, kg; and LHV is the lower heating value,
kJ/kg. Only in unusual circumstances can the HHV be captured. Most likely, QL is lost
to the atmosphere and therefore, unrecoverable. (III.2) indicates there are two sources of
water vapor losses: moisture in the waste and hydrogen in the waste that reacts with
oxygen to form water. 2,440 kJ/kg (or 44 kJ/mol) is the latent heat of vaporization of
water at 25oC.
Example III.1. Typical MSW has a moisture content of around 20%, and roughly 6% of the
dry mass of MSW is hydrogen. Estimate the lower heat value.
1.
2.
3.
4.

The total heating value of 100 kg MSW is 1,290,460 kJ and therefore, the HHV is
1,290,460 kJ/100 kg or 12,900 kJ/kg.
In 1 kg waste, there will be 0.2 kg moisture and 0.8 kg of dry waste. In that dry
waste, there will be 0.80.06 = 0.048 kg of hydrogen.
From (III.2), QL = 2,440(0.2 + (9)(0.048)] = 1,540 kJ/kg.
Therefore, LHV = 12,900 1,540 = 11,360 kJ/kg.

HYDROPWER GENERATION. Hydraulic turbines (i.e., water-driven turbines)

are the modern incarnation of one of the oldest of energy conversion technologies, the
water wheel. Modern hydraulic turbines are designed to more efficiently capture the
energy of flowing water at hydroelectric dams and natural waterfalls like Niagara Falls.
Figure III.1 illustrates a simple sketch of a hydroelectric facility. Water collected behind
a dam is carried through large ducts to the inlet of one or more hydraulic turbines at the
base of the dam. Since the reservoir behind a dam covers a very large surface area, the
water level in the reservoir remains unchanged as a result of the release of water for
hydropower generation. Therefore, the energy available for the conversion to electricity
is the potential energy of the impounded water. Moreover, since the internal energy of
water changes very little between the air-water interface behind a dam (point 1) and tail
water (point 2), and the fact that the surface area of tail water is also large because of
the requirements of reducing the velocity of water after it exits the turbine house to
minimize the potential damages to the downstream infrastructure, then

P P2 P1 Patm Patm 0
u 2 u22 u12 0
z z2 z1 z

(III.4)

41

Figure III.1. Schematic of a hydropower plant.


Therefore, the mechanical energy balance equation can be expressed as:

Q
U
W s m gz

g
m g

(III.5)

The actual power delivered by the hydroelectric plant is turbine W s , where turbine is the
turbine efficiency.
Example III.2. A hydroelectric plant produces 150 MW of electricity. The operating
head is 35 m, and the water flow rate into the turbines is 500 m3/s. Determine the
turbine efficiency. Assume that the friction loss between reservoir and tail water is
negligible

1.

m (500)(1,000) 500,000 kg/s.

2.

turbine W s turbine(500,000)(9.81)(35) 150 106 turbine 0.87.

A major attraction of hydropower generation is that water is a renewable energy source


which is replenished by the natural cycle of evaporation and precipitation. At the same
time, however, there are only limited number of natural waterfalls and river flow capable
of generating significant amounts of electricity. In the U.S., the most attractive sites for
hydropower generation have already been exploited to provide the generating capacity of
76,700 MW (as of 1997). Locations still remain where smaller, low-head hydropower
generation facilities could be constructed, but such sites are typically in remote locations

42
where the difficulty and expense of transmitting the electricity diminish the benefits of
such projects, even in the absence of environmental concerns (e.g., long-term impacts on
land use and ecosystem in the vicinity of hydroelectric dams and displacement of
population and communities due to creation of reservoirs).

STEAM ELECTRIC (THERMAL POWER) PLANTS. Steam turbines are the

most prevalent method used worldwide for spinning the shaft of an electromechanical
generator. High-temperature steam (superheated steam) can be generated to produce a
hundredfold increase in the electrical output of a turbine generator compared to liquid
water alone. Steam turbines provide ~

2
of all the electric power generated in the U.S.
3

Figure III.2 illustrates a basic steam electric plant schematic (i.e., the Rankine cycle).
The closed-cycle arrangement permits the turbine exit pressure to fall below 1 atm
because a vacuum forms in the condenser as vapor turns to liquid. At the lower
pressure, condensation begins at temperatures below 100oC (see Table II.1). More useful
energy can therefore be extracted in the turbine without encountering the problems of
water condensation.

Ws

WC

QH

QC
Figure III.2. The schematic of a thermal power plant (the Rankine cycle).
There are four basic pieces of equipment in a typical steam electric plant: boiler, turbine,
condenser, and pump (see the diagram attached). The boiler is used to generate the
superheated steam at high P and T. Fuel and air (in excess of the stoichiometric amount
required) are introduced through burners protruding from the walls or corners of the
boiler. The boiler itself resembles a large box which can be up to several stories high.
The energy released from fuel combustion inside the combustion chamber heats the
boiler feed water, which flows through pipes embedded in the boiler walls. As the water
turns to steam, it is collected in a manifold and routed to the steam turbine. To
maximize the boiler efficiency, the hot (~ 425oC) .combustion gases exiting the
combustion chamber [flue gas which contains O2, NOX, SO2, N2, H2O(v), and
flyash] are passed through a heat exchanger, i.e., air preheater) to heat the incoming air
stream. This reduces the amount of fuel needed to heat the air inside the combustion
chamber. The boiler efficiency ( boiler ~ 88%) is:

43

m H 1 H 4

boiler
m fuel ( LHV ) fuel

(III.6)

where m is the mass rate of the working fluid (i.e., water) through the Rankine

cycle, kg/s; H 1 is the specific enthalpy value of the superheated steam exiting from the

boiler, kJ/kg; and H 4 is the specific enthalpy value of the saturated water entering the

boiler, kJ/kg; and m fuel is the mass rate of fuel burned in the boiler, kg/s. Typical
LHVs for fossil fuels are: 28,400 kJ/kg (bituminous coal), 19,400 kJ/kg (subbituminous
coal), 45,200 kJ/kg (distillate oil), 42,500 kJ/kg (residual oil), and 54,400 (natural gas:
85.3% CH4, 12.6% C2H6, and 2.1% other gases by volume).
The superheated steam produced from the boiler is used to turn the steam turbine,
which in turn rotates the generator shaft in a magnetic field to produce alternating
current (AC). As the superheated steam goes through the turbine, it expands and cools

while producing work. If W s and H 2 are denote as the gross electrical output of the
steam electric plant and the specific enthalpy value of the water/vapor mixture exiting
the turbine, respectively, then the turbine efficiency ( turbine) can be calculated using
(III.7).

m H 1 H 2
Ws
H

H
1
2

turbine

m H1
m H1
H1

H 2 x H 2 H 2O ( v ) (1 x) H 2 H 2O (l )

(III.7)

m 2 H 2O ( v )

m
As the superheated steam goes through the turbine, it condenses and exits the turbine as

a mixture of water/vapor. Therefore, H 2 is the weighted average of H 2 H 2O ( v ) and

H 2 H 2O (l ) , which are the specific enthalpy values of the saturated water vapor and
saturated liquid water at the outlet of the turbine, respectively. x in (III.7) is termed as
quality which indicates the fraction of saturated vapor in the water/vapor mixture

( m 2 H 2O ( v ) is the mass rate of saturated water vapor exiting the turbine, kg/s). The
water/vapor mixture is then condensed in the condenser and exits as a saturated liquid
(because the pump is usually designed to deliver the liquid water only). The amount of

heat removed from the water/vapor mixture in the condenser ( Q C ) is calculated using

44

(III.8), where H 3 is the specific enthalpy value of the saturated water exiting the
condenser. Note that T2 = T3 and P2 = P3.

Q C m H 2 H 3

(III.8)

The pump is used to pressurized the saturated water to that of the superheated steam
exiting the boiler. The work required to pressurize the saturated water is given by:

P P
W C m 4 3
g

(III.9)

where P4 is the absolute pressure at the exit of the pump, N/m2; P3 is the absolute
pressure at the entrance of the pump, N/m2; and is the mass density of water, kg/m3.
(III.9) is derived by assuming that changes in internal energy, kinetic energy, and
potential energy across the pump are negligible. The pump is also assumed to be
frictionless.
The overall plant efficiency (overall ) is:

overall Rankine

W s W C

m fuel ( LHV ) fuel


Note that overall is always << 1

Ws

(III.10)

m fuel ( LHV ) fuel

Tenvironment
= max (Carnot theorem) (T is in oK).
Tboiler

Table III.1 lists the specific enthalpy values of superheated steam at different P and T.
Example III.3. The gross electrical output of a steam electric plant is 500 MW. The
steam flow rate through the boiler and turbine is 642 kg/s. Steam leaves the boiler as
superheated steam at 15 MPa and 560oC, after entering the boiler as saturated water at a
pressure of 15 MPa. The boiler fuel is bituminous coal which is burned at a rate of 47.5
kg/s. Calculate the boiler efficiency and the overall plant efficiency.
1.

From (III.6), boiler

(642)(3,472.1 1,611.0)
0.886 , or 88.6%. The specific
(47.5)(28,400)

enthalpy values of superheated steam at 15 MPa and 500oC and 600oC are
3,310.6 and 3,579.8 kJ/kg, respectively (Table III.1). Therefore, the specific
enthalpy value of superheated steam at 15 MPa and 560oC is

(3,579.8 3,310.6)
60 3,472.1 kJ/kg (intrapolation).
100
500 106
From (III.10), overall
100 37.6%.
(47.5)(28,400)(103 )
3,310.6

2.

45

3.

If the ambient temperature is 20oC (293.15oK), then max 1

293.15

273.15 560

65%.

P (kPa)
1
5
10
50
100
200
400
600
800
1,000
2,000
5,000
10,000
15,000
20,000
30,000

Table III.1.
100oC
200oC
2,688.6 2,880.1
2,688.1 2,879.9
2,687.5 2,879.6
2,682.6 2,877.7
2,676.2 2,875.4
2,870.5
2,860.4
2,849.7
2,838.6
2,826.8

H Values (kJ/kg) of Superheated Steam1.


300oC
3,076.8
3,076.7
3,076.6
3,075.7
3,074.5
3,072.1
3,067.2
3,062.3
3,057.3
3,052.1
3,025.0
2,925.5

400oC
3,279.7
3,279.7
3,279.6
3,279.0
3,278.2
3,276.7
3,273.6
3,270.6
3,267.5
3,264.4
3,248.7
3,198.3
3,099.9
2,979.1
2,820.5
2,161.8

500oC
3,489.2
3,489.2
3,489.1
3,488.7
3,488.1
3,487.0
3,484.9
3,482.7
3,480.5
3,478.3
3,467.3
3,433.7
3,374.6
3,310.6
3,241.1
3,085.0

600oC
3,705.6
3,705.6
3,705.5
3,705.2
3,704.8
3,704.0
3,702.3
3,700.7
3,699.1
3,697.4
3,689.2
3,664.5
3,622.7
3,579.8
3,535.5
3,443.0

700oC
3,928.9
3,928.8
3,928.8
3,928.6
3,928.2
3,927.6
3,926.4
3,925.1
3,923.9
3,922.7
3,916.5
3,897.9
3,866.8
3,835.4
3,803.8
3,739.7

800oC
4,158.7
4,158.7
4,158.7
4,158.5
4,158.3
4,157.8
4,156.9
4,155.9
4,155.0
4,154.1
4,149.4
4,135.3
4,112.0
4,088.6
4,065.3
4,018.5

Reference State: H2O(l) at 0oC, i.e.,

H H 2O (l ) 0 kJ/kg (@ 0oC).

Environmental Control (Thermal Pollution). The heat released from the


condenser must eventually be transferred back to the environment. There are two
approaches that can be used to accomplish the required task. The once-through cooling
approach uses the cooling water that is circulated through the condenser to absorb the
heat released from the water/vapor mixture. Usually, the cooling water is drawn from a
lake or river, heated in the condenser, and returned to that body of water. As a result, no
cooling water is lost in the condenser. On the other hand, the water temperature of the
receiving water body downstream from the point of discharge will be higher than that at
the intake of cooling water. In many cases, the rise in water temperature will alter the
local ecological balance and create thermal pollution problems. A more expensive
approach involves use of cooling towers (or cooling ponds) that transfer the heat directly
into atmosphere by converting the cooling water into vapor rather than into a receiving
water body. The cooling water used will be lost as vapor that is released into the
atmosphere, but the temperature of the water body from where cooling water is drawn
will not be altered. The cooling water requirements can be calculated via (III.11):

m CW

QC
oncethrough
C p H 2O(l )TCW

where mCW

oncethrough

(III.11a)

mCW

lost

QC

(III.11b)

H v (TCW )

is the mass rate of cooling water required in a once-through cooling

system, kg/s; TCW is the allowable temperature increase in the cooling water stream,

46

oC;

mCW

lost

is mass rate of water lost in a cooling tower or a cooling pond, kg/s; and

H v (TCW ) is the latent heat of evaporation at the cooling water temperature TCW (oC),

kJ/kg. Q C is in kJ/s. Figure III.3 shows typical cooling towers as well as a steam
turbine used in thermal power plants.

3 MW Steam Turbine
Figure III.3. Cooling towers and a steam turbine.
Example III.4. A coal-fired power plant converts

1
of the coals energy into electrical
3

energy. The electrical power output of the plant is 1,000 MW. The other 2/3 of the energy
content of the coal is rejected to the environment as waste heat. About 15% of the waste
heat goes up the smokestack and the other 85% is taken away by cooling water that is
drawn from a nearby river. The river has an upstream flow of 100.0 m3/s and a
temperature of 15oC. If the cooling water is only allowed to rise in temperature by 10oC,
what flow rate from the stream would be required? The heat capacity of water is 4.184
kJ/kg-oC.
1.
2.

Input Power = (3)(Output Power) = 3,000 MW.


Total losses to cooling water and stack = 2,000 MW, with stack losses = 300 MW
and cooling water losses = 1,700 MW.

3.

The rate of change in enthalpy of the cooling water is H m C p T = 1,700 MW.

4.

Now, Cp = 4,184 J/kg-oC, T = 10oC, and 1 W = 1 J/s, then

47

m CW oncethrough
5.

1,700 10 6
= 40.6103 kg/s = 40.6 m3/s (cooling water flow
(4.184)(10)

rate).
Since 1,700 MW must be returned back to the river with a flow rate of 100 m3/s,
then the
temperature rise in river at the point of discharge of cooling water is

T
6.

7.

1,700 106
= 4.1oC.
(4.184)(100)

Since the cooling water flow rate is about 41% of the river flow rate (too high), it
creates an unacceptable increase in river temperature (i.e., 4.1oC) downstream
from the power plant. Therefore, alternatives for removing waste heat may be
necessary.
Now, assume that the waste heat is removed in a cooling tower (or cooling pond)
by evaporating the water at 15oC. Since the latent heat of vaporization at 15oC is

2,465 kJ/kg, then m CW lost


8.

9.

1,700 10 6
= 689.7 kg/s = 0.69 m3/s (makeup

2,456

water flow rate).


Since the makeup water flow rate is < 1% of the river flow rate, this option
appears to be attractive. However, the capital costs of building the cooling facility
and the annual operating and maintenance (O&M) costs of operating the facility
need to be considered before making the final recommendations.
If the cooling tower (or cooling pond) is being operated at a higher temperature,
say, 50oC, will this help to reduce the makeup water flow rate? Since the heat of
vaporization at 50oC is 2,382.9 kJ/kg (Table II.2), the amount of heat required to
bring the water temperature from 15oC (makeup water) to 50oC (water to be
evaporated) (sensible heat) is (4,184)(50 15) = 146.44 kJ/kg.

1,700 106
Therefore, the amount of makeup water needed is mCW lost
=
2,382.9 164.44

0.67 kg/s or 0.67 m3/s (no much reduction!).


Environmental Control (Flyash Emissions). Modern steam electric plants are
equipped with a variety of technologies to reduce or eliminate pollutant emissions. The
following pollutant emissions are typical for coal-fired plants: flyash (fine ash particles),
CO2, SO2, NOX (NO + NO2) heat, water pollutants, and solid wastes (i.e., bottom ashes
collected from the boiler). Most modern coal-fired plants employ electrostatic
precipitators (ESPs) to capture nearly all of flyash emissions (Figure III.4). A DC
electric field is imposed between a wire and a pair of plates suspended in the flue gas
flow path. As the flue gas flows between two plates, ash particles in the flue gas are
bombarded with negative ions, taking on negative electrical charges. Electrostatic
attraction pulls the charged particles toward the positively charged plates, where they are
collected. At intervals the electric field is momentarily relaxed, allowing the ash particles
to fall into a collection hopper. Commercial ESPs contain many plates to ensure that all
the flue gas into a collection hopper is treated. The total ESP plate area (A, m2) needed
to achieve a given overall removal efficiency ( ESP ) is:

48

1: Smoke particles pick up a negative charge. 2: Smoke particles are attracted to the collecting
plates. 3: Collecting plates are knocked to remove the smoke particles.

Figure III.4. The schematic of a typical electrostatic precipitator (ESP).

V gas 1

A
ln
w 1 ESP

1.667

(Deutsch-Anderson Equation)

(III.12)

where V gas is the volumetric gas flow rate (m3/s) and w is the effective particle drift
velocity perpendicular to the direction of gas flow (m/s). w can be expressed as a
function of sulfur content, with all other parameters held fixed at typical values (Table
III.2). ESPs use a large number of plates spaced about 30 cm apart, with both sides of
each plate serving as collectors. As a result, a large surface area can be attained. Fabric
filters (baghouse) also are effective in capturing PM.
Table III.2. w Values.
Application
Utility Flyash
Pulverized Coal Flyash
Pulp & Paper Mills
Sulfuric Acid Mist
Cement (wet process)
Cement (dry process)
Gypsum
Smelter

w (cm/s)
4.0-20.4
10.1-13.4
6.4-9.5
5.8-7.6
10.1-11.3
6.4-7.0
15.8-19.5
1.8

Application
Open-Hearth Furnace
Blast furnace
Hot Phosphorous
Flash Roaster
Multiple-Hearth Roaster
Catalyst Dust
Cupola

w (cm/s)
4.9-5.8
6.1-14.0
2.7
7.6
7.9
7.6
3.0-3.7

49
Environmental Control (SO2 Emissions). Coal combustion is the major source of
SO2 emissions at coal-fired plants. Flue gas desulfurization (FGD) systems have been
required on all new coal-fired plant in the U.S. since 1978 to achieve the highest levels of
SO2 removal. The most widely used FGD technology employs a slurry of pulverized
limestone mixed with water to remove SO2 via chemical reactions taking place in a vessel
commonly known as a scrubber:

1
SO2 ( g ) CaCO3 ( s) 2 H 2O(l ) O2 ( g ) CO2 ( g ) CaSO4 2 H 2O( s)
2
CaSO4 2 H 2O( s) gypsum

(III.13)

Example III.5. An existing 500 MW coal-fired power plant (bituminous coal) operates
at an overall efficiency of 36% and an annual capacity factor of 65%. To comply with
national acid rain control requirements, the plant decides to install a wet limestone
scrubber that is capable of reducing SO2 emissions by 95%. The scrubber requires a
reagent stoichiometry of 1.03, i.e., 3% more limestone than theoretically needed to
remove a mole of SO2. Calculate for this plant (a) its new annual SO2 emissions, and (b)
the annual quantity of limestone required.
a.1.
a.2.
a.3.

The maximum energy output of the plant is: (500 MW)(1,000 kW/MW)(24
hrs/day)(365 days/yr) = 4.380109 kW-hr/yr.
Since the annual capacity factor is 65%, the actual annual power output is
(0.65)(4.380109) = 2.847109 kW-hr/yr.
Therefore, the rate of fuel energy input =

(2.847 109 )(3,600)


2.847 1013 kJ/yr.
0.36
a.4.

2.847 1013
The amount of bituminous coal burned each year =
1.002 109
28,400

a.5.

kg/yr.
Since the sulfur content of bituminous coal is 1.5% (weight), then the amount of
sulfur emitted each year is: (0.015)(1.002109) = 1.50107 kg/yr, or the amount

(64)(1.50 107 )(0.97)


of SO2 emitted each year is:
2.91 107 kg/yr (about 2 to
32
a.6.
b.

5% of sulfur in coal are trapped in ash; 64 is the molecular weight of SO2; and 32
is the atomic weight of sulfur).
Therefore, the new SO2 emissions = (0.05)(2.91107) = 1.46107 kg/yr.
(III.13) shows that the theoretical reagent requirement is 1.00 mole CaCO3/mol
SO2 removed, versus 1.03 moles CaCO3/mol SO2 removed, or

(1.03)(100)
1.6094 kg CaCO3/kg SO2 removed. Therefore, the annual amount
64
of limestone required = (1.6094)(0.95)(2.91107) =4.45107 kg/yr.
Environmental Control (NOX Emissions). To reduce NOX emissions, two general
methods are used. The 1st method, combustion modification, alters the design of the
combustion chamber to affect the temperature, time, and other parameters that control
NOX formation. Typically, combustion modification methods reduce NOX up to ~ 50%.
The 2nd method of NOX control employs a chemical treatment system to remove NOX

50
from the flue gas. This type of system is analogous to the FGD system for SO2 removal.
The most prevalent postcombustion NOX control technology is selective catalytic
reduction (SCR). A chemical catalyst, which is similar to the ones used in automobile
catalytic converters, is used to selectively reduce NOX in the flue gas to N2. SCR
operation requires temperatures of roughly 400oC, so the SCR reactor is usually located
at the boiler exit. In power plants, however, ammonia (NH3) is injected into the flue gas
stream to achieve good NOX reduction:

1
3
NO NH 3 O2 N 2 H 2O
4
2
1
3
NO2 2 NH 3 O2 N 2 3H 2O
2
2

(III.14)

In practice, some excess ammonia is required to obtain desired NOX reduction (70 to
90% reduction).
Environmental Control (Water Pollution). See the Section on Environmental
Control (Thermal Pollution).
Environmental Control (Solid Waste Management). The large quantities of ash
particles collected at coal-fired power plants represent a major solid waste management
problem. For plants with large ash ponds, the final ash disposal site is often the pond
itself. Otherwise, the pond is periodically dredged, and the ash is trucked to an
engineered landfill site. In recent years many utilities have begun to utilize dry flyash
collection systems to avoid the use of water altogether, and the collected ash is disposed
of directly in an engineered landfill. The ash and FGD waste can be recycled and used as
aggregates for road construction, additives for cement manufacturing, or other useful
purposes (~ 30% of the roughly 100 million tons of ash collected in the U.S. power plants
is sold). The gypsum produced in modern FGD systems, after the impurities are
removed, can be sold as a commercial by-product to produce wallboard or other
building materials.
Example III.6. Calculate the mass of solid waste produced each year by the FGD system
described in Example III.5. Assume that the FGD waste consists of gypsum plus
unreacted limestone. Further assume that the final waste product contains 15% moisture
(occluded water) by weight, typical of the dewatering technology used to separate FGD
solids from the wet scrubber slurry.
1.

Because one mole of SO2 removed produces one mole of gypsum, then

mgypsum
mSO2

172
= 2.6875 kg gypsum/kg SO2 removed.
64
100
0.0469 kg limestone/kg SO2 removed.
64

2.

Unreacted limestone = 1.6094

3.

Therefore, total dry waste = 2.6875 + 0.0469 = 2.7344 kg dry waste/kg SO2
removed or

2.7344
3.2168 kg wet waste/kg SO2 removed
0.85

(3.2168)(2.765107)
= 8.89107 kg FGD waste/yr.

51

WIND POWER (Figure III.5). Wind turbines are used to convert the kinetic

energy of air into rotation of the rotor blade to drive electric generator. Wind turbine
blades are designed in the shape of an airfoil, similar to the wings of an airplane, so as to
be able to take maximum advantage of the aerodynamic forces. The following equations
can be used to rate a wind turbine:
3
A airuair
2
0.593Pwind

Pwind
Pmax

turbine

(III.15)

Pelec
3
A airuair
2

where Pwind is the wind power (or the equivalent electrical power of the wind), W;

D 2
4

, where D is the tip-to-tip diameter of the circle swept out by the rotating

blades, m2; air is the density of air under the conditions quoted, kg/m3 (e.g., 1.205 kg/m3
for dry air @ 25oC); uair is the wind velocity, m/s; Pmax is the maximum useful power
available from the wind, W; 0.593 is the Betz limit; turbine is the overall efficiency of the
wind turbine; and Pelec is the electrical power output from the wind turbine generator
system, W. Commercial wind turbines have Pelecs ranging from 250 to 750 kW.
Typically, a number of wind turbines are connected together to produce a wind farm
capable of generating large amounts of power. A typical 25 MW wind farm might
include 50 wind turbines, each rated at 500 kW. The total land area required for such a
facility would be roughly 20 40 hectares/MW, depending on terrain and turbine
configuration. The turbine structures themselves, however, occupy only about 5 to 10%
of the total land area.
Example III.7. A wind turbine with a rotor diameter of 50 m operates on a hilltop
where the wind is blowing at 9 m/s. The air temperature is 10oC, and the corresponding
air density is 1.25 kg/m3. Determine (1) the equivalent electrical power of the wind
under these conditions, (2) the maximum power for the wind turbine, and (3) the actual
electrical power generated if the overall turbine generator efficiency is 34%.
3
A airuair
( )(50) 2 (1.25)(9)3
= 895 kW.

2
(2)(4)
0.593Pwind (0.593)(895) = 531 kW.

1.

Pwind

2.

Pmax

3.

Pelec

3
A airuair

(0.34)(895) = 304 kW.


turbine
2

52

Windmill for Low Wind Areas


Figure III.5. Wind turbines and configurations.

GEOTHERMAL ENERGY. Geothermal power is energy generated by heat stored

beneath the Earth's surface. Geothermal power supplies 0.416% of the world's energy.
Geothermal comes from the Greek words geo, meaning earth, and therme, meaning
heat. Prince Piero Ginori Conti tested the first geothermal power plant on 4 July 1904,
at the Larderello dry steam field in Italy. The largest group of geothermal power plants
in the world is located in The Geysers, a geothermal field in California. Three
geothermal power plant technologies are currently used to convert hydrothermal fluids
to electricity, depending on the state of the fluid (whether steam or water) and its temp:
dry steam, flash, and binary cycle (Figure III.6).
Dry steam power plants systems were the oldest type of geothermal power generation
plants built. They use the steam from the geothermal reservoir as it comes from wells,
and route it directly through turbine/generator units to produce electricity. These plants
emit only excess steam and very minor amounts of gases. Flash steam plants are the
most common type of geothermal power generation plants in operation today. They use
water at temperatures greater than 360F (182C) that is pumped under high pressure to
the generation equipment at the surface. Fluid is sprayed into a tank held at a much
lower pressure than the fluid, causing some of the fluid to rapidly vaporize, or "flash."

53

Figure III.6. Geothermal power technologies.


The vapor then drives a turbine, which drives a generator. If any liquid remains in the
tank, it can be flashed again in a second tank to extract even more energy. Binary cycle
geothermal power generation plants differ from dry steam and flash steam systems in
that the water or steam from the geothermal reservoir never comes in contact with the
turbine/generator units.
Most geothermal areas contain moderate-temperature water (below 400F). Energy is
extracted from these fluids in binary-cycle power plants. Hot geothermal fluid and a
secondary (hence, "binary") fluid with a much lower boiling point than water pass
through a heat exchanger. Heat from the geothermal fluid causes the secondary fluid to
flash to vapor, which then drives the turbines. Because this is a closed-loop system,
virtually nothing is emitted to the atmosphere. Moderate-temperature water is by far the
more common geothermal resource, and most geothermal power plants in the future will
be binary-cycle plants.
Steam and hot water reservoirs are just a small part of the geothermal resource. The
earth's magma and hot dry rock will provide cheap, clean, and almost unlimited energy

54
as soon as the technologies are developed to use them. In the meantime, because they're
so abundant, moderate-temperature sites running binary-cycle power plants will be the
most common electricity producers. Before geothermal electricity can be considered a
key element of the U.S. energy infrastructure, it must become cost-competitive with
traditional forms of energy. The U.S. DOE is working with the geothermal industry to
achieve $0.03 to $0.05 per kilowatt-hour. There will be about 15,000 megawatts of new
capacity within the next decade.

SOLAR ENERGY. The earth receives 174 petawatts (1741015 J/s) of incoming solar

radiation (insolation) at the upper atmosphere (Figure III.7). While traveling through
the atmosphere, 6% of the insolation is reflected and 16% is absorbed. Average
atmospheric conditions (e.g., cloud, dust, and pollutants) further reduce insolation by
20% through reflection and 3% through absorption. These atmospheric conditions not
only reduce the quantity of light reach the earths surface but also diffuse roughly 20% of
the incoming light and filter portions of its spectrum. After passing through the
atmosphere roughly half the insolation is in visible electromagnetic spectrum with the
other half mostly in the infrared (IR) spectrum, and a small part of ultraviolet (UV)
radiation.
The absorption of solar energy by atmospheric convection (sensible heat transport) and
by the evaporation and condensation of water vapor (latent heat transport) drive the
winds and the water cycle. Upon reaching the surface, sunlight is absorbed by the
oceans, earth, and plants. The energy captured in the oceans is ultimately responsible
for temperature-driven ocean currents such as the thermohaline cycle and wind driven
currents such as the Gulf Stream. The energy absorbed by the earth in conjunction
that recycled by the greenhouse effects warms the surface to an average temperature of
approximately 14oC. The small portion of solar energy captured by plants and other
phototrophs is converted to chemical energy via photosynthesis. In North America, the
average insolation at the ground level over an entire year (including nights and periods
of cloudy weather) lies between 125 and 375 W/m2.
Water Heating (Figure III.8). Solar hot water systems use sunlight to heat water.
Commercial solar water heaters began appearing in the United States in the 1890s.
These systems saw increasing use until the 1920s but were thereafter gradually replaced
by relatively cheap and more reliable conventional heating fuels. The economic
advantage of conventional heating fuels has varied over time resulting in periodic
interest in solar hot water; however, solar hot water technologies have yet to show the
sustained momentum they lost in the 1920s. That being said, the recent price spikes and
erratic availability of conventional fuels is renewing interest in solar heating
technologies. As of 2005, the total installed capacity of solar hot water systems is 88
GW-hr and growth is 14% per year. China is the world leader in the deployment of
solar hot water systems with 80% of the market. Israel is the per capita leader in the use
of solar hot water with 90% of homes using this technology. In the United States heating
swimming pools is the most successful application of solar hot water. Solar water
heating is highly efficient (up to 86%) and is particularly appropriate for low
temperature (25-65C) applications such as domestic hot water, heating swimming pools
and space heating.

55

Figure III.7. Earths energy fluxes.


The basic components of a solar water heating systems are solar thermal collectors, a
storage tank and a circulation loop. There are three basic classifications of solar water
heaters. Batch systems which consist of a tank that is directly heated by sunlight. These
The basic components of a solar water heating systems are solar thermal collectors, a
storage tank and a circulation loop. There are three basic classifications of solar water
heaters. Batch systems which consist of a tank that is directly heated by sunlight. These
are the oldest and simplest solar water heater designs, however; the exposed tank can be
susceptible to cooldown. Active systems which use pumps to circulate water or a heat
transfer fluid. Passive systems which circulate water or a heat transfer fluid by natural
circulation. These are also called thermosiphon systems.
Solar Ponds (Figure III.9). A solar pond is a pool of salt water that collects and
stores solar energy. A solar pond consists of layers of water that successively increased
from a weak salt solution at the top to a high salt solution at the bottom. This in turn
yields a density gradient that prevents convective currents. As a result, the temperature
at the bottom layer could be as high as 100oC.
Generally, there are three main layers. The top layer is cold and has relatively little salt
content. The bottom layer is hot, up to 100C and is very salty. Separating these two

56

Figure III.8. Solar water heaters.


layers is the important gradient zone (i.e., halocline) where the salt content increases
with depth. Water in the gradient cannot rise because the water above it has less salt
content and is therefore lighter. The water below it has a higher salt content and is
heavier. Therefore, the stable gradient zone suppresses convection and acts as a
transparent insulator, permitting sunlight to be trapped in the hot bottom layer from
which useful heat may be withdrawn or stored for later use. If the water is relatively
transluent, and the pond's bottom has high optical absorption, then nearly all of the
incident solar radiation (sunlight) will go into heating the bottom layer. The heat
trapped in the salty bottom layer can be used for many different purposes, such as the
heating of buildings or industrial hot water, or to drive a Rankine cycle turbine, or a
Stirling engine for generating electricity. The solar ponds are particularly attractive for
rural areas in developing countries. Ponds with vary surface areas can be set up for just
the cost of the clay or plastic pond liner. However, the evaporated surface water needs to
be constantly replenished and the accumulating salt crystals have to be removed and can
be both a valuable by-product and a maintenance expense.

Figure III.9. Solar pond.

