Organic micropollutants in coastal waters from NW Mediterranean Sea: sources distribution and potential risk.

This study provides a first estimation on the sources, distribution and risk of organic micropollutants (OMPs) in coastal waters from NW Mediterranean Sea. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, polybrominated diphenyl ethers, phthalates and alkylphenols were analyzed by solid phase extraction and gas chromatography coupled to tandem mass spectrometry (SPE-GC-EI-MS/MS). River waters and wastewater treatment plant effluents discharging to the sea were identified as the main sources of OMPs to coastal waters, with an estimated input amount of around of 25,800 g d(-1). The concentration of ΣOMPs in coastal areas ranged from 17.4 to 8442 ng L(-1), and was the highest in port waters, followed by coastal and river mouth seawaters. A summarized overview of the patterns and sources of OMP contamination on the investigated coastal sea waters of NW Mediterranean Sea, as well as of their geographical distribution was obtained by Principal Component Analysis of the complete data set after its adequate pretreatment. Alkylphenols, bisphenol A and phthalates were the main contributors to ΣOMPs and produced an estimated significant pollution risk for fish, algae and the sensitive mysid shrimp organisms in seawater samples. The combination of GC-MS/MS, chemometrics and risk analysis is proven to be useful for a better control and management of OMP discharges.

[1]  Damià Barceló,et al.  Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain). , 2006, Environmental pollution.

[2]  A. Valavanidis,et al.  Polycyclic aromatic hydrocarbons in surface seawater and in indigenous mussels (Mytilus galloprovincialis) from coastal areas of the Saronikos Gulf (Greece) , 2008 .

[3]  M. Blanchard,et al.  Phthalate removal throughout wastewater treatment plant: case study of Marne Aval station (France). , 2009, The Science of the total environment.

[4]  M. Ehrhardt,et al.  Phthalate esters in the Kiel Bight , 1980 .

[5]  D. Barceló,et al.  Occurrence of sulfonamide residues along the Ebro River basin: removal in wastewater treatment plants and environmental impact assessment. , 2011, Environment international.

[6]  D. Barceló,et al.  Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain). , 2008, Environmental pollution.

[7]  D. Barceló,et al.  Chemical monitoring and occurrence of alkylphenols, alkylphenol ethoxylates, alcohol ethoxylates, phthalates and benzothiazoles in sewage treatment plants and receiving waters along the Ter River basin (Catalonia, N. E. Spain) , 2006, Analytical and bioanalytical chemistry.

[8]  P. Garrigues,et al.  Polycyclic aromatic hydrocarbon (PAH) burden of mussels (Mytilus sp.) in different marine environments in relation with sediment PAH contamination, and bioavailability , 1999 .

[9]  A. Buccolieri,et al.  Organic pollutants (PAHs, PCBs) in sediments from the Mar Piccolo in Taranto (Ionian Sea, Southern Italy). , 2007, Marine pollution bulletin.

[10]  S. Lacorte,et al.  Determination and occurrence of phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs in an industrial sewage grid discharging to a Municipal Wastewater Treatment Plant. , 2009, The Science of the total environment.

[11]  F. Borrull,et al.  Determination of organic contaminants in coastal water , 2004 .

[12]  W. Giger,et al.  Behaviour of alkylphenol polyethoxylate surfactants in the aquatic environment—I. Occurrence and transformation in sewage treatment , 1994 .

[13]  U. Zoller.  Estuarine and coastal zone marine pollution by the nonionic alkylphenol ethoxylates endocrine disrupters: is there a potential ecotoxicological problem? , 2006, Environment international.

[14]  J. Obbard,et al.  Chlorinated pesticides and PCBs in the sea-surface microlayer and seawater samples of Singapore. , 2005, Marine pollution bulletin.

[15]  D. Walling,et al.  PCB congener dynamics in a heavily industrialized river catchment. , 2003, The Science of the total environment.

[16]  E. C. Soo,et al.  Estrogenic compounds in seawater and sediment from Halifax Harbour, Nova Scotia, Canada , 2009, Environmental toxicology and chemistry.

[17]  Thomas Otto,et al.  Occurrence of phthalates and bisphenol A and F in the environment. , 2002, Water research.

