Emerging Contaminants and Current Issues

REVIEW
pubs.acs.org/ac
Water Analysis: Emerging Contaminants and Current Issues

Susan D. Richardson*, and Thomas A. Ternes
National Exposure Research Laboratory, U.S. Environmental Protection Agency, Athens, Georgia 30605, United States
Federal Institute of Hydrology, Koblenz, D-56068 Germany
CONTENTS
Background
Major Analysis Trends
Sampling and Extraction Trends
Chromatography Trends
Use of Nanomaterials in Analytical Methods
Other Particularly Creative Methods
Emerging Contaminants
General Reviews
New Regulations/Regulatory Methods
New Proposed Regulation for Perchlorate in
U.S. Drinking Water
The New Contaminant Candidate List-3 (CCL-3)
The Draft Third Unregulated Contaminants
Monitoring Rule (UCMR-3)
New Regulatory Methods for Drinking Water
EPA Method 539: Hormones
EPA Method 538: Pesticides, Quinoline, and
Other Organic Contaminants
EPA Method 524.3: Purgeable Organic Compounds
EPA Method 1615: Enteroviruses and Noroviruses
Sucralose and Other Articial Sweeteners
Antimony
Nanomaterials
PFOA, PFOS, and Other Peruorinated Compounds
Pharmaceuticals and Hormones
Environmental Impacts of Pharmaceuticals
Biological Transformation Products
Elimination/Reaction During Oxidative Water
Treatment
Opiates and Other Drugs of Abuse
Antidepressants
Antiviral Drugs
Glucocorticoids
Antimycotics and Antibiotics
Thyroid Hormones
Drinking Water Analysis
Beta-Blockers
Multiresidue Methods
New SPE Materials/Procedures
New Derivatization Method
Enantiomers
r 2011 American Chemical Society
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Bioassays
Drinking Water and Swimming Pool Disinfection
By-Products
Drinking Water DBPs
Combining Chemistry with Toxicology
Discovery of New DBPs
New Methods
Near Real-Time Methods
Improved Method for Total Organic Chlorine and
Bromine
Alternative Disinfection Technologies Using Iodine,
UV, and Other Treatments
Nitrosamines
Mechanisms of Formation
DBPs of Pollutants
New Swimming Pool Research
Sunscreens/UV Filters
Brominated Flame Retardants
Benzotriazoles
Dioxane
Siloxanes
Naphthenic Acids
Musks
Pesticide Transformation Products
Perchlorate
Algal Toxins
Microorganisms
Contaminants on the Horizon: Ionic Liquids
Biographies
Acknowledgment
References
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BACKGROUND
This biennial review covers developments in water analysis for
emerging environmental contaminants over the period of
20092010. A few signicant references that appeared between
January and February 2011 are also included. Analytical Chemistrys policy is to limit reviews to a maximum of 250 signicant
Special Issue: Fundamental and Applied Reviews in Analytical
Chemistry
Published: June 14, 2011
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dx.doi.org/10.1021/ac200915r | Anal. Chem. 2011, 83, 46144648
Analytical Chemistry
Table 1. List of Acronyms
APCI
REVIEW
Table 1. Continued
atmospheric pressure chemical ionization
APPI
atmospheric pressure photoionization
BP-3
benzophenone-3
BSTFA
bis(trimethylsilyl)triuoroacetamide
CCL
DBPs
Contaminant Candidate List

disinfection byproducts
E1
estrone
E2
17-estradiol
E3
estriol
EE2
17R-ethinylestradiol
ECD
electron capture detection
EDCs
endocrine disrupting compounds
ELISA
EPA
enzyme-linked immunosorbent assay

Environmental Protection Agency
ESA
ethane sulfonic acid
ESI
electrospray ionization
FT
Fourier-transform
FTOHs
uorinated telomer alcohols
GC
gas chromatography
HAAs
haloacetic acids
HXLPP
IC
hypercrosslinked polymer resin

ion chromatography
ICP
inductively coupled plasma
IR
infrared
LC
liquid chromatography
MALDI
matrix-assisted laser desorption ionization
4-MBC
4-methylbenzylidene camphor
MCL
maximum contaminant level
MIMS
MRM
membrane introduction mass spectrometry

multiple reaction monitoring
MS
mass spectrometry
MSTFA
N-methyl-N-trimethylsilyltriuoroacetamide
MX
3-chloro-(4-dichloromethyl)-5-hydroxy-2(5H)-furanone
NCI
negative chemical ionization
NDMA
N-nitrosodimethylamine
NMR
NOM
nuclear magnetic resonance

natural organic matter
N-EtFOSAA
N-ethyl peruorooctane sulfonamide acetate
OC
octocrylene
ODPABA
octyl-dimethyl-p-aminobenzoic acid
PCBs
polychlorinated biphenyls
PBDEs
polybrominated diphenyl ethers
PFCs
peruorinated compounds
PFCAs
peruorocarboxylic acids
PFDA
peruorodecanoic acid
PFHxA
peruorohexanoic acid
PFHpA
peruoroheptanoic acid
PFNA
peruorononanoic acid
PFOA
peruorooctanoic acid
PFOS
peruorooctane sulfonate
PFOSA
peruorooctane sulfonamide
PFPrA
peruoropropanoic acid
PFUnDA
peruoroundecanoic acid
REACH
Registration, Evaluation, and Authorization of Chemicals
SPE
solid phase extraction
SPME
solid phase microextraction
THMs
trihalomethanes
TOF
time-of-ight
UCMR-3
UPLC
the third Unregulated Contaminants Monitoring Rule

ultraperformance liquid chromatography
WWTP
wastewater treatment plant
references and to mainly focus on new trends. Even with a more

narrow focus, only a small fraction of the quality research
publications could be discussed. As a result, as with the previous
review on Water Analysis in 2009,1 this review will not be
comprehensive but will highlight emerging contaminant groups
and discuss representative papers. I write a similar review article
on Environmental Mass Spectrometry, which also focuses on
emerging contaminants.2 That review article is somewhat
dierent from this one, in that it focuses on mass spectrometry
methods and applications and includes measurements of air, soil/
sediments, and biological samples, in addition to water. This
Review on Water Analysis focuses only on water measurements
and applications but includes other methodologies besides
mass spectrometry. I am excited to have Thomas Ternes join
me this year (as in 2005) to cover the section on Pharmaceuticals
and Hormones. Because Thomas is an international leader in this
area, this Review will be much better with his contribution. We
welcome any comments you have on this Review (richardson.
susan@epa.gov).
Numerous abstracts were consulted before choosing the best
representative ones to present here. Abstract searches were
carried out using Web of Science, and in many cases, full articles
were obtained. A table of acronyms is provided (Table 1) as a
quick reference to the acronyms of analytical techniques and
other terms discussed in this Review. A table of useful Websites is
also provided (Table 2).
Major Analysis Trends. One of the hottest trends is the use of
high resolution mass spectrometry (MS) with liquid chromatography (LC) to identify unknown contaminants or to provide
further selectivity for known analytes. Full scan and high resolution mass spectrometry have been used with gas chromatography
(GC) in a similar fashion for decades, enabling the identification
of many environmental contaminants. With recent instrumental
development for LC/mass spectrometers, especially time-offlight (TOF), this full scan and high resolution/accurate mass
benefit is now being utilized both for target analytes and also for
identifying nontarget analytes that are highly polar, nonvolatile,
or of high molecular weight and are not amenable to GC. As a
result, within a single analytical run, both target and nontarget
analytes can be analyzed or identified. In comparison to triple
quadrupole mass spectrometers, which operate at unit resolution
and generally in the selected reaction monitoring (SRM) or
multiple reaction monitoring (MRM) modes for specific target
analytes, TOF-mass spectrometers are capable of acquiring fullscan mass spectra at high resolution for all analytes without loss
in sensitivity. Because most TOF mass spectrometers have a
resolution of at least 10 000 at full-width-half-maximum (fwhm)
peak height, isotopic patterns are evident and empirical formulas
and chemical structures can be proposed for unknowns or
confirmed for target analytes. This also makes it possible to use
mass spectral libraries and enable the data file to be reinterrogated months later to find additional unknown contaminants.
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dx.doi.org/10.1021/ac200915r |Anal. Chem. 2011, 83, 46144648
In addition to TOF-mass spectrometers, linear ion trap-Fourier
transform (FT)-Orbitrap mass spectrometers are also now being
used for similar high resolution-full scan applications. Examples
of the use of high resolution-MS in this Review include the
identification of pharmaceutical and pesticide transformation
products and naphthenic acids.
Researchers are also increasingly using isotopically labeled
standards (deuterated or 13C-labeled) to allow more accurate
quantication in a variety of sample matrixes (especially for wastewater samples, where matrix eects and ion suppression can be
substantial). Atmospheric pressure photoionization (APPI) is also
increasingly being used with LC/MS because it provides improved
ionization for more nonpolar compounds, such as nanomaterials
(e.g., fullerenes), polybrominated diphenyl ethers (PBDEs), and
naphthenic acids discussed in this Review. Finally, nuclear magnetic
resonance (NMR) spectroscopy is increasing in use, as it can
provide detailed structural information to conrm tentative
structures proposed by LC/MS/MS. In this regard, it is increasingly used to conrm structures of pharmaceutical transformation
products. Because NMR is not as sensitive as MS, preparative LC
is often used to collect enough material in fractions to enable the
analysis of unknowns in complex environmental mixtures.
Sampling and Extraction Trends. Solid phase extraction
(SPE) remains the most popular means of extraction and
concentration, and a new SPE device called Bag extraction was
reported during the last 2 years. This bag-SPE consists of
polystyrenedivinylbenzene enclosed in a woven polyester fabric,
which can be immersed in water samples for solid phase
extraction. Measured concentrations of pharmaceuticals have been
shown to be comparable for bag-SPE vs Oasis HLB extraction.
Benefits include the ease of handling, unattended water extraction, and that no filtration is needed. In addition, new SPE
sorbents are available, including Oasis MCX and hypercrosslinked polymer resin (HXLPP) that are being used to capture a
broader range of analytes within a single extraction. Solventless
extraction techniques, such as solid phase microextraction (SPME),
single-drop microextraction (SDME), stir bar sorptive extraction,
and hollow-fiber membrane microextraction, also continue to be
used in many applications. Polar organic chemical integrative
samplers (POCIS) are also popular. These POCIS extraction
devices have membranes that allow polar contaminants to be
passively extracted from water and wastewater and can allow
higher concentration factors and a more integrated sampling (vs
spot sampling) over time.
The use of molecularly imprinted polymers (MIPs) for selective
extraction of environmental contaminants has also continued to
grow. MIPs are synthetic polymers made with specic recognition sites that are complementary in shape, size, and functional
group to the analyte of interest. The recognition sites mimic the
binding sites of antibodies and enzymes. Because they are highly
specic to the target analytes of interest, MIPs can be used to extract
and isolate them from other matrix components in a complex
mixture. MIPs have now been synthesized for a number of emerging
contaminants, including pharmaceuticals, pesticides, pesticide
metabolites, endocrine disrupting compounds (EDCs), and algal
toxins. Examples are cited in this Review for pharmaceuticals.
Chromatography Trends. The fastest growing chromatography trend continues to be the use of ultraperformance liquid
chromatography (UPLC). UPLC is a recently developed LC
technique that uses small diameter particles (typically 1.7 m) in
the stationary phase and short columns, which allow higher
pressures and, ultimately, narrower LC peaks (510 s wide). In
REVIEW
addition to providing narrow peaks and improved chromatographic separations, UPLC dramatically shortens analysis times,
often to 10 min or less. Another significant chromatography trend is
the use of two-dimensional GC (GCGC). GCGC enables
enhanced separations of complex mixtures through greater
chromatographic peak capacity and allows homologous series
of compounds to be easily identified. It also enables the detection
of trace contaminants that would not have been identified
through traditional GC. TOF-MS is often used as the detector
for GCGC because of its rapid acquisition capability. Examples
of the use of GCGC in this Review include the measurement of
benzotriazoles, benzothiazoles, and benzosulfonamides.
Use of Nanomaterials in Analytical Methods. In addition to
nanomaterials being a class of emerging contaminant, they are
also being applied in creative ways to aid in the measurement of
other emerging contaminants. For example, carbon nanohorns
were used in electrochemical immunosensors to enable the rapid
detection of microcystin-LR (an algal toxin) in water. Gold
nanoparticle labeling was also used with ICP-MS in a new method
to measure E. coli O157:H7 in water. This method took advantage of
the signal amplification property of gold nanoparticles, monoclonal antibody recognition, and the high sensitivity of ICP-MS.
Other Particularly Creative Methods. In addition to the
creative use of nanomaterials mentioned above, the last 2 years
has seen other particularly creative methods worthy of mention.
One such method involved a new microsensor array imprinted
onto ordinary compact discs (CDs) to measure microcystins in
water. Immunoreactions were detected with a DVD drive, which
displayed the readouts in minutes. This method was simple,
sensitive, and rapid and could be used in a high-throughput
capacity for field use. Another creative method for UV filters
involved the use of direct analysis in real-time (DART)-MS to
directly analyze the surface of a polydimethylsiloxane-coated stir
bar previously used to extract the UV filters from water. While
stir-bar sorptive extraction is commonly used in many environmental applications, the direct analysis of analytes sorbed onto these
stir bars is a new, creative application that makes the method much
more simple and rapid and still allows low ng/L detection limits.
Emerging Contaminants. This year, there is one new contaminant class added as a contaminant on the horizon to watch:
ionic liquids. Ionic liquids are organic salts with a low melting
point (<100 C) that are being promoted as green chemistry
replacements to traditional solvents used in industry because
they have low volatility and flammability. They are currently one
of the hottest areas in chemistry, with many papers and reviews
highlighting ionic liquids as a state-of-the-art, innovative approach to sustainable chemistry. However, there is limited
toxicity and environmental data for these new green solvents,
and there is the potential that they may pose a threat to aquatic
and terrestrial ecosystems. While not volatile, most ionic liquids
are highly water-soluble and chemically and thermally stable,
creating the potential for entry and persistence in the environment. The state-of-the-science on their environmental fate and
toxicity, along with a discussion of their properties and uses,
appears at the end of this Review.
Other emerging contaminants discussed include sucralose
(and other articial sweeteners), nanomaterials, peruorinated
compounds (PFCs), pharmaceuticals, hormones, drinking water
disinfection byproducts (DBPs), sunscreens/UV lters, brominated
ame retardants (including polybrominated diphenyl ethers),
benzotriazoles, naphthenic acids, antimony, siloxanes, musks, algal
toxins, perchlorate, dioxane, pesticide transformation products,
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REVIEW
Table 2. Useful Websites

Website
www.epa.gov
comments
U.S. EPAs Website
www.epa.gov/safewater/methods/analyticalmethods.html
U.S. EPA approved methods for drinking water compliance monitoring
www.epa.gov/microbes/ordmeth.htm
drinking water methods developed by U.S. EPAs National Exposure Research Laboratory
www.standardmethods.org/
link to Standard Methods Online
www.astm.org
link to ASTM International methods
http://ec.europa.eu/environment/chemicals/reach/reach_intro.htm
REACH Website
and microorganisms. These continue to be intense areas of

research. An ongoing trend in research for most of these
emerging contaminants continues to be investigating ways to
remove them from environmental waters (e.g., through advanced
oxidation, photolysis, microbial degradation, etc.). Because researchers often nd that the contaminants are not completely
removed with these technologies, the identication of intermediates
and degradation products becomes important, as well as the
evaluation of resulting toxicity or biological activity for the transformation products. In this regard, there are many more researchers
who are combining analytical chemistry with eects research.
GENERAL REVIEWS
This section includes general reviews relating to water analysis
and emerging contaminants. Reviews that relate to specic areas
(e.g., PFCs, pharmaceuticals, DBPs) can be found in those
specic sections. Many reviews have been published over the
last two years that relate to environmental mass spectrometry,
and a few focus specically on emerging contaminants. My other
biennial review on Environmental Mass Spectrometry published
in 2010 discussed advances in mass spectrometry research for the
same emerging contaminants discussed in this current Review,
along with melaminecyanuric acid.2
Rubio and Perez-Bendito published an excellent review on the
recent advances in environmental analysis, including discussions
of sampling and sample preparation techniques, separation and
detection techniques, calibration, and environmetrics (data
analysis).3 Emerging contaminants were the focus of several
reviews over the past 2 years. For example, Alvarez and JonesLepp published a new review on sampling and analysis of
emerging contaminants in surface water, groundwater, and soil
and sediment pore water.4 Wells et al., discussed occurrence, fate,
treatment, modeling, and toxicity/risk assessment of emerging
pollutant studies published in 2009.5 Murray et al. reviewed
occurrence and toxicity data for three classes of trace pollutants
and emerging contaminants (industrial chemicals, pesticides,
pharmaceuticals, and personal care products) and prioritized
them for potential regulation and treatment.6
Verlicchi et al. discussed hospital euents as a source of
emerging pollutants and outlined dierent treatment options for
removing them, including physicochemical treatment, biological
treatment, reverse osmosis, nanoltration, ozonation, advanced
oxidation processes, disinfection, and use of constructed wetlands.7
Contaminants highlighted included pharmaceuticals, radionuclides, solvents, and disinfectants. Snow et al. reviewed the detection,
occurrence, and fate of emerging contaminants in agricultural
environments, which included discussions of pharmaceuticals,
hormones, veterinary antibiotics, antibiotic resistant genes, and
prions.8 Matamoros et al. reviewed the advances in determining
degradation intermediates for personal care products in the
environment.9 Contaminants included stimulants, fragrances,

sunscreens, antimicrobials, and insect repellents.
Several reviews focused on LC/MS trends for measuring
emerging contaminants. For example, Petrovic et al. reviewed
LC/MS methods used for pharmaceuticals, drugs of abuse, polar
pesticides, PFCs, and nanomaterials.10 Krauss et al. reviewed the
use of LC with high resolution-MS for target screening and
identication of unknowns.11 The development of highly resolved and accurate hybrid tandem mass spectrometers, such as
quadrupole (Q)-TOF and linear ion trap/Orbitrap instruments,
as well as improved automated software, have enabled more
reliable target analysis of highly polar compounds, as well as
screening for unknowns. Similarly, Pitarch et al. discuss an
analytical strategy based on the use of LC and GC with triple
quadrupole and TOF mass spectrometers for measuring target
organic contaminants in wastewater.12 This strategy was demonstrated for 60 compounds from dierent chemical families, many
of which are priority contaminants in the European Union Water
Directive, and was also eective for identifying nontarget compounds, due to accurate mass and full scan capability of TOF-MS.
UPLC/MS was the focus of a review by Guillarme et al., who
discussed its use for analyzing environmental samples, biological
uids, foods, and plant extracts.13 Applications to metabolomics
were also highlighted. The application of capillary electrophoresis
(CE)/MS in the trace analysis of environmental and food contaminants was the focus of another review by Robledo and Smyth.14
Low molecular weight amines, nitroaromatics, alkylphosphonic
acids, azo dyes, antidepressants, and antibiotics were included.
While not reviews themselves, a few additional papers are
noteworthy for general applicability in analyzing emerging contaminants in environmental samples. Two papers focused on the
use of computer-aided techniques for identifying organic contaminants and transformation products. In the rst, Kern et al.
combined LC/high resolution-MS with a target list of predicted
microbial degradation products to screen for transformation
products of 52 pesticides, biocides, and pharmaceuticals in
surface waters from Switzerland.15 Using this procedure, 19
transformation products were identied, including some that
are rarely reported. In the second, Rosal et al. detailed the
development and interlaboratory verication of LC/MS libraries
for identifying environmental contaminants, including pesticides, illicit drugs, and pharmaceuticals.16 When comparing
library searching results, the libraries from two manufacturers
instruments exhibited dierent ion abundance ratios in their
mass spectra, but the NIST search engine match probability was
96% or greater for 64 out of 67 compounds evaluated.
NEW REGULATIONS/REGULATORY METHODS

New Proposed Regulation for Perchlorate in U.S. Drinking
Water. The big news for this year is that the U.S. Environmental
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REVIEW
Table 3. Recent U.S. Rules/Regulations

rule/regulation
Website
Stage 2 D/DBP Rule
http://water.epa.gov/lawsregs/rulesregs/sdwa/stage2/regulations.cfm
Contaminant Candidate List (CCL)-3
http://water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.cfm
Draft Third Unregulated Contaminants Monitoring

