CIVI6671

FATE AND TRANSPORTATION OF CONTAMINANTS IN THE ENVIRONMENT

PROJECT REPORT
FATE AND TRANSPORT OF ARSENIC IN GANGA RIVER

Submitted By:

Submitted To:

Damandeep Singh (6888933)

Dr. Zhi Chen

Executive Summary:
It has been studied that high arsenic concentration groundwater was not related to the having
arsenic concentration in the rocks. The arsenic from the solid phase to groundwater is mobilized
by specific bio geological triggers or the mobilized arsenic has the enough duration to
accumulate and not to be flushed away that should be retained in the aquifer. In other words, the
arsenic released from the source should be fast that the groundwater flushing rate.
Transportation of arsenic due to the oxidisation of As bearing pyrites minerals. Insoluble arsenic
bearing minerals are easily oxidized when they are exposed to atmosphere by releasing the
as(III), sulfate and ferrous iron. The arsenic is occurring form soil beds and discharge into the
water and flowing in the water along the direction of flow. The motion of arsenic is due to bulk
motion of the flow called advection. The concentration of arsenic is increasing and has been
transporting to different points. The slow effects of arsenic are cancer and especially the children
are being affected by it. Arsenic is present in both organic as well as inorganic form, which also
decreases the concentration of dissolved oxygen of river. Thus, causes death of fishes. The
various surface water sources linked to Ganga water are contaminated by high concentration of
arsenic. More than the half of the wells Bengal is contaminated by arsenic having value 50-90
g/l. the various samples were taken from different points and maximum of were having
concentration more than desired value.

Introduction:
Arsenic is a chemical element occurs in many minerals mostly in conjunction with metals.
Arsenic and its compounds are poisonous and occurs in environment both naturally and due to
human activities. It exist in organic and inorganic form. But inorganic form is being generally
considered as more toxic. It can exist in nature in many different forms in combining with other
elements. Inorganic arsenic mainly exists in four forms are generally known as valency or
oxidation states. A valency measures the ability of a compound to form bond with other elements
for example Hydrogen. It can exist in four valences states -3, 0, +3 and +5. The dominants forms
of arsenic are Arsenite having valency of 3 and Arsenate having valency of 5. The elemental
arsenic itself has not any tendency of solubility in water but in combination of other element it
has a wide range of solubility depending upon the surrounding conditions.
Fate of arsenic in environment
Arsenic is getting into water due to dissolution of minerals, rocks and ores from mining wastes,
industrial outflow or effluent and atmospheric deposition. In surface water the most commonly
occurring form of Arsenic is arsenic (5). But in groundwater the arsenic (3) is the most common
form present.
Arsenic is a natural occurring material which is mostly distributed in the crust of the earth. It
occurs in nature in natural states one is yellow and other is gray. Arsenic is present in
environment in more than 200 mineral spices and among them the most common is arsenopyrite.
It has been estimated that approximately one third of the atmospheric flux of arsenic is due to
nature. It is also estimated that volcanic action is the most important natural source of arsenic in
environment. It is founded there is increase in concentration of dissolved arsenic in water due to
increase in pH.

 Forms of Arsenic:
Inorganic Arsenic of geological region is to be found in groundwater and in several parts of the
world it is uses as a drinking purposes. Inorganic Arsenic forms oxides which are colorless and
easily soluble in water and after which forma acid solutions. In case of inorganic is mainly
bounded with oxygen, sulfur and chlorine
Organic Arsenic is mainly found in marine organisms like fishes in the form of
tetramethylarsonium, arsenocholine and arsenobetaine and are also found in some terrestrial
species. In case of organic it combines with hydrogen and carbon and thus forms organic
compounds in animals and plants.

