Emerging Contaminants and Current Issues

8/18/2019 Emerging Contaminants and Current Issues

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Published: June 14, 2011

r 2011 American Chemical Society 4614 dx.doi.org/10.1021/ac200915r | Anal. Chem. 2011, 83, 4614–4648

REVIEW

pubs.acs.org/ac

Water Analysis: Emerging Contaminants and Current Issues

Susan 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 Germany

’CONTENTS

Background 4614

Major Analysis Trends 4615

Sampling and Extraction Trends 4616

Chromatography Trends 4616

Use of Nanomaterials in Analytical Methods 4616

Other Particularly Creative Methods 4616

Emerging Contaminants 4616

General Reviews 4617New Regulations/Regulatory Methods 4617

New Proposed Regulation for Perchlorate in

U.S. Drinking Water 4617

The New Contaminant Candidate List-3 (CCL-3) 4618

The Draft Third Unregulated Contaminants

Monitoring Rule (UCMR-3) 4618

New Regulatory Methods for Drinking Water 4618

EPA Method 539: Hormones 4620

EPA Method 538: Pesticides, Quinoline, and

Other Organic Contaminants 4620

EPA Method 524.3: Purgeable Organic Compounds 4620

EPA Method 1615: Enteroviruses and Noroviruses 4620

Sucralose and Other Articial Sweeteners 4621

Antimony 4622

Nanomaterials 4622

PFOA, PFOS, and Other Peruorinated Compounds 4623

Pharmaceuticals and Hormones 4626

Environmental Impacts of Pharmaceuticals 4627

Biological Transformation Products 4627

Elimination/Reaction During Oxidative Water

Treatment 4628

Opiates and Other Drugs of Abuse 4628

Antidepressants 4629Antiviral Drugs 4629

Glucocorticoids 4629

Antimycotics and Antibiotics 4629

Thyroid Hormones 4629

Drinking Water Analysis 4629

Beta-Blockers 4629

Multiresidue Methods 4629

New SPE Materials/Procedures 4630

New Derivatization Method 4630

Enantiomers 4630

Bioassays 4630

Drinking Water and Swimming Pool Disinfection

By-Products 4630

Drinking Water DBPs 4630

Combining Chemistry with Toxicology 4631

Discovery of New DBPs 4631

New Methods 4631

Near Real-Time Methods 4632

Improved Method for Total Organic Chlorine andBromine 4632

Alternative Disinfection Technologies Using Iodine,

UV, and Other Treatments 4632

Nitrosamines 4633

Mechanisms of Formation 4634

DBPs of Pollutants 4635

New Swimming Pool Research 4635

Sunscreens/UV Filters 4636

Brominated Flame Retardants 4637

Benzotriazoles 4638

Dioxane 4638

Siloxanes 4638Naphthenic Acids 4638

Musks 4639

Pesticide Transformation Products 4639

Perchlorate 4640

Algal Toxins 4641

Microorganisms 4642

Contaminants on the Horizon: Ionic Liquids 4643

Biographies 4644

Acknowledgment 4644

References 4644

’BACKGROUND

This biennial review covers developments in water analysis foremerging environmental contaminants over the period of 20092010. A few signicant references that appeared between January and February 2011 are also included. Analytical Chem-istry’s policy is to limit reviews to a maximum of 250 signicant

Special Issue: Fundamental and Applied Reviews in AnalyticalChemistry


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4615 dx.doi.org/10.1021/ac200915r | Anal. Chem. 2011, 83, 4614–4648

Analytical Chemistry REVIEW

references and to mainly focus on new trends. Even with a morenarrow focus, only a small fraction of the quality researchpublications could be discussed. As a result, as with the previousreview on Water Analysis in 2009,1 this review will not becomprehensive but will highlight emerging contaminant groupsand discuss representative papers. I write a similar review articleon Environmental Mass Spectrometry, which also focuses onemerging contaminants.2 That review article is somewhatdiff erent 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. ThisReview on Water Analysis focuses only on water measurements

and applications but includes other methodologies besidesmass spectrometry. I am excited to have Thomas Ternes joinme this year (asin 2005) to cover the section on Pharmaceuticalsand Hormones. Because Thomas is an international leader in thisarea, this Review will be much better with his contribution. We welcome any comments you have on this Review ([email protected]).

Numerous abstracts were consulted before choosing the bestrepresentative ones to present here. Abstract searches werecarried out using Web of Science , and in many cases, full articles were obtained. A table of acronyms is provided (Table 1) as aquick reference to the acronyms of analytical techniques andother terms discussed in this Review. A table of usefulWebsites isalso provided (Table 2).

Major Analysis Trends. One of the hottest trends is the use of high resolution mass spectrometry (MS) with liquid chromatog-raphy (LC) to identify unknown contaminants or to providefurther selectivity for known analytes. Full scan and high resolu-tion mass spectrometryhave been used with gaschromatography (GC) in a similar fashion for decades, enabling the identificationof many environmental contaminants. With recent instrumentaldevelopment for LC/mass spectrometers, especially time-of-flight (TOF), this full scan and high resolution/accurate mass benefit is now being utilized both for target analytes and also foridentifying nontarget analytes that are highly polar, nonvolatile,or of high molecular weight and are not amenable to GC. As aresult, within a single analytical run, both target and nontarget

analytes can be analyzed or identified. In comparison to triplequadrupole mass spectrometers, which operate at unit resolutionand generally in the selected reaction monitoring (SRM) ormultiple reaction monitoring (MRM) modes for specific targetanalytes, TOF-mass spectrometers are capable of acquiring full-scan mass spectra at high resolution for all analytes without lossin sensitivity. Because most TOF mass spectrometers have aresolution of at least 10 000 at full-width-half-maximum (fwhm)peak height, isotopic patterns are evident and empirical formulasand chemical structures can be proposed for unknowns orconfirmed for target analytes. This also makes it possible to usemass spectral libraries and enable the data file to be reinterro-gated months later to find additional unknown contaminants.

Table 1. List of Acronyms

APCI atmospheric pressure chemical ionization

APPI atmospheric pressure photoionization

BP-3 benzophenone-3

BSTFA bis(trimethylsilyl)tr iuoroacetamide

CC L Contam inant Candidate List

DBPs dis infection byproductsE1 estrone

E2 17 β-estradiol

E3 estriol

EE2 17R-ethinylestradiol

ECD electron capture detection

EDCs endocrine disrupting compounds

ELISA enzyme-linked immunosorbent assay

EPA Environmental Protection Agency

ESA ethane sulfonic acid

ESI electrospray ionization

FT Fourier-transform

FTOHs uorinated telomer alcohols

GC gas chromatography HAAs haloacetic acids

HXLPP hypercrosslinked polymer resin

IC ion chromatography

IC P inductively coupled plasma

IR infrared

LC liquid chromatography

MALDI matrix-assisted laser desorption ionization

4-MBC 4-methylbenzylidene camphor

MCL maximum contaminant level

MIMS membrane introduction mass spectrometry

MRM multiple reaction monitoring

MS mass spectrometry

MSTFA N -methyl- N -trimethylsilyltriuoroacetamide

MX 3-chloro-(4-dichloromethyl)-5-hydroxy-2(5H )-furanone

NCI negative chemical ionization

NDMA N-nitrosodimethylamine

NMR nuclear magnetic resonance

NOM natura l organic m atter

N -EtFOSAA N -ethyl peruorooctane sulfonamide acetate

OC octocrylene

ODPABA octyl-dimethyl- p-aminobenzoic acid

PCBs polychlorinated biphenyls

PBDEs polybrominated diphenyl ethers

PFCs peruorinated compounds

PFCAs per

uorocarboxylic acidsPFDA peruorodecanoic acid

PFHxA peruorohexanoic acid

PFHpA peruoroheptanoic acid

PFNA peruorononanoic acid

PFOA peruorooctanoic acid

PFOS peruorooctane sulfonate

PFOSA peruorooctane sulfonamide

PFPrA peruoropropanoic acid

PFUnDA peruoroundecanoic acid

REACH Registration, Evaluation, and Authorization of Chemicals

SPE solid phase extraction

Table 1. ContinuedSPME solid phase microextraction

THMs trihalomethanes

TOF time-of-ight

UCMR-3 the third Unregulated Contaminants Monitoring Rule

UPLC ultraperformance liquid chromatography

WWTP wastewater treatment plant


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In addition to TOF-mass spectrometers, linear ion trap-Fouriertransform (FT)-Orbitrap mass spectrometers are also now beingused for similar high resolution-full scan applications. Examplesof the use of high resolution-MS in this Review include theidentification of pharmaceutical and pesticide transformationproducts and naphthenic acids.

Researchers are also increasingly using isotopically labeled

standards (deuterated or 13

C-labeled) to allow more accuratequantication in a variety of sample matrixes (especially for wastewater samples, where matrix eff ects and ion suppression can besubstantial). Atmospheric pressure photoionization (APPI) is alsoincreasingly being used with LC/MS because it provides improvedionization for more nonpolar compounds, such as nanomaterials(e.g., fullerenes), polybrominated diphenyl ethers (PBDEs), andnaphthenic acids discussed in this Review. Finally, nuclear magneticresonance (NMR) spectroscopy is increasing in use, as it canprovide detailed structural information to conrm tentativestructures proposed by LC/MS/MS. In this regard, it is increas-ingly used to conrm structures of pharmaceutical transformationproducts. Because NMR is not as sensitive as MS, preparative LCis 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 andconcentration, and a new SPE device called Bag extraction wasreported 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 phaseextraction. Measured concentrations of pharmaceuticals have beenshown to be comparable for bag-SPE vs Oasis HLB extraction.Benefits include the ease of handling, unattended water extrac-tion, and that no filtration is needed. In addition, new SPEsorbents are available, including Oasis MCX and hypercross-linked polymer resin (HXLPP) that are being used to capture a broader range of analytes within a single extraction. Solventless

extraction techniques, such as solid phase microextraction (SPME),single-drop microextraction (SDME), stir bar sorptive extraction,and hollow-fiber membrane microextraction, also continue to beused in many applications. Polar organic chemical integrativesamplers (POCIS) are also popular. These POCIS extractiondevices have membranes that allow polar contaminants to bepassively extracted from water and wastewater and can allow higher concentration factors and a more integrated sampling (vsspot sampling) over time.

