Air pollution
Week 8
C&D Chapters 15, 24 and 28
Liquid
Aggregate gases (sulfate, nitrate)
Gases
COx
SOx
NOx
PAH
Photochemical pollution
Aldehydes, electrophilic HCs
Oxidative, carcinogenic?
Types of Exposures:
Continuous
Repeated
Low
High (acute)
Combustion pollutants
VOCs
NOx
N-organics
Halo-organics
Metals
CO
Sources of combustion
Tobacco
Power plants
Incinerators
Automobiles
Industry
Diesel pollutants
Particulate matter
C + PAHs + N-aromatics
Gases
NOx, CO, SOx
VOCs
formaldehyde, acrolein, aldehydes
Respiratory inflammation
Cytotoxicity to airway cells
Beijing
Delhi
Santiago
Mexico City
Indoor pollutants
Non-specific symptoms
Household vs work space
Sick building syndrome (20% exposed)
In the lungs
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
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
Sources
Combustion - oil and coal
Industry
Automobiles
Tobacco smoke
Biomass burning
Metal smelters
NAAQS:
PM10: 50ug/m3, annual
150ug/m3, 24h
PM2.5 15ug/m3, annual
65ug/m3, 24h
Particulates - features
Physical size
Large
Small ~10um
Fine ~2.5um
Chemical reactivity
Shape (fibers)
Water content
(<10um)
(<2.5um)
(<0.1um)
respirable
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
- starting at 10ug/m3
Eye irritation
Respiratory tract infection
Exacerbation of asthma
Bronchial irritation
Heart disease
Possibly cancer (controversial) (diesel, TiO2, talc,
carbon black, toner black)
Less soluble
H2S, ozone
Reacts with H2O and forms sulfurous acid (H 2SO3), 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
SO2 continued
Absorption at upper respiratory tract
(sulfite, bisulfite)
Sources
NO oxidation
High To combustion (automobiles, power plants)
Indoor - kerosene, gas stoves, ETS
Silos in farming (75-100ppm)
Gas pollutants - CO
Properties
NAAQS: 9ppm, 8h
35ppm, 1h
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
Bad O3 - troposphere
NAAQS: 0.12ppm, 1h
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
NO2
O2 + O
O3 + NO
uv
NO + O
O3
O2 + NO2
Twist:
In absence of HC- the reaction reaches equilibrium
O3
Photochemical pollution
uv
NO2
O2
Hydrocarbons
O3
O3
O
H2O
2 (HO )
Ultimate toxicant:
No enzyme can
detoxify it
Only protection:
prevention of its
FEV
0.5ml
1
0.12 - 0.4 ppm for 2-3 h
ppb
Ozone levels
ppb
300
240
200
180
LA, 8h-ave
120
Effects on lung 100
function observed 90
80
US-EPA 8h ave
70
60
WHO 8h ave
50
40
20
ppm
0.30
LA, until 1998
0.24
0.20
LA, 1h-ave
0.18 EU 1h ave
US-EPA 1h ave
0.12
0.10 Italy study (low exposu
0.09
0.08 WHO 1h ave
0.07
0.06
0.05
0.04
Baseline
0.02
R C
Alcoxyl radical
RO
Alkoperoxyl radical
Nitrous acid
Nitric acid
RO2 (ROO )
HONO
HONO2
Hydroxyl radical
HO
Hydroperoxy radical
(RO )
(HO )
HO2
(HOO )
Effects of O3 on proteins:
Oxidation of:
sulphydryls
amines
alcohols
aldehydes
Aminoacids targets:
cystein
methionine
tryptophan
tyrosine
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
H2O
aldehydes
Hydroxyhydroperoxy compound
HO
H2O2
Malondialdehyde (MDA
8-isoprostane
LTB4 (PMN chemotractant)
Lipid peroxidation
cascade
Strand breaks
Blocked DNA replication
Formation of adducts
L-arginine + O2
NAD(P)+
H+
HOOH + H+ +Cl-
NO2
NO
Oxidase
NAD(P)H + O2
H+
MPO
O2
H20
HOCl
Fenton
HO
O2
Cl-
Metabolic enzymes:
SOD
Catalase
GPX
GSTs
Include
Aliphatic
Alcohols (ethylene glycol, MTBE)
Aldehydes (formaldehyde)
Aromatic (benzene, toluene, xylene)
Halogenated (TCE, PERC, Methylene Chloride)
Polycyclic (PAHs)
Other (Carbon disulfide)
Aldehydes
Formaldehyde
H2C=O
Acrolein
H2C=CHCH=O
Air exposure
Cigarette smoke
Unfiltered cigarettes
Vegetarian diet
Drinking water
Soil (urban)
0.02-3ug/day
0.1-0.25ug/cig
2-5ug/day
3-9ug/day
0.2-120ng/day
0.003-0.4ug/day
* Menzie et.al. 1992, Env. Sci and Technol. Vol. 26: p.1278
Primary Stds.
Carbon Monoxide
9 ppm
(10 mg/m3)
35 ppm
(40 mg/m3)
Lead
1.5 g/m3
Averaging Times
Secondary Stds.
8-hour(1)
None
1-hour(1)
None
Quarterly Average
Same as Primary
Same as Primary
0.053 ppm
Nitrogen Dioxide
Particulate Matter
(PM10)
Particulate Matter
(PM2.5)
Ozone
Sulfur Oxides
(100 g/m3)
Revoked(2)
150 g/m3
24-hour(3)
15.0 g/m3
35 g/m3
24-hour(5)
0.08 ppm
8-hour(6)
Same as Primary
0.12 ppm *
1-hour(7)
Same as Primary
0.03 ppm
0.14 ppm
-------
------------0.5 ppm
(1300 g/m3)
Same as Primary
http://www.epa.gov/air/criteria.html
US Regulation history
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/
Time series
National Morbidity, Mortality and Air Pollution Study (NMMAPS)
Air Pollution and Health, a European Approach (APHEA)
PIC: products of
incomplete combustion