new developments in the trace analysis of organic water pollutants

MINI-REVIEW

New developments in the trace analysis of organicwater pollutants

Klaus Fischer & Elke Fries & Wolfgang Körner &

Christina Schmalz & Christian Zwiener

Received: 2 December 2011 /Revised: 26 January 2012 /Accepted: 28 January 2012 /Published online: 24 February 2012# Springer-Verlag 2012

Abstract Challenging tasks, increasing demands, and newgenerations of powerful analytical instruments initiated con-siderable progress in aquatic environmental analysis and ledto a considerable improvement of analytical performanceduring the last few years. The ever growing number ofemerging pollutants is tackled by specific and highly sensi-tive analytical methods with detection limits of a few nano-gram per liter and even lower. Wide-scope monitoringtechniques and multiclass and multiresidue analysis allowfor the simultaneous determination of hundreds of com-pounds. The high mass resolution capability and mass accu-racy of advanced mass spectrometric instruments, i.e., time-of-flight (TOF) MS or Fourier transform (FT)–Orbitrap MS,enable combined target and non-target analysis, including the

identification of metabolites and abiotic degradation prod-ucts. This minireview highlights some of the most recentdevelopments in the trace analysis of important organicwater pollutants and focuses on some specific groups ofemerging contaminants, i.e., pharmaceuticals, flame retard-ants, disinfection by-products, surfactants, per- and poly-fluorinated compounds, benzotriazoles, and benzothiazoles,as well as on the identification of transformation productsand on non-target analysis. References were selectedaccording to their exemplary and innovative character andto their practical relevance.

Keywords Water analysis . Emerging pollutants .

Pharmaceuticals . Flame retardants . Disinfectionby-products . Perfluorinated compounds . Benzotriazoles .

Transformation products . Multiresidue analysis . Non-targetanalysis

Introduction

Themodern aquatic environmental analysis is confrontedwithvarious challenges. The number of emerging pollutants issteadily increasing without being freed from its responsibilityto observe the classic contaminants, e.g., aminopolycarboxy-late complexing agents (EDTA, DTPA), linear alkylbenzene-sulfonates and their degradation products, organic disinfectionby-products like haloacetic acids, and polar herbicides such astriazines, glyphosate, and others (Reemtsma and Jekel 2006;Giger 2009). Especially, pharmaceuticals, including anti-biotics, antimycotics, and antiviral drugs, constitute anever growing source of aquatic contamination, involvingrisks not only for human health, but for aquatic organismsas well (Glassmeyer et al. 2008; Calisto and Esteves 2009;Fatta-Kassinos et al. 2011a).

K. Fischer (*)Department of Analytical and Ecological Chemistry,University of Trier,Behringstr. 21,54296 Trier, Germanye-mail: [email protected]

E. FriesInstitute of Environmental Systems Research,University of Osnabrück,Barbarastr. 12,49076 Osnabrück, Germany

W. KörnerUnit Analysis of Organic Compounds,Bavarian Environment Agency,Bürgermeister-Ulrich-Str. 160,86179 Augsburg, Germany

C. Schmalz :C. ZwienerEnvironmental Analytical Chemistry, Center for AppliedGeoscience (ZAG), Eberhard Karls University Tübingen,Hölderlinstr. 12,72074 Tübingen, Germany

Appl Microbiol Biotechnol (2012) 94:11–28DOI 10.1007/s00253-012-3929-z

During the last years, the formation of metabolites andabiotic transformation products of aquatic micropollu-tants in surface and ground waters from bank filtration,wastewater, and drinking water treatment has attractedmajor concern, which is a further challenge for environ-mental analysis. Meanwhile, it is widely accepted thatthe environmental risk assessment of a man-made chem-ical has to include the formation, environmental fate, andbioactivity of its transformation products. They can bemore persistent and more (eco-)toxic than the parentcompounds, and often, they are essentially more polar,resulting in an altered environmental distribution behavior,e.g., in a higher mobility in aquatic systems (Sinclair andBoxall 2003; Van Zelm et al. 2010; Fatta-Kassinos et al.2011b). The development and beginning technical imple-mentation of advanced sewage treatment technologies (4thtreatment stage), e.g., advanced oxidation processes likeozonation, addition of hydrogen peroxide, or combinationof UV irradiation with H2O2 dosage, has led to the formationof further transformation products, whose characterization isone of the newer analytical tasks (Dodd et al. 2009, 2010;Yuan et al. 2009; Rosal et al. 2010).

Rising quality standards for surface and groundwaterby new regulations and legislations, e.g., in the EuropeanCommunity by adoption of the Water Framework Directive(European Commisson 2000) and of the GroundWater Direc-tive (European Commission 2006), water monitoring pro-grams were widened, and many new target compounds wereincluded (Reemtsma et al. 2006; Loos et al. 2010).

But, more important, the degree of fulfillment of thesedirectives cannot be assessed by measuring target compoundsonly. As a consequence, non-target analysis has rapidly grownin the last years, and several new methodical approaches havebeen developed (Gómez et al. 2009; Krauss et al. 2010; Petriet al. 2010; Schwarzbauer and Ricking 2010).

To meet all of these requirements, a tremendous increaseof the analytical performance in terms of sensitivity, resolu-tion, structure elucidation, analyte capacity, speed, and dataprocessing is necessary. Advanced mass spectrometry tech-niques contribute to the achieved analytical progress to ahigh extent. Triple quadrupole (QqQ) MS systems are nowdefining the “entrance level” of ultratrace analysis, whereastime-of-flight (TOF) instruments, quadrupole ion traps(QIT), and, as most powerful system, Fourier transformion cyclotron resonance (FT-ICR) MS are superior inresolving power and mass accuracy, but not necessarily insensitivity. To enhance the performance of MS systems byimplementation of additional mass fragmentation capabili-ties and to circumvent lower sensitivities, e.g., provided byTOF-MS, combinations of two different MS types, i.e.,quadrupole/TOF (QTOF) or linear ion trap–Fourier transform(FT)–Orbitrap, so-called hybrid instruments, are in use(Krauss et al. 2010).

Since many of the emerging contaminants and of theirtransformation products are polar, hyphenation of MSdetection with liquid chromatography is common. Here, theultraperformance liquid chromatography (UPLC) marks afurther considerable analytical progress. This LC techniquecombines higher chromatographic resolution and sensitivitywith drastically reduced analysis times and sample volumes(Tamtam et al. 2009). For an unambiguous identification ofnon-target compounds and of transformation products, nucle-ar magnetic resonance (NMR) spectroscopy is increasinglyapplied (Godejohann et al. 2009; Prasse et al. 2011). SinceNMR is not as sensitive as MS, usually an enrichmentof the interesting compounds by collection of chromatographicfractions is required.

Because slightly polar and non-polar compounds stillcontribute to aquatic pollution, analytical advancement hasnot omitted gas chromatography (GC). A trend towards two-dimensional GC (GCxGC) is recognizable, combined withTOF-MS as a very fast mass detector (Korytar et al. 2005;Skoczynska et al. 2008; Muscalu et al. 2011).

MS systems would not be suited for high-throughputelucidation of unknowns without improved and accelerateddata processing. Huge spectral libraries are to be searchedwith refined algorithms to retrieve data patterns presentingfingerprints of the recorded compounds. Analyte spectra arenot only compared with those stored in internal or externallibraries, but also with in-silico generated spectra and spec-tral sequences from new software tools of computationalmass spectrometry (Neumann and Böcker 2010). Transfor-mation pathway prediction databases like the University ofMinnesota Pathway Prediction System UM-PPS have alsobeen used to propose possible candidates for transformationproducts (Kern et al. 2009; Helbling et al. 2010a, b).

This condensed synopsis of current trends in the traceanalysis of organic water pollutants, which is far from beingcomplete, might illustrate the multitude of ongoing develop-ments in this field of environmental analysis. The reviewfocuses on some analytical hot spots like pharmaceuticalsand hormones, flame retardants, disinfection by-products,polyfluorinated compounds, and benzotriazoles. Specialattention is paid to the identification of transformation prod-ucts, tomulticlass andmultiresiduemethods, and to non-targetanalysis. The most recent references were selected accordingto their innovative character, their importance for the field, andtheir practical relevance. Many further sources which are notmentioned herewith are covered in recent review papers byRichardson (2010) and Richardson and Ternes (2011).

Pharmaceuticals and hormones

Pharmaceuticals (Ph) comprise more than 3,000 active com-pounds with quite different structures, functional groups,

12 Appl Microbiol Biotechnol (2012) 94:11–28

and, hence, physical–chemical properties. Only a smallfraction has been analyzed so far in water and soil, the majorenvironmental compartments in which Ph are introduced,for example by wastewater effluents, sewer leakages, andother point sources, and by fertilization with sewagesludge or manure. Ph and hormones are new emergingcontaminants and in the focus of research and regulationbecause of their widespread occurrence in surface waters,detection in drinking water, and possible estrogenic andecotoxicological effects. Natural and synthetic estrogens like17α-ethinylestradiol (EE2), 17α-estradiol, 17β-estradiol(E2), equilenin, equilin, estriol (E3), estrone (E1), mestranol,or norethindrone and antibiotics from the compound classespenicillins, sulfonamides, tetracyclines, and macrolides are ofmajor concern due to their high estrogenic potency and theirability to promote the development of bacterial resistance,respectively. A most recent review by Richardson and Ternes(2011) covers occurrence, fate, removal, and analysis of phar-maceuticals and hormones in water. It is also reported that theantibiotic erythromycin and nine hormones are included in theNew Contaminant Candidate List-3 of the U.S. EPA and thatthe Ph diclofenac and ibuprofen, and the hormones EE2 andE2 are in the list of priority substances of the EU WaterFramework Directive. Kumar and Xagoraraki (2010) priori-tized the monitoring of Ph and personal care products in USwaters and in finished drinking water. They developed acomprehensive ranking system based on the four criteria (1)occurrence, (2) drinking water treatment, (3) ecologicaleffects, and (4) health effects. Further reviews report on recenttrends in LC-MS analysis of organic contaminants (Petrovic etal. 2010) and the determination of transformation products ofpersonal care products including antimicrobials (Matamoroset al. 2009).

The analysis of Ph is still dominated by LC-tandem massspectrometric techniques as already reported some years ago(Zwiener and Frimmel 2004). Major trends are the use ofultraperformance liquid chromatography (UPLC) and ofmultiresidue analysis methods (Hao et al. 2008; Rodil etal. 2009; Al-Odaini et al. 2010; Nödler et al. 2010), theincreased consideration of transformation products (Zwiener2007; Radjenović et al. 2009; Kormos et al. 2010; Prasse etal. 2011), and, most importantly, the application of LC-high-resolution mass spectrometry (LC-HRMS) with QTOF(quadrupole time-of-flight)-MS and linear ion trap/FT-MSinstruments (Ibáñez et al. 2008; Gómez et al. 2010; Krausset al. 2010). LC-HRMS, especially LC-QTOF-MS and LC-Orbitrap-HRMS instruments, can operate in a fast full scanmode without loss of sensitivity, providing accurate massdata and isotopic patterns. This enables both target and non-target screening in one run. For example, Gómez et al.(2010) used LC-QTOF-MS for rapid automated screeningand confirmation of 87 Ph and 300 pesticides based on aself-created database which included accurate mass data,

characteristic fragment ions, isotopic patterns, and retentiontimes. In an effluent wastewater sample, 463 potential com-pounds were found in the database using the exact mass.Taking the retention time and the exact mass into account,the number of database matches could be reduced to 51compounds. Isotopic and fragmentation patterns from in-source and MS-MS CID (collision induced dissociation)are further means to increase selectivity. For example, theisobaric and co-eluting compounds pentoxifylline (m/z279.1452; RT 6.081 min) and sulfamethazine (m/z279.0910; RT 6.173 min) could be distinguished by char-acteristic fragment ions. Common fragments can also linkparent compounds to unknown metabolites. More informa-tion on identification of metabolites and small moleculesfrom MS data, including databases and computational toolsfor library searches and de novo deduction of structures,can be found in reviews (Neumann and Böcker 2010;Schymanski et al. 2011). There is still a need for LC-MSdatabases of environmental contaminants with suitableinformation, e.g., on accurate mass, fragmentation pattern,and retention time.

The introduction of ultraperformance liquid chromatog-raphy (UPLC) was certainly a step forward in LC. The useof sub-2-μm particles tremendously improved chromato-graphic resolution and increased peak capacity at decreasedHPLC run times. However, the small peak widths in therange of a few seconds require very fast MS detectors tocollect enough data points to sufficiently reconstruct thepeak shape (Guillarme et al. 2010).