The use of molecularly imprinted polymers (MIPs) for selectiveextraction of environmental contaminants has also continued togrow. MIPs are synthetic polymers made with specic recogni-tion sites that are complementary in shape, size, and functionalgroup to the analyte of interest. The recognition sites mimic the

binding sites of antibodies and enzymes. Because they are highly specic to the target analytesof interest, MIPs can be used to extractand isolate them from other matrix components in a complex mixture.MIPshave nowbeensynthesizedfor a number ofemergingcontaminants, including pharmaceuticals, pesticides, pesticidemetabolites, endocrine disrupting compounds (EDCs), and algaltoxins. Examples are cited in this Review for pharmaceuticals.

Chromatography Trends. The fastest growing chromatog-raphy trend continues to be the use of ultraperformance liquidchromatography (UPLC). UPLC is a recently developed LCtechnique that uses small diameter particles (typically 1.7 μm) inthe stationary phase and short columns, which allow higherpressures and, ultimately, narrower LC peaks (510 s wide). In

addition to providing narrow peaks and improved chromato-graphic separations, UPLC dramatically shortens analysis times,often to 10 min or less. Another significant chromatography trend isthe use of two-dimensional GC (GCGC). GCGC enablesenhanced separations of complex mixtures through greaterchromatographic peak capacity and allows homologous seriesof compounds to be easily identified. It also enables the detection

of trace contaminants that would not have been identifiedthrough traditional GC. TOF-MS is often used as the detectorfor GCGC because of its rapid acquisition capability. ExamplesoftheuseofGCGC in this Review include the measurement of benzotriazoles, benzothiazoles, and benzosulfonamides.

Use of Nanomaterials in Analytical Methods. In addition tonanomaterials being a class of emerging contaminant, they arealso being applied in creative ways to aid in the measurement of other emerging contaminants. For example, carbon nanohorns were used in electrochemical immunosensors to enable the rapiddetection of microcystin-LR (an algal toxin) in water. Goldnanoparticle labeling wasalsoused with ICP-MSin a newmethodto measure E. coliO157:H7 in water. This methodtook advantage of the signal amplification property of gold nanoparticles, mono-

clonal antibody recognition, and the high sensitivity of ICP-MS.Other Particularly Creative Methods. In addition to the

creative use of nanomaterials mentioned above, the last 2 yearshas seen other particularly creative methods worthy of mention.One such method involved a new microsensor array imprintedonto ordinary compact discs (CDs) to measure microcystins in water. Immunoreactions were detected with a DVD drive, whichdisplayed the readouts in minutes. This method was simple,sensitive, and rapid and could be used in a high-throughputcapacity for field use. Another creative method for UV filtersinvolved the use of direct analysis in real-time (DART)-MS todirectly analyze the surface of a polydimethylsiloxane-coated stir bar previously used to extract the UV filters from water. Whilestir-bar sorptive extraction is commonly used in many environ-

mental applications, the direct analysis of analytessorbed ontothesestir bars is a new, creative application that makes the method muchmore simple and rapid and still allows low ng/L detection limits.

Emerging Contaminants. This year, there is one new con-taminant class added as a “contaminant on the horizon” to watch:ionic liquids. Ionic liquids are organic salts with a low meltingpoint (


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and microorganisms. These continue to be intense areas of research. An ongoing trend in research for most of theseemerging contaminants continues to be investigating ways toremove them from environmental waters (e.g., through advancedoxidation, photolysis, microbial degradation, etc.). Because re-searchers often nd that the contaminants are not completely removed with these technologies, the identicationof intermediatesand degradation products becomes important, as well as theevaluation of resulting toxicity or biological activity for the transfor-mation products. In this regard, there are many more researchers

who are combining analytical chemistry with eff

ects research.

’GENERAL REVIEWS

This section includes general reviews relating to water analysisand emerging contaminants. Reviews that relate to specic areas(e.g., PFCs, pharmaceuticals, DBPs) can be found in thosespecic sections. Many reviews have been published over thelast two years that relate to environmental mass spectrometry,and a few focus specically on emerging contaminants. My other biennial review on Environmental Mass Spectrometry publishedin 2010 discussed advances in mass spectrometry research for thesame emerging contaminants discussed in this current Review,along with melaminecyanuric acid.2

Rubio and Perez-Bendito published an excellent review on therecent advances in environmental analysis, including discussionsof sampling and sample preparation techniques, separation anddetection techniques, calibration, and environmetrics (dataanalysis).3 Emerging contaminants were the focus of severalreviews over the past 2 years. For example, Alvarez and Jones-Lepp published a new review on sampling and analysis of emerging contaminants in surface water, groundwater, and soiland sediment pore water.4 Wells et al., discussed occurrence, fate,treatment, modeling, and toxicity/risk assessment of emergingpollutant studies published in 2009.5 Murray et al. reviewedoccurrence and toxicity data for three classes of trace pollutantsand emerging contaminants (industrial chemicals, pesticides,pharmaceuticals, and personal care products) and prioritized

them for potential regulation and treatment.6 Verlicchi et al. discussed hospital effluents as a source of

emerging pollutants and outlined diff erent treatment options forremoving them, including physicochemical treatment, biologicaltreatment, reverse osmosis, nanoltration, ozonation, advancedoxidation processes, disinfection, and use of constructed wetlands.7

Contaminants highlighted included pharmaceuticals, radionu-clides, solvents, anddisinfectants.Snow et al.reviewedthe detection,occurrence, and fate of emerging contaminants in agriculturalenvironments, which included discussions of pharmaceuticals,hormones, veterinary antibiotics, antibiotic resistant genes, andprions.8 Matamoros et al. reviewed the advances in determiningdegradation intermediates for personal care products in the

environment.9 Contaminants included stimulants, fragrances,sunscreens, antimicrobials, and insect repellents.

Several reviews focused on LC/MS trends for measuringemerging contaminants. For example, Petrovic et al. reviewedLC/MS methods used for pharmaceuticals, drugs of abuse, polarpesticides, PFCs, and nanomaterials.10 Krauss et al. reviewed theuse of LC with high resolution-MS for target screening andidentication of unknowns.11 The development of highly re-solved and accurate hybrid tandem mass spectrometers, such asquadrupole (Q)-TOF and linear ion trap/Orbitrap instruments,

as well as improved automated software, have enabled morereliable target analysis of highly polar compounds, as well asscreening for unknowns. Similarly, Pitarch et al. discuss ananalytical strategy based on the use of LC and GC with triplequadrupole and TOF mass spectrometers for measuring targetorganic contaminants in wastewater.12 This strategy was demon-strated for 60 compounds from diff erent chemical families, many of which are priority contaminants in the European Union WaterDirective, and was also eff ective for identifying nontarget com-pounds, dueto accuratemass andfull scan capability of TOF-MS.

UPLC/MS was the focus of a review by Guillarme et al., whodiscussed its use for analyzing environmental samples, biologicaluids, foods, and plant extracts.13 Applications to metabolomics were also highlighted. The application of capillary electrophoresis

(CE)/MS in the trace analysis of environmental and food con-taminants was the focus of another review by Robledo andSmyth.14

Low molecular weight amines, nitroaromatics, alkylphosphonicacids, azo dyes, antidepressants, and antibiotics were included.

While not reviews themselves, a few additional papers arenoteworthy for general applicability in analyzing emerging con-taminants in environmental samples. Two papers focused on theuse of computer-aided techniques for identifying organic con-taminants and transformation products. In the rst, Kern et al.combined LC/high resolution-MS with a target list of predictedmicrobial degradation products to screen for transformationproducts of 52 pesticides, biocides, and pharmaceuticals insurface waters from Switzerland.15 Using this procedure, 19transformation products were identied, including some that

are rarely reported. In the second, Rosal et al. detailed thedevelopment and interlaboratory verication of LC/MS librariesfor identifying environmental contaminants, including pesti-cides, illicit drugs, and pharmaceuticals.16 When comparinglibrary searching results, the libraries from two manufacturers’instruments exhibited diff erent ion abundance ratios in theirmass spectra, but the NIST search engine match probability was96% or greater for 64 out of 67 compounds evaluated.

’NEW REGULATIONS/REGULATORY METHODS

New Proposed Regulation for Perchlorate in U.S. DrinkingWater. The big news for this year is that the U.S. Environmental

Table 2. Useful Websites

Website comments

www.epa.gov U.S. EPA ’s Website

www.epa.gov/safewater/methods/analyticalmethods.html U.S. EPA approved methods for drinking water compliance monitoring

www.epa.gov/microbes/ordmeth.htm drinking water methods developed by U.S. EPA ’s National Exposure Research Laboratory

www.standardmethods.org/ link to Standard Methods Online

www.astm.org link to ASTM International methods

http://ec.europa.eu/environment/chemicals/reach/reach_intro.htm REACH Website


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Protection Agency (EPA) has decided to regulate perchlorateunder the Safe Drinking Water Act (http://water.epa.gov/drink/contaminants/unregulated/perchlorate.cfm). This deci-sion reverses a 2008 preliminary determination. Perchlorate ishighly water-soluble, is environmentally stable, accumulates inplants, and is of concern because it can disrupt the thyroid’sability to produce hormones needed for normal growth anddevelopment. As such, it has been a concern for the U.S. EPA,dating back to 1998 when it was placed on the original Con-taminant Candidate List for drinking water (CCL-1) and later onthe CCL-3. National data collected from the Unregulated Con-

taminants Monitoring Rule (UCMR) revealed that more than4% of the public drinking water systems in the U.S. haddetectable perchlorate, and the U.S. EPA decided there was ameaningful opportunity for health risk reduction for 5 to 16million people. The U.S. EPA intends to publish the proposedregulation for public review and comment within 24 months, with a proposed maximum contaminant limit (MCL) at thattime. A final regulation would be promulgated within 18 monthsafterward. Interestingly, two states had already regulated per-chlorate earlier: California (2007), with an MCL of 6 μg/L, andMassachusetts (2006), with an MCL of 2 μg/L.

