introduction to edcs and perfluorinated compounds - … to edcs and... · introduction to edcs and...

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Analysis, fate and risks of organic contaminants in river basins under water scarcity Valencia, 7-8 February 2011 Introduction to EDCs and perfluorinated compounds: general environmental problems, regulations in US and Europe, toxic effects and environmental levels Damià Barceló, Mira Petrovic, Marinella Farré IDAEA-CSIC, Department of Environmental Chemistry, Barcelona, Spain ICRA - Catalan Institute for Water Research, Girona, Spain Outline 1. EDCs Definition, History, Effects in wildlife and humans Mode of action, Compounds and sources EU and US legislation Specific groups of EDCs 1. Steorid sex hormones 2. Alkylphenolic non-ionic surfactans and related compounds 3. Phthalates 4. Brominated flame retardants 5. Polychlorinated compounds 6. Bisphenol A Environmental levels, Determination of EDCs (general aspects) 2. Perfluorinated compounds

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Page 1: Introduction to EDCs and perfluorinated compounds - … to EDCs and... · Introduction to EDCs and perfluorinated compounds: ... CH3 CH3 C CH3 O HO CH3 OH C CH H H ... Contraceptive

Analysis, fate and risks of organic contaminants in river basins under water scarcity Valencia, 7-8 February 2011

Introduction to EDCs and perfluorinated compounds: general environmental problems,

regulations in US and Europe, toxic effects and environmental levels

Damià Barceló, Mira Petrovic, Marinella Farré

IDAEA-CSIC, Department of Environmental Chemistry, Barcelona, Spain

ICRA - Catalan Institute for Water Research, Girona, Spain

Outline

1. EDCsDefinition, History, Effects in wildlife and humansMode of action, Compounds and sourcesEU and US legislationSpecific groups of EDCs

1. Steorid sex hormones2. Alkylphenolic non-ionic surfactans and related compounds3. Phthalates4. Brominated flame retardants5. Polychlorinated compounds6. Bisphenol A

Environmental levels, Determination of EDCs (general aspects)

2. Perfluorinated compounds

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Endocrine Disrupting Chemicals (EDCs)

“An exogenous substance that causes adverse health effects in an intact organism, or its progeny, consequent to changes in endocrine function”

(European Commission)

“An exogenous agent that interferes with the synthesis, secretion, transport, binding, action or elimination of natural hormones in the body that are responsible for the maintenance of homeostasis, reproduction, development and/or behaviour”

(EPA)

History

1938 1996

1st EU actionThe impact of endocrine disruptors on human health and wildlife, Keybridge, UK

1st evidence of the estrogenic activity ofsynthetic compounds (EC Dodds and W Lawson)

1962

Silent SpringRaquel Carson

1979

DES

1985 1992

McLachlanColburn—Conferences—

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1997: “Our Stolen Future” by Theo Colburn indicates human and ecological dangers of EDCs

2000s: Global research efforts on EDC toxicity, occurrence, treatment strategies, and prevention

• Decreased fertility & growth• Sex alteration• Poor hatching/egg shell thinning• Abnormal thyroid function

Well-documented effects in wildlife

Some examples include: •reproductive effects in Baltic seals, •eggshell thinning in birds of prey, •decline in the alligator population in a polluted lake, •general declines in frog populations, •effects on the reproduction and development of fish, •development of male sex organs in female marine organisms such as whelks.

Aquatic animals are the most affected, especially carnivores, because they are atthe top of the "food chain".

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Suspected effects in humans

• Malformations of newborns • Undescended testicles• Abnormal sperm• Low sperm counts• Abnormal thyroid function• Possible breast, testicular,

prostate cancer• Other effects

How do the EDCs act ?

Substances can interact with endocrine systems and cause a disruption tonormal functions in several ways:

• They can act like a natural hormone and bind to a receptor. This causes a similar response by the cell, known as an agonist response.

• They can bind to a receptor and prevent a normal response, known as anantagonistic response.

• A substance can interfere with the way natural hormones and receptors aresynthesized or controlled.

