Effect-related monitoring: estrogen-like substances in groundwater

Background, aim, and scope Concentration monitoring as a basis for risk assessment is a valid approach only if there is an unambiguous relation between concentration and effect. In many cases, no such unambiguous relation exists, since various substances can exert the same effect with differing pote...

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Veröffentlicht in:Environmental science and pollution research international 2010-02, Vol.17 (2), p.250-260
Hauptverfasser: Kuch, Bertram, Kern, Frieder, Metzger, Jörg W., von der Trenck, Karl Theo
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Kern, Frieder
Metzger, Jörg W.
von der Trenck, Karl Theo
description Background, aim, and scope Concentration monitoring as a basis for risk assessment is a valid approach only if there is an unambiguous relation between concentration and effect. In many cases, no such unambiguous relation exists, since various substances can exert the same effect with differing potencies. If some or all of these substances contributing to a biological effect are unknown, effect-related monitoring becomes indispensable. Endocrine-disrupting substances in water bodies, including the groundwater, are a prominent example of such a case. The aim of the investigations described here was to detect hormonally active substances in the groundwater downstream of obsolete landfills by using the E-screen assay and to possibly assign the biological effect to individual chemical compounds by means of instrumental analyses carried out in parallel. Materials and methods Grab samples of the groundwater were collected downstream from abandoned landfills and prepared by liquid/liquid extraction. The total estrogenic activity in these samples was determined in vitro by applying the E-screen assay. The human breast cancer cells (MCF-7) used in the E-screen proliferate in response to the presence of estrogenically active compounds. Expressed in concentration units of the reference substance 17β-estradiol (E2), the test system allows the quantification of estrogenicity with a limit of detection (LOD) in the range of 0.1 ng/L. Aliquots of the samples were screened using gas chromatography/mass spectrometry (GC/MS) in order to quantify known estrogenically active substances and to identify unknown compounds. Estrogen-positive samples were extracted at different pH values, split into acidic, neutral, and basic fractions and analyzed by GC/MS, searching for individual components that display estrogenic activity. Results and discussion Estrogenic activity exceeding the LOD and the provisional benchmark of 0.5 ng E2/L was found at three out of seven abandoned waste disposal sites tested. The low concentrations of known xenoestrogens such as bisphenol-A, nonylphenols, or phthalic acid esters determined by GC/MS, however, were not sufficient to explain the detected activity. Neither natural nor synthetic hormones have caused the activity because these chemical structures are readily degradable and cannot persist in abandoned landfills for decades. The highest activity in the E-screen assay was found in the acidic fractions. Hydroxy-polychlorinated biphenyls (PCBs), hydro
doi_str_mv 10.1007/s11356-009-0234-1
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In many cases, no such unambiguous relation exists, since various substances can exert the same effect with differing potencies. If some or all of these substances contributing to a biological effect are unknown, effect-related monitoring becomes indispensable. Endocrine-disrupting substances in water bodies, including the groundwater, are a prominent example of such a case. The aim of the investigations described here was to detect hormonally active substances in the groundwater downstream of obsolete landfills by using the E-screen assay and to possibly assign the biological effect to individual chemical compounds by means of instrumental analyses carried out in parallel. Materials and methods Grab samples of the groundwater were collected downstream from abandoned landfills and prepared by liquid/liquid extraction. The total estrogenic activity in these samples was determined in vitro by applying the E-screen assay. The human breast cancer cells (MCF-7) used in the E-screen proliferate in response to the presence of estrogenically active compounds. Expressed in concentration units of the reference substance 17β-estradiol (E2), the test system allows the quantification of estrogenicity with a limit of detection (LOD) in the range of 0.1 ng/L. Aliquots of the samples were screened using gas chromatography/mass spectrometry (GC/MS) in order to quantify known estrogenically active substances and to identify unknown compounds. Estrogen-positive samples were