Recent advances in the mass spectrometric analysis related to endocrine disrupting compounds in aquatic environmental samples.

An overview of mass spectrometric methods used for the determination of endocrine disrupting compounds (EDCs) in environmental samples is presented. Among the EDCs we have selected five groups of compounds that are of priority within European Union and US research activities: alkylphenols, polychlorinated compounds (dioxins, furans and biphenyls), polybrominated diphenyl ethers, phthalates and steroid sex hormones. Various aspects of current LC-MS and GC-MS methodology, including sample preparation, are discussed.

[1]  U. Brinkman,et al.  Determination of phenolic compounds in surface water using on-line liquid chromatographic precolumn-based column-switching techniques , 1994 .

[2]  C. Iden,et al.  Analysis of alkylphenol ethoxylate metabolites in the aquatic environment using liquid chromatography-electrospray mass spectrometry. , 2000, Analytical chemistry.

[3]  Ruthann A. Rudel,et al.  Identification of Alkylphenols and Other Estrogenic Phenolic Compounds in Wastewater, Septage, and Groundwater on Cape Cod, Massachusetts , 1998 .

[4]  John P. Sumpter,et al.  Long-Term Temporal Changes in the Estrogenic Composition of Treated Sewage Effluent and Its Biological Effects on Fish , 2000 .

[5]  A. Marinoni,et al.  Characterization of Recalcitrant Intermediates from Biotransformation of the Branched Alkyl Side Chain of Nonylphenol Ethoxylate Surfactants , 1998 .

[6]  R. Macdonald,et al.  Persistence of Nonylphenol Ethoxylate Surfactants and Their Primary Degradation Products in Sediments from near a Municipal Outfall in the Strait of Georgia, British Columbia, Canada , 1999 .

[7]  D. Barceló,et al.  Identification of polar, ionic, and highly water soluble organic pollutants in untreated industrial wastewaters , 1999 .

[8]  D. Lubda,et al.  Alkyl diol silica: restricted access pre-column packings for fast liquid chromatography-integrated sample preparation of biological fluids. , 2001, Journal of chromatography. A.

[9]  C. Crescenzi,et al.  Occurrence and abundance of dicarboxylated metabolites of nonylphenol polyethoxylate surfactants in treated sewages , 2000 .

[10]  C. Kelly Analysis of steroids in environmental water samples using solid-phase extraction and ion-trap gas chromatography-mass spectrometry and gas chromatography-tandem mass spectrometry. , 2000, Journal of chromatography. A.

[11]  K. Ballschmiter,et al.  Determination of endocrine-disrupting phenolic compounds and estrogens in surface and drinking water by HRGC-(NCI)-MS in the picogram per liter range. , 2001, Environmental science & technology.

[12]  M. Oehme,et al.  Isomer-selective determination of tetrachlorodibenzo-p-dioxins using hydroxyl negative ion chemical ionization mass spectrometry combined with high-resolution gas chromatography. , 1984, Analytical chemistry.

[13]  D. Barceló,et al.  Determination of steroid sex hormones and related synthetic compounds considered as endocrine disrupters in water by liquid chromatography-diode array detection-mass spectrometry. , 2000, Journal of chromatography. A.

[14]  S. N. Pedersen,et al.  Quantification of the xenoestrogens 4-tert.-octylphenol and bisphenol A in water and in fish tissue based on microwave assisted extraction, solid-phase extraction and liquid chromatography-mass spectrometry. , 1999, Journal of chromatography. A.

[15]  J. Caixach,et al.  Microwave vs. Soxhlet for the extraction of PCDDs and PCDFs from sewage sludge samples , 1998 .

[16]  W. C. Brumley,et al.  Determination of Phthalates in Water and Soil by Tandem Mass Spectrometry Under Chemical Ionization Conditions with Isobutane as Reagent Gas , 1994 .

[17]  F Ventura,et al.  Simultaneous determination of halogenated derivatives of alkylphenol ethoxylates and their metabolites in sludges, river sediments, and surface, drinking, and wastewaters by liquid chromatography-mass spectrometry. , 2001, Analytical chemistry.