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EDCs Do Not Follow a “Typical” Carcinogenic Dose:ResponseCurve

Dose

Response

“Safe”“Typical”Carcinogenic Response

EDC Response

Timing of Exposure is Critical

SOME CATEGORIES OF SUBSTANCES WITH REPORTED ENDOCRINE-DISRUPTING PROPERTIES*

SUBSTANCE EXAMPLES USES MODES OF ACTIONNaturally occurringPhytoestrogens Isoflavones; Present in plant material Estrogenic and

anti-estrogeniclignans; coumestans

Female sex hormones 17-β estradiol; Produced naturally in animals Estrogenicestrone (including humans)

SyntheticPolychlorinated Dioxins By-products from incineration

and industrial chemical processesAnti-estrogenic

organic compounds

Polychlorinated biphenyls(PCBs)

Organochlorinepesticides

DDT; dieldrin; lindane Insecticides Estrogenic andanti-estrogenic

Organotins Tributyltin Anti-fouling agent

Alkylphenols Nonylphenol Used in production of NPEOs andpolymers, degradation product

Estrogenic

Alkylphenol ethoxylates Nonylphenol ethoxylate Surfactants EstrogenicPhthalates Dibutyl phthalate (DBP); Plasticisers Estrogenic

butylbenzyl phthalate (BBP)Bi-phenolic compounds Bisphenol-A Component in polycarbonate Estrogenic

plastics and epoxy resinsSynthetic steroids Ethinyl estradiol Contraceptives Estrogenic

*Environment Agency, R&D Technical Summary P38, 1999.

Dielectric fluids

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Potential Sources

Incineration, LandfillPolychlorinated Compounds - Polychlorinated Dioxins, Polychlorinated Biphenyls

Industrial And Municipal EffluentsAlkylphenolics (Surfactants and Their Metabolites): NonylphenolPhthalates (Found In Placticisers): Dibutyl Phthalate, Butylbenzyl Phthalate

Municipal Effluent And Agricultural RunoffNatural Hormones; Synthetic Steroids - 17-B-Estradiol, Estrone, Testosterone; Ethynyl

EstradiolPulp Mill Effluents

Phytoestrogens - Isoflavones, Lignans, CoumestansAgricultural Runoff / Atmospheric Transport

Organochlorine Pesticides DDT, Dieldrin, Lindane

Agricultural RunoffPesticides Currently In UseAtrazine, Trifluralin, Permethrin

HarborsOrganotins: Tributyltin

EU adopted Strategy for EDCs (March 30,2000) (5257/00)

URGENT NEED to establish monitoring programs and to assess hazards and risks of EDCs

Establishment of PRIORITY LIST of substances, i.e., EU 33 priority substances within Water Framework Directive include EDCs: Octylphenol, Nonylphenol and Di(2-ethylhexyl)phthalate (DEHP)

In the medium-long-term, EU Directives for EDCs and identification of substitutes

The whole approach is to be based on the PRECAUTIONARY PRINCIPLE

EU Regulations

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Establishment of a priority list of substances

Legislative actions - Water Framework Directive - in 2 years (20 years, phase out)

Sweden Workshop on EDCs, June 2001 recommendations on Monitoring were:

Study “hot-spots” (near WWTPs),

Fill the gap between research/monitoring

Implementation of the EU Strategy for EDCsCOM(2001) 262 , 14-06-2001

EU Regulations

US Regulations

1962: Public Health Services Standard

– EDCs such as arsenic, cadmium, and phenols

1974: EPA establishes Safe Drinking Water Act

– Maximum Contaminant Limits (MCLs)

– Synthetic chemicals including pesticides

Recent US Legislation (Amendments):

– Safe Drinking Water Act, Nov. 1995

– Food Quality Protection Act, Aug. 1996

1996: EPA forms the Endocrine Screening and Testing Advisory

Committee (EDSTAC)

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EDSTAC– Purpose of EDSTAC: design a screening and testing program– Final report issued in August 1998 outlining a three tiered approach

(screening/testing/assessment) for evaluation of over 87,000 compounds

1998 - On-Going – EPA’s Endocrine Disruptor Screening Program (EDSP)– EPA is conducting a mass screening of compounds to determine their

endocrine disruption potential, if any.

