water analysis emerging contaminants and current issues

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REVIEW pubs.acs.org/ac

Water Analysis: Emerging Contaminants and Current IssuesSusan D. Richardson*, and Thomas A. Ternes

National Exposure Research Laboratory, U.S. Environmental Protection Agency, Athens, Georgia 30605, United States Federal Institute of Hydrology, Koblenz, D-56068 GermanyBioassays Drinking Water and Swimming Pool Disinfection By-Products Drinking Water DBPs Combining Chemistry with Toxicology Discovery of New DBPs New Methods Near Real-Time Methods Improved Method for Total Organic Chlorine and Bromine Alternative Disinfection Technologies Using Iodine, UV, and Other Treatments Nitrosamines Mechanisms of Formation DBPs of Pollutants New Swimming Pool Research Sunscreens/UV Filters Brominated Flame Retardants Benzotriazoles Dioxane Siloxanes Naphthenic Acids Musks Pesticide Transformation Products Perchlorate Algal Toxins Microorganisms Contaminants on the Horizon: Ionic Liquids Biographies Acknowledgment References 4630 4630 4630 4631 4631 4631 4632 4632 4632 4633 4634 4635 4635 4636 4637 4638 4638 4638 4638 4639 4639 4640 4641 4642 4643 4644 4644 4644

CONTENTSBackground Major Analysis Trends Sampling and Extraction Trends Chromatography Trends Use of Nanomaterials in Analytical Methods Other Particularly Creative Methods Emerging Contaminants General Reviews New Regulations/Regulatory Methods New Proposed Regulation for Perchlorate in U.S. Drinking Water The New Contaminant Candidate List-3 (CCL-3) The Draft Third Unregulated Contaminants Monitoring Rule (UCMR-3) New Regulatory Methods for Drinking Water EPA Method 539: Hormones EPA Method 538: Pesticides, Quinoline, and Other Organic Contaminants EPA Method 524.3: Purgeable Organic Compounds EPA Method 1615: Enteroviruses and Noroviruses Sucralose and Other Articial Sweeteners Antimony Nanomaterials PFOA, PFOS, and Other Peruorinated Compounds Pharmaceuticals and Hormones Environmental Impacts of Pharmaceuticals Biological Transformation Products Elimination/Reaction During Oxidative Water Treatment Opiates and Other Drugs of Abuse Antidepressants Antiviral Drugs Glucocorticoids Antimycotics and Antibiotics Thyroid Hormones Drinking Water Analysis Beta-Blockers Multiresidue Methods New SPE Materials/Procedures New Derivatization Method Enantiomersr 2011 American Chemical Society

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BACKGROUND This biennial review covers developments in water analysis for emerging environmental contaminants over the period of 20092010. A few signicant references that appeared between January and February 2011 are also included. Analytical Chemistrys policy is to limit reviews to a maximum of 250 signicantSpecial Issue: Fundamental and Applied Reviews in Analytical Chemistry Published: June 14, 20114614dx.doi.org/10.1021/ac200915r | Anal. Chem. 2011, 83, 46144648

Analytical Chemistry Table 1. List of AcronymsAPCI APPI BP-3 BSTFA CCL DBPs E1 E2 E3 EE2 ECD EDCs ELISA EPA ESA ESI FT FTOHs GC HAAs HXLPP IC ICP IR LC MALDI 4-MBC MCL MIMS MRM MS MSTFA MX NCI NDMA NMR NOM N-EtFOSAA OC ODPABA PCBs PBDEs PFCs PFCAs PFDA PFHxA PFHpA PFNA PFOA PFOS PFOSA PFPrA PFUnDA REACH SPE atmospheric pressure chemical ionization atmospheric pressure photoionization benzophenone-3 bis(trimethylsilyl)triuoroacetamide Contaminant Candidate List disinfection byproducts estrone 17-estradiol estriol 17R-ethinylestradiol electron capture detection endocrine disrupting compounds enzyme-linked immunosorbent assay Environmental Protection Agency ethane sulfonic acid electrospray ionization Fourier-transform uorinated telomer alcohols gas chromatography haloacetic acids hypercrosslinked polymer resin ion chromatography inductively coupled plasma infrared liquid chromatography matrix-assisted laser desorption ionization 4-methylbenzylidene camphor maximum contaminant level membrane introduction mass spectrometry multiple reaction monitoring mass spectrometry N-methyl-N-trimethylsilyltriuoroacetamide 3-chloro-(4-dichloromethyl)-5-hydroxy-2(5H)-furanone negative chemical ionization N-nitrosodimethylamine nuclear magnetic resonance natural organic matter N-ethyl peruorooctane sulfonamide acetate octocrylene octyl-dimethyl-p-aminobenzoic acid polychlorinated biphenyls polybrominated diphenyl ethers peruorinated compounds peruorocarboxylic acids peruorodecanoic acid peruorohexanoic acid peruoroheptanoic acid peruorononanoic acid peruorooctanoic acid peruorooctane sulfonate peruorooctane sulfonamide peruoropropanoic acid peruoroundecanoic acid Registration, Evaluation, and Authorization of Chemicals solid phase extraction