[18]  W. Ding,et al.  Analysis of nonylphenol polyethoxycarboxylates and their related metabolites by on-line derivatization and ion-trap gas chromatography-mass spectrometry. , 1999, Journal of chromatography. A.

[19]  J. Vílchez,et al.  Determination of bisphenol A (BPA) in water by gas chromatography-mass spectrometry , 1997 .

[20]  Lawrence H. Keith,et al.  Analysis of Environmental Endocrine Disruptors , 1999 .

[21]  R. Maguire,et al.  Occurrence of alkylphenols and alkylphenol mono- and diethoxylates in natural waters of the Laurentian Great Lakes basin and the upper St. Lawrence River , 1997 .

[22]  D. Barceló,et al.  Optimization of congener-specific analysis of 40 polybrominated diphenyl ethers by gas chromatography/mass spectrometry. , 2002, Journal of mass spectrometry : JMS.

[23]  K. Fytianos,et al.  Organic pollutants in biological waste water treatment. Results of mass and tandem mass spectrometry of the flow injection mode compared with liquid chromatographic examinations: Polar compounds under positive ionization , 1999 .

[24]  Hing-Biu Lee,et al.  Determination of 4-Nonylphenol in Effluent and Sludge from Sewage Treatment Plants , 1995 .

[25]  J. Vílchez,et al.  Determination of bisphenol A in water by micro liquid-liquid extraction followed by silylation and gas chromatography-mass spectrometry analysis. , 1998, Journal of chromatographic science.

[26]  H. B. Lee,et al.  Determination of 17 beta-estradiol and its metabolites in sewage effluent by solid-phase extraction and gas chromatography/mass spectrometry. , 1998, Journal of AOAC International.

[27]  D. Barceló,et al.  Determination of steroid sex hormones and related synthetic compounds considered as endocrine disrupters in water by fully automated on-line solid-phase extraction-liquid chromatography-diode array detection. , 2001, Journal of chromatography. A.

[28]  J. Caixach,et al.  Characterization of polyethoxylated surfactants and their brominated derivatives formed at the water treatment plant of Barcelona by GC/MS and FAB mass spectrometry , 1988 .

[29]  Edwin J. Routledge,et al.  Identification of Estrogenic Chemicals in STW Effluent. 1. Chemical Fractionation and in Vitro Biological Screening , 1998 .

[30]  D. Barceló,et al.  Pressurized liquid extraction followed by liquid chromatography-mass spectrometry for the determination of alkylphenolic compounds in river sediment. , 2002, Journal of chromatography. A.

[31]  D. Barceló,et al.  Determination of anionic and nonionic surfactants, their degradation products, and endocrine-disrupting compounds in sewage sludge by liquid chromatography/mass spectrometry. , 2000, Analytical chemistry.

[32]  Roberta Curini,et al.  Monitoring Natural and Synthetic Estrogens at Activated Sludge Sewage Treatment Plants and in a Receiving River Water , 2000 .

[33]  M. Reinhard,et al.  Identification and quantification of halogenated and non-halogenated octylphenol polyethoxylate residues by gas chromatography/mass spectrometry using electron ionization and chemical ionization , 1988 .

[34]  Shane A. Snyder,et al.  Analytical Methods for Detection of Selected Estrogenic Compounds in Aqueous Mixtures , 1999 .

[35]  D. Barceló,et al.  Sequential solid phase extraction protocol followed by liquid chromatography–atmospheric pressure chemical ionization–mass spectrometry for the trace determination of non ionic polyethoxylated surfactants in tannery wastewaters , 1999 .

[36]  S. R. Cole,et al.  Isolation of the components of a complex mixture by means of column switching for their enhanced detection by mass spectrometry. , 2001, Journal of chromatography. A.

[37]  M. Pettersson,et al.  ETHINYLOESTRADIOL - AN UNDESIRED FISH CONTRACEPTIVE , 1999 .

[38]  D. Barceló,et al.  Occurrence and distribution of nonionic surfactants, their degradation products, and linear alkylbenzene sulfonates in coastal waters and sediments in Spain , 2002, Environmental toxicology and chemistry.

