RISK ASSESSMENTRISK ASSESSMENT

Emissions

Transport and Fate

Concentrations

Exposure

Dose

Dose-response Relationship

Health RiskHealth Risk

Schematic overview of a Health Risk Assessment

EMISSIONSEMISSIONS

The Problem

•There are some 100,500 (European Inventory of Existing Commercial Substances (EINECS) chemicals in current commercial production, with approximately 1000 being added each year.

•Of these, perhaps 500 to 1000 substances are of environmental concern because of their presence in detectable quantities in various components of the environment, their toxicity, their tendency to bioaccumulate, their persistence or their potential for long range transport to regions remote from their location of use.

Environmental Pollutants

Existing Chemical Substances :

•Macrocontaminants: (O3 , SO2 , CO, CO2 , NOx, PM)

•Microcontaminants•Drugs

•Pesticides

•Industrial Chemicals

•Food additives

•Pathogens

TOXIC COMPOUNDSTOXIC COMPOUNDS

•Metals: •Carcinogens: As, Cd, Cr, Ni•No carcinogens: Hg, Pb

•Semivolatile Organic Compounds: • PAHs: Polycyclic Aromatic Hydrocarbons• PCBs: Polychoro biphenyl• PCDD/Fs: Polychloro dibenzo dioxins and Polychloro dibenzo furans• PCNs:Polychlorinated Naphtalenes

•Volatile Organic Compounds: VOCs

•Pesticides

Heavy Metals

•Mercury: Organic : CH3Hg+,(CH3)2 HgInorganic: Hg0, Hg2+, Hg2

2+

•Arsenic: organic and inorganic

•Lead

•Nickel

•Chromium: Cr+3 ,Cr+6

Mercury

•Primary antropogenic fonts: (10-30% of total emissions)coal-fired power plantsmetal smeltingincineratorschoroalkaly productionalkaline batteriestermometersmunicipal waste combustor

•Natural fonts: volatilization from soil and waterweathering o bedrockvolcanic emissions

Global emissions to atmosphere : 106 kg/y

Elementary mercury

*High vapor pressure: is not considered to accumulate in soilcan absorb to plants

*Low solubility in water

*Residence time in atmosphere: 1 year Deposition flux is not considered in air dispersion models because deposition flux to soil appears negligible

*Human intake: via inhalation

*Affections: System nervous (irritability, insomnia, headaches, memory loss) Affection to kidney an respiratory system

Methyl- mercury (CH3Hg+)

•High lipid solubility

•Ability to passively diffuse plasma membranes

•Main route of human exposure: Ingestion of contaminated fish and vegetables

Air, water, sediment mercury distribution

0

0.05

0.1

0.15

g/g

1996 1997 1998 2000

Nivells de Hg en sòls

Mercury

Soils

0

0.1

0.2

g/g

1996 1997 1998 2000

Nivells de Hg en herbes

Grass

Arsenic

•Use : * In production of semiconductors

* Agriculture

•Antropogenic input: copper smelting coal combustion

•Natural emissions: volatilization from soil volcanic activities

•ToxicologyChronic exposure increase lung cancer and skin tumors

0

5

10

15

g/g

1996 1997 1998 2000

Nivells d'As en sòls

Arsenic

Soils

0

0.1

0.2

g/g

1996 1997 1998 2000

Nivells d'As en herbes

Grass

Chromium

•Use: *Catalyst in ammoniac synthesis*Production of alloys and steels*Leader treatment

•Chromium (III) is an essential element in humans•Chromium (VI) is highly toxic

•Inhalation of Cr (VI) 1.- Affects respiratory tract: bronchitis, decreased pulmonary

function, pneumonia, asthma 2.- Cause lung cancer

0

10

20

30

g/g

1996 1997 1998 2000

Nivells de Cr en sòls

Chromium

Soils

0

0.5

1

g/g

1996 1997 1998 2000

Nivells de Cr en herbes

Grass

Lead

•Use:Pb-pigmentsAdditive to gasolineAccumulatorsRadiation protection

•Sources:Anthropogenic sources contribute 1 to 2 orders of magnitude greater than natural sources to lead emissions.

•Health effects: tiredness, headache, myasthenia and anemia.

- On the blood pressure and interference with vitamin D.- On the intelligence and on the neuropsychological performance.