extracted at different pH values, split into acidic, neutral, and basic fractions and analyzed by GC/MS, searching for individual components that display estrogenic activity. Results and discussion Estrogenic activity exceeding the LOD and the provisional benchmark of 0.5 ng E2/L was found at three out of seven abandoned waste disposal sites tested. The low concentrations of known xenoestrogens such as bisphenol-A, nonylphenols, or phthalic acid esters determined by GC/MS, however, were not sufficient to explain the detected activity. Neither natural nor synthetic hormones have caused the activity because these chemical structures are readily degradable and cannot persist in abandoned landfills for decades. The highest activity in the E-screen assay was found in the acidic fractions. Hydroxy-polychlorinated biphenyls (PCBs), hydroxylated polycyclic aromatic hydrocarbons (PAHs) and hetero-PAHs, as well as alkylphenols could be identified as further compounds with possible hormonal activity. Conclusions Estrogenically active substances may occur in the groundwater below obsolete landfills, especially those that contain PCBs or waste from gasworks. These substances are not part of analytical programs routinely applied to contaminated sites and may therefore escape detection and assessment. Analyses using the E-screen assay and GC/MS in parallel have shown that the total estrogenic activity found in groundwater samples is to be ascribed to a multitude of individual compounds, some of which cannot be quantified due to lack of standard substances or assessed due to lack of a standardized procedure for determination of their estrogenic potency. By comparison with provisional guide values for estradiol (0.5 ng/L) and ethynylestradiol (0.3 ng/L), the damaging potential of the total estrogenic activity in groundwater samples can in fact be assessed, but specific remediation measures are impossible unless the hormonal activity can be attributed to individual chemical substances. Recommendations and outlook On the one hand, further analyses of samples taken from possible pollution sources should be conducted in order to characterize the extent of groundwater pollution with xenoestrogens. On the other hand, the most potent individual compounds should be identified according to their estrogenic potency. To this end, bioassay-directed fractionation and structure elucidation should be carried out with concentrated samples.</description><identifier>ISSN: 0944-1344</identifier><identifier>EISSN: 1614-7499</identifier><identifier>DOI: 10.1007/s11356-009-0234-1</identifier><identifier>PMID: 19730910</identifier><language>eng</language><publisher>Berlin/Heidelberg: Springer-Verlag</publisher><subject>17β-Estradiol ; Alkylphenols ; Aquatic Pollution ; Atmospheric Protection/Air Quality Control/Air Pollution ; Bioassays ; Biological Assay ; Biological effects ; Bisphenol A ; Cell Line, Tumor ; Chemical and Biological Environmental Monitoring • Series • Research Article ; Chemical compounds ; Chemical contaminants ; Chromatography ; Disposal sites ; Earth and Environmental Science ; Ecotoxicology ; Endocrine disruptors ; Endocrine Disruptors - analysis ; Endocrine Disruptors - toxicity ; Environment ; Environmental Chemistry ; Environmental Health ; Environmental monitoring ; Environmental Monitoring - methods ; Esters ; Estrogenic activity ; Estrogens ; Estrogens - analysis ; Estrogens - toxicity ; Fractionation ; Fresh Water - chemistry ; Gas chromatography ; Gas Chromatography-Mass Spectrometry ; Groundwater ; Groundwater pollution ; Hormones ; Humans ; Hydrocarbons ; Industrial wastes ; Landfill ; Landfills ; Mass spectrometry ; Mass spectroscopy ; Organic chemicals ; PCB ; Phenols ; Phthalic acid ; Pollutants ; Pollution sources ; Polychlorinated biphenyls ; Polychlorinated Biphenyls - analysis ; Polychlorinated Biphenyls - toxicity ; Polycyclic aromatic hydrocarbons ; Polycyclic Aromatic Hydrocarbons - analysis ; Polycyclic Aromatic Hydrocarbons - toxicity ; Risk assessment ; Scientific imaging ; Studies ; Toxicity ; Waste disposal ; Waste disposal sites ; Waste Water Technology ; Water analysis ; Water Management ; Water Pollutants, Chemical - analysis ; Water Pollutants, Chemical - toxicity ; Water pollution ; Water Pollution Control ; Water sampling ; World War I ; Xenoestrogens</subject><ispartof>Environmental science and pollution research international, 2010-02, Vol.17 (2), p.250-260</ispartof><rights>Springer-Verlag 2009</rights><rights>Springer-Verlag 2010</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c402t-44a2c11215402b0c8e3d0b5cfe02af1a1298fa51930a21ed40094afddc2f000e3</citedby><cites>FETCH-LOGICAL-c402t-44a2c11215402b0c8e3d0b5cfe02af1a1298fa51930a21ed40094afddc2f000e3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1007/s11356-009-0234-1$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1007/s11356-009-0234-1$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,780,784,27924,27925,41488,42557,51319</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/19730910$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kuch, Bertram</creatorcontrib><creatorcontrib>Kern, Frieder</creatorcontrib><creatorcontrib>Metzger, Jörg W.