Table 1. ContinuedSPME THMs TOF UCMR-3 UPLC WWTP solid phase microextraction trihalomethanes time-of-ight the third Unregulated Contaminants Monitoring Rule ultraperformance liquid chromatography wastewater treatment plant

references and to mainly focus on new trends. Even with a more narrow focus, only a small fraction of the quality research publications could be discussed. As a result, as with the previous review on Water Analysis in 2009,1 this review will not be comprehensive but will highlight emerging contaminant groups and discuss representative papers. I write a similar review article on Environmental Mass Spectrometry, which also focuses on emerging contaminants.2 That review article is somewhat dierent from this one, in that it focuses on mass spectrometry methods and applications and includes measurements of air, soil/ sediments, and biological samples, in addition to water. This Review on Water Analysis focuses only on water measurements and applications but includes other methodologies besides mass spectrometry. I am excited to have Thomas Ternes join me this year (as in 2005) to cover the section on Pharmaceuticals and Hormones. Because Thomas is an international leader in this area, this Review will be much better with his contribution. We welcome any comments you have on this Review (richardson. susan@epa.gov). Numerous abstracts were consulted before choosing the best representative ones to present here. Abstract searches were carried out using Web of Science, and in many cases, full articles were obtained. A table of acronyms is provided (Table 1) as a quick reference to the acronyms of analytical techniques and other terms discussed in this Review. A table of useful Websites is also provided (Table 2). Major Analysis Trends. One of the hottest trends is the use of high resolution mass spectrometry (MS) with liquid chromatography (LC) to identify unknown contaminants or to provide further selectivity for known analytes. Full scan and high resolution mass spectrometry have been used with gas chromatography (GC) in a similar fashion for decades, enabling the identification of many environmental contaminants. With recent instrumental development for LC/mass spectrometers, especially time-offlight (TOF), this full scan and high resolution/accurate mass benefit is now being utilized both for target analytes and also for identifying nontarget analytes that are highly polar, nonvolatile, or of high molecular weight and are not amenable to GC. As a result, within a single analytical run, both target and nontarget analytes can be analyzed or identified. In comparison to triple quadrupole mass spectrometers, which operate at unit resolution and generally in the selected reaction monitoring (SRM) or multiple reaction monitoring (MRM) modes for specific target analytes, TOF-mass spectrometers are capable of acquiring fullscan mass spectra at high resolution for all analytes without loss in sensitivity. Because most TOF mass spectrometers have a resolution of at least 10 000 at full-width-half-maximum (fwhm) peak height, isotopic patterns are evident and empirical formulas and chemical structures can be proposed for unknowns or confirmed for target analytes. This also makes it possible to use mass spectral libraries and enable the data file to be reinterrogated months later to find additional unknown contaminants.4615dx.doi.org/10.1021/ac200915r |Anal. Chem. 2011, 83, 46144648

Analytical Chemistry In addition to TOF-mass spectrometers, linear ion trap-Fourier transform (FT)-Orbitrap mass spectrometers are also now being used for similar high resolution-full scan applications. Examples of the use of high resolution-MS in this Review include the identification of pharmaceutical and pesticide transformation products and naphthenic acids. Researchers are also increasingly using isotopically labeled standards (deuterated or 13C-labeled) to allow more accurate quantication in a variety of sample matrixes (especially for wastewater samples, where matrix eects and ion suppression can be substantial). Atmospheric pressure photoionization (APPI) is also increasingly being used with LC/MS because it provides improved ionization for more nonpolar compounds, such as nanomaterials (e.g., fullerenes), polybrominated diphenyl ethers (PBDEs), and naphthenic acids discussed in this Review. Finally, nuclear magnetic resonance (NMR) spectroscopy is increasing in use, as it can provide detailed structural information to conrm tentative structures proposed by LC/MS/MS. In this regard, it is increasingly used to conrm structures of pharmaceutical transformation products. Because NMR is not as sensitive as MS, preparative LC is often used to collect enough material in fractions to enable the analysis of unknowns in complex environmental mixtures. Sampling and Extraction Trends. Solid phase extraction (SPE) remains the most popular means of extraction and concentration, and a new SPE device called Bag extraction was reported during the last 2 years. This bag-SPE consists of polystyrenedivinylbenzene enclosed in a woven polyester fabric, which can be immersed in water samples for solid phase extraction. Measured concentrations o


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