Rule (UCMR-3)
http://water.epa.gov/lawsregs/rulesregs/sdwa/ucmr/ucmr3/index.cfm
UCMR-2 national occurrence data
http://water.epa.gov/lawsregs/rulesregs/sdwa/ucmr/data.cfm#ucmr2010
Protection Agency (EPA) has decided to regulate perchlorate

under the Safe Drinking Water Act (http://water.epa.gov/
drink/contaminants/unregulated/perchlorate.cfm). This decision reverses a 2008 preliminary determination. Perchlorate is
highly water-soluble, is environmentally stable, accumulates in
plants, and is of concern because it can disrupt the thyroids
ability to produce hormones needed for normal growth and
development. As such, it has been a concern for the U.S. EPA,
dating back to 1998 when it was placed on the original Contaminant Candidate List for drinking water (CCL-1) and later on
the CCL-3. National data collected from the Unregulated Contaminants Monitoring Rule (UCMR) revealed that more than
4% of the public drinking water systems in the U.S. had
detectable perchlorate, and the U.S. EPA decided there was a
meaningful opportunity for health risk reduction for 5 to 16
million people. The U.S. EPA intends to publish the proposed
regulation for public review and comment within 24 months,
with a proposed maximum contaminant limit (MCL) at that
time. A final regulation would be promulgated within 18 months
afterward. Interestingly, two states had already regulated perchlorate earlier: California (2007), with an MCL of 6 g/L, and
Massachusetts (2006), with an MCL of 2 g/L.
Another new direction being considered by the U.S. EPA in its
new drinking water strategy is to address contaminants as groups
rather than individually. Of course, this was done in the past
somewhat with regulating trihalomethanes (THMs) and haloacetic acids (HAAs) but has not generally been used for other
contaminants. This group approach is intended to speed up
action on new and emerging threats to drinking water, and the
rst group selected for consideration is 16 volatile organic
compounds (VOCs) that may cause cancer (http://water.epa.
gov/lawsregs/rulesregs/sdwa/dwstrategy/upload/FactSheet_
DrinkingWaterStrategy_VOCs.pdf). Recent U.S. Rules and Regulations are summarized in Table 3.
The New Contaminant Candidate List-3 (CCL-3). In September 2009, the U.S. EPA published the final CCL-3, which is a
drinking water priority contaminant list for regulatory decision
making and information collection. The listed contaminants are
known to occur or anticipated to occur in drinking water systems
and will be considered for potential regulation. This final CCL-3
contains 104 chemicals or chemical groups and 12 microbial
contaminants (Table 4) and is somewhat different than the
original proposed CCL-3 in 2008. This final CCL-3 now includes
perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate
(PFOS), 3 pharmaceuticals (erythromycin, 17R-ethinylestradiol
[EE2], and nitroglycerin [also used as an explosive]), 8 hormones (17R-estradiol, 17-estradiol, equilenin, equilin, estriol,
estrone, mestranol, and norethindrone), and several DBPs
(chlorate, formaldehyde, acetaldehyde, and 5 nitrosamines), as
well as pesticides, pesticide degradation products, metals, industrial solvents/ingredients, and specific algal toxins (microcystinLR, anatoxin-a, and cylindrospermopsin). The U.S. EPA is also
currently considering available occurrence, toxicity, bioaccumulation, and other data for the chemical contaminants on the
CCL-3 to make a preliminary decision whether to regulate any
of them.
For this CCL-3 eort, there was a major change in how it was
developed. The U.S. EPA undertook a broader and more
comprehensive screening process of potential contaminants and
used a new mechanism for allowing the general public, stakeholders, agencies, and industry to nominate chemicals, microorganisms, or other materials for consideration. In the new
process, a broadly dened universe of potential drinking water
contaminants was identied, assessed, and reduced to a preliminary CCL (PCCL) using simple screening criteria that indicate
public health risk and the likelihood of occurrence in drinking
water. The PCCL contaminants were then assessed in more detail
using available occurrence and toxicity data, and a draft CCL-3
was proposed. Outside expert panels (including the Science
Advisory Board) were then asked to comment on this draft list,
and the list changed substantially following their recommendation. Further details on the CCL-3 process can be found at http://
water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.cfm.
The Draft Third Unregulated Contaminants Monitoring
Rule (UCMR-3). The Draft UCMR-3 was proposed on February
17, 2011 (http://water.epa.gov/lawsregs/rulesregs/sdwa/ucmr/
ucmr3/index.cfm) and is an updated version of the earlier
UCMR-1 (1999) and UCMR-2 (2007). Table 5 lists the contaminants proposed to be monitored under the UCMR-3, along
with their approved methods. Contaminants include hormones,
PFCs, VOCs, metals, dioxane, chlorate, and viruses. The UCMR3 requires drinking water utilities to monitor for 30 contaminants
(28 chemicals and 2 viruses) during 20132015. Twenty-four of
these contaminants are also on the CCL-3. The 6 chemicals not
on the CCL-3 include testosterone, 4-androstene-3,17-dione,
and 4 PFCs: perfluorobutanesulfonic acid (PFBS), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonic acid (PFHxS),
and perfluorononanoic acid (PFNA). The UCMR is used to
provide national occurrence data for priority unregulated contaminants for future regulatory consideration. This Rule helps to
support the Safe Drinking Water Act and Amendments, which
requires that, at least once every five years, the U.S. EPA identify a
list of no more than 30 unregulated contaminants to be monitored. The Draft UCMR-3 is divided up into two groups of
contaminants (Table 5). All public water systems serving more
than 10 000 people and a representative sample of 800 systems
serving 10 000 or fewer people are required to conduct Assessment Monitoring (List 1) during a continuous 12-month period
during January 2013December 2015. In addition, a targeted
group of 800 systems serving 1000 or fewer people will conduct
prescreen testing for two List 3 viruses during a 12-month
period from January 2013December 2015.
New Regulatory Methods for Drinking Water. Four new
drinking water methods were developed by the U.S. EPA
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Table 4. Final Contaminant Candidate List-3 (CCL-3)
REVIEW
Table 4. Continued
Hexane
Chemical Contaminants
Hydrazine
1,1,1,2-Tetrachloroethane
Mestranol
1,1-Dichloroethane
1,2,3-Trichloropropane
Methamidophos
Methanol
1,3-Butadiene
Methyl bromide (Bromomethane)
1,3-Dinitrobenzene
Methyl tert-butyl ether
1,4-Dioxane
Metolachlor
17R-Estradiol
Metolachlor ethanesulfonic acid (ESA)
1-Butanol
2-Methoxyethanol
Metolachlor oxanilic acid (OA)
2-Propen-1-ol
3-Hydroxycarbofuran
Molybdenum
Nitrobenzene
4,40 -Methylenedianiline
Nitroglycerin
Acephate
N-Methyl-2-pyrrolidone
Acetaldehyde
N-Nitrosodiethylamine (NDEA)
Acetamide
N-Nitrosodimethylamine (NDMA)
Acetochlor
Acetochlor ethanesulfonic acid (ESA)
N-Nitroso-di-n-propylamine (NDPA)
Acetochlor oxanilic acid (OA)

Acrolein
N-Nitrosopyrrolidine (NPYR)
Norethindrone (19-Norethisterone)
Alachlor ethanesulfonic acid (ESA)
n-Propylbenzene
Alachlor oxanilic acid (OA)
o-Toluidine
R-Hexachlorocyclohexane
Oxirane, methyl-
Aniline
Oxydemeton-methyl
Bensulide
Benzyl chloride
Oxyuorfen
Butylated hydroxyanisole
Captan
Peruorooctane sulfonic acid (PFOS)

Peruorooctanoic acid (PFOA)
Chlorate
Permethrin
Chloromethane (Methyl chloride)
Profenofos
Clethodim
Quinoline
Cobalt
RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine)
Cumene hydroperoxide
Cyanotoxins (Anatoxin-a, Microcystin-LR, and Cylindrospermopsin)
sec-Butylbenzene
Dicrotophos
Dimethipin
Tebuconazole
Tebufenozide
Dimethoate
Tellurium
Disulfoton
Terbufos
Diuron
Terbufos sulfone
Equilenin
Thiodicarb
Equilin
Erythromycin
Thiophanate-methyl
Estradiol (17-estradiol)
Estriol
Tribufos
Triethylamine
Estrone
Triphenyltin hydroxide (TPTH)
Ethinyl estradiol (17R-ethinyl estradiol)
Urethane
Ethoprop
Vanadium
Ethylene glycol
Vinclozolin
Ethylene oxide
Ethylene thiourea
Ziram
Molinate
N-Nitrosodiphenylamine (NDPhA)
Perchlorate
Strontium
Toluene diisocyanate
Microbial Contaminants
Fenamiphos
Germanium
Adenovirus
Caliciviruses
Halon 1011 (bromochloromethane)
Campylobacter jejuni
HCFC-22
Enterovirus
Formaldehyde
4619
Table 4. Continued
Escherichia coli (0157)
REVIEW
Table 5. Draft Unregulated Contaminants Monitoring Rule

(UCMR)-3 Contaminants and Approved Methods
Helicobacter pylori
List 1. Assessment Monitoring

Contaminant
Method
Hepatitis A virus
Legionella pneumophila
Mycobacterium avium
Hormones
Naegleria fowleri
17-Estradiol
EPA Method 539
Salmonella enterica
17R-Ethinylestradiol
EPA Method 539
Shigella sonnei
(Table 6): Method 539 (hormones), 538 (pesticides, quinoline,

and other organic contaminants), 524.3 (purgeable organic
compounds), 1615 (enteroviruses and noroviruses). These are
mostly directed toward the measurement of CCL/UCMR
chemicals in drinking water. The U.S. EPAs Office of Water
also has a nice Website that lists all EPA approved methods for
drinking water compliance, which include methods developed
for inorganics (including metals), radionuclides, and organic
contaminants (http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods.cfm). Note that this Website address is
different from past years. This Website provides a link not only to
EPA Methods but also to methods developed by ASTM International, Standard Methods, the U.S. Geological Survey (USGS),
the U.S. Department of Homeland Security, Waters Corp., and
other organizations, which are approved to use for drinking water
compliance in the United States.
EPA Method 539: Hormones. In 2010, a new EPA method
was created for measuring 7 hormones in drinking water: EPA
Method 539, Determination of Hormones in Drinking Water by
Solid phase Extraction (SPE) and Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC/ESI-MS/MS)
(http://water.epa.gov/scitech/drinkingwater/labcert/upload/
met539.pdf). The hormones include 16R-hydroxyestradiol (estriol),
17-estradiol, 17R-ethinylestradiol, testosterone, estrone,
4-androstene-3,17-dione, and equilin. Most of these hormones
are included on the U.S. EPAs new CCL-3. Detection limits
range from 0.04 to 2.9 ng/L.
EPA Method 538: Pesticides, Quinoline, and Other Organic
Contaminants. In 2009, a new EPA method was created for
measuring pesticides, quinoline, and other organic contaminants
in drinking water: EPA Method 538, Determination of Selected
Organic Contaminants in Drinking Water by Direct Aqueous
Injection-Liquid Chromatography/Tandem Mass Spectrometry
(DAI-LC/MS/MS) (www.epa.gov/microbes/Method%20538_
Final.pdf). Analytes include acephate, aldicarb, aldicarb sulfoxide,
dicrotophos, diisopropyl methylphosphonate (DIMP), fenamiphos
sulfone, methamidophos, oxidemeton-methyl, quinoline, and thiofanox. Minimum reporting levels ranged from 0.011 to 1.5 g/L.
EPA Method 524.3: Purgeable Organic Compounds. In 2009,
a new EPA method was created for measuring purgeable organic
compounds in drinking water: Measurement of Purgeable Organic
Compounds in Water by Capillary Column Gas Chromatography/
Mass Spectrometry (www.epa.gov/ogwdw000/methods/pdfs/
methods/met524-3.pdf). A total of 86 analytes can be measured
with this purge-and-trap GC/MS method, including a few new
analytes that were not part of previous versions of this method: 1,3butadiene, chlorodifluoromethane, diisopropyl ether (DIPE),
methyl acetate, tert-amyl ethyl ether (TAEE), tert-amyl methyl
ether (TAME), tert-butyl alcohol (TBA), and tert-butyl ethyl ether
(ETBE). Detection limits range from 7.7 to 140 ng/L.
(ethinyl estradiol)
16R-Hydroxyestradiol (estriol)
EPA Method 539
Equilin
EPA Method 539
Estrone
Testosterone
EPA Method 539

EPA Method 539
4-Androstene-3,17-dione
EPA Method 539
Volatile Organic Compounds

1,2,3-Trichloropropane
EPA Method 524.3
1,3-Butadiene
EPA Method 524.3
Chloromethane (methyl chloride)
EPA Method 524.3
1,1-Dichloroethane
EPA Method 524.3
n-Propylbenzene
Bromomethane (methyl bromide)
EPA Method 524.3

EPA Method 524.3
sec-Butylbenzene
EPA Method 524.3
Chlorodiuoromethane (HCFC-22)
EPA Method 524.3
Bromochloromethane (halon 1011)
EPA Method 524.3
Synthetic Organic Compounds

1,4-Dioxane
EPA Method 522

Metals
Vanadium
EPA 200.8 Rev 5.4, ASTM D5673
Molybdenum
Cobalt
EPA 200.8 Rev 5.4, ASTM D5673

EPA 200.8 Rev 5.4, ASTM D5673
Strontium
EPA 200.8 Rev 5.4, ASTM D5673

Oxyhalide Anion
Chlorate
EPA Method 300.1, ASTM

D658108, Standard Methods
4110D (1997)
Peruorinated Compounds
Peruorooctane sulfonate (PFOS)
EPA Method 537.1
Peruorooctanoic acid (PFOA)
EPA Method 537.1
Peruorononanoic acid (PFNA)

Peruorohexane sulfonic
EPA Method 537.1

EPA Method 537.1
acid (PFHxS)
Peruoroheptanoic
EPA Method 537.1
acid (PFHpA)
Peruorobutane sulfonic
EPA Method 537.1
acid (PFBS)
Prescreening Testing (List 3)
Contaminant
Method
Enteroviruses
EPA Method 1615
Noroviruses
EPA Method 1615
EPA Method 1615: Enteroviruses and Noroviruses. In

December 2010, a new EPA method was created for measuring
enteroviruses and noroviruses in water (http://www.regulations.
4620
REVIEW
Table 6. New Regulatory Methods

method
analytes
Website
EPA Method 539
hormones
http://water.epa.gov/scitech/drinkingwater/labcert/upload/met539.pdf
EPA Method 538
pesticides, quinoline, and other organic contaminants
www.epa.gov/microbes/Method%20538_Final.pdf
EPA Method 524.3
purgeable organic compounds
www.epa.gov/ogwdw000/methods/pdfs/methods/met524-3.pdf
EPA Method 1615
enteroviruses and noroviruses
http://www.regulations.gov/#!documentDetail;D=EPA-HQ-OW-2009-0090-0029
gov/#!documentDetail;D=EPA-HQ-OW-2009-0090-0029).
This method uses filtration, extraction of RNA, and real-time
quantitative polymerase chain reaction (PCR) for detection.
Detection limits are reported in terms of most probable
number (MPN) of infectious units per liter; detection limits
are 0.01 MPN/L (surface water) and 0.002 MPN/L (groundwater).
SUCRALOSE AND OTHER ARTIFICIAL SWEETENERS

Sucralose (also known as Splenda or SucraPlus) is a relatively
new articial sweetener that is now widely used in North
American and Europe. It may seem like an odd compound to
include as an emerging contaminant, but it is now being found in
environmental waters and is extremely persistent (half-life up to
several years).2 It is made by chlorinating sucrose, where three
hydroxyl groups are replaced by chlorine atoms. Sucralose is heat
stable, which is why it has replaced other articial sweeteners
(such as aspartame) for baking and is now widely used in soft
drinks because of its long shelf life. So far, at least 9 research
groups have investigated its occurrence and fate in the environment: the Norwegian Institute for Air Research,2 the Swedish
Environmental Research Institute,2 and the European Commissions Joint Research Centre17 and most recently from researchers at the University of North Carolina-Wilmington,18 the Water
Technology Center in Karlsruhe, Germany,19,20 the Swiss Federal Research Station in Wadenswil, Switzerland,21 the University
of Colorado,22 and Linkoping University (Sweden) together
with the Swiss Federal Institute of Aquatic Science and Technology (EAWAG).23 In the groundbreaking multicountry study in
Europe,17 Loos et al. used a SPE-LC/negative ion-electrospray
ionization (ESI)-MS/MS method with isotope dilution to measure sucralose at a detection limit of 10 ng/L. One hundred and
twenty samples were collected from rivers in 27 European
countries, and sucralose was found up to 1 g/L, predominantly
in samples from the United Kingdom, Belgium, The Netherlands, France, Switzerland, Spain, Italy, Norway, and Sweden,
with only minor levels (<100 ng/L) detected in samples from
Germany and Eastern Europe, suggesting a lower use of sucralose
in those countries. Mead et al. presented the rst ndings of
sucralose in the United States, as well as the rst measurements in
coastal and open ocean waters.18 SPE, derivatization with Nmethyl-N-trimethylsilyltriuoroacetamide (MSTFA), and quantication by GC/MS were used to measure sucralose in estuarine
and coastal waters from North Carolina (NC), Louisiana, and the
Florida Keys. The highest concentrations were from treated
wastewater euents (119 g/L) in NC, with decreasing concentrations in the receiving waters of the Cape Fear River Estuary
(NC) (372 ng/L), and levels up to 67, 147, and 392 ng/L in
waters from the Gulf Stream, Northern Florida Keys, and Middle
Florida Keys, respectively. This study highlighted the persistence
and widespread distribution of sucralose, with incorporation into
a major oceanographic current (the Gulf Stream), where global
distribution could take place.
Scheurer et al. reported a new SPE-LC/ESI-MS/MS method

for measuring 7 articial sweeteners (sucralose, acesulfame,
cyclamate, saccharin, aspartame, neotame, and neohesperidin
dihydrochalcone (NHDEC)) in environmental waters and used
this method to measure their occurrence in German wastewater
treatment plants, surface waters, and soil aquifer treatment
euents.19 Quantication limits ranged from 1 to 10 ng/L, with
no substantial ion suppression. Four articial sweeteners
(sucralose, acesulfame, saccharin, and cyclamate) were found
in the wastewater inuent and euent samples, at concentrations
ranging from 34 to 50 g/L for acesulfame and saccharin, up to
190 g/L for cyclamate, and below 1 g/L for sucralose in
inuents. Acesulfame and sucralose were not well removed in
wastewater treatment, whereas saccharin and cyclamate were
removed at >94%. Acesulfame was more persistent during soil
aquifer treatment than in conventional wastewater treatment,
such that acesulfame was still present in groundwater after a
residence time of 1.5 year. In surface waters, acesulfame was the
predominant articial sweetener found, with concentrations
exceeding 2 g/L; saccharin and cyclamate were found at levels
between 50 and 150 ng/L, and sucralose was found at 60 to
80 ng/L, with one sample exceeding 100 ng/L.
Following this wastewater study, Scheurer et al. also investigated the eectiveness of drinking water treatment in removing
four articial sweeteners: sucralose, acesulfame, saccharin, and
cyclamate.20 Six full-scale drinking water treatment plants were
investigated, which used bank ltration, articial recharge, occulation, ozonation, granular activated carbon (GAC) ltration,
and disinfection with chlorine and chlorine dioxide. Acesulfame
and sucralose proved to be the most recalcitrant. Acesulfame was
the only articial sweetener detected in nished drinking water,
up to several hundred ng/L. Acesulfame and sucralose were not
biodegraded during river bank ltration, and sucralose was
persistent against ozone, with transformation <20% in lab and
eld tests. However, remaining levels could be subsequently
removed using GAC ltration. On the other hand, acesulfame
reacted readily with ozone, but ozone levels typically used in
drinking water treatment would only remove 1860%. The
remaining acesulfame could then be somewhat removed using
GAC ltration. Ozonation byproducts are yet to be identied.
Saccharin and cyclamate were removed completely in all drinking
water treatment plants using river bank ltration or articial
groundwater recharge. One point of interest was that the
structurally similar acesulfame and saccharin (both with a
sulfonamide moiety in their ring structures) behaved completely
dierent during ozonation, and the initial point of attack for
ozone on the molecules is not known.
Buerge et al. developed an online-SPE-LC/MS/MS method
to measure 4 articial sweeteners (sucralose, acesulfame, saccharin,
and cyclamate) in environmental waters.21 All 4 articial
sweeteners were found in most samples analyzed, with acesulfame detected at the highest levels. Acesulfame was consistently
detected in untreated and treated wastewater (1246 g/L), in
4621
most surface waters (up to 2.8 g/L), in 65% of the groundwater
samples investigated (up to 4.7 g/L), and even in several tap
water samples (up to 2.6 g/L) in Switzerland. Because of it
recalcitrance to transformation, acesulfame was viewed as an
ideal marker for the detection of domestic wastewater in
environmental waters, particularly groundwater. Using acesulfame as a chemical marker, the percent contribution of domestic
wastewater to environmental waters could be determined. For
example, acesulfame levels were used to estimate a 1020%
contribution from domestic wastewater to groundwater in the
lower Glatt valley in Switzerland. This method is sensitive
enough to detect as low as a 0.05% contribution.
Ferrer and Thurman developed a SPE-LC/TOF-MS method
to measure sucralose, aspartame, and saccharin in wastewater,
surface water, groundwater, and soft drinks.22 The presence of
the articial sweeteners could be conrmed by accurate mass
measurements. Analysis of several wastewater, surface water, and
groundwater samples revealed relatively high levels of sucralose,
up to 2.4 g/L. Sucralose was frequently detected, whereas
saccharin was only detected in one wastewater sample, and
aspartame was not detected in any samples. It is likely that
aspartame and saccharin are easily biodegraded, due to reactive
chemical moieties in these molecules. Finally, Neset et al.
combined substance-ow modeling with water and wastewater
sampling to establish the current extent of sucralose emissions
from consumption.23 Sucralose was measured in wastewater
treatment plant inuents and euents in Sweden and also
upstream and downstream of the receiving stream and in a
nearby lake. Samples were measured using a SPE-LC/OrbitrapMS/MS method. This study revealed that several small sources
contributed to the loading coming from households, small
businesses, and industry, which was in contrast to a consumption
pattern seen two years earlier.
ANTIMONY
Antimony, which can have both acute and chronic toxicity
eects, is regulated in drinking water in the United States,
Canada, Europe, and Japan at action levels ranging from 2 to 6
g/L. Antimony contamination can result from copper or lead
smelting or from petroleum reneries, but new studies have
shown that it can also leach from polyethylene terephthalate
(PET) plastic water bottles.2 Antimony trioxide is used as a
catalyst in the manufacture of PET plastics, which can contain
>100 mg/kg of antimony. Keresztes et al. used inductively
coupled plasma ICP-MS to measure antimony leaching from
PET bottles into carbonated (sparkling) and noncarbonated
(still) mineral waters purchased in Europe.24 Storage conditions
(time, temperature, exposure to light) were also investigated. In
general, antimony levels were higher in the carbonated waters,
and levels exceeded 2 g/L under extreme light and temperature
storage conditions (6070 C, 23 W daylight lamp for 116 h).
Antimony leaching varied over an order of magnitude among the
waters investigated.
Reimann used ICP-MS to investigate the type of bottle on the
leaching of antimony (and other metals/elements) into bottled
water.25 Glass bottles, hard PET bottles, and soft PET bottles of
dierent colors were investigated by purchasing bottled waters in
supermarkets across Europe, rinsing the bottles and relling with
high purity (deionized) water at pH 6.5 and also at pH 3.5 to
investigate the eect of pH. Antimony was found to have a 21
higher concentration when sold in PET bottles, but glass could
REVIEW
also leach antimony in acidied waters, up to 0.45 g/L after 150

