1- Fuentes y clasificación de loscontaminantes orgánicos antropogénicos

Jordi DachsDepartamento de Química Ambiental,

Instituto de Diagnóstico Ambiental y Estudios del Agua de BarcelonaConsejo Superior de Investigaciones Científicas (CSIC)

Objetivos

- Perturbaciones antropogénicas de la quimiosfera

- ¿Es posible cuantificar y caracterizar las perturbacionesquímicas por compuestos sintéticos?

- Transporte y sumideros de contaminantes orgánicos a escala global.

- Evaluación de riesgo de las familias de compuestosquímicos antropogénicos.

- Cambio climático y la quimiosfera tóxica

Anthropogenic perturbations of the chemosphere

- Emissions from fossil fuels (CO2, CO, NO, hydrocarbons….).

- Emissions from combustion processes (Dioxins and Furans, PAHs, …)

- Sinthetic chemicals used in industry and consumer products.

- Emission of anthropogenic aerosols.

- Changes in atmospheric chemistry and composition produced by all the above perturbations.

Emissions from Gasoline Combustion

Schauer et al. Environ. Sci. Technol. 40, 1169-1180, 2002.

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Gas absorption

(Schauer et al. ES&T 2002)

More than 95% of anthropogenic emissions of OC are as gas phase compounds

Semivolatile Compounds Dominate Air to Water Fluxes of OC

Emissions

Emissions from Gasoline Combustion

Shauer et al. Environ. Sci. Technol. 40, 1169-1180, 2002.

Semi-Volatile Aliphatic Hydrocarbons in Petroleum(Quantified by GC-MS)

Cn = CnH2n+2

CPI = Odd Cn/Even Cn = 1

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The UCM has a toxic effect in marine organisms(Rowland et al. ES&T 2001, Donkin et al. 2003…)

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Aliphatic Hydrocarbons in theNE Atlantic atmosphere

UCM

UCM

Gas Phase --- 312 nmol m-3

CPI =1.2

Aerosol Phase --- 40 nmol m-3

(6% of total AOC)

CPI =1.9

The anthropogenic chemosphere(from non-combustion sources)

- There are more than 8 millions substances available…

-There are over 200.000 substances registered and in use, most of them in low volume production (less than 1 ton/year).

-The world production of synthetic chemicals is of 3 108

tons y-1 (1993).

The anthropogenic chemosphere(except from combustion sources)

- New chemicals are produced every year

CG

CWCP

CAIntercambioAire-Agua

Sorción-desorción

Sorción-desorción

DeposiciónSeca

DeposiciónHúmeda

Flujosverticales

Procesos físico-químicos y biogeoquímicosEcosistemas acuáticos

Advección y difusión turbulenta

Bioacumulación

Aportescontinentales

Transporteatmosférico

The anthropogenic chemosphere(not including combustion sources)

-About 30.000 chemicals are commercially available and have a production higher than 1 ton/year.

-10000 chemicals have a production higher than 4.5 tons y-1.

- 4000 chemicals have a production higher than 1000 tons y-1.

Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.

The anthropogenic chemosphere, last 30 years(not including combustion sources)

Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.

Risk criteria to identify priority chemicals(PBT chemicals)

- Production volume- Use profile- Physical-chemical characteristics:

- Persistent- Bioaccumulative- Toxicity- Potential for long range transport.- Other

- Influence of atmospheric chemistry ( freons)- alteration of pH (oxides of sulfur…)- chelating capacity- odor- color- ability to cause foaming (detergents…)- formation of toxic metabolites…

¿Qué contaminantes orgánicos estudiar?