Compound
Arsenic

Molecular formula
As

Arsenic sulfide

As2S3

Arsenic trioxide

As2O3

Arsenic pentoxide

As2O5

Dimethylarsinic acid (DMA)

(CH3)2AsO(OH)

Monomethylarsonic acid (MMA

(CH3)AsO(OH)2

Potassium arsenate
Lead arsenate

PbHAsO4
PbHAsO4

Potassium arsenite

KAsO2HAsO2

Potassium arsenate

KH2AsO4

 Production of Arsenic
Burning of fossil fuel, mining, smelting of non-ferrous metals are the major industrial process
which contribute arsenic contamination air, water and soil. It is evident that uses of arsenic in
pesticides that have contaminated the agricultural lands. The use of arsenic in preservation of
timber causes ground water contamination. The major natural source of transportation of arsenic
in water are wind and soil erosion.
The major modes of biotransformation of arsenic are redox transformation between arsenic and
arsenate, biosynthesis of organic arsenic compounds and methylation and reduction of arsenic.
Elemental arsenic is by reduction of arsenic trioxide with charcoal. It has been estimated that the
most of the production of arsenic nearly used in three different areas.

The 70% is uses for timber treatment copper chromate arsenate (CCA),
The 22% of the total is in agriculture purposes such as pesticides to improve the soil quality and

feed additive in poultry to increase feed efficiency.

The remaining 8% is in others such as weathering of arsenic containing minerals and ores, use in
medicines, in industrial uses of arsenic include doping of solid state devices, bronzing and laser
material.
However, this is not the problem because this can be monitored and controlled. But it is
dangerous when the arsenic gets into the groundwater and make it poisonous and unfit for
drinking.

 Effects of Arsenic
Arsenic toxicity is the global problem that is affecting millions of the humans. The arsenic
contamination is caused from natural geological sources for example leachate means leaching of
arsenic through leaching into the unconfined aquifer. It is produced from mining and others
various industrial processes. The intense arsenic poisoning initially causes the vomiting,
diarrhea, nausea.

Objectives:
Millions of acres of basin containing arsenic in surface and subsurface water have been identified
in Ganga River. Long time has been spending on testing and other various methods to calculate
the arsenic concentration in water. To, successfully model the fate and transportation of arsenic
in Ganga River, three factors- advection, adsorption and fugacity has been calculated to know the
fate of arsenic in Ganga River. By advection, the flux in the direction of flow is calculated. The
adsorption is calculated to know the concentration of arsenic that has been adsorbed on the
surfaces of sediments. The method of fugacity is calculated to calculate how adsorbent easily
dissolve the contaminant. The overall objective of this project is to develop models to support
the fate of arsenic by usage of hypothetical and actual sample values. The Ganga River has many
other toxic and harmful contaminants in it but arsenic shows slow and longtime effects of it that
a person suffers throughout the life so it is necessary to know what the fate of arsenic in river is
and how it transports in river in various other places. The aquatic life is also under danger of the
arsenic which has indirectly been consumed by the society through fishes as food.
To calculate the advection means its direction of flow by the mean of bulk motion of River water.
To find the absorbed concentration of arsenic on absorbate
To calculate the fugacity capacity and the concentration in air, water and fishes.

Case study:

 Affected media (The Ganga River)

In the culture of India Ganga has a unique position. From times the River is consider as devotion
and worship but due to disposal of waste that has been contaminating day by day. As Ganga
water all over the world because of its holy water and which are known for its curative water.
However, it also a big life- support system for Indians. This has a great importance because
37 percent density of population is inhibited on Ganga basin.
47 percent of the total irrigated area in India is located in the basin of Ganga.
The river Ganga is a trans-boundary river between two countries India and Bangladesh. It flows
from state Uttarakhand and flows south and then through east continue to flow through Bay of
Bengal. The Ganga is the third largest River in all around the world in case of discharge.
This river is the sacred believes in Hindu religion who worship her as a god. But on the other
dark side it was given a rank of third most polluted river in all around the world in 2007.
The adverse effects are not only influence the human but also the aquatic life under the water.
Because of the contaminants and discharge of waste make it polluted. It is recorded that more
than 140 species and some are under the endangered category, for example Ganga river dolphins.
The has been seen that the most of the steps were taken to clean it but all have been failure due to
the lack of planning, technical methods and lack of support from religion authorities.
Ganga is extreme polluted river and cause pollution to the nearby living people. The sewage is
being discharged from many cities along with municipal waste the industrial waste is also being
discharged without treated them. The problem is increasing day by day because many people are
dependent upon Ganga river water to fulfill their requirements. They use Ganga water for
purposes like washing cooking bathing and many other purposes.