57
Photovoltaics. A solar cell or photovoltaic cell is a device that converts light into
Electricity using the photovoltaic effect. The 1st working solar cells were constructed by
Charles Fritts in 1883. These prototype cells were made of selenium and achieved
efficiencies of around 1%. Following the fundamental work of Russel Ohl in the 1940s,
researchers Gerald Pearson, Clavin Fuller, and Daryl Chapin created the silicon solar cell
in 1954. Until recently, their uses have been limited because of high manufacturing
costs. One cost effective use has been in very low-power devices such as calculators with
LCDs. Another use has been in remote applications such as roadside emergency
telephones, remote sensing, cathodic protection of pipe lines, and limited "off grid" home
power applications. A third use has been in powering orbiting satellites and spacecraft.
To take advantage of the incoming electromagnetic radiation from the sun, solar panels
can be attached to each house or building. The panels should be mounted perpendicular
to the arc of the sun to maximize usefulness. The easiest way to use this electricity is by
connecting the solar panels to a grid tie inverter. However, these solar panels may also
be used to charge batteries or other energy storage devices. Solar panels produce more
power during summer months because they receive more sunlight. Total peak power of
installed PV cells is around 6,000 MW as of the end of 2006. Installed PV cells are
projected to increase to over 9,000 MW in 2007. This is only one part of solar-generated
electric power. Declining manufacturing costs (dropping at 3 to 5% a year in recent
years) are expanding the range of cost-effective uses. The average lowest retail cost of a
large photovoltaic array declined from $7.50 to $4 per watt between 1990 and 2005.
With many jurisdictions now giving tax and rebate incentives, solar electric power can
now pay for itself in five to ten years in many places. "Grid-connected" systems, those
systems that use an inverter to connect to the utility grid instead of relying on batteries,
now make up the largest part of the market. In 2003, worldwide production of solar
cells increased by 32%. Between 2000 and 2004, the increase in worldwide solar energy
capacity was an annualized 60%. 2005 was expected to see large growth again, but
shortages of refined silicon have been hampering production worldwide since late 2004.
Analysts have predicted similar supply problems for 2006 and 2007.
Solar Power Plants. Solar power plants use a variety of methods to collect sunlight.
Concentrating solar thermal (CST) systems (Figure III.10) use lenses or mirrors and
tracking systems to focus a large area of sunlight into a small beam. CST technologies
require direct insolation to perform properly. This requirement makes them
inappropriate for significantly overcast locations. The three basic CST technologies are
the solar trough, solar power tower, and parabolic dish. Each technology is capable of
producing high temperatures and correspondingly high thermodynamic efficiencies but
they vary in the way they track the sun and focus light. A solar trough consists of a linear
parabolic reflector which concentrates light on a receiver positioned along the reflector's
focal line. These systems use single-axis tracking to follow the sun. A working fluid (oil,
water) flows through the receiver and is heated up to 400C before transferring its heat
to a distillation or power generation system. Trough systems are the most developed
CST technology. The Solar Electric Generating System (SEGS) plants in California and
Plataforma Solar de Almera's SSPSDCS plant in Spain are representatives of this
technology. A power tower consists of an array of flat reflectors (heliostats) which
concentrate light on a central receiver located on a tower. These systems use dual-axis
tracking to follow the sun. A working fluid (air, water, molten salt) flows through the
receiver where it is heated up to 1,000C before transferring its heat to a power
generation or energy storage system. Power towers are less advanced than trough
systems but they offer higher efficiency and energy storage capability. The Solar Two in

58

Figure III.10. Solar power plants.


Daggett, California and the Planta Solar 10 (PS10) in Sanlucar la Mayor, Spain are
representatives of this technology. A parabolic dish or dish/engine system consists of a
stand-alone parabolic reflector which concentrates light on a receiver positioned at the
reflector's focal point (see the attached photo). These systems use dual-axis tracking to
follow the sun. A working fluid (hydrogen, helium, air, water) flows through the receiver
where it is heated up to 1,500C before transferring its heat to a sterling engine for power
conversion.

59
BIOGAS PRODUCTION FROM ORGANIC WASTE MATEWRIALS. The
production of biogas (primarily CH4 and CO2) production from organic matter is
achieved via anaerobic fermentation and oxidation processes. Figure III.11 illustrates 4
key steps are involved in the overall anaerobic fermentation and oxidation of waste
materials: (1) hydrolysis, (2) acidogenesis, (3) acetogenesis, and (4) methanogenesis.
Since complex organic materials generally contain large molecules such as arbohydrates,
fats, and proteins, these molecules must be broken down into their smaller constituent
parts in order for the microbes to tap into the energy potential in the subsequent
degradation steps. The process of breaking these large molecules and dissolving the
smaller constituents into solution by extracellular enzymes (e.g., cellulases,
hemicellulases, amylases, lipases, and proteases) is referred to as hydrolysis. In the
hydrolysis step, the complex organic molecules are broken down into simple sugars, fatty
acids, and amino acids, as well as small amounts of acetic acid, H2, and CO2.

Figure III.11. Reaction pathways in anaerobic ferementation and oxidation.


Acetic acid and H2 produced in the hydrolysis step can be used directly by methanogens.
Other molecules such as amino acids, sugars, and some fatty acids with a chain length
that is greater than acetic acid must first be catabolized into compounds that can be
directly utilized by methanogens. The biological process of acidogenesis, which is similar
to the way that milk sours, is where these reactions are carried out the acidogenic (or
fermentative) microbes. Here volatile fatty acids are created along with NH3, CO2, and
H2S as well as other by-products. The third step is acetogenesis where simple molecules
created through the acidogenesis step phase are further digested by acetogens to produce
largely acetic acid as well as H2 and CO2. For instance, -oxidation of butyrate produces
acetate and H2 whereas decarboxylation of propionate produces acetate, H2, and produce
CO2, which are the precursors of methanogenesis [see (III.16) and (III.17),
respectively]. The free energy changes associated with the conversion of propionate
and butyrate to acetate and H2 requires that low H2 concentrations in the system (i.e.,
< 10-4 atm) or the reaction will not proceed.

CH 3CH 2CH 2COO 2H 2O 2CH 3COO 2H 2 H


CH 3CH 2COO 3H 2O CH 3COO HCO3 3H 2 H

(III.16)
(III.17)

Non-methanogenic microbes that carry out the first three steps in anaerobic fementation
and oxidation includes Clostridium ssp., Peptococcus anaerobus, Bifidobacterium spp.,
Lactobacillus, Actinomyces, Staphylococcus, and Escherichia coli.

60
An important immediate product of the anaerobic fermentation and oxidation is H2. The
biologically-mediated reaction pathways of certain compounds may be altered if H2 is
present at a high concentration. For instance, CH3COOH may react with H2 and CO2 to
form CH3CH2COOH. As a result, the reaction as depicted in (III.18) would hinder the
progress of methanogenesis which utilizes CH3COOH as a major substrate.

CH 3COOH 3H 2 CO2 CH 3CH 2COOH 2H 2O

(III.18)

Methanogenesis is carried out by a group of organisms known collectively as


methanogens. Methanogens are classified as archaea, a group quite distinct from
bacteria. They are common in wetlands and in the guts of animals such as ruminhants
and humans. Moreover, in marine sediments methanogens are generally proliferate
below the top layers where sulfates are absent. Methanogens also exist in extreme
environments such as hot springs and hydrothermal vents at the deep ocean floor. Two
groups of methanogens are involved in CH4 production. One group, termed aceticlastic
methanogens, split acetate into CH4 and CO2. The second group, terms hydrogenutilizing methanogens, use H2 as the electron donor and CO2 as the electron acceptor to
produce CH4. Acetogens are also able to use CO2 to oxidize H2 and form acetic acid
(CH3COOH). An example of methanogens is Methanosarcina barkeri (Figure III.13)
which has been isolated from mud samples in lakes and bogs and municipal wastewater
samples. M. barkeri also lives in the rumen of cows where it helps digest the organic
matter for the cow. It is highly adaptable to its environment because of its ability to
utilize a variety of substrates, as shown in (III.19). As a result, it is potentially useful as
an agent to carry out the desired biochemical reactions. Although methanogens do not
function under aerobic conditions, however, they can survive under the oxygen stress
conditions for a prolonged period of time. M. barkeri, which possesses a superoxide
dismutase (SOD) enzyme, is able to survive longer than the others when oxygen is
present.

CH 3OH
4CH 3OH 3CH 4 HCO3 H H 2O
4CH 3OH CH 3COO 4CH 4 2 HCO3 H
CH 3OH H 2 CH 4 H 2O

CH 3 NH 3 / CH 3 2 NH 2 / CH 3 3 NH
4CH 3 NH 3 3H 2O 3CH 4 HCO3 H 4 NH 4

2CH 3 2 NH 2 3H 2O 3CH 4 HCO3 H 2 NH 4

(III.19)

4CH 3 3 NH 9 H 2O 9CH 4 3HCO3 3H 4 NH 4


CO2
4 H 2 H HCO3 CH 4 3H 2O
CH 3COO
CH 3COO H 2O CH 4 HCO3
HCOO-: Formic Acid, CH3OH: Methanol, (CH3)3N: Methylamine, and CH3COOH: Acetic Acid.

61
Factors Affecting Anaerobic Fermentation and Oxidation. A variety of factors
affect the rates of anaerobic fermentation and oxidation (Table III.3). Anaerobic
bacteria consortia can endure temperatures ranging from < 0oC to > 57oC. Optimal
temperatures are at about 37oC (mesophilic) and 54oC (thermophilic). Microbial
activities fall off significantly between about 39o and 52oC and gradually from 35oC to
0oC. Studies conducted in the north-central U.S. suggest that maximum net biogas
production can occur in anaerobic sludge at temperatures as low as 22oC. The bioreactor
contents should be void of dissolved oxygen and free from inhibitory concentrations of
heavy metals and sulfides. Also, the aqueous pH in the bioreactor should range from 6.6
to 7.6. Sufficient alkalinity should be present to ensure that the aqueous pH will not
drop below 6.2, because methanogens cannot function properly below this point.
Alkalinity ranging from 1, 000 to 5,000 mg/L as CaCO3 and the total VOA (volatile
organic acid) concentration less than 250 mg/L as CH3COOH should be maintained in
the anaerobic bioreactor to ensure satisfactory results. Other factors affecting the rate
and amount of biogas output include pH, water/solid (W/S) ratio, carbon/nitrogen
(C/N) ratio, degree of mixing, particle matter in the materials being treated (i.e., amount
and size distribution), and bioreactor/digester retention time. Pre-sizing and mixing of
the feed materials with high solid contents for consistency permit the bacteria to work
more quickly. Bicarbonate (HCO3-) in various forms can be added to maintain a desired
and consistent pH. The feed stream with a high nitrogen content may need to be diluted
with the anaerobic bioreactor effluent stream to ensure an adequate feed C/N ratio at
20/1 to 30/1. Moreover, the addition of essential nutrients may be required to ensure
healthy methanogenic growth (Table III.4).
Table III.3. Factors Affecting Anaerobic Fermentation and Oxidation.
Environmental Factor

Range

pH

6.8 to 7.2

Temperature

30 to 40oC (optimal: 35oC) (mesophilic)


50 to 60oC (optimal: 55oC) (thermophilic)

Total Alkalinity

3,000 to 5,000 mg/L as CaCO3

Total VOA

< 250 mg/L as CH3COOH

Cu+2

< 150 mg/L

Ni+2

< 200 mg/L

Zn+2

< 350 mg/L

Cr+6
ORP

< 200 mg/L


-510 to -540 mv

Biogas. Biogas, which primarily consists of CH4 and CO2, is a major end-product of
anaerobic fermentation and oxidation. Table III.5 lists typical constituents found in
biogas. Large quantities of H2S can be produced from the anaerobic treatment of liquid
waste streams from industries such as molasses fermentation, yeast production,
monosodium glutamate production, and petroleum refining. In addition to its toxicity,
the combustion of H2S produces H2SO4 which is highly corrosive. Therefore, the
removal of H2S from the biogas prior to its uses in CHP (combined heat and power)
generation is required. The amount of CH4 produced can be accounted for by the
amount of COD removed during anaerobic fermentation and oxidation. The
stoichiometric COD of CH4 is the amount of oxygen needed to oxidize CH4 to CO2 and

62
H2O:

CH 4 2O2 CO2 2H 2O

(III.20)

According to (III.20), the stoichiometric COD of CH4 is 2(32) = 64 g O2/mol CH4. COD
is the preferred concentration parameter for the waste streams with unspecified
characteristics (see Example III.7).
Table III.4. Nutritional Requirements of Methanogens.
Substance
Na+
K+
Ca+2
Mg+2
N
Fe+3
Co+2
P
Thiamine (C12H17N4OS)

Concentration (mg/L)
125-500
200-400
100-200
75-125
60-130
1-10
1-10
1-5
1-5

Table III.5. Typical Biogas Composition.


Component
Methane (CH4)
Carbon Dioxide (CO2)
Nitrogen (N2)
Hydrogen (H2)
Hydrogen Sulfide (H2S)
Ammonia (NH3)
Oxygen (O2)

% (volume)
50-80
20-40
0-5
0-1.0
0.05-1.0
0.02-0.5
0-0.5

Example III.7. Determine the amount of methane produced per kg COD stabilized.
Use glucose, methanol, and acetate as the starting compounds. COD: chemical oxygen
demand.

Glucose (C6H12O6):

C6 H12O6 3CH 4 3CO2


C6 H12O6 6O2 6 H 2O 6CO2
1.

1 g C6H12O6 consumes 1.067 g O2 (i.e.,

192
) when it is completely oxidized.
180

Therefore, the COD of C6H12O6 is 1.067 g O2/g C6H12O6. 1 g C6H12O6 produces


0.267 g CH4 (i.e.,
(i.e.,
2.

48
). Therefore, 0.25 g CH4 is produced per g COD stabilized
180

0.267
0.25 ).
1.067

Since 1 mole (16 g) CH4 occupies 22.4 L of volume at STP, 0.25 g CH4 will have a

63

volume of 0.35 L at STP (i.e.,

(22.4)(0.25)
0.35 ). In other words, 0.35 m3 CH4
16

is produced per kg COD stabilized at STP.

Methanol (CH3OH):

4CH 3OH 3CH 4 2 H 2O CO2


2CH 3OH 3O2 4 H 2O 2CO2
1.

1 g CH3OH consumes 1.5 g O2 (i.e.,

96
) when it is completely oxidized.
64

Therefore, the COD of CH3OH is 1.5 g O2/g CH3OH.


2.

48
48
) g CH4 (i.e.,
). Therefore, 0.25 g CH4 is
128
128
0.375
produced per g COD stabilized (i.e.,
), or 0.35 m3 CH4 is produced per kg
1.5
1 g CH3OH produces 0.375 (

COD stabilized at STP.

Acetate (CH3COOH):

CH 3COOH CH 4 CO2
CH 3COOH 2O2 2 H 2O 2CO2
1.
2.

1 g CH3COOH consumes 1.067 g O2 when it is completely oxidized, i.e., the COD


of CH3COOH is 1.067 g O2/g CH3COOH.
1 g CH3COOH produces 0.267 g CH4, or 0.25 g CH4 is produced per g COD
stabilized, or 0.35 m3 CH4 is produced per kg COD stabilized at STP.
Therefore, 0.35 m3 CH4 is produced per kg COD stabilized at STP that is
independent of the starting compound used.

Heat Value Calculations (Mesophilic Case). Since biogas is a major end-product of


the anaerobic fermentation and oxidation, the cost-effectiveness of the anaerobic
biotechnology for a specific application is very often determined by the net energy value
that can be recovered. In addition to satisfying the heating and power requirements of
running the anaerobic treatment facility, the extra amount of biogas produced can
conceivably be utilized at other locations to defray the energy costs involved. Example
A.1. in the Appendix presents detailed energy balance calculations involved in the
combustion of biogas. The enthalpy tables are prepared and used as the means to
account for the energy values of all species participate in the combustion reaction. The
heat energy recovered is then used to produce a saturated steam stream in a boiler.
Example A.2. in the Appendix illustrates the calculations of heating requirements of a
mesophilic anaerobic bioreactor.

64
ENERGY CONVERSION EFFICIENCIES.
Electric Power Plants.
Hydroelectric
Fuel Cell (Hydrogen)
Coal-Fired Generator
Oil-Burning Generator
Nuclear Generator
Photovoltaic Cell

90%
80%
38%
38%
30%
10%

Space Heating.
Electric Resistance
99%*
High-Efficiency Gas Furnace
90%
Typical Gas Furnace
70%
Efficient Wood Stove
65%
Typical Wood Stove
40%
* Note that 60-70% of the energy in the original fuel is lost in electric power generation.

Lighting.
Sodium Vapor Lamp
66%*
Fluorescent Bulb
25%*
Incandescent Bulb
5%*
Gas Flame
1%
* Note that 60-70% of the energy in the original fuel is lost in electric power generation.

Inefficiencies in Electricity Generation and Consumption (Figure III.12). A


thermal power plant can only cature ~35% of energy value in fuel as electricity. The rest
is released back to the environment as waste heat. The electricity generated is
transmitted to individual consumers via high-voltage transmission lines which are highly
efficient with ~ 10% losses. If incandescent light bulbs are used, then only ~ 5% of the
electricity delivered a household is used. The overall efficiency in energy generation and
consumption ( overall ) in this example is therefore:

overall generationtransmission utilization (0.35)(0.90)(0.05) = 0.016.


Three Alternatives for Meeting Household Energy Needs (example).
Electricity supplies are very efficient when electrical power is needed. When only heat is
needed, the electrical supply is a very inefficient form of delivery. The following
alternatives are illustrated for a house which requires 10 kW of heating power and 1 kW
of electrical power. A natural gas (NG) thermal power plant is used to generate
electricity with 33% efficiency. If this house is powered only by electricity, then 33 kW of
gas is used to meet 11 kW of electrical needed of the house (alternative 1). If NG is used
to heat the house with a 95% efficient gas heater, then 3 kW of gas is used to meet 1 kW
of electrical needed of the house. The total NG requirement is therefore: 3

10
13.5
0.95

kW (alternative 2). If a 60% efficient, NG-fed fuel cell is used to generate the electricity
for the house, then 1.67 kW NG is needed to run the fuel cell. The fuel cell will produce
0.67 kW waste heat which can be captured for heating the house. Therefore, the

65
total NG requirement for the house is: 1.67 + (10 0.67) = 11 kW (alternative 3).
Evidently, alternative 2 is best because a fuel cell is rather expensive as compared to a
gas heater.

1 0.35

2 0.90

3 0.05

Figure III.12. Inefficiencies in electricity generation and consumption.


Improving Energy Efficiency. A key means of reducing environmental impacts in
the operation of steam electric plants is to improve the efficiency of the energy
conversion process. If less primary energy (i.e., fuel energy) is needed to produce
electricity, the magnitude of environmental impacts will be reduced accordingly. The
opportunities of improving the overall energy efficiency of the steam electric plants are
examined herein.
Increasing Operating Temperatures. The laws of thermodynamics (e.g., Carnot
theorem) pose a substantial barrier for power plants using conventional Rankine cycles
to achieve high efficiencies. As previously discussed, overall is always << 1

Tenvironment
=
Tboiler

max (T is in oK). However, overall can be increased by increasing the operating


temperature of the boiler ( Tbolier ). For example, gas turbines today operate at inlet
temperatures of approximately 1,300oC, compared to about 1,100oC a decade ago. Each

66
55oC increment adds about 1 percentage point to the overall efficiency. For coal-fired
power plants, the use of supercritical (the supercritical fluid cannot be classified as
either a steam or a liquid) boilers can achieve an overall 43% (including full
environmental controls) by increasing the steam pressure and temperature to 31 MPa
and 590oC, compared to typical conditions of 17 MPa and 540oC for conventional boilers
with an overall 37%. Advances in materials science and engineering are therefore
critical to achieving significant advances in boiler design.
Cogeneration. It is sometimes unnecessary to dump all the condenser heat into a nearby
water body, and the heat recovered can provide hot water to nearby residences or
industries thereby yielding significant savings on their energy bills. If temperatures are
needed, steam can be extracted from the turbine at higher temperatures and pressures.
This type of combined heat and power (CHP) system is known in the U.S. as
cogeneration. An economic price must be paid, however, for the additional piping and
other equipment needed to supply the steam or hot water to customers outside the
power plant. In most situations, this cost far exceeds the value of the heat supplied
because most potential customers are remote from the power plant. Therefore,
cogeneration systems have found limited applications in the U.S., typically at large
industrial complexes that require both heat and electricity continuously. Cogeneration
typically increases the efficiency of fuel utilization up to 80%.
Advanced Cycles. The use of advanced cycles is another important way to increase the
efficiency of electric power generation. One promising method to make coal-fired power
plants more efficient is a combined-cycle system integrated with coal gasification, or an
integrated gasification combined cycle (IGCC) system (Figure III.13). In this system,
coal reacts chemically with steam and oxygen at high temperature and pressure to form a
fuel gas mixture consisting mainly of H2, CO, and CH4 (synthetic gas or syngas). O2
levels in the gasifier are kept low to create a chemically reducing environment to avoid
the formation of H2O(v) and CO2. Impurities such as sulfur and ash are removed by
efficient environmental control systems, leaving a clean fuel gas whose energy content is
about 15 to 20% that of natural gas. This fuel gas is then used to generate electricity. An
IGCC system can achieve an overall 40%. The fuel gas produced can also be used to
synthesize liquid fuels and chemicals as well as produce electricity. IGCC systems
also reduce solid wastes by converting sulfur impurities into H2SO4 or elemental sulfur
by-products. At the present time, the principle drawback of the IGCC system is its high
capital costs.
Another promising technology is the integrated gas turbine/fuel cell technology. The
highest-efficiency plants under development combine advanced gas turbines with
advanced fuel cells. A high-temperature fuel cell would first generate electricity
electrochemically using natural gas as the feed gas. The exhaust gas from the fuel cell
would then drive a gas turbine to generate additional power. An alternative design using
coal would first employ a coal gasifier to generate a clean fuel gas for the fuel cell.
Another advantage of gasification is that it offers an efficient route for separating and
capturing CO2 as a potential carbon management strategy to address the issue of global
warming. Such systems are at least a decade or two away for commercialization.

67

Figure III.13. The schematic of an IGCC system.


Resource Recovery from Wastes.
Refused-Derived Fuel (RDF). RDF is a fuel produced by shredding and dehydrating
solid MSW with a waste converter technology (Figure III.14). RDF consists largely of
organic components of MSW municipal waste such as plastics and biodegradable wastes.
RDF processing facilities are normally located near a source of MSW and, while an
optional combustion facility is normally close to the processing facility, it may also be
located at a remote location. Non-combustible materials such as glass and metals are
removed during the post-treatment processing cycle with cycle with an air knife or other
mechanical separation processing. The residual materials can be sold in their processed
forms (depending on the process treatment) or they may be compressed into pellets,
bricks or logs and used for other purposes either stand-alone or in a recursive recycling
process.

Figure III.14. RDF logs.

68
Biomass-Based Fuels. Biomass as the solar energy stored in chemical form in plant and
animal materials is among the most versatile resources on earth. It provides not only
food but also energy, building materials, paper, fabrics, medicines and chemicals.
Biomass has been used for energy purposes ever since man discovered fire. Today,
biomass fuels can be utilized for tasks ranging from heating the house, producing
electricity, or fuelling a car. Table III.6 summarizes some basic biomass data.

Table III.6. Basic Biomass Data.


Total World Biomass Content: 1.881015 kg.
Total Mass in Tropical Forests: 1.031015 kg.
Total Mass in Temperate Forests, Savanna, and Tundra: 0.791015 kg.
Total Marine Biomass Content: 4.001012 kg.
Terrestrial Biomass per Capita: 3.10103 kg.
Energy Stored in Terrestrial Biomass: 2.501019 kJ.
Net Annual Production of Terrestrial Biomass: 4.001012 kg.
Rate of Energy Storage by Terrestrial Biomass: 3.001015 kJ/year.
Total Consumption of All Forms of Energy: 4.001017 kJ/year.
Biomass Energy Consumption: 1.881015 kg 5.501016 kJ/year.

Rural economic development in both developed and developing countries is one of the
major benefits of biomass. Increase in farm incomes and market diversification,
reduction of agricultural commodity surpluses and derived support payments,
enhancement of international competitiveness, revitalization of retarded rural
economies, and reduction of negative environmental impacts are most important issues
related to utilization of biomass as energy source. The new incomes for farmers and
rural population improve the material welfare of rural communities and this might result
in a further activation of the local economy. In the end, this will mean a reduction in the
emigration rates to urban environments, which is very important in many areas of the
world.
The number of jobs created (for production, harvesting, and use) and the industrial
growth (from developing conversion facilities for fuel, industrial feedstocks, and power)
would be enormous. For instance, the U.S. Department of Agriculture estimates that
17,000 jobs are created per every million of gallons of ethanol produced, and the Electric
Power Research Institute has estimated that producing 5 quadrillion Btus (British
Thermal Units) of electricity on 50 million acres of land would increase overall farm
income by $12 billion annually (the U.S. consumes about 90 quadrillion Btus annually).
By providing farmers with stable income, these new markets diversify and strengthen the
local economy by keeping income recycling through the community.
The use of biomass energy has many unique qualities that provide environmental
benefits. It can help mitigate climate change, reduce acid rain, soil erosion, water
pollution and pressure on landfills, provide wildlife habitat, and help maintain forest
health through better management.
Climate change is a growing concern world-wide. Human activity, primarily through the
combustion of fossil fuels, has released hundreds of millions of tons of so-called
greenhouse gases (GHGs) into the atmosphere. GHGs include such gases as carbon
dioxide (CO2) and methane (CH4). The concern is that all of the GHGs in the atmosphere
will change the earths climate, disrupting the entire biosphere which currently supports
life as we know it. Biomass energy technologies can help minimize this concern.

69
Although both CO2 and CH4, the latter is 20 times more potent (though shorter-lived in
the atmosphere) than the former. Capturing CH4 from landfills, wastewater treatment,
and manure lagoons prevents CH4 from being vented to the atmosphere and allows the
energy to be used to generate electricity or power motor vehicles. All crops, including
biomass energy crops, sequester carbon in the plant and roots while they grow, providing
a carbon sink. In other words, CO2 released while burning biomass is absorbed by the
next crop growing. This is called a closed carbon cycle. In fact, the amount of carbon
sequestered may be greater than that released by combustion because most energy crops
are perennials, they are harvested by cutting rather than uprooting. Thus the roots
remain to stabilize the soil, sequester carbon and to regenerate the following year.
Acid rain is caused primarily by the release of sulphur and nitrogen oxides from the
combustion of fuels like coal. Acid rain has been implicated in the killing of lakes, as well
as impacting humans and wildlife in other ways. Since biomass has practically no
sulphur content, and easily mixes with coal, co-firing is a very simple way of reducing
sulphur emissions and thus, reduce acid rain. Co-firing refers to burning biomass
jointly with coal in a traditionally coal-fired power plant or heating plant.
Biomass crops can reduce water pollution in a number of ways. Energy crops can be
grown on more marginal lands, in floodplains, and in between annual crops areas. In all
these cases, the crops stabilize the soil, thus reducing soil erosion. They also reduce
nutrient run-off, which protects aquatic ecosystems. Their shade can even enhance the
habitat for numerous aquatic organisms like fish. Moreover, because energy crops tend
to be perennials, they do not have to be planted every year. Since farm machinery
spends less time going over the field, less soil compaction and soil disruption takes
place. Another way biomass energy can reduce water pollution is by capturing the
methane, through anaerobic digestion, from manure lagoons on cattle, hog and poultry
farms. These enormous lagoons have been responsible for polluting rivers and streams
across the country. By utilizing anaerobic digesters, the farmers can reduce odor,
capture the CH4 for energy, and create either liquid or semi-solid soil fertilizers which
can replace petroleum-based fertilizers. Table III.7 summarizes a variety of biomass
sources that are being studied for biodiesel productions, and Table III.8 summarizes the
processing technologies that can be used to produce biomass-derived products.
Table III.7. Biomass Sources for Biodiesel Productions.
Feedstock
Yield (Liters/Hectare1)
Soya
60-75
Rapeseed
165-220
Mustard
220
Palm
975
Algae
15,000
1 1 hectare = 104 m2 = 2.5 acres.

70

Table III.8. Technologies to Produce Biomass-Derived Products.

71

IV. EMERGING WATER POLLUTION ISSUES


GREATEST ENGINEERING ACHIEVEMENTS OF THE 20TH CENTURY
[National Academy of Engineering, Washington, D.C. (2005)].
Rank
1
2
3
4
5
6
7

Achievement
Electrification
Automobile
Airplane
Water Supply & Distribution
Electronics
Radio & Television
Agricultural Mechanization

Rank
11
12
13
14
15
16
17

8
9
10

Computers
Telephone
Air Conditioning & Refrigeration

18
19
20

Achievement
Highways
Spacecraft
Internet
Imaging
Household Appliances
Health Technologies
Petroleum & Petrochemical
Technologies
Laser & Fiber Optics
Nuclear Technologies
High-Performance Materials

HISTORY OF THE DEVELOPMENT OF MODERN WATER SUPPLY


AND TREATMENT SYSTEMS.
Year
4000 B.C.

3000 -1500 B.C.


1500 B.C.
5th Century B.C.
3rd Century B.C.
340 B.C. - 225 A.D.
1676
1703
1746
1804
1807
1829
1835
1846
1854

Event
Ancient Sanskrit and Greek writings recommended water treatment methods. In the Sanskrit Ousruta
Sanghita it is noted that impure water should be purified by being boiled over fire, or being heated in the
sun, or by dipping a heated iron into it, or it may be purified by filtration through sand and coarse gravel
and then allowed to cool.
Minoan civilization in Crete developed technologies so advanced that they could only be compared to
modern urban water systems developed in Europe and North American in the second half of the 19th
century. Technologies were exported to Mediterranian region.
Egyptians reportedly used the chemical alum to cause suspended particles to settle out of water. Picture
of clarifying devices depicted on the wall of the tomb of Amenophis II at Thebes and later in the tomb of
Rameses II.
Hippocrates, the father of medicine, noted that rainwater should be boiled and strained. He invented the
Hippocrates sleeve, a cloth bag to strain rainwater.
Public water supply systems were developed at the end of 3rd century B.C. in Rome, Greece, Carthage,
and Egypt.
Roman engineers created a water supply system that delivered water (130 million gallons per day, MGD)
to Rome through aqueducts.
Anton van Leeuwenhoek first observed microorganisms under the microscope.
French scientist La Hire presented plan to French Academy of Science proposing that every household
have a sand filter and rainwater cistern.
French scientist Joseph Amy was granted the first patent for a filter design. By 1750 filters composed of
sponge, charcoal, and wool could be purchased for home use.
The first municipal water treatment plant was installed in Paisley, Scotland. The filtered water was
distributed by a horse and cart.
Glasgow, Scotland, was one of the first cities to pipe treated water to consumers.
Installation of slow sand filters in London, England.
Dr. Robert Dunlingsen, in his book Public Health, recommended adding a small quantity of chlorine to
make contaminated water potable.
Ignaz Semmelweiss (Vienna) recommended that chlorine be used to disinfect the hands of physicians
between each visit to a patient. Patient mortality dropped from 18 to 1 percent as a result of this
action.
John Snow showed that a terrible epidemic of Asiatic cholera could be traced to water at the Broad
Street Well (London), which had been contaminated by the cesspool of a cholera victim recently
returned from India. Snow, who did not know about bacteria, suspected that an agent present that
replicated itself in the sick individuals in great numbers, exited through the alignment canal, and was
transported by the water supply to new victims. Dr. Falipo Pacini, in Italy, identified the organisms

72

1856
1874
1880
1881
1883
1884
1892
1893
1897
1902
1903
1906
1908
1911
1914
1941
1942
1974

that caused Asiatic cholera, but his discovery was largely unnoticed.
Thomas Hawksley, a civil engineer, advocated continuously pressurized water systems as a strategy
to prevent external contamination.
Slow sand filters were installed in Poughkeepsie and Hudson, New York.
Karl Eberth isolated the organism (Salmonella typhosa) that caused typhoid fever.
Robert Koch demonstrated in the laboratory that chlorine would inactivate bacteria.
Carl Zeiss marketed the first commercial research microscope.
Professor Escherich isolated organisms from the stools of a cholera patient that he initially thought were
the cause of cholera. Later it was found that similar organisms were also present in the intestinal tracts of
every healthy individual as well. Organism was eventually named for him (Escherichia coli).
Robert Koch proved that Asiatic cholera was due to a bacterium, Vibrio cholera, which he called the
common bacillus because of its comma-like shape.
First sand filter built in America for the express purpose of reducing the death rate of the population
supplied was constructed in Lawrence, Massachusetts. To this end, the filter proved to be a great success.
G.W. Fuller studied rapid sand filtration (2 gallons/ft2-day) and found that bacterial removals were much
better when filtration was proceeded by good coagulation and sedimentation.
The first drinking water supply was chlorinated in Middlekerke, Belgium. Process was actually a
Ferrochlor process wherein calcium hypochlorite and ferric chloride were mixed, resulting in both
coagulation and disinfection
The iron and lime process of treating water (softening) was applied to Mississippi River water supplied to
St. Louis, Missouri.
First use of ozone as disinfectant in Nice, France. First use of ozone in the U.S. occurred four decades
later.
George Johnson, a member of Fullers consulting firm, helped install continuous chlorination in Jersey
City, New Jersey.
Johnson published Hypochlorite Treatment of Public Water Supplies, in which he demonstrated that
for contaminated supplies filtration alone was not enough. Adding chlorination to the process of water
treatment greatly reduced the risk of bacterial contamination.
U.S. Public Health Service (U.S. PHS) used Smiths fermentation test for coliform to set standards for the
bacteriological quality of drinking water. The standards applied only to water systems that provided
drinking water to interstate carriers like ships and trains
85% of the water supplies in the U.S. were chlorinated, based on a survey conducted by U.S. PHS.
U.S. PHS adopted the first comprehensive set of drinking water standards
Dutch and American studies demonstrated that chlorination of water formed trihalomethanes.
Passage of the Safe Drinking Water Act (SDWA).

WATER SUPPLY AND DISTRIBUTION SYSTEMS (Figure IV.1). Water


supply and distribution system (or network) is a system of engineered hydrologic and
hydraulic components which supply and distribute the water. Such a system typically
includes:
1.

The watershed (or catchment) (1) which is an area of land that catches water
from precipitation and snowmelt. The water then drains to a common waterway,
such as, a stream, lake, aquifer, or wetland;

2.

Raw (untreated) water collection point (above or below ground) where the water
accumulates, such as a lake, a river, or groundwater from an underground
aquifer. Raw water (usually water being transferred to the water purification
facilities) may be transferred using uncovered ground-level aqueducts, covered
tunnels, or underground water pipes (3a).

73

Figure IV.1. The schematic of a water supply and distribution system.


3.

Water purification facilities (2) where raw water is treated using modern
treatment technologies/practices to ensure that the quality of the treated water
meets stringent standards.

