typical sediment contaminants - typical sediment contaminants. distribution of contaminants surface

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  • Typical sediment contaminants

    Distribution of contaminants surface waters between water, air and sediments/suspended matter according to partitioning coefficients.

    High lipophilicity (octanol/water partitioning coefficients kOW) and low volatility from water (Henry coefficient) support accumulation in sediments and suspended matter.

  • Typical sediment contaminants Polycyclic aromatic hydrocarbons (PAHs) Class of organic pollutants with two or more condensed aromatic rings

    fluorenenaphthalene anthracene phenanthrene pyrene fluoranthene

    chrysene benz[a]anthrace benzo[a]pyrene benzo[e]pyrene perylene

    benzo[k]fluoranthene indeno[1,2,3-cd]pyrene

    benzo[ghi]perylene

    Examples

    + methyl and ethyl derviatives

    coronene

  • Typical sediment contaminants Polycyclic aromatic hydrocarbons (PAHs) Properties: •lipophilic: log kOW: 3.3 (naphthalene) to 7.6 (coronene) and higher •water solubility low: 30 mg/L (naphthalene) to 0.00014 mg/L (coronene) •many PAHs genotoxic, mutagenic and carcinogenic (most of them after enzymatic activation (indirect mutagens) •always occurring in mixtures of hundreds of compounds

    Major sources pyrogenic (incomplete combustion) petrogenic (handling of coal and petroleum)

    coal coking (blowing off volatiles at 2000°C)

    http://upload.wikimedia.org/wikipedia/commons/b/bd/Coke_Ovens_Abercwmboi.jpg

  • Typical sediment contaminants Polycyclic aromatic hydrocarbons (PAHs)

    Major sources aluminium production (coal anodes) domestic

    heating

    motor vehicle traffic forest fires

    coal-fired power plants

    Incineration of refuse

    http://upload.wikimedia.org/wikipedia/commons/f/fc/Coal-fired_power_station_Werdohl_Elverlingsen_Germany.jpg http://www.northlineexpress.com/itemdesc.asp?ic=5NP-1600CN http://en.wikipedia.org/wiki/Image:Aluminumfoil.jpg http://upload.wikimedia.org/wikipedia/commons/f/fb/Wsa-lightning-complex_fire_ron-gregory.jpg

  • Typical sediment contaminants Halogenated aromatic hydrocarbons

    Polychlorinated biphenyls (PCBs)

    ClxCly

    used in/as transformers, capacitors, hydraulic fluids, flame retardants…….

    Properties: •209 Congeners. Commercial products (e.g. Aroclors) are mixtures of 50 or more. •Viscous liquids •High dielectric constants, high thermal conductivity, high flash point •very resistant to oxidation, reduction, addition, elimination and electrophilic substitution ⇒ very persistent •produced in the U.S. since 1929 (later also in Europe, Japan, USSR)

  • Typical sediment contaminants Polychlorinated biphenyls (PCBs)

    Properties: •highly lipophilic (log KOW 4.6 to > 8) •low water solubility (2 mg/L (MCB) to 10-6 mg/L (DCB) •bioaccumulating •globally distributed •high concentration in the arctic (global distillation), accumnulation in polar bears, seals… ⇒ hazard for ecosystem and human health

  • Typical sediment contaminants Polychlorinated biphenyls (PCBs)

    Toxic/ecotoxic effects

    1968 mass poisoning in Japan with PCB contaminated rice bran oil ⇒ Yusho Disease in over 14,000 people

    Particularly the co-planar PCB congeners are highly toxic to humans and animals (dioxin-like toxicity)

    Toxicity to humans: Chloracne, liver damage, dermal and ocular lesions, lowered immune response, carcinogenicity, poor cognitive development of children.

  • Typical sediment contaminants Polychlorinated biphenyls (PCBs)

    Toxicity to animals:

    Acute effects: Liver damage and death (e.g. 400,000 birds 1968 in Japan after feeding on PCB contaminated poultry feed)

    At smaller concentrations effects on immune system, behavioral alterations, impaired reproduction).

    Particularly severe: accumulation in and effects on top predators like the white tailed see eagle. Clutch of 2 dead eggs in a

    white-tailed sea eagle nest

    Accumulation in aquatic food webs from sediments via invertebrates and fish to top predators (biomagnification)

  • Typical sediment contaminants Polychlorinated biphenyls (PCBs)

    Several large scale environmental contamination incidents

    U.S. New York State: 1947 to 1977 release of 590 tons of PCBs by a capacitor manufacturing plant. Very high levels in fish ⇒ ban of all fishing Multiple remediation activities still going on

    U.S. Dumping of reject capacitors and PCB oils down drains of Westinghouse Electric (Bloomfield, Indiana). Contamination of sewage treatment plant. Sludge was used for farms and gardens.

    http://www.bloomingtonalternative.com/articles/2008/03/23/9191

  • Typical sediment contaminants Halogenated aromatic hydrocarbons

    Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs)