Another new direction being considered by the U.S. EPA in itsnew drinking water strategy is to address contaminants as groupsrather than individually. Of course, this was done in the past

somewhat with regulating trihalomethanes (THMs) and haloa-cetic acids (HAAs) but has not generally been used for othercontaminants. This group approach is intended to speed upaction on new and emerging threats to drinking water, and therst group selected for consideration is 16 volatile organiccompounds (VOCs) that may cause cancer (http://water.epa.gov/lawsregs/rulesregs/sdwa/dwstrategy/upload/FactSheet_ DrinkingWaterStrategy_VOCs.pdf). Recent U.S. Rulesand Reg-ulations are summarized in Table 3.

The New Contaminant Candidate List-3 (CCL-3). In Sep-tember 2009, the U.S. EPA published the final CCL-3, which is adrinking water priority contaminant list for regulatory decisionmaking and information collection. The listed contaminants areknown to occur or anticipated to occur indrinking water systems

and will be considered for potential regulation. This final CCL-3contains 104 chemicals or chemical groups and 12 microbialcontaminants (Table 4) and is somewhat different than theoriginal proposed CCL-3 in 2008. This final CCL-3 nowincludesperfluorooctanoic acid (PFOA) and perfluorooctane sulfonate(PFOS), 3 pharmaceuticals (erythromycin, 17R-ethinylestradiol[EE2], and nitroglycerin [also used as an explosive]), 8 hor-mones (17R-estradiol, 17 β-estradiol, equilenin, equilin, estriol,estrone, mestranol, and norethindrone), and several DBPs(chlorate, formaldehyde, acetaldehyde, and 5 nitrosamines), as well as pesticides, pesticide degradation products, metals, indus-trial solvents/ingredients, and specific algal toxins (microcystin-LR, anatoxin-a, and cylindrospermopsin). The U.S. EPA is also

currently considering available occurrence, toxicity, bioaccu-mulation, and other data for the chemical contaminants on theCCL-3 to make a preliminary decision whether to regulate any of them.

For this CCL-3 eff ort, there was a major change in how it wasdeveloped. The U.S. EPA undertook a broader and morecomprehensive screening process of potential contaminants andused a new mechanism for allowing the general public, stake-holders, agencies, and industry to nominate chemicals, micro-organisms, or other materials for consideration. In the new process, a broadly dened “universe” of potential drinking water

contaminants was identied, assessed, and reduced to a prelimin-ary CCL (PCCL) using simple screening criteria that indicatepublic health risk and the likelihood of occurrence in drinking water. The PCCL contaminants were then assessedin more detailusing available occurrence and toxicity data, and a draft CCL-3 was proposed. Outside expert panels (including the Science Advisory Board) were then asked to comment on this draft list,and the list changed substantially following their recommenda-tion. Further details on theCCL-3 process can be found at http:// water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.cfm.

The Draft Third Unregulated Contaminants MonitoringRule (UCMR-3). The Draft UCMR-3 was proposed on February 17, 2011 (http://water.epa.gov/lawsregs/rulesregs/sdwa/ucmr/ucmr3/index.cfm) and is an updated version of the earlier

UCMR-1 (1999) and UCMR-2 (2007). Table 5 lists the con-taminants proposed to be monitored under the UCMR-3, along with their approved methods. Contaminants include hormones,PFCs, VOCs, metals, dioxane, chlorate, and viruses. The UCMR-3 requires drinking water utilities to monitor for 30 contaminants(28 chemicals and 2 viruses) during 20132015. Twenty-four of these contaminants are also on the CCL-3. The 6 chemicals noton the CCL-3 include testosterone, 4-androstene-3,17-dione,and 4 PFCs: perfluorobutanesulfonic acid (PFBS), perfluoro-heptanoic acid (PFHpA), perfluorohexane sulfonic acid (PFHxS),and perfluorononanoic acid (PFNA). The UCMR is used toprovide national occurrence data for priority unregulated con-taminants for future regulatory consideration. This Rule helps tosupport the Safe Drinking Water Act and Amendments, which

requires that, at least once every five years,the U.S. EPA identify alist of no more than 30 unregulated contaminants to be mon-itored. The Draft UCMR-3 is divided up into two groups of contaminants (Table 5). All public water systems serving morethan 10 000 people and a representative sample of 800 systemsserving 10 000 or fewer people are required to conduct Assess-ment Monitoring (List 1) during a continuous 12-month periodduring January 2013December 2015. In addition, a targetedgroup of 800 systems serving 1000 or fewer people will conductprescreen testing for two “List 3” viruses during a 12-monthperiod from January 2013December 2015.

New Regulatory Methods for Drinking Water. Four new drinking water methods were developed by the U.S. EPA

Table 3. Recent U.S. Rules/Regulations

rule/regulation Website

Stage 2 D/DBP Rule http://water.epa.gov/lawsregs/rulesregs/sdwa/stage2/regulations.cfm

Contaminant C andidate Lis t (CC L)-3 http://water.epa .gov/scitech/drinkingwater/dws/ccl/ccl3.cfm

Draft Third Unregulated Contaminants Monitoring

Rule (UCMR-3) http://water.epa.gov/lawsregs/rulesregs/sdwa/ucmr/ucmr3/index.cfm

UC MR-2 national occurrence data http://water.epa .gov/lawsregs/rulesregs/sdwa/ucm r/data .c fm#ucmr2010


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Table 4. Final Contaminant Candidate List-3 (CCL-3)

Chemical Contaminants

1,1,1,2-Tetrachloroethane

1,1-Dichloroethane

1,2,3-Trichloropropane

1,3-Butadiene

1,3-Dinitrobenzene

1,4-Dioxane

17R-Estradiol

1-Butanol

2-Methoxyethanol

2-Propen-1-ol

3-Hydroxycarbofuran

4,40-Methylenedianiline

Acephate

Acetaldehyde

Acetamide

Acetochlor

Acetochlor ethanesulfonic ac id (ESA)

Acetochlor oxanilic acid (OA)

Acrolein

Alachlor ethanesulfonic acid (ESA)

Alachlor oxanilic ac id (OA)

R-Hexachlorocyclohexane

Aniline

Bensulide

Benzyl chloride

Butylated hydroxyanisole

Captan

Chlorate

Chloromethane (Methyl chloride)

ClethodimCobalt

Cumene hydroperoxide

Cyanotoxins (Anatoxin-a, Microcystin-LR, and Cylindrospermopsin)

Dicrotophos

Dimethipin

Dimethoate

Disulfoton

Diuron

Equilenin

Equilin

Erythromycin

Estradiol (17 β-estradiol)

EstriolEstrone

Ethinyl estradiol (17R-ethinyl estradiol)

Ethoprop

Ethylene glycol

Ethylene oxide

Ethylene thiourea

Fenamiphos

Formaldehyde

Germanium

Halon 1011 (bromochloromethane)

HCFC-22

Table 4. ContinuedHexane

Hydrazine

Mestranol

Methamidophos

Methanol

Methyl bromide (Bromomethane)

Methyl tert-butyl ether

Metolachlor

Metolachlor ethanesulfonic acid (ESA)

Metolachlor oxanilic acid (OA)

Molinate

Molybdenum

Nitrobenzene

Nitroglycerin

N -Methyl-2-pyrrolidone

N -Nitrosodiethylamine (NDEA)

N -Nitrosodimethylamine (NDMA)

N -Nitroso-di-n-propylamine (NDPA)

N -Nitrosodiphenylamine (NDPhA) N -Nitrosopyrrolidine (NPYR)

Norethindrone (19-Norethisterone)

n-Propylbenzene

o-Toluidine

Oxirane, methyl-

Oxydemeton-methyl

Oxy uorfen

Perchlorate

Peruorooctane sulfonic acid (PFOS)

Peruorooctanoic acid (PFOA)

Permethrin

Profenofos

QuinolineRDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine)

sec-Butylbenzene

Strontium

Tebuconazole

Tebufenozide

Tellurium

Terbufos

Terbufos sulfone

Thiodicarb

Thiophanate-methyl

Toluene diisocyanate

Tribufos

Triethylamine

Triphenyltin hydroxide (TPTH)

Urethane

Vanadium

Vinclozolin

Ziram

Microbial Contaminants

Adenovirus

Caliciviruses

Campylobacter jejuni

Enterovirus


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(Table 6): Method 539 (hormones), 538 (pesticides, quinoline,and other organic contaminants), 524.3 (purgeable organiccompounds), 1615 (enteroviruses and noroviruses). These aremostly directed toward the measurement of CCL/UCMR chemicals in drinking water. The U.S. EPA ’s Office of Wateralso has a nice Website that lists all EPA approved methods fordrinking water compliance, which include methods developedfor inorganics (including metals), radionuclides, and organiccontaminants (http://water.epa.gov/scitech/drinkingwater/lab-cert/analyticalmethods.cfm). Note that this Website address is

different from past years. This Website provides a link not only toEPA Methods but also to methods developed by ASTM Inter-national, StandardMethods, the U.S. Geological Survey (USGS),the U.S. Department of Homeland Security, Waters Corp., andother organizations, which areapproved to usefor drinking watercompliance in the United States.