4.

A pipe network for distribution of treated water (usually underground) (3, 3a3d)to the consumers such as private houses; industrial, commercial, or
institution establishments; and other usage points (e.g., such as fire hydrants)
(4).

5.

Water storage facilities such as reservoirs, water tanks, and water towers (5) are
used to store water to meet demands that are highly time dependent. Smaller
water systems may store the water in cisterns or pressure vessels. Tall buildings
may also need to store water locally in pressure vessels in order for the water to
reach the upper floors.

74
6.

Additional water pressurizing components such as pumping stations may need to


be situated at the outlets of underground or above ground reservoirs or cisterns if
gravity flow is unfeasible.

7.

Connections to the sewers (underground pipes, or aboveground ditches in some


developing countries) are generally found downstream of the water consumers,
but the sewer system is considered to be a separate system, rather than part of
the water supply and distribution system.

WATER TREATMENT METHODS. To better understand how the treatment


methods developed, it is appropriate to consider their evolution. A summary of the
methods used for the treatment of water at the beginning of the 20th century (except for the
membrane separation) is presented in Table IV.1.
Table IV.1. Water Treatment Methods.
Method
Mechanical Separation

Coagulation
Chemical Purification
Disinfection

Biological Processes

Aeration

Boiling
Membrane Separation

Agent/Objectives
Gravitational Sedimentation, Screening (screens, scrubbers, and filters),
and Adhesion (scrubbers and filters).
Chemical treatment resulting in drawing matters together into groups,
thereby making them more susceptible to removal by mechanical
separation but without any significant chemical changes in the water.
Lime Softening, Iron Removal, and Neutralization of Objectionable Acids.
The processes that utilize ozone (O3), chlorine (Cl2), or cupric sulfate
(CuSO4) to poison or kill objectionable organisms without at the same
time adding substances objectionable or poisonous to the users of the
water.
Oxidation of organic matter as food by organisms thereby resulting in its
destruction.
Death of objectionable organisms, resulting from the production of
unfavorable conditions, such as absence of food (removed by the
purification processes) and killing by antagonistic organisms.
Evaporation of (1) dissolved gases that produce objectionable tastes and
odors, and (2) carbonic acid that is the carbon source supporting the
chemoautotrophic bacterial growths.
Addition of oxygen for certain chemical purifications and growth of
water-purifying organisms.
Best household method of protection from disease-carrying waters.
Complete rejection of pathogens of zoonotic origin that can survive a
water supply that is completely free of wastewater contamination.
Desalination.

It is interesting to note that these methods are still in use today. The most important
modern technological development in the field of water treatment is the use of membrane
technology. Membrane filtration was widely used for beverages in the mide-1960s to
replace heat pasteurization as a means of purification and microbial stabilization. In
virtually all of these applications the membranes were treated as disposal items. The idea of
treatment large volumes of drinking water in this manner was untenable. The development
of membrane filtration fibers in the mid-1980s that could be backwashed after each use
permitted uses on a continuous basis for a long period of time. In the last decades of the
20th century there were numerous manufacturers of commercial membrane filtration
systems and municipal water treatment plants as large as 3105 m3/day were under

75
construction. Membranes are arguably the most important development in the treatment
of drinking water since the year 1900 because they offer the potential for complete and
continuous rejection of microbiological contaminants on the basis of size exclusion.
Desalination membranes offer the opportunities of converting salty and brackish water into
drinking water for semi-arid and arid areas where fresh water resources are scarce. Two
examples of water treatment systems are shown in Figures IV.2 and IV.3.

Figure IV.2. A conventional water treatment system.

EFFECTS OF DEVELOPMENT ON STREAM FLOW/STORMAWATER


MANAGEMENT. As precipitation hits the ground there is a fork in the pathway of
the water cycle. Water from rainfall or snowmelt may infiltrate into the ground, or it
may runoff the surface. Several factors such as surface characteristics (porosity and
slope), nature of soil, amount of precipitation, and rate of precipitation influence which
direction the water goes. River flow curves in Figure IV.4 are recorded for three similar
storms (i.e., similar intensity and duration) on Brays Bayou in Houston, Texas, before,
during, and after development. The increasing height of the surge (i.e., crest in river
flow) occurring with the progress of development clearly indicates that surface runoff is
becoming predominant, because the paved surfaces have much less capacities in
intercepting and retaining rainfalls as compared to surfaces covered with trees and
shrubs.
Stormwater management deals with problems such as excessive runoffs, river bank
erosion, and flooding. In a heavy rainfall a hectare (2.5 acres) parking lot may generate
runoff at the rate of 6 m3/min. Therefore, traditional stormwater management practices
focus on rapid drainage. Recent stormwater management practices promote reverse
philosophy hold stormwater at or near where it falls and let it drain away slowly or
infiltrate. As a result, the techniques of building parking lots with porous surfaces, and
designing rooftops, parking lots, and other flat surfaces so that they pond the water and
let it trick away slowly are becoming popular. Stormwater may be a cheap source of water

76
(i.e., gray water) for many uses; e.g., runoff from the paved park lot of a car dealership can
be collected and stored in an underground storage tank and then used to wash cars.

Figure IV.3. Desalination scheme using reverse osmosis membranes.

140
Brays Bayou, Houston, Texas
120
June 23-27, 1960

River Flow (m /s)

100

80
May 12-19, 1953

60

40

20
September 23-25, 1941
0
0

20

40

60

80

100

Time (hours)

Figure IV.4. The effects of land development on peak river flows.

POINT/NON-POINT POLLUTION SOURCES (Figure IV.5). Non-point (or


distributed) source (NPS) pollution, unlike pollution from industrial and municipal
wastewater treatment plants, comes from many diffuse sources. NPS pollution is caused
by rainfall or snowmelt moving over and through the ground. As the runoff moves, it
picks up and carries away natural and human-made pollutants, finally depositing them
into lakes, rivers, wetlands, coastal waters, and even our underground sources of
drinking water. These pollutants include: (1) excess fertilizers, herbicides, and
insecticides from agricultural lands and residential areas; (2) oil, grease, and toxic
chemicals from urban runoff and energy production; (3) sediment from improperly

77
managed construction sites, crop and forest lands, and eroding riverbanks; (4) salt
from irrigation practices and acid drainage from abandoned mines; and (5) bacteria and
nutrients from livestock, pet wastes, and faulty septic systems. Atmospheric deposition
and hydromodification are also sources of NPS pollution. In many states NPS pollution
is the leading remaining cause of water quality problems. The effects of NPS pollutants
on specific waters vary and may not always be fully assessed. However, these pollutants
have harmful effects on drinking water supplies, recreation, fisheries, and wildlife.

Figure IV.5. Point and non-point pollution sources.

MUNICIPAL WASTEWATERS. Municipal wastewaters come from many


sources, including homes, apartments, businesses, and industries (those located in the
cities served by the municipal sewer systems). For old cities such as Philadelphia,
municipal wastewaters also include stormwater runoffs. The wastewater volumetric flow
rates and the contaminant types and concentrations vary substantially from day to day,
during the day, and from city to city. However, contaminating materials account for
only 0.1% of total weight of a typical municipal wastewater, but such small quantities of
contaminants still render the wastewater unsafe for aquatic life and unsuitable for
beneficial usage. The removal of these contaminating materials is a very slow process.
Since the number of contaminants found in municipal wastewaters is almost limitless,
multistep treatment processes, each with a sufficient large degradation capacity, are
usually required to ensure that treated wastewaters can safely be returned back to the
environment without damaging the aquatic habitats.
The measurements of contaminants in municipal wastewaters are restricted to a few
general classes, i.e., physical, chemical, and biological characteristics. Important

78

Inorganic Suspended Solids


Organic Colloidal Materials

Dissolved Materials

Solids/Silt/Clay.
Fecal Matter (undigested materials, cellulose, and bacteria).
Garbage (from disposals).
Cloth Fibers (from laundry).
Paper Fibers (from tissues)
Nutrients: Detergents (phosphates) and urine (phosphate,
ammonium, nitrate, potassium, sodium, calcium, sulfate, etc.).
Toxic Wastes (mostly from industries): heavy metals (copper,
mercury, cadmium, chromium, tin, zinc, lead, arsenic, etc.).
Non-Biodegradable Organic Compounds.

physical characteristics include solids (total, dissolved, suspended, and settleable),


turbidity, color, and temperature. Important chemical characteristics include pH,
metals, organic matter, nitrogenous matter, phosphorous, sulfur, and dissolved gases.
Important biological characteristics include pathogenic organisms, bacteria, protozoa,
helminthes, and viruses.
Organic compounds are normally composed of a combination of carbon, hydrogen, and
oxygen, together with nitrogen, phosphorous, and sulfur in some cases. Theorganic
matter in municipal wastewaters typically consists of protein (40-60%), carbohydrates
(25-50%), and oils and fats (8-12%). Urea, the major constituent of urine, is another
important organic compound contributing to fresh municipal wastewaters. Because urea
decomposes rapidly, it is seldom found in other than very fresh municipal wastewaters.
In addition, municipal wastewaters contain small quantities of a very large number of
synthetic organic molecules, with structures ranging from simple to extremely complex.
Over the years, a number of different analyses have been developed to determine the
organic content of municipal wastewaters. In general, the analyses may be classified into
those used to measure aggregate organic matter comprising a number of organic
constituents with similar characteristics that cannot be distinguished separately, and
those analyses used to quantify individual organic compounds. The concentration of
organic matter in municipal wastewaters is often measured in terms of it oxygen
demand, since dissolved oxygen (DO) is essential to sustaining the aquatic life and many
organics consume oxygen as they undergo degradation. The depletion of oxygen
inventories in surface water bodies will decimate fish and other forms of aquatic life and
create septic or anaerobic conditions. The oxygen demand of organic matter can be
measured as either biochemical oxygen demand (BOD) or chemical oxygen demand
(COD). The measurements are good with DO concentrations > 1 mg/L.
Biochemical Oxygen Demand. BOD is a gross parameter that is widely used as a
means to measure the concentration of a biodegradable organic chemical. BOD is the
amount of oxygen required by the microorganisms to fully oxidize a given organic
chemical to CO2 and H2O. Therefore, BOD is always proportional to the organic
chemical concentration. BOD is a convenient parameter to use, especially when a group
of unknown but biodegradable organic chemicals is present. So, always think BOD as
the concentration parameter (i.e., C = BOD).
There are two types of BOD: CBOD and NBOD. See the following reaction expressions.

Cn H aOb N c (n

a b 3c
a 3c
)O2 Bacteria

nCO2 ( ) H 2O cNH 3
4 2 4
2 2

(IV.1)

79
NH 3 2O2 Bacteria

NO3 H H 2O

(IV.2)

In (IV.1), the amount of oxygen required by heterotrophic bacteria to remove the


organic material present (i.e., carbon oxidation) is referred to as CBOD. In (IV.2), the
amount of oxygen required by chemoautrotrophic bacteria to oxidize ammonia to nitrate
(nitrification) is referred to as NBOD. 4.57 g O2 are needed to oxidize 1 g NH3-N to NO3-N. As a result, any discharge containing significant amounts of CBOD and/or NBOD will
deplete the dissolved oxygen (DO) inventories in the surface water body downstream
from the point of discharge, primarily caused by the indigenous bacterial activities in
water.
Chemical Oxygen Demand. The equivalent amount of oxygen required to oxidize
any organic matter in a municipal wastewater sample by means of a strong chemical
oxidizing agent (e.g., potassium dichromate, K2Cr2O7) is called COD. The sample is
oxidized with excess amounts of K2Cr2O7 and concentrated H2SO4. A catalyst, silver
sulfate (AgSO4), is used to assist the oxidation reaction and mercuric sulfate (HgSO4) is
used to prevent the oxidation of chloride (Cl-). The sample mixed with the chemicals (in
a capped vial) are digested at 130oC for 2 hours to convert practically all of the organic
matter to CO2 and H2O. The difference between the initial amount and the final amount
of K2Cr2O7 is the COD of the sample tested.
a 8d 3c

3
Cn H a Ob N c dCr2O72 (8d c) H

nCO2
H 2O cNH 4 2dCr
2

2n a b c
d

3 6 3 2

(IV.3)

Wastewater treatment and management terminologies that are commonly used are
summarized in the Appendix.
Municipal Wastewater Treatment Technologies (Figures IV.6 and IV.7).
municipal wastewater treatment as it is commonly practiced in the U.S. consists of three
stages: pretreatment, primary treatment, and secondary treatment. These stages
remove most of the organic matter including microorganisms, but they do not remove
dissolved nutrients (i.e., nitrogen and phosphorous). Additional treatment, referred to
as advanced treatment or tertiary treatment, is now being practiced to remove
dissolved nutrients and other constituents (e.g., dissolved solids) to render the treated
municipal wastewater reusable.
Pretreatment involves the steps required before removal of actual contaminants can
begin. The municipal wastewater stream may carry large pieces of debris such as rags,
plastic bags, and coarse sand (or grit). If these materials remain, they will clog or hinder
later treatment stages. They are removed by letting the municipal wastewater stream
flow through a bar screen, a row of bars mounted about 2.5 cm apart. Debris is
mechanically removed from the screens and taken to be incinerated or landfilled. Coarse
sand or grit are then removed by passing the municipal wastewater stream through grit
chambers where its velocity is slowed just enough the permit such materials to settle.
The settled materials are mechanically removed from these tanks and then landfilled.
Primary treatment involves the gravitational settling of heavier particles or organic
matter that are removed in grit chambers in large primary clarifiers where the

80

Figure IV.6. Flow scheme of a typical municipal wastewater treatment plant.


municipal wastewater stream flows very slowly to render it nearly motionless for several
hours. About 30 to 50% of the total settleable solid matter is removed. At the same
time, fatty or oily materials float to the top and are skimmed off. The materials removed
are known as the primary sludge which requires separate treatment and disposal.
Secondary treatment is also called biological treatment because it employs organisms
that literally consume the organic matter and convert it through cellular respiration and
reproduction to CO2, H2O, and new cells. Either attached-growth processes (e.g.,
trickling filters) or suspended-growth processes (e.g., activated sludge processes) are
used for secondary treatment. Through primary and secondary treatments, 85 to 90% of
the total organic matter is removed. The excess cells produced are removed in final

81

Figure IV.7. A municipal wastewater treatment plant. DAF: dissolved air flotation.
clarifiers (physically similar to primary clarifiers) as the secondary sludge or biological
sludge. The municipal wastewater stream after secondary treatment is disinfected with
either chlorine gas (Cl2) or chlorine dioxide (ClO2) to reduce disease hazards and
enhance public health safety prior to its final discharge into the environment. Secondary
treatment is unable to remove nutrients such as nitrogen and phosphorous that may
cause eutrophication in surface water bodies. When eutrophication is a problem, then
secondary treatment is needed to be upgraded to advanced treatment or tertiary
treatment. Novel treatment technologies are available to render the municipal
wastewaters reusable after advanced treatment.
Recall that 30 to 50% of the organic matter in a municipal wastewater stream is removed
in the primary treatment as the primary sludge. Primary sludge is a black, foul-smelling,
syrupy liquid of about 98% water and 2% organic matter that includes many pathogenic
organisms. Both primary and secondary sludge streams can be treated in anaerobic
sludge digesters (at either 35oC or 55oC) to produce methane (CH4) as a gaseous fuel.
The quantity of CH4 that can be produced is roughly 0.03 m3 per day per person served
(or 0.35 m3/kg COD removed at 25oC and 1 atm). The stabilized sludge after anaerobic
digestion is usually odorless with little hazards. It is essentially the same as humus
resulting from decay in natural eco-systems. It can be used as the soil conditioner to
improve the soil quality.
RIVERS. Rivers serve as the major routes by which continental rain and the
contaminants reach the oceans. Rivers do not contain a very large percentage of the total

82
water on the earth (i.e., 0.0001%), but their importance cannot be overlooked since they
play a significant role in the transport of water as well as dissolved and suspended matter
(including contaminating materials). Rivers have played an important role in human
development as well. As result of human proximity, rivers have been considerably
affected by activities ranging from agriculture and flood control to the input of human
and industrial wastes. In general, the rivers can be classified on the basis of their water
quality that is safe for the intended uses. For instance, the water quality of a class A
river should be sufficiently good to satisfy the requirements for water contact
recreational activities. Contaminants commonly found in surface water bodies include:
(1) oxygen-demanding organic and inorganic materials, (2) nutrients such as nitrogen
(organic and inorganic) and phosphorous (organic and inorganic), (3) pathogens, (4)
suspended solids (stormwater and soil erosion), (5) salts (deicing applications and
seawater intrusion), toxic chemicals and metals (organic and inorganic), and heat
(cooling water discharges). These contaminants may come from a variety of sources that
include: (1) municipal discharges (wastewaters and stormwaters), (2) industrial
discharges, (3) agricultural runoffs (fertilizers, pesticides, and animal wastes), and
isolated areas (e.g., office parks, apartment complexes, etc.).
Class

Remarks

Water contact recreation (including swimming)

Able to support fish and wildlife

Public water supply

Agricultural and industrial uses

Applications of CFSTR/PFR Models to Surface Water Bodies. The following 2


examples illustrate that both CFSTR and PFR models can be applied to assess the water
quality in surface water bodies (i.e., rivers, streams, lakes, and reservoirs).
Example IV.1. An industry is applying for permission to discharge its wastewater into an
adjacent pond that is linked to a river at point 1 (see the attached diagram). The pond water is
then mixed with the river water at point 2. A fish hatchery located 2 km downstream from
point 2 obtains its makeup water directly from the river at point 3 (i.e., the water quality at
point 3 is a major concern in this application). Recommendations are sought to satisfy both
parties (i.e., industry and fish hatchery). It was previously determined that the wastewater to
be discharged contains an undesirable compound that needs to be strictly regulated. (1) Pond
dimension: L:W:D = (50 m):(20 m):(3 m), (2) wastewater discharge rate: 2,000 m3/day, (3)
average river flow rate: 100,000 m3/day, (4) average river dimension: W: 10 m, D: 3 m, (5)
compound concentration in wastewater: 100 mg/L, and (6) desired compound concentration
at point 3: < 0.01 mg/L.
Moreover, (1) the compound undergoes 1st-order degradation in water [in situ 1st-order rate
constants are 1.2 day-1 (pond) and 0.7 day-1 (river)], (2) the pond is completely mixed under
most circumstances, (3) the river is free of the compound in question upstream from point 2,
and (4) the estimated annual treatment cost to remove the compound prior the discharge into
the pond is:

$
( R)(V )0.356(12,000) , where R is fractional removal and V is in m 3/day.
year

83

River (PFR System)


2

1
Fish Hatchery
Pond (CFSTR System)
Wastewater
1.

V (pond) = (50)(20)(3) = 3,000 m3. The HRT of wastewater in the pond

3,000
= 1.5 days.
2,000

2.
3.

The distance between 2 and 3 x23 = 2,000 m.


Average cross-section area of the river A = (10)(3) = 30 m2.

4.

Travel time between 2 and 3 t *

5.

Since the river flow rate is >> the wastewater flow rate and the average crosssectional area of the river is small, we can assume that both flows will be

(2,000)(30)
= 0.59 days.
(100,000 2,000)

completely mixed at point 2. Therefore, C2

6.
7.
8.

C1 (2,000)
0.02C1 , where
100,000 2,000

C1 is the compound concentration at point 1 and C2 is the compound


concentration at point 2.
Assuming that the river can be modeled as a PF system (why?), then
*

C3 C2ekt (0.02C1 )e(0.7)( 0.59) 0.013C1 0.01 C1 0.76 mg/L.


In other words, the compound concentration leaving the pond must be < 0.76
mg/L, say, let C1 = 0.5 mg/L ( a better margin of safety).

Option 1: The wastewater, after treatment, is discharged into a completely mixed pond.
1.

2.

In this case, the compound concentration after treatment is:


Cin C1 (1 k ) (0.5)(1 1.2 1.5) = 1.4 mg/L. The required fraction removal =
0.986.
Annual treatment cost is: (0.986)(2,000)0.356(12,000) = $177,103/yr.

Option 2: Modify the hydraulic characteristics of the pond through partition, i.e., the
pond is divided into 10 narrow channels (each channel has a width of roughly 5 m and a

84
length of 20 m). (see the attached diagram). As a result, the pond behaves like a PFR
system. The cost of partition should be modest since the pond is shallow and is relatively
small.

1.
2.
3.

In this case, the compound concentration after treatment is:


Cin C1ek (0.5)e(1.2)(1.5) = 3.02 mg/L. The required fraction removal is: 0.970.
Annual treatment cost is: (0.970)(2,000)0.356(12,000) = $174,229/yr.
Annual savings in treatment costs as compared to Option 1 are: $177,103 $174,229 = $2,874/yr (too small!).

Option 3: Dig a new, partitioned pond with a suitable size. Make the wastewater to flow
through these two ponds in series. Find the size of the new pond such that no treatment
is required. In this case, Cin 100 (0.5)e( x )(1.2)(1.5) x 3.0 . In other words, the new
pond should have a size twice the existing pond and it can be partitioned into 20 narrow
channels. Again, the costs of digging and partitioning this new pond with 20 narrow
channels should not be excessive. Therefore, it is evident that Option 3 is the best one to
recommend.
Example IV.2. The river and tributary shown below have flow rates of 4.0 and 0.5

m3/s, respectively. The river flow splits at point A that yields V AB = 2.8 m3/s and V AC =
1.2 m3/s. The physical and flow characteristics of the system are summarized as follows:
Section

Volume (m3)

Flow Characteristics

AB

15,000

Plug Flow

BC

10,000

Plug Flow

AC

30,000

Plug Flow

135,000

Completely Mixed

(1) Determine the steady-state concentration of a pollutant at point C (CC) for the
following
conditions: r (degradation rate) = kC, k = 0.5 day-1, C1 = 50 g/m3 (concentration at
point 1), and CA = 100 g/m3 (concentration at point A). (2) If the steady-state
concentration at point C (CC) is to be reduced to 50% of the level calculated in (1), which
of the following options will produce the best result: (a) reduce C1 to 25 g/m3 and CA 50
g/m3, (b) reduce C1 to zero, and (c) reduce CA to 25 g/m3?

85

1.1.

Section A-B: CB

1.2.

Section B:

(0.7)(4)(CB

A B

A B

C Ae

kt*A B

100e

( 0.5)(15, 000)
( 0.7 )( 9 )( 86, 400)

) (C1 )(0.5) [(0.7)(4) 0.5]CB

= 97 g/m3 (PFR system).

(0.5)(135,000)(CB )
0 CB =
86,400

72.7 g/m3 (CFSTR system).


1.3.

Section B-C: CC

BC

CB e

kt*BC

72.7e

( 0.5)(10, 000)
[( 0.7 )( 4 )0.5]( 86, 400)

= 71.4 g/m3 (PFR

system).

Tributary

1
B

River

1.4.

Section A-C: CC

1.5.

Therefore, CC

ISLAND

AC

C Ae

kt*AC

(0.7)(4)(CC

100e

( 0.5)( 30, 000)


( 0.3)( 4 )( 86, 400)

) (0.3)(4)(CC
4.0 0.5

BC

AC

= 86.5 g/m3 (PFR system).

= 75.4 g/m3 (CFSTR

system).
2.

Now, the required CC is 37.7 g/m3. The calculations follow the same steps as 1.1
to 1.5.

a.
b.
c.

C1 = 25 g/m3 and CA = 50 g/m3 CC = 37.7 g/m3.


C1 = 0 g/m3 and CA = 100 g/m3 CC = 63.7 g/m3.
C1 = 50 g/m3 and CA = 25 g/m3 CC = 19.7 g/m3.

3.

Therefore, c > a > b (option b will not meet the requirement).

Superposition Technique. Recall that a river can be modeled as PFR system because

86
its longitudinal dimension is significant as compared to its lateral dimensions. If a
species i is consumed in the river at a first-order rate, then at steady state,
kx

kx

dC
kC 0 C ( x) C (0)e u Ci e u
dx

(IV.4)

where C(x) is the concentration of species i at the downstream location x, Ci = C(0) is the
concentration of species i at the location x = 0, k is the first-order decay rate coefficient,
and u is the average river flow velocity. Any river that can be modeled by (IV.4) is
referred to as a homogenous linear system. A mathematical technique applicable to a
homogeneous linear differential equation such as (IV.4) is the superposition technique.
Let C1(x) and C2(x) be the solutions of (IV.4). By substituting C(x) = C1(x) + C2(x) and its
derivative into (IV.4), then

dC
d (C1 C2 )
kC u
k (C1 C2 )
dx
dx
dC
dC
u 1 kC1 u 2 kC2 0
dx
dx

(IV.5)

Therefore, (IV.5) suggests that C(x) is also a solution of (IV.4). See the following
example.
Example IV.3. A river receives two pollution loads as shown in the attached diagram. The
following information is available:
1.
2
3.
4.
5.
6.
7.

Wastewater discharge rate: 2,000 m3/day (location 1) and 1,000 m3/day (location 2).
Wastewater compound concentration: 200 mg/L (200 g/m3).
Average river flow rate upstream from location 1: 50,000 m3/day.
Average river dimension: W: 10 m, D: 3 m.
In situ first-order rate constant k = 0.7 day-1.
The river is free of the compound in question upstream from point 1.
The wastewater stream mixes immediately and completely with the river flow at the
point of discharge.

Find the concentration of the compound in river 4,000 m downstream from location 1.

River

1 (x = 0 m)

2 (x = 1,000 m)

87
I.

Solution Approach 1.

I.1.

The compound concentration in river @ location 1 is: C (0)

7.69 mg/L.
I.2.

u (1 2)

2,000 50,000
= 1,733.3 m/day.
10 3

( 0.7 )(1, 000)


1, 733.3

I.3.

C (1,000) 7.69e

I.4.

The compound concentration in river @ location 2 is:

I.5.

200 2,000
=
2,000 50,000

= 5.13 mg/L (immediate upstream @ location 2).

5.13 52,000 200 1,000


52,000 1,000

= 8.81 mg/L.
52,000 1,000
= 1,766.7 m/day.
u (2 3)
10 3

( 0.7 )( 3, 000)
1, 766.7

I.6.

C ( x 4,000) C ( x 3,000) 8.81e

II.

Solution Approach 2 (Superposition Technique).

II.1.

C1 ( x 4,000) 7.69e

II.2.

1,000 200
C2 ( x 3,000)
e
50,000 1,000

II.3.

Therefore, C(4,000) = 1.53 + 1.14 = 2.67 mg/L.

'

( 0.7 )( 4, 000)
1, 733.3

= 2.68 mg/L.

= 1.53 mg/L.

( 0.7 )( 3, 000)
50, 0001, 000
103

= 1.14 mg/L.

BIOACCUMULATION AND BIOMAGNIFICATION. Some of the chemicals,


e.g., heavy metals and halogenated hydrocarbons, may be ingested with food or water are
neither broken down nor excreted readily. Instead, they accumulate in the body,
concentrating in the liver or other specific organs until they reach damaging levels. This
phenomenon is called bioconcentration or bioaccumulation. When the phenomenon of
bioaccumulation is put into the context of a food chain, each successive consumer receives a
more contaminated food supply and, in turn, accumulates the contaminant to yet a higher
level. For instance, scientists have observed that the concentration of the pesticide DDT
was magnified some 10 million-fold as it passed through the food chain (biomagnification)
(Figure IV.8).
One of the most distressing aspects of bioaccumulation One of the most distressing aspects
of bioaccumulation One of the most distressing aspects of bioaccumulation and
biomagnification is that the diseases which they cause, e.g., cancer, liver and kidney
dysfunction, and birth defects, may not appear many years after the initial exposure. By
that time is extremely difficult, if not impossible, to determine the real cause of the disease
and too late for the individual concerned to do much, if anything, about it. The
bioconcentration process can be seen as a balance between two kinetic processes, uptake
(e.g., inhalation, ingestion, and dermal contact) and depuration (e.g., excretion, urination,
and perspiration) as quantified by first-order rate constants k1 and k2, respectively. The rate
of change of contaminant concentration in an organism is given by:

88

DDT (C14 H 9 Cl5 )

Figure IV.8. Bioconcentration and biomagnification.

dCB
dC
k
k1CM k2CB B 0 k1CM k2CB CB 1 CM ( BCF )CM
dt
dt
k2

(IV.6)

Ambient Environment (e.g., water)


Uptake

Organism

Depuration

where CB is the biotic phase concentration (i.e., the concentration in the organism), CM is
the concentration in the environmental medium, and BCF is the bioconcentration factor.
BCF expresses the bioconcentration (or bioaccumulation) of hydrophobic compounds that
tend to accumulate in the fat of animals. Although BCF is defined under the equilibrium
conditions when the organism has been exposed to the contaminant for a prolong period of
time, however, BCF is a good indicator of the bioaconcentration potential of a contaminant.
The bioaccumulation of some anthropogenic, hydrophobic compounds in various
organisms is summarized as follows where environmental medium is water (i.e., CM is CW).
Compound
Aldrin
Chlordane
DDT
Dieldrin
PCB

Organism
Catfish//Buffalo Fish
Algae
Algae//Oyster//Trout
Trout
Yellow Perch

BCF
1,590//30,000
302
500//70,000//200
3,300
17,000

CW (g/L)
0.044//0.007
6.610-3
0.01610-3//0.1//20
2.3
1.0

89
PCBs IN THE AQUATIC ENVIRONMENT. PCBs (polychlorinated biphenyls)
are stable, non-flammable oils (also a poor conductor of electricity) once used
extensively as transformer and hydraulic fluids, especially for transformer applications,
in which power surges can cause arcs and ignite insulation oils. Aroclor is the trade
name used by Monsanto for PCBs. The basic unit of PCBs is the aromatic hydrocarbon
biphenyl (Figure IV.9). The biphenyl molecule has 10 sites where chlorine can be
substituted for hydrogen atoms; 5 position in one ring (left) are numbered 2 through 6
(counterclockwise), and 5 positions in another ring (right) are numbered 2' through 6'
(clockwise). In assigning location numbers to the chlorine atoms, lower number (primed
or unprimed) take precedence over higher numbers, and unprimed number are listed
over equivalent primed numbers. Chlorination yields up to 207 products (called
congeners because they are all formed together by the same basic process of
chlorination) with the substitution of one to ten chlorine atoms on the biphenyl
molecule.

Biphenyl (C12H10)

Figure IV.9. Polychlorinated biphenyl (PCB) molecule.

90
PCBs are often considered as groups of molecules containing the same number of
chlorine atoms, although the locations of chlorine substitution may be different (i.e.,
PCBs with the same number of chlorine atoms are known as isomers). In the U.S., PCBs
have been marketed by Monsanto under the trademark Aroclor. International
names include Fenchlor (Italy), Kaneclor (Japan), Pyralene (France), and Clophen
(Germany). The difference in chlorination are noted by four-digit numbers after the
name of Aroclor, such as Aroclor 1221 or Aroclor 1232. The first two digits refer to 12
carbons in biphenyl. For all Aroclor but one, the last two digits of the four-digit term
represent the % of chlorination by mass of the PCB mixtures (e.g., Aroclor 1248 is a
mixture containing 48% by weight of chlorine). The one exception is Aroclor 1016, which
is 41% chlorinated. Since PCBs have a very low water solubility and a very high affinity
towards particles (especially Those with a high organic carbon content) (Table , the
environmental fate of PCBs is strongly influenced by these important properties. When
PCBs are released into a surface water body (e.g., a river), they are either (1) present as
oil droplets in water (due to a low water solubility) or (2) adsorbed on the suspended
particles in water (due to a low water solubility and a small Henrys law constant). As a
result, the settling velocities of PCB droplets and/or PCB-coated suspended particles and
the flow velocity of the water in the river will determine whether or not the PCBs
released will stay in the control volume (i.e., reach the bottom sediments and stay there)
or be carried away from the control volume (i.e., move with the river water to
downstream locations outside the control volume). These phenomena should be
analyzed before the environmental fate of PCBs can be assessed.
Aroclor 1016

Aroclor 1232

Aroclor 1248

Aroclor 1260

Vapor Pressure1
(mm Hg) @ 20oC

410-4

410-4

410-4

410-4

Henrys Law
Constant2
(atm-m3/mol) @ 25oC

3.310-4

8.6410-4

3.510-4

7.110-4

LD503
(oral rat) (mg/kg)

2,300

4,470

11,000

1,315

Water Solubility
~ 100
~ 100
~ 100
~ 100
(g/L)
1 The vapor pressure of a species is a measurement of its volatility (i.e., the tendency to
accumulate in the
gas phase). 2 Henrys law constant is a measurement of the concentration distribution of a species
between the liquid phase and the gas phase under the equilibrium conditions. The concentration
in the gas phase is
expressed in terms of the partial pressure of the species. A species with a high Henrys law
constant
shows that it tends to accumulate in the gas phase. 3 LD50 is a parameter used for defining the
degree of acute toxicity. It is a calculated dose of a material that is expected to cause the death of
50% of an entire defined experimental animal population. It is determined from the exposure to
the material by any route other than inhalation of a significant number from that population. By
comparison, 2,3,7,8-TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxine) has an LD50 = 0.02 mg/kg (i.e.,
a taste of 2,3,7,8-TCDD will probably kill a 70-kg person).