[39]  M Castillo,et al.  Monitoring of endocrine disruptors in surface waters by the yeast recombinant assay , 2001, Environmental toxicology and chemistry.

[40]  W Giger,et al.  Persistent organic chemicals in sewage effluents. 3. Determinations of nonylphenoxy carboxylic acids by high-resolution gas chromatography/mass spectrometry and high-performance liquid chromatography. , 1987, Environmental science & technology.

[41]  D. Sedlak,et al.  Analysis of estrogenic hormones in municipal wastewater effluent and surface water using enzyme‐linked immunosorbent assay and gas chromatography/tandem mass spectrometry , 2001, Environmental toxicology and chemistry.

[42]  D. Barceló Applications of LC-MS in environmental chemistry , 1996 .

[43]  J. Beens,et al.  Comprehensive two-dimensional gas chromatography: a hyphenated method with strong coupling between the two dimensions. , 1999, Journal of chromatography. A.

[44]  D. Barceló,et al.  Characterization of organic pollutants in industrial effluents using liquid chromatography–atmospheric pressure chemical ionization–mass spectrometry , 1997 .

[45]  D. Jahr Determination of alkyl, chloro and mononitrophenols in water by sample-acetylation and automatic on-line solid phase extraction-gas chromatography-mass spectrometry , 1998 .

[46]  K. Boos,et al.  The use of restricted-access media in HPLC, Part II : Applications , 1997 .

[47]  J. L. Vidal,et al.  A restricted access medium column for the trace determination of triadimefon and tetraconazole in water with large-volume injection coupled-column RPLC with UV detection , 2000 .

[48]  M. Splendore,et al.  A comparison of three mass spectrometric methods for the determination of dioxins/furans 5 5 Dedicat , 2000 .

[49]  H. Schröder Analysis of polar organic pollutants in the Elbe river by flow injection analysis and high-performance liquid chromatography with tandem mass spectrometry. , 1997, Journal of chromatography. A.

[50]  A. D. Vethaak,et al.  Analysis and occurrence of estrogenic hormones and their glucuronides in surface water and waste water in The Netherlands. , 1999, The Science of the total environment.

[51]  F. Borrull,et al.  Comparison of different fibers for the solid-phase microextraction of phthalate esters from water. , 2001, Journal of chromatography. A.

[52]  K. Ballschmiter,et al.  Determination of endogenous and exogenous estrogens in effluents from sewage treatment plants at the ng/L-level , 2000, Fresenius' journal of analytical chemistry.

[53]  F. Hernández,et al.  Strategies in Using Analytical Restricted Access Media Columns for the Removal of Humic Acid Interferences in the Trace Analysis of Acidic Herbicides in Water Samples by Coupled Column Liquid Chromatography with UV Detection , 1999 .

[54]  B. Sellergren,et al.  Evaluation of a multidimensional solid-phase extraction platform for highly selective on-line cleanup and high-throughput LC-MS analysis of triazines in river water samples using molecularly imprinted polymers. , 2001, Analytical chemistry.

[55]  B. Herradón,et al.  Feasibility of high-performance immunochromatography as an isolation method for PCBs and other dioxin-like compounds. , 2001, Analytical chemistry.

[56]  W. Ding,et al.  Analysis of nonylphenol polyethoxylates and their degradation products in river water and sewage effluent by gas chromatography-ion trap (tandem) mass spectrometry with electron impact and chemical ionization. , 1998, Journal of chromatography. A.

[57]  C. Metcalfe,et al.  Distribution of alkylphenol compounds in great lakes sediments, United States and Canada , 1998 .

[58]  T. S. Thompson,et al.  Application of tandem quadrupole mass spectrometry for the ultra-trace determination of polychlorinated dibenzo-p-dioxins and dibenzofurans , 1990 .

[59]  H. Q. Li,et al.  Assessment of the pollutant elimination efficiency by gas chromatography/mass spectrometry, liquid chromatography-mass spectrometry and -tandem mass spectrometry. Comparison of conventional and membrane-assisted biological wastewater treatment processes. , 2000, Journal of chromatography. A.

[60]  V. Lopez-Avila,et al.  Microwave-Assisted Extraction of Organic Compounds from Standard Reference Soils and Sediments , 1994 .