days in a dark green glass bottle. For plastic bottles, the soft PET
bottles and dark blue hard PET bottles leached the most
antimony at near-neutral pH (6.5). Finally, Cheng et al. assessed
antimony and other metal leaching into water from plastic bottles
that had been previously recycled.26 They investigated factors
that could aect leaching, including cooling with frozen water,
heating with boiling water, microwave, low pH, outdoor sunlight
irradiation, and in-car storage. Heating and microwaving led to
the highest antimony leaching relative to controls, whereas low
pH, outdoor sunlight irradiation, and in-car storage had no
signicant eect. Results also revealed partial antimony leaching
from PET bottles comes from the plastic surface during the
manufacturing process, while major antimony leaching comes
from conditional changes.
NANOMATERIALS
There remains an ongoing research boom in the area of
nanomaterials, with many companies and universities expanding
their eorts. New university departments have been developed
around the study of nanomaterials, and government investment
in nanotechnology has dramatically increased in the last 10 years.
In my searching on Web of Science this year, nearly 5000
citations appeared in the literature for just the last 2 year period
that this Review covers. This included 565 review articles on
nanomaterials. There is even a monthly journal called ACS Nano
(created in 2008). Most nanomaterial research is centered on
developing new uses for nanomaterials and new products with
unique properties, but on the other side, there is also signicant
concern regarding nanomaterials as environmental contaminants. As such, nanomaterials are the focus of a large initiative
at the U.S. EPA, under which research on nanomaterial fate,
transport, and health eects is being conducted. Nanomaterials
are 1 to 100 nm in size and can have unique properties, including
high strength, thermal stability, low permeability, and high
conductivity. In the near future, nanomaterials are projected to
be used in areas such as chemotherapy, drug delivery, and
labeling of food pathogens (nanobarcodes). The chemical
structures of nanomaterials are highly varied, including fullerenes, nanotubes, quantum dots, metal oxanes, TiO2 nanoparticles, nanosilver, and zerovalent iron nanoparticles.
Most environmental concerns center on the potential human
and ecological eects, and most methods use techniques other
than mass spectrometry, such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic
force microscopy (AFM), quartz crystal microbalance, energy
dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy, static light scattering (SLS), particle electrophoresis,
LC/UV, Raman spectroscopy, and NMR spectroscopy. In addition, most studies are carried out in clean systems and not in
real environmental systems.
As mentioned earlier, there were numerous reviews published
for nanomaterials, even in the environmental arena. As a result,
only a very few reviews could be cited here, such that I could also
highlight new studies. In 2010, a special series of 8 nano papers
(4 reviews and 4 technical papers) was published in Journal of
Environmental Quality. Top experts in the eld led o this special
issue with a review of the environmental occurrence, behavior, fate,
and ecological eects of nanoparticles.27 Within this review article
are discussions of risks and release of engineered nanomaterials,
key research areas and needs, and sustainable development of
4622
engineered nanomaterials. Important questions raised include:
How much will be released? In which environmental compartments will they reside? What are the environmentally relevant
forms of the material? How do environmental conditions determine the engineered nanomaterial form? Lin et al. published
another review in this series on the fate and transport of
engineered nanomaterials in the environment, which included
aggregation and suspension behavior, and how factors such as
natural colloids, natural organic matter, pH, and ionic strength
can inuence this behavior.28 Future research directions and
outlook were also presented. The authors also point out how few
studies have investigated nanomaterials in the natural aquatic
environment, and how such studies are needed. Hotze et al.
reviewed nanomaterial aggregation and outlined challenges to
understanding transport and reactivity in the environment.29
Techniques for assessing the colloidal properties of engineered
nanoparticles were highlighted by Chen et al. in another review,
and they also discussed recent ndings for fullerene C60 and
multiwalled carbon nanotubes.30 Techniques discussed included
transmission electron microscopy (TEM), scanning electron
microscopy (SEM), and atomic force microscopy (AFM)
(for particle size and imaging); energy dispersive X-ray spectroscopy (EDS) (for measuring elemental bulk composition); X-ray
photoelectron spectroscopy (for characterizing surface composition and charge), particle electrophoresis (for determining a
particles migration rate and electrokinetic properties); and static
light scattering (SLS) (for studying aggregate structures), among
other techniques.
Isaacson et al. published a thorough review on the quantitative
analysis of fullerene nanomaterials, which included a report on
the state-of-the-art analytical methods for quantifying them,
analytical challenges to overcome, and how improvements in
analytical methodologies will play an essential role in advancing
our understanding of fullerene nanomaterial occurrence, transport, and eects.31 In particular, analytical methods need to
provide chemically explicit information, such as molecular weight
and the number and identity of surface functional groups (which
can be achieved with mass spectrometry), and increased availability is needed for well characterized authentic standards,
reference materials, and isotopically labeled internal standards.
Ecotoxicity and analysis of nanomaterials in the aquatic environment was the focus of another review by Farre et al.32 Ecotoxicity
data crossed several dierent species of aquatic organisms,
including zebra sh, Daphnia magna, Vibrio scheri, and rainbow
trout. Analysis techniques summarized included dynamic light
scattering (DLS), TEM, SEM, atomic absorption spectroscopy,
anodic stripping voltammetry, UVvis spectroscopy, and LC/
MS techniques. The analysis, behavior, and ecotoxicity of carbonbased nanomaterials were the focus of another review by Perez
et al., with special emphasis on surface properties and interactions with natural organic matter.33
Previous studies have investigated the release of nanosilver
from socks and other clothing treated with nanosilver; Benn
et al. followed up this early work with an investigation of
nanosilver release from many consumer products, including a
shirt, a medical mask and cloth, toothpaste, shampoo, detergent, a towel, a toy teddy bear, and two humidiers.34 Silver
concentrations ranged from 1.4 to 270 000 g Ag per g of
product. Products were washed with 500 mL of tap water to
assess potential release of silver. SEM conrmed the presence of
silver nanoparticles in most products, as well as in the wash
water samples.
REVIEW
In one of the few published MS methods for nanomaterials,

Isaacson and Bouchard used asymmetric ow eld-ow fractionation (AF4), DLS, and LC/APPI-MS to determine aggregate
size distributions of C60 fullerenes in aqueous systems.35 This is
the rst method to use AF4 for fractionating a colloidal suspension of aqueous C60, which provided improved particle size
characterization. The authors also made a strong case for the use
of MS over other detection techniques, due to the unambiguous
determination of the mass of C60 in each size fraction. With this
method, aqueous C60 aggregates were shown to contain size
distributions between 80 and 150 nM (for 58% of the mass),
<80 nm (5% of the mass), and 150 to 260 nm (14% of the mass).
Farre et al. reported the rst determination of C60 and C70
fullerenes and N-methylfulleropyrrolidine C60 in suspended
material of wastewater euents.36 Ultrasonic extraction was used
to extract the nanomaterials from suspended solids, and LC/
MS/MS was used for quantication. Fullerenes were reported to
be found in 50% of the samples analyzed from 22 wastewater
treatment plants in Catalonia (Spain), with nine samples reported in the g/L concentration range.
Quantum dots were the focus of another study by Navarro
et al. who investigated natural organic matter-mediated phase
transfer in the aquatic environment.37 This study presented the
rst evidence of the stabilization of quantum dots in water by
humic substances in real environmental samples. Holbrook et al.
reported the impact of source water quality on multiwalled
carbon nanotube coagulation.38 Results indicated that multiwalled carbon nanotube coagulation in the natural environment
is likely to be limited and that potential removal in drinking water
treatment by coagulation is likely to be highly variable, such that
other removal processes downstream, such as ltration, will be
important in their removal.
The eect of UV irradiation on nanomaterials was the focus of
several studies. For example, Hwang and Li investigated the
photolysis of aqueous C60 under environmentally relevant
conditions.39 Surface oxygenation and hydroxylation were observed after UVA irradiation, as detected using X-ray photoelectron spectroscopy (XPS) and attenuated total reectance
(ATR)-FT-infrared (IR) analysis; complete mineralization was
not observed. Qu et al. investigated aggregation behavior of nC60
nanoparticles before and after UVA irradiation.40 In NaCl
solutions, surface oxidation induced by UV irradiation increased
the nC60 stability, due to an increased negative surface charge and
reduced particle hydrophobicity. In contrast, UV irradiation
reduced nC60 stability in CaCl2, due to interactions of Ca2
with the negatively charged functional groups on the UVirradiated nC60 surface, and consequent neutralization of charge.
These results highlighted the importance of nC60 surface chemistry in its environmental transport and fate.
PFOA, PFOS, AND OTHER PERFLUORINATED

COMPOUNDS
Peruorinated compounds (PFCs), also referred to as uorotelomer acids, alcohols, and sulfonates, have been manufactured
for more than 50 years and have been used to make stain
repellents (such as polytetrauoroethylene and Teon) that
are widely applied to fabrics and carpets. They are also used in
the manufacture of paints, adhesives, waxes, polishes, metals,
electronics, re-ghting foams, and caulks, as well as grease-proof
coatings for food packaging (e.g., microwave popcorn bags,
French fry boxes, hamburger wrappers, etc.). PFCs are unusual
4623
chemically, in that they are both hydrophobic (repel water) and
lipophobic (repel lipids/grease), and they contain one of the
strongest chemical bonds (CF) known. Because of these
properties, they are highly stable in the environment (and in
biological samples) and have unique proles of distribution in the
body. During 20002002, an estimated 5 million kg/yr was
produced worldwide, with 40% of this in North America. Two of
these PFCs, peruorooctane sulfonate (PFOS) and peruorooctanoic acid (PFOA), have received the most attention. PFOS was
once used to make the popular Scotchgard fabric and carpet
protector, and since 2002, it is no longer manufactured in the
U.S., due to concerns about widespread global distribution in the
blood of the general population and in wildlife, including remote
locations in the Arctic and North Pacic Oceans. Like PFOS,
PFOA is ubiquitous at low levels in humans, even in those living
far from any obvious sources.1
In January 2005, the U.S. EPA issued a draft risk assessment of
the potential human health eects associated with exposure to
PFOA (www.epa.gov/oppt/pfoa/pubs/pfoarisk.html), and in
January 2006, the U.S. EPA invited PFC manufacturers to
participate in a global stewardship program on PFOA and related
chemicals (www.epa.gov/oppt/pfoa/pubs/stewardship). Participating companies agreed to reduce PFOA from emissions and
product content by 95% by 2010 and to work toward eliminating
PFOA in emissions and products by 2015. The U.S. EPA has now
listed PFOA and PFOS on the new CCL-3 (http://water.epa.
gov/scitech/drinkingwater/dws/ccl/ccl3.cfm). In Europe, the
European Food Safety Authority has established tolerable daily
intakes for PFOA and PFOS (www.efsa.europa.eu/en/efsajournal/pub/653.htm), and there are new restrictions on the use of
PFOS as part of the European Unions REACH program
(http://ec.europa.eu/enterprise/sectors/chemicals/les/reach/
restr_inventory_list_pfos_en.pdf).
Potential health concerns include developmental toxicity,
cancer, and bioaccumulation. Research questions include understanding the sources of PFOA and other PFCs, their environmental fate and transport, pathways for human exposure and
uptake, and potential health eects. It is hypothesized that the
widespread occurrence of PFOA and other uoro-acids is partly
due to the atmospheric or oceanic transport of the more volatile
uorinated telomer alcohols (FTOHs) and subsequent transformation into PFOA and other uoro-acids via metabolism and
biodegradation. Recent studies support this hypothesis. There is
also evidence that PFOA itself is volatile.
PFOS, PFOA, and other PFCs are included in the National
Health and Nutrition Examination Survey (NHANES) being
conducted by the Centers for Disease Control and Prevention
(CDC) to provide a better assessment of the distribution of these
chemicals in adults and children in the United States (www.cdc.gov/
nchs/nhanes.htm). The National Toxicology Program is also studying PFOA and several other peruorocarboxylic acids (PFCAs) and
peruorosulfonates (PFSAs) to better understand their toxicity and
persistence in human blood (http://ntp.niehs.nih.gov).
While PFOS and PFOA were the rst uorinated surfactants
to receive considerable attention, research has rapidly expanded
beyond these two contaminants to other long-chain peruorinated acids and various precursors. In addition, there is increased
focus on shorter chain forms, e.g., peruorobutanoic acid
(PFBA) and PFBS, as manufacturers are beginning to shift to
lower molecular weight PFCs. Rayne and Forest published an
extensive critical review of physicochemical properties, levels,
and patterns in waters and wastewaters and treatment methods
REVIEW
for peruoroalkylsulfonic and carboxylic acids.41 Ahrens published a critical review on the occurrence and fate of PFCs in the
aquatic environment, which also identied knowledge gaps
and presented recommendations for future work.42 These
recommendations included research on key loss processes and
deposition, the relationship between sources and aqueous environmental concentrations, solid/water partitioning or air
water exchange, transport mechanisms, and the extent to which
PFCs undergo long-range global transport, seasonality, and longterm changes, as well as the need to establish a global monitoring
program for PFCs in river water and seawater.
Martin et al. published a thought-provoking review and perspective on PFOS precursors (which the authors called PreFOS) as
determinants of human and environmental PFOS exposure.43
This PreFOS material and the fate processes that transform it
into PFOS and contribute to exposure are not well characterized.
The authors point out that the yield of PFOS from abiotic
degradation of commercially important PreFOS material is negligible, but in vivo biotransformation is important. Ocean waters
can vary in the proportion of PFOS vs PreFOS, as well as whales
and humans who are exposed in dierent regions. The authors
present two new source tracking principles, which are based on
PFOS isomer patterns and PFOS enantiomers in human serum.
New methods to measure PFCs in water include an interesting
new use of nanoparticles to extract PFCs from water. In this
method, Zhang et al. synthesized chitosan-coated octadecylfunctionalized magnetite nanoparticles and used them as an
adsorbent to extract PFCs from water.44 LC/MS/MS was used
for detection. Concentration factors of 1000 could be achieved
with 500 mL of water, and detection limits of 0.24, 0.093, 0.24,
0.14, 0.075, 0.24, and 0.17 ng/L were obtained for PFOA, PFOS,
PFNA, peruorodecanoic acid (PFDA), peruoroundecanoic
acid (PFUnDa), peruorododecanoic acid (PFDoDa), and peruorotetradecanoic acid (PFTA), respectively, in wastewater.
Willie et al. developed a new method for 14 PFCs in surface
water, seawater, and wastewater using LC/TOF-MS.45 The use
of very narrow mass tolerance windows (<10 ppm) resulted in
high selectivity for these analytes. Limits of quantication ranged
from 2 to 200 ng/L. Using this method, the authors were also
able to detect PFCs in waters from the North Sea, the Scheldt
estuary, and harbors on the Belgian coast. Another method using
automated in-tube SPME coupled to LC/MS was developed by
Saito et al. for measuring PFOA and PFOS.46 This method
oered detection limits of 1.5 and 3.2 ng/L for PFOA and PFOS,
respectively, and LC/MS separations could be achieved in 10
min for a 40 L water sample.
Tap water was the focus of new occurrence studies the past 2
years. For example, Mak et al. conducted a large multicountry
study, measuring 20 PFCs in drinking water from China, Japan,
India, the U.S., and Canada between 2006 and 2008.47 LC/ESIMS/MS was used for measurement. PFOS, PFHxS, PFBS,
peruoropropane sulfonate (PFPrS), peruoroethane sulfonate
(PFEtS), peruorooctane sulfonamide (PFOSA), N-ethyl peruorooctane sulfonamide acetate (N-EtFOSAA), PFDoDa, PFUnDa, PFDA, PFNA, PFHpA, peruorohexanoic acid (PFHxA),
peruoropentanoic acid (PFPeA), PFBA, and peruoropropanoic acid (PFPrA) were all detectable in the tap water samples.
Drinking water from Shanghai (China) contained the highest
concentrations of total PFCs (mean of 130 ng/L). Interestingly,
Beijing (China) had the lowest overall levels (mean of 0.71 ng/L),
which was attributed to the use of activated carbon in their
drinking water treatment. In general, tap water from the U.S. and
4624
Canada contained similar levels to those found in China. Levels
were low in India, but only a single tap water sample was
collected from the 3 cities in India sampled. In addition to PFOA
and PFOS, shorter-chain PFCs (including PFBA, PFBS, PFHxA,
and PFHxS) were also prevalent in drinking water. Quinete et al.
measured PFCs in tap water, surface water, and biota in Brazil.48
This study represents one of the rst to measure PFCs in water
from South America. PFOS, PFOA, and PFHxS were detected in
all drinking water samples at levels up to 6.7, 2.8, and 1.0 ng/L,
respectively. Proles were somewhat dierent from those in
other countries.
Quinones and Snyder measured PFCs in drinking water and
associated surface, ground, and wastewater in the U.S.49 Seven
drinking water plants located in dierent regions of the U.S. were
sampled 4 times a year during 2008, including some that are
highly impacted by treated wastewater. In treated wastewater, the
average total PFC concentrations ranged from 70 to 260 ng/L,
with predominant contributions from PFHxA, PFOA, and
PFOS. For drinking water plants, the plant regarded as nonimpacted (by wastewater) had no detectable PFCs, whereas
those impacted by treated wastewater had frequent detection for
PFCs. PFCs containing 8 carbons or less were the most
frequently detected in nished drinking water, and PFOA had
the highest overall concentration at any site.
Loos et al. carried out a large multicountry European study of
polar organic persistent pollutants in groundwater, which included PFCs, as well as pharmaceuticals, hormones, pesticides,
pesticide transformation products, benzotriazoles, alkylphenol
compounds, caeine, diethyltoluamide (DEET), and triclosan.50
PFOS, PFOA, PFHpA, and PFHxS were among the chemicals
detected the most often at the highest concentrations, with
maximum levels of 135, 39, 21, and 19 ng/L, respectively.
Compared to river water, groundwater was less contaminated,
in general. Interestingly, compounds found at the highest
frequency were not always those found at the highest concentrations; for example, PFOA had the highest frequency of detection
(66%), but its maximum concentration was lower than PFOS
and some other chemicals measured in this study. In another
paper, Pistocchi and Loos provided a map of European
emissions and concentrations of PFOS and PFOA.51 A spatially
distributed data set of PFOS and PFOA concentrations were
used together with average river ow to estimate their overall
aqueous emissions in Europe. The total discharge across the
whole European river network to coastal areas was estimated
to be 20 and 30 tons/year for PFOS and PFOA, respectively
(for 2007).
The ux of PFCs through wet deposition (rain) was the focus
of a study by Kwok et al., who collected samples from Japan, the
U.S., France, China, and India.52 This is one of the few studies todate to measure occurrence of PFCs in precipitation, and it
helped in understanding the scavenging of PFCs in rainwater.
Higher total PFCs were found in the rst rain even when a larger
rainfall occurred in a second event. PFPrA was detected in all of
the rain samples, and average total PFC concentrations ranged
from 1.40 to 18.1 ng/L for the 7 cities studied. The greatest levels
were found in Tsukuba, Japan, and the lowest levels were in
Patna, India. PFPrA, PFOA, and PFNA were the dominant PFCs
in Japanese and U.S. rainwater.
Eschauzier et al. published an interesting study of PFCs in
inltrated Rhine River water and rainwater in coastal dunes from
The Netherlands.53 PFBS was found at the highest concentration
of all PFCs, up to 37 ng/L in inltrated river water. These levels
REVIEW
were signicantly higher than those found in inltrated rainwater,