</creatorcontrib><creatorcontrib>von der Trenck, Karl Theo</creatorcontrib><title>Effect-related monitoring: estrogen-like substances in groundwater</title><title>Environmental science and pollution research international</title><addtitle>Environ Sci Pollut Res</addtitle><addtitle>Environ Sci Pollut Res Int</addtitle><description>Background, aim, and scope Concentration monitoring as a basis for risk assessment is a valid approach only if there is an unambiguous relation between concentration and effect. In many cases, no such unambiguous relation exists, since various substances can exert the same effect with differing potencies. If some or all of these substances contributing to a biological effect are unknown, effect-related monitoring becomes indispensable. Endocrine-disrupting substances in water bodies, including the groundwater, are a prominent example of such a case. The aim of the investigations described here was to detect hormonally active substances in the groundwater downstream of obsolete landfills by using the E-screen assay and to possibly assign the biological effect to individual chemical compounds by means of instrumental analyses carried out in parallel. Materials and methods Grab samples of the groundwater were collected downstream from abandoned landfills and prepared by liquid/liquid extraction. The total estrogenic activity in these samples was determined in vitro by applying the E-screen assay. The human breast cancer cells (MCF-7) used in the E-screen proliferate in response to the presence of estrogenically active compounds. Expressed in concentration units of the reference substance 17β-estradiol (E2), the test system allows the quantification of estrogenicity with a limit of detection (LOD) in the range of 0.1 ng/L. Aliquots of the samples were screened using gas chromatography/mass spectrometry (GC/MS) in order to quantify known estrogenically active substances and to identify unknown compounds. Estrogen-positive samples were extracted at different pH values, split into acidic, neutral, and basic fractions and analyzed by GC/MS, searching for individual components that display estrogenic activity. Results and discussion Estrogenic activity exceeding the LOD and the provisional benchmark of 0.5 ng E2/L was found at three out of seven abandoned waste disposal sites tested. The low concentrations of known xenoestrogens such as bisphenol-A, nonylphenols, or phthalic acid esters determined by GC/MS, however, were not sufficient to explain the detected activity. Neither natural nor synthetic hormones have caused the activity because these chemical structures are readily degradable and cannot persist in abandoned landfills for decades. The highest activity in the E-screen assay was found in the acidic fractions. Hydroxy-polychlorinated biphenyls (PCBs), hydroxylated polycyclic aromatic hydrocarbons (PAHs) and hetero-PAHs, as well as alkylphenols could be identified as further compounds with possible hormonal activity. Conclusions Estrogenically active substances may occur in the groundwater below obsolete landfills, especially those that contain PCBs or waste from gasworks. These substances are not part of analytical programs routinely applied to contaminated sites and may therefore escape detection and assessment. Analyses using the E-screen assay and GC/MS in parallel have shown that the total estrogenic activity found in groundwater samples is to be ascribed to a multitude of individual compounds, some of which cannot be quantified due to lack of standard substances or assessed due to lack of a standardized procedure for determination of their estrogenic potency. By comparison with provisional guide values for estradiol (0.5 ng/L) and ethynylestradiol (0.3 ng/L), the damaging potential of the total estrogenic activity in groundwater samples can in fact be assessed, but specific remediation measures are impossible unless the hormonal activity can be attributed to individual chemical substances. Recommendations and outlook On the one hand, further analyses of samples taken from possible pollution sources should be conducted in order to characterize the extent of groundwater pollution with xenoestrogens. On the other hand, the most potent individual compounds should be identified according to their estrogenic potency. To this end, bioassay-directed fractionation and structure elucidation should be carried out with concentrated samples.