Flame retardants

“Flame retardants are added to different materials to reducethe risk of fire. They save lives, prevent injuries and prop-erty losses, and protect the environment by helping to pre-vent fires from starting and to limit fire damage” (EuropeanFlame Retardants Association 2011). “In Western Europe,the average annual growth rate for 2007–2012 for all flameretardant chemicals is expected to be just over 3% in volumeterms. Flame retardant consumption in Central and EasternEurope/Russia is about 5–10% the size of the WesternEuropean (EU 15) market; however this market is growingfaster, with 5–7% average annual growth as a result of risingfire safety standards and harmonization with EU regulations”(Fink et al. 2008).

The benefits of flame retardants must necessarily bebalanced with the risks posed by these high productionvolume chemicals for humans and ecosystems (Shaw et al.2010). Therefore, knowledge of their environmental fateand a constant monitoring in various environmental mediaare necessary, and sensitive, specific, and reliable analyticalmethods are required.

Appl Microbiol Biotechnol (2012) 94:11–28 13

Organophosphorus flame retardants

Aryl and alkyl phosphates are main product families oforganophosphorus flame retardants (OFRs). According toa higher effectiveness, OFRs are often chlorinated. Theproportions of OFRs or chlorinated OFRs in Europe were16% of the total tonnage of flame retardants in 2007 (Fink etal. 2008). Today, OFRs almost occur in all environmentalcompartments (see Reemtsma et al. 2008 and referencestherein). According to their mobility and low degradability,OFRs have been also detected in groundwater particularlyunder anaerobic conditions (Fries and Puettmann 2003).Especially, chlorinated OFRs are persistent in the environ-ment (Kawagoshi et al. 2002). Lately, OFRs have been alsodetected in soils (Fries and Mihajlović 2011). European riskassessments exist already for tris(2-chloroethyl) phosphate(TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP),and tris[(2-chloro-1-(chloromethyl)ethyl]phosphate (TDCP)(European Commission 2008a, b, 2009). TCEP and TCPPare on the second and fourth priority lists, respectively,under the Council Regulation (EEC) No. 793/93 on theevaluation and control of the risks of existing substances(European Commission 1995, 2000a, b).

A detailed review on analytical methodologies for OFRsin water and air is given by Quintana et al. (2008). Althoughgas chromatography (GC) is still the common analyticaltechnique for analyzing OFRs in environmental samples,the authors expect an increase in the number of applicationsof liquid chromatography (LC) coupled to tandem massspectrometry (MS/MS). Besides well-established extractiontechniques like liquid–liquid extraction (Andresen et al. 2004)and solid-phase extraction (SPE) (Fries and Puettmann 2001),solid-phase microextraction (SPME) turned out to bealso a forward-looking extraction technique for this purpose(Rodríguez et al. 2006).

OFRs were also analyzed in sediments (Kawagoshi etal. 1999; Martínez-Carballo et al. 2007; García-Lopez etal. 2009), although the number of applications is stillmuch lower than that for water. The bioconcentration ofOFRs (triaryl phosphates) by fish is known for decades(Muir et al. 1983). Campone et al. (2010) presented ananalytical method for the analysis of certain OFRs in fishtissues for the first time.

Brominated flame retardants

About 25% of the amount of chemicals used as flameretardants in plastic materials are polybrominated organiccompounds with increasing worldwide production volume(Covaci et al. 2011). At least 75 different brominated flameretardants (BFRs) have been commercially produced (Alaeeet al. 2003). Since most of these substances are used as

additives in polymers and thus not chemically bound intothe polymer matrix, diffuse release into the environmentduring product life cycle is possible. Due to persistenceand bioaccumulation (de Wit 2002), the technical mixturesof penta- and octabrominated diphenyl ethers (Penta- andOctaBDE) were banned in new products in the EUsince 15 August 2004 (Directive 2003). Further, DecaBDEhas been banned in electrical and electronic applications inthe EU since 1 July 2008 (European Court of Justice 2008).All other BFRs can still be used worldwide without anyrestrictions.

Since most of the BFRs are non-polar, hydrophobicsubstances with very low water solubilities in the micro-gram per liter to picogram per liter range, these substanceshave a strong tendency to adsorb to suspended particulatematter and sediments in surface water (Covaci et al.2011). Therefore, analysis of water is of minor importancefor the majority of BFRs. Nevertheless, the main conge-ners of technical PentaBDE are priority substances accord-ing to annex X of the European Union Water FrameworkDirective with environmental quality standards for surfacewater (EU 2008).

PBDEs (polybrominated diphenylether) are enrichedfrom water samples either by liquid–liquid extraction witha non-polar solvent or by SPE using a hydrophobic C18material after addition of corresponding 13C12-labeled inter-nal standards. For GC-MS analysis of PBDEs and othernon-polar BFRs, generally, a short column (10–20 m) witha thin (0.1-μm film thickness) non-polar stationary phase isused. The MS is run either with electron impact ionization(EI-MS) or negative chemical ionization (NCI-MS). Chem-ical ionization generally yields lower limits of detection, butmonitoring of the bromide ion only (m/z079 and 81) doesnot allow the use of chemically identical 13 C-labeled internalstandards (Covaci et al. 2011). Besides GC-MS, LC-MS/MSmay be an alternative detection method for non-polar BFRs(Zhou et al. 2010), e.g., technical hexabromocyclododecane(HBCD), used in polystyrenes, consists mainly of the threemajor diastereomers α-, β-, and γ-HBCD. While thermalrearrangement of HBCD diastereomers above 160 °C restrictsGC-MS analysis to determination of total HBCD, separationof α-, β-, and γ-HBCD by LC-MS/MS is possible (Abdallahet al. 2008). There are few papers reporting picogram per literto nanogram per liter levels of several BFRs in sea andfreshwater (Covaci et al. 2011).

For extraction of non-polar BFRs from sediments andsewage sludge, soxhlet extraction and accelerated solventextraction are the preferred methods, mainly using toluene,dichloromethane (DCM), n-hexane/acetone (1/1, v/v), n-hexane/DCM (1/1, v/v), and toluene/acetone (1/1, v/v). Forclean-up of the extracts, liquid chromatographic methodswith common adsorbents as well as gel permeation chroma-tography are used. Due to the chemical stability of BFRs,


destructive clean-up methods like sulfuric-acid-impregnatedsilica columns are also successfully applied (Covaci et al.2011). A multicomponent GC-MS method for sedimentusing GC-HRMS has been published by Kolic et al. (2009).

Several BFRs like tetrabromobisphenol A and bromo-phenols have a semipolar character and moderate watersolubility due to their phenolic functional groups. The anal-ysis of phenolic BFRs is similar to that of non-polar BFRs;however, LC-MS/MS methods have generally more advan-tages and thus wider application than GC-MS methods.López et al. (2009) have published an overview of themethods for determination of phenolic BFRs in water, whileCovaci et al. (2009) describe the analytical aspects of tetra-bromobisphenol A.

One of the major challenges of PBDE analysis at lowlevels is the minimization and control of laboratory blankvalues due to their widespread use in products and mate-rials. This issue needs special attention also for analysis ofother BFRs and future method development. There is aneed for robust, sensitive, and flexible multicomponentmethods especially since further BFRs will be of environ-mental relevance in the future. The availability of more13C-labeled internal standards is a prerequisite for morereliable methods.

Besides BFRs, the chlorinated flame retardant DechloranePlus (DP) and related compounds have been produced fornearly 50 years in the USA and can be used in electrical andelectronic applications as well as for plastic roofing materials(OxyChem 2011) but were only detected in 2006 and later inthe environment close to the production site (Hoh et al. 2006;Qiu and Hites 2008; Sverko et al. 2010). Obviously, DP is soldand used worldwide since it has been found in ambient air andseawater from the northern and southern hemisphere (Mölleret al. 2010). An overview of the analytical chemistry ofdechloranes, which is similar to that of non-polar BFRs, isgiven by Sverko et al. (2011).

Disinfection by-products

Microbiologically safe drinking and swimming pool waterplays a decisive role in human health. Chlorine, chlor-amines, chlorine dioxide, and ozone are the most commondisinfectants. Increasing interest is on UV irradiationand advanced oxidation processes (AOPs). Besides killingbacteria, disinfectants can react with water constituents ofnatural and anthropogenic origin to yield partly toxic disin-fection by-products (DBPs). DBPs comprise oxygenated andhalogenated compounds. In drinking water, more than 600DBPs were identified, and only few of them are regulated andcontrolled (Richardson et al. 2007). More efforts have beenmade with LC-MSmethods to analyze further new and highlypolar DBPs (Zwiener and Richardson 2005). For example,

Zhao et al. (2010) identified the suspected bladder carcino-gens 2,6-dichloro-1,4-benzoquinone; 2,6-dichloro-3-methyl-1,4-benzoquinone; 2,3,6-trichloro-1,4-benzoquinone; and2,6-dibromo-1,4-benzoquinone in chlorinated drinking waterwith SPE and LC-MS-MS. Unexpectedly, negative ESI(electrospray ionization) produced the reduced [M+H]-ions of the halogenated quinones. Further, DBPs can resultfrom the chlorination of organic contaminants (Richardsonand Ternes 2011; Quintana et al. 2010). Many of the DBPsare chlorinated volatile organic compounds (VOC). Basically,all methods for VOC detection in water are suitable for theiranalysis as static headspace-GC-MS and purge-and-trap-GC-MS. A relatively new and sensitive method is GC-MS afterheadspace solid-phase microextraction (HS-SPME). Therecently developed German guideline DIN 38407-41(2011) on this multicomponent method for both halogenatedand halogen-free VOC is currently the basis for developmentof an ISO guideline.

The presence of amino acids during chlorination leads toformation of (chloro-)aldehydes, (chloro-)nitriles, chlor-amines, and (chloro-)aldimines which may be responsiblefor odor problems (Freuze et al. 2004, 2005). Since GCanalysis of (chloro-)aldimines is difficult due to their ther-mal instability and low half-life times in water (Brosillon etal. 2009), there is hardly any data on this group of DBPswith suspected low odor thresholds. LC-MS techniques maybe an alternative; however, chromatographic separation byHPLC is yet incomplete and requires long retention times(Grübel et al. 2011).

In swimming pool water, further reaction products andhigher concentrations of nitrogenous DBPs could be founddue to the input of the bathers (Zwiener et al. 2007; Richardsonet al. 2010). Richardson et al. (2010) applied low- and high-resolution GC-MS techniques and detected more than 100mostly new chlorinated and brominated DBPs in swimmingpool waters. Nitrogenous, brominated, and iodinated DBPsare, in general, more toxic than chlorinated ones (Muellner etal. 2007). A focus is currently on trichloramine (NCl3), avolatile, irritating, and rather instable compound formed byreaction of chlorine with urea and other nitrogenous com-pounds (Schmalz et al. 2011a, b). In Germany, a technicalstandard of 0.2-mg m-3 NCl3 in indoor pool air has beenproposed (German Federal Environmental Agency 2011).The instability of NCl3 is the major challenge for quantitativeanalysis methods, since a standard is neither stable enough norcommercially available. Two analysis methods are currentlyused: (1) for gas phase samples: reduction of NCl3 on a filterimpregnated with As2O3 and measurement of the formedchloride by ion chromatography (Hery et al. 1995) and (2)for aqueous samples: membrane inlet mass spectrometry(MIMS) (Weaver et al. 2009). MIMS is a direct inlet techniquewhere the aqueous sample is separated from the gas inlet of theMS by a silicone membrane. Volatile and non-polar analytes


can be transported through the membrane by an absorption/diffusion mechanism and therefore directly reach the ionsource of the MS without any separation (Fig. 1a). Isobaricinterferences of the analyte fragments from other compoundscan limit the applicability. In Fig. 1, the trace of a SIM (selectedion monitoring) ion current (b) and the mass spectra oftrichloromethane (c) and trichloramine (d) are shown. How-ever, both methods still lack a sound calibration based on anauthentic standard.

Nitrosamines

Nitrosamines are a class of compounds with high genotox-icity and carcinogenicity (Richardson et al. 2007), and theyare found after disinfection with chloramination, chlorina-tion in the presence and absence of ammonia, and treatmentwith chlorine dioxide (Chen and Young 2008; Planas et al.2008; Zhao et al. 2008; Zhou et al. 2009). Ozonation studieswith nitrosamine precursors and natural water samplesshowed partly contradictory results for the formation ofnitrosamines. Whereas a decreasing NDMA (nitrosodime-thylamine)-formation potential after preozonation of naturalwaters has been reported by Lee et al. (2007a, b), otherstudies show that ozonation increased NDMA formation(Oya et al. 2008; Schmidt and Brauch 2008; Zhao et al.2008; von Gunten et al. 2010). For example, 50% of themetabolite N,N-dimethylsulfamide (DMS) of the fungicidetolylfluanide is converted to NDMA during ozonation(Schmidt and Brauch 2008).

NDMA is the most analyzed nitrosamine in waste watertreatment effluents, ground water, river water (Huy et al.2011), drinking water, and swimming pool water. Typicalconcentrations of NDMA are in secondary waste watereffluents below 10 ng L-1. High NDMA concentrations ofup to 5 μg L-1 have been reported for chlorinated waste watertreatment effluents. Inmost drinkingwater samples, NDMA isbelow the detection limit (Nawrocki and Andrzejewski 2011).