Length of Ganga River

2,525km

Basin

1,080,000 km2

Discharge

12,500m3/s

Maximum discharge

70,000 m3/s

Minimum discharge

2,000 m3/s

The natural concentration of arsenic in soil is approximately in a value below 10mg/kg. Arsenic
contamination in ground water and its consequences are firstly observed in 1983 when 63
patients from 3 villages has been identified. But at present time 3000 villages are affected by
arsenic and many are being affected by it. The total area of nine districts is 38865 kilometer
square and 4.3 million respectively.
A medical survey conducted where 95000 people were clinically examined from the areas which
are arsenic affected and 10100 people (9.4% including 2% children) were founded arsenic skin
lesions. Among them at least 100 cancer and few hundreds were suffering from Bowens disease.
A test was performed where 35000 water samples were taken from arsenic affected villages
among them 85% samples were having arsenic more than permissible range by WHO I.e. 50
microgram per liter.
However, it can arise major disorders when it gets into groundwater. The worst case in Ganga
River where Arsenic has acute effects in groundwater. Arsenic rich groundwater mainly occurs in
Bengal Delta Plain, covering the state of West Bengal the other adjoining country like
Bangladesh and also extending to other states of India like Jharkhand, Bihar, Assam, Uttar
Pradesh and other Northeastern states of India. The Ganga-Brahmaputra river basin is the 13 th
largest river basin in the world. It has an annual run-off of about 1400 billion cubic meter. In
West- Bengal, Arsenic contamination water supplies was first detected.

The effects of Arsenic on human health is a serious concern through the worldwide. Arsenic in
groundwater and its collection in plants and animals has a menacing proportion in west Bengal in

India. It was founded in various researches that the children are mostly affected by Arsenic
polluted groundwater. The symptoms found in their bodies are spotted melanosis, spotted
keratosis and defuse melanosis on feet, palm and other parts of body. Long term exposure to
Arsenic can also cause cancer and disturbance in nervous system and person can lead to death.
The World Health Organization (WHO) has proclaimed that if a person starts drinking pure water
in place of Arsenic contaminated water, he can bring back to a good health by removing or
flushing then Arsenic from the body. Arsenic in groundwater above the permissible limit i.e.
0.05mg/lt (WHO maximum permissible limit) has been found in six districts in West Bengal in
India covering an area of 34,000km per sq. with a population of 30 million. At present time it is
estimated that 37 administrative blocks by the side of Ganga River and adjoining areas are
affected. The areas that are affected by arsenic are situated in upper delta plain. Thousands of
tube wells are founded to be contaminated by arsenic in these regions. In these regions the major
water demand is met from groundwater.
According to Paul Deverill, the Project officer of child environment for UNICEF, has confirmed
that the most arsenic contamination at toxic level affected state in India is West Bengal. In
arsenic affected areas approximately 90% of the children below age 11 years showed elevated
level of arsenic in hair and nails.
Most of the habitants are very poor and neither can afford access to any kind of alternative
drinking water nor can afford any treatment for the bad effects of arsenic poisoning in
groundwater. In India arsenic contamination has been linked directly to the digging of deep tube
wells to fulfill the demand of water because in many areas of West Bengal the surface water
bodies are greatly polluted by industrial effluents and discharge from sewage plants. From
villages 312 more than 8000000 habitants are drinking contaminated water and among them at
least 175000 habitants are suffering from arsenical skin lesions.

Proposed method:

 Flux calculation
Calculation of advection flux
It depends upon the concentration and the flow velocity
J = C. V
The flux (J) shows the motion of the arsenic in the direction of flow
Average concentration of arsenic is 50 g/L
Velocity of low is 4 m/s
J = 50 g/l X 4 m/s
2
2
= 20 X 10 g m .s

Analyses of the arsenic content of 206 tube wells (95% of the total) showed that 56.8%
exceeded arsenic concentrations of 50g/l

Adsorption
In groundwater systems arsenic mobility mostly affected by the adsorption reaction. It is
generally a result following.

Presence of ions
Solid surface properties
pH
Arsenic species
Arsenic adsorption is influenced by the surface charge and charge on the material can be due to
change pH

Freundlich method of adsorption

The Freundlich equation or Freundlich adsorption isotherm, is a curve which relates the
concentration of the arsenic on the surface of the iron (Fe) to the concentration of the arsenic in
the water of the river where arsenic is dissolved.