0

20

40

60

80

g/g

1996 1997 1998 2000

Nivells de Pb en sòls

Lead

Soils

0

2

4

g/g

1996 1997 1998 2000

Nivells de Pb en herbes

Grass

Ni in soil Ni in grass1.4

0.8

1

0.8

1.2

Old

MSW

I + u

rban

Old

MSW

I + in

dust

rial

New

MSW

I

Rural

+ res

iden

tial

Cemen

t pla

nt0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

mg

/kg

d.m

15.6

78.7

13.06

10.1

Old

MSW

I + u

rban

Old

MSW

I + in

dust

rial

New

MSW

I

Rural

+ res

iden

tial

Cemen

t pla

nt0

2

4

6

8

10

12

14

16

18

mg

/kg

d.m

80.9

50.9

2232.2

16.1

Old

MSW

I + u

rban

Old

MSW

I + in

dust

rial

New

MSW

I

Rural

+ res

iden

tial

Cemen

t pla

nt0

20

40

60

80

100

mg

/kg

d.m

Pb in soil Pb in grass

2.9

2.2

0.90.6 0.6

Old

MSW

I + u

rban

Old

MSW

I + in

dust

rial

New

MSW

I

Rural

+ res

iden

tial

Cemen

t pla

nt0

0.5

1

1.5

2

2.5

3

3.5

mg

/kg

d.m

Characteristics of (POPs)(POPs) Toxic Substances

• Toxicity

• Accumulate in the bodies of animals when ingested: (bioacumulation)

• Increase in concentration as they move up the food chain: (biomagnification)

•Persistence: ability to exit unchanged for years

•Potential for long-range transport

Destilation process

SEMIVOLOTILE ORGANIC COMPOUNDS

•PAHs: Polyharomatic Hidrocarbons

•PCBs: Polychlorinated biphenils

•PCDD/Fs: Polychlorinated dibenzo-p-dioxins (PCDDs) and

dibenzofurans (PCDFs)

•PCNs : Polychlorinated Naphthalenes

•PBDE: Polybrominated Diphenyl Ethers

Chemical structure of decabromodiphenyl ether

POLYCYCLIC AROMATIC HYDROCARBONS (PAHs)

•Antropogenic input: Incomplete burning (coal, oil, gas, wood, garbage, tobacco and charbroiled meat).

Surface water through discharges from industrial plants and waste water treatment plants.

Released to soils at hazardous waste sites if they escape from storage containers.

•Routes of exposure: inhalation, dermal, oral •Stored in: kidneys, liver, and fat. Smaller amounts in spleen, adrenal glands, and ovaries.

• acenaphthene • acenaphthylene • anthracene • benz[a]anthracene • benzo[a]pyrene • benzo[e]pyrene • benzo[b]fluoranthene • benzo[g,h,i]perylene • benzoIj]fluoranthene • benzo[k]fluoranthene • chrysene • dibenz[a,h]anthracene • fluoranthene • fluorene • indeno[ 1,2,3-c,d]pyrene • phenanthrene • pyrene

PAHs considered as toxic (17)•There are more than 100 different PAHs

PAHs

Released to the atmosphere: are subject to short- and long-range transport and are removed by wet and dry deposition onto soil, water, and vegetation.

In surface water: can volatilize, photolyze, oxidize, biodegrade, bind to suspended particles or sediments, or accumulate in aquatic organisms (with bioconcentration factors in the 10-10,000 range).

In sediments: can biodegrade or accumulate in aquaticorganisms.

In soil: can volatilize, undergo abiotic degradation (photolysis and oxidation), biodegrade, or accumulate in plants. PAHs in soil can also enter groundwater and be transportedwithin an aquifer.

PCBs

•Are a family of 209 chemical compounds

•Uses: . Between 1930 and 1970, 1.4 billion pounds of PCBs were manufactured in the United States.

-Dielectric fluid-Flame retardant-Industrial lubricant fluid-Electrical insulators in transformers, capacitors, and other electrical equipment

•Characteristics of PCBs

•High toxicity•High persistence•Very stables•Resistant to acid o strong base hydrolysis•No biodegradable•Insoluble in water•Very soluble in organic solvents

PCBs

•Biological effect:-Hepatic damage-Dermal disorders-Reproductive toxicity-Teratogenicity-Reproductive problems-Lower fertility-Changes in appearance or behavior

-Hepatic cancer-Breast cancer

PCDD/Fs

Although 210 different congeners exist, only 17 are considered toxic: Polychlorinateddibenzo-p-dioxins (PCDDs) (7)

Polychlorinated dibenzo-p-furans (PCDFs) (10)

The most toxic : 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)

•Production source emissions: Natural :volcanoes and forest fires Antropogenic:as by-product of a number of human activities

including combustion processes

Adverse effects:Reproductive and developmental disorders Suppression of the immune system Cancer.