and it is in stark contrast to the more typical higher levels of
PFOA and PFOS generally reported in the environmental
waters. Concentrations of PFOA, PFHxA, PFHpA, PFBS, PFOS,
and PFHxS in inltrated river water showed an increasing trend
with decreasing age of water. Nakayama et al. carried out a study
of PFCs in the Upper Mississippi River Basin (U.S.), one of the
largest watersheds in the world.54 PFCs were found in 94% of the
177 samples collected, with 80% of these <10 ng/L. The most
abundant PFCs were PFBA, PFOS, PFHxA, and PFHpA; the
highest levels were from PFBA (458 ng/L), PFOS (245 ng/L),
and PFOA (125 ng/L). Relatively high levels of PFBA likely
reect a shift toward the manufacture of lower molecular
weight PFCs in the U.S. Results indicated multiple sources and
a continuous increase in PFC loading as the river owed
through the basin. Many localized areas with elevated PFC
inputs were identied. Lake Superior water was the focus of a
study by Scott et al. who investigated the trends and sources of
PFCs.55 PFOA was the major PFC in Lake Superior, with
concentrations ranging from 0.07 to 1.2 ng/L, which were
generally 1.52 greater than PFOS levels. Wastewater treatment plants contributed up to 20 higher concentrations of
PFOA relative to intake water from Lake Superior. Overall,
tributaries and precipitation were estimated to be the major
sources of PFCAs and peruoroalkanesulfonates (PFSs), and
PFCAs were found throughout the water column, into the
deepest areas of the lake.
The Atlantic Ocean was the focus of a study by Ahrens et al.,
who measured PFCs in waters collected on a sampling trip from
Las Palmas (Spain) to St. Johns (Canada) and from the Bay of
Biscay (Spain) to the South Atlantic Ocean.56 This study
provided the rst concentration data for PFOSA, PFHxA, and
PFHpA in the Atlantic Ocean. Results showed decreasing
concentrations from the Bay of Biscay to the South Atlantic
Ocean, and a concentration drop-o close to the Labrador Sea.
Maximum levels were found for PFOSA, PFOS, and PFOA at
302, 291, and 229 pg/L, respectively. In samples south of the
equator, only PFOSA was detected, and below 4 degrees South,
no PFCs were detected. Goksoyr et al. measured PFCs and other
contaminants in the Pacic Ocean during the Norwegian Tangaroa Balsa Raft expedition that crossed the Pacic (from Peru to
Polynesia) in 2006.57 Semipermeable membrane devices
(SPMDs) were used for sampling, and this raft provided a unique
opportunity for minimal disturbance of the environment during
sampling because no machinery or generators were used. This
raft was constructed of balsa from the rainforests of Ecuador
according to ancient traditions of the Peruvian Indians
(incidentally, a photo of this raft is given in the article, and it is
a must-see). Of the PFCs, only PFOS was detected in the ocean
waters at subpg/L levels. Overall, most contaminants either were
not detected or were detected at only minute levels.
Initially, PFCs were measured in the U.S., Japan, and Western
Europe, but measurements are now expanding to many other
countries, including China, India, Thailand, and Brazil. For
example, Yeung et al. measured PFCs in surface water and biota
in the Ganges River and other water bodies in India.58 PFOS was
the dominant compound found, up to 3.91 ng/L in river water.
Long-chain PFCAs were not detected in the waters, but interestingly, were found in biota.
Several fate and transport studies have also been conducted.
For example, Murakami et al. investigated sources of PFCs in
groundwater in Tokyo.59 PFOS was more abundant in groundwater
4625
than in river waters, wastewaters, and street runo, indicating
that it was likely produced by degradation of precursors. Soil
column tests also supported this. Wastewater and surface runo
contributed 5486% and 1646%, respectively, of PFCAs to
groundwater. Stemmler and Lammel investigated pathways of
PFOA to the Arctic, including oceanic currents and atmospheric
transport.60 A spacially resolved global multicompartment model
suggested that oceanic transport was the dominant source of
PFOA to the Arctic, delivering an estimated 14.8 t/a. Benskin
et al. applied an isomer proling method to assess the contribution of electrochemical and telomer manufacturing processes to
PFCs measured in North America, Asia, and Europe.61 Electrochemical uorination produces a mixture of branched and linear
isomers, whereas telomerization typically produces more linear
structures. A sensitive LC/MS/MS method was then used to
quantify these isomers to allow this source attribution. With the
exception of 3 sites in Japan, >80% of the total PFOA was from
electrochemical manufacturing.
In another study, Fromel and Knepper investigated biotransformation as a source of uorotelomer ethoxylates in the
environment.62 These compounds, which are polyethoxylated
2-peruoroalkylethanols, have been largely disregarded in previous studies of PFCs, despite their high production and application amounts. Aerobic biotransformation tests showed that a
commercial uorotelomer ethoxylate mixture rapidly transformed, with a half-life of approximately 1 day. LC/MS/MS
was used to elucidate the structures of the transformation products,
which revealed oxidation of the ethoxylate to the carboxylic acid,
followed by sequential shortening of the ethoxylate units, leading
to uorotelomer carboxylates, including a small amount of PFOA
and PFHxA. Plumlee et al. investigated the indirect photolysis
(with hydroxyl radical) of PFCs, including N-ethyl peruorooctane sulfonamidoethanol (N-EtFOSE), N-EtFOSAA, and peruorooctane sulfonamide acetate (FOSAA).63 A proposed reaction
pathway for the degradation of N-EtFOSE to other peruoroalkanesulfonamides and PFOA included oxidation and N-dealkylation steps. PFOSA and PFOA were the nal degradation
products. Indirect photolysis was suggested to be an important
pathway, due to the slow rates expected for biotransformation
and weak sorption.
Finally, Qu et al. investigated the photoreductive deuorination of PFOA in water, as a potential removal technology.64 In
these experiments, UV photolysis led to the generation of
hydrated electrons, which were able to eciently deuorinate
PFOA (98% release of uoride). Besides uoride, additional
intermediates were identied and quantied, including formic
acid, acetic acid, 6 short-chain PFCAs (C1C6), triuoromethane,
and hexauoroethane. With these data, two major deuorination
pathways were proposed (1) direct cleavage of CF bonds
attacked by hydrated electrons as the nucleophiles and (2)
stepwise removal of CF2 by UV irradiation and hydrolysis.
PHARMACEUTICALS AND HORMONES

Pharmaceuticals and hormones have become crucial emerging
contaminants, due to their presence in environmental waters
(following incomplete removal in wastewater treatment or pointsource contaminations), threat to drinking water, and concern
about possible estrogenic and other eects, both to wildlife and
humans. A major concern for pharmaceuticals also includes the
development of bacterial resistance (creation of Super Bugs)
from the release of antibiotics to the environment, and there are
REVIEW
also new concerns that antibiotics will decrease biodegradation of

leaf and other plant materials, which serves as the primary food
source for aquatic life in rivers and streams. It is estimated that
approximately 3000 dierent substances are used as pharmaceutical ingredients, including painkillers, antibiotics, antidiabetics,
betablockers, contraceptives, lipid regulators, antidepressants
and impotence drugs. However, only a very small subset of these
compounds has been investigated in environmental studies so
far. Pharmaceuticals are introduced not only by humans, but also
through veterinary use for livestock, poultry, and sh farming.
Various drugs are commonly given to farm animals to prevent
illness and disease and to increase the size of the animals. One
lingering question is whether the relative low environmental
concentration levels of pharmaceuticals (generally ng/L range)
would cause adverse eects in humans or wildlife. Pharmaceuticals and hormones are now included on the U.S. EPAs nal
CCL-3 (http://water.epa.gov/scitech/drinkingwater/dws/ccl/
ccl3.cfm). One typical pharmaceuticals (erythromycin) and
one explosive (nitroglycerin) that is also be used as pharmaceutical and nine natural and synthetic hormones (17R-ethinylestradiol [EE2], 17R-estradiol, 17-estradiol [E2], equilenin,
equilin, estriol [E3], estrone, mestranol, and norethindrone)
are included as priority drinking water contaminants, based on
health eects and occurrence in environmental waters. For the
revision of the list of priority substances within the EU water
framework directive (2000) describing the chemical status of
European rivers, streams, and lakes) two pharmaceuticals (diclofenac and ibuprofen) and two hormones (EE2 and E2) are
suggested. There are also increasing source-to-tap studies
considering the fate of pharmaceuticals from wastewaters to
river waters, to source waters, and to nished drinking water,
such that the complete cycle of pharmaceutical fate is being
considered.
Innovative analytical instrumentation, such as hybrid mass
spectrometry enables the identication and quantication of
organic pollutants including pharmaceuticals and hormones down
to the lower nanogram per liter and nanogram per kg range in
environmental matrices and drinking water. While most organic
contaminants are entering wastewater without being metabolized,
pharmaceuticals are frequently transformed in the body and a
combination of non-altered pharmaceuticals and their metabolites
are excreted by humans.65 Microbial transformation products
(TPs) of pharmaceuticals and hormones can be formed during
biological wastewater treatment, from contact with sediment and
soil, as well as during bank ltration. Furthermore, TPs can be
formed by UV irradiation in surface waters and during oxidative
treatment processes, such as ozonation and chlorine disinfection.
Still, LC/tandem-MS is the method of choice for the determination of all classes of pharmaceuticals in aqueous matrices. ESI and
APCI are the most commonly used LC interfaces. Major innovations have been made in modern hybrid mass spectrometry systems
(e.g., linear ion trap/FT-MS, Q-TOF-MS) coupled to liquid
chromatography, providing accurate masses of the analytes and
information for mass fragments, which can be used to identify the
chemical structures. Radjenovic et al. published a review of the
literature using MS to elucidate the formation of pharmaceutical
TPs during oxidative wastewater and drinking water treatment.66 A
few rapid biochemical techniques, such as biosensors and immunoassays, have also been recently developed for selected pharmaceuticals. Further innovations have been made in rapid on-line
extraction and bag extraction, as well as on-line derivatization
techniques in combination with GC/MS(/MS) detection.
4626
Environmental Impacts of Pharmaceuticals. While many
pharmaceuticals can have an acute or chronic effect on aquatic or
other organisms, most of the lowest observed effect concentrations (LOECs) are substantially above the environmental concentrations that have been observed (ng/L to low g/L).
However, there are a few notable exceptions, where chronic
toxicity LOECs approach levels observed in wastewater effluents.
For chronic toxicity, these include salicylic acid, diclofenac,
propranolol, clofibric acid, carbamazepine, and fluoxetine. For
example, for diclofenac, the LOEC for fish toxicity was in the
range of wastewater concentrations, and the LOEC of propranolol and fluoxetine for zooplankton and benthic organisms was
near the maximum measured in wastewater effluents. The
antibiotic ciprofloxacin has also been shown to have effects on
plankton and algae growth at environmentally relevant
concentrations.1 Estrogenic effects on wildlife are quite possible
with the contraceptive 17R-ethinylestradiol (EE2), as it can
induce estrogenic effects in fish at extremely low concentrations
(low and sub-ng/L). Effects include alteration of sex ratios and
sexual characteristics, and decreased egg fertilization in fish.1 An
article in Nature (Oaks et al., 2004) highlighted that residues of
veterinary used diclofenac probably caused renal failure of
vultures and hence lead to a dramatic decline (> 95 %) of the
vulture population in Pakistan.67 Experts estimate the vulture
loss at 40 million, and it is being called the worst case of wildlife
poisoning ever, far eclipsing the numbers of birds affected by
DDT a few decades ago.
Biological Transformation Products. Even though TPs have
gained increasing interest as water contaminants, only a few
studies have investigated the formation and fate of biological TPs
of pharmaceuticals in contact with biologically active matrixes,
such as activated sludge or sediments. One reason is the
challenge of structural elucidation of TPs present at low concentrations in natural matrixes. Sophisticated analytical techniques
are needed, such as hybrid high-resolution mass spectrometry
and NMR.68 Although the target compound is known, with a few
exceptions of very simple reactions (e.g., hydrolysis of amides
and esters), quadrupole-MS and even high resolution-MS (e.g.,
LC/Orbitrap-MS) are often not sufficient to obtain or confirm
chemical structures of TPs. The TP structure suggestions based
on exact masses and mass fragments have to be confirmed by
alternative analytical methods or chemical reactions specifically
altering the new functional moieties formed. Possibilities of
analytical methods include a wide variety of currently available
NMR techniques or, to a much less extent, IR spectroscopy.
However, a drawback of both techniques is the elevated quantity
and the high purity needed for isolated standards. In those cases,
where no authentic standard is available and only MS spectra of
TPs have been obtained, we might better define the suggestions
of the chemical TP structures as tentative identifications unless
further plausibility criteria are fulfilled, confirming the proposed
chemical structures. A comprehensive overview of the literature
regarding the detection and identification of pharmaceutical TPs
until 2008 is provided by Celiz et al.69
Several recent studies indicated that the majority of pharmaceutical TPs formed under aerobic conditions have a slightly
modied molecular structure featuring increased polarity, due to
the introduction of hydroxyl, carboxyl, or keto moieties.70,71 On
the basis of the similarity of their molecular structure to the
parent compound, a signicant number of TPs are expected to
possess comparable biological activity as their chemical
precursors.72 However, the enhanced polarity improves the
REVIEW
permeability of these compounds for several water treatment

