What is air pollution

The result of emission into the air of

hazardous substances at a rate that
exceeds the capacity of natural
processes in the atmosphere to
convert, deposit, or dilute them…
 Factors that affect air pollution
• Emissions (traffic, industrial, domestic)
• Geography (terrain)
• Weather conditions (rain, winds, humidity)
• Season
• Time of day
• Population density
• Indoor vs outdoor
 Types of air pollutents
 Aerosols  Gases
– Particulates solid phase COx
• Dust SOx
• Ash
NOx
• Fumes
PAH
– Solid and liquid
• Smoke (from combustion)
• Coastal aerosols
– Liquid
– Aggregate gases (sulfate, nitrate)
Six primary or “criteria” air pollutants

• Carbon monoxide (CO)

• Ozone (O3)
• Nitrogen dioxide (NO2)
• Sulfur oxides (SOx)
• PM2.5 and PM10
• Lead (Pb)
Sources of combustion
• Tobacco
• Power plants
• Incinerators
• Automobiles
• Industry
 What is Ozone?

An odorless, colorless gas

composed of three oxygen atoms.

Ozone in the upper atmosphere protects us

from the sun’s harmful ultraviolet rays.

At ground-level in the air we breathe,

ozone (smog) poses serious risks to human health.
 Where Does Ozone Come From?
Ozone is created by a chemical reaction:

+ = O3

VOC + NOx + Heat + Sunlight = Ozone

VOC (Volatile Organic Compounds) and NOx

(Nitrogen Oxides) come from motor vehicles,
power plants, industrial facilities, and other
sources.
 Why is Ozone Bad to Breathe?
• The average adult breathes enough air to fill over 3,000 balloons
each day. Children breathe even more!

• Ozone can irritate lungs and airways, and cause inflammation

much like a sunburn on your lungs.

• Ozone can aggravate respiratory illnesses like asthma.

• 10 to 20% of summertime respiratory-related hospital visits in

the Northeast are associated with ozone pollution.

• Children and people with chronic lung diseases are

particularly at risk.
 Health Effects of Exposure to
Ozone
• Coughing

• Nose and throat irritation

• Chest pain

• Reduced lung function

• Increased susceptibility to respiratory illnesses

• Aggravation of asthma
 The Air Quality Index
Air Quality Index (AQI) Levels of Health
Values Concern
0 to 50 Good
51 to 100 Moderate
Unhealthy
101 to 150
for Sensitive Groups
151 to 200 Unhealthy
201 to 300 Very Unhealthy
301 to 500 Hazardous
 Air Pollution

– The maps you just saw

show ozone smog levels
on two days last summer.
Good
Moderate
– This map shows Unhealthy for
sensitive groups
the highest ozone levels Unhealthy
recorded in 2001. Very Unhealthy
 Diesel pollutants
• Particulate matter
– C + PAHs + N-aromatics
• Gases
– NOx, CO, SOx
• VOCs
– formaldehyde, acrolein, aldehydes

• Respiratory inflammation
• Cytotoxicity to airway cells
 Outdoor air pollution

Beijing

Delhi
 Outdoor air pollution

Santiago

Mexico City
 Indoor pollutants
• Non-specific symptoms
• Household vs work space
• Sick building syndrome (20% exposed)
– Cigarette smoke, combustion products
– Biological agents (infections, allergens)
– Additional factors (stress, fatigue, diet,
alcohol)
Indoor air pollution: Poor countries
 In the lungs…
• Site of deposition along tract
• Solubility in respiratory fluids
• Reactivity with membranes
• Infiltration (alveolar gas exchange)
• Level of exposure
• Duration of exposure
• Respiratory rate
• Pre existing conditions (heart, lung)
 Absorption in lungs
• As gas, directly into blood stream
• As particles, deposited onto bronchiolar and
alveolar surface
– Uptake by phagocytosis
– Trigger of inflammatory response
– Trigger of allergic response
– Lung tissue scaring
Basic structure of respiratory tract
Measurements of lung volume
 Typical lung volume measurements from normal
lung, obstructive airway disease, and restrictive lung
disease
Normal, Obstructive and Restrictive Patterns
of Forced Expiration

