受城市農(nóng)業(yè)和工業(yè)污染影響的流域有機(jī)污染物及其轉(zhuǎn)化產(chǎn)物的時(shí)空評(píng)估外文文獻(xiàn)

Spatio temporal evaluation of organic contaminants and their transformation products along a river basin affected by urban agricultural and industrial pollution Mar a Jos G mez a b c Sonia Herreraa c David Sol a c Eloy Garc a Calvoa c Amadeo R Fern ndez Albac a IMDEA Water Madrid Institute for Advanced Studies Water Punto Net Edifi cio ZYE 2 Parque Cient fi co Tecnol gico de la Universidad de Alcal 28805 Alcal de Henares Madrid Spain b Department of Chemical Engineering University of Alcal 28871 Alcal de Henares Madrid Spain c Pesticide Residue Research Group University of Almer a 04120 Almer a Spain a b s t r a c ta r t i c l ei n f o Article history Received 20 October 2011 Received in revised form 11 January 2012 Accepted 12 January 2012 Available online 10 February 2012 Keywords River water Wastewater Personal care products Pesticides Policycyclic aromatic hydrocarbons Degradation products This study aims to assess the occurrence fate and temporal and spatial distribution of anthropogenic contami nants in a river subjected to different pressures industrial agricultural wastewater discharges For this pur pose the Henares River basin central Spain can be considered a representative basin within a continental Mediterranean climate As the studied river runs through several residential industrial and agricultural areas it would be expected that the chemical water quality is modifi ed along its course Thereby the selection of sam pling pointsand timing ofsamplecollection arecriticalfactorsinthemonitoring ofa river basin Inthisstudy six different monitoring campaigns were performed in 2010and contaminants were measuredat the effl uent point of the main wastewater treatment plant WWTP in the river basin and at fi ve different points upstream and downstream from the WWTP emission point The target compounds evaluated were personal care products PCPs polycyclic aromatichydrocarbons PAHs and pesticides Results showthat theriver isclearlyinfl uenced by wastewater discharges and also by its proximity to agricultural areas The contaminants detected at higher concentrations were the PCPs The spatial distribution of the contaminants indicates that the studied contami nantspersistalongtheriver InthetimeperiodstudiednogreatseasonalvariationsofPCPsattherivercollection pointswereobserved Incontrast atemporaltrendofpesticidesandPAHswasobserved Besidesthetargetcom pounds othernewcontaminants wereidentifi edand evaluatedinthewatersamples someofthembeinginves tigated for the fi rst time in the aquatic environment The behaviour of three important transformation products was also evaluated 9 10 anthracenodione galaxolide lactone and 4 amino musk xylene These were found at higher concentrations than their parent compounds indicating the signifi cance of including the study of trans formation products in the monitoring programmes 2012 Elsevier B V All rights reserved 1 Introduction Anthropogenic pollution in environmental waters caused by pres sure factors such as agriculture industry and human sewage is an issue of great concern since together with population growth and climate change it can have large scale adverse impacts on the quality of the basins The main tool of European water policy in reducing chemical pollution of surface water bodies is the Water Framework Directive WFD European Union Directive 2000 which sets out a strategy to combat water pollution This involves establishing a list of substances that pose a signifi cant risk to the aquatic environment European Union Decision 2001 As part of this strategy the list is intended to be reviewed and updated every four years to defi ne envi ronmental quality standards EQSs that allow a suffi cient level of protection for surface waters European Community Directive 2008 Nevertheless there are other families of unregulated com pounds such as pharmaceuticals chemicals from consumer products or other chemicals of agricultural or industrial origin generally known as emerging which can alter water quality both chemical and ecological either because they present some of the priority pol lutants characteristics or because of their continuous and extensive entry into the water cycle In addition to this organic contaminants are also transformed in WWTPs and in the environment and while some of the resulting transformation products are known to be more abundant or more toxic in the aquatic environment than their parent compounds