91
Adsorption on the Water-Soil Interface. Adsorption is the physical and/or
chemical
process in which a substance accumulates at the solid-liquid interface or gas-liquid
interface.
Examples include the adsorption of a gas (adsorbate) on a solid (adsorbent) or a liquid
on a
solid. Sorption is the combined process of adsorption of a solute (sorbate) at a solid
surface
(sorbent) and partitioning of the solute into the organic carbon (OC) that has coated the
solid
surface. Electrostatic forces, van der Waals force, and hydrogen bonding are the basic
physical/
chemical forces that cause adsorption to occur. Hydrophobic bonding can also account
for the
interaction with a surface in soil and sediment environments. (IV.7) and (IV.8) are two
commonly used expressions that describe the adsorption phenomena occurring on
water-solid
interfaces:
1
n
e

q KC (Freundlich Isotherm Equation)


q K 'Ce (Linear Isotherm Equation)

(IV.7)
(IV.8)

where q is the equilibrium solid-phase concentration, mg sorbate/g sorbent; K is the


1

Freundlich capacity parameter, (mg sorbate/g sorbent)(L water/mg sorbate) n ; Ce is the


equilibrium liquid-phase concentration, mg/L; n is the Freundlich intensity parameter;
and K ' is the equilibrium constant between an aqueous (or gaseous) and a solid phase,
mL/g or L/kg. (IV.4) is very useful in describing the fate of many anthropogenic organic
compounds in soil (or sediment)-water environmental compartments. However, K ' is
chemical-specific which will be tedious and expensive to measure. As a result, the
following procedure has been developed to estimate K ' . For an organic chemical A,

K OW

Aoc tan ol
Awater

log( K OC ) 0.903 log( K OW ) 0.094

(IV.9)

K ( K OC )( f OC )
'

where K OW is the octanol-water partition coefficient; K OC is the soil-water partition


coefficient normalized to organic carbon, mL/g organic carbon or L/kg organic carbon;
and f OC is the fraction od organic carbon for a specific soil or sediment. K OW is easily
measurable in the laboratory. If an organic chemical, A, is mixed in a sealed container
that contains equal volumes of octanol (C8H17OH) and water, after equilibration and
separation of the water and octanol phases, the concentrations of A in these phases are
measured (i.e., [A]octanol and [A]water) and K OW is then calculated by (IV.9). Octanol is

92
commonly used because it has similar partition characteristics as compared to lipids. As
a result, K OW is also very useful in the subject areas of bioaccumulation and
bioconcentration.
Example IV.4. Anthracene (C14H10) has contaminated harbor sediments, and the solid
portion of sediments is in equilibrium with the pore water. If the organic carbon content of
sediments is 5% and the soil sediment anthracene concentration is 50 g/kg sediment, what is
the pore water concentration of anthracene at equilibrium? The log( K OW ) for anthracene is
4.45.
1.
From log( KOC ) 0.903 log( KOW ) 0.094 , then K OC 10 4.11 mL/g organic
carbon.
2.
Now fOC = 0.05, then K ' ( KOC )( f OC ) = 664 mL water/g sediment.
3.

Therefore, Ce

q
50
= 0.078 g/L water.

'
K 664

Example IV.5. A typical value of fOC for particles suspended in the upper waters (epilimnion)
of Lake Superior is 0.2. What is the ratio of sorbed to dissolved PCB (polychlorinated biphenyl)
in these upper waters? Assume the log( K OC ) for PCB equals 6.
1.

From log( K OC ) = 6, then KOC = 106 mL/g organic carbon.

2.

Now fOC = 0.2, then K ' ( KOC )( f OC ) = 2105 mL water/g particle = 2105 L
water/kg particle.

3.

But K '

4.

PCB sorbed on every kilogram of suspended particles, there


q

Ce PCB dissolved

are 2105 times more PCB than there is in every liter of water.
In Lake Superior there typically only 0.5 mg/L (0.510-6 kg/L) of suspended
particles in upper waters. Therefore, in each liter of water only 10% of the PCB
gets sorbed onto particles. However, sedimentation of theses suspended particles
is one method by which PCBs are removed from the water column.
Chemical

log( K OW )

Phthalic Acid (C12H14O4)


Benzene (C6H6)
Trichloroethene (C2HCl3)
Tetrachloroethene (C2Cl4)
Toluene (C7H8)
2,4-D (C8H6Cl2O3)
Naphthalene (C10H8)
1,2,4,5-Tetrachlorobenzene (C6H2Cl4)
Phenanthrene (C14H10)
Pyrene (C16H10)
2,3,7,8-TCDD (C12H4Cl4O2)

0.73
2.13
2.42
2.53
2.73
2.81
3.36
4.05
4.46
5.09
6.64

Gravitational Settling of Particles through a Fluid (Stokes Law). When a


particle

93
settles through a fluid (e.g., water or air) by gravity, its settling velocity is dependent on
three
forces acting on the particle: gravitational force, buoyancy force, and drag force. When
these
forces are in equilibrium, the settling velocity of the spherical particle will become
constant
which is defined as the terminal settling velocity (vs, m/s):

vs

gd p2 ( p f )
18

(Stokes law)

(IV.10)

where dp is the diameter of the particle (m), p is the density of the particle (kg/m3), f is
the
density of the fluid (kg/m3), and is the dynamic viscosity of the fluid (N-s/m2).
A fluid carrying particles enters a control volume (e.g., a settling chamber or the air
pocket above

a city) at a volumetric flow rate of V . The volume of the c.v. is V and the top area of the
c.v. is
Atop. Then, the depth of the c.v. is

V
V
h . The HRT of the fluid in the c.v. is .
Atop
V

The
farthest distance any particle has to fall is h, and the particle must fall this distance
within in

hV
order to be removed. Therefore, the fraction of the particles with vs
= vso can
V
be
completely removed, regardless of the location upon entering the c.v. A fraction of the
particles
with vs

can also be removed, but depending on their location upon entering the c.v.

It is

hV
seen from Figure VI.9 that, A represents the trajectory of particles with vs
V
which can
be removed in the c.v. B represents the trajectory of particles with vs

which enters

the c.v. at
the upper left corner and as a result, cannot be removed. C represents the trajectories of
particles
with vs

, but enter the c.v. at locations other than the upper left corner. The particles

following the top C trajectory cannot be removed in the c.v., whereas the particles
following the
bottom C trajectory can be removed in the c.v.

94

Therefore, the percentage that particles with vs vso is removed due to gravity ( Rvs )
depends on the location where the particles enter the c.v. The entry location is expressed
in terms of a vertical height h ' , which is measured from the bottom of the c.v. Particles
with a small vs should enter the c.v. at a small h ' in order to be removed, i.e.,

Rvs

h'
v
100% s 100%
h
vso

(IV.11)

Therefore, the total fraction of particles removed in the c.v. due to gravity (RT) is:

Atop

h
h

Fluid Flow Path

A: Complete Removal.
B: No Removal.
C: Partial Removal.

Particle Settling
Path
Actual Particle Trajectory

Figure IV.9. Particle trajectory in a horizontally flowing environmental


medium.
XC

RT (1 X C )

vs
dX
vso

(IV.12)

hV
V
vso

V
Atop
where (1 XC) is the fraction of particles with vs vso , and the integral term in (IV.12) is
the fraction of particles with vs vso that is removed. X is referred to as the weight
fraction of remaining which is the weight fraction of particles with vs < the stated value.
Example IV.6. A suspension of PCB droplets entering into a specific section of a river

95
has the following size distribution and settling characteristics:

vs

3.05

1.52

0.61

0.31

0.23

0.16

(m/min)
X

0.55

0.46

0.35

0.21

0.11

0.03

It was estimated that vso for the suspension of PCB droplets is 2.83 m/min. How much
PCB droplets can be removed in the c.v. due to gravity?
1.
Prepare an X versus vs plot as shown below. From the plot it is found that
roughly 53% of PCB droplets in the suspension have a vs < 2.83 m/min.
Therefore, 1 XC = 1 0.53 = 0.47.
The integral term in (IV.8) is the area, which is bound by the Y-axis, the
horizontal line at X = 0.53, and the curve linking the data points, divided by vso .

2.

The area is graphically calculated as 0.396. Therefore, RT 0.47

0.396
= 0.61.
2.83

0.6

Weigh Fraction of Remaining (X)

0.53
0.5

0.4

0.3

0.2

0.1
2.83 m/min
0.0
0.0

0.4

0.8

1.2

1.6

2.0

2.4

2.8

3.2

vs (m/min)

It is often assumed that, when a waste stream is released into a river, an immediate and
complete mixing occurs at the point of discharge. In reality, this seldom happens.
Instead, dilution and mixing occur slowly as the contaminants flow downstream. The
distance required for complete mixing laterally (Lm) depends on river geometry and flow
properties. Lm can be estimated as:

Lm 2.6

uw2
(side bank discharge)
h

Lm 1.3

uw2
(midstream discharge)
h

(IV.13)
where Lm is the distance from the source to the zone where the discharge has been well
mixed laterally, ft; u is the average river flow velocity, ft/s; w is the average river width,
ft; and h is the average river depth, ft. (IV.13) should always be used to the cases that
involve PCBs because of concerns about the toxicity of PCBs. A large Lm value implies
that the PCB concentration in the vicinity of waste discharge may be very high to require
immediate attention. The units used in (IV.13) are specified and cannot be changed.

96
If Mtotal is the total mass of PCBs released into non-flow environmental compartments at
t = 0,
then PCBs will partition between compartments until the equilibrium conditions are
reached (it
will usually take a long time to reach the equilibrium conditions). Since PCBs can be
assumed to
be non-biodegradable and non-reactive, the total mass released at t = 0 must equal to the
sum of
masses in respective environmental compartments under the equilibrium conditions, as
shown
in the table below.
Compartments

Partition Relationship

Mass Balance

Water/Sediments

Csediment = KOCfOCCwater

Mtotal = Msediment + Mwater

Water/SS

CSS = KOCfOCCwater

Mtotal = MSS + Mwater

Water/Fish

Cfish = (BCF)Cwater

Mtotal = Mfish + Mwater

The units used must be consistent! If the volume of water is not specified, the
calculations can be
based on 1 L of water. Mass of suspended solids (SS, mg) = (SS, mg/L)(water volume,
L). BCF
is the bioconcentration factor, which can be calculated directly from KOW via a number of
empirical expressions shown in (IV.14).

log( BCF ) 0.542 log( K OW ) 0.124


log( BCF ) 0.850 log( K OW ) 0.700
log( BCF ) 0.935 log( K OW ) 1.495

(IV.14)

log( BCF ) 0.830 log( K OW ) 1.710


Compound Group
Monochlorobiphenyl
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
KOC is in L/kg.

Cl
Atoms/Biphenyl
1
2
3
4
5
6
7
8
9
10

# of Isomers

log(KOC)

BCF (L/kg)

3
12
24
42
46
42
24
12
3
1

4.7
5.1
5.5
5.9
6.3
6.7
7.1
7.5
7.9
--

590
215
49,000
73,000
46,000
------

REDUCTION OF INDUSTRIAL CLEANING WATER USAGE. Cleaning and


degreasing operations are commonly used by industry to remove dirt, oil, and grease
from both process input materials and finished products. It is used in the metal
finishing industry following machining and after each metal plating or surface finishing

97
step that the part undergoes. Circuit boards and other electronic equipment must also
be scrupulously clean, both before and after application of the printed circuit. A
commonly used cleaning method consists of placing the part to be cleaned in a rinse tank
or consecutively in several rinse tanks containing either stagnant or flowing water. The
objective is to transfer the contaminants on the surface of the manufactured part to the
water by dissolution and dilution. This is the typical process used to remove excess
plating solution dragged out of a plating bath. However, it is useful only for removing
materials that are water soluble.
A single stagnant rinse tank can serve as a cleaning device, but it is not very effective and
cleaning ability decreases dramatically with time as the level of contaminants in the rinse
tank builds. Large quantities of water are needed to effect cleaning. A series of stagnant
rinse tanks improves the situation since each subsequent rinse tank in the progression
contains fewer contaminants than the previous one, but this is still not very efficient. By
using a flowing tank or series of tanks, cleaning efficiency can be significantly increased
and water use decreased. Running the rinse water through the rinse tanks
countercurrent to the flow of the pieces being cleaned provides the best and most
efficient cleaning possible. Each additional cleaning step in the series contains cleaner
water and improves the cleaning operation, but there is a limit to this improvement.
Generally, little benefit is achieved by operating more than 3 countercurrent tanks in
series.
Single-Stage Rinsing Operation. Rinse water requirements needed to achieve a
given
allowable contaminant concentration on the rinsed workpiece (or dragout) can be
determined by
use of mass balances. For a single-stage rinsing operation as shown below, the mass
balance
equation can be written as:

98

VC

V D ( N dragout)(VC )

CP

C1

VR
CR 0

VR
C1

Desired Concentration

V D C P V R C R V D C1 V R C1

VR VD

(C1 C P ) C P
VD
(C R C1 )
C1

(IV.15)

where CP is the constituent concentration in the plating bath, C1 is the constituent


concentration in the completely-mixed rinse tank (and waste effluent stream), CR is the

constituent concentration in the clean rinse water (CR 0), V D is the equivalent

volumetric flow rate of dragout from the plating bath and from the rinse tank, and V R is

the volumetric flow rate of the rinse water to the rinse tank. V D can be estimated as:

V D ( N dragout)(VC )

(IV.16)

where N dragout is the number of dragouts being processed per unit of time, and VC is the

99
constituent volume on the individual dragout which is assumed to be constant.
Remember that C1 is specified at a low value.
Multi-Stage Rinsing Operation (3 rinsing tanks in series with separate
inflows of
rinse water). The mass balance equation for the first rinse tank (RT1) is the same as
(IV.15).

V D ( N dragout)(VC )

CP

C2

C1

VR

VR

CR 0

VR

CR 0

VR

C1

C2

Desired Concentration
The mass balance equations for RT2 and RT3 are (CR 0 and the volumetric flow of

rinse water to each rinse tank is constant at V R ):

V D C1 V R CR V D C2 V R C2
V D C2 V R CR V D C3 V R C3

VR

VD

(IV.17)

C1 C2 C2 C3

C2
C3

Combining the 3rd equation in (IV.17) with the 2nd equation in (IV.15), then

C13 C3C12 2CPC3C1 C3CP2 0

(IV.18)

Since both CP and C3 are specified, then (IV.18) can be solved for C1. By substituting C1
into the

2nd equation in (IV.15), V R can be determined for a given V D .

100
Multi-Stage Rinsing Operation (3 countercurrent rinsing tanks in series
with a
single inflow of rinse water).

V D ( N dragout)(VC )

CP

C2

C1

VR
CR 0

VR

C2

VR
C1

Desired Concentration

For a countercurrent rinse tank series shown below, a single rinse water stream is
introduced to
the last rinse tank in the series and then flows in a countercurrent fashion to the first
rinse tank

before being discarded. In this case, V R and V D are the same for each rinse tank. The
mass
balance equations for the 1st rinse tank and the remaining rinse tanks (note that CR 0)
are:

V D CP V R C2 V D C1 V R C1 RT 1

V D C1 V R C3 V D C2 V R C2 RT 2

(IV.19)

V D C2 V D C3 V R C3 RT 3
2.

For a specified C3 values, the equations in (IV.19) can be solved simultaneously

for C1, C2, and V R .

101
Example IV.7. A metal plating firm operates a chromium plating bath that has 85,000 mg/L
chromium and a dragout of 0.060 L/min. What rinse water flow rate is needed to keep the
chromium concentration on the rinsed workpiece at 25 mg/L? Assume that the clean rinse
water contains no chromium. Compare (1) a single running rinse tank; (2) series rinsing with
three rinse tanks; and (3) a countercurrent rinsing process with three rinse tanks.

(0.060)(25 85,000)
= 204 L/min.
(0 25)

1.1.

From (IV.15), V R

2.1.

From (IV.18), C1 is estimated to be 5,900 mg/L (by iteration).

2.2.

From the 2nd equation in (IV.15), V R

2.3.

Therefore, total rinse water requirement is: (0.86)(3) = 2.58 L/min.

2.4.

From the 3rd equation in (IV.17), C2

3.1.

From (IV.19), V R is estimated to be 0.88 L/min (by iteration).

3.2.

From the 3rd equation in (IV.19), C2

3.3.

(0.060)(85,000)
= 0.86 L/min.
5,900
(0.060)(85,000)
= 385 mg/L.
0.860 0.060

(25)(0.880 0.060)
= 392 mg/L.
0.060
(392)(0.880 0.060) (25)(0.880)
From the 1st equation in (IV.19), C1
=
0.060
5,775 mg/L (waste effluent stream concentration).

V. EMERGING AIR POLLUTION ISSUES


INDOOR AIR POLLUTION.
Sources and Exposure Guidelines of Indoor Air Pollutants.
Pollutants & Indoor Sources
Friable Asbestos: Fireproofing, thermal and acoustic insulation, and
decoration.
Hard Asbestos: Vinyl floor and cement products.
Carbon Monoxide(CO): Kerosine and gas space heaters, gas stoves,
wood stoves, fireplaces, and smoking.
Formaldehyde (HCHO): Particleboards, paneling, plywood, carpets,
ceiling tiles, urea-formaldehyde foam insulation, and other
construction materials.
Inhalable Particle Matter: Smoking, vacuuming, wood stoves, and
fireplaces
Nitrogen Dioxide (NO2): Kerosine and gas space heaters and gas
stoves.
Ozone (O3): Photocopy machines and electrostatic air cleaners.

Guidelines
0.2 fibers/mL for fibers longer than 5 m.
10 mg/m3 (8 hours).
40 mg/m3 (1 hour).
120 g/m3.
50 to 110 g/m3 (annually).
150 to 350 g/m3 (24 hours).
100 g/m3 (annually).
235 g/m3 (once a year).

102
Radon (Rn-222) & Radon Progeny: Diffusion from soil, groundwater,
and building materials.
Sulfur Dioxide (SO2): Kerosine space heaters.
Volatile Organics (VOCs): Cooking, smoking, room deodorizers,
cleaning sprays, paints, varnishes, solvents, carpets, furniture, and
draperies.

0.01 working level (annually).


80 g/m3 (annually).
365 g/m3 (24 hours).
None available.

Some Interesting Statistics:


U.S.
LDC1 (urban)
Indoors: 89%.
Indoors: 79%.
Outdoors: 5%.
Outdoors: 21%.
In Vehicles: 6%.
1 LDC: less developed countries.

LDC (rural)
Indoors: 65%.
Outdoors: 35%.

PM Emissions (U.S.)
PM Exposure (U.S.)
Coal-Fired Power Plants: 97%.
Coal-Fired Power Plants: 2%.
ETS1: 3%.
ETS: 98%.
1 ETS: environmental tobacco smoking. Per capita emissions of PM (particulate matter): 1.6
kg/person
(coal-fired power plants), 0.05 kg/person (ETS).
Benzene Emissions
(U.S.)
Cars: 82%.
Industry: 14%.
Personal and Homes: 3%.
Cigarettes: 0.1%.

Benzene Exposure (U.S.)


Care Exhaust: 18%.
Personal Activities (e.g., driving, consumer products): 18%.
Home Sources (e.g., paints, petrol): 16%.
Cigarettes: 40%.
ETS: 5%.
Industry: 3%.

Important Indoor Air Pollutants.


Radon. Radon is the invisible, radioactive atomic gas that results from radioactive decay
of some
forms of uranium that may be found in rock formations beneath buildings or in certain
building
materials themselves. Radon is probably the most pervasive serious hazard for indoor
air in the
U.S. and Europe, probably responsible for tens of thousands of lung cancer deaths per
annum.
There are relatively simple tests for radon gas, but these tests are not commonly done,
even in
areas of known systematic hazards. Radon is a very heavy gas and thus will tend to
accumulate at
the floor level. Building materials can actually be a significant source of radon, but very
little
testing is done for stone, rock or tile products brought into building sites. The half life
for radon
is 3.8 days indicating that once the source is removed, the hazard will be greatly reduced
within a
few weeks.

103

Molds and Other Allergens. These biological agents can arise from a host of means, but
there
are two common classes: (a) moisture induced growth of mold colonies and (b) natural
substances released into the air such as animal dander and plant pollen. Moisture
buildup inside buildings may arise from water penetrating compromised areas of the
building envelope or skin, from plumbing leaks, from condensation due to improper
ventilation, or from ground moisture penetrating a building slab. In areas where
cellulosic materials (paper and wood, including drywall) become moist and fail to dry
within 48 hours, mold colonies can propagate and release allergenic spores into the air.
In many cases, if materials have failed to dry out several days after the suspected water
event, mold growth is suspected within wall cavities even if it is not immediately visible.
Through a mold investigation, which may include destructive inspection, one should be
able to determine the presence or absence of mold. In a situation where there is visible
mold and the indoor air quality may have been compromised, a mold remediation may
be needed. Indoors, mold growth can be inhibited by keeping humidity levels below fifty
percent and by eliminating leaks or moisture condensation and accumulation. There are
some varieties of mold that contain toxic compounds (mycotoxins). However, exposure
to hazardous levels of mycotoxin via inhalation is not possible in most cases, as toxins
are produced by the fungal body and are not at significant levels in the released spores.
The primary hazard of mold growth, as it relates to indoor air quality, comes from the
allergenic properties of the spore cell wall. More serious than most allergenic properties
is the ability of mold to trigger episodes in persons that already have asthma, a serious
respiratory disease.
Carbon Monoxide. One of the most acutely toxic indoor air pollutants is carbon
monoxide (CO), a colorless, odorless gas that is a byproduct of incomplete combustion of
fossil fuels. Common sources of carbon monoxide are tobacco smoke, space heaters
using fossil fules, defective central heating furnaces and automobile exhaust.
Improvements in indoor levels of CO are systematically improving from increasing
numbers of smoke-free resutrants and other legislated non-smoking buildings. By
depriving the brain of oxygen, high levels of carbon monoxide can lead to nausea,
unconsciousness and death.
Legionella. Legionellosis or Legionnaire's Disease is caused by a waterborne bacterium
that grows best in slow moving or still warm water. The primary route of exposure is
aerosolization, most commonly from evaporative cooling towers or showerheads. A
common source of Legionella in commercial buildings is from poorly placed or
maintained evaporative cooling towers, which often release aerosolized water that may
enter nearby ventilation intakes. Outbreaks in medical facilities and nursing homes,
where patients are immuno-suppressed and immuno-weak, are the most commonly
reported cases of Legionellosis. More than one case has involved outdoor fountains in
public attractions. The presence of Legionella in commercial building water supplies is
highly under-reported, as healthy people require heavy exposure to acquire infection.
Legionella testing typically involves collecting water samples and surface swabs from
evaporative cooling basins, shower heads, faucets, and other locations where warm water
collects. The samples are then cultured and colony forming units (cfu) of Legionella are
quantified as cfu/L. Legionella is a parasite of protazoans such as amoeba, and thus
requires conditions suitable for both organisms. The bacterium forms a biofilm which is
resistant to chemical and antimicrobial treatments, including chlorine. Remediation for

104
Legionella outbreaks in commercial buildings vary, but often include very hot water
flushes (70C), sterilization of standing water in evaporative cooling basins, replacement
of shower heads, and in some cases flushes of heavy metal salts. Preventative measures
include adjusting normal hot water levels to allow for 50C at the tap, evaluating facility
design layout, removing faucet aerators, and periodic testing in suspect areas.
Asbestos Fibers. Many common building materials used before 1975 contain asbestos,
such as some floor tiles, ceiling tiles, taping muds, pipe wrap, mastics and other
insulation materials. Normally significant releases of asbestos fiber do not occur unless
the building materials are disturbed, such as by cutting, sanding, drilling or building
remodelling. There are particularly stringent regulations applicable to schools.
Inhalation of asbestos fibers over long exposure times is associated with increased
incidence of lung cancer. While smokers have a greater risk of lung cancer than asbestos
workers that do not smoke, smokers that are exposed to high levels of asbestos over
many years have a much greater risk of developing lung cancer than either smokers that
have not been exposed to asbestos, or persons that have been exposed to high levels of
asbestos that do not smoke.
Carbon Dioxide. Carbon dioxide (CO2) is a surrogate for indoor air pollutants emitted by
humans and correlates with human metabolic activity. Carbon dioxide at levels that are
unusually high indoors may cause occupants to grow drowsy, get headaches, or function
at lower
activity levels. Humans are the main indoor source of carbon dioxide. Indoor levels are
an
indicator of the adequacy of outdoor air ventilation relative to indoor occupant density
and
metabolic activity. To eliminate most indoor air quality complaints, total indoor carbon
dioxide
should be reduced to below 600 ppmv above outdoor levels. NIOSH (National Institute
of
Occupational Safety and Health) considers that indoor air concentrations of carbon
dioxide that
exceed 1,000 ppmv are a marker suggesting inadequate ventilation (1,000 ppmv equals
0.1%).
ASHRAE (American Society of Heating, Refrigerting and Air-Conditioning Engineers)
recommends that carbon dioxide levels not exceed 700 ppmv above outdoor ambient
levels. The
UK standards for schools say that carbon dioxide in all teaching and learning spaces,
when
measured at seated head height and averaged over the whole day should not exceed
1,500 ppmv.
The whole day refers to normal school hours (i.e., 9.00 A.M. to 3.30 P.M.) and includes
unoccupied periods such as lunch breaks. Canadian standards limit carbon dioxide to
3,500
ppmv.
Figure V.1 illustrates sources of indoor air pollutants in homes.

105

Figure V.1. Sources of indoor air pollutants in homes.


Analysis of Indoor Air Pollution. Just with outdoor air, the amount of air available
to dilute
pollutants is an important indicator of indoor air pollution. Indoor air can be exchanged
with
outdoor air by any combination of the following three mechanisms: infiltration, natural
ventilation, and forced ventilation. Infiltration is the term used to describe the natural
air
exchange that occurs between a building and its environment when doors and windows
are
closed. That is, it is leakage that occurs through various cracks and holes that exists in
the
building envelope. Natural ventilation is the air exchange that occurs when windows or
doors
are purposely opened to increase air circulation. Forced ventilation occurs when
mechanical air
handling systems induce air exchange using fans or blowers.
Nationwide, roughly 10% of total energy consumption is attributed to the losses caused
by infiltration. Since infiltration is quite easily and cheaply controlled, it is not
surprising that tightening buildings has become a popular way of saving energy.
However, this process of saving energy also exacerbates indoor air quality problems
unless the sources of indoor air pollution were simultaneously reduced. The infiltration
sites in homes include: chimneys, ducts, vents, dropped ceilings, whole house fans,
plumbing, door frames, windows, exhaust vents above stoves, fireplaces, and electrical
outlets. Infiltration is driven by pressure differences between the inside of the building
and the outdoor air. These pressure differences can be caused by wind, or by inside-to-

106
outside temperature differences. Wind blowing against a building creates higher
pressure on one side of the building than the other, inducing infiltration through cracks
and other openings in the walls. Temperature induced infiltration (stack effect) is
influenced less by holes in the walls than by various openings in the floors and ceilings.
In the winter, warm air rises in the building and exits through breaks in the ceilings and
draws in cooler air through floor openings. As a result, infiltration rates are influenced
not only by how fast the wind is blowing and how great the temperature difference is
between inside and outside, but also by the locations of the leaks in the building
envelope. Greater leakage areas in the floors and ceilings encourage stack-driven
infiltration, while leakage areas in vertical surfaces encourage wind-driven infiltration.
Figure V.2 illustrates the infiltration sites in homes.

Figure V.2. Infiltration sites in homes.


While it is usually assumed that increasing the infiltration rates will improve indoor air
quality, it may not be the case when radon is emitted from the soil under a building. For
radon, wind-driven infiltration helps reduce indoor radon concentrations by allowing
radon-free fresh air to blow into the building. Stack-driven infiltration, which draws air
through the floor, may actually induce new radon to enter the building, negating the
cleaning that infiltration usually causes Figure V.2). Infiltration rates may be expressed
in units such as m3/hr or ft3/min (cfm). More often the units are given in air changes
per hour (ach). The air exchange rate in air changes per hour is simply the number of
times per hour that a volume of air equal to the volume of space in the house is
exchanged with outside air (0.5 ach to 1.0 ach in American homes). A basic mass
balance equation of indoor air pollution in the building, assuming that the air mass in
the building is completely mixed, yields:

dC
V Ci M V C kVC
dt
M

V DCi
( D k ) t
C (t )
C (0)e ( D k )t
1 e
Dk

V
D
V

(V.1)

107
where V is the air volume in the building, m3; D is the air exchange rate (or dilution rate),
hr-1; M is the source emission rate in the building, mg/h; C is the indoor pollutant
concentration, mg/m3; Ci is the ambient pollutant concentration, mg/m3; and k is the
first-order decay rate, hr-1. Some of the pollutants such as CO and NO can be treated as
non-reactive (i.e., k = 0). Some useful information is listed below.
1.

Measured Emission Rates (M) for Various Sources (mg/hr).


Source

CO

NOX-N

SO2

HCHO

Gas Range
- Oven
- One Top Burner

1,900
1,840

52
83

0.9
1.5

23
16

Kerosene Heater
- Convective
- Radiant

71
590

122
15

---

1.1
4.0

One Cigarette

86

0.05

--

1.44

2.

First-Order Pollutant Decay Rate (k, hr-1).

Pollutant

CO

NO

NOX-N

HCHO

SO2

0.0

0.0

0.15

0.40

0.23

PM (< 0.5
m)
0.48

Radon
7.610-3

Example V.1. An unvented, portable, radiant heater, fueled with kerosene, is tested
under controlled laboratory conditions. After running the heater for two hours in a test
chamber with a 46 m3 volume and an infiltration rate of 0.25 ach, the concentration of
CO reaches 20 mg/m3. Initial CO in the laboratory is zero, and the ambient CO is
negligible throughout the run. Treating CO as a non-reactive pollutant, find the rate at
which the heater emits CO. If the heater were to be used in a small home to heat 120 m3
of space having 0.4 ach, predict the steady-state indoor CO concentration.
1.

With Ci = C(0) = k = 0, then the 2nd equation in (V.1) can be simplified to:

M
2.
3.

DVC (t )
.
1 e Dt

(0.25)(46)(20)
= 585 mg/hr.
1 e ( 0.25)( 2)
M
585
From the 2nd equation in (V.1), C ()
= 12.2 mg/m3

DV (0.4)(120)
Therefore, M

(steady-state concentration). This steady-state indoor CO concentration exceeds


the 8-hour ambient standard of 10.0 mg/m3.

URBAN/REGIONAL AIR POLLUTION. Air pollutants in urban/regional areas

are from two major sources: stationary (point) and mobile (non-point) sources. As a
pollutant mixes with a large air mass, its concentration diminishes by dilution. With
sufficient dilution, concentration is reduced to or below a threshold level which is
assumed to cause no ill effects. Soil microbes or other abiotic processes may absorb and
assimilate pollutants, removing them from the system entirely. Therefore, the
assumption that nature will take care of pollutants may be true. Unfortunately, modern

108
civilization produces pollutants in such quantities and kinds that this assumption does
not hold. A temperature inversion may cause episodes of high concentration of air
pollutants. Normally, air temperatures are highest at the ground level and decrease at
higher elevations. Since warmer air rises, pollutants are carried upward and diluted in
the air above. A temperature inversion is a situation in which a layer of warmer air
overlies cooler air at the ground level. This in turn blocks the normal updrafts and
causes pollutants to accumulate like cigarette smoke in a closed room.
Urban Smog. When oxides of nitrogen, VOCs (volatile organic carbons), and sunlight
come together, they can initiate a complex set of reactions that produce a number of
secondary pollutants known as photochemical oxidants. Ozone (O3) is the most
abundant of the photochemical oxidants and it is the one for which an ambient air
quality standard has been written. Although ozone is responsible for many of the
undesirable properties of photochemical smog, from chest constriction and irritation of
the mucous membrane in the people to the cracking of rubber products and damage to
vegetation, it is not itself a cause of the eye irritation that is our most common complaint
about smog. Eye irritation is caused by other components of photochemical smog,
principally formaldehyde (HCHO), peroxybenzoyl nitrate (PBzN), peroxyacetyl nitrate
(PAN), and acrolein (CH2CHCOH).
7 oxides of nitrogen are known to occur: NO, NO2, NO3, N2O, N2O3, N2O4, and N2O5, the
only two that are important air pollutants are nitric oxide (NO) and nitrogen dioxide
(NO2). There are two sources of nitrogen oxides (or NOX) when fossil fuels are burned.
Thermal NOX is created when nitrogen and oxygen in the combustion air are heated to a
high enough temperature (roughly 1,000oK) to oxidize the nitrogen. Fuel NOX results
from the oxidation of nitrogen compounds that are chemically bound in the fuel
molecules. Natural gas has almost no nitrogen compounds and some coal has as much
as 3% (by weight) of nitrogen compounds. Fuel NOX is the dominant source of total NOX
emissions. Almost all NOX emissions are in the form of NO, which is a colorless gas that
has no known adverse health effects at concentrations found in the atmosphere.
However, NO can oxidize to NO2 that irritates the lungs, causes bronchitis and
pneumonia, and lowers resistance to respiratory infections. NOX can also react with
VOCs in the presence of sunlight to form photochemical oxidants that have adverse
health consequences.
VOCs include unburnt hydrocarbons that are emitted from tailpipes and smoke stacks
when fossil fuels are not completely combusted, along with gaseous hydrocarbons that
enter the atmosphere when solvents, fuels, and other organics evaporate. In addition,
there are natural sources of reactive hydrocarbons such as deciduous trees and shrubs
that emit isoprene (CH2CCH3CHCH2), and conifers that emit pinene and limonene.
Transportation sector is responsible for about one-third of anthropogenic VOC
emissions. From 1984 to 1993, VOC emissions from motor vehicles decreased by about
25%. Reformulated gasoline (which is less volatile) and the decline in the percentage of
dirtier, older vehicles on the road account for such a drop. As emissions from motor
vehicles become less significant, other sources, such as gasoline-powered lawnmowers,
outboard motors, barbeque starter fluids, and oil-based paints, begin to look more
important and are beginning to be regulated as well. Industrial sources account for twothirds of VOC emissions, with much of that being caused by vaporization of
hydrocarbons. Less than 2% of VOCs result from fossil-fuel combustion in power plants
and industrial boilers.