The Freundlich isotherm is expressed as

X /M = Kp1/n
It can also be expressed by taking the log on both sides
Log X/M = log K + 1/n (log p)
Where X= mass of adsorbate
M = mass of adsorbent
P= equilibrium pressure of adsorbate
C = equilibrium concentration of adsorbate in solution.

And, K and n are the constants for arsenic at a particulate temperature

Log Csorb = log k f

+nlogC w

By plotting a graph the constants are calculated on the basis of calculated values the computed
Csorb is calculated then the percentage error is calculated by using the equation
Csorb
Csorb Computed Csorb /
Percentage error =

sample

Concentration
(mg/l)

C sorbed Log X

Log Y

Computed Percentage
C sorbed error (%)

1.58

2.5

0.1986

0.3979

1.7716

29.13

0.78

1.32

-0.1079

0.1205

0.9673

26.71

0.14

0.36

-0.8538

-0.4436

0.2219

38.36

0.06

0.192

-1.2218

-0.7166

0.1073

44.09

0.02

0.036

-1.6987

-1.4436

0.0418

-16.28

0.006

0.022

-2.2218

-1.6575

0.0149

32.28

*Hypothetical values are used for calculations.

 FUGACITY
Fugacity shows the tendency of escape of the contaminant
The partial pressure of the contaminant on the phase
It is measured in units of pressure (Pa)
Fugacity is applicable for all media
It express the potential in a measureable quantity
Fugacity capacity Z
Z is the number of moles of a substance that you can add to 1m3 of a phase or medium in order
to raise the fugacity of
the chemical in that phase by 1 Pa.
Expresses the ability of a medium to dissolve a chemical
substance
The ratio of Z values for a chemical substance is equivalent
to the chemicals partition coefficient K.
Fugacity capacity is defined as the number of moles of a substance (contaminant) that is to be
3
added in 1 m

In fugacity approach the concentration of the contaminant that is arsenic which is equal to the
fugacity capacity times the fugacity.
C=Z*F
Then mass is equal to
M = C.V
As, C = Z. F
M = Z. V. F

Fugacity approach notation

Notation

Parameters

Units

Fugacity

Pa

Fugacity capacity

Mass

Concentration

Volume

Universal gas constant

Temperature

Henrys constant

Mole pa-1 m3
Mole
Mole m-3
M3
Pa m3 mole-1 k-1
Kelvin
Pa m3 mole-1

Fugacity Calculations
Assume volume of air

1017m3

Volume of Ganga River

2 * 1015 cubic feet

For average weight of arsenic in river can be calculated by product of arsenic concentration and
volume of river.
As average concentration was founded 50g/l so volume of River is 2*1015 m3 so,
Weight of arsenic in River =50g/l X 2 X1015 ft3 X28.31 L/ft.3
=2831 kg
Assume BCF = 5.6 L/kg
Assume density of fish 2 g/cm3
Temperature of water in river 20C

Assume Henry constant = 3 x103 atm m3/mole

Surface OH + H3AsO4 Surface H3AsO4
Molecular weight of H3AsO4 = 141g/mole
2831 X 103 gram
Number of moles =
141 g/mole

= 2000 moles

Fugacity constants
Z air = 1/RT

1
ATM
.0821 L .
. ( 20+ 273 ) k
MOLE. k

Z water = 1/KH =

= 41.58 moles/atm.m3

1
3
3 X 10 atm . m3 /mole = 333moles/ atm.m
3

Z fish = density of fish X BCF/KH

= 2 mole/atm.m3
Calculations fugacity Equilibrium
f=

total number of moles

(Z .V )

=2000/ (Z air Vair + Z water Vwater + Z fish Vfish)

=2000/ (41.58moles/atm.m3 X 1017m3 + 333moles/atm.m3 X 5.58 1013 + 2 mole/atm.m3 X 3m3)
f= 44.88 X 10-17 moles/atm
Mass (air) = f . Vair Zair
= 44.88 X 10-17moles/atm X 1017m3 X 41.58 moles