Bester 2009 Gatermann et al 1998 G mez et al 2010 Kern et al 2009 the majority of the transformation products which are present have most likely not even been identifi ed yet Thus envi ronmentaloccurrence of synthetic organic compounds can be substan tially underestimated when transformation products are ignored Science of the Total Environment 420 2012 134 145 Corresponding author at IMDEA Water Madrid institute for advanced studies C Punto Net 4 2 Floor Edifi cio ZYE Parque Cient fi co Tecnol gico de la Universidad de Alcal 28805 Alcal de Henares Madrid Spain Tel 34 91 830 59 62 fax 34 91 830 59 61 E mail address mjramos ual es M J G mez 0048 9697 see front matter 2012 Elsevier B V All rights reserved doi 10 1016 j scitotenv 2012 01 029 Contents lists available at SciVerse ScienceDirect Science of the Total Environment journal homepage It is necessary to conduct a more complete and accurate chemical quality assessment of the water To carry out this task multi residue methods which cover several families of organic micro pollutants as well as their major transformation products are needed to obtain realistic results Evidently this approach requires adequate instru mentation capable of acquiring full mass range spectra with ade quate sensitivity as well as software to process a large amount of data in an automated way as possible To assess pollution in these waters a promising approach would be a target analysis supplemen ted by a screening analysis both using the same data fi le G mez et al 2009 2010 Krauss et al 2010 Pitarch et al 2010 Portol s et al 2011 In this study an analytical method based on stir bar sorptive extraction SBSE followed by comprehensive two dimensional gas chromatography GCxGC TOF MS G mez et al 2011 has shown itself to be a powerful analytical tool allowing us to investigate the presence of several organic contaminants in the water samples that did not form a part of the previous list of target contaminants Inordertoobtain signifi cantinformation about thechemicalquality of a river basin in addition to requiring a comprehensive investigation aboutthe occurrenceand concentrationlevels of organic contaminants informationaboutthe temporaland spatialtrends alongits river course is relevant Assessmentshouldbecarried outon i possiblechanges in water quality due to seasonal drought scenarios infl uenced by climate change or higher pressures caused by agglomeration and ii local impactsduetothepresenceofhigherconcentrationhotspots continuous inputs proximity to WWTPs and or industrial and agricultural areas There are few studies on the occurrence of organic micro contaminants in Spanish river waters and there are fewer studies on theirtransformationproducts TheEbroriverbasin inthenortheastern part of Spain has been the most studied C spedes et al 2005 2006 Gros et al 2007 Hildebrandt et al 2008 Kuster et al 2008 Navarro et al 2010 The Henares River is located in the centre of Spain Madrid This area is the most densely populated in Spain Recently some studies have investigated the presence of micro contaminants within the Henares river basin and in other rivers in the Madrid region However all of them have focused solely on monitoring polar contam inants mostlypharmaceutically activecompounds G mezetal 2010 Gonz lez Alonso et al 2010 Mart nez Bueno et al 2010 2011 Valc rcel et al 2011 Nonetheless to the authors knowledge PCPs PAHs and most of the pesticides included as target analytes in the pre sent study have never or only occasionally been investigated in this area The detection of PCPs in wastewater and rivers around Madrid has only been reported in one study carried out by our research group G mez et al 2009 However a spatial and temporal evaluation of the contaminants along the rivers was not performed In this context the aim of the present study was to investigate the chemical water status of the Henares river basin It can be considered a representative basin both in terms of fl ow levels and population pressure within a continental Mediterranean climate Because of the different pressures to which the river is subjected industrial agricul tural wastewater discharges it would be expected that the chemical water quality is modifi ed along its course Thus in this study the oc currence concentration levels and temporal and spatial distribution of 55 selected organic contaminants have been evaluated in the Henares River belonging to the PCPs PAH and pesticide classes see Table 1 In addition to the investigation of emerging