EPA Method 539: Hormones. In 2010, a new EPA method was created for measuring 7 hormones in drinking water: EPA Method 539, Determination of Hormones in Drinking Water by Solid phase Extraction (SPE) and Liquid Chromatography Electro-spray IonizationTandem Mass Spectrometry (LC/ESI-MS/MS)(http://water.epa.gov/scitech/drinkingwater/labcert/upload/met539.pdf). The hormones include 16R-hydroxyestradiol (estriol),17 β-estradiol, 17R-ethinylestradiol, testosterone, estrone,4-androstene-3,17-dione, and equilin. Most of these hormonesare included on the U.S. EPA ’s new CCL-3. Detection limitsrange from 0.04 to 2.9 ng/L.

EPA Method 538: Pesticides, Quinoline, and Other OrganicContaminants. In 2009, a new EPA method was created formeasuring pesticides, quinoline, and other organic contaminantsin drinking water: EPA Method 538, Determination of SelectedOrganic Contaminants in Drinking Water by Direct AqueousInjection-Liquid Chromatography/Tandem Mass Spectrometry (DAI-LC/MS/MS) (www.epa.gov/microbes/Method%20538_ Final.pdf). Analytes include acephate, aldicarb, aldicarb sulfoxide,dicrotophos, diisopropyl methylphosphonate (DIMP), fenamiphossulfone, methamidophos, oxidemeton-methyl, quinoline, and thio-

fanox. Minimum reporting levels ranged from 0.011 to 1.5 μg/L.EPA Method 524.3: Purgeable Organic Compounds.In 2009,

a new EPA method was created for measuring purgeable organiccompounds in drinking water: Measurement of Purgeable OrganicCompounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry (www.epa.gov/ogwdw000/methods/pdfs/methods/met524-3.pdf). A total of 86 analytes can be measured with this purge-and-trap GC/MS method, including a few new analytes that were not part of previous versions of this method: 1,3- butadiene, chlorodifluoromethane, diisopropyl ether (DIPE),methyl acetate, tert -amyl ethyl ether (TAEE), tert -amyl methylether (TAME), tert -butyl alcohol (TBA), and tert -butyl ethyl ether(ETBE). Detection limits range from 7.7 to 140 ng/L.

EPA Method 1615: Enteroviruses and Noroviruses. InDecember 2010, a new EPA method was created for measuringenteroviruses and noroviruses in water (http://www.regulations.

Table 4. Continued Escherichia coli (0157)

Helicobacter pylori

Hepatitis A virus

Legionella pneumophila

Mycobacterium avium

Naegleria fowleri

Salmonella enterica

Shigella sonnei

Table 5. Draft Unregulated Contaminants Monitoring Rule(UCMR)-3 Contaminants and Approved Methods

List 1. Assessment MonitoringContaminant Method

Hormones

17 β-Estradiol EPA Method 539

17R-Ethinylestradiol

(ethinyl estradiol)

EPA Method 539

16R-Hydroxyestradiol (estriol) EPA Method 539

Equilin EPA Method 539

Estrone EPA Method 539

Testosterone EPA Method 539

4-Androstene-3,17-dione EPA Method 539

Volatile Organic Compounds

1,2,3-Trichloropropane EPA Method 524.3

1,3-Butadiene EPA Method 524.3

Chloromethane (methyl chloride) EPA Method 524.3

1,1-Dichloroethane EPA Method 524.3

n-Propylbenzene EPA Method 524.3

Bromomethane (methyl bromide) EPA Method 524.3

sec-Butylbenzene EPA Method 524.3

Chlorodiuoromethane (HCFC-22) EPA Method 524.3

Bromochloromethane (halon 1011) EPA Method 524.3

Synthetic Organic Compounds

1,4-Dioxane EPA Method 522

Metals

Vanadium EPA 200.8 Rev 5.4, ASTM D5673

Molybdenum EPA 200.8 Rev 5.4, ASTM D5673

Cobalt EPA 200.8 Rev 5.4, ASTM D5673

Strontium EPA 200.8 Rev 5.4, ASTM D5673

Oxyhalide Anion

Chlorate EPA Method 300.1, ASTM

D658108, Standard Methods

4110D (1997)

Peruorinated Compounds

Peruorooctane sulfonate (PFOS) EPA Method 537.1

Peruorooctanoic acid (PFOA) EPA Method 537.1

Peruorononanoic acid (PFNA) EPA Method 537.1

Peruorohexane sulfonic

acid (PFHxS)

EPA Method 537.1

Peruoroheptanoic

acid (PFHpA)

EPA Method 537.1

Peruorobutane sulfonic

acid (PFBS)

EPA Method 537.1

Prescreening Testing (List 3)

Contaminant Method

Enteroviruses EPA Method 1615

Noroviruses EPA Method 1615


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gov/#!documentDetail;D=EPA-HQ-OW-2009-0090-0029).This method uses filtration, extraction of RNA, and real-timequantitative polymerase chain reaction (PCR) for detection.Detection limits are reported in terms of most probablenumber (MPN) of infectious units per liter; detection limitsare 0.01 MPN/L (surface water) and 0.002 MPN/L (groundwater).

’SUCRALOSE AND OTHER ARTIFICIAL SWEETENERS

Sucralose (also known as Splenda or SucraPlus) is a relatively new articial sweetener that is now widely used in North American and Europe. It may seem like an odd compound to

include as an emerging contaminant, but it is now being found inenvironmental waters and is extremely persistent (half-life up toseveral years).2 It is made by chlorinating sucrose, where threehydroxyl groups are replaced by chlorine atoms. Sucralose is heatstable, which is why it has replaced other articial sweeteners(such as aspartame) for baking and is now widely used in softdrinks because of its long shelf life. So far, at least 9 researchgroups have investigated its occurrence and fate in the environ-ment: the Norwegian Institute for Air Research,2 the SwedishEnvironmental Research Institute,2 and the European Commis-sion’s Joint Research Centre17 and most recently from research-ers at the University of North Carolina-Wilmington,18 the WaterTechnology Center in Karlsruhe, Germany,19,20 the Swiss Fed-eral Research Station in W €adenswil, Switzerland,21 the University

of Colorado,22

and Link €oping University (Sweden) together with the Swiss Federal Institute of Aquatic Science and Technol-ogy (EAWAG).23 In the groundbreaking multicountry study inEurope,17 Loos et al. used a SPE-LC/negative ion-electrospray ionization (ESI)-MS/MS method with isotope dilution to mea-sure sucralose at a detectionlimit of ∼10 ng/L. One hundred andtwenty samples were collected from rivers in 27 Europeancountries, and sucralose was found up to 1 μg/L, predominantly in samples from the United Kingdom, Belgium, The Nether-lands, France, Switzerland, Spain, Italy, Norway, and Sweden, with only minor levels (94%. Acesulfame was more persistent during soilaquifer treatment than in conventional wastewater treatment,such that acesulfame was still present in groundwater after aresidence time of 1.5 year. In surface waters, acesulfame was thepredominant articial sweetener found, with concentrationsexceeding 2 μg/L; saccharin and cyclamate were found at levels between 50 and 150 ng/L, and sucralose was found at 60 to80 ng/L, with one sample exceeding 100 ng/L.

Following this wastewater study, Scheurer et al. also investi-gated the eff ectiveness of drinking water treatment in removingfour articial sweeteners: sucralose, acesulfame, saccharin, andcyclamate.20 Six full-scale drinking water treatment plants were

investigated, which used bank

ltration, arti

cial recharge,

oc-culation, ozonation, granular activated carbon (GAC) ltration,and disinfection with chlorine and chlorine dioxide. Acesulfameand sucralose proved to be the most recalcitrant. Acesulfame wasthe only articial sweetener detected in nished drinking water,up to several hundred ng/L. Acesulfame and sucralose were not biodegraded during river bank ltration, and sucralose waspersistent against ozone, with transformation


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most surface waters (up to 2.8 μg/L), in 65% of the groundwatersamples investigated (up to 4.7 μg/L), and even in several tap water samples (up to 2.6 μg/L) in Switzerland. Because of itrecalcitrance to transformation, acesulfame was viewed as anideal marker for the detection of domestic wastewater inenvironmental waters, particularly groundwater. Using acesul-fame as a chemical marker, the percent contribution of domestic

wastewater to environmental waters could be determined. Forexample, acesulfame levels were used to estimate a ∼1020%contribution from domestic wastewater to groundwater in thelower Glatt valley in Switzerland. This method is sensitiveenough to detect as low as a 0.05% contribution.

Ferrer and Thurman developed a SPE-LC/TOF-MS methodto measure sucralose, aspartame, and saccharin in wastewater,surface water, groundwater, and soft drinks.22 The presence of the articial sweeteners could be conrmed by accurate massmeasurements. Analysis of several wastewater, surface water, andgroundwater samples revealed relatively high levels of sucralose,up to 2.4 μg/L. Sucralose was frequently detected, whereassaccharin was only detected in one wastewater sample, andaspartame was not detected in any samples. It is likely that

aspartame and saccharin are easily biodegraded, due to reactivechemical moieties in these molecules. Finally, Neset et al.combined substance-ow modeling with water and wastewatersampling to establish the current extent of sucralose emissionsfrom consumption.23 Sucralose was measured in wastewatertreatment plant inuents and effluents in Sweden and alsoupstream and downstream of the receiving stream and in anearby lake. Samples were measured using a SPE-LC/Orbitrap-MS/MS method. This study revealed that several small sourcescontributed to the loading coming from households, small businesses, and industry, which was in contrast to a consumptionpattern seen two years earlier.