processes such as adsorptive ltration (e.g., activated carbon),
underground soil passage, or bank ltration. As consequence, the
likelihood increases that TPs are contaminating groundwater and
drinking water.73
Several enzyme-catalyzed reactions are quite commonly involved in the transformation of pharmaceuticals: mono- and
dihydroxylation, alcohol and aldehyde oxidation, ester and amide
hydrolysis, N-dealkylation, N-deacetylation, and decarboxylation. For the rst time, Radjenovic et al. have elucidated the
amide hydrolysis of the betablocker atenolol to atenolol acid and the
hydroxylation of the hypoglycemic agent glibenclamide in contact with activated sludge. LC/Qq-TOF-MS and LC/Qq-linear
ion trap-MS techniques were used for measurement.74 Helbling
et al. reported for the rst time the amide hydrolysis of the
antiepileptic levitiracetam by LC/Orbitrap-MS.75 Furthermore,
they found in contact with activated sludge the demethylation of
diazepam, which is already known from human metabolism, as
well as the hydroxylation of diazepam. By the same authors, TPs
of the antihypertensive valsertan were identied using LC/
Orbitrap-MS. Transformation took place by amide hydrolysis,
transamination, and subsequent oxidation to a carboxylic acid.
Trautwein et al. described the dealkylation of the antihypertensive verapamil76 using LC/ion trap-MS, and Kern et al. showed,
in addition to verapamil, the dealkylation of the antidepressant
venlaaxine by LC/Orbitrap-MS.77 Calza et al. reported the
identication of 11 TPs of the antibiotic spiramycin by LC/MS/
MS in river water by hydroxylation, N-demethylation, and
cleavage of sugar moieties.78 Using LC/Qq-TOF-MS, Kosjek
et al. reported the identication of 2 TPs for diclofenac during
nitrication formed by (a) decarboxylation and (b) amide
formation, as well as the formation of p-chlorophenol from the
ether cleavage of clobric acid.79 The oxidation of the antihistamine ranitidin at the amine and the thiol moiety forming two TPs
was reported by Kern et al. using LC/Orbitrap-MS.80 Applying
LC/Qq-linear ion trap-MS and 1H and 13C NMR, Schulz et al.81
and Kormos et al.68,73 identied 46 TPs from four X-ray contrast
media (iopromide, iomeprol, iopamidol, and iohexol) formed by
N-dealkylation, N-deacetylation, oxidation, and decarboxylation.
Twelve of these TPs have been reported in surface water,
groundwater, and drinking water, up to several hundreds of ng/L.
O-Desmethylnaproxen, the main metabolite of naproxen, was
identied by enantioselective-GC/MS in surface water and wastewater treatment plant (WWTP) euents at high ng/L levels.
Prasse et al. reported the biotransformation of the two antiviral
drugs, acyclovir (ACV) and penciclovir (PCV), in contact with
activated sludge.82 TPs were identied using LC/Orbitrap-MS
and 1 D (1H NMR, 13C NMR) and 2D (1H, 1H-COSY, 1H-13Cheteronuclear single quantum coherence [HSQC]) NMR spectroscopy. Structural elucidation of TPs revealed that transformation took place at the side chain, leaving the guanine moiety
unaltered. The oxidation of the primary hydroxyl group in ACV
resulted in the formation of carboxy-acyclovir. For PCV, several
enzymatic reactions occurred, such as the oxidation of terminal
hydroxyl groups and -oxidation followed by acetate cleavage.
Carboxy-ACV was detected in surface and drinking water, with
concentrations up to 3200 ng/L and 40 ng/L, respectively.
Perez-Parada et al. reported the identication of TPs of the
antibiotic amoxicillin in wastewater and surface water using LC/
Q-TOF-MS.83 The cleavage of the beta lactam ring led to
diastereomers of amoxilloic acid and amoxicillin diketopiperazine. The latter has been detected in wastewater and river water.
4627
The biological transformation of the contraceptive EE2 was
investigated by several authors.84,85 Skotnicka-Pitak et al. elucidated the formation of a TP after hydrolysis and oxidation of the
ethinyl group, as well as a hydroxylated TP by LC/ion trap-MS
and 1H NMR.84 The hydroxylated TP was also reported by Yi
and Harper, and additionally, the formation of a sulfate conjugate
using thin layer chromatography (TLC) and 1H NMR.85 Testosterone was shown to be very stable to biological degradation,
but it can be slowly transformed under solar irradiation. Several
photoproducts, such as hydroxylated derivatives resulting from
photohydration of the enone group, a spiro-compound, or
(1,5,10)-cyclopropyl-17-hydroxyandrostane, were identied
by TOF-MS, LC/MS, GC/MS, IR, and NMR.
The identication of nitrophenolic TPs of acetaminophen in
samples from full-scale WWTPs indicated that abiotic nitration is
occurring in biological wastewater treatment.86 Wick et al.
reported that the opium alkaloid codeine was transformed with
activated sludge into at least 18 TPs, when applying a multistep
approach with LC/Orbitrap-MS and 1D and 2D NMR.87 Most
of the TPs identied had only slightly modied molecular
structures, featuring double bond shifts, introduction of hydroxyl
moieties, or amine demethylation. The transformation pathway
of codeine with activated sludge was characterized by a combination of biologically and chemically mediated reactions. For
morphine, 10 TPs similar to those observed for codeine were
detected, including the main TPs morphinone and 14-hydroxymorphinone. In addition to the codeine-like TPs, an additional
nine TPs were tentatively identied for morphine, including the
morphine dimer pseudomorphine and 2-nitro-derivatives. Since
nitrophenolic compounds are frequently of toxicological concern, the role of abiotic reactions for the transformation of micropollutants deserves further attention. Finally, dihydrocodeine
was transformed into hydrocodone and isodihydrocodeine.87
Elimination/Reaction During Oxidative Water Treatment.
Several studies confirmed the efficiency of oxidation processes,
such as ozonation, advanced oxidation, or ferrate (Fe(VI)), for the
transformation of micropollutants. However, it cannot be ruled
out that oxidation leads to persistent oxidation products which are
of toxicological concern. This might be even more relevant for
chlorination, since chlorinated products frequently possess a high
toxicological potential. It is, therefore, crucial to identify the
oxidation products formed. This is only possible when advanced
mass spectrometry is used, such as LC/Q-TOF-MS, LC/OrbitrapMS, or LC/Qq-linear ion trap-MS, and NMR techniques.
Hollender et al. showed that ozone transformed most investigated pharmaceuticals and their metabolites (>70) when
applied in full-scale post-treatment of a municipal WWTP.88
This was especially true for those pharmaceuticals that contain
electron-rich moieties. Dodd et al. investigated the ozonation
TPs of beta-lactam antibiotics penicillin G and cephalexin.89 The
TPs were identied as (R)-sulfoxides, using 1H NMR, 13C NMR,
and LC/Orbitrap-MS. While penicillin G-sulfoxide was recalcitrant toward ozone but readily transformed by OH radicals
(HO), the cephalexin sulfoxides were degraded by both ozone
and OH radicals. According to Dodd et al., ozonation leads to
structural modication sucient to eliminate the antibacterial
activity for 13 antibiotics from 9 structural classes.90 Using LC/
Qq-linear ion trap-MS, Benner et al. identied a large number of
oxidation products after ozonating membrane concentrates
containing elevated concentrations of pharmaceuticals, such as
the beta-blockers propranolol and metoprolol.91,92 The betablockers were attacked by ozone at the secondary amino group,
REVIEW
yielding hydroxyl amine and aldehyde moieties, due to ringopening on the aromatic rings.
A novel oxidation technology using ferrate [Fe (VI)] in water
and wastewater treatment were reported by Lee et al.93 and
Hu et al.94 Lee et al. showed that pharmaceuticals containing
electron-rich moieties are transformed by more than 85%.93
Although Fe (VI) treatment was slightly less eective than ozone,
it has the benet of the simultaneous removal of phosphate. Hu
et al. reported that Fe (VI) was able to transform the antiepileptic
carbamazepine.94 Similar to ozone, it attacks olenic moieties in
the central heterocyclic ring, leading to ring-opening and formation of several TPs, which were identied by LC/ESI-MS/MS. The
oxidation by KMnO4 led to comparable TPs, without showing a
pH dependence. However, similar to ozonation, neither Fe(VI)
nor KMnO4 mineralized the target pharmaceuticals.
The chlorination of water containing EE2 and bromide led to
halogenated TPs, such as 4-chloro-, 2,4-dichloro-, 4-bromo-, or
2,4-dibromo-EE2.95 The authors concluded that bromine produced from oxidation of Br is mainly responsible for the
halogenation of EE2. Mash reported that the synthetic androgen
trenbolone is highly reactive toward hypochlorite.96 Chlorination leads to a large number of TPs containing up to two chlorine
atoms and up to two additional oxygen atoms. Quintana et al.
investigated the transformation of seven acidic pharmaceuticals
and two metabolites by LC/Q-TOF-MS.97 The authors observed chlorinated and brominated products of salicylic acid,
naproxen, and diclofenac. The nonhalogenated diclofenac was
further transformed by decarboxylation and hydroxylation. It is
interesting to note that halogenated derivatives of salicylic acid
were detected in wastewater and even in drinking water using
LC/MS/MS. The oxidation of seven uoroquinolones and three
structurally related amines with ClO2 revealed that the piperazine ring is the primary reactive center, leading to dealkylation,
hydroxylation, and an intramolecular ring closure at the piperazine moiety.98 The formation of halogenated products was not
observed.
Yuan et al. reported the degradation of four pharmaceuticals
(ibuprofen, phenazone, diphenhydramin, and phenytoin) by
UV/H2O2 and UV.99 Several photodegradation intermediates
were identied by GC/MS. The suitability of UV/H2O2 treatment for the removal of pharmaceuticals was also mentioned by
Rosario-Ortiz et al.100 They clearly demonstrated that the
ecacy of UV/H2O2 treatment is inuenced by the euent
organic matter and its reactivity toward OH radicals. X-ray
contrast media can be transformed by advanced oxidation
processes. The second order reaction rate constants with HO
ranged between 9.58 108 (diatrizoate) and 3.42 109 M1s1
(iopamidol).
Opiates and Other Drugs of Abuse. Several analytical
methods have been reported for the determination of drugs of
abuse in wastewater and environmental samples, primarily using
LC/MS/MS. The determination of these drugs in wastewater
and surface water can be used for environmental forensic
investigations, which is possible due to the high sensitivity of
the analytical methods.
Analytical methods and environmental occurrence of amphetamines and methamphetamines are reviewed by Boles and
Wells.101 Opioids (oxycodone and methadone) and other pharmaceuticals, such as muscle relaxants, were detected by LC/MS/
MS at elevated concentrations, up to 1700 g/L (oxycodone)
and 3800 g/L (metaxolone) in WWTP euents connected to
pharmaceutical formulation facilities.102 Median concentrations of
4628
4 compounds (methadone, oxycodone, metaxolone, and butalbital)
ranged from 3.4 to >400 g/L in this WWTP euent, indicating that
formulation facilities are a potential source for environmental pharmaceutical contamination. Vazquez-Roig et al. developed an analytical
method using SPE and LC/MS/MS for the determination of 14
drugs of abuse and their metabolites (e.g., cannabinoids, amphetamine-like compounds, opiates, and cocainics).103 The best recoveries
were obtained using Oasis HLB (200 mg), after comparing seven
dierent SPE materials. Limits of quantication of <1 ng/L were
achieved. Bijlsma et al. used Oasis MCX for SPE and UPLC/MS/MS
when determining amphetamines, amphetamine-like stimulants,
cocaine, its metabolites, and a cannabis metabolite in surface water
and wastewater.104 A direct injection method for LC/MS/MS
detection was described by Bisceglia et al., who simultaneously
determined 23 dierent drugs of abuse down to <50 ng/L.105
Gonzales-Marino et al. compared MIPs with mixed mode (Oasis
MCX) and hydrophilic balance (Oasis HLB) sorbents.106 They
concluded that MIPs rendered cleaner extracts with less matrix eects
and lower limits of detection, as well as better recoveries and precision.
The amphetamines MDA and MDMA (also known as Ecstasy)
were found after MIP extraction and LC/MS/MS detection at 420
ng/L levels. GC/MS detection after derivatization by MSTFA was
described for the determination of drugs of abuse, such as cocaine and
its metabolite benzoylecgonine. A spatial and seasonal variation of
cocaine and its metabolite benzoylecgonine was investigated in
Belgium by van Nuijs et al. using SPE and hydrophilic interaction
liquid chromatography (HILC)/MS/MS detection.107 On the
basis of the measurements, the authors found in the WWTP
Brussel-Noord no signicant dierences between cocaine consumption during the investigated seasons (summer/autumn
2007, winter 2007/2008) but a constant monthly use and
elevated peaks during the weekends.
Antidepressants. Ferrer and Thurman reported for the first
time the determination of the antidepressant lamotrigine and its
conjugate 2-N-glucruonide by SPE and LC/Q-TOF-MS in
wastewater, surface water, groundwater, and drinking water.108
A surprisingly high mean concentration of 209 ng/L of the
glucuronide conjugate was found in surface water, indicating that
this conjugate is passing WWTPs without a major cleavage. On
the basis of these results, it should be recommended to include
the conjugates (N- and O-glucuronides) in current monitoring
programs in order to get the entire loads of pharmaceuticals
present in wastewater and environmental matrixes. However, the
lack of commercially available reference standards of glucuronide
conjugates has to be solved. Antidepressants were also detected
in two U.S. streams, due to point discharges of WWTP
effluents.109 Metcalfe et al. reported the analysis of 6 antidepressants and 5 human metabolites in Canadian WWTPs and river
water.110 Maximum concentrations were found for venlafaxine
and its two metabolites O- and N-desmethyl venlafaxine, with
mean concentration levels in a municipal WWTP of 2.1 and 1.1
g/L and in rivers of 0.109 and 0.047 g/L, respectively. Calisto
et al. reported the results of a review on occurrence, persistence,
fate, toxicity, and analytical methods for psychiatric pharmaceuticals, including sedatives, aniolytics, hypnotics, and antidepressants in environmental matrixes.111 A MIP SPE was applied by
Demeestere et al. prior to the detection of antidepressants by
UPLC/MS/MS.112 Matrix effects were significantly reduced due
to the selectively of the MIP retaining serotonin reuptake
inhibitors paroxetine, fluoxetine, and citalopam.
Antiviral Drugs. A LC/ESI-MS/MS method was developed
for the determination of 9 antiviral drugs (acyclovir, abacavir,
REVIEW
lamivudine, nevirapine, oseltamivir, penciclovir, ribavirin, stavudine, and zidovudine) and one active metabolite (oseltamivir
carboxylate) in raw and treated wastewater, as well as surface
water.113 Concentrations in surface waters were mostly in the
lower ng/L range, with a maximum of 190 and 170 ng L1 for
acyclovir and zidovudine, respectively. The antiviral metabolite
oseltamivir carboxylate was detected in WWTP effluents and
rivers in Japan using UPLC/MS/MS.114 During the flu seasons,
the authors detected concentrations of oseltamivir carboxylate in
WWTP effluents up to 293 ng/L and in rivers up to 190 ng/L.
Glucocorticoids. Schriks et al. reported an innovative study
on the detection of glucocorticoids in various Dutch wastewaters
using LC/Orbitrap-MS.115 In hospital wastewater, they identified cortisone, cortisol, prednisone, prednisolone, and triamcinolone amide, with concentrations between 13 and 1918 ng/L,
concluding that triamcinolone amide, dexamethasone, and prednisolone are mainly contributing to the glucocorticogenic
activity detected in wastewater.
Antimycotics and Antibiotics. Lindberg et al. described the
analysis of six antimycotics in wastewater and sludge by SPE and
LC/MS/MS detection.116 Fluconazole was the only antimycotic
detected in raw wastewater and WWTP effluent, with concentrations ranging from 90 to 140 ng/L. In contrast, clotrimazole,
ketoconazole, and econazole were present in all sludge samples
but not in the WWTP effluents. For the determination of 6
tetracyclines and 10 of their human metabolites, an analytical
method was developed by Jia et al. using Oasis HLB extraction,
cleanup by Oasis MAX (mixed mode strong anion exchange),
and LC/MS/MS detection.117 SPME with micellar desorption
coupled to LC-fluorescence detection was applied for the
determination of five fluorochinolones.118 Limits of quantification (LOQs) of less than 1 ng/L were attained.
Thyroid Hormones. Svanfelt et al. developed an analytical
method for the determination of thyroid hormones (thyronine
derivatives) in different types of waters.119 They applied SPE and
LC/tandem-MS and attained LOQs down to 10.584.9 ng/L
for raw wastewater and 1.113.3 ng/L in tap water. In WWTP
influents and effluents, 3,5,30 ,5-tetraiodo-L-thyronine was found
at 64 and 22 ng/L, respectively.
Drinking Water Analysis. In U.S. drinking water and accompanying source waters, Benotti et al. monitored 51 emerging
pollutants between 2006 and 2007.120 Among the most frequently detected compounds were several pharmaceuticals (e.g.,
atenolol, carbamazepine, gemfibrozil, naproxen, sulfamethoxazole, and trimethoprim). Median concentrations were <10 ng/L,
except sulfamethoxazole, which was 12 ng/L.
Beta-Blockers. Seasonal variations in the occurrence and fate
of beta-blockers and the antiepileptic carbamazepine were investigated in a Swedish river-lake system by Daneshvar et al.121
They identified a significant natural attenuation of the betablocker loads in the summer time and less reduction of the loads
in the winter time, probably mainly due to biodegradation. Carbamazepine loads were not reduced at all. Scheurer et al. reported
enormous matrix effects for the determination of beta-blockers in
wastewater and sludge using LC/ESI-MS/MS.122 Only the use of
appropriate 13C- or 2H-labeled surrogate standards were able to
compensate these losses to an acceptable level.
Multiresidue Methods. Huerta-Fontela et al. reported a
multiresidue method to determine 49 pharmaceuticals and 5
metabolites using UPLC/MS/MS within 9 min.123 A rapid
screening method was described by Gros et al., who were able
to detect 73 pharmaceuticals in surface water and wastewater
4629
using LC/Qqlinear ion trap-MS.124 Loos et al. described a first
pan-European reconnaissance of the occurrence of polar organic
persistent compounds, including pharmaceuticals, in European
groundwater from 23 countries.125 Carbamazepine was the only
pharmaceutical that was present above the quality standard for
pesticides in groundwater of 0.1 g/L.
New SPE Materials/Procedures. Bag-SPE, consisting of
20 mg of polystyrenedivinylbenzene enclosed in a woven polyester fabric, was immersed into 20 mL samples for solid phase
extraction.126,127 Although recoveries were lower in comparison to Oasis HLB, the concentrations determined in raw and
treated wastewater were comparable for most pharmaceuticals
(e.g., diclofenac, metoprolol, oxazepam, cyclofosfamide, gemfibrozil,
and furosemide). Benefits the authors mentioned included the
ease of handling, unattended water extraction, and that no
filtration is needed. Ten pharmaceuticals were detected in coastal
water, with concentrations ranging from 4 to 210 ng/L. Hypercrosslinked polymer resin (HXLPP), a mixed-mode polymeric
sorbent in the form of monodisperse microspheres, was used
off-line and online.128,129 For online extraction of river water
(250 mL) and WWTP effluents (100 mL), the HXLPP was
modified with 1,2-ethylenediamine (EDA) moieties, enabling its
application as a weak anion exchange (WAX) sorbent. Online
solid phase extraction of large-volume (10 mL) injections
coupled to LC/MS/MS was applied for simultaneous quantification of 14 organic trace pollutants, including 8 pharmaceuticals.130
Detection limits ranged from 0.6 to 6 ng/L.
New Derivatization Method. Migowska et al. described a
new derivatization method using trimethylsilyldiazomethane
(TMSD) for the determination of nonsteroidal anti-inflammatory
drugs (NSAIDs) by GC/MS.131 The instrumental detection limits
of ibuprofen, ketoprofen, and naproxen were down to 2 ng.
Enantiomers. Barreiro et al. developed an analytical method to
determine the enantiomers of omeprazole in wastewater and
estuarine water samples by a two-dimensional LC system using a
column-switching method.132 An octyl restricted-access media
bovine serum albumin column (RAM-BSA C8) was used to
exclude macromolecules, followed by a polysaccharide-based chiral
column coupled to UV/vis or ion trap-MS. On the basis of the
elevated limit of detection of 5 g/L, the enantiomers were detected
in the influent of municipal WWTPs but not in the effluents.
Bioassays. Bahlmann et al. developed an enzyme-linked
immunosorbent assay (ELISA) for the detection of the antiepileptic carbamazepine in surface water and wastewater.133 The
immunoassay is based on monoclonal antibodies and a novel
enzyme conjugate that links the hapten via a hydrophilic peptide
(triglycine) spacer to horseradish peroxidase. They achieved
detection limits of 24 ng/L and a quantification range of 50
50 000 g/L. The ELISA displayed cross-reactivities for 10,11
epoxy-carbamazepine and 2-hydroxy-carbamazepine of 83 and
14%, respectively.
DRINKING WATER AND SWIMMING POOL DISINFECTION BY-PRODUCTS

Drinking Water DBPs. Drinking water DBPs are formed by
the reaction of disinfectants (chlorine, chloramines, ozone,
chlorine dioxide, etc.) with natural organic matter (NOM) and
bromide or iodide in source waters. They can also form by the
reaction of disinfectants with other organic contaminants, and
there is an increasing amount of research in this area. One
particularly important discovery in this regard was the formation
REVIEW
of high levels of N-nitrosodimethylamine (NDMA) in drinking

water that resulted from the reaction of ozone with a microbial
transformation product of a fungicide (tolylfluanid) used in
Europe.2 New areas in drinking water DBP research include
the study of highly genotoxic or carcinogenic DBPs that have
been recently identified, issues with increased formation of many
of these with the use of alternative disinfectants (e.g., chloramines and ozone), and routes of exposure besides ingestion. In
this regard, there have been several recent studies of DBPs in
swimming pools. Other trends include the development of
UPLC/MS/MS methods and the combination of analytical
chemistry with toxicology to account for toxicological effects with
DBPs measured. In addition, near real-time methods are being
developed, which could give drinking water utilities a better
understanding and control over DBP levels received by consumers and improve exposure characterizations for epidemiologic studies.
Toxicologically important DBPs include brominated, iodinated, and nitrogen-containing DBPs (N-DBPs). Brominated
DBPs are generally more carcinogenic than their chlorinated
analogues, and new research is indicating that iodinated compounds are more toxic than their brominated analogues.1 Brominated and iodinated DBPs form due to the reaction of the
disinfectant (such as chlorine) with natural bromide or iodide
present in source waters. Coastal cities, where groundwaters and
surface waters can be impacted by salt water intrusion, and some
inland locations, whose surface waters can be impacted by natural
salt deposits from ancient seas or oil-eld brines, are examples of
locations that can have high bromide and iodide levels. A
signicant proportion of the U.S. population and several other
countries now live in coastal regions that are impacted by
bromide and iodide; therefore, exposures to brominated and
iodinated DBPs are of growing interest. Early evidence in
epidemiologic studies indicates that brominated DBPs may be
associated with reproductive and developmental eects, as well as
cancer. Brominated and iodinated DBPs of interest include iodoacids, bromonitromethanes, iodo-trihalomethanes (iodo-THMs),
brominated forms of MX (3-chloro-4-(dichloromethyl)-5hydroxy-2(5H)-furanone), haloaldehydes, and haloamides. Iodinated DBPs are increased in formation with chloramination, and
bromonitromethanes are increased with the use of preozonation.
Besides haloamides, other N-DBPs of interest include NDMA
and other nitrosamines, which can form with either chloramination or chlorination (if nitrogen-containing coagulants are used
in treatment). Five nitrosamines (NDMA, N-nitrosodiethylamine, N-nitrosodipropylamine, N-nitrosodiphenylamine, and
N-nitrosopyrrolidine), as well as formaldehyde (which is a DBP
from treatment with ozone, chlorine dioxide, or chlorine), are
currently listed on the U.S. EPAs new Contaminant Candidate
List (CCL-3) (http://water.epa.gov/scitech/drinkingwater/dws/
ccl/ccl3.cfm). Chloramination has become a popular alternative
to chlorination for plants that have diculty meeting the regulations with chlorine, and its use has increased with the new Stage 2
Disinfectants (D)/DBP Rule (http://water.epa.gov/lawsregs/
rulesregs/sdwa/stage2/regulations.cfm).
Potential health risks from DBPs include cancer and reproductive/developmental eects, with bladder cancer showing the
most consistency in human epidemiologic studies from several
countries. While this Review does not typically cover toxicology
or epidemiology studies, an important epidemiologic study was
just published that bears mentioning here. Cantor et al. conducted a new case-control bladder cancer study and found an
4630
enhanced risk for bladder cancer (odds ratio 5.9) for people with
a particular genotype, which can be found in approximately 25%
of the U.S. population.134 Their study also found that dermal/
inhalation exposure from showering, bathing, and swimming was
a signicant risk factor. The ndings strengthen the hypothesis
that DBPs cause bladder cancer and suggest possible mechanisms, as well as classes likely to be implicated.
Several reviews have been published the last 2 years on DBPs.
For example, Krasner published a review on the formation and
control of emerging DBPs of health concern.135 Emerging DBPs
discussed included iodo-THMs, haloaldehydes, halonitromethanes,
and nitrosamines. Some emerging DBPs are associated with
impaired drinking water supplies (e.g., impacted by treated
wastewater, algae, and iodide). Examples of treatment techniques
to control their formation are given, including predisinfection
with chlorine, chlorine dioxide, or ozone to destroy precursors
for NDMA formation and the use of bioltration to reduce levels
of ozone DBPs. Charrois published a nice review on the analysis
of emerging DBPs in drinking water, which included detailed
discussions on dierent analytical techniques that can be used to
measure classes of emerging DBPs.136 In addition, Charrois
presented a nice historical perspective on the beginnings of this
research area, with mention to the Water Chlorination Conferences begun by Robert Jolley (also published in a series of
books), on up to the establishment of a Gordon Research
Conference on Drinking Water DBPs in 2006. Swimming pool
DBPs were also discussed.
Richardson published a new review on DBP formation and
occurrence in drinking water.137 This review provides a comprehensive listing of >600 DBPs identied from dierent disinfectants and disinfectant combinations (updating a 1998 encyclopedia article containing these original comprehensive lists) and
includes discussion of formation and occurrence, issues with
alternative disinfectants, route of exposure, and formation of
pollutant DBPs. Weinberg reviewed modern approaches for
analyzing DBPs in drinking water, which included a summary of
methods for measuring regulated and emerging DBPs, including
iodo-THMs, halonitromethanes, nitrosamines, haloacetamides,
and halofuranones.138
Combining Chemistry with Toxicology. More studies are
combining DBP identification/measurement efforts with toxicology to understand their potential health effects. For example,
Pressman et al. report the second phase of a large integrated
multidisciplinary study (called the Four Lab Study) involving the
collaboration of chemists, toxicologists, engineers, and risk
assessors from the 4 National Research Laboratories of the
U.S. EPA, as well as collaborators from academia and the water
industry.139 This paper described a new procedure for producing
chlorinated drinking water concentrates for animal toxicology
experiments, the comprehensive identification of >100 DBPs,
and quantification of 75 priority and regulated DBPs. Complex
mixtures of DBPs were produced by concentrating natural source
waters with reverse osmosis membranes, followed by addition of
bromide and treatment with chlorine. When the NOM was
concentrated first and disinfected with chlorine afterward, DBPs
(including volatiles and semivolatiles) were formed and maintained in a water matrix suitable for animal studies. DBPs were
relatively stable over the course of the animal studies (125 days)
with multiple chlorination events (every 514 days), and a
significant proportion of the total organic halogen was accounted
for through a comprehensive identification approach. Many
DBPs were reported for the first time, including previously
REVIEW
undetected and unreported haloacids and haloamides. The