[18]  E. González‐Mazo,et al.  Simultaneous determination of pesticides, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in seawater and interstitial marine water samples, using stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry. , 2007, Journal of chromatography. A.

[19]  K. Tollefsen,et al.  Occurrence and removal of selected organic micropollutants at mechanical, chemical and advanced wastewater treatment plants in Norway. , 2006, Water research.

[20]  S K Brar,et al.  Physico-chemical pre-treatment and biotransformation of wastewater and wastewater sludge--fate of bisphenol A. , 2010, Chemosphere.

[21]  Hans Sanderson,et al.  Ranking and prioritization of environmental risks of pharmaceuticals in surface waters. , 2004, Regulatory toxicology and pharmacology : RTP.

[22]  E. Manoli,et al.  Polycyclic aromatic hydrocarbons in waste waters and sewage sludge: Extraction and clean-up for HPLC analysis with fluorescence detection , 1996 .

[23]  J. Albaigés,et al.  Screening ecological risk assessment of persistent organic pollutants in Mediterranean sea sediments. , 2007, Environment international.

[24]  Beiling Liu,et al.  Use of existing water, sediment, and tissue data to screen ecological risks to the endangered Rio Grande silvery minnow. , 2010, The Science of the total environment.

[25]  T. Pham,et al.  PCBs and PAHs in the Montreal urban community (Quebec, Canada) wastewater treatment plant and in the effluent plume in the St. Lawrence River , 1997 .

[26]  D. Pont,et al.  Poly-aromatic hydrocarbon (PAH) inputs from the Rhône River to the Mediterranean Sea in relation with the hydrological cycle: impact of floods. , 2008, Marine pollution bulletin.

[27]  Damià Barceló,et al.  Distribution of endocrine disruptors in the Llobregat River basin (Catalonia, NE Spain). , 2005, Chemosphere.

[28]  R. Brain,et al.  Probabilistic hazard assessment of environmentally occurring pharmaceuticals toxicity to fish, daphnids and algae by ECOSAR screening. , 2003, Toxicology letters.

[29]  N Etxebarria,et al.  Development of a stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry method for the simultaneous determination of several persistent organic pollutants in water samples. , 2007, Journal of chromatography. A.

[30]  U. Zoller,et al.  The case of the nonionic alkylphenol ethoxylates in the Mediterranean Sea region: is there a problem? , 2004, Water science and technology : a journal of the International Association on Water Pollution Research.

[31]  A. Jungbauer,et al.  Monitoring of estrogen mimics by a recombinant yeast assay: synergy between natural and synthetic compounds? , 1999, The Science of the total environment.

[32]  Joop L. M. Hermens,et al.  Estimating total body residues and baseline toxicity of complex organic mixtures in effluents and surface waters , 1997 .

[33]  F. Galgani,et al.  Assessment of polycyclic aromatic hydrocarbon concentrations in mussels (Mytilus galloprovincialis) from the Western basin of the Mediterranean Sea , 2011, Environmental monitoring and assessment.

[34]  D. Barceló,et al.  Environmental risk assessment of pharmaceuticals in rivers: relationships between hazard indexes and aquatic macroinvertebrate diversity indexes in the Llobregat River (NE Spain). , 2010, Environment international.

[35]  J. Albaigés,et al.  Assessment of the Mediterranean sediments contamination by persistent organic pollutants. , 2007, Environmental pollution.

[36]  Romà Tauler,et al.  Stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry: an effective tool for determining persistent organic pollutants and nonylphenol in coastal waters in compliance with existing Directives. , 2010, Marine pollution bulletin.

[37]  C. Basheer,et al.  Analysis of endocrine disrupting alkylphenols, chlorophenols and bisphenol-A using hollow fiber-protected liquid-phase microextraction coupled with injection port-derivatization gas chromatography-mass spectrometry. , 2004, Journal of chromatography. A.

[38]  N. Jonkers,et al.  Fate of nonylphenol ethoxylates and their metabolites in two Dutch estuaries: evidence of biodegradation in the field. , 2003, Environmental science & technology.