2001 – Low-dose Peer Review – Evaluate reported low-dose reproductive and developmental effects and

dose-response relationships – National Toxicology Program (NTP) and the National Institute of

Environmental Health Sciences (NIEHS)

US Regulations

Specific groups of EDCs

1. Steorid sex hormones

2. Alkylphenolic non-ionic surfactans and related compounds

3. Phthalates

4. Brominated flame retrardants

5. Polychlorinated compounds

6. Bisphenol A

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Steroid sex hormons

ESTROGENSNatural hormones:

EstradiolEstriolEstrone

Synthetic compounds:Ethynyl estradiolDiethylstilbestrol

PROGESTOGENSNatural hormones:

Progesterone

Synthetic compounds:NorethindroneLevonorgestrel

H O

CH 3OH

H O

CH 3OH

H

H

O

CH 3

CH 3

CCH 3

O

H O

CH 3OH

C HC

HH

H

CHC

O HCH 3

O

1 mg norethindrone acetate20-35 μg ethynyl estradiol

The “day-after” pill

750 μg levonorgestrel

Contraceptive pills

Birth-control pills

Estrogens (20 to 50 µg daily)– Ethynyl estradiol– Mestranol

Progestogens (30 µg to 2 mg daily)– Ethynodiol diacetate– Levonorgestrel– Norethindrone

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Uses (other than contraception)

• Estrogens:

– Management of menopausaland postmenopausalsyndrome

– Physiological replacementtherapy

– Prostatic cancer and breastcancer in postmenopausalwomen

• Progestogens:

– Infertility– Endometriosis– Certain breast and

endometrial cancers– Menstrual disorders

* Doses up to 400 mg daily

Environmental fate, toxicity and estrogenic effectsof steroid sex hormones and related synthetic

compounds

Aqueous concentration that may induce estrogenic effects: 0.1-10 ng/L (E2, EE)

Relative estrogenic potency (relative to 17β-estradiol)

Estrogen receptor Uterine weight Response of Vitellogenesisbinding affinity doubling potency MCF7 cells

Estradiol 1.0 1.0 1.0 1.0Diethylstilbestrol 0.4 2.5 0.1Estrone 0.05Ethynyl estradiol >1.0

Biodegradation: synthetic estrogens are more persistent than natural estrogens

Half-life in surface water:estradiol <3-27 days ⇒ estroneethynyl estradiol > 26 days

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Nonionic surfactantsAlkylphenol ethoxylates

nonionics49%

anionics41%

amphoterics2%cationics

8%

AEO; 65%

APEO 9%other nonionics; 13%

Fatty amine/acidethoxylates; 13%

OOH

C9H19

n

n=1-20

Nonylphenol ethoxylates(NPEOs)

- Non-ionic surfactantsindustrial formulation (textile, tannery, pulp and paper industries)

- Pesticides adjuvants- Paint ingredients- Wetting agents

• Global production is well over 500.000 tons • Use restricted in many countries• Throughout northern Europe (Scandinavian countries, England, Germany) a

voluntary ban on NPEO use in household cleaning products began in 1995, and restrictions on industrial cleaning applications in 2000

• South Europe - use in industrial formulations not restricted• USA, Spain – not restricted

Alkylphenol ethoxylates

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Increasing polarityPossible contamination

of groundwaters

Breakdown pathway of NPEOs

Increasing toxicity

Increasingbioconcentration

Increasingpersistence

C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OH

C9H19 O CH2CH2O H9

C9H19C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

C9H19C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OHC9H19C9H19 OH

Increasing toxicity

Increasingbioconcentration

Increasingpersistence

C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OH

C9H19 O CH2CH2O H9

C9H19C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

C9H19C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OHC9H19C9H19 OH

Main concern - Reproductive toxicity of some degradation products

Alkylphenols(NP and OP)

OH

R

Short alkylphenol ethoxylates (APEOs)