    O

    O

    Cl

    Cl

    Cl

    Cl O

    Cl

    Cl Cl

    Cl

    Most toxic representatives of dioxin-like toxicity (see PCBs)

    Very persistent

    Byproduct of organic synthesis of halogenated aromatic compounds and incineration processes

    2,3,7,8-TCDD 2,3,7,8-TCDF

  • Seveso accident 1976: Explosion in factory producing 2,4,5- trichlorophenol Emission of 1 to 3 kg 2,3,7,8-TCDD 3300 animals domestic animals died at once, 80.000 very slaughtered 200 severe cases of cloracne Pregnant women were advised to abort

    Latest victim of PCDD/Fs:

    Typical sediment contaminants Halogenated aromatic hydrocarbons

    Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs)

    Agent orange (2,4,5- Trichlorophenoxyacetic acid and 2,4- Dichlorophenoxy-acetic acid) contaminated with 2,3,7,8-TCDD applied by U.S. American troops in 1961-1971 against Vietnam

    Still 500.000 citizens suffer from remote damages due to TCDD (cancer, malformations……)

    http://upload.wikimedia.org/wikipedia/commons/8/82/Defoliation_agent_spraying.jpg http://upload.wikimedia.org/wikipedia/commons/b/b4/2%2C4%2C5-T.svg

  • Typical sediment contaminants Halogenated aromatic hydrocarbons

    Polychlorinated naphthalenes (PCNs) Cl

    Cl

    Cl

    Cl Sources: •technical products (e.g. Halowax) mainly used in electrical industry •byproducts of industrial processes (e.g. chloralkali electrolysis – binders of graphit electrodes) •incineration processes (fly ash)

    Dioxin-like acting planar halogenated aromatic hydrocarbons Very lipohilic and persistent

  • Typical sediment contaminants Halogenated aromatic hydrocarbons

    Polybrominated biphenyls (PBBs) and

    Polybrominated diphenylethers (PBDEs)

    Br

    BrBr

    Br

    O Br

    Br

    Br

    Br

    •Used as flame retardants •In 1970s technical mixtures of penta to decabromo congeners produced •Because of high potential of less brominated congeners to bioaccumulate today only decabromo diphenylethers •Similar health effects to PCBs, PCDD/Fs and PCNs

  • Typical sediment contaminants Halogenated aromatic hydrocarbons DDT (dichloro-diphenyl-trichloroethane) and metabolites

    • Insecticide •very toxic to insects: opens Na ion channels in neurons

    • low acute toxicity to humans and mammals

    p,p’-DDT

    o,p’ DDT (impurity in technical DDT)

    p.p’-DDE (dichloro-diphenyl- dichloroethene)

    p,p’-DDD (dichloro- diphenyl-dichloroethane)

    major transformation products in the environment

    http://upload.wikimedia.org/wikipedia/en/e/e3/DDT.jpg http://upload.wikimedia.org/wikipedia/commons/c/c8/PpDDT.svg http://upload.wikimedia.org/wikipedia/commons/e/e3/OpDDT.svg http://upload.wikimedia.org/wikipedia/commons/d/d0/PpDDE.svg http://upload.wikimedia.org/wikipedia/commons/5/51/PpDDD.svg

  • Typical sediment contaminants DDT (dichloro-diphenyl-trichloroethane) and metabolites

    Application: Agriculture and disease control (e.g. Malaria, Typhus)

    History: 1874 synthesized for the first time by Othmar Zeidler 1939 discovery of insecticide activity by Paul Hermann Müller (Nobel

    Prize 1948) 1943/44 typhus epidemic in Neapel - application for control of lice as

    insect vectors for typhus agents during second world war intensive use for control of biting midges and Malaria

    1945 license for application in agriculture in USA, later also in Europe 1950s “Maikäferkrieg” in Switzerland (big amounts

    of DDT sprayed from airplanes) → damaging bees and other important insects

    1947-1960s Control of the “Ulmensplintkäfer” in the U.S. → disappearance of birds

    http://upload.wikimedia.org/wikipedia/commons/c/c3/Scolytus_scolytus_1_meyers_1888_v16_p352.jpg

  • Typical sediment contaminants DDT (dichloro-diphenyl-trichloroethane) and metabolites

    1956 control of “Schwammspinner” in the State of New York on 12.000km2 → fish kills, milk couldn’t be sold any more

    1983/84 application of 600 t of DDT to control “Borkenkäfer”

    Intensive use of DDT till today against Anopheles to control Malaria in tropical countries

    http://upload.wikimedia.org/wikipedia/commons/f/f3/Lymantria_dispar01.jpg http://upload.wikimedia.org/wikipedia/de/f/f8/Bk1.jpg http://upload.wikimedia.org/wikipedia/commons/4/46/Anopheles_gambiae_mosquito_feeding_1354.p_lores.jpg

  • Typical sediment contaminants

    Rachel Carson

    1962 Publication of “Silent Spring” by Rachel Carson → Risks and Damages by DDT and other pesticides → Starting po

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