environmental health air pollution week 8 c&d chapters 15, 24 and 28
TRANSCRIPT
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Environmental Health
Air pollution Week 8
C&D Chapters 15, 24 and 28
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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…
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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
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Types of air pollution Aerosols
– Particulates solid phase• Dust• Ash• Fumes
– Solid and liquid• Smoke (from combustion)• Coastal aerosols
– Liquid – Aggregate gases (sulfate, nitrate)
GasesCOxSOxNOxPAH
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Six primary or “criteria” air pollutants
• Carbon monoxide (CO)
• Ozone (O3)
• Nitrogen dioxide (NO2)
• Sulfur oxides (SOx)
• PM2.5 and PM10
• Lead (Pb)
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Types of air pollution
• Individual pollutants• Reducing pollution (SO2)
– Acid rain (fog)– Corrosive, eroding
• Photochemical pollution– Aldehydes, electrophilic HCs– Oxidative, carcinogenic?
• Mixtures and complex patterns
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Types of Exposures:
ContinuousRepeated
LowHigh (acute)
Respiratory response (endpoints):
Macroscopic (e.g. coughing, FEV)
Histological
Marked variability in responses - susceptibility
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Combustion pollutants
• VOCs
• NOx
• N-organics
• Halo-organics
• Metals
• CO
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Sources of combustion
• Tobacco
• Power plants
• Incinerators
• Automobiles
• Industry
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Diesel pollutants
• Particulate matter – C + PAHs + N-aromatics
• Gases – NOx, CO, SOx
• VOCs – formaldehyde, acrolein, aldehydes
• Respiratory inflammation• Cytotoxicity to airway cells
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Outdoor air pollution
Beijing
Delhi
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Outdoor air pollution
Mexico City
Santiago
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Indoor pollutants• Non-specific symptoms• Household vs work space• Sick building syndrome (20% exposed)
– Cigarette smoke, combustion products– Organic offgasing (glue, fabrics, furnishings)– Biological agents (infections, allergens)– Additional factors (stress, fatigue, diet,
alcohol)
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Indoor air pollution: Poor countries
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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)
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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
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Basic structure of respiratory tract
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Measurements of lung volume
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Typical lung volume measurements from normal lung, obstructive airway disease, and restrictive lung
disease
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Normal, Obstructive and Restrictive Patterns of Forced Expiration
FVC = forced vital capacity FEV1 = forced expiratory volume at 1st second of active exhalationFEF25-75 = maximal mid-expiratory flow rate FEF75 = forced expiratory flow after 75% of expelled volume
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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– Biomass burning– Metal smelters
NAAQS: PM10: 50ug/m3, annual
150ug/m3, 24h PM2.5 15ug/m3, annual
65ug/m3, 24h
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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)
• Fine PM2.5 (<2.5um)
• Ultrafine (<0.1um)
• Chemical reactivity
• Shape (fibers)
• Water content
respirable
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Deposition of particles in humans
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Parameters influencing
particle deposition
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Alveolar injury and responses
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Urban Particulates
• In the <2.5um range
• Large water content, trace metals, acid gases, organic chemicals, biological
• Rather uniform distribution
• Include diesel
• In the <2.5um range
• Large water content, trace metals, acid gases, organic chemicals, biological
• Rather uniform distribution
• Include diesel
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Health effects of particulate pollutants
• Eye irritation• 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
- starting at 10ug/m3
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Gaseous pollutant features
• Chemical reactivity (ozone)
• Solubility in water– Soluble
• Ambient (NOx, SOx)
• Occupational (Hydrochloric acid, Ammonia)
– Less soluble• H2S, ozone
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Gas pollutants - SO2
• Properties– 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)
NAAQS: 0.03ppm, annual 0.14ppm, 24h
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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
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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 100g/m3 : lower respiratory damage,
macrophage mediated
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Gas pollutants -NO2
• 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
NAAQS: 0.05ppm, annual
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Gas pollutants - CO
• Properties– 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
NAAQS: 9ppm, 8h 35ppm, 1h
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Gas pollutants - O3
Good O3 - stratosphere
Bad O3 - troposphere
• 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
NAAQS: 0.12ppm, 1h 0.08ppm, 8h
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Photochemical pollution
NO2 NO + O
O2 + O O3
O3 + NO O2 + NO2
uv
Twist:
In absence of HC- the reaction reaches equilibrium
Car emitted HC- (PAH) react with O. ….
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HC- + O. Oxidized free radicals NO
NO2 + Aldehydes
O3
Balance of photochemical reaction shifts toward O3 build-up!!
Hydrocarbons shift photochemical reaction…
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Photochemical pollution
uvO3
NO2
HydrocarbonsO2
O2.