contaminants priority pollutants are included in the list of target compounds in order to verify if the WFD requirements are fulfi lled in the studied river basin Other non target compounds including important trans formation products of the target compounds have also been investi gated Additionally contaminant concentrations have been analyzed in the effl uents from the Alcala de Henares WWTP to determine a possible relation between river water contamination and wastewater effl uent discharges This work provides the fi rst general overview of the occurrence of these compounds in this area 2 Experimental section 2 1 Chemicals and reagents For this study a group of 55 non polar or semi polar organic pol lutants were selected belonging to different compound categories Table 1 27 pesticides 15 polycyclic aromatic hydrocarbons PAHs and 13 personal care products PCPs The reference compounds used as surrogate standards were pyrene d10 benzo a pyrene d12 and atrazine d5 More information can be found elsewhere G mez et al 2011 2 2 Effl uent wastewater and river water sampling Treated wastewater samples were taken from the effl uent of the Alcal de Henares WWTP a town with about 200 000 inhabitants located within the Community of Madrid in central Spain This plant applies a pretreatment for solid removal a primary treatment Table 1 List of target compounds included in the study Non priority substancesPriority substances Chemical class CompoundLog KowCompoundLog Kow PCPs Synthetic fragrances Galaxolide5 9 Tonalide5 7 Phantolide4 9 Traseolide5 4 Musk ketone4 3 Musk xylene4 4 UV fi lters4 MBC5 1 Oxybenzone3 79 2 EHMC5 8 AntisepticsTriclosan4 76 Biphenylol3 09 Chlorophene3 6 AntioxidantBHT5 1 Pesticides Iprodione3 00 endosulfan3 83 Dizinon3 81 endosulfan3 83 Vinclozolin3 1Endosulfan sulphate3 66 Terbutylazine3 21Atrazine2 61 Terbutryn3 74Simazine2 18 Metolachlor3 13Lindane3 72 Procymidone3 08Chlorpyriphos ethyl4 96 Methidation2 2Alachlor3 52 Molinate3 21Chlorfenvinphos trans cis 3 81 Chlorpyrifos methyl4 31 Trifl uralin5 34 Methoxychlor5 08Endrin5 2 Dieldrin5 4 Aldrin6 5 DDT p p 6 91 DDE o p 6 51 Hexachlorobenzene5 73 PAHs Acenaphthene3 92Anthracene4 45 Acenaphthylene4 07Benzo a pyrene5 97 Benzo a anthracene5 79 Benzo k fl uoranthene6 84 Chrysene5 73Benzo g h i perylene6 63 Dibenzo a h anthracene 6 5Fluoranthene5 16 Fluorene4 18Indeno 1 2 3 cd pyrene6 7 Phenanthrene4 46Naphthalene3 3 Pyrene4 88 BHT Butylated hydroxytoluene 4 MBC 4 methylbenzyledene camphor 2 EHMC 2 ethylhexyl methoxycinnamate Priority substances included in the European Union Water Framework Directive 135M J G mez et al Science of the Total Environment 420 2012 134 145 to eliminate suspended material an activated sludge biological treat ment and fi nal clarifi cation This WWTP discharges directly into the Henares River The river samples analyzed in this study were collected at different points along the Henares River Fig 1 covering an area of about 1000 km2 The width of the river in most of the sampling points is about 10 m The samples were taken at the middle of the river width Sampling was carried out 20 m and 1150 m downstream from the Alcal de Henares WWTP emission point and 35 000 24 000 and 6000 m upstream of the WWTP Effl uents are well mixed with the river water at the sampling points downstream the WWTP The river runs through several residential industrial and agricultural areas In addition other WWTPs in small towns discharge their emissions di rectly into the Henares River or into streams fl owing into the river A total of thirty six water samples thirty river and six effl uent waste water samples were analyzed in six different monitoring campaigns performed in April May and June 2010 The effl uents were taken directly from the WWTP output During the studied period the fl ow of the river has not changed signifi cantly The mean fl ow rate ranged from 5 66 to 7 68 at river points upstream of the WWTP and between 12 13 and 13 94 at the points downstream from the WWTP emission point Grab water samples 2 L were collected in clean amber glass bot tles Before sample collection each bottle was thoroughly pre rinsed with MilliQ water and then with the same water as that being collected Once in the laboratory located in Alcal de Henares Madrid all the samples were stored at 4 C prior to analysis this was performed within 24 h so as to avoid any degradation During sampling physico chemical measurements were taken including temperature pH con ductivity and dissolved oxygen 2 3 Sample