•Processes that generate dioxins:•Fuel combustion, •Waste combustion, •Chemical manufacturing, •Pesticide manufacturing, •Wastewater disinfection, •Polyvinyl chloride (PVC) manufacturing, •Chlorine pulp and paper bleaching

•Non-combustion sources of dioxin include :•Operations such as chemical and pesticide manufacturing processes, •Wastewater treatment operations (including land application ofbiosolids/sludge)•Metal smelting and refining•Elemental chlorine pulp and paper bleaching•Pressure treated wood manufacturing.

PCDD/Fs in soil

11.7

3.6

0.9 0.7 0.3

Old

MSW

I + u

rban

Old

MSW

I + in

dust

rial

New

MSW

I

Rural

+ res

iden

tial

Cem

ent pl

ant0

2

4

6

8

10

12

14

ng

ITEQ

/kg

d.m

0.7

1.3

0.2

0.4

0.2

Old

MSW

I + u

rban

Old

MSW

I + in

dust

rial

New

MSW

I

Rural

+ res

iden

tial

Cem

ent pl

ant0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

ng

ITEQ

/kg

d.m

PCDD/Fs in grass

2,3

,7,8

-TCDD

1,2

,3,7

,8-PeC

DD

1,2

,3,4

,7,8

-HxC

DD

1,2

,3,6

,7,8

-HxC

DD

1,2,

3,7,

8,9-

HxCDD

1,2

,3,4

,6,7

,8-H

pCDD

OCDD

2,3

,7,8

-TCDF

1,2,

3,7,

8-Pe

CDF

2,3

,4,7

,8-PeC

DF

1,2,

3,4,

7,8-

HxCDF

1,2,

3,6,

7,8-

HxCDF

1,2,

3,7,

8,9-

HxCDF

2,3

,4,6

,7,8

-HxC

DF

1,2,

3,4,

6,7,

8-HpC

DF

1,2,

3,4,

7,8,

9-HpC

DF

OCDF

0

2

4

6

8

10

12

14

16

ng/k

g d

.m

2000

2001

2,3

,7,8

-TCDD

1,2

,3,7

,8-PeC

DD

1,2

,3,4

,7,8

-HxC

DD

1,2

,3,6

,7,8

-HxC

DD

1,2,

3,7,

8,9-

HxCDD

1,2

,3,4

,6,7

,8-H

pCDD

OCDD

2,3

,7,8

-TCDF

1,2,

3,7,

8-Pe

CDF

2,3

,4,7

,8-PeC

DF

1,2,

3,4,

7,8-

HxCDF

1,2,

3,6,

7,8-

HxCDF

1,2,

3,7,

8,9-

HxCDF

2,3

,4,6

,7,8

-HxC

DF

1,2,

3,4,

6,7,

8-HpC

DF

1,2,

3,4,

7,8,

9-HpC

DF

OCDF

0

0.5

1

1.5

2

ng/k

g d

.m

2000

2001

Soils

Herbage

ng I-TEQ/kg d.m.0.15 0.08

ng I-TEQ/kg d.m.

0.28 0.27

Volatile Organic Compounds

They are 125 compounds regulated under the Safe Drinking Water Act.

•Halogenated alkanes (chloromethane, di...

•Halogenated alkenes (chloroethene..)

•Aromatic Hydrocarbons (benzene, styrene, naphtalene..)

•Halogenated aromatics (chlorobenzene..)

•Others (aldehides and nitriles)

Pesticides

•Use: to kill nuisance organisms

•Types: - Herbicides: Kill weeds and other plants - Insecticides: Kill insects- Fungicides: Kill fungi

•Characteristics:ToxicBioaccumulativePersistent

Pesticides:

•Organophosphate pesticides

•Carbamate pesticides

•Organichlorine insecticide

Characteristics: Toxic, bioaccumulative and persistent

http://www.eper.cec.eu.int

EPER is the European Pollutant Emission Register - the first European-wide register of industrial emissions into air and water.

9342 industrial facilities of the Member States of the EU

Have an inventory of the principal emissions coming from the principal industrial complex enclosed in the 96/61/CE Directive (IPPC).

Homework Report. Theme 2

Web page: EPER (http://www.eper-es.com)European Pollutant Emission Register (EPER).

Theme 2.- Look for information about the following chemical products: Benzene, Phenols, Tetrachloroethylene, Polycyclic aromatic hydrocarbons

a) Industrial activities that emit theses compounds to air and water

b) kg /year of all European industries

c) % Emitted by Spain