109
Formation of Photochemical Smog (or Smog). Important reactions that cause
the formation of smog in urban air mass are summarized in (V.2):

VOCs NOX h Smog


N 2 O2 2 NO
2 NO O2 2 NO2
NO2 h NO O

(V.2)

O O2 M O3 M
O3 NO O2 NO2
where h represents a photon (with wavelength < 0.39 m) and M represents a
molecule (usually oxygen and nitrogen since they are most abundant in the air). 1st
equation: formation of photochemical smog, 2nd equation: combustion of fossil fuel, 3rd
equation: oxidation of NO, 4th equation: photolysis, 5th equation: formation of O3, and 6th
equation: formation of NO2 (or destruction of O3).
A Box Model for Urban Air Pollution. Valuable insights can be gained by
describing mathematically the accumulation of pollutants over an urban area. Although
sophisticated computer models are available, a simple representation of the scenario is
often capable of producing useful information for making critical decisions to rectify the
problems. The box model, which models the air mass over an urban area as a CFSTR
system (Figure V.3), is a simple but useful first approximation tool for such tasks. The
box has horizontal dimensions x and y (the dimensions of the urban area) and height
H (H is also referred to as the atmospheric mixing height and for a typical urban area it
is about 1,000 m). H can be much smaller than 1,000 m when thermal inversion occurs
above the urban area. Let u be the average wind velocity (L/T) with the wind direction
parallel to the x dimension of the urban area, M= mA = mxy be the mass emission
rate of the pollutant from the surface (M/T) (m is the emission rate per unit surface area,
M/L2-T), R1 be the mass removal rate of the pollutant in the air mass due to the
processes of dry deposition (M/L3-T), R2 be mass removal rate of the pollutant in the air
mass due to other processes (e.g., photolysis) (M/L3-T), and P be the mass generation
rate of the pollutant in the air mass (M/L3-T). Then,

C
uHyC o uHyC M R1 Hxy R2 Hxy PHxy
t
v
C
u
M
dC C o C m v d

(C o C )
d C R2 P

C R2 P
t x
Hxy H
dt

H H

Hxy

dC
m C C o vd
0

C R2 P
dt
H

H
where Co is the background pollutant concentration (M/L3), C is the pollutant
concentration in

(V.3)

110

Wind (u, Co)

Wind (u, C)

Air Mass
H

1
2
Urban Area
y
x

1: Pollutant Dry Deposition Velocity (vd).


2: Total Pollutant Emission Rate from the Surface (M = mxy).
Figure V.3. A box model for the air mass over an urban area.

x
is
u
the residence time (T). vd is a parameter used to describe how rapidly the pollutant
(either solid particles or aerosol particles) is removed from the air mass by deposition
onto the ground (usually by gravity). The mass flux (F, M/L2-T) of dry deposition (i.e.,

the urban air mass (M/L3), vd is the pollutant dry deposition velocity (L/T), and

the mass rate at which the pollutant is deposited onto a unit surface area) is usually
expressed as: F = vdC.
Example V.2. The city of Leadville (dimensions: 120 km 120 km) is characterized by
an average daily emission rate of 5,000 kg/d of lead into the atmosphere from auto
exhaust and industrial processes. The background concentration of atmospheric lead is
0.1 g/m3. During a typical hot summer day in Leadville the atmospheric mixing height
is 500 m and the average wind velocity is 2 m/s. A typical lead deposition velocity for
similar meteorological conditions is 0.05 cm/s. (1) What is the steady-state
concentration of lead in the urban air? (2) What (if anything) must Leadville citizens do
to achieve an atmospheric lead concentration of 0.4 g/m3? (3)What if the air quality
target is 0.15 g/m3?
1.1.

(5,000)(1,000)(106 )
x
(120)(1,000)
=
16.7 hrs, m
= 15 g/m2-hr, and
2
u
(2)(3,600)
(24)(120)(1,000)
vd = 0.05 cm/s = 1.8 m/hr.

1.2.

From the

4th

C o H m (0.1)(500) (15)(16.7)

0.57
equation in (V.3), C
H vd
500 (1.8)(16.7)

g/m3.
2.1.
Under the conditions specified, the only variable the citizens of Leadville can
readily control is the lead emission rate, m. From the 3rd equation in (V.3),

111

m
2.2.
3.

C ( H vd ) C o H

(0.4)500 (1.8)(16.7) (0.1)(500)


9.7 g/m2-hr.
16.7

Therefore, the reduction in m is 5.3 g/m2-hr ( 35% reduction).


If the target atmospheric lead concentration is 0.15 g/m3, then m = 1.8 g/m2hr ( 90% reduction).

The Photochemical Cycle of NOX and Formation of Ozone. From (V.2) the
following
kinetic expressions for the formation of O3 in the urban areas can be formulated:

RO3 k1[O2 ][O]


R phtolysis k 2 [ NO2 ]
RNO2 k3[ NO][O3 ]
R photolysis RNO2 [O3 ]

(V.4)

k 2 [ NO2 ]
k3[ NO]

The 4th equation in (V.4) describes the photo-stationary state relationship in the urban
air. First,
[O3] depends on directly on sunlight intensity through the photolytic rate constant, k2.
Therefore, [O3] is expected to be highest during the sunny midday and to decline to near
zero
overnight. Second, [O3] depends on the relative amounts of [NO2] and [NO]. Since NOX
emissions in an urban area are mainly NO with little NO2, the initial equilibrium O3
concentration as shown by the 4th equation in (V.4) will be low. As NO is oxidized to
NO2, the
ratio of

[ NO2 ]
will change with time. However, the reaction equations in (V.2) indicate
[ NO]

that
each time a molecule of NO reacts, a molecule of NO2 is produced, and vice versa; the
sum of
their concentrations will always remain constant (i.e., [NO] + [NO2] = [NOX]). As a
result, the
equilibrium ozone concentration can be calculated by:

k
[O3 ] 0.5 [ NO]0 [O3 ]0 2 0.5
k3

k
k
[ NO]0 [O3 ]0 2 4 2 [ NO]0 [O3 ]0
k3

k3
(V.5)

where the subscript 0 indicates the initial concentration at t = 0.


VOCs and Formation of O3 (Figure V.4). The O atoms formed via reactions shown
in (V.2)
can react with water vapor in the atmosphere to form two hydroxyl radicals. The
hydroxyl radical
will react with VOCs (RH) in the atmosphere that lead to the conversion of NO to NO2:

112

O H 2O 2OH
RH OH NO RCHO H 2O NO2

(V.6)

By converting NO that destroys O3 to NO2 that produces O3, VOCs provide the fuel for
the NOX
photochemical cycle engine that produces O3. If the amount of NOX in the urban air is
constant, the maximum amount of O3 that will be formed will increase rapidly at low
VOC
concentrations. At high VOC concentrations, on the other hand, NOX will become a
limiting
factor and further increases in VOC concentration will not yield continuing increases in
O3
concentrations. Region AB in Figure V.4 represents the case in which the urban air mass
is
saturated with VOCs, so reducing them a little has a negligible effect; there are still
plenty
of VOCs left to convert the available NO to NOX, forming O3. A significant reduction in
VOCs is
needed to bring the O3 concentration from B to C.

X: Initial VOC Concentration.


Y: Maximum O3 zone Concentration.
The NOX concentration in the urban air mass is constant.

Figure V.4. Predicted maximum O3 concentration as a function of VOC level


for constant NOX.
NOX and Formation of O3 (Figure V.5). NOX plays a dual role in the formation of
O3:
formation and destruction of O3 according to (V.2). As a result, if the VOC

113
concentration in the
urban air is held constant, the maximum O3 concentration will increase with increasing
NOX
concentration until a maximum value is reached (point B in Figure V.5). Beyond that,
the
maximum O3 concentration will decrease even the NOX concentration is continuously
increased.
This is a typical result when two counter-reaction mechanisms exist in the same system.
If point
A is the current situation in the urban air mass, then at a constant VOC level, the
reduction in
NOX emissions will actually increase the O3 concentration significantly.
Ozone Isopleth Diagram (Figure V.6). The ozone isopleth diagram is prepared
based on the
assumptions that the box model previously presented is applicable and that VOC and
NOX
concentrations in the atmosphere are proportional to their respective source emission
rates. It is
useful to devise the strategies for smog control in a given urban area. The diagram
separates the

X: Initial NOX Concentration.


Y: Maximum O3 Concentration.
The VOC concentration in the urban air mass is constant.

Figure V.5. Predicted maximum O3 concentration as a function of NOX level


for constant VOC.

114

Figure V.6. The ozone isopleth diagram.


Figure V.6. The ozon isopleths diagram.
diagram into two regions: VOC-limited regime (point A) and NOX-limited region (point
B). Labels on curved lines are the peak O3 concentrations in ppbv in an air mass. The
initial VOC level represents a weighted sum of all VOC mole fractions, where the
weighting factor is equal to the number of carbon atoms per molecule.
Ozone Formation Potentials of VOCs. In the discussions so far, all hydrocarbon
compounds have been lumped together and included under VOCs. However, not only
there are hundreds of unique hydrocarbon compounds in the atmosphere, but different
compounds are emitted from different sources. The approaches summarized below take
into account of the ozone formation potentials of different hydrocarbon compounds.
Approach

Remarks
Only consider the mass of carbon in VOC molecules.
Reactivity is not considered.
n

Carbon Mass

Calculate

M c
i 1

Reactive Organic Gas (ROG)


(Carbon Mass)

i i

for both current and new situations and

compare the difference (i is referred to as the ith VOC molecule, Mi is


the emission rate of the ith VOC molecule, and ci is the % of carbon
in the ith VOC molecule).
Use kOH of ethane (C2H6) as the dividing line. Any VOCs with kOHs
> kOH (C2H6) are considered as reactive and included in the
calculation.
n

Calculate

M c
i 1

i i

for both current and new situations and

compare the difference.


kOH
(cm3/molecule-s)

Calculate

(k
i 1

) M i for both current and new situations and

OH i

compare the difference.

115
MIR
(g O3 formed/g VOC emitted)

Calculate

(MIR) M
i 1

for both current and new situations and

compare the difference.

In the above table, kOH is the rate constant for the 2nd equation in (V.6). Typically, [OH]
5106
to 10106 molecules/cm3. MIR (maximum incremental reactivity) is defined as:

[O3 ]

MIR IR max
[VOC ] max

(V.7)

where IR is the incremental reactivity which is defined as the amount of O3 formed


perunit mass of a specific VOC added to or subtracted from the overall VOC mixture in a
given air mass. If the difference ( = new current) is > 0, the calculation indicates the
situation will get worse. Table V.1 summarizes kOH and MIR values for selected VOCs at
298oK (25oC).
Table V.1. kOH and MIR values for selected VOCs at 298oK (25oC).
Compound

kOH 1012 (cm3/molecule-s)

Methane (CH4)
Carbon Monoxide (CO)
Acetone (CH3COCH3)
Ethane (C2H6)
Methanol (CH4O)
Propane (C3H8)
2-Butanone (MEK) (CH3COC2H5)
Benzene (C6H6)
n-Butane (C4H10)
Methyl tert-Butyl Ether (MTBE)
[CO(CH3)4]
Ethanol (C2H5OH)
2,2,4-Trimethlypentane [C5H9(CH3)3]
Toluene (C7H8)
Ethene (C2H4)
n-Octane (C8H18)
Ethyl tert-Butyl Ether [CO(C2H5)4]
Formaldehyde (HCHO)
Acetaldehyde (CH3CHO)
m-Xylene (C8H10)
Propene (C3H6)
1,2,4-Trimethylbenzene [C6H3(CH3)3]
o-Cresol (C6H4OHCH3)
a-Pinene
trans-2-Butene (CH3CHCHCH3)
Isoprene (CH2CCH3CHCH2)

0.006
0.21
0.22
0.25
0.94
1.1
1.1
1.2
2.4
2.9

MIR (g O3 formed /g VOC


emitted)
0.0016
0.065
0.49
0.36
0.65
0.57
1.4
0.81
1.18
0.73

3.3
3.6
6.0
8.5
8.7
8.8
9.4
16
24
26
32
42
54
64
101

1.7
1.34
5.1
8.3
0.69
2.2
6.6
6.3
14.2
11.0
5.3
2.5
3.9
13.2
9.3

Example V.3. An air pollution source in an urban area emits the following pollutants
(kg/day): CO, 1.3; ethane (C2H4), 2.0; and acetaldehyde (CH3CHO), 1.5. A new
technology is proposed to reduce the contribution of this source to O3 formation. The
expected new emissions (kg/day) would be: CO, 10; acetone (C3H6O), 0.3; and methanol
(CH4O), 11. Compare the emissions from two technologies using (1) the carbon mass

116
approach, (2) the ROG carbon mass approach, (3) the kOH reactivity scale, and (4) the
MIR reactivity scale. Based on the results, is it a good idea to use the new technology to
reduce the O3 formation?
1.1
1.2.
1.3.
1.4.

12
24
24
= 3.2 kg C/day.
2 1.5
28
28
44
12
36
12
The new carbon emissions are: 10
= 8.6 kg C/day.
0.3 11
28
58
32
Therefore, 8.6 3.2 = 5.4 kg C/day > 0.
The current carbon emissions are: 1.3

By this measure, O3 formation is predicted to increase using the new technology.

24
24
= 2.5 kg C/day.
1.5
28
44

2.1.

The current ROG carbon emissions are: 2

2.2.

The new ROG carbon emission is: 11

2.3.
2.4.
3.1.
units.
3.2.
units.
3.3.
3.4.
4.1.
4.2.
4.3.
4.4.
5.

Therefore, 4.1 2.5 = 1.6 kg C/day > 0


By this measure, O3 formation is predicted to increase using the new technology.
The current emissions are: (1.1 0.21 2 8.5 1.5 16) 1012 = 41.3 reactivity

12
= 4.1 kg C/day.
32

The new emissions are: (10 0.21 0.3 0.22 11 0.94) 1012 = 12.5 reactivity
Therefore, 12.5 41.3 28.8 reactivity units < 0.
By this measure, O3 formation is predicted to decrease using the new technology.
The current MIR is: (1.2 0.065 2 8.3 1.5 6.3) = 26.1 kg O3/day.
The new MIR is: (10 0.065 0.3 0.49 11 0.65) = 7.1 kg O3/day.
Therefore, 7.1 26.1 19.0 kg O3/day.
By this measure, O3 formation is predicted to decrease using the new technology.
The first two approaches indicate that the new technology would increase the O3
formation in the region. However, according to the 3rd and 4th approaches, the
new technology would decrease the O3 formation in the region, especially the
MIR approach predicts a significant decrease of 19 kg O3 per day. So it would
indeed be a good idea to use the proposed new technology to reduce the O3
formation in the region.

ACID PRECIPITATION. Emissions of sulfur and nitrogen oxides react with water
vapor in the atmosphere to form their respective acids (i.e., H2SO4 and HNO3) which
come back down as dry acid deposition or mixed with water, causing the precipitation to
be abnormally acidic. Coal-burning power plants are primarily responsible for the
emissions of sulfur dioxide and nitrogen dioxide. The emissions from the tall stacks of
coal-burning power plants located in the Ohio River Valley tend to migrate to New
England and eastern Canada. Tail-pipe emissions from motor vehicles are the other
major sources of nitrogen dioxide.
The average acidity of rainfall in Scandinavia, the northeastern U.S., Canada, and parts
of Europe has increased steadily over the past 40 years. There seem no question that
this change is primarily due to the increased emissions of sulfur oxides (SOX) and
nitrogen oxides (NOX) that have accompanied the greatly increased economic activities
(and hence increased combustion of fuels) in or upwind of these regions. SOX and NOX

117
are slowly oxidized over several hours to several days to sulfuric acid (H2SO4) [(V.8)]
and nitric acid (HNO3) [(V.9)]. They then are generally captured by raindrops and
returned to the Earths surface as acid precipitation. The common name is acid rain,
but the complete description includes acidic rain, acidic snow or hail, acids adsorbed on
falling dust particles, etc. In addition, hydrochloric acid (HCl) can be directly released
from coal combustion and MSW incineration. Figure V.7 illustrates how acid
precipitation is formed in the atmosphere.

O3 h O2 O

SO2 h SO2
SO2 O2 SO3 O
SO2 O SO3
SO3 H 2O H 2 SO4

(V.8)

OH NO2 HNO3
NO2 O3 NO3 O2

(V.9)

NO2 NO3 N 2O5


N 2O5 H 2O 2HNO3

Rain falling through a perfectly unpolluted atmosphere will arrive at the earths surface
with a pH

Figure V.7. The formation of acid precipitation in the atmosphere.


of about 6.5 because of the carbon dioxide in the atmosphere:

CO2 H 2O H 2CO3 H HCO3

(V.10)

Carbonic acid (H2CO3) is a weak acid, and (V.10) is reversible, with the acid
concentration in the rain depending on the concentration of carbon dioxide in the air.
Generally, any rain with a pH < 5.6 (i.e., an H+ concentration > 10-5.6 mol/L) is
considered acidic, but damages to animals (or fish) and plants are not evident until a pH
of about < 4.5 is reached. Although damages to

118
human health have not been shown, acid damages to the ecology of mountain lakes and
forests are well documented. The transport distances between emission and
precipitation are generally hundreds of miles, so that local control seems futile in many
cases. The effects of acid precipitation on materials are emerging quite clearly. Acids
degrade building materials, especially limestone, marble, various commonly used metals
such as galvanized steel, and certain paints. In fact, the increased rate of weathering and
erosion of building surfaces and monuments was one of the first indications of adverse
impacts from acid precipitation. It is important to note however, that adding acid to a
solution may have little or no effects on pH, depending on whether or not the solution
has buffers. Buffers are substances capable of neutralizing added hydrogen ions. The
available buffering of an aquatic ecosystem (e.g., a lake) is not only a function of its
chemical characteristics, but also nearby soils through which water percolates as it
travels from land to the system concerned. Therefore, information on the pH of
precipitation alone, without taking into account the chemical characteristics of the
receiving water body and surrounding soils, is a poor indicator of the potential effects of
acid precipitation on an aquatic ecosystem. Most aquatic ecosystems are buffered by
bicarbonate (HCO3-), which is related to carbonic acid by:

H 2CO3 H HCO3

(V.11)

Note that the reaction of hydrogen ions with bicarbonate removes bicarbonate from the
solution so, unless there is a source of new bicarbonate, its concentration will decrease as
more acid is added. At some point, there may be so little bicarbonate left that relatively
small additional inputs of acid will cause pH to decrease rapidly. This phenomenon
leads to one way to classify lakes in terms of their acidification. As shown in Figure V.8,
a bicarbonate lake (I) shows little decrease in pH as hydrogen ions are added, until pH
drops to about 6.3. As pH drops below this point, the bicarbonate buffering is rapidly
depleted and the lake enters a transitional state (a transition lake, II). Transition lakes
with pH between 5.0 and 6.0 are very sensitive to small changes in acid. Below pH 5.0,
the lake is unbuffered and chronically acidic (an acid lake, III). In a Norwegian study,
684 lakes were categorized into bicarbonate, transition, and acid lakes. For each
category observations of fish populations were made which indicated the strong
dependency of fish population on the degree of acidification in lakes.

119

Figure V.8. Lakes and their abilities to resist pH changes.


Fish Population
()
No Fish
Sparse
Good
Overpopulated

Bicarbonate Lakes
(129)
10%
25%
55%
10%

Transition Lakes
(332)
25%
60%
10%
5%

Acid Lakes
(223)
75%
25%
0%
0%

Example V.4. The total annual U.S. emissions of SO2 in 1997 were 20.4 million tons.
If it is assumed that 25% of total emissions was in the Midwest-Ohio Valley area, and
50% of that came to ground as acid precipitation in a 1.0106 km2 area in the
northeastern U.S. and southeastern Canada, and that average precipitation over that
area is 1 m/yr, by how much would this SO2 (if all converted to H2SO4) change the pH of
the rain water which was 5.6?
1.
2.
3.
4.
5.

Annual U.S. SO2 emissions = 20.4106 ton = 3.21011 moles.


Annual precipitation = (1.01012 m2)(1m) = 1015 L.
Since each mole of SO2 produces two moles of H+ ions, so the increase in [H+] =
(2)(0.25)(0.50)(3.21011 moles)(1015 L)-1 = 7.2310-5 mol/L.
The original [H+] = 10-5.6 = 2.5110-6 mol/L.
The total new [H+] = 2.5110-6 + 7.2310-5 = 7.4810-5 mol/L or the new pH =
4.13.

Control of SOX and NOX (Motor Vehicles). During the exhaust stroke of an
internal combustion engine, combustion gases are pushed through the exhaust manifold
and out the tailpipe, and it is in this exhaustion system that most of the control of
automobile emissions now occurs. The most commonly used systems for treatment of
exhaust gases are thermal reactors, exhaust gas recirculation (EGR) systems and
catalytic converters. A thermal reactor is basically

120
an afterburner that encourages the continued oxidation of CO and unburned
hydrocarbons (HC)
after these gases have left the combustion chamber (i.e., engine). The reactor consists of
a multipass, enlarged exhaust manifold with an external air source. Exhaust gases are kept hot
in the
thermal reactor and enough oxygen is provided to allow combustion to continue outside
the
engine itself, thereby reducing CO and HC emissions. Usually, the carburetor is
designed to
cause the engine to run rich in order to provide sufficient unburned fuel in the thermal
reactor to
allow combustion to take place. This has the secondary effects of modestly reducing NOX
emissions, but fuel consumption is increased. Some degree of control of NOX can be
achieved by
relatively inert gas that is added to the incoming air/fuel mixture absorbs some of the
heat
generated during combustion without affecting the air/fuel ratio. The heat absorbed
helps
reduce the combustion temperature, and, therefore, helps decrease the production of
NOX. The
coupling of exhaust gas recirculation with a thermal reactor (Figure V.9), reduces the
emissions
of all three pollutants, CO, HC, and NOX, but at the expense of performance and fuel
economy.
The most popular approach to control automobile emissions is the three-way catalytic
converters (three-way just means that it handles CO, HC, and NOX). A three-way
catalytic converter is able
to oxidize CO and HC to CO2 while reducing NOX to N2 all in the same catalyst bed.
These catalytic converters are very effective in controlling emissions, and they have the
advantage of allowing the engine to operate at near optimal conditions. Catalytic
converters can be destroyed very quickly if leaded fuels are burned. Three-way catalytic
converters are very effective once they are warmed up, but when they are cold, as well as
when there are spurts of sudden acceleration or deceleration, they release excessive
amounts of pollution that offset much of their perceived benefits. Those shortcomings
can be addressed by using the new multiple catalytic converters to be on the market very
soon. Another way to help reduce motor vehicle emissions is to provide more oxygen for
combustion by incorporating oxygen-containing additives in gasoline. The most
common additives are ethanol or MTBE. MTBE has certain advantages over ethanol: it
has a higher octane number (% volume of C8H18 in the mixture of C8H18 and C7H16) and it
is not as volatile. But MTBE may cause nausea, dizziness, and headaches. Benzene,
toluene, and xylene (BTX) have been used to substitute tetraethyllead as octane
enhancers. BTX

121

Figure V.9. Exhaust gas recirculation system.


hydrocarbons are more reactive than normal gasoline constituents and they can increase
the formation of photochemical smog.
The utilization of alternative fuels other than gasoline and diesel has been promoted as a
feasible means to reduce emissions that cause photochemical smog and acid
precipitation. In addition, a number of bio-based fuels (or biofuels) that can be used to
reduce the consumptions of gasoline and diesel in transportation sectors are also
promoted. The consumption of gasoline in the U.S. would increase to roughly 290
billion gallons in 2050 if the gas mileage requirements remain unchanged. On the other
hand, it is estimated that roughly 67% of the U.S. transportation fuel demands in 2050
can be met with biomass ethanol that is produced with current agricultural crop/plant
residue mix if 50 mpg requirements are imposed.
Fuel

Methanol (CH3OH)

M85
Gasoline/Ethanol (Flex Fuel)

Compressed Natural Gas (CNG)

R1
Corn Ethanol

Remarks
It has a high octane number than gasoline and a lower flame
temperature than gasoline and diesel. As a result, it reduces
NOX, CO, and HC emissions. However, it is difficult to start
engines in cold conditions, because methanol is less volatile. In
addition to a higher formaldehyde emission (toxic), methanol
itself is also is highly toxic.
The fuel has 85% methanol and 15% gasoline. The octane
rating is 102 (87-92 for gasoline). The driving distance is about
60% of that of gasoline.
Gasohol contains 10% ethanol (C2H5OH) and 90% gasoline and
E85 contains 85% ethanol and 15% gasoline. The flex fuel has a
lower CO and HC emissions than gasoline. Also, ethanol is a
renewable resource.
It is used in the fleets of trucks, delivery vans, and buses. It has
low CO, HC, particulate, and toxic emissions, but higher NOX
emissions than gasoline.

rGHG (kg/m3)2,3

Remarks
The yield is about 0.46 m3/ha. The U.S. produced
1.84107 m3 @ $288/m3 (2006). Most ethanol is sold as

122
1.3

1,943

Cane Ethanol

8.0

1,080

Cellulosic Ethanol

2.0-36.0

228

Biodiesel

2.5

912

Algal Oil

--

--

R is the energy yield ratio defined as

a gasoline additive (e.g., to replace MTBE, a suspected


carcinogen) or, as E85 fuel.
The yield is about 0.92-1.38 m3/ha. Brazil produced
1.84107 m3 @ $230/m3 (2005). The stalk is 20% sugar
and the waste can be burned to power the distillery and
thereby, lowering fossil fuel uses.
Can be produce3d from agricultural residues (e.g., stalks
and leaves), forestry residues (e.g., wood chips, sawdust,
and tree barks), municipal solid wastes (e.g., paper
products and household garbage), paper pulp, and
switchgrass which can grow on marginal land. No
current commercial productions.
Biodiesel is made by chemically altering plant oils.
Germany is the worlds leading producer of biodiesel
using canola oil (2.32106 m3 in 2005). Biodiesel is
primarily produced from soybeans in the U.S (yield:
0.09 m3/ha).
Algae can grow in the presence of sunlight by absorbing
and utilizing CO2 in fossil-fuel power plant gas
emissions (theoretical yield: 7.67 m3/ha). No current
commercial productions.

EP
, where EP is the energy value of 1 kg biofuel (kJ)
EU

and EU is the fossil-fuel energy consumed per kg biofuel produced (kJ). 2 rGHG is the greenhouse
gas (GHG) emission rate (production and use). 3 rGHG (gasoline) is 2,448 kg/m3 and rGHG (diesel)
is 2,808 kg/m3.

Control of SOX and NOX (Stationary Sources).


Approach

Examples

Pre-Combustion Controls

Examples include switching to fuels with less sulfur or


nitrogen contents in power plants (emissions can be reduced
by anywhere from 30 to 90%). In some cases fossil fuels can
be physically, chemically, or biologically treated to remove
some of the sulfur or nitrogen before combustion.

Combustion Controls

Examples include new burners in power plants that reduce


NOX emissions and new fluidized bed boilers that reduce both
NOX and SOX.

Post-Combustion Controls

Capture emissions after they have been formed but before they
are released to the air. On power plants, these may be
combinations of particulate collection devices (e.g., dust bags
and electrostatic precipitators) and flue-gas desulfurization
techniques (e.g., dry and wet scrubbers).

OZONE DEPLETION.
Formation and Destruction of O3 (Chapman Mechanism) (Figure V.10). In
the stratosphere (10 to 45 km), ozone (O3) is created, destroyed, and then recreated by
several natural chemical reactions [(V.12)]. The 1st reaction in (V.12) (i.e., photolysis) is
caused by solar irradiation at wavelengths < 240 nm (UV-C). The 3rd reaction (i.e.,
absorption of UV) is caused by solar irradiation at wavelengths 240 nm < < 320 nm

123
(UV-B and UV-C). The 4th reaction describes the reformulation of ozone.

Figure V.10. Destruction of O3 in the stratosphere.

O2 h 2O

CCl3 F h Cl CCl2 F ( 230nm)

O2 O O3

Cl O3 ClO O2

O3 h O O2

ClO O Cl O2

O3 O 2O2

Cl CH 4 HCl CH 3

(V.13)

(V.12)
However, the introduction of some anthropogenic chemicals has disrupted ozones
natural cycle. This has resulted in enhanced destruction rates of ozone, which has led to
ozone depletion in the stratosphere [(V.13), mid-altitude, 25 40 km]. Over a month, a
chlorine atom in the stratosphere will destroy roughly 100,000 ozone molecules before it
eventually reacts with the small amount of natural methane found in the stratosphere
[i.e., (V.13)]. The HCl molecule formed will be washed out by rain and eventually
transported down to the troposphere (in a matter of months).
The unit introduced by Dr. Gordon M.B. Dobson (1889-1976, a geophysicist at the
University of Oxford) is used to measure the amount of trace gases such as O3 in the
atmosphere. One DU refers to a layer of O3 that would be 10 m thick at 0oC and 1 atm.
For instance, 300 DU of O3 brought down to the earths surface at 0oC and 1 atm would
occupy a layer only 3 mm thick. One DU is 2.71016 O3 molecules per cm2, or
2.71020/m (Example. V.5).
Example V.5. Calculate the number of molecules of O3 per cm2 of the earth surface for
1 DU (Dobson Unit) assuming the ideal gas law is applicable.

124

pO3VO3

1.

nO3

2.

nO3 N a

RTO3

(ideal gas law).

pO3VO3
RTO3

Na

nO3 N a
A

pO3 N a VO3
RTO3

pO3 N a
RTO3

hO3 , where nO3 is the number

of moles of O3, pO3 is the pressure of pure O3, VO3 is the volume of pure O3, R is the
universal gas constant, TO3 is the temperature of pure O3, A is the area of the earths
surface, and hO3 is the height of a layer of pure O3. Note that nO3 N a is the number of
molecules of O3. Therefore, nO3 N a

(1)(6.023 1023 )
(0.01)(103 )(104 ) = 2.691016
5
(8.2110 )(273)

molecules of O3/cm2.
3.

Also,1 DU = 4.4615 x 10-4 mol O3/m2 or 2.1415 x 10-5 kg O3/m2 .

Figure V.11 illustrates the data on Antarctic O3 concentration in October each year from
1980 to 2007.
Atmospheric Absorption of Solar Radiation. Atmospheric absorption of solar
radiation is governed by the interaction between photons and matter. If radiation of
incipient intensity Io traverses an absorber of unit area and thickness z, then the intensity
will be reduced to I in accordance with Beer-Lambert law:

I I o e z
T

I
e z
Io

(V.14)

where is the absorptivity or extinction coefficient, L-1 (Figure V.12); and T is the
transmittance.
Example V.6. If there is a 1% decrease of O3 in the ozone layer, what is the percentage
of increase in UV transmittance? Assume that at 1atm and 0oC the ozone layer thickness
is 0.34 cm.
1.

Differentiating (V.14) yields:

125

TOMS: Total Ozone Mapping Spectrometer.

Figure V.11. Antarctic O3 concentration in October each year from 1980 to


2007.

Figure V.12. UV attenuation in the ozone layer.

126

dT
e z T
dz
dT
zdz
dz
T
z

(I)

2.

For the critical regime of sunburn and skin cancer, the wavelength falls between
290 and 310 nm. From the diagram shown below, the product of z is 1.7 at 310
nm and 17 at 290 nm.

3.

Therefore, from (I), a 1% decrease in ozone layer (i.e.,

4.

increase in T at 310 nm and a 17% increase in T at 290 nm.


At 260 nm, the increase in T is roughly 100%.

dz
0.01 ) gives a 1.7%
z

Ozone Depletion Potential (ODP). ODP is defined as the ratio of the loss of total O3
due to
emission of a unit mass of a compound to the loss of total O3 due to emission of a unit
mass of
CFC-11 (CFCl3).
Example V.7. If HCFC-22 (CF2HCl) is used to substitute CFC-12 (CF2Cl2), what
reduction in stratospheric ozone depletion would occur?
1.

2.

Let I = the ratio of the loss of total O3 due to emission of a unit mass of HCFC-22
to the loss of total O3 due to emission of a unit mass of CFC-12. Let II = the ratio
of the loss of total O3 due to emission of a unit mass of HCFC-22 to the loss of
total O3 due to emission of a unit mass of CFC-11. Let III = the ratio of the loss of
total O3 due to emission of a unit mass of CFC-11 to the loss of total O3 due to
emission of a unit mass of CFC-12.
Then, I = (II)(III)-1. Now, II = 0.034, and III-1 = 0.82 (see the table on the next
page), then I = (0.034)(0.82)-1 = 0.042.

Species
CFC-11
CFC-12
CFC-113
HCFC-22
HCFC-123
HCFC-124
HCFC-141b
HFC-134a
Halon-1211
Halon 1301
Methyl
Chloroform
Methyl Bromide

Formula
CFCl3
CF2Cl2
C2F3Cl3
CF2HCl
C2F3HCl2
C2F4HCl
C2FH3Cl2
C2H2F4
CF2ClBr
CF3Br
CH3CCl3

ODP Relative to CFC-11


1.0
0.9
0.9
0.04
0.014
0.03
0.10
< 510-4
5.1
13.0
0.12

GWP Relative to CFC-11


1.0
2.1
1.3
0.4
0.02
0.12
0.16
0.33
-1.4
0.03

CH3Br

0.6

--

ODP: ozone depletion potential. GWP: global warming potential.

Example V.8. What is the chemical composition of CFC-115? What is the CFC number

127
for C2H2F4? What is H-2402? Halo is referred to as chlorine, fluorine, and bromine.
The following formulae are useful:

CFC xyz xyz 90 x ' y ' z '


H wxyz
x is the number of C, y is the number of H, and z ' is the number of F.
'

'

w is the number of C, x is the number of F, y is the number of Cl, and z is the number of
Br.
1.
2.
3.
4.
5.

CFC-115: adding 90 to 115 gives 205. Therefore, a molecule contains 2 carbons,


no hydrogen, and 5 fluorine atoms.
Since two carbon have six bonding sites (# of bonding sites = 2n + 2, where n is
the # of carbon), five of which are taken by fluorine, the remaining site is taken
by chlorine. The chemical formula is therefore C2F5Cl.
C2H2F4 has two carbon atoms, two hydrogen atoms, and four fluorine atoms.
Subtracting 90 from 224 gives 134.
Since there is no chlorine, this halocarbon is a hydrofluorocarbon, or HFC-134.
H-2402 has two carbon atoms, four fluorine atoms, zero chlorine, and two
bromine atoms. Therefore, H-2402 is C2F4Br2.