new concentration procedure not only produced a concentrated
drinking water suitable for animal experiments but also provided
a greater TOC concentration factor (136), enhancing the
detection of trace DBPs that are often below detection using
conventional approaches.
Discovery of New DBPs. Increasingly, ESI-MS/MS is being
used to discover new, highly polar DBPs. For example, Qin et al.
reported the first haloquinone DBP found in drinking water, 2,6dichloro-1,4-benzoquinone, using SPE and LC/MS/MS.140
Quantitative structure-toxicity relationship (QSTR) analysis
had predicted that haloquinones are highly toxic and may be
formed during drinking water treatment. The chronic lowest
observed adverse effect levels (LOAELs) of haloquinones are
predicted to be in the low g/kg body weight per day range, which
is 1000 lower than most regulated DBPs, except bromate. This
new DBP was found in drinking water treated with chlorine and
chloramines, as well as chloramines and UV irradiation, at levels
ranging from 5.3 to 54.6 ng/L. It has a predicted LOAEL of 49
g/kg body weight per day. This effort was followed up by
another effort from Lis research group, in which 3 additional
haloquinones were identified for the first time in drinking water
using LC/ESI-MS/MS: 2,6-dichloro-3-methyl-1,4-benzoquinone, 2,3,6-trichloro-1,4-benzoquinone, and 2,6-dibromo-1,4benzoquinone.141 Following their discovery in chlorinated drinking water, they were quantified, along with 2,6-dichloro-1,4benzoquinone. Levels ranged from 0.5 to 165 ng/L. An unusual
feature about these compounds is that, using negative ion-ESI,
they form (M H) ions through a reduction step, rather than
the classic (M H) ions that are typically observed with
negative ionization. The authors used tandem-MS and accurate
mass measurements to confirm the identity of these unusual ions.
Ding and Zhang used UPLC/ESI-MS/MS to provide a more
comprehensive picture of polar iodinated DBPs formed in
drinking water.142 Precursor scans of iodine (m/z 126.9) allowed
iodinated DBPs to be detected in simulated drinking waters
treated with chlorine, monochloramine, and chlorinechloramine.
A total of 17 iodo-DBPs were tentatively identied, with chloramination producing the most iodo-DBPs, followed by chlorine
chloramine, then chlorination. Tentatively identied compounds
included iodoacetic acid, chloroiodoacetic acid, (E)- and (Z)iodobutenedioic acid, 4-iodobenzoic acid, 3-iodophthalic acid,
2,4-diiodobenzoic acid, 5,6-diiodosalicylic acid, and 5,6-diiodo-3ethylsalicylic acid. In addition, two nitrogenous iodo-DBPs were
found in chloraminated and chlorineammonia treated waters,
but the ion abundances were too low to propose structures for
them. In another paper, Zhai and Zhang developed a new ESI/
MS/MS method for dierentiating ESI adducts of common
drinking water DBPs from higher molecular weight DBPs.143
Using this method, they also proposed structures for several new
brominated DBPs in simulated drinking water. Finally, Peter and
von Gunten used SPME-GC/MS/olfactory detection to identify
2,4,6-trichloroanisole, following a taste and odor episode in a
drinking water system in Switzerland.144 This DBP has a very low
odor threshold of 30 pg/L, and it was found up to 24 ng/L in
drinking water but only in distribution systems and not in the raw
source waters or nished waters from the plant. Laboratory
studies showed that trichlorophenol was an important precursor,
chlorine played a key role as a residual disinfectant, and 2,4,6trichloroanisole was only formed in the presence of biolms.
New Methods. Several other methods have been developed
for DBPs. Shi and Adams created a rapid ion chromatography
4631
(IC)/ICP-MS method for simultaneously measuring iodoacetic
acids, bromoacetic acids, iodate, bromate, iodide, and bromide.145
Method detection limits ranged from 0.33 to 0.72 g/L for
iodinated DBPs, and 1.36 to 3.28 g/L for brominated DBPs.
However, mono-, di-, and trichlorinated species could not be
detected because the sensitivity of ICP-MS for chlorine is poor.
This method was successfully applied to measuring brominated
and iodinated DBPs in drinking water, groundwater, surface
water, and swimming pool water.
Several methods focused on derivatizing reagents to improve
the analysis/identication of DBPs. For example, Vincenti et al.
synthesized a novel derivatizing agent, 5-chloro-2,2,3,3,4,4,5,
5-octauoropentyl chloroformate (ClOFPCF), and used it for
the direct derivatization of highly polar DBPs in drinking
water.146 This derivatizing agent was specically designed to
derivatize carboxyl, hydroxyl, and amine groups, forming multiply substituted nonpolar derivatives that can be easily extracted
from water and determined by GC/negative chemical ionization
(NCI)-MS. The entire procedure from raw aqueous samples to
ready-to-inject hexane solutions of the derivatives requires <10
min. Using this method, 13 unknown highly polar DBPs were
identied in ozonated fulvic and humic acid solutions and in real
ozonated drinking water. Kubwabo et al. developed a new
method using N-methyl-bis-triuoroacetamide (MBTFA) derivatization and GC/ion trap-MS/MS to measure MX (3-chloro4-(dichloromethyl)-5-hydroxy-2(5H)-furanone) in drinking
water.147 This new method resulted in a signicant reduction
in analysis time and improved detection limits (7.7 ng/L) over
previous methods. The triuoroacylated MX was shown to be
stable for 30 days in an excess of the derivatization reagent, and
this method was used to measure MX in several drinking water
samples, where it was detected up to 517 ng/L. Finally, Banos
and Silva used in situ derivatization/preconcentration with
dansylhydrazine, which was rst adsorbed on a reverse phaseC18 mini-column, to allow low ng/L detection of aldehydes in
water.148 This simple method required only 10 mL of sample and
used LC with chemiluminscence for detection.
Near Real-Time Methods. Researchers continue to pursue the
development of new instruments to enable real-time measurements of DBPs in drinking water, which would be a tremendous
benefit to drinking water utilities and to epidemiologists, who
could obtain more accurate exposure information for their studies.
To this end, Emmerts group at the University of Memphis has
been very active in designing such instruments. The latest development by his group includes a new instrument that can selectively
measure THMs and HAAs in near real-time directly from drinking
water distribution systems.149 The instrument uses a capillary
membrane sampler-flow injection analyzer and is based on the
fluorescence of the reaction of nicotinamide in basic solution with
THMs and HAAs. The analyzer alternates sampling between two
sample loops connected to a capillary membrane sampler, which
discriminates between the volatile THMs and the nonvolatile
HAAs. Method detection limits for the 4 regulated THMs and 5
regulated HAAs (chloro-, dichloro-, trichloro-, bromo-, and dibromoacetic acid) were 2.5 and 3.3 g/L, respectively. This
method compared favorably to EPA Methods 502.2 and 552.3
in chlorinated and chloraminated distribution systems and provided automated online sampling with hourly sample analysis rates.
Improved Method for Total Organic Chlorine and Bromine. A few years ago, Minears group at the University of Illinois
pioneered the development of a method to speciate total organic
halogen (TOX), such that total organic chlorine (TOCl), total
REVIEW
organic bromine (TOBr), and total organic iodine (TOI) could

be differentiated. This method involves the sorption of analytes
onto activated carbon, followed by removal of inorganic analytes,
combustion of the activated carbon, bubbling the combustion gas
into ultrapure water, and injection of this water onto an ion
chromatograph for measurement of chloride, bromide, and
iodide. The original TOX measurement served a useful purpose
in providing an idea of the total halogenated material formed in
chlorinated and other disinfected waters, so that it could be
determined how much of the halogenated DBPs were being
accounted for through quantification of targeted DBPs. This
measurement has been widely used and has revealed that more
than 50% of the halogenated DBPs in drinking water are still not
accounted for. The development of the TOCl/TOBr/TOI
method allowed an even finer distinction of these DBPs and
has become an important measurement because of increased
toxicity among the brominated and iodinated DBPs. Li et al.
discovered that a portion of the TOCl (20%) can be reduced to
chloride by the activated carbon, which can lead to an underestimation of TOCl. The authors discovered that ozone can be
used to oxidize the activated carbon to eliminate this problem.150
A follow-up paper by Li et al. revealed that 10% of TOBr can
also sometimes be reduced by the activated carbon, and the
authors were able to use aqueous solutions of ozone to improve
the TOBr measurement.151 Interestingly, TOI does not appear
to suffer from the same issues.
Alternative Disinfection Technologies Using Iodine, UV,
and Other Treatments. Two papers investigated DBP formation from point-of-use treatments. In the first, Smith et al.
measured the formation of iodo-DBPs (iodo-THMs and iodoacids) and nitrosamines from 3 different iodine point-of-use
treatments that are used for the military in remote locations
(iodine tincture), campers and hikers (iodine tablets), and the
new Lifestraw, a reusable device marketed toward rural consumers in developing countries that uses an iodinated anion
exchange resin material with activated carbon post-treatment.152
Controlled laboratory experiments were carried out using four
different source waters with widely ranging dissolved organic
carbon, specific UV absorbance (SUVA), and bromide levels.
GC/EI-MS and derivatization with GC/NCI-MS were used to
measure the iodo-THMs and iodo-acids, respectively; GC/CIMS/MS (EPA Method 521) was used to measure the nitrosamines. TOCl, TOBr, and TOI were also measured using the
combustion-IC method described earlier. Iodoform was the
predominant iodo-DBP formed and was substantial, at roughly
2060% on a molar basis of the chloroform formation observed
during treatment of the same waters with a 6-fold higher oxidant
concentration. Iodine tincture produced the highest levels iodoform, which ranged from 114 to 268 g/L for treatments.
Despite higher iodine residuals, iodoform formation during
treatment with iodine tablets was lower, ranging from 74 to
132 g/L. While dichloroiodomethane and chlorodiiodomethane were detected, they were more than an order of
magnitude lower concentration than iodoform. Iodoacetic acid,
bromoiodoacetic acid, diiodoacetic acid, (E)-3-bromo-3-iodopropenoic acid, and (E)-2-iodo-3-methylbutenedioic acid were
also formed with iodine tincture treatment, with diiodoacetic acid
and iodoacetic acid dominant in this class, but present at <11% of
the iodoform levels. Lifestraw, which showed no iodine residual,
produced the lowest iodo-DBPs among the 3 iodine treatments,
with iodoform detected in only one of the disinfected waters at
23 g/L. TOI dominated with iodine tincture, while TOCl
4632
dominated with chlorine and chloramine treatment, carried out
for comparison. On the basis of previous measurements of mammalian cell cytotoxicity of the individual THMs, a person consuming
drinking water treated with iodine tincture would receive the
same THM-associated cytotoxic exposure in 419 days as a
consumer of the same waters treated with a 6-fold higher dose of
chlorine over 1 year. Finally, nitrosamines were measured in samples
from the Lifestraw because nitrosamines can form from the
contact of oxidants with ion-exchange resins. While nitrosamines
were initially observed in the first few flushes of water through the
Lifestraw, they rapidly declined to low levels (34 ng/L).
In another study, Lantagne et al. investigated DBP formation
in sodium dichloroisocyanurate point-of-use treatment that is
used in Tanzania.153 THMs were measured in 6 source waters,
some of which were highly turbid waters. No sample collected
at 1, 8, or 24 h after disinfection exceeded the World Health
Organization (WHO) guideline values for individual or total THMs.
Chlorine residual and THM formation were not signicantly
dierent than when sodium hypochlorite treatment (a form of
chlorine commonly used in full-scale drinking water treatment
plants) is used.
UV treatment is gaining popularity in the U.S. because it is
eective against resistant pathogens, including Cryptosporidium,
and it has not been found to directly produce DBPs. However,
studies are nding that when UV (particularly medium pressureUV) is used along with postchlorination, it can enhance the
formation of some DBPs. Low-pressure UV emits only 254 nm
light, but medium-pressure UV emits a much broader spectrum
(often 200400 nm). Dotson et al. investigated DBP formation
from the use of UV and UV/H2O2 (advanced oxidation).154 At a
UV dose of 1000 mJ/cm2, THM levels increased by up to 4 g/
mg-C and 13 g/mg-C when treated with low- and mediumpressure UV, respectively. Addition of hydrogen peroxide was
shown to increase THM formation up to 25 g/mg-C and 37
g/mg-C, respectively. In another study, Reckhow observed an
increase in formation of trichloronitromethane (chloropicrin)
and 1,1,1-trichloropropanone when medium-pressure UV was
followed by chlorination.155 In contrast, low-pressure UV did not
cause an increase in trichloronitromethane formation. The
authors propose that photonitration leads to the formation of
new nitroorganics during UV treatment and these form halonitromethanes during subsequent chlorination.
The formation of iodo-DBPs from the use of manganese(IV)
dioxide treatment was investigated by Gallard et al.156
Manganese(IV) dioxide is sometimes used as a catalyst in
drinking water treatment to oxidize Mn(II) to Mn(IV) dioxide
so that it can be subsequently removed by ltration. Because
Mn(IV) dioxide was previously shown to oxidize iodide to iodine
at neutral pH, the authors investigated the potential for iodoDBP formation. In the presence of NOM, adsorbable organic
iodine (AOI) was observed following treatment with Mn(IV)
dioxide, and iodoacetic acid and iodoform were measured as
DBPs. At very high NOM/Mn(IV) dioxide ratios, iodoform was
not observed, due to inhibition of the catalytic eect of Mn(IV)
dioxide by NOM sorbing onto the manganese dioxide.
Nitrosamines. Nitrosamines continue to be of interest, since
they were discovered to be DBPs in 2002. NDMA is a probable
human carcinogen, and there are toxicological concerns regarding other nitrosamines. NDMA was initially discovered in
chlorinated drinking waters from Ontario, Canada, and has since
been found in other locations. The detection of NDMA in
drinking water is largely due to improved analytical techniques
REVIEW
that have allowed its determination at low ng/L concentrations.

NDMA is generally present at low ng/L in chloraminated/
chlorinated drinking water, but it can be formed at much higher
levels in wastewater treated with chlorine. It was also recently
shown to form when waters containing a microbial degradation
product of the fungicide, tolylfluanid, were ozonated.2 NDMA is
not currently regulated in the United States for drinking water,
but it is regulated in Ontario, Canada, at 9 ng/L under Ontarios
Safe Drinking Water Act (http://www.e-laws.gov.on.ca/html/
regs/english/elaws_regs_030169_e.htm). A Canadian national
drinking water guideline for NDMA is also under development
(www.hc-sc.gc.ca/ewh-semt/consult/_2010/ndma/draft-ebaucheeng.php). NDMA was included in the U.S. EPAs second
Unregulated Contaminants Monitoring Rule (UCMR-2), along
with 5 other nitrosamines (N-nitrosodiethylamine, N-nitrosodibutylamine, N-nitrosopropylamine, N-nitrosomethylethylamine,
and N-nitrosopyrrolidine), and national occurrence data are
currently available (http://water.epa.gov/lawsregs/rulesregs/
sdwa/ucmr/data.cfm#ucmr2010). In addition, NDMA and 4
other nitrosamines are also on the U.S. EPAs final CCL-3
(http://water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.cfm).
Zhao et al. investigated the role of diphenylamine as a
precursor in the formation of N-nitrosodiphenylamine (NDPhA)
and determined the eect of pH and chloramination conditions
on its formation.157 Diphenylamine was determined to be a key
precursor, and controlled experiments revealed that chloramines
are also essential to NDPhA formation, with increasing formation at increasing pH (from 4 to 10). In addition, two new DBPs,
phenazine and a chlorinated phenazine derivative, were identied
for the rst time using LC/MS/MS and GC/MS. These new
DBPs were detected only in the treated water and not in the
raw water.
A fascinating study by Kemper et al. investigated the role of
several consumer products (shampoos, laundry detergents, dish
washing liquids, and fabric softeners) in the formation of
nitrosamines.158 This study was conducted in order to address
the question surrounding relatively high levels of nitrosamines in
treated wastewaters that are correlated with wastewaters impacts,
rather than total dissolved organic nitrogen. Nitrosamines were
formed from several of these products when they were reacted
with monochloramine or chlorine, and the authors showed clear
evidence that quaternary amines (including polymers) used in
these products form nitrosamines. In fact, the quaternary amine
polymers were more reactive than the monomers, and preozonation or prechlorination did not signicantly reduce nitrosamine
formation. EPA Method 521 (GC/CI-MS/MS) was used for the
measurements. There was also important new information on
the reaction of monochloramine and chlorine with the polyDADMAC polymers used as coagulants in drinking water
treatment. Results showed that the polymers themselves are
reacting with chlorine to form NDMA and other nitrosamines.
This was proven by synthesizing polyDADMAC (to control the
purity and eliminate contribution of monomers). These ndings
are important because nitrosamine formation is often attributed
to lower order amine impurities, but these results clearly show
that quaternary amine polymers can form NDMA.
Other new studies investigated the role of anion-exchange
resins and water treatment polymers in the formation of nitrosamines. For example, strong base anion-exchange resins were
investigated in a study by Kemper et al.159 These resins (which
contain quaternary amine functional groups) represent an important option for water utilities and homeowners to address
4633
growing concerns with nitrate, arsenate, and perchlorate contamination. Nitrosamines were released from the resins when they
were new (up to 10 ng/L), but levels decreased with time after
multiple regeneration cycles, indicating that releases may eventually subside. When chlorinated or chloraminated water was
passed through the resins, nitrosamine levels increased to
20100 ng/L. Dimethylnitramine (DMNA) was also formed
with chlorine at signicant levels; trichloronitromethane
(chloropicrin) was formed to a lesser extent. EPA Method 521
was used to measure nitrosamines and DMNA. No N-DBPs were
found in the cation exchange-based point-of-use devices that are
used by homeowners. Water treatment polymers (including
polyamines and poly(diallyldimethylammonium chloride)
[polyDADMAC]) were investigated as sources of nitrosamines
by Park et al.160 Overall, polyamines had greater NDMA formation potential than polyDADMAC, and NDMA formation from
both polymers was strongly related to polymer degradation and
dimethylamine release during chloramination. The tertiary amine
chain of the polyamines plays a major role, while the quaternary
ammonium group of polyDADMAC played a major role.
Goslan et al. published the rst nitrosamine occurrence in
Scotland, in which nitrosamines and other N-DBPs were measured,
and the impact of secondary disinfectants was investigated.161
There is not currently a regulation in the UK for nitrosamines,
but there is a guideline that requires water utilities to contact local
health professionals if concentrations exceed 10 ng/L. EPA
Method 521 (GC/CI-MS/MS) was used to measure nitrosamines, and a modied EPA Method 551.1 (GC-electron capture
detection [ECD]) was used to measure haloacetonitriles and
chloropicrin. Over the 3 seasons sampled among 7 water utilities
in Scotland, NDMA was found in only one of the utilities
sampled, up to 26 ng/L in drinking water treated with chloramines. Templeton and Chen reported measurements of NDMA
and 7 other nitrosamines in the United Kingdom.162 NDMA was
found only in a few samples from one distribution system, slightly
above the detection limit of 0.9 ng/L. Otherwise, the majority of
the samples collected from 6 systems contained no detectable
levels. However, N-nitrosobutylamine (NDBA) was consistently
detected on one distribution system, up to 6.4 ng/L.
DBPs from wastewater euents were the focus of another
occurrence study by Krasner et al.163 Chlorinated wastewaters
from 23 wastewater treatment plants in the U.S. were studied
across dierent seasons. Nitrosamines, iodo-THMs, haloacetaldehydes, halonitromethanes, and THMs were measured using
GC/MS and GC/ECD. Disinfection and oxidation practices had
a profound impact on the types and levels of DBPs formed.
Wastewater treatment plants that did not achieve breakpoint
chlorination (which would eectively have chloramination conditions) formed lower levels of halogenated DBPs but produced
a substantial amount of NDMA (up to 3165 ng/L). N-Nitrosomorpholine was also frequently detected. On the other hand,
plants that achieved breakpoint chlorination formed considerable amounts of THMs, HAAs, haloacetaldehydes, and haloacetonitriles. This study revealed how wastewater treatment plant
discharges can be a source of a wide range of halogenated and
nonhalogenated DBPs of health concern, which is important for
an increasing number of water reclamation programs in arid
regions of the United States.
Mechanisms of Formation. Typically, HOCl is assumed to
be the active oxidant when chlorine is used in drinking water
treatment. However, Sivey et al. provided evidence that a littleknown chlorine monoxide (Cl2O) species is the predominant
REVIEW
chlorinating agent during the chlorination of the herbicide