[61]  M. Riekkola,et al.  Reversed phase HPLC coupled on‐line to GC by the vaporizer/precolumn solvent split/gas discharge interface; analysis of phthalates in water , 1997 .

[62]  Y. Tondeur,et al.  Optimization of a hybrid-mass spectrometer method for the analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans , 1989 .

[63]  J. J. Ryan,et al.  Determination of brominated diphenyl ethers (BDEs) and levels in Canadian human milks , 2000 .

[64]  R. Kumar A mass spectral guide for quick identification of phthalate esters , 1999 .

[65]  J. Caixach,et al.  Identification of surfactants in water by fab mass spectrometry , 1989 .

[66]  A. Johnson,et al.  Estimating steroid oestrogen inputs into activated sludge treatment works and observations on their removal from the effluent. , 2000, The Science of the total environment.

[67]  M. Waldock,et al.  Concentrations of alkylphenols in rivers and estuaries in England and Wales , 1995 .

[68]  C. Iden,et al.  Distribution and fate of neutral alkylphenol ethoxylate metabolites in a sewage-impacted urban estuary. , 2001, Environmental science & technology.

[69]  Ursula Obst,et al.  A new concept for the bioeffects-related analysis of xenoestrogens: Hyphenation of receptor assays with LC-MS , 1999 .

[70]  C. Iden,et al.  Determination of steroid estrogens in wastewater by immunoaffinity extraction coupled with HPLC-electrospray-MS. , 2001, Analytical chemistry.

[71]  H. Mol,et al.  Determination of endocrine disruptors in water after derivatization with N-methyl-N-(tert.-butyldimethyltrifluoroacetamide) using gas chromatography with mass spectrometric detection. , 2000, Journal of chromatography. A.

[72]  B. Larsen,et al.  Use of supercritical fluid extraction in the analysis of polychlorinated dibenzodioxins and dibenzofurans , 1994 .

[73]  A. Laganà,et al.  Trace analysis of estrogenic chemicals in sewage effluent using liquid chromatography combined with tandem mass spectrometry. , 2000, Rapid communications in mass spectrometry : RCM.

[74]  D. Barceló,et al.  Estrogenicity determination in sewage treatment plants and surface waters from the Catalonian area (NE Spain) , 2000 .

[75]  J D Berset,et al.  Determination of phthalates in crude extracts of sewage sludges by high-resolution capillary gas chromatography with mass spectrometric detection. , 2001, Journal of AOAC International.

[76]  C. Metcalfe,et al.  Distribution of degradation products of alkylphenol ethoxylates near sewage treatment plants in the lower Great Lakes, North America , 2000 .

[77]  D. Barceló,et al.  On-line solid-phase extraction in liquid chromatography using restricted access pre-columns for the analysis of s-triazines in humic-containing waters , 1996 .

[78]  A. Hogenboom,et al.  On-line Trace Level Determination of Polar Organic Microcontaminants in Water Using Various Pre-column–Analytical Column Liquid Chromatographic Techniques With Ultraviolet Absorbance and Mass Spectrometric Detection , 1997 .

[79]  Damià Barceló,et al.  Review of analytical methods for the determination of estrogens and progestogens in waste waters , 2001, Fresenius' journal of analytical chemistry.

[80]  T. Croley,et al.  Mass spectrometry applied to the analysis of estrogens in the environment. , 2000, Rapid communications in mass spectrometry : RCM.

[81]  M. Vitali PHTHALATE ESTERS IN FRESHWATERS AS MARKERS OF CONTAMINATION SOURCES- A SITE STUDY IN ITALY , 1997 .

[82]  M. Reinhard,et al.  Occurrence of brominated alkylphenol polyethoxy carboxylates in mutagenic waste water concentrates , 1982 .

[83]  T. Croley,et al.  Mass spectrometric study of persistent acid metabolites of nonylphenol ethoxylate surfactants. , 2000, Journal of mass spectrometry : JMS.

[84]  Eva Jakobsson,et al.  Gas chromatographic identification and quantification of polybrominated diphenyl ethers in a commercial product, Bromkal 70-5DE , 1998 .