’ANTIMONY

Antimony, which can have both acute and chronic toxicity eff ects, is regulated in drinking water in the United States,Canada, Europe, and Japan at action levels ranging from 2 to 6 μg/L. Antimony contamination can result from copper or leadsmelting or from petroleum reneries, but new studies haveshown that it can also leach from polyethylene terephthalate(PET) plastic water bottles.2 Antimony trioxide is used as acatalyst in the manufacture of PET plastics, which can contain>100 mg/kg of antimony. Keresztes et al. used inductively coupled plasma ICP-MS to measure antimony leaching fromPET bottles into carbonated (sparkling) and noncarbonated(still) mineral waters purchased in Europe.24 Storage conditions(time, temperature, exposure to light) were also investigated. In

general, antimony levels were higher in the carbonated waters,and levels exceeded 2 μg/L under extreme light and temperaturestorage conditions (6070 C, 23 W daylight lamp for 116 h). Antimony leaching varied over an order of magnitude among the waters investigated.

Reimann used ICP-MS to investigate the type of bottle on theleaching of antimony (and other metals/elements) into bottled water.25 Glass bottles, hard PET bottles, and soft PET bottles of diff erent colors were investigated by purchasing bottled waters insupermarkets across Europe, rinsing the bottles and relling withhigh purity (deionized) water at pH 6.5 and also at pH 3.5 toinvestigate the eff ect of pH. Antimony was found to have a 21higher concentration when sold in PET bottles, but glass could

also leach antimony in acidied waters, up to 0.45 μg/L after 150days in a dark green glass bottle. For plastic bottles, the soft PET bottles and dark blue hard PET bottles leached the mostantimony at near-neutral pH (6.5). Finally, Cheng et al. assessedantimony andothermetal leaching into water from plastic bottlesthat had been previously recycled.26 They investigated factorsthat could aff ect leaching, including cooling with frozen water,

heating with boiling water, microwave, low pH, outdoor sunlightirradiation, and in-car storage. Heating and microwaving led tothe highest antimony leaching relative to controls, whereas low pH, outdoor sunlight irradiation, and in-car storage had nosignicant eff ect. Results also revealed partial antimony leachingfrom PET bottles comes from the plastic surface during themanufacturing process, while major antimony leaching comesfrom conditional changes.

’NANOMATERIALS

There remains an ongoing research boom in the area of nanomaterials, with many companies and universities expandingtheir eff orts. New university departments have been developed

around the study of nanomaterials, and government investmentin nanotechnology has dramatically increased in the last 10 years.In my searching on Web of Science this year, nearly 5000citations appeared in the literature for just the last 2 year periodthat this Review covers. This included 565 review articles onnanomaterials. There is even a monthly journal called ACS Nano(created in 2008). Most nanomaterial research is centered ondeveloping new uses for nanomaterials and new products withunique properties, but on the other side, there is also signicantconcern regarding nanomaterials as environmental contami-nants. As such, nanomaterials are the focus of a large initiativeat the U.S. EPA, under which research on nanomaterial fate,transport, and health eff ects is being conducted. Nanomaterialsare 1 to 100 nm in size and can have unique properties, including

high strength, thermal stability, low permeability, and highconductivity. In the near future, nanomaterials are projected to be used in areas such as chemotherapy, drug delivery, andlabeling of food pathogens (“nanobarcodes”). The chemicalstructures of nanomaterials are highly varied, including fuller-enes, nanotubes, quantum dots, metal oxanes, TiO2 nanoparti-cles, nanosilver, and zerovalent iron nanoparticles.

Most environmental concerns center on the potential humanand ecological eff ects, and most methods use techniques otherthan mass spectrometry, such as transmission electron micro-scopy (TEM), scanning electron microscopy (SEM), atomicforce microscopy (AFM), quartz crystal microbalance, energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spec-troscopy, static light scattering (SLS), particle electrophoresis,

LC/UV, Raman spectroscopy, and NMR spectroscopy. In addi-tion, most studies are carried out in “clean” systems and not inreal environmental systems.

As mentioned earlier, there were numerous reviews publishedfor nanomaterials, even in the environmental arena. As a result,only a very few reviews could be cited here, such that I could alsohighlight new studies. In 2010, a special series of 8 nano papers(4 reviews and 4 technical papers) was published in Journal of Environmental Quality. Top experts in the eld led off this specialissue with a review of the environmental occurrence, behavior, fate,and ecological eff ects of nanoparticles.27 Within this review articleare discussions of risks and release of engineered nanomaterials,key research areas and needs, and sustainable development of


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engineered nanomaterials. Important questions raised include:How much will be released? In which environmental compart-ments will they reside? What are the environmentally relevantforms of the material? How do environmental conditions deter-mine the engineered nanomaterial form? Lin et al. publishedanother review in this series on the fate and transport of engineered nanomaterials in the environment, which included

aggregation and suspension behavior, and how factors such asnatural colloids, natural organic matter, pH, and ionic strengthcan inuence this behavior.28 Future research directions andoutlook were also presented. The authors also point out how few studies have investigated nanomaterials in the natural aquaticenvironment, and how such studies are needed. Hotze et al.reviewed nanomaterial aggregation and outlined challenges tounderstanding transport and reactivity in the environment.29

Techniques for assessing the colloidal properties of engineerednanoparticles were highlighted by Chen et al. in another review,and they also discussed recent ndings for fullerene C60 andmultiwalled carbon nanotubes.30 Techniques discussed includedtransmission electron microscopy (TEM), scanning electronmicroscopy (SEM), and atomic force microscopy (AFM)

(for particle size and imaging); energy dispersive X-ray spectro-scopy (EDS) (for measuring elemental bulk composition); X-ray photoelectron spectroscopy (for characterizing surface composi-tion and charge), particle electrophoresis (for determining aparticle’s migration rate and electrokinetic properties); and staticlight scattering (SLS) (for studying aggregate structures), amongother techniques.

Isaacson et al. published a thorough review on the quantitativeanalysis of fullerene nanomaterials, which included a report onthe state-of-the-art analytical methods for quantifying them,analytical challenges to overcome, and how improvements inanalytical methodologies will play an essential role in advancingour understanding of fullerene nanomaterial occurrence, trans-port, and eff ects.31 In particular, analytical methods need to

provide chemically explicit information, suchas molecularweightand the number and identity of surface functional groups (whichcan be achieved with mass spectrometry), and increased avail-ability is needed for well characterized authentic standards,reference materials, and isotopically labeled internal standards.Ecotoxicity and analysis of nanomaterials in the aquatic environ-ment was the focus of another review by Farreetal.32 Ecotoxicity data crossed several diff erent species of aquatic organisms,including zebra sh, Daphnia magna , Vibrio scheri , and rainbow trout. Analysis techniques summarized included dynamic lightscattering (DLS), TEM, SEM, atomic absorption spectroscopy,anodic stripping voltammetry, UV vis spectroscopy, and LC/MS techniques. The analysis,behavior, and ecotoxicity of carbon- based nanomaterials were the focus of another review by Perez

et al., with special emphasis on surface properties and interac-tions with natural organic matter.33

Previous studies have investigated the release of nanosilverfrom socks and other clothing treated with nanosilver; Bennet al. followed up this early work with an investigation of nanosilver release from many consumer products, including ashirt, a medical mask and cloth, toothpaste, shampoo, deter-gent, a towel, a toy teddy bear, and two humidiers.34 Silverconcentrations ranged from 1.4 to 270 000 μg Ag per g of product. Products were washed with 500 mL of tap water toassess potential release of silver. SEM conrmed thepresence of silver nanoparticles in most products, as well as in the wash water samples.

In one of the few published MS methods for nanomaterials,Isaacson and Bouchard used asymmetric ow eld-ow fractio-nation (AF4), DLS, and LC/APPI-MS to determine aggregatesize distributions of C60 fullerenes in aqueous systems.

35 This isthe rst method to use AF4 for fractionating a colloidal suspen-sion of aqueous C60 , which provided improved particle sizecharacterization. The authors also made a strong case for the use

of MS over other detection techniques, due to the unambiguousdetermination of the mass of C60 in each size fraction. With thismethod, aqueous C60 aggregates were shown to contain sizedistributions between 80 and 150 nM (for 58% of the mass),


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chemically, in that they are both hydrophobic (repel water) andlipophobic (repel lipids/grease), and they contain one of thestrongest chemical bonds (CF) known. Because of theseproperties, they are highly stable in the environment (and in biological samples) and have unique proles of distributionin the body. During 20002002, an estimated 5 million kg/yr wasproduced worldwide, with 40% of this in North America. Two of

these PFCs, per

uorooctane sulfonate (PFOS) and per

uorooc-tanoic acid (PFOA), have received the most attention. PFOS wasonce used to make the popular Scotchgard fabric and carpetprotector, and since 2002, it is no longer manufactured in theU.S., due to concerns about widespread global distribution in the blood of the general population and in wildlife, including remotelocations in the Arctic and North Pacic Oceans. Like PFOS,PFOA is ubiquitous at low levels in humans, even in those livingfar from any obvious sources.1

In January 2005, the U.S. EPA issued a draft risk assessment of the potential human health eff ects associated with exposure toPFOA (www.epa.gov/oppt/pfoa/pubs/pfoarisk.html), and in January 2006, the U.S. EPA invited PFC manufacturers toparticipate in a global stewardship program on PFOA and related

chemicals (www.epa.gov/oppt/pfoa/pubs/stewardship). Parti-cipating companies agreed to reduce PFOA from emissions andproduct content by 95% by 2010 and to work toward eliminatingPFOA in emissions andproducts by 2015. TheU.S. EPAhas now listed PFOA and PFOS on the new CCL-3 (http://water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.cfm). In Europe, theEuropean Food Safety Authority has established tolerable daily intakes for PFOA and PFOS (www.efsa.europa.eu/en/efsajour-nal/pub/653.htm), and there are new restrictions on the use of PFOS as part of the European Union’s REACH program(http://ec.europa.eu/enterprise/sectors/chemicals/les/reach/restr_inventory_list_pfos_en.pdf).