dimethenamid.164 The influence of free available chlorine and
pH and the kinetics of these reactions were consistent with Cl2O
being the active species under typical drinking water treatment
conditions. Some early reports identifying Cl2O as an active
chlorinating species appeared in the 1970s and 1980s, but the
literature has been quiet since on this topic; it is quite likely that it
could have been the active reactant species in other reactions but
has not been considered. As a consequence, the authors suggest
that some apparent rate constants in the literature may not be
valid. Chu et al. investigated precursors of dichloroacetamide, the
most common haloamide formed in chlorinated and chloraminated drinking water.165 In a reservoir in China, dissolved organic
matter was separated into 6 fractions by a series of resin elutions,
and hydrophilic dissolved organic matter was found to form the
highest levels of dichloroacetamide. Fluorescence excitationemission matrix spectra revealed that a mass of proteinlike substances in this fraction, made up of amino acids, were
likely the dichloroacetamide precursors. Subsequent reactions of
20 amino acids with chlorine revealed that 7 amino acids
(aspartic acid, histidine, tyrosine, tryptophan, glutamine, asparagine, and phenylalanine) could form dichloroacetamide during
chlorination, with yields of 0.231, 0.189, 0.153, 0.104, 0.078,
0.058, and 0.050 mmol/mol amino acid.
Halonitromethane formation was the focus of another study
by Hu et al.166 Formation potential tests conrmed earlier work
showing that ozonation followed by postchlorination produced
the highest halonitromethane levels, and fractionation of NOM
revealed a signicantly higher reactivity of hydrophilic NOM
than hydrophobic or transphilic NOM. The best correlation
between halonitromethane formation and various water quality
parameters was with the ratio of dissolved organic carbon to
dissolved organic nitrogen. Dabrowska and Nawrocki carried out
a study to address past controversies regarding the formation of
trichloroacetaldehyde (chloral hydrate, CH) in drinking water.167
Haloaldehydes are the third most prevalent class of DBP (behind
the THMs and HAAs), and CH is the most common one in this
class. The authors carried out reactions in dierent source waters
in Poland (with widely dierent TOC and water quality). In
addition, nished drinking water samples were collected from
full-scale plants. Results showed that CH formation depends
more on the type of NOM than on its quantity and that
increasing chlorine dose leads to higher concentrations of CH,
with reactions taking place with NOM as long as chlorine is
available in the water. Higher pH forms higher levels of CH, and
preozonation signicantly increases its formation, as observed
previously in the literature. Further, biological ltration did not
remove all CH precursors.
Finally, Krasner et al. published a nice study on the impact of
wastewater treatment processes on organic carbon, organic
nitrogen, and DBP precursors in euent organic matter.168 This
study represents the rst large-scale assessment of the critical
water quality parameters that aect the formation of DBPs
during drinking water treatment relative to the discharge of
upstream wastewater treatment plants. Source waters are increasingly receiving treated wastewater, and as such, there is
indirect, unintentional reuse of wastewater in many drinking
water systems. In this study, 23 wastewater treatment plants were
sampled, and regulated and priority unregulated DBPs were
measured. Results showed that nitrication has a profound
impact on many measures of euent water quality, including
formation potentials for a diverse group of priority DBPs of
4634
health concern. Complete nitrication reduced biodegradable
organic carbon (BDOC) levels and changed the ratio of BDOC/
dissolved organic carbon (DOC). Nitrication reduced the UV
absorbance at 254 nm, but it also increased the specic UVA/
DOC ratio, which was attributed to the preferential removal of
the nonhumic fraction of DOC during biological treatment. The
euent organic carbon was composed of hydrophilic and
biodegradable DOM, as well as hydrophobic and recalcitrant
DOM, whose proportions changed with advanced biological
treatment. The onset of nitrication in these plants produced
lower precursor levels for HAAs and nitrogenous DBPs
(halonitriles and NDMA), but THM precursors were relatively
unaected by the level of wastewater treatment.
DBPs of Pollutants. Studies of DBPs are going beyond the
classic DBPs formed by the reaction of NOM with disinfectants, such that reactions of environmental pollutants with
disinfectants are increasingly being studied. Contaminant DBPs
have been recently reported from herbicides, pharmaceuticals,
personal care products, microcystins, and terpenoids. Some of
this research has been conducted in order to find ways to degrade
and remove these contaminants from wastewater effluents and
drinking water sources, but some of this research is being
conducted to determine the fate of these contaminants in
drinking water treatment. It is not surprising that DBPs can
form from these contaminants, as many of them have activated
aromatic rings or other structural groups that can readily react
with oxidants like chlorine and ozone. However, until recently,
these types of DBPs were not investigated.
DBPs formed by the reaction of chlorine with triazine
herbicides were the focus of an article by Brix et al.169 UPLCQ-TOF-MS/MS was used to tentatively identify 4 new DBPs
from ametryn, prometryn, and terbutryn, which had higher
toxicities than the parent herbicides. Wang et al. investigated
DBPs formed by chlorine dioxide treatment of uoroquinolone
antibiotics and structurally related amines.170 The piperazine ring
of the uoroquinolones was the primary reactive center toward
chlorine dioxide, followed by fragmentation, dealkylation, hydroxylation, and intramolecular ring closure at the piperazine
moiety. However, the quinolone ring remained mostly intact,
which is strongly related to the antimicrobial property. Chlorination byproducts of the cyanobacterial toxin microcystin-LR were
the focus of a new study by Merel et al., who used linear ion trapQ-Orbitrap-MS to identify the products.171 Microcystin-LR was
totally transformed within 2 min, and 8 new byproducts were
identied, including chloro-microcystin, chloro-dihydroxy-microcystin, dichloro-dihydroxy-microcystin, trichloro-hydroxymicrocystin, and several dihydroxy-microcystins.
Also, several other examples were highlighted earlier in the
Pharmaceuticals and Hormones section. These included ozone
byproducts of antibiotics and beta-blockers; chlorine byproducts
of EE2, trenbolone, salicyclic acid, naproxen, diclofenac, and
uoroquinolones; UV/H2O2 byproducts of X-ray contrast
media; and ferrate byproducts of carbamazepine.
New Swimming Pool Research. Swimming pools are being
recognized as an important source of exposure to DBPs. Health
concerns include increased risk of bladder cancer from exposure
to indoor pools and increased risk of asthma for both indoor and
outdoor pools.1 Richardson et al. carried out a comprehensive
DBP characterization and assessed the mutagenicity in two
public swimming pools, one chlorinated and one brominated,
that were part of a human exposure study focused on respiratory
and genotoxicity biomarkers.172 More than 100 DBPs were
REVIEW
measured, including many nitrogenous DBPs likely formed by

nitrogen-containing inputs from human inputs (urine, sweat,
skin cells). In addition, several new DBPs were identified that
have not previously been reported for either swimming pool
water or drinking water. Bromoform levels were higher in the
brominated pool, but brominated DBPs were also identified in
the chlorinated pool, due to source waters (from Barcelona) that
were already high in bromide. Mutagenicity results showed that
these pool waters had a similar mutagenicity to chlorinated
drinking water, but the toxicity was higher.
Volatile DBPs in a chlorinated indoor swimming pool were the
focus of a study by Weaver et al., who used membrane ionization
mass spectrometry (MIMS) for their measurement.173 Eleven
pools were investigated over a 6 month period, and 11 volatile
DBPs were identied as follows: monochloramine, dichloramine,
trichloramine, chloroform, bromoform, bromodichloromethane,
dibromochloromethane, cyanogen chloride, cyanogen bromide,
dichloroacetonitrile, and dichloromethylamine. In a fascinating
study involving continuous real-time measurements, Kristensen
used MIMS for online monitoring of the dynamics of THM
concentrations in a warm public swimming pool.174 The MIMS
instrument performed unsupervised for more than a year, with
only short interruptions for lament replacements every 68
weeks. Online monitoring revealed the daily cycles of chloroform
and bromodichloromethane concentrations, which increased
during the pools closing hours and decreased during opening
hours. Daily concentrations of 30100 g/L for chloroform
were observed, and 510 g/L levels of bromodichloromethane
were observed, except for short bursts in bromodichloromethane
levels (up to 100 g/L) that were linked to salt addition (sodium
chloride) used to electrolytically generate chlorine for disinfection. Lower THM levels correlated to the operation of a strong
water jet system.
Blatchley and Cheng conducted experiments to elucidate the
reaction mechanism of free chlorine with urea.175 Urea is an
important swimming pool precursor, introduced by human urine,
and it is known to react with chlorine to form trichloramine, a
respiratory irritant that is suspected in the cases of asthma of elite
swimmers. Results showed multiple N-chlorination steps, with
initial formation of N-chlorourea, subsequent formation of a fully
chlorinated urea molecule, which undergoes further hydrolysis
and additional chlorination to yield trichloramine as an intermediate. Trichloramine can then be hydrolyzed to yield monochloro- and dichloramine, with subsequent decay to stable end
products, including N2 and nitrate. Conversion of urea-nitrogen
to nitrate was found to be pH dependent. The aquatic fate of
sunscreen agents in model swimming pools was the focus of a
study by Nakajima et al., who used GC/MS to identify the
chlorination byproducts.176 Octyl-4-methoxycinnamate (OMC)
and octyl-4-dimethylaminobenzoate (ODPABA) reacted with
hypochlorite to produce chlorine-substituted products as intermediates, which were weakly mutagenic in Salmonella (TA 100).
Finally, Kulshrestha et al. reported a new total N-nitrosamine
(TONO) assay for application to swimming pools.177 This
method was a modied version of a method previously developed for the measurement of nitrite, S-nitrosothiols, and
N-nitrosamines in biological samples and involves their reduction
to nitric oxide by acidic tri-iodide, followed by chemiluminescent
detection of the evolved nitric oxide in the gas phase. Method
detection limits of 62 pM (5 ng/L as NDMA) were achieved for
1 L pool water samples extracted with liquidliquid extraction.
Evaluation of potential interfering species indicated that only
4635
nitrite and S-nitrosothiols were a concern, and both interferences
were eectively eliminated using group-specic sample pretreatments previously used for biological samples. This method was
subsequently applied to TONO measurements in pools and their
corresponding tap water sources.
SUNSCREENS/UV FILTERS
UV lters used in sunscreens, cosmetics, and other personal
care products have increased in interest due to their presence in
environmental waters and their potential for endocrine disruption and developmental toxicity. A few UV lters have been
shown to have estrogenic eects similar to E2 (a natural
estrogen), as well as the potential for developmental toxicity.1
Environmental levels of UV lters are not far below the doses that
cause toxic eects in animals. There are two types of UV lters:
organic UV lters, which work by absorbing UV light, and
inorganic UV lters (TiO2, ZnO), which work by reecting
and scattering UV light. Organic UV lters are increasingly used
in personal care products, such as sunscreens, cosmetics, beauty
creams, skin lotions, lipsticks, hair sprays, hair dyes, and shampoos. Examples include benzophenone-3 (BP-3), ODPABA,
4-methylbenzylidene camphor (4-MBC), ethylhexyl methoxycinnamate (EHMC), octocrylene (OC), iso-amylmethoxycinnamate (IAMC), and phenylbenzimidazole sulfonic acid (PBSA).
The majority of these are lipophilic compounds (low water
solubility) with conjugated aromatic systems that absorb UV
light in the wavelength range of 280315 nm (UVB) and/or
315400 nm (UVA). Most sunscreen products contain several
UV lters, often in combination with inorganic micropigments.
Because of their use in a wide variety of personal care products,
these compounds can enter the aquatic environment indirectly
from bathing or washing clothes, via wastewater treatment plants
and directly from recreational activities, such as swimming and
sunbathing in lakes and rivers.
Diaz-Cruz and Barcelo published a review on UV lters,
summarizing analytical methods and ecotoxicological eects.178
The authors discussed the fact that biological activity is not well
predicted from the chemical data alone and that EC50 values for
hormonally active UV lters were similar to those for other
known environmental xenoestrogens (in the low M range).
Gaps in knowledge pointed out by the authors include a need to
assess and understand the activity of mixtures of UV lters and
the need for integrated chemical and biological testing.
New methods continue to be developed, including ones using
UPLC/MS, LC/MS, direct analysis in real-time (DART)-MS,
SPME-GC/MS, and dispersive liquidliquid microextraction
(DLLME)-GC/MS. Wick et al. developed a multiresidue method using LC/ESI-MS/MS and LC/APCI-MS/MS for determining 36 emerging contaminants, including 5 UV lters, in raw and
treated wastewater, activated sludge, and surface water.179 Quantication limits ranged from 0.5 to 5 ng/L and 2.550 ng/L in
surface waters and wastewater, respectively. Maximum concentrations up to 5.1 and 3.9 g/L were found in raw wastewater for
the BP-4 and PBSA, respectively. This method also allowed the
rst identication of an antidandru compound (climbazole) in
wastewater up to 1.4 g/L. Pedrouzo et al. created the UPLC/
MS/MS method using stir-bar sorptive extraction to measure 4
UV lters (DHMB, BP-3, OC, and ODPABA) and antimicrobial
compounds (triclosan and triclocarban) in surface water and
wastewater.180 Detection limits of 2.5 ng/L (river water) and
510 ng/L (raw and treated wastewater) were achieved. Using
REVIEW
this method, BP-3 was found up to 127 ng/L in wastewater

inuents and up to 28 ng/L in river waters.
DART-MS was used in a creative method by Haunschmidt
et al. to measure 7 UV lters in environmental waters.181 Stir-bar
sorptive extraction was used to extract analytes from the water,
and DART-MS was used to directly analyze the analytes from the
surface of the polydimethylsiloxane-coated stir bars. Detection
limits of <40 ng/L were achieved, and the new method was crossconrmed using a thermodesorption-GC/MS method, which
produced comparable concentrations when tested on lake water
samples. SPME-GC/MS/MS was the focus of a method by
Negreira et al., who measured 3 UV lters and hydroxylated
benzophenones in water.182 The analytes were extracted and
concentrated onto a SPME ber, followed by on-ber silylation
and measurement with GC/MS/MS. The entire process took 40
min and provided limits of quantication of 0.5 to 10 ng/L.
DLLME-GC/MS was used in a new method by Tarazone et al. to
measure hydroxylated benzophenones UV lters in seawater
samples.183 Under optimized conditions, 1000 L of acetone
(dispersive solvent), containing 60 L of chloroform (extraction
solvent), was injected into a 5 mL aqueous sample (adjusted to
pH 4 and containing 10% NaCl). DLLME extracts were evaporated
under an air stream and reconstituted with bis(trimethylsilyl)triuoroacetamide (BSTFA) to derivatize the target analytes to
their trimethylsilyl derivatives, followed by analysis with GC/MS.
Detection limits ranged from 32 to 50 ng/L. Oliveira et al. created a
new automated sample pretreatment/detection method using inline SPE with multisyringe-lab-on-valve and LC/diode array-UV
detection.184 Samples could be automatically processed every 9
min, and detection limits ranged from 0.45 to 3.2 g/L.
New occurrence studies include one from Fent et al. who
demonstrated the widespread occurrence of estrogenic UV lters
in aquatic ecosystems in Switzerland.185 POCIS was used with
LC/MS/MS and GC/MS to measure the UV lters in biota and
river water sampled at 10 sites above and below wastewater
treatment plants. BP-3, 4-MBC, and EHMC ranged from 6 to 68
ng/L in river water, and EHMC was accumulated in biota.
Wastewater was found to be the most important source of these
UV lters, and no signicant in-stream removal was observed in
the rivers. Leal et al. measured UV lters and other xenobiotic
contaminants in gray water and investigated biological treatment
systems (aerobic, anaerobic, and combined anaerobicaerobic)
for their removal.186 Due to limited freshwater resources, gray
water, which is the euent from domestic washing activities (e.g.,
laundry, dishwashing, bathing), is increasingly being explored for
reuse in applications, such as landscape irrigation and toilet
ushing. In this study, all xenobiotics were detected in gray water
samples at low g/L levels, with lower levels following biological
treatment. Generally, removal eciencies were higher under
aerobic conditions, however, most xenobiotics were still detected
in the biologically treated gray water. The UV lters PBSA and
EHMC were among the most persistent compounds found.
Estimated estrogenic potential of the euent ranged from 0.07
to 0.72 ng/L of 17-estradiol equivalents.
Several good fate studies have also been published on UV
lters. For example, Rodil et al. investigated the photostability of
UV lters used in sunscreens and combined this with investigations of toxicity of the resulting photolysis products.187 During
exposure to articial sunlight over 72 h, 3 of the UV lters were
found to degrade, with half-lives of 2059 h. Structural changes
included isomerization and polymerization for IAMC, EHMC,
and 4-MBC, and dealkylation for ODPABA, which formed stable
4636
photoproducts. Stir-bar sorptive extraction with GC/MS and
liquid desorption-LC/MS were used to analyze the UV lters and
their degradation products. A few of the UV lters were found to
be toxic for algae, but EHMC, IAMC, and ODPABA degraded
quickly during UV radiation, and the corresponding phytotoxicity of the reaction mixtures was low. OC, BP-3, and 4-MBC were
stable to irradiation. Finally, as mentioned earlier in the DBP
section, Nakajima et al. investigated the fate of OMC and
ODPABA (used in sunscreens) in model chlorinated swimming
pool waters using GC/MS.176 ODPABA was found to react
rapidly with free chlorine at pH 7.0, whereas OMC reacted rather
slowly under the same conditions. Both produced chlorinesubstituted byproducts as intermediates, which decomposed
via cleavage of the ester bonds. These byproducts were weakly
mutagenic in Salmonella TA 100 (Ames assay).
BROMINATED FLAME RETARDANTS

Brominated ame retardants have been used for many years in
a variety of commercial products including childrens sleepwear,
foam cushions in chairs, computers, plastics, and electronics.
Brominated ame retardants work by releasing bromine free
radicals when heated, and these free radicals scavenge other free
radicals that are part of the ame propagation process. The use of
these ame retardants is believed to have successfully reduced
re-related deaths, injuries, and property damage. However,
there is concern because of their widespread presence in the
environment and in human and wildlife samples, as well as their
presence in locations far from where they were produced or used.
Polybrominated diphenyl ethers (PBDEs) have been a popular
ingredient in ame retardants since the polybrominated biphenyls were banned about 30 years ago. They are environmentally
persistent, lipophilic, and bioaccumulate in animals and humans.
PBDEs are made up of 209 possible congeners containing
between 1 and 10 bromine atoms, and of these, 23 congeners
are of environmental signicance.1 In recent years, PBDE levels
have been increasing signicantly. The greatest health concern
comes from recent reports of developmental neurotoxicity in
mice, but there are also concerns regarding the potential for
hormonal disruption and, in some cases, cancer. In 2004, the
European Union banned the use of the penta- and octa-BDEs
and, later in 2008, banned deca-BDEs.1
In 2004, the major U.S. manufacturer of PBDE-based ame
retardants (Great Lakes Chemical) voluntarily stopped producing the penta- and octa-BDEs. However, deca-BDE is still being
manufactured and used. Earlier studies had suggested that decaBDE was too large to bioaccumulate and would not be a risk to
humans. However, research now shows that it can accumulate in
animal tissues (including people) and that it can debrominate in
the environment and metabolically form the lower brominated
species (including the octa- and penta-BDEs).1 Several U.S.
states banned the penta- and octa-BDEs in 2006, and in
December 2009, two U.S. producers of deca-BDE agreed to
voluntarily phase it out in the United States (www.epa.gov/
oppt/existingchemicals/pubs/actionplans/deccadbe.html). In
addition, the U.S. EPA issued a new rule in 2006 to complement
the phase-out of the octa- and penta-BDEs, ensuring that no new
manufacture or importation of these chemicals can occur without
rst being subject to U.S. EPA evaluation (www.epa.gov/EPATOX/2006/June/Day-13/t9207.htm).
However, despite the halt in manufacture of most of these
PBDEs in North America and Europe, they are still present in
REVIEW
many consumer products sold previously and can be released