Currently, there are no federal drinking water guidelines forNDMA in Canada or USA. Only California and Ontariohave developed a notification level and a drinking waterquality standard of 9 and 10 ng L-1 NDMA, respectively.In Germany, health-based values for NDMA are 10 ng L-1

(German Federal Environment Agency 2003; Charrois etal. 2007; Nawrocki and Andrzejewski 2011). BesidesNDMA, other nitrosamines have been identified in watersamples (Table 1). NMOR and NPIP are the most analyzednitrosamines with maximum concentrations in the range of5 ng L-1.

The analysis of NDMA and other nitrosamines is chal-lenging due to the low concentration, the polar character,and low molecular weight of the analytes. Mostly usedmethods are based on SPE with activated carbon and elutionwith dichloromethane (EPA 521). Planas et al. (2008)developed a method for nine nitrosamines based onautomated SPE on coconut charcoal EPA 521 cartridgesand isotope dilution GC-HRMS with electron impactionization at 35 eV. Method detection limits range between0.08 and 1.7 ng L-1. Pozzi et al. (2011) used chemical ioniza-tion with methanol and selected ion storage (SIS) on an iontrap MS to achieve detection limits of 1–2 ng L-1. Zhaoet al. (2009) used high-field asymmetric waveform ionmobility spectrometry (FAIMS) to reduce backgroundinterferences for seven nitrosamines analyzed by nano-ESI-FAIMS-MS-MS. Thermally instable nitrosamineslike N-nitrosodiphenylamine require LC methods. Forexample, Krauss and Hollender (2008) set up a methodfor nine nitrosamines in wastewater by SPE and LC-MSusing a linear iontrap-orbitrap MS at a resolving powerof 25,000–40,000. For SPE, a combination of an RPcartridge on top of a carbon cartridge to adsorb the lesspolar nitrosamines and most matrix components on theRP material to save the carbon material for the most polarnitrosamines was applied (Krauss and Hollender 2008).Wang et al. (2011) used UPLC-ESI-MS-MS to improvethe sensitivity.

aqueous sample

inMS

membranecell

He

aqueous sample

out

(a) (b)

(c) (d)

Fig. 1 Scheme of membraneinlet mass spectrometry(MIMS) (a) Selected ionmonitoring (SIM) trace of anaqueous sample (b) and massspectra of trichloromethane (c)and trichloramine (d)


Surfactants and their degradation products

Surfactants are usually divided into four subgroups:

1. Anionic surfactants with linear alkylbenzene sulfonates(LAS; containing alkyl chains with 10 to 13C-atoms) asmost important substance group. Furthermore, variousalkylsulfonates, aryl and alkyl sulfates, alkylethersul-fates, and fatty acid esters belong to this category.

2. Cationic surfactants, mostly aryl or alkyl ammoniumcompounds.

3. Non-ionic surfactants like alkyl[phenol] polyethoxy-lates (APEO) and aliphatic alcohol ethoxylates.

4. Amphoteric surfactants having betaine structure likecocamidopropyl betaine.

Anionic and non-ionic surfactants can be poly- or per-fluorinated. The analysis of these compounds is subject ofthe following chapter.

The environmental analysis of tensides focuses on LASand their degradation products, e.g., sulfophenyl carboxylates(SPC), as well as on APEO and their main transformationproducts, i.e., nonylphenol (NP) isomers and nonylphenole-thoxycarboxylates (NPEC). Some of the latter compounds aremore persistent and more toxic than the parent chemicals, andNPs are identified as endocrine disruptors (ED). Many guide-lines and regulations exist for the control and limitation of theemission of surfactants and detergents into the aquatic envi-ronment. In the European Union, the basis for all national

ordinances is the European Detergent Regulation 648/2004/EEC (European Commission 2004). Therefore, NPs andrelated alkylphenols are often integrated in broader measur-ing programs to monitor or to screen for EDs in sewagetreatment plant effluents, surface waters, and sediments.Owing to their ionic or polar nature, surfactants are mostlyanalyzed by reversed phase (RP)—or mixed mode (RPcombined with polar interactions and ion exchange)—LC.GC is restricted to NP and other alkylphenols, NPEC, andto their non-ionic degradation products (Gallart-Ayola et al.2010; Klontza et al. 2010; Luo et al. 2010; Sánchez-Avilaet al. 2010). Bruzzoniti et al. (2008) used anion exchangechromatography in combination with SPE-enrichment on anSDB-1 cartridge for the quantification of alkylsulfonicacids, arylsulfonic acids, and alkylsulfates in seawater.Detection limits between 4.0 and 5.8 μg L-1 were achievedwith conductivity measurement in the suppressed mode.Micellar electrokinetic capillary chromatography–UV detec-tion in combination with MS/MS substance identificationwas applied to determine NP and NP ethoxylates in waste-water after sample extraction with toluene. LOQs (limit ofquantification) were in the range of 12.7 to 30.8 μg L-1

(Núnez et al. 2009).Most of the LC procedures used SPE as sample pretreat-

ment method, whereas headspace solid-phase microextrac-tion (SPME) in combination with inline derivatization(Klontza et al. 2010) or liquid–liquid microextraction ofmethylated analyte derivates was conducted prior to GC

Table 1 Nitrosamines and their occurrence in water samples

Name Abbreviation WWTP effluent Drinking water Swimming pool water

N-nitrosodimethylamine NDMA xa,e xb,c,f,g,h,i,j xf,k

N-nitrosodiethylamine NDEA xa xb,d,f,h xf

N-nitrosodi-n-propylamine NDPA xd

N-nitrosodi-n-butylamine NDBA xa xd,h xk

N-nitrosomorpholine NMOR xa,e xd,f,h,i,j

N-nitrosomethylethylamine NMEA xh

N-nitrosodiphenylamine NDPhA xc,h

N-nitrosopyrrolidine NPYR xa xb,c,f,i,j xd,f

N-nitrosopiperidine NPIP xa xc xk

a Krauss and Hollender 2008b Planas et al. 2008c Zhao et al. 2006d Pozzi et al. 2011e Schreiber and Mitch 2006f Jurado-Sánchez et al. 2010g Van Huy et al. 2011hWang et al. 2011i Charrois et al. 2004j Charrois et al. 2007kWalse and Mitch 2008


measurement (Luo et al. 2010). In one case, a liquid ioniccrystal (1-octyl-3-methylimidazolium hexafluorophosphate)was applied in temperature-controlled ionic liquid disper-sive liquid-phase microextraction of 4-n-nonylphenol and 4-tert-octylphenol from aqueous samples prior to HPLC-fluorescence (FL) detection (Zhou et al. 2011). LODs (limitof detection) in the range of 0.23–0.48 μg L-1 were reported.SPE-HPLC-FL was applied for online monitoring of LAS ina wastewater treatment plant. The LC-separation columnconsisted in a polar-embedded RP material. With an SPEcartridge load of 5 mL of sample, LODs of about 1.5 to8 μg L-1 were reached (Crey-Desbiolles et al. 2009).

Fluorescence detection in combination with or as analternative to MS detection plays a role in the determinationof alkylphenolethoxylates and of their degradation products(NP and octylphenol) as well (Morales et al. 2009).

The high mass resolution capacity of TOF-MS is utilizedto screen wastewaters, seawater samples, and marine sedi-ments for a broad range of surfactants and of their degrada-tion products. Besides others, various LAS, NPEOs,alcoholethoxylates, sulphophenylcarboxylic acids, NPECs,and polyethylene glycols (degradation products of APEO)were detected (Lara-Martin et al. 2011). This paper presentssome of the first data relative to the occurrence of PEG insediments where concentrations were generally higher (upto 1,490 μg kg-1) than those for other classes of targetedsurfactants and their metabolites. As an outcome of the non-target analysis of polar contaminants in freshwater sedi-ments influenced by pharmaceutical industry, polypropyleneglycols (n03–16), LAS, and benzalkonium surfactants weredetected by UPLC-QTOF-MS (Terzic and Ahel 2011). Asdemonstrated by Eganhouse et al. (2009), the combinationof TOF-MS with two-dimensional GC offers the ability ofan isomer-specific determination of 4-NP, 2-NP, and decyl-phenols in wastewater and in contaminated groundwater. Allmajor 4-NP isomers and a number of previously unrecog-nized components were identified.

SPE-LC-ESI-MS/MS served as analytical tool for thequantification of alkylphenols and their correspondingethoxylates (n01–12) together with various endocrine dis-ruptors in sewage (Vega-Morales et al. 2010). LODs rangedbetween 0.5 and 60 ng L-1. With essentially the same tech-nique, Jonkers et al. (2009) investigated the occurrence andtransformation products of APEO in wastewater and surfacewaters. Due to high removal efficiencies provided by waste-water treatment plants, APEO-levels were generally low inplant effluents and river waters, but nonylphenoxy aceticacids or nonylphenols could be detected in some cases.

Cationic surfactants are relatively seldom addressed byenvironmental analysis. For this purpose, Peng et al. (2011)applied online polymer monolith microextraction coupled toHPLC-MS. Microextraction was performed with a poly(methacrylic acid-co-ethylene dimethacrylate) monolith,

followed by separation on a mixed-mode column packedwith octyl and sulfonic acid co-bonded silica. LODs werefound to be in the range of 15–24 ng L-1.

Comparing various LC-MS interfaces and LC-systems,4-NP and 4-tert-octylphenol were determined together withother estrogenic chemicals in water after extraction andderivatization either with dansyl chloride or with pentafluor-obenzyl bromide by LC-MS/MS (Lien et al. 2009). The bestanalytical performance was achieved with the dansylatedcompounds working with an ESI interface in the positivemode. Based on selected reaction monitoring (SRM), LODsof 0.23–0.01 ng L-1 were attained with treated sewage andriver water.

Per- and polyfluorinated compounds

The ubiquitous occurrence and accumulation of per- andpolyfluoroalkyl compounds (PFCs) in the environment hasbecome an important topic in environmental research in thelast 10 years. Due to the very strong C−F bond, PFCs areextremely persistent under environmental conditions. Ana-lytical chemistry has mainly focused on the determination ofperfluoroalkylcarboxylic acids (PFCAs) and perfluoroalkyl-sulfonic acids (PFSAs). Due to their amphoteric characterand chemical stability, perfluorooctanoic acid (PFOA), per-fluorooctanesulfonic acid (PFOS), and other so-called per-fluorinated tensides (PFTs) have been used as surfactants ina wide range of production processes and products, e.g.,synthesis of fluoropolymers, galvanic processes, fire fight-ing foams, textiles, carpets, food packaging materials, etc.,for about 60 years. Because of their relatively good watersolubility, ground and surface water are primary environ-mental compartments for the distribution of PFTs which aregradually leached out from contaminated soils (Skutlarek etal. 2006).

For trace analysis of PFTs in water, enrichment by solid-phase extraction (SPE) using a weak anion exchanger fol-lowed by determination with HPLC coupled to tandem massspectrometry with electron spray ionization (HPLC-ESI-MS/MS) is state of the art yielding limits of quantificationin the range of 1 ng L-1. Since most PFCAs and PFSAs havebecome available as 13 C-labeled reference compounds,addition of these internal standards before extraction andquantification by isotope dilution method is possible andstrongly recommended in several guidelines. While the ISOguideline 25101 (2009) describes a method for PFOS andPFOA only, the German guideline DIN 38407-42 (2011)has been validated for C4- to C10-perfluorocarboxylic acidsand, besides PFOS, also for C4- and C6-perfluorosulfonicacids. This guideline emphasizes the need to quantify thebranched isomers which contribute up to 70% to the totalpeak area of PFOS but generally less than 20% for PFCAs.


One critical issue of PFT analysis in water is the adsorp-tion of long-chain PFCAs to the surfaces of samplingvessels. This topic and other critical issues have recentlybeen summarized by Berger et al. (2011) and van Leeuwen etal. (2009).

Due to their environmental persistence and (bio)accumu-lation, PFOA and PFOS have been banned for most appli-cations in Europe and North America. In 2009, PFOS waslisted under the Stockholm Convention on persistent organicpollutants. These PFCs are mainly being substituted bypartially fluorinated substances. Most important are the so-called fluorotelomers, i.e., the two carbon atoms next to thefunctional group have no fluorine, especially the fluoro-telomer alcohols as 8:2 FTOH (1H,1H,2H,2H-perfluorode-canol) and 6:2 FTOH (1H,1H,2H,2H-perfluorooctanol).Moreover, fluorotelomers are formed from polyfluoroalkylphosphate esters (PAPs, diPAPs) as described by D'eon andMabury (2011). There is evidence that fluorotelomers aretransformed to the corresponding perfluoroalkylcarboxylicacids by atmospheric oxidation reactions and microbial deg-radation processes, e.g., 8:2 FTOH is transformed to PFOA(Dinglasan et al. 2004; Ellis et al. 2004).