OOH

Rn

n=1-2

Alkylphenoxy carboxylates

(APECs)

nOCH2COOHO

R n=0-1

Halogenated derivatives formed during chlorination (in the presence of bromide) at water treatment works

OOH

Rn

X

nOCH2COOH

O

R

XOH

R

X

Halogenated alkylphenols

(XAPs)

Halogenated alkylphenoxy carboxylates (XAPECs)

Halogenated alkylphenol ethoxylates (XAPEOs)

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Halogenated alkylphenolic compounds

• Posses higher acute toxicity to Daphnia magna than non-halogenated precursors1

• Suspected mutagens2

• Halogenated nonylphenolic derivatives retain a significant affinity for the estrogen receptors suggesting that they may be able to disturb the hormone imbalance of exposed organisms3

1H. Maki et al., Environ. Toxicol. Chem. 19982M. Reinhard et al, Environ. Sci. Technol. 19823N. García-Reyero, V. Requena, M. Petrovic, B. Fischer, P.D. Hansen, D. Barceló, B. Piña Environ. Toxicol. Chem. 2004

Breakdown during sewage treatment (AST)(according Ahel, Wat. Res. 1995)Ultimate biodegradation of NPEOs <40%

40-45% ends up in secondary effluent

20 % in sludge

Primary Effluents

68%

20%

5%7%

NPnEONP1EO+NP2EO

NP1EC+NP2ECNP

20%

25%47%

8%

Secondary Effluents Digested Sludge

5%

95%

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NPEC NP NPEO halogenated derivatives

Average composition of nonylphenolic compounds after chlorination

(calculated on a molar basis)

Flocculation sludgeChlorinated river waterRiver water

13%

48%

After: Petrovic et al. ES&T, 2003

Environmental fate, toxicity and estrogeniceffects of alkylphenolic compounds

The relative estrogenic potency (relative to 17β-estradiol) in-vitro(according Jobling and Sumpter, Aquatic. Toxicol. 1993)NP 9.0 x 10-6

OP 3.7 x 10-5

NP1EC 6.3 x 10-6

NP2EO 6.0 x 10-6

NP10EO 2.0 x 10-7

Toxicity EC50, 48 h (Daphnia magna) 1.5 mg/L (NPEO), 0.18 mg/L (NP)Bioconcentration factor: algae 6600-7700 (NP), 3500-5000 (NP1EO)

mussel 3400 (NP)

Aqueous concentration that may induce estrogenic effect: 1-20 μg/L

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Estrogenic potential of halogenated alkylphenoliccompounds

RYA Dose/response curves

Halogenated NPs – weaker estrogens than NP

Relative affinity as calculated from the ELRA

Halogenated NPs – significant affinity for ER

Competition assay

Halogenated NPECs – strong antiestrogens

Antiestrogenic assay

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Phthalates

COO-R1

COO-R2

R1 R2 Name AcronymCH3 Dimethyl phthalate DMP

CH2CH3 Diethyl phthalate DEP(CH2)3CH3 Dibutyl phathalate DBP

(CH2)3CH3 CH2C6H5 Butylbenzyl phthalate BBP

CH2CH(CH2CH3)(CH2)3CH3 Bis(2-ethylhexyl) phthalate DEHP

C8H17 Di-n-octyl phthalate DnOP

Phthalates from the “Priority pollutant” list according to the US EPA

Plasticizers used in the manufacturing of PVC, epoxy resins and cellulose esters, adhesiveformulations

- medical products, cosmetics, packaging offood (limited extent)

Environmental fate, toxicity and estrogeniceffects of phthalates

Environmental risk limits ERL (sediment containing 10% organic matter)according to Wezel et al. Ecotoxicol. Environ. Saf. (2000)DEHP 1,000 μg/kg (fresh weight)DBP 700 μg/kg

The relative estrogenic potency (relative to 17β-estradiol) in-vitroBBP 10-4 - 10-6

DBP 10-5 - 10-7

DEHP 10-5

In-vivo tests (mouse and rat)Endocrine disruptive effects observed for DBP, DEHP, BBP, DEP and DHP