Ozone Depletion in Stratosphere. Hydrochlorofluorocarbons (HCFCs) and


hydrofluorocarbons (HFCs) are substitutes for CFCs since their lifetimes are shorter and
their breakdowns are relatively quick. HCFCs and HFCs have a modest potential to
affect ozone. HFCs contain no chlorine atoms to threaten the ozone layer, but they
contribute to global warming. According to the Montreal Protocol on Substances that
Deplete the Ozone Layer, all CFCs should be banned by 1996 and all HCFCs will be
banned by 2030. HFCs will be restricted if other alternatives exist.
CFC
CFC-11
CFC-12
CFC-113
CFC-114
Carbon
Tetrachloride
Methyl Chloroform

Formul
a
CCl3F
CCl2F2
C2Cl3F3
C2Cl2F4
CCl4

H-1211
H-1301
H-2402
HCFC-22

CH3CCl3
CBrF2Cl
CBrF3
C2Br2F4
CHF2Cl

HCFC-141b
HCFC-142b

C2H3FCl2
C2H3F2Cl

Main Uses

ppt1

Aerosol propellant and foam blowing.


Aerosol propellant, foam blowing, and refrigerant.
Solvent.
Aerosol propellant and refrigerant.
Solvent.

268
503
82
20
132

(years)
50
102
85
300
42

Solvent.
Fire retardant.
Fire retardant.
Fire retardant.
Aerosol propellant, foam blowing, refrigerant, fire
retardant, and solvent.
Foam blowing and solvent.
Foam blowing and solvent.

135
7
3
0.7
100

4.9
20
65
20
12.1

2
6

9.4
18.4

Atmospheric concentration (1992) in ppt = parts per trillion (molecules/molecules).

A Box (Atmosphere) Model on Ozone Destruction by CFCs. As in the case of


modeling the air pollution phenomena in an urban area, the box model approach can
also be used to describe the accumulation of CFCs in the atmosphere. Since CFCs are
emitted across the globe use to their widespread usage, the CFC concentration in the

128
atmosphere is assumed to be uniform. The box model is constructed by the following
steps.

dm
.
dt

1.

Rate of change of CFC mass in the box over time is

2.

CFC flow into the box = 0 (there are no CFCs in the outer space). CFC flow out of
the box = 0 (there are no CFCs in the outer space).
Emission within the box = P. Removal of CFCs within the box = R = km.
Therefore,

3.

dm
km P
dt
m(t ) m0e

1
k

mN a
M i Nm

C (t )

P 1 e

(V.15)

t
t

m0 N a PN a
1 e
e
M i Nm
M i N m

where k is the first-order rate coefficient, m0 is m at t = 0, is the atmospheric lifetime, C


is the
CFC i concentration as fraction, Na is Avogadro number (6.0231023 molecules/mole),
Mi is the
molecular weight of CFC i, and Nm is the number of air molecules in the atmosphere
(1.11044
molecules).
Example V.9. The production of CFC-11 throughout the 1960s averaged about 1.21011
g/yr. Assume that t = 0 corresponds to the beginning of 1960 and that m0 = C0 = 0. Also
assume that all of the compound produced each year is emitted to the atmosphere in the
same year. If the emission rate of CFC-11 in the 1960s continued indefinitely, calculate
the steady-state mass and concentration of this CFC. How long would it take for the
concentration to reach 98% of the steady-state value?
1.

From the 1st equation in (V.15),

dm
0 mSS P (1.2 1011)(50) 61012
dt

g.

PN a (6 1012 )(6.023 1023 )

0.241109
44
M i Nm
(136)(1.110 )

2.

CSS C ()

3.

= 0.241 ppb (molecule/molecules basis).


From the 5th equation in (V.15),

129

C (t )
1 e

4.

PN a
1 e
M i N m
t
50

CSS 1 e

C (t )

0.98

CSS

Therefore, t = 196 years.

GREENHOUSE GASES (GHGs) AND GLOBAL WARMING.


Atmospheric Composition (% volume):
Nitrogen

78

Nitrogen

21

Argon

0.9

Carbon Dioxide

0.03

Carbon dioxide (CO2), methane (CH4), and water vapor are transparent to incoming
short-wavelength solar rays, but which retain the long-wavelength infrared rays.
Moreover, they also block a large fraction of the earths emitted long-wavelength
radiations. Therefore, they are referred to as greenhouses gases (GHGs).
CO2 Emissions Caused by Fuel Burning (1998):
Sources

Pg (as C) (1 Pg = 11015 g = 1 billion tons)

Petroleum

2.5

Coal

2.2

Gas

1.0

Biomass

1.0

6.7

1.

Current atmospheric CO2 concentration is about 360 ppmv (i.e., 360 m3 CO2 per
106 m3 air). ppmv is defined as parts per million (volume).

2.

360 ppmv CO2 =

(360)(44)
= 0.707 g CO2/m3 air. Under the standard
(10 )(22.4 103 )
6

conditions, 1 g mole CO2 is equivalent to 44 g CO2 which has volume of 22.4


liters.

(0.707)(12)(5.11018 )(1.29)
=
44

3.

Total atmospheric CO2 inventory (as C) (1998) =

4.
5.

7621015 g C = 762 Pg C = 762 billion tons C. The atmospheric density is


assumed as 1.29 kg air/m3. The total weight of the atmosphere is 5.11018 kg air.
1 ppmv CO2 = (762/360) = 2.12 Pg C = 2.12 billion tons C.
The atmospheric CO2 concentration increases at a rate of 1.5 ppmv/year since
1958. Therefore, the airborne fraction of CO2 =

1.5 24
= 0.5 (50%).
44

130
6.

The remaining CO2 emitted is most absorbed by the oceans, which contain large
quantities of CO2 in the form of HCO3-. The Earths oceans also support large
quantities of phytoplankton cells which perform photosynthesis that consumes
CO2. When phytoplankton cells die they eventually settle to the ocean floor
where the CO2 fraction incorporated in phytoplankton cells will be immobilized
for a long time without being immediately released back to the atmosphere, i.e.,
the Earths oceans is a major CO2 sink. Other possible uptakers of CO2 are the
living green plants. Experimental studies have shown that plant growth increases
in the presence of increased CO2 concentration.

Major CH4 Emission Sources. CH4 accounts for about 15-20% of greenhouse gases
in the
atmosphere and CO2 accounts for about 60%.
Fossil Fuels

26%

Enteric Fermentation

22%

Rice Paddies

16%

Biomass Burning

11%

Landfills

11%

Municipal Wastewaters

7%

Animal Wastes

7%

N2O. Nitrous oxide (N2O) is the result of increasing fossil fuel emissions, biomass
burning, and
nitrogen fertilizer applications worldwide. As ammonia-nitrogen is oxidized in the soil
and
nitrate is denitrified, N2O represents an intermediate oxidation state, which is volatilized
to the
atmosphere. N2O is a difficult gas to control, because fertilizer applications of ammonia,
ammonia nitrate, and ammonia sulfate are likely to increase worldwide.

NH 4 N 2 N 2O NO2 NO3

(V.16)

Chlorofluorocarbons (CFCs). Chlorofluorocarbon concentrations are also


increasing, and
they have a long half-life in the atmosphere. They are used as refrigerants, blowing
agents, and
cleaning chemicals in the microelectronic industry. Two of the most widely used are
CFC-11
(trichlorofluoromethane, CFCl3) and CFC-12 (dichloro-difluoromethane, CF2Cl2). Due to
a slow
reaction rate with hydroxyl radical, OH, in the lower atmosphere, CFCs are transported
into
the stratosphere (upper atmosphere), where they deplete the ozone layer that shields the
earth
from harmful UV radiation.

131

Summary of Major Anthropogenic Greenhouse Gases.

Gases

Concentration
(ppmv)

Greenhouse
Contributio
n (%)

Rate of
Increase
(%/year)

Half-Life
(years)

Relative
Greenhouse Effect

CO2

360

60

0.4-0.5

1 (per kg)
1 (per mole)

CH4

1.7

15-20

0.7-0.9

70

70 (per kg)
25 (per mole)

N2O

0.31

0.2

200

200 (per kg)


200 (per mole)

O3

0.01-0.05

0.1-0.5

1,800

1,800 (per kg)


2,000 (per mole)

CFCl3

0.28 (ppbv)

0-4

4,000

4,000 (per kg)


12,000 (per mole)

CF2Cl2

0.48 (ppbv)

0-4

6,000

6,000 (per kg)


15,000 (per mole)

Global Carbon Cycle. Figure V.13 shows the main reservoirs and transfer processes in
the
global carbon cycle. The carbon cycle begins with the primary environmental reservoir
of
carbon, the CO2 present in the air and/or dissolved in water. Through photosynthesis,
carbon
atoms from CO2 are incorporated into glucose (C6H12O6) and then into other organic
molecules
that make up all plant tissues. They may then be passed to consumers and/or
decomposers
through feeding. As plants themselves or any consumer or decomposer breaks down
organic
molecules through cell respiration to release energy, the carbon atoms are returned to
the air or
water as CO2 molecules. If organic materials are simply burned they also are returned
CO2 to the
air. In either case, it may be reabsorbed by plants and repeat the cycle.
Another interesting and important aspect of the carbon cycle is that in ancient geological
times
(hundreds of millions of years ago) much of the organic matter produced in
photosynthesis was
neither consumed nor decomposed; it accumulated and was buried under sediments. As
a result
of millions of years under heat and pressure in the earth, this detritus has been
converted to
crude oil, natural gas, and coal the fossil fuels that are mining or pumping today.

132

CO2 H 2O H 2CO3 H HCO3

(V.17)

Figure V.14 shows upward trends (~ 4%/decade) in mean annual CO2 concentrations at
Point
Barrow, Alaska; Mauna Loa, Hawaii; and the South Pole. The annual rhythm is due to
the season
variation in plant and soil absorption and release, chiefly in the northern hemisphere. A
rapid
increase in atmospheric CH4 concentration in the 20th century is also evident by the data
shown
in Figure V.15.

Figure V.13. Global carbon cycle.

133
Fundamentals of Greenhouse Effects. The basic processes governing the earths
temperature and climate are related to radiative heat exchange between the earth and
sun.
Any objective with a temperature above absolute zero continuously radiates energy. The
amount
of energy radiated depends on the temperature of the material and the nature of its
radiating
surface. The maximum amount of energy, in the form of heat, can be radiated by a body
at a
given temperature is given by the Stefan-Boltzmann equation:

Q max AT 4

(V.18)

Figure V.14. Upward trends (~ 4%/decade) in mean annual CO2


concentrations at
Point Barrow, Alaska; Mauna Loa, Hawaii; and the South Pole.

where Q max is the maximum rate of energy radiated (W), is the Stefan-Boltzmann
constant
(5.6710-8 W/m2-oK4), A is the surface area of the body (m2), and T is the absolute
temperature of the body (oK). Any body radiating the energy at this maximum rate is
known as a black body.
The radiant heat reaching the earth from the sun closely approximates the radiation

134
from a black body at T = 5,800oK. the amount of solar energy incident on the earths
atmosphere averages about 342 W/m2 (So) based on the surface area of the earth (4R2,
R is the radius of the earth).
A Simple Earth Energy Balance Without Atmosphere. As illustrated in Figure
V.16, I is
the incoming solar radiation (So). Part of this incoming solar radiation is reflected back
out to
space (II, II = aSo, where a is called albedo which is about 0.31 for the earths surface).
Therefore, the rate of solar radiation absorbed by the earths surface, IV, is (1 a)So. If
the
earths surface is assumed to approximate a black body, then the outgoing rate of
radiation from
the unit earths surface area to space, III (or V), is Te4 , where Te is the earths surface
temperature. At steady state, therefore,

Figure V.15. Atmospheric CH4 concentrations.


1

(1 a) So 4
(1 a) So T Te


4
e

(V.19)

or Te = 254oK = 19oC, which suggests a cold and inhospitable earth! The actual earths
surface
temperature is about 15oC, which is a result of the presence of greenhouse gases (GHGs)
in the
earths atmosphere.

135

Figure V.16. Energy fluxes of the earth without the atmosphere.


Figure V.17 depicts the absorption spectra for the key gases of concern in the
atmosphere, along with their effects on incoming solar radiation and outgoing infrared
radiation emitted by the earths surface. Most of the long-wavelength energy radiated by
the earth is absorbed by water vapor, CO2, CH4, O2, N2O, and O3. Water vapor, which is
by far the most important GHG, absorbs thermal radiation with wavelengths < 8 m or >
18 m. CO2 shows a strong absorption band centered at 15 m, as well as bands centered
at 2.7 m and 4.3 m. Between 7 m and 15 m there is a relatively clear sky for
outgoing thermal radiation, referred to as the atmospheric radiative window.
Essentially all incoming solar radiation with wavelengths < 0.3 m (ultraviolet) is
absorbed by O2 and O3. Radiatively active gases that absorb wavelengths >
4 m are called GHGs. This absorption heats the atmosphere, which, in turn, radiates
energy back to the earth as well as out to space. These GHGs act as a thermal blanket
around the globe, raising the earths surface temperature beyond 19oC.

136

Figure V.17. Absorption spectra of atmospheric gases.


A More Realistic Earth Energy Balance. To derive an energy balance, all energy
flows are
expressed in terms of heat fluxes. For outgoing radiations, all surfaces are assumed to
radiate as
black bodies. According to Figure V.18, I = So = 342 W/m2 and II = 107 W/m2.
Therefore, the
net solar energy input to the atmosphere is Sa = 235 W/m2, which is partially absorbed
by the
atmosphere and partially by the earths surface.

137

Figure V.19. Energy fluxes of the earth with the atmosphere.


Now, III is the radiation from the atmosphere to the earths surface which is assumed to
be
identical to the radiation from the atmosphere out to space, IV is the part of the net
incoming
solar energy that is absorbed by the atmosphere (Sa), V is the part of the net incoming
solar
energy that is absorbed by the earths surface [(1 Sa)], and VI is the radiation from the
earths
surface to the atmosphere.
Since both the atmospheric temperature (Ta) and the earths surface temperature (Te) are
unknown, two independent equations are needed to solve the problem. At steady state,
then

S a Te4 2Ta4
(1 ) S a Ta4 Te4

(V.20)

For = 0.29, then Te = 17oC, which is close to the actual earths surface temperature at
about
15oC.
Radiative Forcing (F). Figure V.20 depicts the radiative equilibrium and imbalance
situations in the troposphere where GHGs and aerosols are generally confined. The
length of each arrow in the diagram represents the magnitude of radiative heat flux
(W/m2) at the tropopause, which is the upper boundary of the troposphere
approximately 10 km above the

138
earths surface.

Figure V.20. Radiative equilibrium and imbalance situations in the


troposphere.
The top left figure represents the initial radiative equilibrium conditions that result in a
zero net
energy flux. The top right figure represents the temporary imbalance that results from
the
addition of a GHG like CO2. More of the outgoing radiation is now absorbed in the
atmosphere,
so the incoming solar radiation exceeds the outgoing radiation. Such changes in the
average net
radiation at the tropopause result in a net decrease of outgoing radiation per unit of area.
In this
case, a positive radiative forcing would occur. The bottom left figure shows a change in
solar
radiation input that perturbs the earths energy balance to produce a radiative forcing
even
nothing is added to the atmosphere. If the solar radiation input were increased by a
specific
amount, a positive radiative forcing would occur, tending to warm the planet.
Radiative forcing also can be induced by changes in earths albedo. The addition of

139
aerosols
(suspensions of fine particles less than 10 m in diameters) to the atmosphere tends to
reflect
incoming solar radiation back to space thereby increasing the earths albedo. As a result,
more
radiation is leaving at the tropopause than coming in, resulting in a net decrease in heat
flux. In
this case, a negative radiative forcing would occur as shown by the bottom right figure. A
general
expression for radiative forcing (F) combines the overall changes in incoming solar
radiation
with the overall changes in outgoing radiation at the tropopause:

Q
Q
F out in q out q in
A
A

q out q out initial q out after

q in q in

(V.21)

initial

q in

after

where the subscripts in represents the incoming solar radiation, out the outgoing
radiation,
initial the conditions before perturbations, and after the conditions after perturbations.
Example V.10. (1) An increase in atmospheric CO2 concentration reduces the outgoing
IR radiation at the tropopause from 235 to 233 W/m2. The incoming solar radiation and
albedo do not change. Calculate F. (2) An increase in atmospheric sulfate aerosol
from combustion of coal and oil adds 0.5 W/m2 to the global average flux of radiation
reflected by the troposphere (albedo). Calculate F.

1.1.

q in 0 (since there are no changes in incoming solar radiation and albedo).

1.2.
1.3.
2.1.

q out 235 233 2 W/m2.


Therefore, F = 2 0 = 2 W/m2 > 0 (net warming).
Denote the initial outgoing radiation as x W/m2.

2.2.

q in 0 (since there is no change in incoming solar radiation).

2.3.
2.4.

q out x ( x 0.5) 0.5 W/m2.

Therefore, F = 0.5 0 = 0.5 W/m2 < 0 (net cooling).

Radiative Forcing (F) versus Concentration (C).

140
F k1 (C C0 )
F k 2

C C0

(V.22)

C
F k3 ln
C0
The 1st equation in (V.22) is for the low concentration conditions, the 2nd equation for
the moderate concentration concentrations, and the 3rd equation for the high
concentration conditions.
GHG

F (W/m2)

CO2

C
F 6.3 ln
C0

CH4

F 0.036 C C0

F 0.14 C

N2O

Remarks
C is in ppmv.
C < 1,000 ppmv.

C is in ppbv.
C < 5,000 ppbv.
C is in ppbv.
C < 5,000 ppbv.
C is in ppbv.

O3

F 0.02C C0

CFC-11 (CFCl3)

F 0.22(C C0 )

CFC-12 (CF2Cl2)

F 0.28(C C0 )

C is in ppbv.
C < 2 ppbv.
C is in ppbv.
C < 2 ppbv.

Global Warming Potential (GWP). The GWP is a weighting factor that enables
comparisons
to be made between the global warming impact of 1 kg of any GHG and 1 kg of CO2. For
instance,
the 20-year GWP for N2O is 280, which means 1 kg N2O emitted today will exert 280
times as
much global warming over the next 20 years as would 1 kg of CO2 emitted today. The
GWP is a
ratio of the cumulative radiative forcing for 1 kg of a GHG over some period of time to
the
cumulative radiative forcing for 1 kg of CO2, over that same period of time.
Mathematically, the
GWP can be expressed as:
T

GWP oT
GHG

o FCO2 RCO2 (t )dt FCO2


F
GHG
FCO
2

FGHG RGHG (t )dt

1 e

T
RCO2 (t )dt
o

o RGHG (t )dt

T
o RCO2 (t )dt
(V.23)

141
where FGHG is the radiative forcing of the GHG in question per kg (W/m2-kg), FCO2 is
the radiative forcing of CO2 per kg (W/m2-kg), RGHG (t ) is the fraction of the 1 kg of GHG
remaining in the atmosphere at time t, RCO2 (t ) is the fraction of the 1 kg of CO2
remaining in the atmosphere at time t, T is the time period for cumulative effects (years),
and is the atmospheric lifetime (or time constant) of the GHG in question (years). Note
that RGHG (0) 1 kg.
T (years)

0 RCO2 (t )dt (years)

20
100
500

13.2
43.1
138.0

Example V.10. 1 kg of HFC-143a (CF3CH2F) in the atmosphere causes a radiative


forcing that is 4,129 times the forcing of 1 kg CO2. The decay of HFC-134a is exponential
with a time constant of 14.6 years. Estimate the GWP over 20-year and 500-year
periods.

1.

2.
3.

20

(14.6)1 e 14.6
4,129

3,400.
GWP20

1
13
.
2

500

(14.6)1 e 14.6
4,129

= 435.
GWP500

138.0
1

Notice how the relatively short time constant of HFC-134a results in a much
higher GWP in the 20-year time period than it does over the much longer 500year period.

Reducing GHG Gas Emissions.


Strategy

Reducing Energy Intensity

Reducing Carbon Intensity

Reducing Non-CO2 Emissions

Remarks
A change in the makeup of industries, e.g., a decline in
energy-intensive industries (e.g., steel manufacturing) and a
rise in light industries (e.g., semiconductor assembly).
Efficiency improvements that provide economic incentives,
e.g., the replacement of incandescent light bulbs by LEDs.
Alternative energy sources that emit less carbon than fossil
fuels.
Carbon sequestration via biomass absorption of CO2 and
new techniques to capture and sequester CO2.
Capture of CH4 leaked from landfills and underground
coal seams.
Reduction in fertilizer uses to control N2O emissions.
Replacements of CFCs by HCFCs and HFCs.

Example V.11. Compare the carbon emissions to heat household water using the

142
following three energy systems: (1) a very good, 37% efficient coal-fired power plant
delivering electricity to a 100% efficient electric water heater, (2) a new, 45% efficient
natural-gas-fired combined cycle power plant delivering electricity to a 100% efficient
electric water heater, and (3) an 85% efficient gas-fired water heater. Each system is
provided with 100MJ of energy. The LHV (low heating value) carbon intensity values for
coal, natural gas, and oil are 25.8, 15.3, and 20.0 g C/MJ, respectively.
1.

Since 2,580 g of carbon will be released to generate 37 MJ of electricity,


therefore, the carbon emission is

2.

Since 1,530 g of carbon will be released to generate 45 MJ of electricity, therefore,


the carbon emission is

3.

2,580
= 69.7 g C/MJ.
37

1,530
= 34.0 g C/MJ.
45

Since 1,530 g of carbon will be released to capture 85 MJ to heat the water, the
carbon emission is

1,530
= 18.0 g C/MJ.
85

Example V.12. Consider two fuel systems each delivering 100 MJ of energy to some
end use that burns the fuel releasing CO2. One system delivers the amount of energy in
the form of coal. In the other methane is the fuel, but the pipeline leaks 1 MJ of methane
for every 100 MJ it delivers to the end user. Compare the 20-year, emission-weighted
global warming potentials (GWPs) of the two systems. HHV and LHV values for
methane are 890 and 802 kJ/mol, respectively. Methane has 56 times the warming
potential of CO2 over the 20-year period.

CH 4 2O2 CO2 2H 2 O
1.

Since the LHV carbon intensity for coal is 25.8 g C/MJ, then CO2 emission from
coal burning is

2.

(25.8)(100)(44)
= 9,460 g CO2.
12

Since burning 1 mole of methane releases 802 kJ of energy (LHV) while


producing 1 mole of carbon dioxide, then the LHV carbon intensity for methane

(12)(1,000)
= 15.0 g C/MJ (1 mole of carbon dioxide has 12 g of C).
802
(15)(100)(44)
CO2 emission from burning CH4 =
= 5,500 g CO2.
12
is

3.
4.
5.
6.

Methane leaked = (1 MJ)(16 g CH4/mol)(0.802 MJ/mol)-1 = 19.95 g CH4.


For the coal system all the emissions are in the form of CO2, which by definition
has GWP = 1. Then, for coal, GWP20 = 9,460 g CO2.
For the methane system, GWP20 = 5,500 + (19.95)(56) = 6,617 g CO2.
Therefore, the ratio of the two system is

6,617
= 0.70 (i.e., methane reduces the
9,460

warming impact by 30%).

VI. Environmental Risk Assessment

143

One of the most important changes in environmental policy in the 1980s was the
acceptance of the role of risk assessment and risk management in environmental
decision making. It was assumed in early environmental legislation (e.g., the Clean Air
and Clean Water Acts) that contaminants have thresholds, and that exposure to
concentrations below these thresholds would produce no adverse health effects.
However, many toxic substances are carcinogens, and carcinogenesis is assumed to
consist of one or more stages at the cellular level beginning with a single-cell mutation,
at which point cancer is initiated, i.e., no threshold exists for cancer-causing chemicals.
Therefore, any concentration is a risk.
Hazardous wastes have been generated from essentially all industrial activities. Prior to
the passage and promulgation of federal legislation in the later 1970s, hazardous wastes
were often disposed of in pits, ponds, and lagoons, on surface soils, and in landfills. The
Resource Conservation and Recovery Act (RCRA) was passed in 1976 to provide cradleto-grave management of hazardous wastes; it was amended as Hazardous and Solid
Waste Amendments (HSWA) in 1984. Hazardous waste generators, transporters, and
treatment/storage/disposal facility operators have responsibilities that provide
safeguards against improper hazardous waste disposal. The Comprehensive
Environmental Response, Compensation and Liability Act (CERCLA), or Superfund, was
passed in 1980 to provide a mechanism for the mitigation of chronic environmental
damage, particularly the cleanup of contaminated sites. Superfund was amended in
1986 as the Superfund Amendments and Reauthorization Act (SARA). Hazardous
wastes are defined by RCRA, hazardous substances by CERCLA, and hazardous
materials by Department of Transportation regulations. The current estimate of
hazardous waste generation in roughly 750 million tons (680.4106 metric tons) per year
in the United States. Most of the waste is classified as corrosive, and can be treated by
neutralization.
The assessment of health effects on workers, the general public, and the environment is
often required in hazardous waste management. A multi-step risk assessment process is
often used to assess health and ecological risks at Superfund sites as well as to evaluate
the effectiveness of remedial alternatives in attaining a required level of cleanup. For
most contaminants that are considered hazardous under CERCLA, specific cleanup
requirements have not been established. For instance, not all soils at sites containing
PCP (pentachlorophenol, C6Cl5OH) are remediated to a certain level, e.g., 1 mg/kg.
Rather, each site is assessed individually and remediated to a predetermined level of
risk, e.g., one cancer case per million people. The rationale of using risk assessment can
best be illustrated by comparing two very different sites. Figure VI.1 illustrates a highrisk site, although containing only 10 mg/kg PCP, is near a house and a drinking water
well. As a result, remediation to low levels would be necessary to protect public health.
On the other hand, at the low-risk site (Site B), a PCP-bearing sludge (10,000 mg/kg)
has been buried, but there are no receptors nearby and the low rate of PCP migration in
clay subsurface materials (low permeability) would further reduce the risk. Therefore,
the best remedial option would be to leave the buried sludge in place, where slow natural
attenuation processes would eventually result in its degradation.

House
Site A
Well

144

10 mg PCP/kg

10 m

Sandy Soil

Groundwater

Site B
20 m
100 m

10,000 mg PCP/kg
Subsurface Clay Material
Groundwater

Figure VI.1. Risk assessments.


The usual starting point for an explanation of risk is to point out that there is always
some risk associated with human activities. Since risk has no units, additional
clarifications on risk may be needed, e.g., whether the risk is a lifetime risk or an annual
risk, whether it is an average risk to the general public or a risk faced by individuals who
engage in some activities, or whether it is being expressed as a percentage or as a decimal
fraction. Also, environmental risk assessments deal with incremental probabilities of
some adverse health effects occurring. For instance, the U.S. EPA attempts to control
the exposure to toxins to levels that will pose incremental lifetime cancer risks to the
most exposed members of the public of roughly 10-6 (one additional cancer in million
people) to 10-4 (100 additional cancers in million people). Suppose all 300 million
Americans face a 10-6 lifetime risk of cancer from exposure to a particular toxic chemical,
then 300 extra cancers would be observed during their lifetimes. For a typical lifetime of
70 years, then roughly 4 extra cancers would be observed per year in the U.S. In 1992,
roughly 521,000 cancer deaths were reported in the U.S. so 4 extra cancers caused by
toxic exposure would be < 0.001% of the normal rate. Presenting risk as an annual
probability of death to individuals who engage in some activities is a much more
way to express risks than simply looking at the population as a whole. Table VI.1. shows
risk data for some common activities that are a mix of actuarial values and estimates
based on various risk models. It should always be kept in mind that when risks are based
on models, there are generally very large uncertainties in the estimates. Nevertheless,
one of the purposes of risk assessment is to provide a starting point in balancing the
tradeoffs between an acceptable incremental risk and the cost of controlling risk to that
level. For instance, immunizations and phasing out leaded gasoline yield the direct
savings in health care that far exceed the costs associated with the implementation of the
practices.
Table VI.1. Risks Associated with Some Common Activities.

145
Activity/Exposure
Motorcycling
Smoking (all causes)
Smoking (cancer)
Hang Gliding
Coal Mining
Farming
Motor Vehicles
Chlorinated Drinking Water (chloroform)
4 Teaspoons Peanut Butter Daily (aflatoxin)
3 oz Charcoal Broiled Steak Daily (PAH)
10-6 Lifetime Risk

Annual Risk (Deaths/100,000 people at risk)


2,000
300
120
80
63
36
24
0.8
0.8
0.5
0.0014

Four steps have been defined by both the National Academy of Sciences and the U.S.
EPA for the hazardous waste risk assessment:
Hazard Identification. The process of determining whether or not a particular chemical
is causally linked to particular health effects, such as cancer or birth defects. Since
human data are so often difficult to obtain, this step usually focuses on whether a
chemical is toxic in animals or other test organisms.
Dose-Response Assessment. The process of characterizing the relationship between the
dose of an agent administered or received and the incidence of an adverse health effect.
Many different does-response relationships are possible for any given agent depending
on such conditions as whether the response is carcinogenic or non-carcinogenic and
whether the experiment is a one-time acute test or a long-time chronic test. Since most
tests are performed with high doses, the dose-response assessment must include a
consideration for the proper method of extrapolating data to low exposure rates that
humans are likely to experience. Part of the assessment must also include a method of
extrapolating animal data to humans.
Exposure Assessment. The determination of the size and nature of the population that
has been exposed to the toxicant under consideration, and the length of time and
toxicant concentration to which they have been exposed. Consideration must be given to
such factors as the age and health of the exposed population, smoking history, the
likelihood that members of the population might be pregnant, and whether or not
synergistic effects might occur due to exposure to multiple toxicants.
Risk Characterization. The determination of a number that expresses risk, e.g., one in
one hundred (110-2) or one in one million (110-6).
Hazard Identification. The 1st step in a risk assessment is to determine whether or
not the chemicals that a population has been exposed to are likely to have ant adverse
health effects. Figurer VI.2 shows the human circulary system that identifies some of the
principle organs and nomenclature for toxic effects. A toxicant can enter the body using
any of three pathways: by ingestion with food or drink, through inhalation, and by
contact with skin (dermal) or other exterior surfaces, such as the eyes. Once in the body,
the toxicant can be absorbed by the blood and distributed to various organs and systems.
Chemicals that can cause liver damages are called hepatotoxins (e.g., carbon
tetrachloride, CCl4; chloroform, CHCl3; trichloroethylene, C2HCl3; DDT; arsenic; iron;
acetaminophen; and anabolic steroids). Toxicants that damage kidneys are called
nephrototoxins (e.g., cadmium, mercury, lead, and some chlorinated hydrocarbons).

146
Hematotoxicity is the term used to describe the toxic effects of substances on the blood
(e.g., CO and NO3-).

Figure VI.2. The human circulary system and the nomenclature for toxic
effects.
Classification of Toxic Responses. The most important factor that influences
toxicity is the dose, and it has been said that the dose makes the poison. A second
important factor is the time period of exposure. Toxicity is often classified by number or
duration of exposure. Repeated exposures may be classified as acute (< 5% of the
organisms life span), subchronic (5-20% of the life span), and chronic (> 20% of the life
span). For chemicals that are both acutely and chronically toxic, the mechanisms of
toxicity for these two categories are often different. For instance, acute toxicity from a
large dose of chloroform is caused by effects on the central nerve system, which results in
and narcosis. However, consumption of drinking water containing trace concentrations
of chloroform over a lifetime causes liver damage and cancer. Many chemicals that are
acutely toxic may not be chronically toxic and vice versa. For instance, vitamin D taken
in pure form exhibits high acute toxicity. However, low doses of vitamin D such as in the
normal intake of milk are not only nontoxic, but essential for good health. In quantifying
toxic responses, numerical values may be absolute or normalized for body weight (BW).
Dosage is often defined as the total mass of chemical to which an organism is exposed.
Dose, on the other hand, is chemical dosage normalized for body weight. A dose of 8
mg/kg being administered to a 3-kg animal results in a dosage of (8 mg/kg)(3 kg) = 24
mg. There are different ways of defining dose. Administered dose, which is the most
practical for environmental applications is the concentration of chemical to which the
organism is exposed. Intake or uptake dose is the actual amount of chemical absorbed

147
by the organism. Target or effect dose is the amount of chemical reaching the target
organ.
Acute Toxicity. Acute toxicity refers to effects that are caused within a short period of
time after a single exposure to the chemical. One way to describe the acute toxicity of a
chemical is by the amount that is required to kill the organisms. Table VI.2 summarizes
a conventional rating system for the acute toxicity of chemicals in humans.
Table VI.2. Conventional Rating System for Acute Toxicity in Humans.
Toxicity Rating
Practically Nontoxic
Slightly Toxic
Moderately Toxic
Very Toxic
Extremely Toxic
Supertoxic

Probable Lethal Oral Dose (mg/kg BW)


> 15,000
5,000 to 15,000
500 to 5,000
50 to 500
5 to 50
<5

Average Adult
> 1 quart
1 pint to 1 quart
1 ounce to 1 pint
1 teaspoon to 1 ounce
7 drops to 1 teaspoon
< 7 drops

It is noteworthy that not every member of an exposed population will react the same way
to a toxin. As a result, the variations in respo0nses are illustrated with a dose-response
curve that shows the percentage of a population that is affected as a function of the dose
received. S-shaped curves will be yielded when the dose is plotted on a logarithmic scale
(Figure VI.3). The dose is normalized with BW to permit it to be extrapolated to
individuals with different sizes. The dose-response curves generated using animal tests
also permit the extrapolation of the likely effects on a human.

LD50

LD50

LD50

Figure VI.3. Dose-response mortality curves for acute toxicity.