The analysis of saturated and unsaturated fluorotelomercarboxylic and sulfonic acids can be integrated into the SPEand HPLC-MS/MS method for PFCAs and PFSAs(Taniyasu et al. 2005; Dreyer et al. 2010). Gas chromatog-raphy coupled with mass spectrometry using positive chem-ical ionization (GC-PCI-MS) in the selected ion monitoring(SIM) mode is the method of choice for determination offluorotelomer alcohols, acrylates, and methacrylates (Jahnkeet al. 2007) since these substances are volatile organic com-pounds (VOC) with vapor pressures above 10 Pa at 25 °C(Lei et al. 2004). Enrichment of these fluorotelomers fromwater samples has been performed by SPE with a weakanion exchanger (Taniyasu et al. 2005) and by liquid–liquidextraction with tert.-butyl methyl ether after addition ofcorresponding mass-labeled internal standards (Mahmoudet al. 2009).

A number of polyfluorinated substances are used in avariety of products which are precursors for PFOS andother PFSAs under environmental conditions. Two importantgroups are perfluoroalkyl sulfonamides (FASA) and perfluor-oalkyl sulfonamidoethanols (FOSE) (Martin et al. 2010). Thevolatile FASA and FASE can be determined together withfluorotelomer alcohols by GC-PCI-MS as applied byJahnke et al. (2007) for ambient air, as well as togetherwith fluorotelomer carboxylic and sulfonic acids, PFCAs,and PFSAs in water by HPLC-MS/MS after SPE(Taniyasu et al. 2005; Dreyer et al. 2010). The directdetermination of the volatile fluorotelomer alcohols,acrylates and methacrylates, FASA, and FASE in watersamples without an extraction step should be possible byheadspace-GC-MS.

The experience in analysis of polyfluoroalkyl compoundsin water is yet much smaller than that for perfluorinatedsubstances. There is still a need for reliable and sensitivemulticomponent methods, especially since further classes ofPFCs may be of environmental relevance in the future.

Benzotriazoles and benzothiazoles

Benzotriazoles (BTs) like 1H-benzotriazole (1H-BT), 5-methyl-1H-benzotriazole (5Me-BT), and 4-methyl-1H-ben-zotriazole (4Me-BT) are mainly used as corrosion inhibitorsin dishwasher detergents, aircraft anti-icing fluids, automo-tive antifreeze formulations, industrial cooling systems,metal-cutting fluids, brake fluids, and solid cooling lubri-cants; as antifoggants in photography; and as ultravioletlight stabilizers in plastics (U.S. EPA 1997). According totheir relatively low degradability (Pitter and Chudoba 1990),BT is commonly emitted into rivers by waste water effluents(Weiss et al. 2006). On account of their low sorption capac-ity (Hart et al. 2004), BTs occur mostly in the aquaticenvironment (Weiss et al. 2006; Kiss and Fries 2009;Reemtsma et al. 2010; Janna et al. 2011; Kiss and Fries2012). However, the mobility of these polar compounds inthe environment is still not well characterized, although theirpresence in ground water (Cancilla et al. 1998; Hollender2007), bank filtrate (Reemtsma et al. 2010), and drinkingwater have already been reported (van Leerdam et al. 2009).

GC-MS combined with common extraction methods likeLLE or SPE has been demonstrated as an appropriate tool toanalyze BTs in airport influenced water samples (Cancilla etal. 1998; Corsi et al. 2003) but also in river water withLODs for 1H-BT and 5Me-BT of 12 and 8 ng L-1, respec-tively (Kiss and Fries 2009). Slightly higher LODs wereobtained in river water using SPE and comprehensive two-dimensional GC coupled with time-of-flight mass spectro-metric (GCxGC-TOF-MS; Jover et al. 2009). A methodbased on SPE and LC coupled with an LTQ-FT-OrbitrapMS allowed quantifying BT in drinking and surface waterdown to a LOD of 10 ng L-1 (van Leerdam et al. 2009). Toavoid time-consuming extraction and cleaning steps, thedetermination of BTs in directly injected river water andwaste water samples was applied successfully using LC-ESI-MS/MS (Weiss and Reemtsma 2005). Upon their polarcharacter, only a few studies exist on BTs in soils, allcollected at an abandoned airport, where solvent extractionfollowed by LC-MS (Breedveld et al. 2003) or GC-MS(Cancilla et al. 2003) was applied.

Benzothiazole and its derivates also are an important classof industrial chemicals. Benzothiazoles are mainly used asvulcanization accelerators in the manufacture of rubber, aspesticides, as corrosion inhibitors in antifreeze formulations,and as photosensitizers in photography (Brownlee et al. 1992).


Decades ago, benzothiazoles had already been identified astire markers useful as indicators for street runoff as a source ofenvironmental pollution (Spies et al. 1987). Thus, benzothia-zoles are kinds of “old” emerging contaminants that occurubiquitously particularly in the aquatic environment, includ-ing river water (Kloepfer et al. 2005; Grigoriadou et al. 2008;Schwarzbauer and Ricking 2010), riverine runoff (Ni et al.2008), groundwater (Hollender 2007), marine water (Bester etal. 1997), and drinking water (van Leerdam et al. 2009).However, most reports on the occurrence of benzothiazolesin surface water are limited to only a few selected samplinglocations except of the monitoring study presented recently byFries et al. (2011).

So far, the analytical method development has beenfocused on extraction techniques for the analysis of benzo-thiazoles in complex aqueous samples such as waste water.Extraction was performed by LLE (Fiehn et al. 1994), morefrequently by SPE (Kloepfer et al. 2004; Ni et al. 2008; Joveret al. 2009; van Leerdam et al. 2009), and lately by stir barsorptive extraction (SBSE) coupled to thermodesorption(Fries 2011). Benzothiazoles have been analyzed by LC orGC coupled to different detectors, including MS. Cur-rently available analytical techniques based on SPE fol-lowed by GCxGC-TOF-MS (Jover et al. 2009) and LC-LTQ-FT Orbitrap MS (van Leerdam et al. 2009) allowthe detection of benzothiazole in natural surface watersdown to concentrations of 5 and 10 ng L-1, respectively.Although benzothiazoles are relatively polar compounds,their occurrence in estuarine sediments was observeddecades ago using Soxhlet extraction and GC-MS (Spieset al. 1987).

Transformation products

Different analytical strategies are pursued to detect and toidentify metabolites and abiotic degradation productsformed during drinking water processing, sewage treatment,or in the aquatic environment. One approach points to thedegradability of one or of a few structurally related com-pounds trying to identify all transformation products formedunder selected reaction conditions. Another conceptincludes the determination of already known main degrada-tion products into monitoring programs for a greater groupof target micropollutants. A third method combines high-throughput screening for expected (yet analytically con-firmed or model predicted) transformation products byHPLC-HRMS with the sequential discrimination of hithertounknown conversion products within simultaneously gener-ated MS libraries of non-target compounds. The transfor-mation of the opium alkaloid codeine by activated sludgemicroorganisms was elucidated by means of QqQ-LIT-MSand LTQ-FT-Orbitrap-MS. 1H and 13C-NMR measurements

were carried out after isolation of individual TPs (trans-formation products) via semipreparative HPLC and sub-sequent freeze-drying (Wick et al. 2011). In total, 18 TPswere detected, and 8 out of 18 could be unambiguouslyidentified. Most of these TPs exhibited only slightlymodified molecular structures. The transformation path-ways of codeine could be extrapolated to the structurallyrelated alkaloids morphine and dihydrocodeine, resultingin the detection of 17 TPs of morphine and of 2 TPs ofdihydrocodeine.

The biological transformation of the antiviral drugs acy-clovir and penciclovir by activated sludge was studied withsimilar analytical methods and instrumentation (Prasse et al.2011). For acyclovir, only a single TP (Carboxy-Acv) wasfound, whereas eight TPs were identified for penciclovir.Concentrations up to 3.2 μg L-1 of Carboxy-Acv in surfacewater and up to 0.04 μg L-1 in drinking water were mea-sured, respectively.

Several studies aimed on the identification of degradationproducts abiotically formed during sewage treatment byadvanced oxidation processes. Ozonation products of theartificial sweeteners cyclamate and acesulfame were ana-lyzed by a combination of various techniques, includingHPLC-MS/MS, GC-MS, LC-HRMS, ion chromatography,and NMR. Amidosulfonic acid and cyclohexane wereformed as main ozonation products of cyclamate, whereasdihydroxyacetyl sulfamate was the main degradation prod-uct of acesulfame (Scheurer et al. 2011). Applying UPLC-MS/MS with QqQ- and QTOF-detectors, two ozonationproducts of each of the two estrogens 17β-estradiol andestrone were detected. One could be characterized as10-ε-17β-dihydroxy-1,4-estradieno-3-one, and three otherswere tentatively identified (Pereira et al. 2011). These oxida-tion by-products were found to be persistent even after appli-cation of high ozone dosages. Sulfoxides were discovered asozonation products of the antibiotics penicillin G and cepha-lexin, using 1H-NMR, 13 C-NMR, and LC-Orbitrap-MS(Dodd et al. 2010). The sulfoxides of both antibiotics weredegraded by OH radicals further. It was also found that 13antibiotics of 9 structural classes lost their antibacterial activ-ities after ozonation (Dodd et al. 2009). Several products ofthe oxidation of carbamazepine by Fe(VI) compounds weredetected by means of LC-MS/MS (Hu et al. 2009). Iron in itshighest oxidation state attacks, similar to ozone, olefinic unitsin the central heterocyclic ring of the antiepileptic drug, lead-ing to ring opening and the subsequent formation of transfor-mation products.

The simultaneous determination of five triazine herbi-cides (atrazine, simazine, terbuthylazine, terbumeton, terbu-tryn) and of six of their main metabolites in surface andurban wastewater by UPLC-MS/MS revealed that the con-centrations of the degradation products were much higherthan the intact triazines in many cases (Benvenuto et al.


2010). The sulfonic acid and oxanilic acid degradationproducts of the herbicides metolachlor, alachlor, acetochlor,and propachlor were analyzed by HPLC-MS/MS in influ-ents and effluents of 34 WWTPs (wastewater treatmentplants) and in various rivers. It could be demonstrated thatsewage treatment reduced the concentrations of the degra-dation products significantly but not completely, leading tothe detection of some of them in receiving surface waters(Cheng et al. 2010).

Illicit drugs (22) and some of their major metabolites wereanalyzed in surface water and wastewater by LC-QLIT-MSusing two SRM transitions for the simultaneous identificationand quantification of all target compounds (Bueno et al.2011). Illicit drugs (14; cocainics, amphetamine-like com-pounds, cannabinoids, and opiates) and their main degrada-tion products, i.e., benzoylecgonine, ecgonine methylester,3,4-methylendioxymethamphetamine, and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol, were determined by LC-MS/MS invarious Spanish surface waters (Vazquez-Roig et al. 2009).Using oasis HLB cartridges for the enrichment of the analytesfrom 250 mL of water, LOQs in the range from 0.03 to5.13 ng L-1 were attained.

The occurrence of human metabolites and the forma-tion of microbial transformation products of seven phar-maceuticals and of one biocide, predicted by variouscomputed-based biotransformation pathway predictionsystems like UM-PPS (Ellis et al. 2006), CATABOL(Dimitrov et al. 2007), and PathPred (Moriya et al.2010), were targeted by HPLC-high-resolution-MS/MSin activated sludge-seeded batch reactors (Kern et al.2010). Except one, all of the 12 TPs identified couldalso be detected in the effluents of two full-scale mu-nicipal WWTPs. Broadening the scope on transforma-tion products generated during wastewater treatment, theanalysis of target compounds (known and predictedTPs) was combined with non-target screening based onthe high mass resolution capability of LTQ-FT-Orbitrap-MS and the interpretation of MS/MS spectra. Investigat-ing the fate of six pharmaceuticals and six pesticides,prevailingly amide-containing compounds, 26 TPs couldbe identified, some of them for the first time (Helblinget al. 2010a). Using essentially the same analyticalapproach, a screening for 1,794 predicted and experi-mentally observed TPs of 52 pesticides, biocides, andpharmaceuticals in various surface waters in Switzerlandwas conducted (Kern et al. 2009). A six-step funnelingprocedure to identify target TPs was carried out usinghigh mass resolution, check of isotope composition,plausibility of HPLC retention times, and interpretationof MS/MS fragments. In total, 19 TPs were found,including some rarely reported ones (e.g., TPs of thepharmaceuticals venlafaxine and verapamil and of thepesticide azoxystrobin).