Potential health concerns include developmental toxicity,cancer, and bioaccumulation. Research questions include under-

standing the sources of PFOA and other PFCs, their environ-mental fate and transport, pathways for human exposure anduptake, and potential health eff ects. It is hypothesized that the widespread occurrence of PFOA and other uoro-acids is partly due to the atmospheric or oceanic transport of the more volatileuorinated telomer alcohols (FTOHs) and subsequent transfor-mation into PFOA and other uoro-acids via metabolism and biodegradation. Recent studies support this hypothesis. There isalso evidence that PFOA itself is volatile.

PFOS, PFOA, and other PFCs are included in the NationalHealth and Nutrition Examination Survey (NHANES) beingconducted by the Centers for Disease Control and Prevention(CDC) to provide a better assessment of the distribution of thesechemicals in adultsandchildrenin theUnited States(www.cdc.gov/

nchs/nhanes.htm). The National ToxicologyProgram is alsostudy-ingPFOA andseveral otherperuorocarboxylic acids (PFCAs) andperuorosulfonates (PFSAs) to better understand their toxicity andpersistence in human blood (http://ntp.niehs.nih.gov).

While PFOS and PFOA were the rst uorinated surfactantsto receive considerable attention, research has rapidly expanded beyond these two contaminants to other long-chain peruori-nated acids and various precursors. In addition, there is increasedfocus on shorter chain forms, e.g., peruorobutanoic acid(PFBA) and PFBS, as manufacturers are beginning to shift tolower molecular weight PFCs. Rayne and Forest published anextensive critical review of physicochemical properties, levels,and patterns in waters and wastewaters and treatment methods

for peruoroalkylsulfonic and carboxylic acids.41 Ahrens pub-lished a critical review on the occurrence and fate of PFCs in theaquatic environment, which also identied knowledge gapsand presented recommendations for future work.42 Theserecommendations included research on key loss processes anddeposition, the relationship between sources and aqueous environmental concentrations, solid/water partitioning or air

water exchange, transport mechanisms, and the extent to whichPFCs undergo long-range global transport, seasonality, and long-term changes, as well as the need to establish a global monitoringprogram for PFCs in river water and seawater.

Martin et al. published a thought-provoking review and perspec-tive on PFOS precursors (which the authors called “PreFOS”) asdeterminants of human and environmental PFOS exposure.43

This PreFOS material and the fate processes that transform itinto PFOS and contribute to exposure are not well characterized.The authors point out that the yield of PFOS from abioticdegradation of commercially important PreFOS material is negli-gible, but in vivo biotransformation is important. Ocean waterscan vary in the proportion of PFOS vs PreFOS, as well as whalesand humans who are exposed in diff erent regions. The authors

present two new source tracking principles, which are based onPFOS isomer patterns and PFOS enantiomers in human serum.New methods to measure PFCs in water include an interesting

new use of nanoparticles to extract PFCs from water. In thismethod, Zhang et al. synthesized chitosan-coated octadecyl-functionalized magnetite nanoparticles and used them as anadsorbent to extract PFCs from water.44 LC/MS/MS was usedfor detection. Concentration factors of 1000 could be achieved with 500 mL of water, and detection limits of 0.24, 0.093, 0.24,0.14, 0.075, 0.24, and 0.17 ng/L were obtained for PFOA, PFOS,PFNA, peruorodecanoic acid (PFDA), peruoroundecanoicacid (PFUnDa), peruorododecanoic acid (PFDoDa), and per-uorotetradecanoic acid (PFTA), respectively, in wastewater. Willie et al. developed a new method for 14 PFCs in surface

water, seawater, and wastewater using LC/TOF-MS.45

The useof very narrow mass tolerance windows (


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Canada contained similar levels to those found in China. Levels were low in India, but only a single tap water sample wascollected from the 3 cities in India sampled. In addition to PFOA and PFOS, shorter-chain PFCs (including PFBA, PFBS, PFHxA,and PFHxS) were also prevalent in drinking water. Quinete et al.measured PFCs in tap water, surface water, and biota in Brazil.48

This study represents one of the rst to measure PFCs in water

from South America. PFOS, PFOA, and PFHxS were detected inall drinking water samples at levels up to 6.7, 2.8, and 1.0 ng/L,respectively. Proles were somewhat diff erent from those inother countries.

Quinones and Snyder measured PFCs in drinking water andassociated surface, ground, and wastewater in the U.S.49 Sevendrinking water plants located in diff erent regions of the U.S. weresampled 4 times a year during 2008, including some that arehighly impacted by treated wastewater. In treated wastewater, theaverage total PFC concentrations ranged from 70 to 260 ng/L, with predominant contributions from PFHxA, PFOA, andPFOS. For drinking water plants, the plant regarded as non-impacted (by wastewater) had no detectable PFCs, whereasthose impacted by treated wastewater had frequent detection for

PFCs. PFCs containing 8 carbons or less were the mostfrequently detected in nished drinking water, and PFOA hadthe highest overall concentration at any site.

Loos et al. carried out a large multicountry European study of polar organic persistent pollutants in groundwater, which in-cluded PFCs, as well as pharmaceuticals, hormones, pesticides,pesticide transformation products, benzotriazoles, alkylphenolcompounds, caff eine, diethyltoluamide (DEET), and triclosan.50

PFOS, PFOA, PFHpA, and PFHxS were among the chemicalsdetected the most often at the highest concentrations, withmaximum levels of 135, 39, 21, and 19 ng/L, respectively.Compared to river water, groundwater was less contaminated,in general. Interestingly, compounds found at the highestfrequency were not always those found at the highest concentra-

tions; for example, PFOA had the highest frequency of detection(66%), but its maximum concentration was lower than PFOSand some other chemicals measured in this study. In anotherpaper, Pistocchi and Loos provided a map of Europeanemissions and concentrations of PFOS and PFOA.51 A spatially distributed data set of PFOS and PFOA concentrations wereused together with average river ow to estimate their overallaqueous emissions in Europe. The total discharge across the whole European river network to coastal areas was estimatedto be 20 and 30 tons/year for PFOS and PFOA, respectively (for 2007).

The ux of PFCs through wet deposition (rain) was the focusof a study by Kwok et al., who collected samples from Japan, theU.S., France, China, and India.52 This is one of the few studies to-

date to measure occurrence of PFCs in precipitation, and ithelped in understanding the scavenging of PFCs in rainwater.Higher total PFCs were found in the rst rain even when a largerrainfall occurred in a second event. PFPrA was detected in all of the rain samples, and average total PFC concentrations rangedfrom 1.40 to 18.1 ng/L for the 7 cities studied. The greatest levels were found in Tsukuba, Japan, and the lowest levels were inPatna, India. PFPrA, PFOA, and PFNA were the dominant PFCsin Japanese and U.S. rainwater.

Eschauzier et al. published an interesting study of PFCs ininltrated Rhine River water and rainwater in coastal dunes fromThe Netherlands.53 PFBS was found at the highest concentrationof all PFCs, up to 37 ng/L in inltrated river water. These levels

were signicantly higher than those found in inltrated rainwater,and it is in stark contrast to the more typical higher levels of PFOA and PFOS generally reported in the environmental waters. Concentrations of PFOA, PFHxA, PFHpA, PFBS, PFOS,and PFHxS in inltrated river water showed an increasing trend with decreasing age of water. Nakayama et al. carried out a study of PFCs in the Upper Mississippi River Basin (U.S.), one of the

largest watersheds in the world.54

PFCs were found in 94% of the177 samples collected, with 80% of these


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than in river waters, wastewaters, and street runoff , indicatingthat it was likely produced by degradation of precursors. Soilcolumn tests also supported this. Wastewater and surface runoff contributed 5486% and 1646%, respectively, of PFCAs togroundwater. Stemmler and Lammel investigated pathways of PFOA to the Arctic, including oceanic currents and atmospherictransport.60 A spacially resolved global multicompartment model

suggested that oceanic transport was the dominant source of PFOA to the Arctic, delivering an estimated 14.8 t/a. Benskinet al. applied an isomer proling method to assess the contribu-tion of electrochemical and telomer manufacturing processes toPFCs measured in North America, Asia, and Europe.61 Electro-chemical uorination produces a mixture of branched and linearisomers, whereas telomerization typically produces more linearstructures. A sensitive LC/MS/MS method was then used toquantify these isomers to allow this source attribution. With theexception of 3 sites in Japan, >80% of the total PFOA was fromelectrochemical manufacturing.

In another study, Fr€omel and Knepper investigated biotrans-formation as a source of uorotelomer ethoxylates in theenvironment.62 These compounds, which are polyethoxylated

2-peruoroalkylethanols, have been largely disregarded in previous studies of PFCs, despite their high production and applica-tion amounts. Aerobic biotransformation tests showed that acommercial uorotelomer ethoxylate mixture rapidly trans-formed, with a half-life of approximately 1 day. LC/MS/MS was used to elucidate the structures of the transformation products, which revealed oxidation of the ethoxylate to the carboxylic acid,followed by sequential shortening of the ethoxylate units, leadingto uorotelomer carboxylates, including a small amount of PFOA and PFHxA. Plumlee et al. investigated the indirect photolysis(with hydroxyl radical) of PFCs, including N -ethyl peruorooc-tane sulfonamidoethanol ( N -EtFOSE), N -EtFOSAA, and per-uorooctane sulfonamide acetate (FOSAA).63 A proposed reactionpathway for the degradation of N-EtFOSE to other peruoroalk-

anesulfonamides and PFOA included oxidation and N -dealkyla-tion steps. PFOSA and PFOA were the nal degradationproducts. Indirect photolysis was suggested to be an importantpathway, due to the slow rates expected for biotransformationand weak sorption.

Finally, Qu et al. investigated the photoreductive deuorina-tion of PFOA in water, as a potential removal technology.64 Inthese experiments, UV photolysis led to the generation of hydrated electrons, which were able to efficiently deuorinatePFOA (98% release of uoride). Besides uoride, additionalintermediates were identied and quantied, including formicacid, acetic acid, 6 short-chain PFCAs (C1C6), triuoromethane,and hexauoroethane. With these data, two major deuorinationpathways were proposed (1) direct cleavage of CF bonds

attacked by hydrated electrons as the nucleophiles and (2)stepwise removal of CF2 by UV irradiation and hydrolysis.