FVC = forced vital capacity

FEV1 = forced expiratory volume at 1st second of active exhalation
FEF25-75 = maximal mid-expiratory flow rate
FEF75 = forced expiratory flow after 75% of expelled volume
Particulate matter pollution
• Properties - varied
Mixture of solid phase and absorbed materials (organic,
inorganic and biological)
Carbonaceous core 40-60%, C 7%

• Sources
– Combustion - oil and coal
• Industry
• Automobiles
– Tobacco smoke NAAQS:
– Biomass burning
PM10: 50ug/m3, annual
– Metal smelters
150ug/m3, 24h
PM2.5 15ug/m3, annual
65ug/m3, 24h
 Particulates - features
• Physical size
– Large
– Small ~10um
– Fine ~2.5um
• Aerodynamic diameter (size equivalent of density=1)
– Large - local irritation (>100um)
– Inhalable (<100um)
– Thoracic fraction (<20um)
• Coarse PM10 (<10um)
respirable
• Fine PM2.5 (<2.5um)
• Ultrafine (<0.1um)
• Chemical reactivity
• Shape (fibers)
• Water content
Deposition of particles in humans
Parameters
influencing
particle
deposition
Alveolar injury
and responses
 Urban Particulates
• In the <2.5um range
• Large water content, trace metals,
acid gases, organic chemicals,
biological
• Rather uniform distribution
• Include diesel
Health effects of particulate pollutants

• Eye irritation - starting at 10ug/m3

• Respiratory tract infection
• Exacerbation of asthma
• Bronchial irritation
• Heart disease
• Possibly cancer (controversial) (diesel, TiO2, talc,
carbon black, toner black)

• Elevated hospital admissions, mortality

• Causation(s) not fully understood
 Gaseous pollutant features
• Chemical reactivity (ozone)
• Solubility in water
– Soluble
• Ambient (NOx, SOx)
• Occupational (Hydrochloric acid, Ammonia)
– Less soluble
• H2S, ozone
 Gas pollutants - SO2
NAAQS: 0.03ppm, annual
• Properties 0.14ppm, 24h
– Reacts with H2O and forms sulfurous acid (H2SO3), which
oxidizes to sulfuric acid (H2SO4)
– Chemical transformation of other pollutants
– Responsible for acid rain effect
• Sources
– Biomass and fossil fuel combustion
– Industrial emissions, smelters
• Controls
– Low-S fossil fuels (clean coal)
– Emission control devices
• London fog episode (acute)
 SO2 …continued
• Absorption at upper respiratory tract
(sulfite, bisulfite)
• Health effects (starting at <1ppm)
– Respiratory tract irritation, bronchoconstriction
– Pulmonary function impairment
– Increased air flow resistance
– Bronchitis
– Exacerbation of heart diseases
• Short acute: 2min 0.4-1ppm in asthmatics
• Long term, low levels
– Impairs immune pulmonary defenses
– Susceptibility to infections
 Gas pollutants - H2SO4
• Product of SO2
– With metals and water --> sulf. Fly ash and acid rain
• Protonates biomolecules - membrane damage
• Bronchoconstriction
• Increased air flow resistance
• Mucus secretion protects (buffer) - nose inhalation
• Asthmatics are more sensitive
• Acidity interferes with mucociliary clearance
• Chronic exposure to 100g/m3 : lower respiratory damage,
macrophage mediated
 Gas pollutants -NO2
NAAQS: 0.05ppm, annual
• Properties
– Oxidant, less potent than O3
• Sources
– NO oxidation
– High To combustion (automobiles, power plants)
– Indoor - kerosene, gas stoves, ETS
– Silos in farming (75-100ppm)
• Health effects - starting at 1.5-2ppm
– Deep lung irritant - terminal bronchioles
– Alveolar cells, ciliated epithelia, Clara cells
– Similar to ozone but less inflammatory (if < 2-5ppm)
– Enhanced infection, suppression of macrophage action
– Peaks more
 Gas pollutants - CO
NAAQS: 9ppm, 8h
• Properties 35ppm, 1h
– Odorless, heavier than air, stronger binder to Hb than O2
• Sources
– Incomplete combustion
– Traffic (inside the car, parking garages, tunnels is highest)
– Inside cars = 3x urban streets, and = 5x residential streets
• Health effects
– Asphyxiant
– Fatigue, confusion, headaches, dizziness, cardiac function (arrhythmias,
angina)
– Start at 2.5% COHb (0.5% baseline) (air level 50ppm for 90min)
2ppm COHb, no effect
>5ppm COHb, cardiovascular effects
40ppm COHb, is fatal
 Gas pollutants - O3
Good O3 - stratosphere NAAQS: 0.12ppm, 1h
Bad O3 - troposphere 0.08ppm, 8h