Multiclass and multiresidue methods, non-targetanalysis

Depending on the polarity range of the interesting analytegroups, either LC-MS or GC-MS instruments are used forscreening methods covering diverse classes of micropollu-tants, including some of their degradation products and non-target compounds (Gros et al. 2006; Rodil et al. 2009;Kumar and Xagoraraki 2010). With a few exceptions (GC-ECD, LC-DAD), detection is performed by various MStechniques. LC-MS/MS systems were selected for the multi-residue analysis of pharmaceuticals, synthetic hormones,and pesticides. Target compounds (21) were controlled inwater supplies of Cyprus, and ibuprofen and bisphenol-Acould be detected in potable water (Makris and Snyder2010). In combination with SPE enrichment of analytesfrom river water and WWTP effluents, 23 pharmaceuticalsand synthetic hormones from different therapeutic classeswere detected with high sensitivity (LOD between 0.2 and281 ng L-1). Among the monitored compounds, chlorothia-zide was found at the highest level, with concentrations upto 865 ng L-1 in river water (Al-Odaini et al. 2010). Usingonline preconcentration of 0.5 mL of filtered water, LODs inthe range of 1–10 ng L-1 were achieved for the multiresidueanalysis of 95 pesticides and of breakdown products insurface waters (Jansson and Kreuger 2010). Hao et al.(2008) set up a multiresidue analytical method for 38 phar-maceuticals, 10 endocrine disrupting and 3 perfluoroalky-lated compounds. Isotope-labeled compounds (15) wereused as injection internal standards or isotope dilution quan-titation standards and showed that matrix effects could notbe removed by SPE. Based on the high mass resolution andaccuracy of TOF-MS, various rapid wide-scope screeningLC methods were developed. Operating the TOF-MS in twodata acquisition modes simultaneously (low collision energyfor the record of accurate mass data and high collisionenergy for substance fragmentation), 76 illicit drugs, pre-scription drugs with potential for abuse, and some of theirmetabolites were determined in influent and effluent waste-water (Hernández et al. 2011). With a comparable method,river waters and WWTP effluents were screened for nearly400 micropollutants. An omnipresent group of pharmaceu-tically active compounds was identified to contribute toriver water pollution mainly, including, among others, ate-nolol, naproxen, and metabolites of dipyrene. The latter wasdetected in effluents of some WWTPs at concentrationshigher than 20 ng L-1 (Gómez et al. 2010). The non-targetUPLC-QTOF-MS analysis of freshwater sediments influ-enced by pharmaceutical industry revealed various polypro-pylene glycols, alkylbenzene sulfonate, and benzalkoniumsurfactants as well as a number of pharmaceuticals, e.g.,chlorthalidone, warfarin, and macrolide antibiotics, as maincontaminants. Various pharmaceuticals, benzotriazoles, and


illicit drugs were screened in surface, ground, and drinkingwater by LC-LTQ-FT-Orbitrap MS (Hogenboom et al.2009). Identification of some non-target compounds waspossible by additional MS/MS experiments.

Large volume injection is one option to achieve higherdetection sensitivities and less substance discrimination.Relatively common in LC, this technique is of practicalvalue, also for GC. Applying microextraction by packedsorbents coupled with large volume injection GC, it waspossible to determine 41 multiclass priority and emergingpollutants, belonging to PAHs, PCBs, phthalates, nonylphe-nols, and steroid hormones, in wastewater samples (Prieto etal. 2010). Expanding to non-target analytes, a similar ap-proach was followed by Gómez et al. (2009). A fast GC-MSmethod, able to identify and quantify 66 multiclass prioritypollutants in water within 10 min, was recently presented byCherta et al. (2011). To achieve detection limits below10 ng L-1, 250 mL of water samples were extracted byC18-SPE cartridges. For substance identification, the threemost abundant and/or specific ions were monitored for eachcompound, and the intensity ratios were used as confirmatoryparameter.

An even broader range of water pollutants is accessibleby GC-TOF-MS. Around 150 organic contaminants, includ-ing pesticides, PAHs, PCBs, and PBDEs, were rapidly ana-lyzed by this analytical tool in wastewater and surfacewaters (Portolés et al. 2011). Increased chromatographicresolution is provided by comprehensive two-dimensionalgas chromatography (GCxGC). If coupled with a micro-electron capture detector, a diversity of halogenated com-pounds can be analyzed in soils, sediments, and sludges(Muscalu et al. 2011). Many constituents of previouslyunresolved complex mixtures of sediment contaminantswere separated by GCxGC-TOF-MS, creating two dimen-sional substance maps including many chromatographicbands of homologous substance series and of congenergroups (Skoczynska et al. 2008). More than 400 compoundswere tentatively identified from three different solvent frac-tions of the sediments. To monitor 197 non-polar and polarcompounds defined as priority contaminants by the Europe-an Union Water Framework Directive, GC-MS/MS andUPLC-MS/MS were combined. In total, 39 target com-pounds were detected, with diuron and thiabendazolehaving the highest frequencies in WWTP effluents (Pitarchet al. 2010). Additional non-target analysis by GC-TOF-MSand UPLC-QTOF-MS revealed the occurrence of severaldozens of further trace compounds in treated and untreatedsewage.

One of the scarce attempts to utilize capillary liquid chro-matography equipped with a monolithic column for multi-residue analysis was undertaken by Moliner-Martinez et al.(2011). To increase the analytical sensitivity provided bydiode array detection, in-tube solid-phase microextraction

was employed. Injecting 4 mL of whole water samples, LODsin the range of 5–50 ng L-1 were achieved for various groupsof pesticides, including triazines, organophosphorus com-pounds, and phenylureas.

References

Abdallah MAE, Ibarra C, Neels H, Harrad S, Covaci A (2008) Com-parative evaluation of liquid chromatography–mass spectrometryfor the determination of hexabromocyclododecanes and their deg-radation products in indoor dust. J Chromatogr A 1190:333–341

Alaee M, Arias P, Sjödin A, Bergman A (2003) An overview ofcommercially used brominated flame retardants, their applica-tions, their use patterns in different countries/regions and possiblemodes of release. Environ Int 29:683–689

Al-Odaini NA, Zakaria MP, Yaziz MI, Surif S (2010) Multi-residueanalytical method for human pharmaceuticals and synthetic hor-mones in river water and sewage effluents by solid-phase extrac-tion and liquid-chromatography–tandem mass spectrometry. JChromatogr A 1217:6791–6806

Andresen JA, Grundmann A, Bester K (2004) Organophosphorusflame retardants and plasticizers in surface waters. Sci TotalEnviron 332:155–166

Benvenuto F, Marin JM, Sancho JV, Canobbio S, Mezzanotte V,Hernandez F (2010) Simultaneous determination of triazines andtheir main transformation products in surface and urban wastewa-ter by ultra-high-pressure liquid chromatography–tandem massspectrometry. Anal Bioanal Chem 397:2791–2805

Berger U, Kaiser MA, Kärrman A, Barber JL, van Leeuwen SPJ (2011)Recent developments in trace analysis of poly- and perfluoroalkylsubstances. Anal Bioanal Chem 400:1625–1635

Bester K, Huehnerfuss H, Lange W, Theobald N (1997) Results ofnon-target screening of lipophilic organic pollutants in the GermanBight I: benzothiazoles. Sci Total Environ 207:111–118

Breedveld GD, Roseth R, Sparrevik M, Hartnik T, Hem L (2003)Persistence of the de-icing additive benzotriazole at an abandonedairport. Water Air Soil Poll Focus 3:91–101

Brosillon S, Lemasle M, Renault E, Tozza D, Heim V, Laplanche A(2009) Analysis and occurrence of odorous disinfection by-products from chlorination of amino acids in three different drink-ing water treatment plants and corresponding distribution net-works. Chemosphere 77:1035–1042

Brownlee BG, Carey JH, MacInnis GA, Pellizzari IT (1992)Aquatic environmental chemistry of 2-(thiocyanomethylthio)benzothiazole and related benzothiazoles. Environ ToxicolChem 11:1153–1168

Bruzzoniti M, DeCarlo RM, Sarzanini C (2008) Determination ofsulfonic acids and alkylsulfates by ion chromatography in water.Talanta 75:734–739

Bueno MJM, Uclés S, Hernando MD, Fernández-Alba AR (2011)Development of a solvent-free method for the simultaneous iden-tification/quantification of drugs of abuse and their metabolites inenvironmental water by LC-MS/MS. Talanta 85:157–166

Calisto V, Esteves VI (2009) Psychiatric pharmaceuticals in the envi-ronment. Chemosphere 77:1257–1274

Campone L, Piccinelli AL, Östman C, Rastrelli L (2010) Determina-tion of organophosphorous flame retardants in fish tissues bymatrix solid-phase dispersion and gas chromatography. AnalBioanal Chem 397:799–806

Cancilla D, Martinez J, van Aggelen GC (1998) Detection of aircraftdeicing/antiicing fluid additives in a perched water monitoringwell at an international airport. Environ Sci Technol 32:3834–3835


Cancilla DA, Baird JC, Rosa R (2003) Detection of aircraft deicingadditives in groundwater and soil samples from Fairchild AirForce Base, a small to moderate user of deicing fluids. BullEnviron Contam Toxicol 70:868–875

Charrois JWA, Arend MW, Froese KL, Hrudey SE (2004) DetectingN-nitrosamines in drinking water at nanogram per liter levelsusing ammonia positive chemical ionization. Environ Sci Technol38:4835–4841

Charrois JWA, Boyd JM, Froese KL, Hrudey SE (2007) Occurrence ofN-nitrosamines in Alberta public drinking-water distribution sys-tems. J Environ Eng 6:103–114

Chen W-H, Young TM (2008) NDMA Formation during chlorinationand chloramination of aqueous diuron solutions. Environ SciTechnol 42:1072–1077

Cheng X, Shi H, Adams CD, Timmons T, Ma Y (2010) Simultaneousscreening of herbicide degradation byproducts in water treatmentplants using high performance liquid chromatography-tandemmass spectrometry. J Agricult Food Chem 58:4588–4593

Cherta L, Beltran J, Portolés T, Hernández F (2011) Multiclass deter-mination of 66 organic micropollutants in environmental watersamples by fast gas chromatography–mass spectrometry. AnalBioanal Chem. doi:10.1007/s00216-011-5423-3

Corsi SR, Zitomer DH, Field JA, Cancilla DA (2003) Nonylphenole-thoxylates and other additives in aircraft deicers, antiicers, andwaters receiving airport runoff. Environ Sci Technol 37:4031–4037

Covaci A, Voorspoels S, Abdallah MAE, Geens T, Harrad S, Law RJ(2009) Analytical and environmental aspects of the flame retar-dant like tetrabromobisphenol-A and its derivatives. J ChromatogrA 1216:346–363

Covaci A, Harrad S, Abdallah MAE, Ali N, Law RJ, Herzke D, de WitCA (2011) Novel brominated flame retardants: a review of theiranalysis, environmental fate and behaviour. Environ Int 37:532–556

Crey-Desbiolles C, Cavalli S, Polesello S, Valsecchi S (2009) Auto-mated determination of linear alkylbenzene sulphonate (LAS) inwastewater treatment plants effluents using online solid-phaseextraction followed by HPLC with fluorescence detection. TensidSurf Detergents 46:346–351

de Wit CA (2002) An overview of brominated flame retardants in theenvironment. Chemosphere 46:583–624

D'eon JC, Mabury SA (2011) Exploring indirect sources of humanexposure to perfluoroalkyl carboxylates (PFCAs): evaluating up-take, elimination, and biotransformation of polyfluoroalkyl phos-phate esters (PAPs) in the rat. Environ Health Persp 119:344–350

Dimitrov S, Pavlov T, Nedelcheva D, Reuschenbach P, Silvani M, BiasR, Comber M, Low L, Lee C, Parkerton T, Mekenyan O (2007) Akinetic model for predicting biodegradation. SAR QSAR EnvironRes 18:443–457

DIN 38407–41 (2011) Bestimmung ausgewählter leichtflüchtigerorganischer Verbindungen in Wasser–Verfahren mittels Gas-chromatographie und Massenspektrometrie (GC-MS) nachHeadspace-Festphasenmikroextraktion (HS-SPME). Beuth,Berlin

DIN 38407–42 (2011) Bestimmung ausgewählter polyfluorierterVerbindungen (PFC) in Wasser–Verfahren mittels Hochleistungs-Flüssigchromatographie und massenspektrometrischer Detektion(HPLC-MS/MS) nach Fest-Flüssig-Extraktion. Beuth, Berlin

Dinglasan MJA, Ye Y, Edwards EA, Mabury SA (2004) Fluorotelomeralcohol biodegradation yields poly-and perfluorinated acids. En-viron Sci Technol 38:2857–2864

Directive (2003) Directive 2003/11/EC of the European Parliament andof the Council of 6 February 2003. Official Journal L 042, 15/02/2003

Dodd MC, Kohler H-PE, von Gunten U (2009) Oxidation of antibac-terial compounds by ozone and hydroxyl radical: elimination of

biological activity during aqueous ozonation processes. EnvironSci Technol 43:2498–2504