The dose that will kill 50% of a population is designated as LD50 or LC50 (LD: lethal;
dose, LC: lethal concentration). It is seen from Figure VI.3 that chemical A has la lower
LD50 than chemical B and it is always more toxic. However, just because one chemical
has a lower LD50 than another does not necessarily means it is always more toxic.
Chemical A has a lower LD50, which would normally suggest that it is more toxic then
chemical C, but notice it is not as toxic as Chemical C at low doses. So the dose-response
curve does provide more information than a simple table of LD50 doses. LC50 is often
used in the assessment of aquatic toxicity.

148
Initial Screening and Selection of Surrogates. The identities, nomenclatures,
concentrations, and properties for all contaminants should be obtained at a site or
facility. Some of the specific tasks may include sampling, installation of monitoring
wells, chemical analysis, assurance/quality control plans, and data analysis. Since most
sites may contain tens to hundred of chemicals, data collection can become unrealistic
and/or overwhelming. Therefore, the hazard identification usually focuses more on
chemicals that pose the greatest risks, the surrogates. The use of surrogates significantly
reduces the data input for pathway studies. The two most important source
characteristics that are used in screening a large number of chemicals at a site or facility
are their concentrations and toxicities. The procedure for the initial screening of
contaminants to identify surrogates is outlined as follows.
1.
2.
3.
4.

Sort the contaminant data by medium (i.e., soil, miscellaneous solids such as
sludges, surface water, groundwater, and air).
Tabulate the mean and range of concentrations at the site or facility.
List the reference doses (RfDs) for non-carcinogens and slope factors (SFs) for
carcinogens.
Determine the chemical score (i.e., a risk factor) for each contaminant. In
general, the chemical score is:

Rij Cij Tij


Rij

Cij
RfDi

(VI.1)

Rij Cij SFi


R j Rij
i

5.
6.
7.

where Rij is the chemical score for chemical i in medium j; Cij is the concentration
of chemical i in medium j; Tij is the toxicity value for chemical i in medium j; Rij is
the chemical score for chemical i in medium j; RfDi is the reference dose for
chemical i (non-carcinogen), mg/kg-day; SFi is the slope factor for chemical i
(carcinogen), kgday/mg; and Rj is the total chemical score in medium j.
Rank the chemicals by chemical scores for each exposure route (i.e., medium).
Select chemicals comprising 99% of total score (i.e., surrogates).
Further discussions on RfD and SF will be presented later.

Example VI.1. The following pesticides and corresponding concentrations (mg


chemical/kg soil) are found at an abandoned pesticide formulation site: Aldicab, 140;
Captan, 86; Fonofos, 280; Malathion, 65; and Naled, 90. Select the surrogates that
account for 99% of the risk. The pesticides are considered to be non-carcinogenic and
the corresponding oral RfDs (mg/kg-day) are: Aldicab, 0.001; Captan, 0.13; Fonofos,
0.002; Malathion, 0.02; and Naled, 0.002.
1.

Rij Ri

Ci
.
RfDi

2.
Pesticide
Aldicab

Ri (days)
140,000

Rank
1

149
Captan
Fonofos
Malathion
Naled

3.

662
140,000
3,250
45,000

4
1
3
2

The two pesticides that should be selected as surrogates are Aldicab and Fonofos.
However, since the total R is 328,912, the two selected surrogates make up only
85% of the total R. Therefore, Naled must also be considered as a surrogate for
the site in oder to account for 99% of the risk.

Dose-Response Assessment. The fundamental goal of a dose-response assessment


is to obtain a mathematical relationship between the amount of a toxicant that a human
is exposed to and the risk that there will be an unhealthy response to that dose. The
dose-response relationships (or curves) are the result of chronic toxicity, i.e., the
organism is subjected to a prolonged exposure over a considerable fraction of its life. As
a result, the abscissa is the dose, which is usually expressed as the average milligrams of
substance per kg of body weight per day (mg/kg-day) as opposed to the unit of dose (i.e.,
mg/kg) used in acute toxicity assessments. The dose is an exposure averaged over an
entire lifetime (70 years for humans). The ordinate is the response, which is the risk (or
probability) that there will be some adverse health effects. Therefore, response has no
units. For instance, if prolonged exposure to a chemical would be expected to produce
700 cancers in a population of 1 million, the response could be expressed as 0.0007, or
0.07%. The annual risk would be obtained by spreading that risk over an assumed 70year lifetime, yielding a risk of 0.00001, or 110-5 per year. For carcinogens, it is always
assumed that exposure to any amount of the carcinogen will create some likelihood of
cancer, i.e., a plot of response versus dose is required to go through the origin. For noncarcinogens, it is usually assumed that there is some threshold dose, below which there
will be no response. Therefore, the dose-response curves and the methods used to apply
them are quite different for carcinogenic and non-carcinogenic effects.
The most controversial aspect of dose-response curves for carcinogens is the method
chosen to extrapolate from the high doses actually administered to test animals to the
low doses to which humans are likely to be exposed. Even with extremely large
of test animals used in a bioassay, the lowest risks that can be measured are usually a few
percent. Since regulators attempt to control human risks to several orders of magnitude
less than that, there will be no actual animal data anywhere near the range of most
interest. One model, the one-hit model, is commonly used for the extrapolation to low
doses. In the one-hit model, the relationship between the dose (d) and the lifetime risk
(probability) of cancer, P(d), is given as:

P(d ) 1 e ( q0 q1d )
P(0) 1 e q0

(VI.2)

where P(d) is the rate of cancer incidence at the d, %; P(0) is the background rate of
cancer incidence, %; and q0 and q1 are parameters. Now, for small x,

x 2 x3
e 1 x ... 1 x
2! 3!
x

Therefore, for small q0 and q1, P(0) 1 (1 q0) = q0 and

(VI.3)

150

P(d ) 1 (1 q0 q1d ) q0 q1d P(0) q1d P(d ) P(0) A(d ) q1d

(VI.4)

where A(d) is the upper-bound, additional (or incremental) lifetime risk, %. The one-hit
model predicts that for low doses, the additional lifetime probability of cancer is linearly
related to dose. Another model, the multi-stage model, is based on the observation that
tumors are the result of a sequence of biological events:

P(d ) 1 e

qi d i
i 0

(VI.5)

where the individual parameter qi are positive constants picked to best fit the doseresponse data. However, at low doses, the multi-stage model also has the feature of
producing a linear relationship between additional risk and dose.
Potency Factor (PF) or Slope Factor (SF). For chronic toxicity studies, a low dose is
administered over a significant portion of the animals lifetime. The resulting doseresponse curve has the incremental risk of cancer (above the background rate) on the yaxis and the lifetime average daily dose of toxicant along the x-axis. At low doses, where
the dose-response curve is assumed to be linear, the slope of the dose-response curve is
called the potency factor (PF), or slope factor (SF):

SF

A(d )
d

ADI
d CDI
BW

(VI.6)

where ADI is the average daily intake of the chemical, mg/day; and BW is the average
body weight, kg.
Example VI.2. When drinking water is disinfected with chlorine an undesirable
byproduct, chloroform (CHCl3), is formed. Suppose a 70-kg person drinks 2 L of water
every day for 70 years with a chloroform concentration of 0.10 mg/L (the drinking water
standard). (1) Find the upper-bound cancer risk for this individual, A(d). (2) For a city
with 500,000 people (70-year lifetime) drinking the same water, how many extra cancer
per year would be expected? (3) Compare the extra cancers per year caused by
chloroform in the drinking water with the expected number of cancer deaths from all
causes (i.e., 193 per 100,000 per year in the U.S.). The SF (oral route) of chloroform is
6.110-3 kgday/mg.
1.1.
1.2.

2.

(2)(0.1)
= 0.00286 mg/kg-day.
70
A(d ) (SF )(d ) (6.1103 )(0.00286) 17.4 106. So over a 70-year period the

d CDI

upper-bound estimate of the probability that a person will get cancer from this
drinking water is about 17 in one million.
If there are 17.4 cancers per one million people over a 70-year period, then in any
given year in a population of one-half million, the number of cancers caused by

151

chloroform would be
3.

(500,000)(17.4)
= 0.12 cancers/year.
(106 )(70)

The total number of cancer deaths that would be expected in a city of 500,000
people would be
cancers/year.

(500,000)(193)
= 965 cancer deaths/year >> 0.12 new
105

In Example VI.2 it is assumed that everyone drinks 2 L of chloroform-laden water


every day for 70 years. When a risk assessment is made for exposures that do not last for
the entire lifetime, CDI needs to be redefined as follows.

CDI

(CR)( EF )( ED )(C )
( BW )( AT )

(VI.7)

where CR is the rate of contact with the contaminated medium, L/day, mg/day, or
m3/day, depending on the medium; EF is the frequency of exposure to the contaminant,
days/year; ED is the duration of exposure to the contaminant, years; BW is the average
body weight, kg; AT is the period over which the exposure is averaged, days; and C is the
average contaminant concentration during the exposure period, mg/L for a contaminant
in water, mg/mg for a contaminant in soil, and mg/m3 for an airborne contaminant.
(VI.7) can be used to calculate contaminant intake rates for representative members of
the potentially exposed population. Intake rates for each contaminant are calculated for
each potential exposure pathway. EF is given as 350 days/year for a resident, to allow
for vacations, while 250 days/year is used to estimate intake rates for a worker (i.e., 5
days/week, 50 weeks/year). The choice of 70 years for AT in cancer calculations is based
on the assumption that cancer effects are cumulative over a lifetime and that high doses
applied over a short time are equivalent to low doses spread over a longer period. Table
VI.3 summarizes parameter values used in (VI.7).
Table VI.3. Parameter Values Used in (VI.7).
Parameter
CR
EF
ED

Resident
2 L/day (drinking water)
100 mg/day (soil and dust ingestion)
30 m3/day (air inhalation)
350 days/year
Acute event duration or 30 years for
chronic effects (cancer calculations)

Worker
1 L/day (drinking water)
50 mg/day (soil and dust ingestion)
30 m3/day (air inhalation)
250 days/year
Acute event duration or 25 years for
chronic effects (cancer calculations)

BW

70 kg

70 kg

AT

Acute event duration for non-carcinogenic


effects or (365 days/year)(70 years) for
cancer calculation

Acute event duration for non-carcinogenic


effects or (365 days/year)(70 years) for
cancer calculation

Example VI.3. When chlorine is used for disinfection of drinking water, chloroform can be
produced by the reaction of chlorine with residual organics in the water. Estimate the ingestion
intake rate for non-carcinogenic and carcinogenic effects on an adult resident of a home
receiving tap water with an average chloroform concentration of 65 g/L (0.065 mg/L).

152
1. For non-carcinogenic effects, use 30 years for both ED and AT. Then,

CDI noncarcinogenic

(0.065)(2)(350)(30)
= 1.810-3 mg/kg-day.
(70)(365)(30)

2. For carcinogenic effects, use 30 years for ED and 70 years for AT. Then,

CDIcarcinogenic

(0.065)(2)(350)(30)
= 7.610-4 mg/kg-day.
(70)(365)(70)

The Reference Dose (RfD) for Non-Carcinogenic Effects. The key assumption for noncarcinogens is that there is an exposure threshold; that is, any exposure below threshold
would be expected to show no increase in adverse health effects above natural
background rates. One of the principle goals in toxicity tests is to identify and such
thresholds. Unfortunately, for the usual cases, inadequate data are available to establish
such thresholds with any degree of certainty and therefore, it is necessary to introduce a
number of assumptions and definitions. Suppose there is a precise threshold for some
particular toxicant for some particular animal species. In a program animals would be
exposed to a range of doses. Doses below the threshold would elicit no response; doses
above the threshold would produce responses. The lowest dose administered that results
in a response is referred to as the lowest-observed-effect level (LOEL) (Figure VI.4).
Conversely, the highest dose administered that does not create a response is referred to
as the no-observed-effect level (NOEL). LOELs and NOELs are further refined by noting
a distinction between effects that are adverse to health and effects that are not.
Therefore, there are also lowest-observed-adverse-effect-level (LOAEL) and
no-observed-oadverse-effect-level (NOAEL).
The reference dose, RfD, is introduced to give an indication of a level of human exposure
that is likely to be without appreciable risk. The unit of RfD is mg/kg-day average over a
The reference dose, RfD, is introduced to give an indication of a level of human exposure
that is likely to be without appreciable risk. The unit of RfD is mg/kg-day average over a
lifetime. RfD is obtained by dividing the NOAEL by a safety factor of 10 to account for
the differences in sensitivity between the most sensitive individuals (e.g., pregnant
women, babies, and the elderly) and the normal, healthy people in an exposed human
population. Another safety factor of 10 is introduced when the NOAEL is based on
animal data to be extrapolated to humans. Finally, an additional safety factor of 10 is
applied when there are no good human data and the animal data available are limited.
The Hazard Index (HI) for Non-Carcinogenic and Carcinogenic Effects. Since RfD is
established at what is intended to be a safe level for non-carcinogenic effects, well below
the level at which any adverse health effects have been observed, it makes sense to
compare the actual exposure to the RfD to see whether the actual dose is safe. The h
azard quotient (HQ) is based on that concept:

Response
Actual Threshold
RfD

NOAEL

153

0.1: Protection of sensitive population subgroups.


0.01: Extrapolation uncertainty from animal data to human populations.
0.001: Poor data quality.

Figure VI.4. Location of NOAEL and RfD does with respect to the actual
threshold on a typical dose-response curve.

HQ

(CR)( EF )( ED )(C )
( BW )( AT )( RfD )

(VI.8)

A cumulative hazard index (HI) at a contaminate site is calculated by adding the HQs for
all chemicals of concern over all potential exposure pathways. An HI

HQ 1 is
i 1

considered unacceptable level of risk for non-carcinogenic health effects. Potential


carcinogenic health effects are estimated by calculating the individual excess lifetime
cancer risk (IELCR) from the non-carcinogenic intake rate and the slope factor:

IELCR

(CR)( EF )( ED )(C )(SF )


( BW )( AT )

(VI.9)

A cumulative hazard index for a contaminate site is calculated by adding the IELCRs for
all chemicals of concern over all potential exposure pathways. An IELCR < 10-6 to 10-4
(proposed by the U.S. EPA) is considered acceptable level of risk for carcinogenic health
effects.
Example VI.4. Consider the household in Example VI.3, calculate the potential noncarcinogenic health risks associated with ingesting the tap water for an adult resident of
the house.
1.
2.

For non-carcinogenic effects, the HQ for the ingestion pathways is 1.810-3


mg/kg-day. Therefore, the chloroform concentration will not pose a significant
toxic risk to the resident of the house.
For carcinogenic effects, calculate the IELCR for the ingestion pathways:

154
IELCR = (7.610-4)(6.110-3)= 4.610-6. Since the IELCR calculated is near the
bottom of the range of potentially acceptable risk defined by the U.S. EPA, the
chloroform concentration will not pose a potential carcinogenic risk to the
resident of the house.
Table VI.4 summaries oral RfD and SF values for a variety of chemicals.
Table VI.4. Oral RfD and SF values for a variety of Chemicals.
Species

Oral RfD (mg/kg-day)

Oral SF [(mg/kg-day)-1]

Arsenic (inorganic)

3.010-4

1.5

Benzene

--

2.910-2

Benzo(a)pyrene

--

7.3

Cadmium

5.010-4

--

Chlordane

5.010-4

3.510-1

Chloroform

1.010-2

6.110-3

Chromium (VI)

3.010-3

--

1,1-Dichloroethylene

9.010-3

6.010-1

Methyl Mercury

1.010-4

--

Naphthalene

2.010-2

--

PCBs

--

1.0

2,3,7,8-TCDD (dioxin)

--

1.5105

Tetrachloroethylene

1.010-2

5.210-2

Trichloroethylene

6.010-3

1.110-2

Toluene

2.010-1

--

Vinyl Chloride

--

1.9

Residential Exposure Equations for Various Pathways (Table VI.5).

(CR )( ET )( EF )( ED )(C )
( BW )( AT )
( SA)( PC )( ED )(C )( f )
CDI
( BW )( AT )
CDI

(VI.10)

( SA)( AF )( ABS )( EF )( ED )(C )( f ' )


CDI
( BW )( AT )
where ET is the exposure time, hr/day or hr/event; SA is the skin surface area available
for contact, cm2; PC is the chemical-specific dermal permeability constant, cm/hr; f is
the volumetric conversion factor (1 L/1,000 cm3); AF is the soil-to-skin adherence factor,
mg/cm2; ABS is the absorption factor for soil contaminant (unitless); and f ' is the

155
conversion factor for soil (10-6 kg/mg). The 1st equation in (V.10) is for ingestion
(swimming), 2nd equation is for dermal contact (water), and the 3rd equation is for
dermal contact (soil). The following are some actions that increase the risk of death by
10-6:
Living 2 days in New York or Boston (air pollution/heart disease).
Living 2 months with a cigarette smoker (cancer/heart disease).
Flying 1,000 miles by jet (accident).
Living 150 years within 30 kilometers of a nuclear power plant (cancer caused by
radiation).
Table VI.5. Parameter Values Used in (VI.10).
Parameter

Average Body Weight (a)

Average Body Weight (c)


0 to 1.5 years
1.5 to 5 years
5 to 12 years
Daily Water Ingested (a)
Daily Water Ingested (c)

Standard Value

Parameter

Standard Value

70 kg

Skin Surface Available (c)


2 to 6 years (m, f)
6 to 9 years (m, f)
9 to 12 years (m, f)
12 to 15 years (m, f)
15 to 18 years (m)
15 to 18 years (f )

10 kg
14 kg
26 kg

Soil Ingestion Rate (c,1 to 6 years)

200 mg/day

Soil Ingestion Rate (c, > 6 years)


Skin Adherence Factor (potting soil to
hands)
Skin Adherence Factor (kaoline clay to
hands)

100 mg/day
1.45 mg/cm2

2L
1L

Daily Air Breathed (a)

20 m3

Daily Air Breathed (c)

5 m3

Daily Fish Consumed (a)

6.5 g

Contact Rate (swimming)

50 m3/hr

Skin Surface Available (a, m)

1.94 m2

0.72 m2
0.925 m2
1.16 m2
1.49 m2
1.75 m2
1.60 m2

2.77 mg/cm2

Exposure Duration
Lifetime
At one Residence (90th percentile)
National Medium
Average time

70 years
30 years
5 years
365(ED)

Exposure Frequency
Swimming
Eating Fish & Shell Fish

7 days/year
48 days/year

Exposure Time
Shower (90th percentile)
shower (50th percentile)

12 minutes
7 minutes

Skin Surface Available (a, f)


1.69 m2
a: adult, c: child, m: male, and f: female.

Example VI.5. The average daily consumption of locally caught fish by an individual
in the U.S. is estimated be about 54 g. Estimate the lifetime cancer risk from fish taken
from waters containing 0.1 mg/L (100 ppb) of TCE.
1.
2.
3.

The BCF for TCE is 10.6 L/kg.


Therefore, Cfish = (10.6 L/kg)(0.1 mg/L) = 1.06 mg TCE/kg fish.
For a 70-kg person consuming 54 g fish perday, 350 days per year for 30 years,
the chronic daily intake (CDI) can be estimated from (VI.7), i.e.,

156

CDI
4.

(CR)( EF )( ED )(C )
(54 103 )(350)(30)(1.06)
=
= 3.3610-4 mg/kg-day.
(70)(365)(70)
( BW )( AT )

The oral SF for TCE is 1.110-2 (mg/kg-day)-1. Therefore, the upper-bound,


incremental lifetime risk is: A(d) =
(3.3610-4 mg/kg-day)[1.110-2 (mg/kg-day)-1] = 3.610-6.

Exposure Assessment. Once the exposure pathways have been analyzed, an estimate
of the concentrations of toxicants in the air, soil, and food at a particular exposure point
can be made. Then, human contacts with those contaminants must be estimated.
Necessary information includes number of people exposed, duration of exposure, and
amounts of contaminated air, water food, and soil that find their ways into each exposed
persons body. One potential important exposure route is human consumption of
contaminated fish. It is relatively straightforward to estimate the concentrations of
contaminants in water, and it also is reasonable to make estimates of consumption of
fish that individual may consume. However, it is necessary to establish a ling that
permits the estimation of the concentration of a contaminant in fish based on the
contaminant concentration in water. The bioconcentration factor (BCF) is the key link
(Table VI.6).
Table VI.6. Bioconcentration Factors.
Chemical
Aldrin
Arsenic and Compounds
Benzene
Cadmium and Compounds
Carbon Tetrachloride
Chlordane
Chloroform
Chromium III, VI, and Compounds
Copper
DDE
DDT
1,1-Dichloroethylene
Dieldrin
Formaldehyde
Heptachlor
Hexchloroethane
Nickel and Compounds
PCBs
2,3,7,8-TCDD (Dioxin)
Tetrachloroethylene
1,1,1-Trichloroethane
Trichloroethylene (TCE)
Vinyl Chloride

BCF (L/kg)
28
44
5.2
81
19
14,000
3.75
16
200
51,000
54,000
5.6
4,760
0
15,700
87
47
100,000
5,000
31
5.6
10.6
1.17

Cfish can be estimated from the chemical concentration in water (Cwater) via BCF as:

C fish ( BCF )(Cwater )

(VI.11)

Contaminant Degradation. Many toxic chemicals of concern are reactive (i.e., non-

157
conservative) and they degrade with time. Degradation may be result of many processes
such as phase transfer as a chemical volatilizes; chemical transformations if it reacts
with other substances (e.g., with water, hydrolysis, or with light, photolysis); or
transformations mediated by biological activities. The persistence of chemical as it
moves through various environmental compartments may be affected by some
combination of these mechanisms. A convenient way to deal with such complexity is
simply to combine the various degradation processes into a single, overall half-life (t0.5).
Since most degradation reactions occurring in the environment can be modeled as firstorder reactions, then

C (t ) C (0)e kt
0.5C (0) C (0)e kt0.5
t0.5

(VI.12)

ln( 2) 0.693

k
k

Table VI.7. summarizes t0.5 values for a variety of chemicals.


Table VI.7. Half-Life (t0.5) Values for a Variety of Chemicals.
Chemical
Benzene
Benzo(a)pyrene
Carbon Tetrachloride
Chlordane
Chloroform
DDT
1,1-Dichloroethane
Formaldehyde
Heptachlor
Hexchloroethane
PCBs
2,3,7,8-TCDD (Dioxin)
1,1,1-Trichloroethane
Trichloroethylene (TCE)
Vinyl Chloride

t0.5 (days)
6 (air), 1 to 6 (surface water)
1 to 6 (air), 0.4 (surface water)
8,030 (air), 0.3 to 300 (surface water)
40 (air), 420 to 500 (surface water)
80 (air), 0.3 to 30 (surface water)
56 to 110 (surface water)
45 (air), 1 to 5 (surface water)
0.8 (air), 0.9 to 3.5 (surface water)
40 (air), 0.9 (surface water)
7,900 (air), 1.1 to 9.5 (surface water)
58 (air), 2 to 12.9 (surface water)
365 to 730 (surface water)
803 to 1,752 (air), 0.14 to 7 (surface water)
3.7 (air), 1 to 90 (surface water)
1.2 (air), 1 to 5 (surface water)

Example VI.6. An underground storage tank (UST) has been leaking for many years,
contaminating the groundwater and yielding a contaminant concentration directly
beneath the site of 0.30 mg/L. The contaminant is flowing at a rate of 0.5 m/day toward
to public drinking water well 1 km away. The half-life of the contaminant is 10 years. (1)
Estimate the steady-state contaminant concentration at the well. (2) If the slope factor
of the contaminant is 0.02 (mg/kg-day)-1, estimate A(d) if a 70-kg person drinks 2 L of
this water per day for 10 years.

1,000
= 2,000 days.
0.5

1.1.

The time required to travel from the site to the well is:

1.2.

Assuming a first-order degradation for the contaminant, then

158
k

0.693
0.693
= 1.910-4 day-1.

t0.5
(10)(365)
*

4 )( 2, 000)

1.3.

Assuming a plug-flow situation, then Cwell Csiteekt 0.3e(1.910


0.205 mg/L.

2.1.

Now, CDI

2.2.

Therefore, The upper-bound, incremental lifetime cancer risk, A(d), is:


A(d ) (CDI )(SF ) (8.4 104 )(0.02) 1.710-5.

(0.205)(2)(10)(365)
= 8.410-4 mg/kg-day.
(70)(365)(70)

Example VI.7. Chemicals in the environment may undergo natural degradations (i.e.,
biodegradation, photolysis, etc.). Sometimes degradation products may be more
harmful than parent chemicals. For instance, NO is a constituent in the flue gas streams
produced from coal-burning power plants. In the presence of UV, NO reacts with oxygen
and forms NO2. NO does not have adverse health effects under the normal atmospheric
concentrations, however, NO2 causes lung irritation, bronchitis, pneumonia, and
respiratory infections.

N 2 O2

2 NO
h
2 NO O2
2 NO2

Another example is 1,1,1-trichloroethane which is a common solvent (one of least toxic to


humans) used in metal and electronic industries. When 1,1,1-trichloroethane is released
into the an anaerobic environment, it is first degraded via an abiotic reaction step to
form C2H2Cl2, which is then biologically degraded to form vinyl chloride (C2H3Cl), a
carcinogen.
Abiotic
C 2 H 3Cl3
C 2 H 2 Cl 2 H Cl

C 2 H 2 Cl 2 H 2e Biotic

C 2 H 3Cl Cl
Risk Characterization. The final step in risk assessment is to bring the various
studies together into an overall risk characterization. In a simple sense, this step could
be interpreted to mean simply multiplying the exposure (dose, or CDI) by the potency
(i.e., RfD-1 for non-carcinogens and SF for carcinogens) to get individual risk, and then
multiplying that by the number of people exposed to get an estimate of overall risk to
some specific population. While there are obvious advantages to presenting a simple,
single number for extra cancers, or some other risk measures, a proper characterization
of risk should be much more comprehensive. The final expressions of risk derived in this
final step will be used by regulatory decision makers in the process of weighing health
risks against other societal costs and benefits, and the public will use them to decide on
the adequacy of proposed measures to manage the risks. Both groups need to appreciate
the extraordinary leaps of faith that, by necessity, have had to be used to determine these
simple quantitative estimates. Always remember that these estimates are preliminary,
subject to change, and extremely uncertain. A number of questions suggested by the
National Academy of Sciences should be addressed in a final characterization of risk:
1.
2.

What are the statistical uncertainties in estimating the extent of health effects?
What are the biological uncertainties? What are their origins? How will they be
estimated? What effects do they have on quantitative estimates? How will the

159
uncertainties be described to regulatory decision makers?
What dose-response assessments and exposure measurements should be used?
Which population groups should be the primary targets for protection, and which
provide the most meaningful expression of the health risk?

3.
4.

15 most common groundwater contaminants detected at national


superfund sites.
Rank

Contaminant

Common Sources

Trichloroethylene

Lead

Tetrachloroethylene

Benzene

Gasoline, manufacturing

Toluene

Gasoline, manufacturing

Chromium

Methylene Chloride

Zinc

1,1,1-Trichloroethane

10

Arsenic

11

Chloroform

12

1,1-Dichloroethane

13

Trans-1,2-Dichloroethene

14

Cadmium

15

Manganese

Dry cleaning, metal degreasing


Gasoline (before 1975), mining, pipes, manufacturing
Dry cleaning, metal degreasing

Metal plating
Degreasing, solvents, paint removal
Manufacturing, mining
Metal and plastic cleaning
Manufacturing, mining
Solvents
Degreasing, solvents
Degradation product of trichloroethylene
Mining, plating
Manufacturing, mining

Hazardous Waste Generator Classifications.


Small Quantity
Generators (SQGs)

Quantity

On-Site Storage
Time (days)

100-1,000 kg of
hazardous waste per
month and
< 1 kg of acutely
hazardous waste per
month.
180-270

Large Quantity
Generators (LQGs)
> 1,000 kg of hazardous
waste per month or
> 1 kg of acutely
hazardous waste per
month.

< 90

Conditionally
Exempt (SQGs)
< 100 kg of hazardous
waste per month and
< 1 kg of acutely
hazardous waste per
month.

180-270

Analysis of Hazardous Waste Problems.


Variables

Hypothesis to be Tested

160

Sources

Pathways

Receptors

Contaminants
Concentrations
Time
Locations
Media
Rate of migration
Time
Loss and gain functions
Types
Sensitivities
Time
Concentrations
Numbers

Source exists
Source can be contained
Source can be removed and disposed
Source can be treated
Pathway exists
Pathway can be interrupted
Pathway can be eliminated
Receptor is not impacted by migration of
contaminants
Receptor can be relocated
Institutional control can be applied
Receptor can be protected

VII. ENVIRONMENTAL FATE MODELING


The understanding of the behavior of chemicals (primarily organic chemicals) in the

161
biosphere of air, water, soil, sediments, and the diversity of biota is vital to the
preservation and protection of the multimedia environment. The chemicals behave in
accordance with the laws of nature which dictate chemical partitioning tendencies and
rates of transport and transformation. Most fundamentally, the chemicals are subject to
the laws of conservation of mass, or the mass balance. Mathematical modeling
provides a framework in which the fate of chemicals in real environments can be
accurately and conveniently accounted for using the mathematical techniques with
different levels of difficulty.
The concept of fugacity, which was introduced by G.N. Lewis in 1901 as a criterion of
equilibrium, has proven to be a very convenient and elegant method of calculating
multimedia equilibrium partitioning. The fugacity approach of environmental fate
modeling requires that the environment be divided into a number of interconnected
abiotic and biotic compartments. The simplest is a simple 4-compartment system which
is easily understood and illustrates the general principles which are applied in
multimedia calculations. A more complex 8-compartment system is more representative
of real environments, and is correspondingly more demanding of data, and lead to more
lengthy calculations.
ATMOSPHERE.
Air. The layer of the atmosphere which is in most intimate contact with the surface of
the earth is the troposphere, which extends to a height of about 10 km. The temperature,
density, and pressure of the atmosphere fall steadily with increasing height, which is a
nuisance in subsequent calculations. If a uniform density is assumed at atmospheric
pressure, then the entire troposphere can be viewed as being compressed into a height of
about 6 km. Exchange of matter from the troposphere through the tropopause to the
stratosphere is a relatively slow process and is rarely important in environmental
calculations. If the environmental model is concerned with a localized situation, for
example, a state, province, or metropolitan region, it is unlikely that most pollutants
would manage to penetrate higher than about 1,000 to 2,000 m during the time the air
resides over the region. It may therefore be appropriate to reduce the height of the
atmosphere to 1,000 to 2,000 m in such cases. In extreme cases, for example over
small ponds or fields, the accessible mixed height of the atmosphere may be as low as 10
m. Therefore, the evaluative air volume is (1,000 m)(1,000 m)(6,000 m) = 6109 m3.
Aerosol. The atmosphere contains a considerable amount of particular matter or
aerosols which are important in determining the fate of certain chemicals. These
particles may range from water in the form of fog or cloud droplets to dust particles from
soil and smoke from combustion. The concentration of these particles is normally
reported in g/m3. A rural area may have a concentration of about 5 g/m3, and a fairly
polluted urban area a concentration of 100 g/m3. If it is assumed that the particles
have a density of 1.5 g/cm3 and are present at a concentration of 30 g/m3, then in an
evaluative air volume of 6109 m3, there is thus 0.12 m3 (or 120 L) of solid material.
Deposition Processes. The aerosol material has a very large specific surface area and
therefore absorbs, or adsorbs many pollutants, especially those of very low vapor
pressure such as the PCBs or polyaromatic hydrocarbons (PAHs). The chemicals
associated with aerosol particles are subject to two important deposition processes: dry
deposition and wet deposition. In dry deposition the aerosol particles can be regarded as
falling under the influence of gravity to the earths surface. The falling velocity (or

162
deposition velocity) is quite slow and depends on the conditions of atmosphere, the sizes
and properties of aerosol particles, and the nature of the ground surface, but a typical
velocity is about 0.3 cm/s or 10.8 m/h. The result is deposition of (10.8 m/h)[210-11
(volume fraction)](106 m2) or 0.00026 m3/hr or 1.89 m3/yr. The aerosol particles may
be scavenged or swept out of the air by wet deposition with rain drops. As it falls, each
rain drop sweeps through a volume of air about 200,000 times its volume prior to
landing on the land or water surface. It thus has the potential to remove a considerable
amount of aerosol particles from the atmosphere. Rain is, therefore, often highly
contaminated with substances such as PCBs and PAHs. Typical rainfall rates lie in the
range 0.3 to 1 m/yr. If a value of 0.8 m/yr is adopted, then the wet deposition rate is
(0.8 m/yr)(200,000)[210-11 (volume fraction)](106 m2) or 0.00044 m3/hr or 3.20
m3/yr. In the 4-compartment evaluative environment aerosols are ignored, but they are
included in the 8-compartment version.
HYDROSPHERE.
Water. Since 70% of the earths surface is covered by water, the area of water in the
evaluative environments is taken as 700,000 m2. Similarly to the atmosphere, only
near-surface water is accessible to pollutants in the short term. In the oceans, this depth
is about 100 m, but since most situations of environmental interest involve fresh or
estuarine water, it is more appropriate to use a shallower water depth of perhaps 10 m.
This yields a water volume of 7106 m3. If the aim is to mimic the proportions of water
and soil in a political jurisdiction, such as a state or province, the area of water will
normally be considerably reduced to perhaps 15% of the total, giving a volume of about
106 m3.
Water is normally treated as being pure, i.e., containing no dissolved electrolytes, but it
does contain suspended particles or suspended solids (SS). Particular matter in the
water plays a key role in influencing the behavior of chemicals. A very clear water may
have a concentration of particles as low as 1 g/m3, or 1 mg/L. In most cases, the
concentration is higher, in the range of 5 to 20 mg/L. Very turbid, muddy water may
contain over 100 mg/L. Assuming a concentration of 7.5 mg/L and a density of 1.5
g/cm3 gives a volume fraction of particles of about 510-6. Therefore, in the 7106 m3 of
water, there are 35 m3 of particles (or SS).
The particular matter in the water consists of a wide variety of materials. It contains
mineral matter which may be clay or silica in nature. It also contains dead or detrital
organic matter which is often referred to as humin, humic acids, and fulvic acids or,
more vaguely, as organic matter (OM). Typically OM contains 50 to 60% organic carbon
(OC). For convenience, OM = 0.5OC, and the densities for both OM and OC are equal to
that of water. The organic materials in the suspended phases are of great importance
because they have a high sorptive capacity for organic chemicals. It is therefore common
to assign an OC content to these particular phases. In a fairly productive lake the OM
content of particles may be as high as 50%, but for illustrative purposes a figure of 35%
for OM or 16.6% OC is convenient.
Fish and Aquatic Biota. Fish are of particular interest because they are of
commercial and recreational importance to users of water, and they tend to
bioconcentrate or bioaccumulate metals and organic chemicals from water. For
illustrative purposes, it is assumed that all the materials in the water are fish and the
total concentration is about 1 part per million by volume, yielding a volume of fish of