Biodegradation (decreases as the length of the alkyl chain increases)- sewage sludge inocula: >50 - 99% ultimate degradation, 28 daysPrimary degradation half-lives in surface waters <1 day to 2 weeksToxicity EC50, 48 h (Daphnia magna) 3.9 mg/L (DBP)

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Brominated Flame Retardants (BFR)

Main types of BFR– Polybrominated biphenyl (PBB) – Polybrominated diphenyl ether (PBDE)– Tetrabromobisphenol - A (TBBPA) – Hexabromocyclododecane (HBCD) – textiles

Classes of BFRAdditive - mixed into polymers, not chemically bound to plastic (PBB and PBDE)Reactive - chemically bound to plastic (TBBPA)

Uses- Plastic components of computers and televisions- Circuit boards- Seats of cars and buses- Textiles

Polybrominated Polybrominated biphenylsbiphenyls ((PBBsPBBs))209 209 congenerscongeners

Polybrominated Polybrominated diphenylethersdiphenylethers (PBDEs)(PBDEs)209 209 congenerscongeners

x + y = 1-10 x + y = 1-10

HexabromocyclododecaneHexabromocyclododecane (HBCD)(HBCD)3 3 isomersisomers

TetrabromobisphenolTetrabromobisphenol A (TBBPA)A (TBBPA)

BrBr

Br

Br

Br

Br

α-HBCD β-HBCD γ-HBCD

Br

HO

CH3

Br

BrBr

CH3 OH

O

Brx BryBrx Bry

Brominated flame retardants

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Production of BRF

Penta-BDE Octa-BDE Deca-BDE TBBPA HBCD

America 8290 1375 24300 21600 3100

Europe 210 450 7500 13800 8900

Asia 0 2000 23000 85900 3900Total 8500 3825 54800 121300 15900

Estimated world market demand for PBDEs, TBBPA and HBCD in 1999 given in metric tons (www.bsef.com)

- Penta-BDE ban in the European Union effective in 2003. - Penta-BDE consumption has already dropped in Europe, and a

shift in production towards other BFRs like Deca-BDE and HBCD took place.

Hormone disrupting effects of BFR

Heating (for example during manufacture of plastics) and burning of materialscontaining PBBs, PBDEs and other brominated flame retardants can produce polybrominated dibenzo-p-dioxins and dibenzofurans, which have similar toxicological effects to chlorinated dioxines

Low level exposure of young mice to PBDEs causes permanent disturbances in behaviour, memory and learning

PBDEs have been shown to disrupt the thyroid hormone system in rats and mice; these systems are a crucial part of the development of the brain and body

TBBPA is active in a breast cancer cell assay; its chemical structure is very similar to bisphenol A

TBBPA was found to high potential for out-competing the natural hormone, thyroxine.

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PCDDs, PCDFs and PCBsFormed as a byproduct of:- Combustion processes- Metal industry- Chemical manufacturing- Biological and photochemicalprocesses- Reservoir sources

Polychlorinated dibenzo-p-dioxins (PCDDs)

Polychlorinated dibenzofurans (PCDFs)

Polychlorinated biphenyls (PCBs)

Clx Cly

1 1´

2 2´3 3´

4 4´

5 5´6 6´

1

2

3

46

7

89

O

O

Cl Clx y

Clx Cly

O

-high chemical stability-high lipophilicity

BIOCONCENTRATIONBIOMAGNIFICATION

Electrical and flame-retardantproperties; used in:-Hydraulic fluids-Electrical equipment- Sealants- Plasticizers- Paints- Adhesives- Casting agents

Estrogenicity of PCBs and Dioxines

The main oestrogenic effect of PCBs may be due to their hydroxylated metabolites, which are produced when the body attempts to break them down, in addition somePCB congeners may be anti-oestrogenic

Those metabolites with a para-hydroxylation on one of the rings are particularlyeffective at mimicking oestradiol, though others are also oestrogenic

Many PCDDs are known to be toxic and carcinogenic. PCDDs appear to be anti-estrogenic

Exposure to PCBs in food has been linked to delayed brain development andreduced IQ in children

Dioxins alter the immune system

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Bisphenol A (BPA)

OHHO

Global production is more than one million tons per year

Plasticizer

• Bisphenol A is used in the production of epoxy resins and polycarbonate plastics. These plastics are used in many food and drink packaging applications, whilstthe resins are commonly used as lacquers to coat metal products such as foodcans, bottle tops and water supply pipes

• Some polymers used in dental treatment contain Bisphenol-A.