</description><subject>17β-Estradiol</subject><subject>Alkylphenols</subject><subject>Aquatic Pollution</subject><subject>Atmospheric Protection/Air Quality Control/Air Pollution</subject><subject>Bioassays</subject><subject>Biological Assay</subject><subject>Biological effects</subject><subject>Bisphenol A</subject><subject>Cell Line, Tumor</subject><subject>Chemical and Biological Environmental Monitoring • Series • Research Article</subject><subject>Chemical compounds</subject><subject>Chemical contaminants</subject><subject>Chromatography</subject><subject>Disposal sites</subject><subject>Earth and Environmental Science</subject><subject>Ecotoxicology</subject><subject>Endocrine disruptors</subject><subject>Endocrine Disruptors - analysis</subject><subject>Endocrine Disruptors - toxicity</subject><subject>Environment</subject><subject>Environmental Chemistry</subject><subject>Environmental Health</subject><subject>Environmental monitoring</subject><subject>Environmental Monitoring - methods</subject><subject>Esters</subject><subject>Estrogenic activity</subject><subject>Estrogens</subject><subject>Estrogens - analysis</subject><subject>Estrogens - toxicity</subject><subject>Fractionation</subject><subject>Fresh Water - chemistry</subject><subject>Gas chromatography</subject><subject>Gas Chromatography-Mass Spectrometry</subject><subject>Groundwater</subject><subject>Groundwater pollution</subject><subject>Hormones</subject><subject>Humans</subject><subject>Hydrocarbons</subject><subject>Industrial wastes</subject><subject>Landfill</subject><subject>Landfills</subject><subject>Mass spectrometry</subject><subject>Mass spectroscopy</subject><subject>Organic chemicals</subject><subject>PCB</subject><subject>Phenols</subject><subject>Phthalic acid</subject><subject>Pollutants</subject><subject>Pollution sources</subject><subject>Polychlorinated biphenyls</subject><subject>Polychlorinated Biphenyls - analysis</subject><subject>Polychlorinated Biphenyls - toxicity</subject><subject>Polycyclic aromatic hydrocarbons</subject><subject>Polycyclic Aromatic Hydrocarbons - analysis</subject><subject>Polycyclic Aromatic Hydrocarbons - toxicity</subject><subject>Risk assessment</subject><subject>Scientific imaging</subject><subject>Studies</subject><subject>Toxicity</subject><subject>Waste disposal</subject><subject>Waste disposal sites</subject><subject>Waste Water Technology</subject><subject>Water analysis</subject><subject>Water Management</subject><subject>Water Pollutants, Chemical - analysis</subject><subject>Water Pollutants, Chemical - toxicity</subject><subject>Water pollution</subject><subject>Water Pollution Control</subject><subject>Water sampling</subject><subject>World War 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Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kuch, Bertram</au><au>Kern, Frieder</au><au>Metzger, Jörg W.</au><au>von der Trenck, Karl Theo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Effect-related monitoring: estrogen-like substances in groundwater</atitle><jtitle>Environmental science and pollution research international</jtitle><stitle>Environ Sci Pollut Res</stitle><addtitle>Environ Sci Pollut Res Int</addtitle><date>2010-02-01</date><risdate>2010</risdate><volume>17</volume><issue>2</issue><spage>250</spage><epage>260</epage><pages>250-260</pages><issn>0944-1344</issn><eissn>1614-7499</eissn><abstract>Background, aim, and scope Concentration monitoring as a basis for risk assessment is a valid approach only if there is an unambiguous relation between concentration and effect. In many cases, no such unambiguous relation exists, since various substances can exert the same effect with differing potencies. If some or all of these substances contributing to a biological effect are unknown, effect-related monitoring becomes indispensable. Endocrine-disrupting substances in water bodies, including the groundwater, are a prominent example of such a case. The aim of the investigations described here was to detect hormonally active substances in the groundwater downstream of obsolete landfills by using the E-screen assay and to possibly assign the biological effect to individual chemical compounds by means of instrumental analyses carried out in parallel. Materials and methods Grab samples of the groundwater were collected downstream from abandoned landfills and prepared by liquid/liquid extraction. The total estrogenic activity in these samples was determined in vitro by applying the E-screen assay. The human breast cancer cells (MCF-7) used in the E-screen proliferate in response to the presence of estrogenically active compounds. Expressed in concentration units of the reference substance 17β-estradiol (E2), the test system allows the quantification of estrogenicity