• Properties
– Short lived, highly reactive, water soluble
– Scrubbed in nasopharynx
– Reaches terminal bronchioles and alveoli
• Sources
– Photochemical reactions
• Health effects
– Degenerative lung disease
– Loss of lung function
 Photochemical pollution
uv
NO2 NO + O

O2 + O O3

O3 + NO O2 + NO2
Twist:
In absence of HC- the reaction reaches equilibrium

.
Car emitted HC- (PAH) react with O ….
Hydrocarbons shift photochemical reaction…
HC- + O
. Oxidized free radicals
NO

NO2
+ Aldehydes

Balance of photochemical reaction shifts toward O3 build-up!!

O3
 Photochemical pollution
uv
O3
NO2
O2
Hydrocarbons
The O3 molecule is highly reactive
O
.
2
O3
O
. .
2 (HO )

H2O
• Ultimate toxicant:
• No enzyme can detoxify it
• Only protection: prevention
of its formation
 Effects of Ozone on lung function

FEV

0.5ml

(Kinney et.al, 1996)

ppb
1

0.12 - 0.4 ppm for 2-3 h FVC and FEV1

Ozone levels
ppb ppm
300 0.30
240 0.24 LA, until 1998
200 0.20 LA, 1h-ave
180 0.18 EU 1h ave
LA, 8h-ave
120 0.12 US-EPA 1h ave
100 0.10 Italy study (low exposure)
Effects on lung
function observed 90 0.09
80 0.08 WHO 1h ave
US-EPA 8h ave 70 0.07
60 0.06
WHO 8h ave
50 0.05
40 0.04
Baseline
20 0.02
Ambient O3, TSP and SO2
Some nomenclature of oxidative species

O
Aldehydes R C
H

Alcoxyl radical
.
RO (RO )
.
Alkoperoxyl radical
. .
RO2 (ROO )
Nitrous acid HONO
Nitric acid HONO2
Hydroxyl radical HO
. (HO.)
Hydroperoxy radical
.
HO2 (HOO )
.
 Effects of O3 on proteins:
Oxidation of: Aminoacids targets:
• sulphydryls • cystein
• amines • methionine
• alcohols • tryptophan
• aldehydes • tyrosine

Inactivation/inhibition of enzymes in cellular compartments

 Effects of O3 on lipids:
• Polyunsaturated fatty acids (PUFA):
primary target of O3 peroxidation of membrane lipids
• Most important mechanism of O3-induced injury

O3 + PUFA carbonyl oxide

aldehydes H2 O

Hydroxyhydroperoxy compound
HO
.
Lipid peroxidation cascade H2 O 2
Malondialdehyde (MDA)
Lipid fragmentation 8-isoprostane
LTB4 (PMN chemotractant)
Lipid peroxidation
cascade
 Effects on nucleic acids
Electrophiles react with strong nucleophilic atoms of nucleic acids

DNA + HO
. Imidazole ring-opened purines or
ring-contracted pyrimidines

Strand breaks
Blocked DNA replication

Formation of adducts depurination (apurinic sites: mutagenic)