Dodd MC, Rentsch D, Singer HP, Kohler H-PE, von Gunten U (2010)Transformation of β-lactam antibacterial agents during aqueousozonation: reaction pathways and quantitative bioassay ofbiologically-active oxidation products. Environ Sci Technol44:5940–5948

Dreyer A, Matthias V, Weinberg I, Ebinghaus R (2010) Wet depositionof poly- and perfluorinated compounds in Northern Germany.Environ Poll 158:1221–1227

Eganhouse RP, Pontolillo J, Gaines RB, Frysinger GS, Gabriel FLP,Kohler H-PE, Giger W, Barber LB (2009) Isomer-specific determi-nation of 4-nonylphenols using comprehensive two-dimensional gaschromatography/time-of-flight mass spectrometry. Environ SciTechnol 43:9306–9313

Ellis DA, Martin JW, De Silva AO, Mabury SA, Hurley MD, AndersenMPS, Wallington TJ (2004) Degradation of fluorotelomer alco-hols: a likely atmospheric source of perfluorinated carboxylicacids. Environ Sci Technol 38:3316–3321

Ellis LBM, Roe D, Wackett LP (2006) The University of Minnesotabiocatalysis/biodegradation database: The first decade. NucleicAcids Res 34:D517–D521

EU (2008) Guideline 2000/60/EG from 23 Oct. 2000, changed by. OffJ Europ Union L 348(95), 24/12/2008)

European Commission (1995) Commission regulation (EC) No 2268/95 of 27 September 1995 concerning the 2nd list of prioritysubstances as foreseen under Council Regulation (EEC) No 793/93. Off J Europ Union L 231:18–19

European Commission (2000a) Commission regulation (EC) No 2364/2000 of 25 October 2000 concerning the fourth list of prioritysubstances as foreseen under Council Regulation (EEC) No 793/93. Off J Europ Union L 273:5–7

European Commission (2000b) Directive 2000/60/EC of the EuropeanParliament and the Council of 23 October 2000 establishing aframework for community action in the field of water policy. Off JEurop Union L 327

European Commission (2004) Regulation (EC) No 648/2004 of theEuropean Parliament and of the Council of 31 March 2004 ondetergents. Off J Europ Union L 104:1–35

European Commission (2006) Directive 2006/118/EC of the EuropeanParliament and of the Council of 12th December 2006 on theprotection of ground water against pollution and deterioration. OffJ Europ Union L372/19

European Commission (2008a) EU risk assessment report: tris(2-chloro-1-methylethyl) phosphate, TCPP. May, 2008

European Commission (2008b) EU risk assessment report: tris(2-chloro-1[chloromethyl]ethyl) phosphate, TDCP. May, 2008

European Commission (2009) EU risk assessment report: tris(2-chloroethyl) phosphate, TCEP. Final approved version, July,2009

European Court of Justice (2008) Cases C-14/06 and C-295/06, Judge-ment of the Court, 1 April 2008, Directive 2002/95/EC andCommission Decision 2005/717/EC; http://curia.europa.eu(Accessed 13 May 2011)

European Flame Retardants Association (2011) Flame retardants: inte-gral to fire safety. http://www.cefic-efra.com/content/Default.asp?PageID0179. Accessed 13 November 2011

Fatta-Kassinos D, Meric S, Nikolaou A (2011a) Pharmaceuticalresidues in environmental waters and wastewater: current stateof knowledge and future research. Anal Bioanal Chem 399:251–275

Fatta-Kassinos D, Vasquez MI, Kümmerer K (2011b) Transformationproducts of pharmaceuticals in surface waters and wastewaterformed during photolysis and advanced oxidation processes—degradation, elucidation of byproducts and assessment of theirbiological potency. Chemosphere 85:693–709


http://dx.doi.org/10.1007/s00216-011-5423-3

http://curia.europa.eu

http://www.cefic-efra.com/content/Default.asp?PageID=179



Fiehn O, Reemtsma T, Jekel M (1994) Extraction and analysis ofvarious benzothiazoles from industrial wastewater. Anal ChimActa 295:297–305

Fink U, Hajduk F, Mori H, Yang W (2008) Flame retardants, specialtychemicals. SRI Consulting, December 2008

Freuze I, Brosillon S, Herman D, Laplanche A, Démocrate C, Cavard J(2004) Odorous products of the chlorination of phenylalanine inwater: formation, evolution and quantification. Environ Sci Tech-nol 38:4134–4139

Freuze I, Brosillon S, Laplanche A, Tozza D, Cavard J (2005) Effect ofchlorination on the formation of odorous disinfection by-products.Water Res 39:2636–2642

Fries E (2011) Determination of benzothiazole (BT) in untreated wastewater using polar phase stir bar sorptive extraction (SBSE) andGC-MS. Anal Chim Acta 689:65–68

Fries E, Mihajlović I (2011) Pollution of soils with organophospho-rus flame retardants and plasticizers. J Environ Monit 13:2692–2694

Fries E, Puettmann W (2001) Occurrence of organophosphate esters insurface water and ground water of Germany. J Environ Monit3:621–626

Fries E, Puettmann W (2003) Monitoring of the organophosphateesters TBP, TCEP, and TBEP in river water and ground water(Oder, Germany). J Environ Monit 5:346–352

Fries E, Klasmeier J, Gocht T (2011) Occurrence and distribution ofbenzothiazole in the Schwarzbach watershed (Germany). J Envi-ron Monit 13:2838–2843

Gallart-Ayola H, Moyano E, Galceran MT (2010) Recent advances inmass spectrometry analysis of phenolic endocrine disruptors andrelated compounds. Mass Spectrom Rev 29:776–805

García-Lopez M, Rodríguez I, Cela R (2009) Pressurized liquid extrac-tion of organophosphate triesters from sediment samples usingaqueous solutions. J Chromatogr A 1216:6986–6993

German Federal Environment Agency (2003) Evaluation from thepoint of view of health of the presence in drinking water ofsubstances that are not (yet) possible or only partially possibleto evaluate. Bundesgesundheitsblatt GesundheitsforschungGesundheitsschutz 46:249–251 (in German)

German Federal Environment Agency (2011) Risk assessment of tri-chloramine in the air of indoor swimming pools. Bundesgesund-heitsblatt Gesundheitsforschung Gesundheitsschutz 54:997–1004(in German)

Giger W (2009) Hydrophilic and amphiphilic water pollutants: usingadvanced analytical methods for classic and emerging contami-nants. Anal Bioanal Chem 393:37–44

Glassmeyer ST, Kolpin DW, Furlong ET, Focazio MT (2008) Envi-ronmental presence and persistence of pharmaceuticals: an over-view. In: Aga DS (ed) Fate of pharmaceuticals in the environmentand in water treatment systems. CRC Press, Boca Raton, pp 3–52

Godejohann M, Heintz L, Daolio C, Berset J-D, Muff D (2009)Comprehensive non-targeted analysis of contaminated groundwa-ter of a former ammunition destruction site using 1H-NMR andHPLC-SPE-NMR/TOF-MS. Environ Sci Technol 43:7055–7061

Gómez MJ, Gómez-Ramos MM, Agüera A, Mezcua M, Herrera S,Fernandez-Alba AR (2009) A new gas chromatography/massspectrometry method for the simultaneous analysis of target andnon-target organic contaminants in waters. J Chromatogr A1216:4071–4082

Gómez MJ, Gómez-Ramos MM, Malato O, Mezcua M, Férnandez-AlbaAR (2010) Rapid automated screening, identification and quantifi-cation of organic micro-contaminants and their main transformationproducts in wastewater and river waters using liquid chromatogra-phy–quadrupole–time-of-flight mass spectrometry with an accurate-mass database. J Chromatogr A 1217:7038–7054

Grigoriadou A, Schwarzbauer J, Georgakopoulos A (2008) Molecularindicators for pollution source identification in marine and

terrestrial water of the industrial area of Kavala city, NorthGreece. Environ Poll 151:231–242

Gros M, PetrovićM, Barceló D (2006) Multi-residue analytical methodsusing LC-tandem MS for the determination of pharmaceuticals inenvironmental and wastewater samples: a review. Anal BioanalChem 386:941–952

Grübel A, Schmidt W, Imhof L, Wagner M (2011) Disinfection by-products from amino acids—responsible for odour in tap water?Vom Wasser 109:75–81

Guillarme D, Schappler J, Rudaz S, Veuthey J-L (2010) Couplingultra-high-pressure liquid chromatography with mass spectrome-try. TrAC-Trend Anal Chem 29:15–27

Hao C, Zhao X, Tabe S, Yang P (2008) Optimization of a multiresidualmethod for the determination of waterborne emerging organicpollutants using solid-phase extraction and liquid chromatogra-phy/tandem mass spectrometry and isotope dilution mass spec-trometry. Environ Sci Technol 42:4068–4075

Hart DS, Davis LC, Erickson LE, Callender TM (2004) Sorption andpartitioning parameter of benzotriazole compounds. Microchem J77:9–17

Helbling DE, Hollender J, Kohler H-PE, Singer HP, Fenner K (2010a)High-throughput identification of microbial transformation prod-ucts of organic micropollutants. Environ Sci Technol 44:6621–6627

Helbling DE, Hollender J, Kohler H-PE, Fenner K (2010b) Structure-based interpretation of biotransformation pathways of amide-containing compounds in sludge-seeded bioreactors. Environ SciTechnol 44:6628–6635

Hernández F, Biglsma L, Sancho JV, Diaz R, Ibáñez M (2011) Rapidwide-scope screening of drugs of abuse, prescription drugs withpotential for abuse and their metabolites in influent and effluenturban wastewater by ultrahigh pressure liquid chromatography–quadrupole–time-of-flight mass spectrometry. Anal Chim Acta684:87–97

Hery M, Hecht G, Gerber JM, Gendre JC, Hubert G, Rebuffaud J(1995) Exposure to chloramines in the atmosphere of indoorswimming pools. Ann Occupat Hygiene 39:427–439

Hogenboom AC, van Leerdam JA, de Voogt (2009) Accurate massscreening and identification of emerging contaminants in environ-mental samples by liquid chromatography–hybrid linear ion trapOrbitrap mass spectrometry. J Chromatogr A 1216:510–519

Hoh E, Zhu L, Hites RA (2006) Dechlorane Plus, a chlorinated flameretardant, in the Great Lakes. Environ Sci Technol 40:1184–1189

Hollender J (2007) Micropollutants from urban drainage. Occurrencesin Swiss waters and evaluation. GWA 11:843–852 (in German)

Hu L, Martin HM, Arcs-Bulted O, Sugihara MN, Keatling KA,Strathmann TJ (2009) Oxidation of carbamazepine by Mn(VII) and Fe(VI): reaction kinetics and mechanism. EnvironSci Technol 43:509–515

Huy NV, Murakami M, Sakai H, Oguma K, Kosaka K, Asami M,Takizawa S (2011) Occurrence and formation potential of N-nitrosodimethylamine in ground water and river water in Tokyo.Water Res 45:3369–3377

Ibáñez M, Sancho JV, Hernández F, McMillan D, Rao R (2008) Rapidnon-target screening of organic pollutants in water by ultraper-formance liquid chromatography coupled to time-of-light massspectrometry. TrAC-Trend Anal Chem 27:481–489

International Standard ISO 25101 (2009) Water quality—determina-tion of perfluorooctanesulfonate (PFOS) and perfluorooctanoate(PFOA)—method for unfiltered samples using solid phase extrac-tion and liquid chromatography/mass spectrometry

Jahnke A, Ahrens L, Ebinghaus R, Berger U, Barber JL, Temme C(2007) An improved method for the analysis of volatile poly-fluorinated alkyl substances in environmental air samples. AnalBioanal Chem 387:965–975


Janna H, Scrimshaw MD, Williams RJ, Churchley J, Stumpter JP (2011)From dishwasher to tap? Xenobiotic substances benzotriazole andtolyltriazole in the environment. Environ Sci Technol 45:3858–3864

Jansson C, Kreuger J (2010) Multiresidue analysis of 95 pesticides atlow nanogram/liter levels in surface waters using online precon-centration and high performance liquid chromatography/tandemmass spectrometry. J AOAC Int 93:1732–1747

Jonkers N, Kohler H-PE, Dammshäuser A, Giger W (2009) Massflows of endocrine disruptors in the Glatt River during varyingweather conditions. Environ Poll 157:714–723

Jover E, Matamoros V, Bayona JM (2009) Characterization ofbenzothiazoles, benzotriazoles and benzosulfonamides inaqueous matrices by solid-phase extraction followed by com-prehensive two-dimensional gas chromatography coupled totime-of-flight mass spectrometry. J Chromatogr A 1216:4013–4019

Jurado-Sánchez B, Ballesteros E, Gallego M (2010) Screening of N-nitrosamines in tap and swimming pool waters using fast gaschromatography. J Sep Sci 33:610–616

Kawagoshi Y, Fukunaga I, Itoh H (1999) Distribution of organophos-phoric acid triesters between water and sediment at a sea-basedsolid waste disposal site. J Mat Cycles Waste 1:53–61