= 1866.11 mole/lt\
C air

= Z air f i
17
= 41.58 X 44.88 X 10

14
3
= 1.866 X 10
mol/ m

Mass(water) = f . Vwater . Zwater

=44.88 X 10-17moles/atm X 5.58 X1013 X 333moles/atm.m
= 8.34 mole/lt
C water

= Z water f i
17
=333 X 44.88X 10
`

13
=1.4945 X 10
mol/

M3

Mass(fish) = f. Vfish . Zfish

=44.88 X 10-17moles/atm X 3m3X 2moles/atm.m3
= 2.69 X 10-15 moles/lt
c FISH

= Z fish f i
17
= 2 X 44.88 X 10

16
=8.96 X 10
moles/l

So, Higher concentration in air.

Results and Discussion:

2
2
The flux (J) is calculated 20 X 10 gm s and the fugacity method says higher concentration is
14
in air (1.866 X 10

3
mol/ m ) but which is not matching with the standard values as the

concentration of arsenic is higher in case of air but in actual it is higher water. As the volume of
air that has been assumed in the calculations that may vary the results from the actual values
while compared. But in case of adsorption the values are less in negative and values of errors are
also less. As the volume of fishes and the others constants were assumed so that may vary the
actual field values. The application of the methods is based on actual values (from internet) and
the rest are assumed to solve the problems. Due to high turbidity and other heavy depositions
changes the direction of flow and changes the flux at different points.
As the Ganga is big river and most polluted River so that a lot of fund had been required to
perform the various test therefore requirement of high technology. The concentration of arsenic
in some of the points is very high that causes the death of the fishes and other aquatic animals.
For example the dolphin fish of Ganga is under endangered category because of high
consumption of arsenic by them.

References :

http://0-lib.myilibrary.com.mercury.concordia.ca/Open.aspx?id=183131

http://www.sos-arsenic.net/english/arsenic/

http://www.who.int/water_sanitation_health/dwq/chemicals/arsenic.pdf

http://users.physics.harvard.edu/~wilson/arsenic/countries/SDAbstractsSPEAKERS.pdf

http://www.google.ca/url?
sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&docid=mCv8plaB_EfPSM&tbnid=M1E
dTsC3nfByWM:&ved=0CAUQjRw&url=http%3A%2F%2Fwww.chemistrylearning.com
%2Ffreundlich-adsorption-isotherm
%2F&ei=So2VUrDnIJTsoATMgoG4BQ&bvm=bv.57155469,d.cWc&psig=AFQjCNGk4GGVR
W_ygtckRgYMD_vXg4v3Jg&ust=1385619145030379

http://www.cee.mtu.edu/~reh/courses/ce251/251_notes_dir/node4.html

http://www.greenfacts.org/en/arsenic/l-3/arsenic-2.htm#0p0

http://www.who.int/water_sanitation_health/dwq/chemicals/arsenic.pdf

http://www.tripadvisor.in/LocationPhotos-g1584861-d3321240Ganga_Sacred_confluence_of_river_Alaknanda_Bhagirathi_RIversDevprayag_Uttarakhand.html#last

http://www.epa.gov/region1/superfund/sites/devens/296835.pdf

http://www.iisc.ernet.in/currsci/sep102006/599.pdf

http://en.wikipedia.org/wiki/Arsenic

http://www.state.nj.us/dep/dsr/publications/sorption-desorption-yr3-part2.pdf

http://ec.europa.eu/environment/life/project/Projects/index.cfm?
fuseaction=home.showFile&rep=file&fil=Tampereregion_ArsenicTransport.pdf

http://www.sciencedirect.com/science/article/pii/S0301479707000977

http://depts.washington.edu/jkspage/downloaddir/446-12-03.pdf

http://www.mi-wea.org/docs/Rich%20Grant%20-%20BOD%20Land%20Application.pdf

https://www.google.ca/#q=ganga+river

http://www.serdp.org/Program-Areas/Environmental-Restoration/Contaminants-onRanges/Protecting-Groundwater-Resources/ER-1374
http://www.epri.com/abstracts/Pages/ProductAbstract.aspx?
ProductId=000000000001012604&Mode=download

http://www.cgwb.gov.in/documents/papers/incidpapers/Paper%208%20%20Ghosh.pdf