(Hermens, J.L.M. En Toxicology, Niesink R.J.M. (Editor) CRC Press, NewYork, 1996)

log KOW

Persistent Organic Pollutants (POPs)

Persistent Organic Pollutants(POPs)

Physical Chemical Properties

Persistent Organic Pollutants (POPs)Physical Chemical Properties

Table 3.5 (pag. 44 of Mackay)

Persistent Organic Pollutants (POPs)Physical Chemical Properties

Table 3.5 (pag. 44 of Mackay)

Persistent Organic Pollutants (POPs)Physical Chemical Properties

Table 3.5 (pag. 44 of Mackay)

Persistent Organic Pollutants (POPs)Physical Chemical Properties

Table 3.5 (pag. 44 of Mackay)

Persistent Organic Pollutants (POPs)Physical Chemical Properties

Table 3.5 (pag. 44 of Mackay)

Polychlorinated DibenzoDioxins and Furans

(PCDD/Fs)

Cln Clm

O

O

Cln Clm

O

Polychlorinated Biphenyls(PCBs)

Cln Clm

Persistent Organic Pollutants (POPs)

- Used in capacitors and transformers. Other uses in paints, plasticizers, etc.

- Carcinogens. Neurological, reproductive and immune effects.

- By-product of combustion (plastics..)

- Carcinogens.

• Nonylphenols

• Polycyclic Aromatics Hydrocarbons (PAH)

Other POPs ….

- Degradation product of alkylphenolpolyethoxylates (industrial surfactants).

- Endocrine disrupter.

- Produced during the incomplete combustion of organic matter (fossil fuels, vegetation ….).

- Some are carcinogens.

Perfluoroalkyl substances are globally distributed, anthropogenic contaminants.

Perfluoroalkyl acids (PFAs) are synthetic, perfluorinated, straight- or branched-chain organic acids characterized by a carboxylate or sulfonate moiety.

Surface treatment applications to provide soil, oil and water resistance to personal apparel and home furnishings (e.g. carpet cleaner and Goretex®). on paper products to provide grease, water, and oil resistance to plates, food containers, bags, and wrap (Teflon ®)aqueous film-forming foams (AFFF) for fire-fighting,

Global Distribution of POPs in the atmosphere

Pozo et al. Environ. Sci. Technol. 2006.

PCBs PBDEs

Persistent Organic Pollutants

Priority POPs

Anthropogenic perturbations of Coastal regions Chemical family historical or current use application References of occurrence, fate or toxicity

Polychlorinated biphenyls(PCBs) Industrial, various Totten et al. 2001, Yan et al. 2008DDTs Insecticide Roche et al. 2009, Garcia-Flor et al. 2005Hexachlorbenzen (HCB) Insecticide Garcia-flor et al. 2005, Aldrin Insecticide Roche et al 2009Dieldrin Insecticide Roche et al 2009Endrin Insecticide Roche et al 2009Toxaphene Insecticide Maruya & Lee 1998Chlordane Insecticide Offenberg et al. 2004Heptachlor Insecticide Roche et al 2009Polychorinated dibenzodioxins and furans (PCDD/Fs) combustion byproduct Ishaq et al. 2009Hexachlorociclohexanes (HCHs, various) herbicide Roche et al 2009Polycyclic aromatic hydrocarbons (PAHs) combustion byproduct, fossil fuels Gigliotti et al. 2005, Echeveste et al. 2009Polybrominated biphenyl ethers (PBDEs) flame retardant Johnson-Restrepo et al. 2005, Misukawa et al. 2009Hexabromocyclododecane flame retardant Lam et al. 2009, Smorlaz & Berger 2009nonylphenol polyethoxylates (NPEO) surfactant Xie et al. 2006, Bester et al. 2001nonylphenols (NP) degradation producto of NPEO Van Ry et al.2000octylphenols (OP) degradation producto of NPEO Xie et al. 2006, Dachs et al. 1999Bisphenol A various Kang et al. 2006Phthalates plasticizer Mackintosh et al. 2004, Xie et al. 2007Alkanes and other hydrocarbons fossil fuel, combustion byproduct Dachs et al. 1999, Melbye et al. 2009nonresolved hydrocarbons (UCM) fossil fuel Dachs et al. 1999, Melbye et al. 2009chlorinated alkanes Industrial (lubricants, flame retardants, etc) Tomy et al. 2000organotins (Tributiltin, triphenyltin, etc) antifouling agent Diez et al. 2002, Sousa et al. 2009atrazine herbicide Clark et al. 1999, Rohr and Crumrine 2005, Jones and Kerswell 2003simazyne herbicide Clark et al. 1999, Jones and kerswell 2003Diuron biocide Haynes et al. 2000, Jones and Kerswell 2003Hexazinone herbicide Magnuson et al. 2008Endosulfan herbicide Roche et al. 2009, Rohr and Crumrine 2005Linear alkylbenzene sulphonates surfactant Bester et al. 2001, Linear alkylbenzenes subproduct of LAS Gustafsson et al. 2001, Ni et al. 2009bis (4-chlorophenyl)-sulphone plasticizer Olsson & Bergman 1995, Glyphosate herbicide Tsui and Chu 2003Irgarol antifouling agent Hall et al. 2009, Okamura et al. 2000MTBE gasoline aditive Rossell et al. 2006Benzotriazoles UV stabilizers and others Nakata et al. 2009Trialkylamines (TAM) surfactant byproduct Maldonado et al. 1999.2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB) flame retardant Lam et al. 2009 bis-(2-ethylhexyl)-tetrabromophthalate (TBPH) flame retardant Lam et al. 2009Perfluorinated compounds (PFOS, PFOA and others) Industrial and other Nakata et al. 2006polychloronaftalenes Industrial and other Yamashita et al. 2000Drugs of abuse (cocaine, etc) illicit drugs Postigo et al. 2009Pharmaceuticals (various) pharmaceuticals Gros et al. 2007, Fent et al. 2006.Musk fragances fragances Xie et al. 2007sucralose sweetener Mead et al. 2009