163
about 7 m3. In summary, the water thus consists of 7106 m3 of water, containing 35 m3
of particulate matter and 7 m3 of fish or biota.
Deposition Processes. The particular matter in water is important because, like
aerosols in the atmosphere, it serves as a vehicle for the transport of chemicals from the
bulk of the water to the bottom sediments. Hydrophobic substances tend to partition
appreciably onto suspended particles, and are thus subject to fairly rapid deposition.
This deposition velocity is typically 0.5 to 2.0 m/d or 0.02 to 0.08 m/h. This velocity is
sufficient to cause removal of most of suspended matter from most lakes during the
course of a year. Assuming a figure of 510-6 m3 particles per m3 of water and a
deposition velocity of 200 m/yr, the deposition rate will be 0.001 m3 particles per m2 of
sediment area per year, or for an area of 7105 m2, a flow of 700 m3/yr.
BOTTOM SEDIMENTS. The bottom sediments typically consist of 95% water and 5%
particles, and are often highly organic in nature. The bottom sediments may consist of
deposited particles and fecal matter from the water column. They are stirred by
currents, and by the action of the various biota present in this benthic region. The
sediments become more consolidated at greater depths, and the water content tends to
drop toward 50%. The top few centimeters of sediment are occupied by burrowing
organisms which feed on the organic matter and on each other, and generally turn over
(bioturbate) this entire active layer of sediment. Depending on the conditions of the
water column above, this layer may be oxygenated (aerobic or oxic) or depleted of
oxygen (anaerobic or anoxic). This has profound implications on the fate of inorganic
substances such as metals and arsenic but it is relatively unimportant for organic
chemicals, except in that the oxygen status influences the nature of the microbial
community, which in turn influences the availability of metabolic pathways for chemical
degradation. Most of the activity occurs in the top 5 cm of the sediment.
Chemicals present in sediments are primarily removed by degradation, burial, or
resuspension and diffusion back to the water column. For illustrative purposes, a
sediment depth of 3 cm is adopted and the sediment consists of 63% water and 37%
solids by volume. These solids consist of about 10% OM or 5% OC. Living creatures are
included in these figures. It is now possible to assemble an approximate mass balance
for the sediment mineral matter (MM), organic matter (OM), and the organic carbon
(OC). On a 1 m2 basis, the deposition rate may be 0.001 m2/year, or 1,000 cm3/year,
which with a particle density of 1.5 g/cm3 corresponds to a deposition rate of 1,500
g/year (500 g OM and 1,000 g MM). If 40% is resuspended (i.e., 200 g OM and 400 g
MM), then 300 g OM will remain in bottom sediments. Of the remaining 300 g OM, it is
assumed that 233 g is degraded to CO2 and 67 g is buried along with the remaining 600 g
of MM, then the total burial is 667g, which consists of 600 g or 300 cm3 of MM and 67
cm3 of OM (i.e., 10% OM by mass or 18% OM by volume). The total volumetric burial
rate of solids is 367 cm3/year. Now associated with these solids is 633 cm3 of pore water
and therefore, the total volumetric burial rate of solids plus water is approximately 1,000

cm3/year, corresponding to a rise in the sediment-water interface of 1 mm/year. The


percentage of OC in the depositing and resuspending material is 17% while in the buried
material it is 5%. The bottom sediment bulk density, including pore water, is thus 1,300
kg/m3. On a 7105 m2 basis the deposition rate is 700 m3/year, resuspension is 280
m3/year, burial is 257 m3/year, and degradation accounts for the remaining 163 m3/year.
SOIL. A typical soil may consist of 50% solid matter, 20% air, and 30% water, by
volume. The solid matter may consist of about 2% OC or 4% OM. During and after

164
rainfall, water flows vertically downward through the soil and may carry chemicals with
it. During periods of dry weather, water often returns to the surface by capillary action,
again moving the chemicals.
For illustrative purposes, the soil covers an area of 1,000 m by 300 m by 15 cm deep,
which is about the depth to which agricultural soils are plowed. This yields a volume of
45,000 m3. The soil consists of about 50% solids of 4% OM content, or 2% OC by mass.
The porosity of the soil, or void space, is 50%, and consists of 20% air and 30% water.
Assuming a density of the soil solids of 2,400 kg/m3and water of 1,000 kg/m3 gives
masses of 1,200 kg solids and 300 kg water per m3, totaling 1,500 kg, corresponding to
a bulk density of 1,500 kg/m3. Rainwater falls on this soil at a rate of 0.8 m/year. Of
this, perhaps 0.3 m evaporates, 0.3 m runs off, and 0.2 m percolates to depths and
contributes to groundwater flow. This results in water flows of 90,000 m3/year by
evaporation, 90,000 m3/year by runoff, and 60,000 m3/year by percolation to depths,
totaling 240,000 m3/year.
Terrestrial Biota or Plants. Amounts of biomass per m2 vary continuously from zero
in deserts to massive quantities which greatly exceed soil volumes in tropical rain forests.
They also vary seasonally. If it is desired to include vegetation, a typical depth of plant
biomass might be 1 cm. It is convenient to regard the plants as having a volume of
3,000 m3, containing the equivalent of 1% lipid-like materials and 50% water. Plants
are ignored in the simple 4-compartment model, treating the soil as only a simple solid
phase. Figure VII.1 illustrates both 4- and 8-compartment environmental systems.
Compartment
Air
Water
Soil (50% solids, 30% water, and 20% air)
Sediment (37% solids)
Suspended Solids (S.S.)
Aerosols
Aquatic Biota
Terrestrial Biota
Area (m2)
Air-Water: 7105.
Water-Sediment: 7105.
Soil-Air: 3105.

Volume (m3)
6109
7106
4.5104
2.1104
35
0.12
7
3,000

Rain Rate
0.8 m/year or 800,000 m3/year.
560,000 m3/year water.
240,000 m3/year soil.

Sediment Deposition Rates


Deposition: 700 m3/year (solids, 17% OC).
Resuspension: 280 m3/year (solids, 17% OC).
Net Deposition or Burial: 257 m3/year (solids, 5% OC).

Density (kg/m3)
1.2
1,000
1,500
1,300
1,500
1,500
1,000
1,000

Composition
--2% OC
5% OC
16.7% OC
30 g/m3
5% lipid
1 % lipid

Aerosol Deposition Rate (total)


2.1610-4 m3/hr or 1.89 m3/year (dry).
3.6510-4 m3/hr or 3.2 m3/year (wet).

Fate of Water in Soil


Evaporation: 90,000 m3/year.
Surface Runoff: 90,000 m3/year ( water).
Percolation: 60,000 m3/year ( groundwater).
Solids Runoff: 90 m3/year (erosion).

165

Figure VII.1. 4- and 8-comparment environmental systems.


RELATING CONCENTRATION AND FUGACITY (Z VALUES). The concept of
fugacity is the tendency of a given molecular species to escape from one phase to
another. So the higher the fugacity, the lower the chemical concentration. Its units are
pressures. Fugacity is related to the chemical concentration by:

C
Z
C Zf
f

(VII.1)

where f is the fugacity, Pa; C is the chemical concentration, mol/m3; and Z is the fugacity
capacity, mol/m3-Pa. Z is analogous to a heat capacity. If two phases are in equilibrium,
then f1 = f2. A chemical is in equilibrium with several phases, if fAIR = fWATER = fSOIL =
fSEDIMENT = fBIOTA, etc. In other words, under equilibrium conditions there is one f value
which is applicable to all phases involved. The equations for calculating Z values are:

166

Z AIR
ZWATER

1
RT
1 Ce

H Pv

S K p

Z SOIL ( SEDIMENT )
Z BIOTA

B KB
H

S K p ZWATER

B K B ZWATER

(VII.2)

Z SOLUTE( pure)

V Pv
K OW
K OW ZWATER
H
6 106

RTPv

Z OCTANOL
Z AEROSOL

where R is the universal gas constant, Pa-m3/mol-K; T is the absolute temperature, oK; H
is the Henrys law constant, Pa-m3/mol; Ce is the aqueous solubility, mol/m3; Pv is the
vapor pressure, Pa; Kp is the partition coefficient, L/kg; S is the solid density, kg/L; KB is

the bioconcentration factor (BCF), L/kg; B is the biota density, kg/L; V is the solute
molar volume, m3/mol; and KOW is the octanol-water partition coefficient,
dimensionless. The following two equations are also useful for estimating relevant
coefficients in (VII.2):

ln( K OW ) 7.494 ln(Ce )


ln( K B ) 0.85 ln( K OW ) 0.70

(VII.3)

Level I Calculations. The level I calculation applies to steady-state, no-flow systems


(i.e., closed systems) in equilibrium. In these systems the fugacities are equal and
unchanging; there is no reaction, inflow, or outflow. The total amount of the material
released to the environment is given and equals M (moles). In addition, each phase
in equilibrium has a volume of Vi (m3) and a fugacity capacity Zi (i denotes the
compartment i). Moreover, the material is uniformly distributed in each phase. The
following steps can be followed to perform the level I calculation:
n

i 1

i 1

Vi Z i

M Vi C i f Vi Z i f

i 1
n

mi C iVi M mi
i 1

C i fZ i

MZ i
n

Vi Z i

i 1

(VII.4)

167
where Ci is the molar concentration of the material in the phase i, mole/m3; and mi is the
amount of the material in phase i, moles. In many cases, the concentration of the
material in the phase i is expressed as Ci'

(Ci )(MW )(1,000)

, where Ci' is the mass

concentration of the material in the phase i, g/g; MW is the molecular weight of the
material, g/mol; and i is the density of the phase i, kg/m3.
Example VII.1. Calculate the distribution of 100 moles (20 kg) of a hypothetical
chemical hypothene in the simple 6-compartment evaluative environment using the
properties below which applied at 27.5 oC. Assume organic carbon (OC) contents of 2%
and 4% in soil and sediment, respectively.

Temperature: 27.5oC (300.6oK);


Molecular Mass (MW): 200 g/mol;
Water Solubility (Ce): 20 g/m3 (0.1 mol/m3);
Vapor Pressure (Pv): 1.0 Pa (7.510-3 mm Hg or 9.910-6 atm); and
KOW: 100,000.

1.

Air-Water Partition Coefficient and Z Values.

1.1.

1.2.

KAW (Air-Water Partition Coefficient) =

1.3.

ZAIR =

1.4.
1.5.
2.

Ps
= 10 Pa-m3/mol.
Cs
H
= 0.004.
RT

1
= 4.010-4 mol/m3-Pa.
RT
1
ZWATER =
= 0.1 mol/m3-Pa.
H
0.029 101,325
A (Air Density) =
= 1.17 kg/m3 (ideal gas law).
RT
Compartmental Characteristics.
Name

Soil

Sediment

Suspended Solids

Fish

i (kg/m3)

1,500

1,500

1,500

1,000

OC or Lipid
Content fOC (g/g)

0.02

0.04

0.04

0.048

KOC or KOW

41,000

41,000

41,000

100,000

KP = fOC KOC
(or fOC KOW)

820

1,640

1,640

4,800

1,230

2,460

2,460

4,800

123

246

246

480

K PW

K P i
1,000

Zi K PW ZWATER

168

3.

KOC = 0.41KOW.

4.

The Level I calculation performed are summarized in the table shown below.

4.1.

7.24 10 6 , CG (g/m3) = Ci(molecular weight, MW), and

Vi Z i

i 1

CU
4.4.

(CG )(1,000)

Most of the compound is associated with soil and sediment (>77%), 17.4% in the
air, and 5.1% in the water. The concentrations on the g/g basis, on the other
hand, show a different picture. The negligible amount present in fish (i.e.,
0.024%) represents a concentration of 0.70 g/g, which is within a factor of 10 of
levels considered unsafe for human consumption in many cases. The sediment
could obviously act as a source of biotic contamination for a long time.

Vi (m3)
Zi (moles/m3-Pa)
ViZi (moles/Pa)
Ci = fZi
(moles/m3)
mi = CiVi (moles)
%
CG (g/m3)
i (kg/m3)
CU (g/g)

Air
6.0109
4.010-4
2.4106
2.910-9

Water
7.0106
0.1
7.0105
7.210-7

Soil
4.5104
123
5.54106
8.910-4

Sediment
2.1104
246
5.17106
1.810-3

S.S.
35
246
8,610
1.810-3

Fish
7
480
3,360
3.510-3

TOTAL
--1.381107
--

17.4
17.4
5.810-7
1.17
4.910-4

5.1
5.1
1.410-4
1,000
1.410-4

40.0
40.0
0.178
1,500
0.12

37.4
37.4
0.36
1,500
0.24

0.062
0.062
0.36
1,500
0.24

0.024
0.024
0.70
1,000
0.70

100
100
----

Level II. Calculations. The level II calculation applies to steady-state, flow systems
(i.e., open systems) in equilibrium. In these systems the fugacities are equal and
unchanging; there are significant transformations and persistence caused by reactions,
inflow, and outflow. The input of the compound concerned into the evaluative
environment is at steady state. Transformations are induced by photolysis, hydrolysis,
oxidation, biodegradation, and advection of the compound out of the region of interest.
Advection. Advection means the movement of chemical by virtue of it presence in the

medium which happens to be flowing. The rate of advection of a chemical is simply n

(mol/hr), the product of the flowrate of the advecting medium, V (m3/h) and the
concentration of chemical in the medium, C (mol/m3):

n V C

(VII.5)

If pure air and pure water contaminated only by the target chemical are the means that
carry the chemical into the evaluative environment, then the total influx of the target

chemical, ntotal , is:

169

ntotal E V A CIA V W CIW

(VII.6)

where E is the total emission rate of the chemical into the evaluative environment,
mol/h; and the subscripts A, I, and W denote air, input, and water, respectively.
Degrading Reactions. A simple first-order kinetic expression for all reactions involved
will be used. The basic rate equation is VkC (mol/hr), where k is the first-order rate
coefficient (1/hr).
Combined Advection and Reactions. In This case, the mass balance equation is:

ntotal E V A CIA V W CIW = V A C A V W CW Vi kiCi

(VII.7)

Assume a common fugacity f , then in fugacity format,

ntotal = V A C A V W CW Vi kiCi = f V A Z AIR V W ZWATER f Vi Z i ki f Dai Dri


i
i
i
i

(VII.8)
The subscripts a and r denote advection and reaction, respectively. The following steps
can be followed to perform the level II calculation:

1. Dai V A Z AIR V W ZWATER (Advection)


i

2. Dri Vi Z i ki (Reaction)
i

3. ntotal E V A CIA V W CIW = f Dai Dri (Total Influx)

4. f

ntotal
(Fugacity)
Dai Dri
i

5. Ci Zi f mi CiVi m mi
i

6. ta

V i Ci
i

7. t r

m
Vi C i k i
i

Vi Ci
i

V i Ci
i

f Vi Z i

f V i Zi
i

Vi C i
i

Vi C i k i
i

Vi Z i

V A Z AIR V A ZWATER

f Vi Z i
i

f Vi Z i k i
i

8.

1 1 1

to t a t r

Vi Z i
i

Vi Z i k i
i

Vi Z i
i

Dai
i

Vi Z i
i

D ri
i

170

where ta, tr, and to denote advection residence time, reaction residence time, and overall
residence time, respectively.
Example VII.2. Calculate the level II calculations of a hypothetical chemical
hypothene in the simple 4-compartment evaluative environment using the properties
below which applied at 27.5 oC. Assume organic carbon (OC) contents of 2% and 4% in
soil and sediment, respectively.

First-Order Rate Coefficients (1/hr): 0.001, water; 0.01, soil; 0.0001, sediment;
and 0, air.

V A = 107 m3/hr, CIA = 10-6 mol/m3, V W = 1,000 m3/hr, CIW = 0.01 mol/m3, and

E = 100 mol/hr.
Temperature = 27.5oC (300.6oK).
Molecular Weight (MW) = 200 g/mol.
Water Solubility (Cs) = 20 g/m3 (0.1 mol/m3).
Vapor Pressure (Ps) = 1.0 Pa (7.510-3 mm Hg or 9.910-6 atm).
log(KOW) = 5 (or KOW = 100,000).

Vi (m3)
Zi (moles/m3-Pa)
ViZi (moles/Pa)
ki (1/hr)
Dri = ViZiki (moles/Pa-hr)

Dai V i Z i ( moles/Pahr)
Ci (moles/m3)
mi (moles)
%

1.

Air
6.0109
4.010-4
2.4106
0
0
4,000

Water
7.0106
0.1
7.0105
0.001
700
1,000

Soil
4.5104
123
5.54106
0.01
5,540
0

Sediment
2.1104
246
5.17106
0.0001
51.7
0

4.4610-6
2.28104
57.5

1.1510-3
8,050
16.8

0.14
6,400
13.3

0.28
5,900
12.4

Reaction half life ( t0.5

0.693
, hrs): 4, air; 693, water; 69.3, soil, and 6,930,
ki

sediment.

2.

nTotal
100 10 10
f

0.0106.
Dai Dri 4,000 1,000 700 5,540 51.7

3.
4.
5.
6.

CG (g/m3): 9.210-4, air; 0.23, water; 28, soil; and 56, sediment.
CU (g/g): 0.78, air; 0.23, water; 19, soil; and 38, sediment.
m = 48,300 moles.
ta = 1,018 hrs, tr = 665 hrs, and to = 402 hrs.

171

VIII. Appendices
Prefixes Used in the SI System.
Prefix
Yotta
Zeta
Exa
Peta
Tera
Giga
Mega
Kilo
Hector
Deka
Deci
Centi
Milli
Micro
Nano
Pico
Femto
Atto
Zepto
Yocto

Symbol
Y
Z
E
P
T
G
M
K
H
Da
D
C
M

N
P
F
A
Z
Y

Multiples & Submultiples


1024
1021
1018
1015
1012
109
106
103
102
101
10-1
10-2
10-3
10-6
10-9
10-12
10-15
10-18
10-21
10-24

Common Unit Conversions and Derived SI Units.


1 = 10-10 m.
1 m = 100 cm = 3.28 ft = 39.4 in.
1 km = 1,000 m = 0.62 mi.
1 mi2 = 640 acres = 259 hectares.
1 hectare = 104 m2 = 10-2 km2 = 2.47 acres.
1 m3 = 1,000 L = 106 cm3 = 264 gal = 35.3 ft3.
1 acre-foot = 1,233.5 m3.
1 m/s = 2.24 mph (mi/hr) = 3.28 ft/s = 3.6 km/hr.
1 cm/s = 1.97 ft/min.
1 m3/hr = 0.59 cfm (ft3/min) = 6.310-3 MGD (million gallons per day).
1 MGD = 0.0438 m3/s.
1 kg = 2.2 lbm.
1 tonne (metric tone) = 1,000 kg = 1.1 ton (short tone).
1 N = 1 kgm/s2 = 105 dynes = 105 gcm/s2 = 0.225 lbf.
1 atm = 101.3 kPa = 1.013 bar = 14.7 psi = 760 mm Hg = 407 in H2O.
1 Pa = 1 N/m2.
1 J = 1 kgm2/s2 = 107 erg = 107 gcm2/s2 = 0.239 cal = 9.4810-4 Btu.
1 W = 1 J/s = 1 Nm/s = 107 kgm2/s3 = 3.41 Btu/hr = 1.3410-3 hp.
1 M = 1 mole/L, 1 N = 1 eq/L, 1% = 10-2, 1 = 10-3, 1 ppm = 10-6, 1 ppb = 10-9, and 1 ppt = 10-12.

The Gas Constant (R) (oK = 1.8oR, K: Kelvin, R: Rankine).


8.314 m3Pa/moloK
0.08314 Lbar/moloK
0.08206 Latm/moloK

62.36 Lmm Hg/moloK


0.7302 ft3atm/lb-moloR
10.73 ft3psia/lb-moloR

8.314 J/moloK
1.987 cal/moloK
1.987 Btu/lb-moloR

172

Properties of the Earth.


Surface Area
Mass
Mass of Hydrosphere
Mass of Atmosphere
Radius
Gravitational Acceleration (g)

5.11014 m2
6.01024 kg
1.41021 kg
5.31018 kg
6,370 km
9.81 m/s2

Wastewater Treatment and Management Terminologies.

Biosolids

Characteristics
Composition
Constituents
Contaminants/Pollutants
Disinfection
Impurities
Non-Point Sources
Nutrient
Parameter
Point Sources
Pollutants
Reclamation
Recycling
Re-Purification
Reuse
Sludge
Solids

Biosolids are primarily an organic, semi-solid wastewater product that


remain after solids are stabilized biologically or chemically and are
suitable for beneficial uses. Biosolids in which the pathogens (including
enteric viruses, pathogenic bacteria, and viable helminth ova) are
reduced below current detectable levels are referred to as class A
biosolids. Biosolids in which the pathogens are reduced to levels that are
unlikely to pose a threat to public health and the environment under
specific use conditions are referred to as class B biosolids. Class B
biosolids cannot be sold or given away in bags or other containers or
applied on lawns or home gardens.
General classes of wastewater constituents such as physical, chemical,
biological, or biochemical.
The makeup of wastewater, including the physical, chemical, and
biological constituents.
Individual components, elements, or biological entities such as
suspended solids or ammonia nitrogen.
Constituents added to the water supply through use.
Reduction of disease-causing microorganisms by physical or chemical
means.
Constituents added to the water supply through use.
Sources of pollution that originate from multiple sources over a relatively
large area.
An element that is essential for the growth of plants and animals.
Nutrients in wastewater, usually nitrogen and phosphorus, may cause
unwanted algal and plant growths in lakes and streams.
A measurable factor such as temperature.
Pollution loads discharged at a specific location from pipes, outfalls, and
conveyance methods from either municipal wastewater treatment plants
or industrial wastewater treatment plants.
Constituents added to the water supply through use.
Treatment of wastewater for subsequent reuse applications or the act of
reusing treated wastewater.
The reuse of treated wastewater and biosolids for beneficial purposes.
Treatment of wastewater to levels suitable for a variety of applications
including indirect or direct potable reuse.
Beneficial reuse of reclaimed or re-purified wastewater or stabilized
biosolids.
Solids removed from wastewater during treatment.
Materials removed from wastewater by gravity separation (by clarifiers,
thickeners, and lagoons) and are the solid residues from dewatering
operations.

173
Coupled, First-Order Ordinary Differential Equations (ODEs). The general
problem for two coupled, first-order ODEs can be written as follows, where
Si, Ai, Bi, and Li are constants.

dy1
L1 y1 S1 A2 y2
dt
dy2
L2 y2 S 21 A1 y1
dt
y1 (0) B1

(VIII.1)

y2 (0) B2
Rearrange the 2nd equation in (VIII.1) to solve for y1 and then substitute into the 1st
equation in (VIII.1):

d 2 y2
dy
( L1 L2 ) 2 ( L1L2 A1 A2 ) y2 A1S1 L1S 2
2
dt
dt
y2 (0) B2

(VIII.2)

dy2 (0)
S 2 A1B1 L2 B2
dt
The solution to the 1st equation in (VIII.2) is:

y2 (t ) y2,h (t ) y2, p
d 2 y 2 ,h
dy2,h

(
L

L
)
( L1L2 A1 A2 ) y2,h 0
1
2
dt 2
dt
AS LS
y2 , p 1 1 1 2
L1L2 A1 A2

(VIII.3)

The general solution to the 1st equation in (VIII.3) is:

y2,h (t ) Fe r1t Ger2t


r 2 ( L1 L2 )r ( L1L2 A1 A2 ) 0
( L1 L2 ) 1

( L1 L2 ) 2 4 A1 A2
2
2
( L1 L2 ) 1
r2

( L1 L2 ) 2 4 A1 A2
2
2
( S A1B1 ) B2 (r2 L2 ) r2 y2, p
F 2
( L1 L2 ) 2 4 A1 A2
r1

B2 (r1 L2 ) ( S 2 A1B1 ) r1 y2, p


( L1 L2 ) 2 4 A1 A2

(VIII.4)

174
A similar approach is used to solve for y1 and the result is:

y1 (t ) y1,h (t ) y1, p Her1t Je r2t y1, p


A2 S 2 L2 S1
L1L2 A1 A2

y1, p
H
J

( S1 A2 B2 ) B1 (r2 L1 ) r2 y1, p

(VIII.5)

( L1 L2 ) 2 4 A1 A2
B1 (r1 L1 ) ( S1 A2 B2 ) r1 y1, p
( L1 L2 ) 2 4 A1 A2

Example A.1. 1,00o moles/s of biogas (70% CH4 and 30% CO2) @ 25oC and 1 atm is
completely burned in a burner @ 400oC and 1 atm with 10.0% excess dry air preheated
to 100oC. The burner is divided into two chambers: a combustion chamber and a boiler
(see the attached diagram). The dry air is preheated in a preheater using the stack gas
(@ 400oC) released from the combustion chamber. The reaction heat produced in the
combustion chamber is transferred into the boiler where a liquid water stream @ 25oC
and 1 atm is heated to produce a saturated steam @ 100oC and 1 atm. Find the heat
transferred from the combustion chamber into the boiler (kW) and the mass rate at
which the saturated steam is produced (kg/s). The stoichiometric combustion equation
of CH4 is:

CH 4 ( g ) 2O2 ( g ) CO2 ( g ) 2H 2O(v)

Combustion Chamber:

1.

The specific enthalpy of a species i ( H i ) in the combustion chamber can be


calculated as:

o
H i H f

Ti
(C p )i dT
i Tr

where H f is the standard heat of formation of the species i, kJ/mol; Tr is

the reference temperature, oC (or oK); Ti is the actual temperature of the species i,
oC

(or oK) and (C p )i is the specific heat capacity of the species i at constant

pressure, kJ/mol-oC.
2.

The enthalpy table for the stack gas is constructed and shown below. 25oC is
chosen as the reference temperature.

175

1:
2:
3:
4:
5:

700 moles/s CH4 @ 25oC and 1 atm.


Dry Air (10% excess) @ 100oC and 1 atm.
Stack Gas @ 400oC and 1 atm.
Liquid Water @ 25oC and 1 atm.
Saturated Steam @ 100oC and 1 atm.

Reference States: CH4(g), CO2(g), O2(g), N2(g), and H2O(v) @ 25oC and 1 atm.

Substance
n in (moles/s)
H in (kJ/mol)
n out (moles/s)
H out (kJ/mol)

CH4(g)
--H 1 (-74.52)
n 1 (700)

CO2(g)
n 2 (300)
H 2 (-390.61)
n 5 (1,000)
H 5 (-377.16)

O2(g)
n 3 (1,540)
H 3 (2.24)
n 6 (140)
H 6 (11.72)

N2(g)
n 4 (5,793)
H 4 (2.19)
n 7 (5,793)
H 7 (11.15)

H2O(v)
--H 8 (-228.60)
n 8 (1,400)
3.

n1 (1,000)(0.7) = 700 moles/s.

n 2 (1,000)(0.3) = 300 moles/s.

n 3 (1.1)(700)(2) = 1,540 moles/s.

0.79
n 4 (1.1)(700)(2)
= 5,973 moles/s = n 7 .
0.21

176

n 5 300 (700)(1) = 1,000 moles/s.

n 6 1,540 (700)(2) = 140 moles/s.

n 8 (700)(2) = 1,400 moles/s.


4.

o
H 1 = H f

= -74.85 kJ/mol.

CH 4 ( g )

o
H 2 = H f

o
o

H
CO2 ( g ) (100 C ) H CO2 ( g ) ( 25 C ) = -393.51 + 2.90

CO2 ( g )

= -390.61 kJ/mol

o
H 3 = H f

o
o

H
O2 ( g ) (100 C ) H O2 ( g ) ( 25 C ) = 0 + 2.24

O2 ( g )

= 2.24 kJ/mol

o
H 4 = H f

o
o

H
N 2 ( g ) (100 C ) H O2 ( g ) ( 25 C ) = 0 + 2.19

N2 ( g )

= 2.19 kJ/mol.

o
H 5 = H f

o
o

H
CO2 ( g ) ( 400 C ) H CO2 ( g ) ( 25 C ) = -393.51 + 16.35

CO2 ( g )

= -377.16 kJ/mol.

o
H 6 = H f

o
o

H
O2 ( g ) ( 400 C ) H O2 ( g ) ( 25 C ) = 0 + 11.72

O2 ( g )

= 11.72 kJ/mol.

o
H 7 = H f

o
o

H
N 2 ( g ) ( 400 C ) H N 2 ( g ) ( 25 C ) = 0 + 11.15

N2 ( g )

= 11.15 kJ/mol.

o
H 8 = H f

o
o

H
H 2O ( v ) ( 400 C ) H H 2O ( v ) ( 25 C ) = -241.83 + 13.23

H 2O ( v )

= -228.60 kJ/mol.
5.

Therefore, Q H



H i n i H i = -475,517 kW (heat is taken
out i
in

out of the combustion chamber).

Boiler:

1.

The enthalpy table for water (liquid and steam) is constructed and shown below.
25oC is chosen as the reference temperature.

Reference States: H2O(l) @ 25oC and 1 atm.

177
Substance

H2O(l)

H in (kJ/kg)

H 9 (0)

--

--

m out (kg/s)

H out (kJ/kg)

--

--

m (178)

H 10 (2,676)

m (178)

H2O(v)

2.

m in (kg/s)

H 9 = 0 kJ/kg (reference).

H 10 = 2,676 kJ/kg.

Therefore, m

4.

Since the specific volume of the steam @ 100oC and 1 atm is 1.674 m3/kg, the
volumetric rate of steam produced is 106.3 m3/s.

H 10 H 9

475,517
= 178 kg/s.
2,676

3.

Example III.9. A complete-mixed anaerobic bioreactor is designed to treat an


industrial wastewater at a capacity of 1,500 m3/day. The bioreactor contents are to be
heated by the circulation of the mixed liquor through an external hot water heat
exchanger. Assuming that the following conditions apply, find the heating requirement
to maintain the bioreactor temperature at 35oC.
Concrete Bioreactor Dimensions:
- Diameter: 20 m.
- Side Depth: 6 m.
- Center Depth: 9 m.
Heat Transfer Coefficients (Uj, W/m2-oC):
- Dry Earth Embankment (entire depth): 0.7.
- Bioreactor Floor (moist earth): 0.7.
- Roof (exposed to air): 0.9.
Temperatures (oC):
- Ambient Air: -5.
- Earth (next to the wall): 0.
- Earth (below the floor): 10.
- Feed Wastewater Stream: 10.
Specific Heat Capacities (Cp, kJ/kg- oC):
- Feed Wastewater Stream/Bioreactor Contents: 4.184.
Feed COD (mg/L): 10,000.
COD Removal Efficiency (%): 80.

1.

Total Heating Requirements.


The rate of enthalpy required to bring the temperature of incoming wastewater

from 10 oC to 35oC ( H 1 ) is:

H 1 m w (C p ) w T (1,500)(1,000)(4.184)(25) = 1.569108 kJ/day.

where m w is the mass flow rate of feed waste material, kg/day; (C p ) w is the
specific heat capacity of the waste material at constant pressure, kJ/kg-oC (4.184

178
kJ/kg-oC can be used if the waste is liquid); and T is the temperature difference
between the bioreactor and feed waste material, oC.
2.

The rate of enthalpy required to maintain the bioreactor temperature at Tbioreactor

( H 2 ) is:

H 2 U j Aj (Tbioreactor T j )
j

where Uj is the overall heat transfer coefficient of the surface that is exposed to
the environmental medium j, kJ/m2-day-oC (Table 15); Aj is the heat transfer
surface area exposed to the environmental medium j, m2; and Tj is the
temperature of the environmental medium j, oC.
3.

Now, A1 (20)(6) = 377 m2 (wall area).

A2 (10) 10 2 32 = 328 m2 (floor area).


A3 (10) 2 = 314 m2 (roof area).
4.

H 2 377(0.7)(35 0) 328(0.7)(35 10) 314(0.9)(35 5)

86,400
1,000

= 2.27106 kJ/day.
5.

The heating requirement is therefore: H 1 H 2 = 1.592108 kJ/day.


Table A.1. U Values for Various Materials.

Material
Plain Concrete Walls (above ground).
Wall (thickness: 300 mm) without insulation.
Wall (thickness: 300 mm) with air space plus brick facing.
Wall (thickness: 300 mm) with insulation.
Plain Concrete Walls (below ground).
Surround by dry earth.
Surrounded by moist earth.
Plain Concrete Floors.
Floor (thickness: 300 mm) in contact with moist earth.
Floor (thickness: 300 mm) in contact with dry earth.
Floating Covers.
With 35-mm wood deck, built-up roofing, and without insulation.
With 25-mm insulating board installed under roofing.
Fixed Concrete Covers.
Cover (thickness: 100 mm) with built-up roofing, and without insulation.
Cover (thickness: 100 mm) insulated with 25-mm insulating board.
Cover (thickness: 225 mm) without insulation.
Fixed Steel Covers (thickness: 6 mm).

U (W/m2-oC)
4.7-5.1
1.8-2.4
0.6-0.8
0.6-0.7
1.1-1.4
0.6-0.7
0.3-0.4
1.8-2.0
0.9-1.0
4.-5.0
1.2-1.6
3.0-3.6
4.0-5.4