Hormone disrupting effects of BPA• Bisphenol A was first shown to be oestrogenic in 1938, using ovariectomized

rats

• More recently, it was found to be oestrogenic in the MCF-7 human breastcancer cell culture assay in 1993

• The hormonal effects could be measured at concentrations as low as 2-5 ppb(2-5 µg/l).

• Bisphenol A can also act as an antiandrogen, blocking the action ofdihydrotestosterone in a yeast screen containing a human androgen receptor In this screen bisphenol A was approximately as potent as flutamide, a wellknown anti-androgenic chemical.

• Bisphenol A produces identical effects to those produced by oestradiol on ratuterus and vagina; the vagina was particularly sensitive to the chemical

• It has been claimed that bisphenol acts in the same way as female hormones in the area of the developing rat brain which regulates fertility and sexual behaviour

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Environmental levels

Water samples- Wastewater- Suface water- Sea water

Solid samples- Sewage sludge- Soil- Sediment

Matrix (Location) Compounds Concentration(ng/l or ng/g)

WATERWastewaterSTP influent → effluent

(Italy) (Spain)(The Netherlands)

River water(Germany)(UK)(UK) (Spain)(USA)(Canada)

Surface water(The Netherlands)

Drinking water(Germany)(U.K.)

SeawaterSOLID SAMPLESRiver sediment (Germany)River sediment (Spain)Activated and digested sludge (Germany)

Estrogens and progestogensNatural and synthetic estrogensNatural and synthetic estrogens

Natural and synthetic estrogensNatural and synthetic estrogensSynthetic estrogens/progestogensEstrogens and progestogensSteriods and hormonesSteroids

Natural and synthetic estrogens

Natural and synthetic estrogensSynthetic estrogens/progestogens

Natural and synthetic estrogensEstrogens and progestogensNatural and synthetic estrogens

0.4-188 → 0.3-82.1<0.2-115 → <0.2-21.5<0.5-140 → <0.4-47

<0.1-5.1<0.2-172-170.2-71.15-20002-67

0.1-5.5

<0.1-2.1<1-10

<0.2-1.50.05-22.8<2-49

Environmental levels – steroid sex hormones

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Environmental levels – alkylphenolic compoundsMatrix /location Compound Concentration (water)

μg/L

Concentration (sediment/soil)

mg/kg

Freshwater aquatic systems

Spain (Catalonia), water and sediment NPEO, NPEC, NP

<0.1-31 (NPEO)<0.1-15 (NP)

<0.1-35 (NPEC)

0.010-0.820 (NPEC)0.022-0.645 (NP)

Germany (Baden-Württenberg) NP, OP <0.01-0.49 (NP)<0.01-0.19 (OP)

<0.05-0.26 (NP)

USA and Canada (Great Lakes) NP, OP <0.01-0.92 (NP)<0.005-0.084 (OP)<0.02-7.8 (NPE1O)

0.17-72 (NP)<0.01-1.08 (OP)

<0.015-38 (NPE1O)

USA streams (30 rivers) NP, NPEO <0.11-0.64 (NP)<0.06-0.60 (NPE1O)<1.6-14.9 (NPE3-17O)

<0.003-2.96 (NP)<0.003-0.17 (NPE1O)

Italy (river Po) AEO - 0.15-1.05

Japan NPEO, NP, OP 0.04-0.42 (NPE1O)0.04-0.52 (NPE2O)

<0.02-0.3 (NP)

-

Soil

Sludge-amended soil NPEO, NP - 0.11—1.1 (NPE1O)0.095—0.012 (NPE2O)

Sludge-amended soil NPEO, NP, OP - 0.07—1.21 (NPE1O)0.08—0.39 (NPE2O)