[39]  L. Patrolecco,et al.  Occurrence of priority hazardous PAHs in water, suspended particulate matter, sediment and common eels (Anguilla anguilla) in the urban stretch of the River Tiber (Italy). , 2010, Chemosphere.

[40]  D. Aguado,et al.  Occurrence of priority pollutants in WWTP effluents and Mediterranean coastal waters of Spain. , 2011, Marine pollution bulletin.

[41]  B. Jefferson,et al.  Nonylphenol in the environment: a critical review on occurrence, fate, toxicity and treatment in wastewaters. , 2008, Environment international.

[42]  Martin P. Ward,et al.  Organic micropollutants in marine plastics debris from the open ocean and remote and urban beaches. , 2011, Marine pollution bulletin.

[43]  D. Voutsa,et al.  Passive sampling of selected endocrine disrupting compounds using polar organic chemical integrative samplers. , 2008, Environmental pollution.

[44]  J. Villeneuve,et al.  Pesticide and PCB residues in the aquatic ecosystems of Laguna de Terminos, a protected area of the coast of Campeche, Mexico. , 2009, Chemosphere.

[45]  I. Tolosa,et al.  Partitioning of urban wastewater organic microcontaminants among coastal compartments , 1991 .

[46]  R. Tauler,et al.  Impact of pesticides used in agriculture and vineyards to surface and groundwater quality (North Spain). , 2008, Water research.

[47]  Barceló,et al.  Broad spectrum analysis of 109 priority compounds listed in the 76/464/CEE Council Directive using solid-phase extraction and GC/EI/MS , 2000, Analytical chemistry.

[48]  R. Tauler,et al.  Quality assessment of river waters using risk indexes for substances and sites, based on the COMMPS procedure. , 2010, Journal of environmental monitoring : JEM.

[49]  Wolfgang Ruck,et al.  Atmospheric concentrations and air-sea exchanges of phthalates in the North Sea (German Bight) , 2005 .

[50]  J. Santos,et al.  Occurrence and risk assessment of pharmaceutically active compounds in wastewater treatment plants. A case study: Seville city (Spain). , 2007, Environment international.

[51]  J. Albaigés,et al.  Organic contaminant loads into the Western Mediterranean Sea: estimate of Ebro River inputs. , 2006, Chemosphere.

[52]  Z. Vryzas,et al.  Spatial and temporal distribution of pesticide residues in surface waters in northeastern Greece. , 2009, Water research.

[53]  Steven J. Eisenreich,et al.  LC-MS-MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters. , 2007, Chemosphere.

[54]  Yih-Min Sun,et al.  Occurrence of phthalates in sediment and biota: relationship to aquatic factors and the biota-sediment accumulation factor. , 2008, Chemosphere.

[55]  F. Galgani,et al.  Western Mediterranean coastal waters--monitoring PCBs and pesticides accumulation in Mytilus galloprovincialis by active mussel watching: the Mytilos project. , 2010, Journal of environmental monitoring : JEM.

[56]  A. Usobiaga,et al.  Use of experimental design in the optimisation of stir bar sorptive extraction followed by thermal desorption for the determination of brominated flame retardants in water samples , 2008, Analytical and bioanalytical chemistry.

[57]  S. Lacorte,et al.  Spatial distribution and sources of perfluorochemicals in the NW Mediterranean coastal waters (Catalonia, Spain). , 2010, Environmental pollution.

[58]  R. Piazza,et al.  Determination of polychlorobiphenyl congeners (PCBs) in the surface water of the Venice lagoon. , 2005, Marine pollution bulletin.

[59]  A. Farran,et al.  Accumulation and distribution of biogenic and pollutant hydrocarbons, pcbs and ddt in tissues of western mediterranean fishes , 1987 .

[60]  Joana Vicente,et al.  Development of a multi-residue method for the determination of organic micropollutants in water, sediment and mussels using gas chromatography-tandem mass spectrometry. , 2011, Journal of chromatography. A.

[61]  J. Giesy,et al.  Measuring and monitoring persistent organic pollutants in the context of risk assessment. , 2008, Marine pollution bulletin.

[62]  I. Jolliffe.  Principal Component Analysis , 2002 .

[63]  R. Tauler,et al.  Chapter 16 Interpretation of environmental data using chemometrics , 2000 .