Kawagoshi Y, Nakamura S, Fukunaga I (2002) Degradation of organo-phosphoric esters in leachate from a sea-based solid waste disposalsite. Chemosphere 48:219–225

Kern S, Fenner K, Singer HP, Schwarzenbach RP, Hollender J (2009)Identification of transformation products of organic contaminantsin natural waters by computer-aided prediction and high resolu-tion mass spectrometry. Environ Sci Technol 43:7039–7046

Kern S, Baumgartner R, Helbling DE, Hollender J, Singer H, Loos MJ,Schwarzenbach RP, Fenner K (2010) A tiered procedure forassessing the formation of biotransformation products of pharma-ceuticals and biocides during activated sludge treatment. J EnvironMonit 12:2100–2111

Kiss A, Fries E (2009) Occurrence of benzotriazoles in the rivers ofMain, Hengstbach and Hegbach (Germany). Environ Sci PollutRes 16:702–710

Kiss A, Fries E (2012) Seasonal source influence on river mass flowsof benzotriazoles. J Environ Monit. doi:10.1039/C2EM10826G

Kloepfer A, Jekel M, Reemtsma T (2004) Determination of benzothia-zoles from complex aqueous samples by liquid chromatography–mass spectrometry following solid-phase extraction. J Chroma-togr A 1058:81–88

Kloepfer A, Jekel M, Reemtsma T (2005) Occurrence, sources, andfate of benzothiazoles in municipal wastewater treatment plants.Environ Sci Technol 39:3792–3798

Klontza EE, Konkouraki EE, Diamadopoulos E (2010) Determinationof nonylphenol ethoxylates in wastewater samples with SPME/GC-MS. Desal Water Treat 23:80–88

Kolic TM, Shen L, MacPherson K, Fayez L, Gobran T, Helm PA,Marvin CH, Arsenault G, Reiner EJ (2009) The analysis ofhalogenated flame retardants by GC-HRMS in environmentalsamples. J Chromatogr Sci 47:83–91

Kormos JL, Schulz M, Kohler H-PE, Ternes TA (2010) Biotransfor-mation of selected iodinated X-ray contrast media and character-ization of microbial transformation pathways. Environ Sci Technol44:4998–5007

Korytar P, Parera J, Leonards PEG, Santos FJ, de Boer J, BrinkmanUAT (2005) Characterization of polychlorinated n-alkanes usingcomprehensive two-dimensional gas chromatography–electron-capture negative ionization time-of-flight spectrometry. J Chro-matogr A 1086:71–82

Krauss M, Hollender J (2008) Analysis of nitrosamines in wastewater:exploring the trace level quantification capabilities of a hybridlinear ion trap/orbitrap mass spectrometer. Anal Chem 80:834–842

Krauss M, Singer HP, Hollender J (2010) LC-high resolution MS inenvironmental analysis: from target screening to the identificationof unknowns. Anal Bioanal Chem 397:943–951

Kumar A, Xagoraraki I (2010) Pharmaceuticals, personal care productsand endocrine-disrupting chemicals in U.S. surface and finisheddrinking waters: a proposed ranking system. Sci Total Environ408:5972–5989

Lara-Martin PA, Gonzalez-Mazo E, Brownawell BJ (2011) Multi-residue method for the analysis of synthetic surfactants andtheir degradation metabolites in aquatic systems by liquid chro-matography–time-of-flight-mass spectrometry. J Chromatogr A1218:4799–4807

Lee C, Schmidt C, Yoon J, von Gunten U (2007a) Oxidation of N-nitrosodimethylamine (NDMA) precursors with ozone and chlo-rine dioxide: kinetics and effect on NDMA formation potential.Environ Sci Technol 41:2056–2063

Lee C, Yoon J, von Gunten U (2007b) Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the ad-vanced oxidation process ozone/hydrogen peroxide. Water Res41:581–590

Lei YD, Wania F, Mathers D, Mabury SA (2004) Determination ofvapour pressures, octanol-air, and water-air partition coefficientsfor polyfluorinated sulfonamide, sulfonamidoethanols, and telo-mere alcohols. J Chem Eng Data 49:1013–1022

Lien G-W, Chen C-Y, Wang G-S (2009) Comparison of electro-spray ionization, atmospheric pressure chemical ionization andatmospheric pressure photoionization for determining estro-genic chemicals in water by liquid chromatography tandemmass spectrometry with chemical derivatizations. J Chromatogr A1216:956–966

Loos R, Locoro G, Comero S, Contini S, Schwesig D, Werres F, BalsaaP, Gans O, Weiss S, Blaha L, Bolchi M, Gawlik BM (2010) Pan-European survey on the occurrence of selected polar organicpersistent pollutants in ground-water. Water Res 44:4115–4126

López P, Brandsma SA, Leonards PEG, de Boer J (2009) Methods fordetermination of phenolic brominated flame retardants, and by-products, formulation intermediates and decomposition productsof brominated flame retardants in water. J Chromatogr A1216:334–345

Luo S, Fang L, Wang X, Liu H, Ouyang G, Lan C, Luan T (2010)Determination of octylphenol and nonylphenol in aqueous sampleusing simultaneous derivatization and dispersive liquid–liquidmicroextraction followed by gas chromatography–mass spec-trometry. J Chromatogr A 1217:6762–6768

Mahmoud MAM, Kärrman A, Oono S, Harada KH, Koizumi A (2009)Polyfluorinated telomers in precipitation and surface water in anurban area of Japan. Chemosphere 74:467–472

Makris KC, Snyder SA (2010) Screening of pharmaceuticals andendocrine disrupting compounds of water supplies of Cyphus.Water Sci Technol 62:2720–2728

Martin JW, Asher BJ, Beesoon S, Benskin JP, Ross MS (2010) PFOSor PreFOS? Are perfluorooctane sulfonate precursors (PreFOS)important determinants of human and environmental perfluorooc-tane sulfonate (PFOS) exposure? J Environ Monit 12:1979–2004

Martínez-Carballo E, González-Barreiro C, Sitka A, Scharf S, Gans O(2007) Determination of selected organophosphate esters in theaquatic environment of Austria. Sci Total Environ 388:290–299

Matamoros V, Jover E, Bayona JM (2009) Advances in the determi-nation of degradation intermediates of personal care products inenvironmental matrixes: a review. Anal Bioanal Chem 393:847–860

Moliner-Martinez Y, Molins-Legua C, Verdú-Andrés J, Herráez-Hernández R, Campins-Falcó P (2011) Advantages of monolithicover particulate columns for multiresidue analysis of organic pollu-tants by in-tube solid-phase microextraction coupled to capillaryliquid chromatography. J Chrom A 1218:6256–6262


http://dx.doi.org/10.1039/C2EM10826G

Möller A, Xie Z, Sturm R, Ebinghaus R (2010) Large-scale distribu-tion of Dechlorane Plus in air and seawater from the Arctic toAntarctica. Environ Sci Technol 44:8977–8982

Morales TV, Padrón MET, Ferrera ZS, Rodriguez JJS (2009) Determi-nation of alkylphenol ethoxylates and their degradation productsin liquid and solid samples. TrAc-Trend Anal Chem 28:1186–1200

Moriya Y, Shigemizu D, Hattori M, Tokimatsu T, Kotera M, Goto S,Kaneshisa M (2010) PathPred: an enzyme-catalyzed metabolicpathway prediction server. Nucleic Acids Res 38(suppl 2):W138–W143

Muellner MG, Wagner ED, McCalla K, Richardson SD, Woo Y-T,Plewa MJ (2007) Haloacetonitriles vs. regulated haloacetic acids:are nitrogen-containing DBPs more toxic? Environ Sci Technol41:645–651

Muir DCG, Yarechewski AL, Grift NP (1983) Environmental dynam-ics of phosphate esters. III. Comparison of the bioconcentration offour triaryl phosphates by fish. Chemosphere 12:155–166

Muscalu AM, Reiner EJ, Liss SN, Chen T, Ladwig G, Morse D (2011)A routine accredited method for the analysis of polychlorinatedbiphenyls, organochlorine pesticides, chlorobenzenes and screen-ing of other halogenated organics in soil, sediment and sludge byGCxGC-μECD. Anal Bioanal Chem 401:2403–2413

Nawrocki J, Andrzejewski P (2011) Nitrosamines and water. J HazardMater 189:1–18

Neumann S, Böcker S (2010) Computational mass spectrometry formetabolomics: identification of metabolites and small molecules.Anal Bioanal Chem 398:2779–2788

Ni HG, Lu FH, Luo XL, Tian HY, Zeng EY (2008) Occurrence, phasedistribution, and mass loadings of benzothiazoles in riverine run-off of the pearl river delta, China. Environ Sci Technol 42:1892–1897

Nödler K, Licha T, Bester K, Sauter M (2010) Development of a multi-residue analytical method, based on liquid chromatography–tan-dem mass spectrometry, for the simultaneous determination of 46micro-contaminants in aqueous samples. J Chromatogr A1217:6511–6521

Núnez L, Wiedmer SK, Parshintsev J, Hartonen K, Riekkola M-L,Tadeo JL, Turiel E (2009) Determination of nonylphenol andnonylphenol ethoxylates by MEKC. J Sep Sci 32:2109–2116

OxyChem (2011) Dechlorane Plus Manual, http://www.oxy.com/OurBusinesses/Chemicals/Products/Documents/dechloraneplus/dechlorane_plus.pdf (accessed 13 May 2011)

Oya M, Kosaka K, Asami M, Kunikane S (2008) Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and relatedcompounds. Chemosphere 73:1724–1730

Peng X-T, Shi Z-G, Feng Y-Q (2011) Rapid and high-throughputdetermination of cationic surfactants in environmental water samplesby automated on-line polymer monolith microextraction coupled tohigh performance liquid chromatography–mass spectrometry. JChromatogr A 1218:3588–3594

Pereira RO, de Alda ML, Joglar J, Daniel LA, Barceló D (2011)Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water. Chemosphere 84:1535–1541

Petri M, Jiang J-Q, Maier M (2010) Proficiency test of non-targetscreening with gas chromatography mass spectrometry to confirma detected contamination of raw and drinking water. Water SciTechnol 10:806–814

Petrovic M, Farré M, de Alda ML, Perez S, Postigo C, Köck M,Radjenovic J, Gros M, Barceló D (2010) Recent trends in theliquid chromatography–mass spectrometry analysis of organiccontaminants in environmental samples. J ChromA 1217:4004–4017

Pitarch E, Portolés T, Marin JM, Ibáñez M, Albarrán F, Hernández F(2010) Analytical strategy based on the use of liquid chromatog-raphy and gas chromatography with triple–quadrupole and time-

of-flight MS analyzers for investigating organic contaminants inwastewater. Anal Bioanal Chem 397:2763–2776

Pitter P, Chudoba J (1990) Biodegradability of organic substances inthe aquatic environment. CRC Press, Boca Raton

Planas C, Palacios O, Ventura F, Rivera J, Caixach J (2008) Analysis ofnitrosamines in water by automated SPE and isotope dilution GC/HRMS. Talanta 76:906–913

Portolés T, Pitarch E, López FJ, Hernández F (2011) Development andvalidation of a rapid and wide-scope qualitative screening methodfor detection and identification of organic pollutants in naturalwater and wastewater by gas chromatography time-of-flight massspectrometry. J Chromatogr A 1218:303–315

Pozzi R, Bocchini P, Pinelli F, Galletti GC (2011) Determination ofnitrosamines in water by gas chromatography/chemical ioniza-tion/selective ion trapping mass spectrometry. J Chromatogr A1218:1808–1814

Prasse C, Wagner M, Schulz R, Ternes TA (2011) Biotransformation ofthe antiviral drugs acyclovir and penciclovir in activated sludgetreatment. Environ Sci Technol 45:2761–2769

Prieto A, Schrader S, Möder M (2010) Determination of organicpriority pollutants and emerging compounds in wastewater andsnow samples using multiresidue protocols on the basis of micro-extraction by packed sorbents coupled to large volume injectiongas chromatography–mass spectrometry analysis. J Chromatogr A1217:6002–6011

Qiu XH, Hites RA (2008) Dechlorane Plus and other flame retardantsin tree bark from the Northeastern United States. Environ SciTechnol 42:31–36

Quintana JB, Rodil R, Reemtsma T, Garcia-Lopez M, Rodriguez I(2008) Organophosphorus flame retardants and plasticizers inwater and air II. Analytical methodology. TrAC-Trend Anal Chem27:904–915

Quintana JB, Rodil R, Lopez-Mahia P, Muniategui-Lorenzo S,Prada-Rodriguez D (2010) Investigating the chlorination of acidicpharmaceuticals and by-product formation aided by an experimentaldesign methodology. Water Res 44:243–255

Radjenović J, Petrović M, Barceló D (2009) Complementary massspectrometry and bioassays for evaluating pharmaceutical-transformation products in treatment of drinking water and waste-water. TrAC-Trend Anal Chem 28:562–580