’PHARMACEUTICALS AND HORMONES

Pharmaceuticals and hormones have become crucial emergingcontaminants, due to their presence in environmental waters(following incomplete removal in wastewater treatment or point-source contaminations), threat to drinking water, and concernabout possible estrogenic and other eff ects, both to wildlife andhumans. A major concern for pharmaceuticals also includes thedevelopment of bacterial resistance (creation of “Super Bugs”)from the release of antibiotics to the environment, and there are

also new concerns thatantibiotics willdecrease biodegradation of leaf and other plant materials, which serves as the primary foodsource for aquatic life in rivers and streams. It is estimated thatapproximately 3000 diff erent substances are used as pharmaceu-tical ingredients, including painkillers, antibiotics, antidiabetics, betablockers, contraceptives, lipid regulators, antidepressantsand impotence drugs. However, only a very small subset of these

compounds has been investigated in environmental studies sofar. Pharmaceuticals are introduced not only by humans, but alsothrough veterinary use for livestock, poultry, and sh farming. Various drugs are commonly given to farm animals to preventillness and disease and to increase the size of the animals. Onelingering question is whether the relative low environmentalconcentration levels of pharmaceuticals (generally ng/L range) would cause adverse eff ects in humans or wildlife. Pharmaceu-ticals and hormones are now included on the U.S. EPA ’s nalCCL-3 (http://water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.cfm). One typical pharmaceuticals (erythromycin) andone explosive (nitroglycerin) that is also be used as pharmaceu-tical and nine natural and synthetic hormones (17R-ethinyles-tradiol [EE2], 17R-estradiol, 17 β-estradiol [E2], equilenin,

equilin, estriol [E3], estrone, mestranol, and norethindrone)are included as priority drinking water contaminants, based onhealth eff ects and occurrence in environmental waters. For therevision of the list of priority substances within the EU waterframework directive (2000) describing the chemical status of European rivers, streams, and lakes) two pharmaceuticals (di-clofenac and ibuprofen) and two hormones (EE2 and E2) aresuggested. There are also increasing “source-to-tap” studiesconsidering the fate of pharmaceuticals from wastewaters toriver waters, to source waters, and to nished drinking water,such that the complete cycle of pharmaceutical fate is beingconsidered.

Innovative analytical instrumentation, such as hybrid massspectrometry enables the identication and quantication of

organic pollutants including pharmaceuticals and hormones downto the lower nanogram per liter and nanogram per kg range inenvironmental matrices and drinking water. While most organiccontaminants are entering wastewater without being metabolized,pharmaceuticals are frequently transformed in the body and acombination of non-altered pharmaceuticals and their metabolitesare excreted by humans.65 Microbial transformation products(TPs) of pharmaceuticals and hormones can be formed during biological wastewater treatment, from contact with sediment andsoil, as well as during bank ltration. Furthermore, TPs can beformed by UV irradiation in surface waters and during oxidativetreatment processes, such as ozonation and chlorine disinfection.

Still, LC/tandem-MS is the method of choice for the determina-tion of all classes of pharmaceuticals in aqueous matrices. ESI and

APCI are the most commonly used LC interfaces. Major innova-tions have been made in modern hybrid mass spectrometry systems(e.g., linear ion trap/FT-MS, Q-TOF-MS) coupled to liquidchromatography, providing accurate masses of the analytes andinformation for mass fragments, which can be used to identify thechemical structures. Radjenovic et al. published a review of theliterature using MS to elucidate the formation of pharmaceuticalTPs during oxidative wastewater and drinking water treatment.66 A few rapid biochemical techniques, such as biosensors and immu-noassays, have also been recently developed for selected pharma-ceuticals. Further innovations have been made in rapid on-lineextraction and bag extraction, as well as on-line derivatizationtechniques in combination with GC/MS(/MS) detection.


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Environmental Impacts of Pharmaceuticals. While many pharmaceuticals can have an acute or chronic effect on aquatic orother organisms, most of the lowest observed effect concentra-tions (LOECs) are substantially above the environmental con-centrations that have been observed (ng/L to low μg/L).However, there are a few notable exceptions, where chronictoxicity LOECs approachlevels observed in wastewater effluents.

For chronic toxicity, these include salicylic acid, diclofenac,propranolol, clofibric acid, carbamazepine, and fluoxetine. Forexample, for diclofenac, the LOEC for fish toxicity was in therange of wastewater concentrations, and the LOEC of propra-nolol and fluoxetine for zooplankton and benthic organisms wasnear the maximum measured in wastewater effluents. Theantibiotic ciprofloxacin has also been shown to have effects onplankton and algae growth at environmentally relevantconcentrations.1 Estrogenic effects on wildlife are quite possible with the contraceptive 17R-ethinylestradiol (EE2), as it caninduce estrogenic effects in fish at extremely low concentrations(low and sub-ng/L). Effects include alteration of sex ratios andsexual characteristics, and decreased egg fertilization in fish.1 Anarticle in Nature (Oaks et al., 2004) highlighted that residues of

veterinary used diclofenac probably caused renal failure of vultures and hence lead to a dramatic decline (> 95 %) of the vulture population in Pakistan.67 Experts estimate the vultureloss at 40 million, and it is being called the “ worst case of wildlifepoisoning ever” , far eclipsing the numbers of birds affected by DDT a few decades ago.

Biological Transformation Products. Even though TPs havegained increasing interest as water contaminants, only a few studies have investigated the formation and fate of biological TPsof pharmaceuticals in contact with biologically active matrixes,such as activated sludge or sediments. One reason is thechallenge of structural elucidation of TPs present at low con-centrations in natural matrixes. Sophisticated analytical techniquesare needed, such as hybrid high-resolution mass spectrometry

and NMR.68

Although the target compound is known, with a few exceptions of very simple reactions (e.g., hydrolysis of amidesand esters), quadrupole-MS and even high resolution-MS (e.g.,LC/Orbitrap-MS) are often not sufficient to obtain or confirmchemical structures of TPs. The TP structure suggestions basedon exact masses and mass fragments have to be confirmed by alternative analytical methods or chemical reactions specifically altering the new functional moieties formed. Possibilities of analytical methods include a wide variety of currently availableNMR techniques or, to a much less extent, IR spectroscopy.However, a drawback of both techniques is the elevated quantity and the high purity needed for isolated standards. In those cases, where no authentic standard is available and only MS spectra of TPs have been obtained, we might better define the suggestions

of the chemical TP structures as “tentative identifications” unlessfurther plausibility criteria are fulfilled, confirming the proposedchemical structures. A comprehensive overview of the literatureregarding the detection and identification of pharmaceutical TPsuntil 2008 is provided by Celiz et al.69

Several recent studies indicated that the majority of pharma-ceutical TPs formed under aerobic conditions have a slightly modied molecular structure featuring increased polarity, due tothe introduction of hydroxyl, carboxyl, or keto moieties.70,71 Onthe basis of the similarity of their molecular structure to theparent compound, a signicant number of TPs are expected topossess comparable biological activity as their chemicalprecursors.72 However, the enhanced polarity improves the

permeability of these compounds for several water treatmentprocesses such as adsorptive ltration (e.g., activated carbon),underground soil passage, or bank ltration. As consequence, thelikelihoodincreasesthatTPs are contaminating groundwater anddrinking water.73

Several enzyme-catalyzed reactions are quite commonly involved in the transformation of pharmaceuticals: mono- and

dihydroxylation, alcohol and aldehyde oxidation, ester and amidehydrolysis, N -dealkylation, N -deacetylation, and decarboxyla-tion. For the rst time, Radjenovic et al. have elucidated theamide hydrolysis of the betablocker atenolol to atenolol acid and thehydroxylation of the hypoglycemic agent glibenclamide in con-tact with activated sludge. LC/Qq-TOF-MS and LC/Qq-linearion trap-MS techniques were used for measurement.74 Helblinget al. reported for the rst time the amide hydrolysis of theantiepileptic levitiracetam by LC/Orbitrap-MS.75 Furthermore,they found in contact with activated sludge the demethylation of diazepam, which is already known from human metabolism, as well as the hydroxylation of diazepam. By the same authors, TPsof the antihypertensive valsertan were identied using LC/Orbitrap-MS. Transformation took place by amide hydrolysis,

transamination, and subsequent oxidation to a carboxylic acid.Trautwein et al. described the dealkylation of the antihyperten-sive verapamil76 using LC/ion trap-MS, and Kern et al. showed,in addition to verapamil, the dealkylation of the antidepressant venlaaxine by LC/Orbitrap-MS.77 Calza et al. reported theidentication of 11 TPs of the antibiotic spiramycin by LC/MS/MS in river water by hydroxylation, N -demethylation, andcleavage of sugar moieties.78 Using LC/Qq-TOF-MS, Kosjek et al. reported the identication of 2 TPs for diclofenac duringnitrication formed by (a) decarboxylation and (b) amideformation, as well as the formation of p-chlorophenol from theether cleavage of clo bric acid.79 The oxidation of the antihista-mine ranitidinat the amine andthe thiol moietyforming twoTPs was reported by Kern et al. using LC/Orbitrap-MS.80 Applying

LC/Qq-linear ion trap-MS and 1

H and 13

C NMR, Schulz et al.81

and Kormos et al.68,73 identied 46 TPs from four X-ray contrastmedia (iopromide, iomeprol, iopamidol, and iohexol) formed by N -dealkylation, N -deacetylation, oxidation, and decarboxylation.Twelve of these TPs have been reported in surface water,groundwater, and drinking water, up to several hundreds of ng/L.O-Desmethylnaproxen, the main metabolite of naproxen, wasidentied by enantioselective-GC/MS in surface water and wastewater treatment plant (WWTP) effluents at high ng/L levels.Prasse et al. reported the biotransformation of the two antiviraldrugs, acyclovir (ACV) and penciclovir (PCV), in contact withactivated sludge.82 TPs were identied using LC/Orbitrap-MSand 1 D (1H NMR, 13C NMR) and 2D (1H, 1H-COSY, 1H-13C-heteronuclear single quantum coherence [HSQC]) NMR spec-

troscopy. Structural elucidation of TPs revealed that transforma-tion took place at the side chain, leaving the guanine moiety unaltered. The oxidation of the primary hydroxyl group in ACV resulted in the formation of carboxy-acyclovir. For PCV, severalenzymatic reactions occurred, such as the oxidation of terminalhydroxyl groups and β-oxidation followed by acetate cleavage.Carboxy-ACV was detected in surface and drinking water, withconcentrations up to 3200 ng/L and 40 ng/L, respectively.Perez-Parada et al. reported the identication of TPs of theantibiotic amoxicillin in wastewater and surface water using LC/Q-TOF-MS.83 The cleavage of the beta lactam ring led todiastereomers of amoxilloic acid and amoxicillin diketopipera-zine. The latter has been detected in wastewater and river water.