O3
O .
H2O
2 (HO.)
The O3 molecule is highly reactive
• Ultimate toxicant:• No enzyme can detoxify it• Only protection: prevention of its formation
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Effects of Ozone on lung function
ppb
FEV
1
0.5ml
(Kinney et.al, 1996)
0.12 - 0.4 ppm for 2-3 h FVC and FEV1
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ppb ppm0.300.240.200.180.120.100.090.080.070.060.050.040.02
300240200180120100 90 80 70 60 50 40 20
LA, until 1998
US-EPA 1h aveItaly study (low exposure)
WHO 1h ave
EU 1h ave
Baseline
WHO 8h ave
US-EPA 8h ave
Effects on lung function observed
Ozone levels
LA, 1h-ave
LA, 8h-ave
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Ambient O3, TSP and SO2
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Aldehydes R C
Alcoxyl radical RO . (RO.)
Alkoperoxyl radical RO2. (ROO.)
Nitrous acid HONONitric acid HONO2
Hydroxyl radical HO . (HO.)
Hydroperoxy radical HO2. (HOO.)
H
O
Some nomenclature of oxidative species
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Effects of O3 on proteins:
Oxidation of: • sulphydryls• amines• alcohols• aldehydes
Inactivation/inhibition of enzymes in cellular compartments
Aminoacids targets:
• cystein• methionine• tryptophan• tyrosine
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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 oxideH2O
Hydroxyhydroperoxy compound
HO.
H2O2Lipid peroxidation cascade
aldehydes
Lipid fragmentationMalondialdehyde (MDA)8-isoprostaneLTB4 (PMN chemotractant)
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Lipid peroxidation cascade
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Effects on nucleic acids
Electrophiles react with strong nucleophilic atoms of nucleic acids
DNA + HO. Imidazole ring-opened purines or ring-contracted pyrimidines
Strand breaksBlocked DNA replication
Formation of adducts depurination (apurinic sites: mutagenic)
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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
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Inflammatory oxidative burst
Three pathways of HO. generation:
• NAD(P)H oxidase • Nitric oxide synthase (NOS)• Myeloperoxidase (MPO)
HO.
NAD(P)H + O2 O2.
NAD(P)+H+
Fenton
HOOH + H+ +Cl- HOClMPO
Oxidase
L-arginine + O2 NO.NOS
H+
NO2
.
O2
Cl-
L-citruline
H20
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The lung’s defenses:
Antioxidant molecules:
ascorbic acid (vit. C) a-tocopherol (vit. E) uric acid glutathione (GSH)
Metabolic enzymes:
SOD Catalase GPX GSTs
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• 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
Other air pollutants - HAPsOther air pollutants - HAPs
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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)
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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
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• Alkenes (gasoline and aviation fuel) more reactive than alkanes - chains, oxides, halogenated HC
– CNS effects - cramps, tremor– GI tract - nausea, vomiting
VOCs Health EffectsVOCs Health Effects
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Aldehydes
• Formaldehyde H2C=O– 50% of total aldehydes– Water soluble– Steep dose-effect:
0.5-1ppm: odor2-3ppm: mild irritation4-5ppm: 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
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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 EffectsVOCs Health Effects
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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
VOCs Health EffectsVOCs Health Effects
* Menzie et.al. 1992, Env. Sci and Technol. Vol. 26: p.1278
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NAAQS - CAA 1990
• National Ambient Air Quality Standards• ug/m3 or ppm
• National Air Quality and Emissions Trends Report
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NAAQ Standards for six “criteria” pollutants
http://www.epa.gov/air/criteria.html
Pollutant Primary Stds. Averaging Times Secondary Stds.
9 ppm(10 mg/m3)
35 ppm(40 mg/m3)
Lead 1.5 µg/m3 Quarterly Average Same as Primary
0.053 ppm
(100 µg/m3)
Revoked(2) Annual(2) (Arith. Mean)
150 µg/m3 24-hour(3)
15.0 µg/m3 Annual(4) (Arith. Mean)
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) -------
------- 3-hour(1) 0.5 ppm(1300 µg/m3)
Particulate Matter (PM10)
Sulfur Oxides
Particulate Matter (PM2.5)
None
None
Same as Primary
Same as Primary
Nitrogen Dioxide
Carbon Monoxide 1-hour(1)
8-hour(1)
Annual (Arithmetic Mean)
*Applies only in limited areas
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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
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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/
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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)
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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
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Relative contribution of individual air pollutants to lung cancer rates after removing tobacco smoke
cancer (~85%)
PIC: products of incomplete combustion
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US emissions trend for VOCs, NOx, SO2, and PM10, 1900-1990