preparation and instrumental analysis The analyses of water samples were carried out on the total fraction dissolved particulate bystirbarsorptiveextraction SBSE followed bycomprehensive two dimensionalgaschromatography GCxGC TOF MS The procedure was based on previous work in our laboratory G mez et al 2011 Briefl y the extractions were performed with 20 mm 0 5 mm length fi lm thickness PDMS commercial stir bars obtained from Gerstel M lheim a d Ruhr Germany The coated stir bars were thermally desorbed using a commercial thermal desorption unit TDU Gerstel connectedtoaprogrammedtemperature Surface 1000 km2 2 1 E WWTPs 2 3 4 5 Point of WWTP emission 35 km upstream 24 km upstream 6 km upstream 20 m downstream 1 15 km downstream HENARES RIVER BASIN 05102030 N km Fig 1 Map of the study area and sample site locations 136M J G mez et al Science of the Total Environment 420 2012 134 145 vaporisation PTV system injector CIS 4 Gerstel bya heatedtransfer line at 300 C The PTV injector was installed in a GC GC TOF MS sys tem which consisted of an Agilent 7890A Agilent Technologies Palo Alto CA USA gas chromatograph equipped with a secondary oven to fi t the secondary column and a quad jets modulator two cold jets and two hot jets The fi rst column was a 10 m 0 18 mm i d 0 2 m fi lm thickness Rtx 5 coated with 5 diphenyl 95 dimethylpolysilox ane from Restek max prog temp 350 C The second column used was a 1 m 0 1 mm i d 0 10 m fi lm thickness Rxi 17 coated with 50 diphenyl 50 dimethyl polysiloxane from Restek max prog temp 320 C TheMSsystem wasa Pegasus4DTOF fromLECOCorpo ration St Joseph MI USA More information on the analytical proce dure and its validation can be found elsewhere G mez et al 2011 2 4 Automatic identifi cation and quantifi cation of target compounds The instrument control and data processing were conducted with the Leco ChromaTOF version 4 24 software Data processing included automaticpeakfi ndingsusingMSdeconvolutionandspectralsearching against the NIST 2008 and Wiley mass spectral libraries and also using our own user created mass spectral library for target compounds Quantifi cation of target compounds was performed using external standard methodology based on peak areas 2 5 Blank issues Blank contamination is a common problem observed in the deter mination of UV fi lters musk fragrances antioxidants and PAHs at trace levels Thus precautions were taken to prevent contamination from personnel organic solvents equipment and glassware Blank assays were performed routinely employing MilliQ water samples to check for laboratory background levels of the studied compounds Though the detected amounts of the target compounds were low below 5 ng L it was considered necessary to subtract the quantita tive values of the compounds found in the blanks 3 Results and discussion 3 1 Monitoring study Within the Henares river basin the most important agglomeration is Alcala de Henares The main WWTP in this region is located in this town and it discharges treated wastewater effl uents into the river under study To evaluate the impact that the discharge of treated wastewater effl uent has on receiving waters sampling was done at the effl uent point of this treatment plant and at different points up stream and downstream from the Alcal de Henares WWTP emission point Fig 1 In addition pollution contributions from industry or agriculture have also been taken into account Occurrencesandconcentrationsofthetargetcompoundsmeasured intheWWTPeffl uentandtheHenaresRiveraregiveninTable2 where the method limit of quantifi cation MQL and the environmental qual ity standards EQS stipulated by the EU for the priority substances investigated are indicated European Community Directive 2008 The results in the table are the mean of the six sampling campaigns on the WWTP effl uent and at the fi ve sampling sites monitored in the Henares River As can be observed in Table 2 of the 55 target com pounds monitored a total of 34 were never quantifi ed These unde tectedcompoundswere3PCPs phantolide traseolideand chlorophene 20 pesticides iprodione vinclozolin methidation moli nate chlorpyrifos methyl methoxychlor endosulfan endosulfansul phate atrazine simazine lindane alachlor trifl uralin endrin dieldrin aldrin DDT DEE and hexachlorobenzene and 12 PAHs acenaphthene acenaphthylene benzo a anthracene chrysene dibenzo a h anthra cene fl uorene anthracene benzo a pyrene benzo k fl uoranthene and benzo 1 2 3 cd pyrene Table 2 also reveals that the same pollutants found in river wa