2.35—4.61 (NP)

Environmental levels – alkylphenolic compounds

Matrix /location CompoundConcentration

(water)μg/L

Concentration (sediment/soil)

mg/kg

Marine and estuarine environment

Spanish coastal area AEO <0.1-15 0.037-1.3

CDEA <0.05-24 0.03-2.7

NPEO, NPEC, NP

<0.2-11 (NPEO)<0.15-4.1 (NP)

0.01-0.62 (NPEO)<0.01-1.05 (NP)

Venice lagoon (Italy) – Estuarine water NPEO, NPEC 1.1-38.5 (NPEO)a

0.6-102 (NPEC)-

Krka estuary (Croatia) NPEO, NP <0.02-0.44 (NP1EO)0.1-0.7 (NP3-18EO)

<0.02-1.2 (NP)

-

English estuaries NPEO, NP, OP <0.6-76 (NP1+2EO)<0.08-5.8 (NP)

0.16-3.97 (NP1EO)0.03-9.05 (NP)

Italy (Tiber estuary) PEG, MCPEG, DCPEG

0.5-68 (PEG)<0.05-2.1 (MCPEG)

-

The Netherlands (Scheldt Estuary) NPEO, NP, NPEC

0.04-2.7 (NPEO)0.04-2.0 (NP)

0.04-0.25 (NPEO)

USA (Jamaica Bay) NPEO, NP, OPEO, OP

0.16-0.94 (NPEO)0.077-0.42 (NP)

0.05-30 (NPEO)<0.001-0.027 (BrNP)

Israel coast (sea water) NPEO <1.0-25 -

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Environmental levels – PBDEsMatrix (Location) Compounds Concentration

SedimentRiver sediments (Japan)Sediments downstream of a plastic industry (Sweden)

Sediments from a river with textile industries (Sweden)

Sediment (Baltic Sea)River mouth sediments (Europe)

Tetra- + Penta-BDEsBDE-47BDE-99BDE-100BDE-47+99+100BDE-209Sum PBDEBDE-47BDE-99

21 – 59 ng/g490 ng/g750 ng/g170 ng/gnd – 9.6 ng/gnd – 360 ng/gnd – 1.1 ng/g<0.17 - 6.2 ng/g<0.19 – 7.0 ng/g

Sewage SludgeDigested sludge (Gothenburg, Sweden)Sewage sludge (Germany)Digested sludge (Stockholm, Sweden)

Sum PBDESum PBDEBDE-47BDE-99BDE-100BDE-209

20 – 30 ng/g0.4 – 15 ng/g39 – 91 ng/g48 – 120 ng/g11 – 28 ng/g140 – 350 ng/g

BiotaFish from background areas (Sweden)Fish (Sweden)Osprey found dead (Sweden)Marine fish and shellfish (Japan)Freshwater fish (North-Rhine Westphalia)Salmon (Baltic sea)

Cow´s milk (Germany)Reindeer and moose (Sweden)Chickens (US)

Sum PBDEBDE-47+99+100Sum PBDETetra- + Penta-BDEsSum PBDEBDE-47BDE-99Sum PBDESum PBDESum PBDE

26 – 1200 ng/g fat19 – 4600 ng/g fat2100 ng/g fat0.1 – 17 ng/g fat18 -983 ng/g fat167 – 190 ng/g fat52 ng/g fat2.5 – 4.5 ng/g fat0.47 – 1.7 ng/g fat3.6 – 35.1 ng/g fat

Estimating human exposure to PBDE-47 via air, food and dust using Monte Carlo methods.

T.Webster, V.Vieira, A.Schecter. Organohalogen Compds. (2005) 505-508.

Human exposure to BDE-47

BABIES ng/Kg * day %

Dermal contactDietInhalationDustTOTAL

1.5117.9

0.14.5

123.9

1.295.1

0.13.6100

ADULTS ng/Kg * day %

Dermal contactDietInhalationDustTOTAL

0.10.60.00.20.9

10.563.1

2.723.7100

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Feed contamination (for fish) by PBDEs

Global assessment of polybrominated diphenyl ethers in farmed and wild salmonR.A.Hites, J.A.Foran, S.J.Schwager, B.A.Knuth, M.C.Hamilton, D.O.Carpenter.