with a limit of detection (LOD) in the range of 0.1 ng/L. Aliquots of the samples were screened using gas chromatography/mass spectrometry (GC/MS) in order to quantify known estrogenically active substances and to identify unknown compounds. Estrogen-positive samples were extracted at different pH values, split into acidic, neutral, and basic fractions and analyzed by GC/MS, searching for individual components that display estrogenic activity. Results and discussion Estrogenic activity exceeding the LOD and the provisional benchmark of 0.5 ng E2/L was found at three out of seven abandoned waste disposal sites tested. The low concentrations of known xenoestrogens such as bisphenol-A, nonylphenols, or phthalic acid esters determined by GC/MS, however, were not sufficient to explain the detected activity. Neither natural nor synthetic hormones have caused the activity because these chemical structures are readily degradable and cannot persist in abandoned landfills for decades. The highest activity in the E-screen assay was found in the acidic fractions. Hydroxy-polychlorinated biphenyls (PCBs), hydroxylated polycyclic aromatic hydrocarbons (PAHs) and hetero-PAHs, as well as alkylphenols could be identified as further compounds with possible hormonal activity. Conclusions Estrogenically active substances may occur in the groundwater below obsolete landfills, especially those that contain PCBs or waste from gasworks. These substances are not part of analytical programs routinely applied to contaminated sites and may therefore escape detection and assessment. Analyses using the E-screen assay and GC/MS in parallel have shown that the total estrogenic activity found in groundwater samples is to be ascribed to a multitude of individual compounds, some of which cannot be quantified due to lack of standard substances or assessed due to lack of a standardized procedure for determination of their estrogenic potency. By comparison with provisional guide values for estradiol (0.5 ng/L) and ethynylestradiol (0.3 ng/L), the damaging potential of the total estrogenic activity in groundwater samples can in fact be assessed, but specific remediation measures are impossible unless the hormonal activity can be attributed to individual chemical substances. Recommendations and outlook On the one hand, further analyses of samples taken from possible pollution sources should be conducted in order to characterize the extent of groundwater pollution with xenoestrogens. On the other hand, the most potent individual compounds should be identified according to their estrogenic potency. To this end, bioassay-directed fractionation and structure elucidation should be carried out with concentrated samples.</abstract><cop>Berlin/Heidelberg</cop><pub>Springer-Verlag</pub><pmid>19730910</pmid><doi>10.1007/s11356-009-0234-1</doi><tpages>11</tpages></addata></record>
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identifier ISSN: 0944-1344
ispartof Environmental science and pollution research international, 2010-02, Vol.17 (2), p.250-260
issn 0944-1344
1614-7499
language eng
recordid cdi_proquest_miscellaneous_744610850
source MEDLINE; SpringerLink Journals - AutoHoldings
subjects 17β-Estradiol
Alkylphenols
Aquatic Pollution
Atmospheric Protection/Air Quality Control/Air Pollution
Bioassays
Biological Assay
Biological effects
Bisphenol A
Cell Line, Tumor
Chemical and Biological Environmental Monitoring • Series • Research Article
Chemical compounds
Chemical contaminants
Chromatography
Disposal sites
Earth and Environmental Science
Ecotoxicology
Endocrine disruptors
Endocrine Disruptors - analysis
Endocrine Disruptors - toxicity
Environment
Environmental Chemistry
Environmental Health
Environmental monitoring
Environmental Monitoring - methods
Esters
Estrogenic activity
Estrogens
Estrogens - analysis
Estrogens - toxicity
Fractionation
Fresh Water - chemistry
Gas chromatography
Gas Chromatography-Mass Spectrometry
Groundwater
Groundwater pollution
Hormones
Humans
Hydrocarbons
Industrial wastes
Landfill
Landfills
Mass spectrometry
Mass spectroscopy
Organic chemicals
PCB
Phenols
Phthalic acid
Pollutants
Pollution sources
Polychlorinated biphenyls
Polychlorinated Biphenyls - analysis
Polychlorinated Biphenyls - toxicity
Polycyclic aromatic hydrocarbons
Polycyclic Aromatic Hydrocarbons - analysis
Polycyclic Aromatic Hydrocarbons - toxicity
Risk assessment
Scientific imaging
Studies
Toxicity
Waste disposal
Waste disposal sites
Waste Water Technology
Water analysis
Water Management
Water Pollutants, Chemical - analysis
Water Pollutants, Chemical - toxicity
Water pollution
Water Pollution Control
Water sampling
World War I
Xenoestrogens
title Effect-related monitoring: estrogen-like substances in groundwater
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