Reemtsma T, Jekel M (eds) (2006) Organic pollutants in the watercycle. Wiley-VCH, Weinheim

Reemtsma T, Weiss S, Müller J, Petrovic M, González S, Barcelo D,Ventura F, Knepper TP (2006) Polar pollutants entry into thewater cycle by municipal wastewater: a European perspective.Environ Sci Technol 40:5451–5458

Reemtsma T, Quintana JB, Rodil R, García-López M, Rodríguez I(2008) Organophosphorus flame retardants and plasticizers inwater and air I. Occurrence and fate. TrAC-Trend Anal Chem27:727–737

Reemtsma T, Miehe U, Duennbier U, Jekel M (2010) Polar pollutantsin municipal wastewater and the water cycle: occurrence andremoval of benzotriazoles. Water Res 44:596–604

Richardson SD (2010) Environmental mass spectrometry: emergingcontaminants and current issues. Anal Chem 82:4742–4774

Richardson SD, Ternes TA (2011) Water analysis: emerging contami-nants and current issues. Anal Chem 83:4614–4648

Richardson SD, Plewa MJ, Wagner ED, Schoeny R, DeMarini DM(2007) Occurrence, genotoxicity, and carcinogenicity of regulatedand emerging disinfection by-products in drinking water: a reviewand roadmap for research. Mutat Res-Rev Mutat 636:178–242

Richardson SD, DeMarini DM, Kogevinas M, Fernandez P, Marco E,Lourencetti C, Balleste C, Heederik D, Meliefste K, McKagueAB, Marcos R, Font-Ribera L, Grimalt JO, Villanueva CM (2010)What is in the pool? A comprehensive identification of disinfec-tion by-products and assessment of mutagenicity of chlorinated


http://www.oxy.com/OurBusinesses/Chemicals/Products/Documents/dechloraneplus/dechlorane_plus.pdf



and brominated swimming pool water. Environ Health Persp118:1523–1530

Rodil R, Quintana JB, Lopez-Mahia P, Muniategui-Lorenzo S,Prada-Rodriguez D (2009) Multi-residue analytical method for thedetermination of emerging pollutants in water by solid-phase ex-traction and liquid chromatography–tandem mass spectrometry. JChromatogr A 1216:2958–2969

Rodríguez I, Calvo F, Quintana JB, Rubí E, Rodil R, Cela R (2006)Suitability of solid-phase microextraction for the determination oforganophosphate flame retardants and plasticizers in water samples.J Chromatogr A 1108:158–165

Rosal R, Rodriguez A, Perdigon-Melon JA, Petre A, Garcia-Calvo E,Gomez MJ, Aguera A, Fernandez-Alba AR (2010) Occurrence ofemerging pollutants in urban wastewater and their removalthrough biological treatment followed by ozonation. Water Res44:578–588

Sánchez-Avila J, Quintana J, Ventura F, Tauler R, Duarte CM, LacorteS (2010) Stir bar sorptive extraction–thermal desorption–gaschromatography–mass spectrometry: an effective tool for deter-mining persistent organic pollutants and nonyphenol in coastalwaters in compliance with existing directives. Mar Pollut Bull60:103–112

Scheurer M, Godejohann M, Wick A, Happel O, Ternes TA,Brauch H-J, Ruck WKL, Lange FT (2011) Structural elucida-tion of main ozonation products of the artificial sweetenerscyclamate and acesulfame. Environ Sci Pollut. doi:10.1007/s11536-011-0618-X

Schmalz C, Frimmel FH, Zwiener C (2011a) Trichloramine in swim-ming pools—formation and mass transfer. Water Res 45:2681–2690

Schmalz C, Wunderlich HG, Heinze R, Frimmel FH, Zwiener C,Grummt T (2011b) Application of an optimized system for thewell-defined exposure of human lung cells to trichloramine andindoor pool air. J Water Health 9:586–596

Schmidt CK, Brauch H-J (2008) N, N-dimethylsulfamide as precursorfor N-nitrosodimethylamine (NDMA) formation upon ozonationand its fate during drinking water treatment. Environ Sci Technol42:6340–6346

Schreiber MI, Mitch WA (2006) Occurrence and fate of nitrosaminesand nitrosamine precursors in wastewater-impacted surface watersusing boron as a conservative tracer. Environ Sci Technol40:3203–3210

Schwarzbauer J, Ricking M (2010) Non-target screening analysis ofriver water as a compound-related base for monitoring measures.Environ Sci Pollut Res 17:934–947

Schymanski EL, Schulze T, Hermanns J, Brack W (2011) Computertools for structure elucidation in EDA. In: Brack W (ed) Hand-book of environmental chemistry. vol 15: 167-198

Shaw SD, Blum A, Weber R, Kannan K, Rich D, Lucas D, KoshlandCP, Dobraca D, Hanson S, Birnbaum LS (2010) Halogenatedflame retardants: do the fire safety benefits justify the risks? RevEnviron Health 25:261–305

Sinclair CJ, Boxall ABA (2003) Assessing the ecotoxicity of pesticidetransformation products. Environ Sci Technol 37:4617–4625

Skoczynska E, Korytar P, de Boer J (2008) Maximizing chromato-graphic information from environmental extracts by GCxGC-TOF-MS. Environ Sci Technol 42:6611–6618

Skutlarek D, Exner M, Färber H (2006) Perfluorinated surfactants insurface and drinking waters. Environ Sci Pollut Res 13:299–307

Spies RB, Andresen BD, Rice DW (1987) Benzothiazoles in estuarinesediments as indicators of street runoff. Nature 327:697–699

Sverko E, Reiner EJ, Tomy GT, McGrindle R, Shen L, Arsenault G,Zaruk D, MacPherson K, Marvin CH, Helm PA, McCarry BE(2010) Compounds structurally related to Dechlorane Plus insediment and biota from Lake Ontario (Canada). Environ SciTechnol 44:574–579

Sverko E, Tomy GT, Reiner EJ, Li Y-F, McCarry BE, Arnot JA, LawRJ, Hites RA (2011) Dechlorane Plus and related compounds inthe environment: a review. Environ Sci Technol 45:5088–5098

Tamtam F, Mercier F, Eurin J, Chevreuil M, Le Bot B (2009) Ultraperformance liquid chromatography tandem mass spectrometryperformance evaluation for analysis of antibiotics in naturalwaters. Anal Bioanal Chem 393:1709–1718

Taniyasu S, Kannan K, So MK, Gulkowska A, Sinclair E, Okazawa T,Yamashita N (2005) Analysis of fluorotelomer alcohols, fluoro-telomer acids, and short- and long-chain perfluorinated acids inwater and biota. J Chromatogr A 1093:89–97

Terzic S, Ahel M (2011) Nontarget analysis of polar contaminants infreshwater sediments influenced by pharmaceutical industry usingultra-high-pressure liquid chromatography–quadrupole time-of-flight mass spectrometry. Environ Pollut 159:557–566

U.S. EPA (1997) Exposure factors handbook. DCN 20460. U.S. En-vironmental Protection Agency, Washington, DC

van Leerdam JA, Hogeboom AC, van der Kooi MME, de Voogt P(2009) Determination of polar 1H-benzotriazoles and benzothia-zoles in water by solid-phase extraction and liquid chromatogra-phy LTQ FT Orbitrap mass spectrometry. J Mass Spectrom282:99–107

Van Leeuwen SPJ, Swart JP, van der Veen I, de Boer J (2009) Signif-icant improvements in the analysis of perfluorinated compoundsin water and fish: results from an interlaboratory method evalua-tion study. J Chromatogr A 1216:401–409

Van Zelm R, Huijbregts MAJ, Van De Meent D (2010) Transformationproducts in the life cycle impact assessment of chemicals. EnvironSci Technol 44:1004–1009

Vazquez-Roig P, Andreu V, Blasco C, Picó Y (2009) SPE and LC-MS/MS determination of 14 illicit drugs in surface waters from theNatural Park of L'Albufera (València, Spain). Anal Bioanal Chem397:2851–2864

Vega-Morales T, Sosa-Ferrera Z, Santana-Rodriguez JJ (2010)Determination of alkylphenol polyethoxylates, bisphenol-A,17α-ethynylestradiol and 17β-estradiol and its metabolitesin sewage samples by SPE and LC/MS/MS. J Hazard Mater183:701–711

von Gunten U, Salhi E, Schmidt CK, Arnold WA (2010) Kinetics andmechanisms of N-nitrosodimethylamine formation upon ozona-tion of N, N-dimethylsulfamide-containing waters: bromide catal-ysis. Environ Sci Technol 44:5762–5768

Walse SS, Mitch WA (2008) Nitrosamine carcinogens also swim inchlorinated pools. Environ Sci Technol 42:1032–1037

Wang W, Ren S, Zhang H, Yu J, An W, Hu J, Yang M (2011)Occurrence of nine nitrosamines and secondary amines in sourcewater and drinking water: potential of secondary amines as nitro-samine precursors. Water Res 45:4930–4938

Weaver WA, Li J, Wen Y, Johnston J, Blatchley MR, Blatchley ER III(2009) Volatile disinfection by-product analysis from chlorinatedindoor swimming pools. Water Res 43:3308–3318

Weiss S, Reemtsma T (2005) Determination of benzotriazole corrosioninhibitors from aqueous environmental samples by liquid chro-matography–electrospray ionization–tandem mass spectrometry.Anal Chem 77:7415–7420

Weiss S, Jakobs J, Reemtsma T (2006) Discharge of three benzotria-zole corrosion inhibitors with municipal wastewater and improve-ments by membrane bioreactor treatment and ozonation. EnvironSci Technol 40:7193–7199

Wick A, Wagner M, Ternes TA (2011) Elucidation of the transforma-tion pathway of the opium alkaloid codeine in biological waste-water treatment. Environ Sci Technol 45:2761–2769

Yuan F, Hu C, Hu XX, Qu JH, Yang M (2009) Degradation of selectedpharmaceuticals in aqueous solution with UV and UV/H2O2.Water Res 43:1766–1774


http://dx.doi.org/10.1007/s11536-011-0618-X

http://dx.doi.org/10.1007/s11536-011-0618-X

Zhao Y-Y, Boyd J, Hrudey SE, Li X-F (2006) Characterization ofnew nitrosamines in drinking water using liquid chromatogra-phy tandem mass spectrometry. Environ Sci Technol 40:7636–7641

Zhao Y-Y, Boyd JM, Woodbeck M, Andrews RC, Qin F, Hrudey SE,Li X-F (2008) Formation of N-nitrosamines from eleven disin-fection treatments of seven different surface waters. Environ SciTechnol 42:4857–4862

Zhao YY, Liu X, Boyd JM, Qin F, Li J, Li XF (2009) Identification ofN-nitrosamines in treated drinking water using nanoelectrosprayionization high-field asymmetric waveform ion mobility spec-trometry with quadrupole time-of-flight mass spectrometry.J Chromatogr Sci 47:92–96

Zhao Y, Qin F, Boyd JM, Anichina J, Li X-F (2010) Characterizationand determination of chloro- and bromo-benzoquinones as newchlorination disinfection byproducts in drinking water. AnalChem 82:4599–4605

Zhou W-J, Boyd JM, Qin F, Hrudey SE, Li X-F (2009) Formation ofN-nitrosodiphenylamine and two new N-containing disinfectionbyproducts from chloramination of water containing diphenyl-amine. Environ Sci Technol 43:8443–8448

Zhou SN, Reiner EJ, Marvin C, Kolic T, Riddell N, Helm P, Dorman F,Misselwitz M, Brindle ID (2010) Liquid chromatography–

atmospheric pressure photoionization tandem mass spectrometryfor analysis of 36 halogenated flame retardants in fish. J Chroma-togr A 1217:633–641

Zhou Q, Gao Y, Xie G (2011) Determination of bisphenol A, 4-n-nonylphenol, and 4-tert-octylphenol by temperature-controlledionic liquid dispersive liquid-phase microextraction combinedwith high performance liquid chromatography-fluorescence de-tector. Talanta 83:1598–1602

Zwiener C (2007) Occurrence and analysis of pharmaceuticals andtheir transformation products in drinking water treatment. AnalBioanal Chem 387:1159–1162

Zwiener C, Frimmel FH (2004) LC-MS analysis in the aquatic envi-ronment and in water treatment technology—a critical review—part II: applications for emerging contaminants and related pollu-tants, microorganisms and humic acids. Anal Bioanal Chem378:862–874

Zwiener C, Richardson SD (2005) Analysis of disinfection by-productsin drinking water by LC-MS and related MS techniques. TrAC-Trend Anal Chem 24:613–621

Zwiener C, Richardson SD, De Marini DM, Grummt T, Glauner T,Frimmel FH (2007) Drowning in disinfection byproducts?Assessing swimming pool water. Environ Sci Technol 41:363–372