 Effects of O3 on lung function
• Decrement of lung function (FEV1 and FVC1)

• Increased airway responsiveness (non specific)

• Increased epithelial permeability, injury and loss

• May influence allergic sensitization and responsiveness

• May increase sensitivity to infections

• Induces inflammatory reactions following injury

• Exercise increases air flow and penetration

 Inflammatory oxidative burst
.
Three pathways of HO generation:

• NAD(P)H oxidase
• Nitric oxide synthase (NOS)
• Myeloperoxidase (MPO)

L-citruline H+ NO2
.
L-arginine + O2
NOS
NO
.

Oxidase . Fenton
HO
.
NAD(P)H + O2 O2
NAD(P)+
H+ H20
MPO
O2
HOOH + H+ +Cl- HOCl Cl-
 The lung’s defenses:

Antioxidant molecules: Metabolic enzymes:

 ascorbic acid (vit. C)  SOD

 a-tocopherol (vit. E)  Catalase
 uric acid  GPX
 glutathione (GSH)  GSTs
Other air pollutants - HAPs
• Hazardous air pollutants
– Not included in the 6 criteria air pollutants
• Include
– Organic chemicals (acrolein, benzene)
– Minerals (asbestos)
– PAH (benzo[a]pyrene)
– Metals (Hg, Be)
– Pesticides (carbaryl, parathion)
• Some are carcinogenic
 Volatile Organic Pollutants
(VOCs)
• Sources: Petroleum emissions, fuel combustion,
incineration, biomass burning
• Account for ~14% of all air pollution
• Important factor of indoor air pollution
• Types
– Aliphatic
– Alcohols (ethylene glycol, MTBE)
– Aldehydes (formaldehyde)
– Aromatic (benzene, toluene, xylene)
– Halogenated (TCE, PERC, Methylene Chloride)
– Polycyclic (PAHs)
– Other (Carbon disulfide)
 VOCs Health Effects
• Alkanes (solvents, varnishes, lacquers)

– Irritants, lung and skin

– CNS depressants, neuron degeneration,
paralysis
– Pulmonary edema
– React with OH radical in photochemical
pollution
 VOCs Health Effects
• Alkenes (gasoline and aviation fuel) more
reactive than alkanes - chains, oxides,
halogenated HC

– CNS effects - cramps, tremor

– GI tract - nausea, vomiting
 Aldehydes
• Formaldehyde H2C=O
– 50% of total aldehydes
– Water soluble
– Steep dose-effect:
0.5-1ppm: odor
2-3ppm: mild irritation
4-5ppm: intolerable
– Scrubbed in upper respiratory tract, but can also reach
deeper
– Nasal cancer? (rodents but not humans)
• Acrolein H2C=CHCH=O
– 5% of total but more irritating
 VOCs Health Effects
Aromatic hydrocarbons (stable, persistent) - Low water
solubility, volatile, flammable - Priority pollutants (EPA)
• Benzene - most basic
– Carcinogen (epoxide, phenol metabolites)
– CNS toxicity - narcosis
– Irritation (skin, lung)
• Toluene (more lipophilic, but faster metabolism)
– CNS depressant (narcosis, impaired coordination,
headaches)
• Xylene (o-, p-, m-) (very lipophilic)
– CNS depressant (as above)
– Blood cell damage, anemia
– Irritant (skin)
 VOCs Health Effects
Polycyclic aromatic hydrocarbons (PAH) incomplete
combustion of organic materials, incineration, industry, natural processes
– 16 of 126 priority pollutants
– Environmental transport, accumulation
– Photo - bio- degradation

• Carcinogens exposure* (metabolic activation) -

• Air exposure 0.02-3ug/day
• Cigarette smoke 0.1-0.25ug/cig
• Unfiltered cigarettes 2-5ug/day
• Vegetarian diet 3-9ug/day
• Drinking water 0.2-120ng/day
• Soil (urban) 0.003-0.4ug/day