Environ. Sci. Technol. 38 (2004) 4945-4949.

Fish farms

Wild fish

Market fish

Perfluorinated compounds (PFCs)

Perfluorinated = fully fluorinated

Ex. Perfluorooctanoic acid (PFOA , C-8)

Very stable (C-F bond energy 485 kJ/mol)

(C-C 346, C-N 305, C-O 358, C-Cl 327 kJ/mol)

F

F

F F

F

F

F

F

F

F

F

F

F

F

F OH

O

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PFCs Most Common Structures

F

F

F F

F

F

F

O

OH

n=3 - 9

Perfluorocarboxylic acids

SF

F

F F

F

F

F

O

O

O-

n=2, 4, 6

Perfluorosulfonic acids

Fluorotelomer alcohols

F

F

F F

F

F

F OH

n=4, 6, 8

F

F

F F

F

F

F OH

On=4, 6, 8

Telomer acids

F

F

F F

F

F

F

F

F

F

F

F

F

F

F

S

O

O

N

O

OH

RR = methyl, ethyl

Sulfonamides

F

F

F F

F

F

F O

P-O

OOH

n = 4, 6, 8

Phosphate acids

F

F

F F

F

F

F

P

O

R

R

n = 2, 4, 6

Phosphinic / Phosphonic

PFCs Properties

Thermally stable (in excess of 150°C)

Resist degradation (acid, alkali, oxidizing agents, bio…)

Hydrophobic and oleophobic (3 phases in Kow)

Good surfactants, lubricants

Non-flammable

Chemically inert

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Due to PFCs properties are used in a plethora of industrial applications

carpet, upholstery, paper,

textiles, cookware, paint,

polymers, lubricants, flame

retardants, pesticide

formulations…

Due to PFCs properties areGlobally Distributed (environmentally, biologically)

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PFCs Human Exposure Pathways (WATER-FOOD)

PFCs -Biological EffectsBiopersistence: PFOS and PFOA are the most studied and have been

subject to restrictions in both manufacturing and use (3M, 2009). Currently, a high number of new PFCs are in use as alternatives, however these new PFCs can also breakdown to PFOS and PFOA, which would add to the reservoir of these persistent contaminants in the general environment

Bioaccumulation: PFCs accumulate in the liver, blood and breast milk (Lau et al., 2007), where it is primarily attached to proteins. In animal studies, PFCs are linked to bladder cancer (Alexander et al., 2003), liver cancer (Biegler et al., 2001), and developmental and reproductive toxicity (including neonatal mortality) (Lau, 2003) and impairment of thyroid, liver and immune system functions (Lau et al., 2007).

Exposure to PFCs can lead to increase in infertility for women (Biegler et al., 2001) and reproductive tract abnormalities: Cryptorchidism (undescended testicles) and alteration of puberty timing, specially when exposure occurred during early stages of development.PFCs are able to cross the human placenta (Inoue et al., 2004).

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PFCs - Concentration levels in Drinking water

0.650.55

519 598

58 57

8 3

8 2

2 5

8

80

7 2

218

1 1

3 2

3 1

PFOS (ng/L)

PFOA (ng/L)

PFCs - Drinking water

After detection of PFOA in drinking water at concentrations up to 0.64 μg/l in Arnsberg, Sauerland, Germany, the German Drinking Water Commission (TWK) assessed PFCs in drinking water and set for the first time worldwide in June 2006 a health‐based guide value for safe lifelong exposure at 0.3 μg/l (sum of PFOA and PFOS). 

Germany

New and shorter-chained PFCs (C4-C7) and their mixtures are

being introduced as replacements. These "new" compounds could be

main contributors to total PFC levels in drinking water in future.

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PFCs - Concentration levels in Food

PFCsPFCs

Perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and their salts Scientific Opinion of the Panel on Contaminants in the Food chain

The EFSA Journal (2008) Journal number, 653, 1‐131.

PFCs - Concentration levels in Food