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The biological transformation of the contraceptive EE2 wasinvestigated by several authors.84,85 Skotnicka-Pitak et al. eluci-dated the formation of a TP after hydrolysis and oxidation of theethinyl group, as well as a hydroxylated TP by LC/ion trap-MSand 1H NMR.84 The hydroxylated TP was also reported by Yiand Harper, and additionally, the formationof a sulfate conjugateusing thin layer chromatography (TLC) and 1H NMR.85 Tes-

tosterone was shown to be very stable to biological degradation, but it can be slowly transformed under solar irradiation. Severalphotoproducts, such as hydroxylated derivatives resulting fromphotohydration of the enone group, a spiro-compound, or(1,5,10)-cyclopropyl-17 β-hydroxyandrostane, were identied by TOF-MS, LC/MS, GC/MS, IR, and NMR.

The identication of nitrophenolic TPs of acetaminophen insamples from full-scale WWTPs indicated thatabiotic nitration isoccurring in biological wastewater treatment.86 Wick et al.reported that the opium alkaloid codeine was transformed withactivated sludge into at least 18 TPs, when applying a multistepapproach with LC/Orbitrap-MS and 1D and 2D NMR.87 Mostof the TPs identied had only slightly modied molecularstructures, featuring double bond shifts, introduction of hydroxyl

moieties, or amine demethylation. The transformation pathway of codeine with activated sludge was characterized by a combina-tion of biologically and chemically mediated reactions. Formorphine, 10 TPs similar to those observed for codeine weredetected, including the main TPs morphinone and 14-hydro- xymorphinone. In addition to the codeine-like TPs, an additionalnine TPs were tentatively identied for morphine, including themorphine dimer pseudomorphine and 2-nitro-derivatives. Sincenitrophenolic compounds are frequently of toxicological con-cern, the role of abiotic reactions for thetransformationof micro-pollutants deserves further attention. Finally, dihydrocodeine was transformed into hydrocodone and isodihydrocodeine.87

Elimination/Reaction During Oxidative Water Treatment.Several studies confirmed the efficiency of oxidation processes,

such as ozonation, advanced oxidation, or ferrate (Fe(VI)), for thetransformation of micropollutants. However, it cannot be ruledout that oxidation leads to persistent oxidation products which areof toxicological concern. This might be even more relevant forchlorination, since chlorinated products frequently possess a hightoxicological potential. It is, therefore, crucial to identify theoxidation products formed. This is only possible when advancedmass spectrometry is used,suchas LC/Q-TOF-MS, LC/Orbitrap-MS, or LC/Qq-linear ion trap-MS, and NMR techniques.

Hollender et al. showed that ozone transformed most inves-tigated pharmaceuticals and their metabolites (>70) whenapplied in full-scale post-treatment of a municipal WWTP.88

This was especially true for those pharmaceuticals that containelectron-rich moieties. Dodd et al. investigated the ozonation

TPs of beta-lactam antibiotics penicillin G and cephalexin.89 TheTPs were identied as (R)-sulfoxides, using 1H NMR, 13C NMR,and LC/Orbitrap-MS. While penicillin G-sulfoxide was recalci-trant toward ozone but readily transformed by OH radicals(HO•), the cephalexin sulfoxides were degraded by both ozoneand OH radicals. According to Dodd et al., ozonation leads tostructural modication sufficient to eliminate the antibacterialactivity for 13 antibiotics from 9 structural classes.90 Using LC/Qq-linear ion trap-MS, Benner et al. identied a large number of oxidation products after ozonating membrane concentratescontaining elevated concentrations of pharmaceuticals, such asthe beta-blockers propranolol and metoprolol.91,92 The betablockers were attacked by ozone at the secondary amino group,

yielding hydroxyl amine and aldehyde moieties, due to ring-opening on the aromatic rings.

A novel oxidation technology using ferrate [Fe (VI)] in waterand wastewater treatment were reported by Lee et al.93 andHu et al.94 Lee et al. showed that pharmaceuticals containingelectron-rich moieties are transformed by more than 85%.93

Although Fe (VI) treatment was slightly less eff ective thanozone,

it has the bene

t of the simultaneous removal of phosphate. Huet al. reported that Fe (VI) was able to transform theantiepilepticcarbamazepine.94 Similar to ozone, it attacks olenic moieties inthe central heterocyclic ring, leading to ring-opening and forma-tion of several TPs, which were identied by LC/ESI-MS/MS. Theoxidation by KMnO4 led to comparable TPs, without showing apH dependence. However, similar to ozonation, neither Fe(VI)nor KMnO4 mineralized the target pharmaceuticals.

The chlorination of water containing EE2 and bromide led tohalogenated TPs, such as 4-chloro-, 2,4-dichloro-, 4-bromo-, or2,4-dibromo-EE2.95 The authors concluded that bromine pro-duced from oxidation of Br is mainly responsible for thehalogenation of EE2. Mash reported that the synthetic androgentrenbolone is highly reactive toward hypochlorite.96 Chlorina-

tion leads to a large number of TPs containing up to two chlorineatoms and up to two additional oxygen atoms. Quintana et al.investigated the transformation of seven acidic pharmaceuticalsand two metabolites by LC/Q-TOF-MS.97 The authors ob-served chlorinated and brominated products of salicylic acid,naproxen, and diclofenac. The nonhalogenated diclofenac wasfurther transformed by decarboxylation and hydroxylation. It isinteresting to note that halogenated derivatives of salicylic acid were detected in wastewater and even in drinking water usingLC/MS/MS. The oxidation of seven uoroquinolones and threestructurally related amines with ClO2 revealed that the piper-azine ring is the primary reactive center, leading to dealkylation,hydroxylation, and an intramolecular ring closure at the piper-azine moiety.98 The formation of halogenated products was not

observed. Yuan et al. reported the degradation of four pharmaceuticals

(ibuprofen, phenazone, diphenhydramin, and phenytoin) by UV/H2O2 and UV.

99 Several photodegradation intermediates were identied by GC/MS. The suitability of UV/H2O2 treat-ment for the removal of pharmaceuticals was also mentioned by Rosario-Ortiz et al.100 They clearly demonstrated that theefficacy of UV/H2O2 treatment is inuenced by the effluentorganic matter and its reactivity toward OH radicals. X-ray contrast media can be transformed by advanced oxidationprocesses. The second order reaction rate constants with HO•

ranged between 9.58 108 (diatrizoate) and 3.42 109 M1s1

(iopamidol).Opiates and Other Drugs of Abuse. Several analytical

methods have been reported for the determination of drugs of abuse in wastewater and environmental samples, primarily usingLC/MS/MS. The determination of these drugs in wastewaterand surface water can be used for environmental forensicinvestigations, which is possible due to the high sensitivity of the analytical methods.

Analytical methods and environmental occurrence of amphe-tamines and methamphetamines are reviewed by Boles and Wells.101 Opioids (oxycodone and methadone) and other phar-maceuticals, such as muscle relaxants, were detected by LC/MS/MS at elevated concentrations, up to 1700 μg/L (oxycodone)and 3800 μg/L (metaxolone) in WWTP effluents connected topharmaceutical formulation facilities.102 Median concentrations of


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4 compounds (methadone, oxycodone, metaxolone, and butalbital)ranged from3.4 to>400 μg/L inthis WWTP effluent, indicating thatformulation facilities are a potential source for environmental phar-maceutical contamination. Vazquez-Roiget al.developed ananalyticalmethod using SPE and LC/MS/MS for the determination of 14drugs of abuse and their metabolites (e.g., cannabinoids, ampheta-mine-like compounds, opiates, and cocainics).103The best recoveries

were obtained using Oasis HLB (200 mg), after comparing sevendiff erent SPE materials. Limits of quantication of


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using LC/Qq linear ion trap-MS.124 Loos et al. described a firstpan-European reconnaissance of the occurrence of polar organicpersistent compounds, including pharmaceuticals, in Europeangroundwater from 23 countries.125 Carbamazepine was the only pharmaceutical that was present above the quality standard forpesticides in groundwater of 0.1 μg/L.

New SPE Materials/Procedures. Bag-SPE, consisting of

20 mg of polystyrenedivinylbenzene enclosed in a woven polye-ster fabric, was immersed into 20 mL samples for solid phaseextraction.126,127 Although recoveries were lower in compar-ison to Oasis HLB, the concentrations determined in raw andtreated wastewater were comparable for most pharmaceuticals(e.g., diclofenac, metoprolol, oxazepam, cyclofosfamide, gemfibrozil,and furosemide). Benefits the authors mentioned included theease of handling, unattended water extraction, and that nofiltration is needed. Ten pharmaceu

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