[85]  Todd F. Wheeler,et al.  Mass Spectral Characterization of p-Nonylphenol Isomers Using High-Resolution Capillary GC—MS , 1997 .

[86]  D. Barceló,et al.  Use of solid-phase extraction in various of its modalities for sample preparation in the determination of estrogens and progestogens in sediment and water. , 2001, Journal of chromatography. A.

[87]  J. Field,et al.  Nonylphenol polyethoxy carboxylate metabolites of nonionic surfactants in U.S. paper mill Effluents, Municipal sewage treatment plant effluents, and river waters , 1996 .

[88]  A. Kreisselmeier,et al.  Determination of alkylphenols, alkylphenolethoxylates and linear alkylbenezenesulfonates in sediments by accelerated solvent extraction and supercritical fluid extraction , 1997 .

[89]  M. Bartels,et al.  Quantitative Determination of Bisphenol-A in River Water by Cool On-Column Injection-Gas Chromatography-Mass Spectrometry , 1998 .

[90]  M. Weller,et al.  Immunochromatographic techniques – a critical review , 2000, Fresenius' journal of analytical chemistry.

[91]  C. Wahlberg,et al.  Determination of nonylphenol and nonylphenol ethoxylates as their pentafluorobenzoates in water, sewage sludge and biota , 1990 .

[92]  C. Cramers,et al.  High-speed GC-MS , 1998 .

[93]  A. Marcomini,et al.  Monitoring aromatic surfactants and their biodegradation intermediates in raw and treated sewages by solid-phase extraction and liquid chromatography. , 1994, Environmental science & technology.

[94]  A. Marcomini,et al.  Determination of Nonionic Polyethoxylate Surfactants in Environmental Waters by Liquid Chromatography/Electrospray Mass Spectrometry , 1995 .

[95]  Traldi,et al.  Wide band ion isolation in an ion trap for the analysis of polychlorobiphenyls , 1999, Journal of mass spectrometry : JMS.

[96]  H. Okamura,et al.  Halogenation and toxicity of the biodegradation products of a nonionic surfactant, nonylphenol ethoxylate , 1998 .

[97]  A. Marcomini,et al.  Reversed-phase high-performance liquid chromatographic determination of linear alkylbenzene sulphonates, nonylphenol polyethoxylates and their carboxylic biotransformation products , 1993 .

[98]  M. Servos,et al.  Behavior and occurrence of estrogens in municipal sewage treatment plants--I. Investigations in Germany, Canada and Brazil. , 1999, The Science of the total environment.

[99]  P. Zoonen,et al.  Recent and future developments of liquid chromatography in pesticide trace analysis. , 2000, Journal of chromatography. A.

[100]  P. Fürst,et al.  Harmonised quality criteria for chemical and bioassays analyses of PCDDs/PCDFs in feed and food, pt. 1 , 2001 .

[101]  Y. Tondeur,et al.  Choosing between high-resolution mass spectrometry and mass spectrometry/mass spectrometry : environmental applications , 1990 .

[102]  C. Iden,et al.  Analysis of nonylphenol and nonylphenol ethoxylates in environmental samples by mixed-mode high-performance liquid chromatography-electrospray mass spectrometry. , 2001, Journal of chromatography. A.

[103]  D. Barceló,et al.  Analysis of ethoxylated nonionic surfactants and their metabolites by liquid chromatography/atmospheric pressure ionization mass spectrometry. , 2001, Journal of mass spectrometry : JMS.

[104]  M. Ikonomou,et al.  A gas chromatography/high-resolution mass spectrometry (GC/HRMS) method for determination of polybrominated diphenyl ethers in fish. , 2001, Chemosphere.

[105]  M. Ikonomou,et al.  Quantitative determination of nonylphenol polyethoxylate surfactants in marine sediment using normal-phase liquid chromatography-electrospray mass spectrometry. , 1999, Journal of chromatography. A.

[106]  N. Jonkers,et al.  Aerobic biodegradation studies of nonylphenol ethoxylates in river water using liquid chromatography-electrospray tandem mass spectrometry. , 2001, Environmental science & technology.