* Menzie et.al. 1992, Env. Sci and Technol. Vol. 26: p.1278
 NAAQS - CAA 1990
• National Ambient Air Quality Standards
• ug/m3 or ppm

• National Air Quality and Emissions Trends

Report
 NAAQ Standards for
six “criteria” pollutants
Pollutant Primary Stds. Averaging Times Secondary Stds.
9 ppm
8-hour(1) None
(10 mg/m3)
Carbon Monoxide
35 ppm
1-hour(1) None
(40 mg/m3)

Lead 1.5 µg/m3 Quarterly Average Same as Primary

0.053 ppm
Nitrogen Dioxide Annual (Arithmetic Mean) Same as Primary
(100 µg/m3)
Revoked(2) Annual(2) (Arith. Mean)
Particulate Matter
(PM10) 150 µg/m3 24-hour(3)
15.0 µg/m3 Annual(4) (Arith. Mean)
Particulate Matter
Same as Primary
(PM2.5) 35 µg/m3 24-hour(5)
Ozone 0.08 ppm 8-hour(6) Same as Primary

0.12 ppm * 1-hour(7) Same as Primary

0.03 ppm Annual (Arith. Mean) -------

0.14 ppm 24-hour(1) -------
Sulfur Oxides
------- 3-hour(1) 0.5 ppm
(1300 µg/m3)
*Applies only in limited areas http://www.epa.gov/air/criteria.html
 US Regulation history
• 1947 CA - Air pollution control Act
• 1955 - Truman’s Air pollution control Act
• 1963 Federal - Clean Air Act (1967 am)
• 1965 Federal - Motor vehicle Air pollution control Act
• 1970 The Clean Air Act: national level (EPA)
– O3, SO2, NO2, CO, PM, Pb, total hydrocarbons (dropped)
• 1970 Lead is banned as fuel additive
• 1990 CCA amendment: 118 chemicals, some carcinogenic
– Maximum achievable control technology
– Additional risk assessment if health effects beyond the MACT level
– Emission standards for motor vehicles (CO solution - MTBE new
problem)
• 1997 New standard for PM2.5
 Clean Air Mercury and Interstate rules

• On March 15, 2005, EPA issued the Clean Air Mercury Rule to permanently
cap and reduce mercury emissions from coal-fired power plants for the first
time ever. This rule makes the United States the first country in the world to
regulate mercury emissions from utilities.

• On March 10, 2005, in a separate but related action, EPA issued the Clean Air
Interstate Rule (CAIR), a rule that will dramatically reduce air pollution that
moves across state boundaries.

• Together the Clean Air Mercury Rule and the Clean Air Interstate Rule create a
multi-pollutant strategy to reduce emissions throughout the United States.

http://www.epa.gov/air/mercuryrule/
 Epi studies of air pollution
Outdoor studies predominantly
– Cohort studies (Harvard six cities; American Cancer Society;
Adventist Health Study of Smog)
– Biomarkers (breath, BAL, blood)
– Lung function (FEV1, FVC, FEF25-75)
– Symptoms (coughing wheezing, shortness of breath, cardiac
function)
– Long-term/chronic (confounders)
• Retrospective
• Prospective
– Time series
• National Morbidity, Mortality and Air Pollution Study (NMMAPS)
• Air Pollution and Health, a European Approach (APHEA)
 Chronic effects of air pollution
• Los Angeles basin: “aging-like” effect on lung function
• Netherlands: 12y, SO2 and PM
• Rural PA: higher incidence of respiratory symptoms
• Harvard Six Cities Study: >15y, 20,000 people SO2 and
PM
• Overall reduced lung function, bronchitis
• Cancer risk: 2000/year vs 100,000/year from smoking -
associated with PM/VOC combinations
Relative contribution of individual air pollutants to
lung cancer rates after removing tobacco smoke
cancer (~85%)

PIC: products of
incomplete combustion
US emissions trend for VOCs, NOx, SO2,
and PM10, 1900-1990