European Marine Strategy Framework Directive

Production and occurrence of Legacy POPs

Lohmann, R., Breivik, K., Dachs, J., Muir, D. 2007, Environ. Pollut. In press.

Production and Occurrence of Emerging POPs

Potential POPs

Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.

The anthropogenic chemosphere, last 30 years(except from combustion sources)

Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.

Potential POPs

Bioaccumulativeand Persistent

Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.

Potential POPs: Bioaccumulative and Persistent and withlong-range transport potential

Muir & Howard. Environ. Sci. Technol.40, 7157-7166, 2006.

Èpoques i noms: Antropocè

- Holocè- Últims 10000-12000 anys (International Geological congress in Bologna, 1885)

- The earth as modified by Human action (Marsh 1862)

- Antropozoic – Últims centenars d’anys (Stoppani 1873)

- Noösphere - Últims centenars d’anys (Verdnadsky, Teilhard de Chardin, LeRoy 1924).

- Antropocè – Últims 200 anys (Crutzen 2002)

Anthropogenic perturbations of Coastal regions

Steffen et al. 2007

The Anthropocene

Steffen et al. 2007

The anthropocene: Carbon emissions

Steffen et al. 2007

The Anthropocene: Nitrogen Cycle

Steffen et al. 2007

Anthropogenic perturbations of Coastal regions

(Dachs & Méjanelle. Estuariesand Coasts 2010)

The Anthropocene: Do organic pollutants introduce an irreversible change to ecosystems?

-There are 200.000 chemicals currently being manufactured and in commercail use (Muir and Howard 2006), this is a small fraction of the 6 million of organic chemicals ever synthesized (Grzybowski et al. 2009 ).

- The number of high production chemicals has increased almostexponentially during the last 50 years.

- The emissions of organic pollutants are coupled to socio-economic indexes. This is true both for legacy POPs and emerging POPs.

- Presumably the number of pollutants entering the environment has increased exponentially during the last 50 years. The total number of pollutants in the environment is unknown.

- A Fraction of these pollutants is persistent, thus introducing a irreversible modification of the composition of the biosphere.

The Anthropocene: Do organic pollutants introduce an irreversible change to ecosystems?

- There is a need for a real ECO-toxicology, where effects of pollutants areevaluated at ecosystem level in terms of structure and function (Rohr et al. 2006)

- Real mixtures of pollutants in the environment are made of thousands of pollutants. Need for testing of real environmental mixtures.

- Ecosystems and trophic webs are often complex, and effects of pollutantscan be seen at high trophic levels even though their biological effect occurs at a low trophic level (Bacelor et al. 2009).

-Pollutants should be considered as another driver of marine ecosystems, maybe at the same level as nutrients, light regime, etc.

(Dachs & Méjanelle 2010)