into the environment during use and disposal. In addition, there
is still the possibility of importing products that contain them.
Four of the PBDEs (2,20 ,4,40 -tetra-BDE (BDE-47), 2,20 ,4,40 ,5penta-BDE (BDE-99), 2,20 ,4,40 ,5,50 -hexa-BDE (BDE-153), and
2,20 ,4,40 ,6-penta-BDE (BDE-100)) and another brominated
ame retardant (2,20 ,4,40 ,5,50 hexabromobiphenyl (HBB)) were
on the UCMR-2 in the U.S., and national occurrence data are
now available (http://water.epa.gov/lawsregs/rulesregs/sdwa/
ucmr/data.cfm#ucmr2010).
Many review articles have been published on brominated
ame retardants, and one is highlighted here. Daso et al. reviewed
the sources of brominated ame retardants and routes of human
exposure.188 Consumption of contaminated food and water and
inhalation and ingestion of dust, as well as dermal absorption,
were considered important pathways of exposure. Fatty foods,
especially sh, meat, dairy products, and human milk constitute
important routes for human exposure to these contaminants.
Ruan et al. reported the discovery of a new brominated ame
retardant, tris(2,3-dibromopropyl)isocyanurate, in the environment.189 This compound was identied in river water, sediment,
soils, and biota in a factory-polluted area in southern China, up to
163 ng/L in river water. Results also showed a high Kow (log Kow =
7.37) and bioaccumulation factor (log BAF = 4.30).
New methods for measuring brominated ame retardants
include those using LC/APPI-MS/MS and GC/MS. Bacaloni
et al. described a new LC/negative ion-APPI-MS/MS method
for measuring tetrabisphenol A and 5 PBDEs (BDE-47, BDE-99,
BDE-100, BDE-153, and BDE-154) in water.190 A mobile phase
consisting of methanol/acetone/water was used, where acetone
served as the dopant for APPI. Method quantication limits
ranged from 0.2 to 20.3 ng/L. Fontana et al. used cloud point
extraction with ultrasound-assisted back-extraction-GC/MS in a
new method to measure PBDEs in water and soil.191 A nonionic
surfactant (Triton X-114) was used to extract the PBDEs, and
method detection limits of 12 ng/L were achieved.
Studies continue to explore the fate of PBDEs in the environment. For example, Steen et al. investigated the photochemical fate
of hydroxylated PBDEs and their chlorinated derivatives.192 Halogenated dioxins were formed when the four hydroxylated PBDEs
(OH-PBDEs) and polybrominated/chlorinated diphenyl ethers
were photolyzed under sunlight in river and lake water. Dioxin
yields of 0.73.6% were found, with higher yields for 6-hydroxyBDE-47. Wan et al. conducted a study to determine the origin of
OH-PBDEs.193 Results showed that metabolism can also form OHPBDEs from the corresponding methylated PBDEs, which represents a new mechanism that has not been previously explored.
Robrock et al. investigated the aerobic biotransformation of
PBDEs in bacteria using GC/ECD and GC/MS.194 Two PCBdegrading strains of bacteria were found to transform all of the
mono- through penta-BDEs, and one strain transformed one of
the hexa-BDEs. The extent of transformation was inversely
proportional to the degree of bromination. This is the rst report
of aerobic transformation of these PBDEs, as well as the rst
report of the stoichiometric release of bromide during PBDE
transformation. Finally, Bogdal et al. investigated sources of
PBDEs and polychlorinated biphenyls (PCBs) in a Swiss lake.195
For lower brominated PBDEs, 70% and 30% of input to the
lake originated from atmospheric deposition and from tributaries,
respectively. For heavier PBDEs and all PCBs, rivers delivered the
major load (6492%). Wastewater euents were a minor
source, and 5090% was buried in the permanent sediment.
4637
BENZOTRIAZOLES
Benzotriazoles are complexing agents that are widely used as
anticorrosives (e.g., in engine coolants, aircraft deicers, or antifreeze liquids) and for silver protection in dish washing liquids.
The two common forms, benzotriazole and tolyltriazole, are
soluble in water, resistant to biodegradation, and only partially
removed in wastewater treatment. There is also new evidence for
estrogenic eects in vitro but, so far, not in vivo, in recent sh
studies.1 Because of their water solubility, LC/MS and LC/MS/
MS methods have been recently developed for their measurement in environmental waters. While reports of benzotriazoles
are fairly recent (last 67 years), studies indicate that they are
likely ubiquitous environmental contaminants. Benzothiazoles
and benzosulfonamides are also increasingly being measured in
environmental samples. Benzothiazoles are high production
chemicals used as corrosion inhibitors, as biocides in paper and
leather manufacturing, and in the production of rubber. Benzosulfonamides are widely used as plasticizers and intermediates in
the synthesis of sweeteners and can be metabolites of corrosion
inhibitors.1
New methods developed include one by Jover et al. who
investigated the use of GCGC-TOF-MS to measure benzotriazoles, benzothiazoles, and benzosulfonamides in environmental waters.196 SPE was used for extraction, and GCGC improved
separations, enabling the identication of minor components that
might be overlooked with other methods. This method was then
used to measure these analytes in river water, euent from a
wastewater treatment plant, and raw sewage. Orbitrap-MS was
used in another method by van Leerdam et al., who measured 6
benzotriazoles and benzothiazoles in water.197 This LC/linear ion
trap-Orbitrap-MS method enabled improved mass accuracies and
detection limits down to 0.01 g/L. Finally, Wick et al. developed
a multiresidue method using LC/MS/MS that included benzothiazoles, which could be measured at ng/L levels.179
The occurrence and fate of benzotriazoles and benzothiazoles
in constructed wetlands and a wastewater treatment plant was
investigated by Matamoros et al., who used GCGC-TOFMS.198 Benzotriazole removal eciencies ranged from 65 to
70% and 89 to 93% in the conventional wastewater treatment
plant and in the constructed wetlands, respectively. Benzothiazole removal eciencies ranged from 0 to 80% and 83 to 90% in
the conventional wastewater treatment plant and in the constructed wetlands, respectively. Higher degradation in the
constructed wetlands was attributed to the possibility of biodegradation, photodegradation, and plant uptake. Finally, in the panEuropean study mentioned earlier by Loos et al., 1H-benzotriazole
and methylbenzotriazole were measured in >50% of the groundwaters sampled, up to 1.03 and 0.52 g/L, respectively.50
DIOXANE
1,4-Dioxane is a widespread industrial contaminant in environmental waters (often exceeding water quality criteria and
guidelines), has also been found in drinking water, and is a
probable human carcinogen. Dioxane is a high production
chemical and is used as a solvent stabilizer in the manufacture
and processing of paper, cotton, textile products, automotive
coolants, cosmetics, and shampoos, as well as a stabilizer in 1,1,1trichloroethane (TCA), a popular degreasing solvent. In 2002,
more than 500 t of dioxane were produced or imported in the
United States.1 The U.S. EPA has identied dioxane as a high
priority contaminant, and it is currently listed on the new CCL-3
REVIEW
(http://water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.
cfm). There is also an EPA Method (522) for its measurement
(www.epa.gov/microbes/Method%20522_nal%20for%20OGWDW%2009_22_08.pdf). Dioxane is problematic to extract and
measure because it is miscible with water. It is also dicult to
remove from water by air stripping or carbon adsorption.
Environmental investigation and remediation of dioxane and
other solvent stabilizers was the focus of a new book by Mohr.199
This book included a discussion of the chemistry, uses, and
occurrence; environmental fate and transport; sampling and
analysis; toxicology; regulation and risk assessment; remediation
technologies; case studies of releases, treatment and drinking
water contamination; and forensic applications. Lee et al. investigated occurrence patterns and removal eciencies in wastewater treatment for dioxane and other micropollutants.200
Removal eciency of dioxane in most treatment processes was
low (1.116%). However, dissolved air oatation/chemical
coagulation reactor processes and activated carbon ltration
showed relatively high removal eciencies (>80%).
SILOXANES
Siloxanes have become a new area of research. They include
cyclic siloxanes, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6),
and tetradecamethylcycloheptasiloxane (D7) and linear siloxanes, which are used in a number of products, such as cosmetics,
deodorants, soaps, hair conditioners, hair dyes, car waxes, baby
paciers, cookware, cleaners, furniture polishes, and water-repellent windshield coatings. There is concern about potential
toxicity and transport into the environment. They have been
previously measured in wastewater, river water, and landll
biogases.1,2 Price et al. used a Geographic Information System
(GIS)-based water quality model to predict concentrations of D5
in two UK rivers.201 A wastewater ux of 2.4 mg/cap-day was
determined, which was consistent with euent concentrations.
NAPHTHENIC ACIDS
Naphthenic acids (NAs) are a complex mixture of alkylsubstituted acyclic and cyclo-aliphatic carboxylic acids that dissolve
in water at neutral or alkaline pH and have surfactant-like properties. They occur naturally in crude oil deposits across the world (up
to 4% by weight) and have also been recently discovered in coal,
which could be a source of contamination for groundwater.202 In
this new study of contaminated groundwater, NAs were found to
be leaching from coal deposits into wells that were distant from any
petroleum sources. NAs are toxic to aquatic organisms, including
phytoplankton, daphnia, sh, and mammals, and are also endocrine disrupting. Most research has focused on NAs in the oil sands
region in Alberta, Canada, which is one of the highest producers of
crude oil in the world. Caustic hot water is used in the extraction of
crude oil from oil sands, which results in a residual tailing water
(0.1 to 0.2 m3 of tailings per ton of oil sands processed) that
contains high levels of NAs (80 to 120 mg/L) and is very toxic.
The total volume of tailing ponds is projected to exceed 109 m3 by
the year 2020. Little is known about the environmental fate of
NAs. NAs are challenging to measure because they are present as
a complex mixture of isomers and homologues. Understanding
why NAs persist in tailing waters may help in the development
of remediation technologies.
Headley et al. reviewed mass spectrometry techniques for
characterizing NAs in environmental samples and included
4638
discussions of EI, ESI, APCI, GC/MS, LC/MS, GCGC, and high
resolution techniques, including TOF-MS, magnetic sector-MS, and
FT-ion cyclotron resonance (ICR)-MS.203 Data analysis techniques,
such as Kendrick and van Krevelen plots, are also discussed.
Thomas et al. published an eects-directed identication study
of NAs in discharges from oshore oil production in the North
Sea.204 NAs were weak estrogen receptor agonists, accounting
for as much as 65% of the unknown estrogen receptor agonist
potency in the produced waters. Derivatization with GC/high
resolution-TOF-MS was used to measure the NAs, and the Yeast
Estrogen (YES) assay and Yeast Androgen Receptor Binding
Assay (YAS) were used to measure eects of the water fractions
collected. Han et al. estimated the in situ biodegradation of NAs
in oil sands process waters using LC/high resolution-MS.205 A
previous laboratory study had revealed several potential biomarkers of microbial degradation of NAs, and this study examined for
these signatures in aged oil sands process water. Results suggested that the least cyclic fraction undergoes rapid biodegradation in active settling basins, but other fractions appear to be
recalcitrant, with half-lives of 12.813.6 years.
New methods continue to be developed, including one by
Barrow et al., which used APPI and ESI-FT-ICR-MS.206 Use of
APPI led to the observation of the greatest number of components in Athabasca oil sands process water. Oxygenated species
predominated, including NAs. NAs with higher hydrogen deciencies (potentially naphthenoaromatic compounds) were
more abundant using APPI vs ESI. The authors stressed the
importance of the use of dierent techniques to more fully
characterize these complex mixtures because the overall toxicity
is not expected to depend on the NAs alone. Kavanagh et al.
created a simple and rapid method using synchronous uorescence spectroscopy, which could detect the presence of aromatic
acids closely associated with NAs in <5 min without the need for
pretreatment.207 It was suggested that this method could be used
as a rapid screening tool for the movement of oil sands process
water into the environment.
MUSKS
Synthetic musk compounds are widely used as fragrance
additives in many consumer products, including perfumes, lotions,
sunscreens, deodorants, and laundry detergents. They can have
nitroaromatic structures, as in the case of musk xylene (1-tert-butyl3,5-dimethyl-2,4,6-trinitrobenzene) or musk ketone (4-tert-butyl2,6-dimethyl-3,5-dinitroacetophenone), or polycyclic structures, as
in the case of 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN; trade name, tonalide) 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB;
trade name, galaxolide, 4-acetyl-6-tert-butyl-1,1-dimethylindan
(ADBI; trade name, celestolide), dihydropentamethylindanone
(DPMI; trade name, cashmeran), or 5-acetyl-1,1,2,3,3,6-hexamethylindan (AHMI, trade name phantolide). Because they are widely
present in environmental samples, including wildlife and humans, there is growing concern. Musks are highly lipophilic, so
they tend to accumulate in sediments, sludges, and biota. Up to
190 ng/g lipid has been reported in humans.2
New methods utilize SPME and stir bar sorptive extraction.
For example, Silva and Nogueira created a new method using stir
bar sorptive extraction with large volume injection-GC/MS for
measuring celestolide, galaxolide, tonalide, and musk ketone in
environmental waters at 1219 ng/L detection limits.208 The
method, which used 30 mL sample volumes, was demonstrated
REVIEW
on tap water, river water, seawater, and urban wastewater.

Another stir bar sorptive extraction method was created by
Ramirez et al. who used thermal desorption-GC/MS for detection of 9 musks in wastewater, surface water, and RO-treated
water.209 Detection limits of 0.020.3 ng/L could be achieved.
Galaxolide was the most abundant musk found in wastewater (up
to 2069 and 1432 ng/L in inuents and euents, respectively).
Cashmeran, phantolide, and tonalide were also found, up to 94,
26, and 88 ng/L, respectively. Although nitromusks are prohibited for use in cosmetics in Europe, musk xylene and musk ketone
were still detected in wastewater euents and river samples.
Gomez created a new GC/MS method using large-volume
injection with backushing to measure musks and several other
contaminants in wastewaters and surface waters.210 Method
detection limits ranged from 1 to 36 ng/L. In addition, the
authors report a new synthetic fragrance metabolite, 4-amino
musk xylene, which was identied by full scan electron ionization
(EI)-MS. This compound was not present in the NIST library.
Sumner et al. investigated inputs and distributions of synthetic
musk fragrances in estuarine and coastal environments.211 High
concentrations of galaxolide and tonalide were present in wastewater treatment euents, up to 2098 and 159 ng/L, respectively,
which discharged into the Tamar and Plym Estuaries (UK).
Lower concentrations of celestolide, phantolide, musk xylene,
and musk ketone were found (430 ng/L). Levels were rapidly
diluted in the coastal outfall waters. Reiner and Kannan measured
polycyclic musks in water, sediment, and sh from the Upper
Hudson River in New York.212 Galaxolide and tonalide were
detected in water, up to 26 and 23 ng/L, respectively, and
bioaccumulation was observed in several sh species. Clara
et al. measured the occurrence of several musks in wastewater
and surface waters and investigated their fate during wastewater
treatment and anaerobic sludge digestion.213 Major sources of
polycyclic musks were households, whereas industrial inputs
were minor. For galaxolide and cashmeran, 100% of the load in
surface waters was derived from treated wastewater discharges.
Overall removal eciencies ranged from 50% to >95%, with
sludge being the main removal pathway.
Finally, Wombacher and Hornbuckle examined the occurrence
of 8 synthetic musk fragrances in source water and their removal
in dierent stages of conventional drinking water treatment that
used lime softening.214 The compounds were measured in the
water, waste sludge, and air throughout the plant. Galaxolide and
tonalide were detected in 100% of the samples. Total removal
averaged between 67 and 89% and was dominated by adsorption
to water softener sludge. Volatilization, chlorine disinfection, and
disposal of backwash water played a minor role in their removal.
Following drinking water treatment, galaxolide and tonalide were
still found, at low levels in nished waters, with average concentrations of 2.2 and 0.51 ng/L, respectively.
PESTICIDE TRANSFORMATION PRODUCTS

Herbicides and pesticides continue to be the focus of much
environmental research. Recent studies have focused more on
their transformation products because their hydrolysis, oxidation, biodegradation, or photolysis transformation products can
be present at greater levels in the environment than the parent
pesticide and can be as toxic or more toxic. Several pesticide
degradation products are on the U.S. EPAs new CCL-3: alachlor
ethanesulfonic acid (ESA), alachlor oxanilic acid (OA), acetochlor ESA, acetochlor OA, metolachlor ESA, metolachlor OA,
4639
3-hydroxycarbofuran, and terbufos sulfone (http://water.epa.
gov/scitech/drinkingwater/dws/ccl/ccl3.cfm), as well as on
the UCMR-2 (alachlor ESA and OA, acetochlor ESA and OA,
and metolachlor ESA and OA).
LC/MS and LC/MS/MS are now common place for measuring pesticide degradates, which are generally more polar than the
parent pesticides, making LC/MS ideal for their detection. In
addition, researchers are increasingly using UPLC to enable
simultaneous analysis of larger groups of pesticides, and TOFMS and Q-TOF-MS are being used to identify new pesticide
degradates. Vidal et al. published an extensive review on extraction and detection methods for pesticide transformation products in environmental, biological, and food samples and
included a discussion of problems that can be encountered with
their extraction.215 The analysis of target analytes as well as the
identication of unknown compounds with high resolution-MS
are also discussed, and a comprehensive listing of >100 transformation products of 49 dierent pesticides is provided.
Helbling et al. published a new high-throughput procedure for
the elucidation of transformation products (TP) for a broad and
diverse group of pesticides.75 Samples coming from batch
reactors seeded with activated sludge were separated by LC
and analyzed by linear ion trap-Orbitrap-MS. TPs were tentatively identied using a postacquisition data processing method,
which was based on target and nontarget screening of full-scan
MS data, and structures were proposed by interpretation of MS
and MS/MS fragments. Using this procedure, new microbial TPs
were reported for the pesticides. Results showed that the
complementary use of target and nontarget screening allowed
for more comprehensive identication of TPs. UPLC-MS/MS
was used by Benvenuto et al. for a new method to simultaneously
determine triazine and their TPs in surface water and wastewaters.216 Quantication and conrmation could be performed
at ng/L levels. UPLC/MS/MS was also used by Kowal et al. to
measure the polar pesticide transformation product, N,N-dimethylsulfamide, in environmental waters.217 The only sample
preparation step was the addition of an internal standard;
10 ng/L detection limits were achieved. Using this method,
>600 samples of drinking water, surface, water, and groundwaters
were measured in the Rhine and Ruhr region of the North Rhine
River (Germany); approximately 65% of the samples contained
measurable levels, up to 63 g/L.
While most analytical methods developed utilize sophisticated
MS methods, two simpler ones were created recently for
measuring pesticides and their metabolites. For example, Sanchez-Bayo published a new LC/electrochemical (EC) detection
method to measure amitrole, glyphosate, and its aminomethylphosphonic acid metabolite in environmental waters.218 Passive
samplers were used for concentration, and detection limits of
0.03 to 0.3 g/L were achieved. Dispersive liquidliquid microextraction (DLLME) was used with LC-UV detection in another
method by Zhou et al. for measuring dichlorodiphenyltrichloroethane (DDT) and its metabolites in environmental waters.219
Detection limits ranged from 0.32 to 0.51 g/L.
Occurrence and fate studies continue to be conducted for
pesticides and their metabolites. In the pan-European survey
mentioned earlier by Loos et al., pesticide transformation
products were included and were among the most frequently
detected and highest concentration of the many analytes measured in European groundwaters.125 For example, desethylatrazine and desethylterbutylazine were found in 55 and 49% of the
samples, up to 487 and 266 ng/L, respectively. Occurrence and
REVIEW
degradation of N-chloridazon was the focus of a study by

Buttiglieri et al., who measured >500 samples of groundwater,
surface water, and wastewaters using SPE and GC/MS and LC/
MS/MS.220 N-Chloridazon was measured up to 0.89 g/L, and
its degradation product, desphenyl-chloridazon (DPC), was
found at much higher levels, up to 7.4 g/L. Methylated-DPC,
another degradation product, was also detected in surface waters.
In separate aerobic degradation tests, N-chloridazon was completed converted to DPC, which was stable up to 98 days. Chiron
et al. measured pesticides and their transformation products in
southern France.221 MCPA [(4-chloro-2-methylphenoxy)acetic
acid] was found to transform by photolysis according to the
following sequence: MCPA f 4-chloro-2-methylphenol (CMP) f
4-chloro-2-methyl-6-nitrophenol (CMNP). CMNP was more
environmentally persistent than the parent compound. While
nitration of chlorophenols typically reduces their acute toxicity,
there is concern over the genotoxic eects of nitro compounds.
Irradiation experiments suggested that the photonitration of
CMP to CMNP involved nitrogen dioxide, generated from the
photolysis of nitrate and photooxidation of nitrite by OH radical.
Fe(III) is also believed to play a role. Finally, Wang et al.
identied hydrolysis products of dyfonate, an organophosphorus
insecticide, in simulated water treatment using UV and GC/MS
detection.222 Two hydrolysis products were identied: thiophenol and phenyl disulde.
PERCHLORATE
Perchlorate became an important environmental issue following its discovery in a number of water supplies in the western
United States. It has since been found in environmental waters
across the United States and in other parts of the world at g/L
levels, as well as in fresh produce, foods, wines, and beverages
from many countries, including those in Europe and the Far East.
Perchlorate has also been found in biological samples, and it can
be transported by pregnant mothers to their developing baby
across the placental barrier. Perchlorate is increasingly being
found in environmental waters following reworks displays. As a
result, it is now recognized as a worldwide environmental issue,
rather than only being limited to the United States. Ammonium
perchlorate has been used in solid propellants used for rockets,
missiles, and reworks, as well as highway ares. There is also
potential contamination from fertilizers (e.g., Chilean nitrate,
where perchlorate co-occurs naturally), and new work has
revealed other natural sources of perchlorate. In addition, perchlorate can be a contaminant in sodium hypochlorite (liquid
bleach) that is used in drinking water treatment. Perchlorate is an
anion that is very water-soluble and environmentally stable. It can
accumulate in plants (including lettuce, wheat, and alfalfa), which
can contribute to exposure in humans and animals. In addition,
perchlorate is not removed by conventional water treatment
processes, so human exposure could also come through drinking
water. Health concerns arise from perchlorates ability to displace
iodide in the thyroid gland, which can aect metabolism, growth,
and development.
Due to these concerns and due to the proportion of the U.S.
population exposed to it, the U.S. EPA has now decided to
regulate perchlorate under the Safe Drinking Water Act (http://
water.epa.gov/drink/contaminants/unregulated/perchlorate.
cfm). The regulation is currently being developed, and there is
not a proposed MCL as of yet. (See earlier section on
New Regulations/Regulatory Methods for further details.)
4640
Perchlorate was previously on the U.S. EPAs CCL (CCL-1 and
CCL-2 and is now on the CCL-3; http://water.epa.gov/scitech/
drinkingwater/dws/ccl/ccl3.cfm). Perchlorate was also included
in the rst UCMR (http://water.epa.gov/lawsregs/rulesregs/
sdwa/ucmr/data.cfm). The U.S. EPA established a reference
dose of 0.0007 mg/kg/day, which translates to a drinking water
equivalent level (DWEL) of 24.5 g/L.1 Prior to this national
decision to regulate, California had already issued a state regulation of 6 g/L (in 2007) (www.cdph.ca.gov/certlic/drinkingwater/Pages/Perchlorate.aspx), and several states had issued
advisory levels, ranging from 1 to 18 g/L (www.epa.gov/
fedfac/documents/perchlorate_links.htm#state_adv). There
are several EPA Methods for measuring perchlorate in water,
including EPA Method 314.2 (2-dimensional IC with suppressed
conductivity detection), EPA Method 331 (LC/ESI-MS/MS),
and EPA Method 332 (IC/ESI-MS/MS) (www.epa.gov/safewater/methods/analyticalmethods_ogwdw.html; www.epa.gov/
nerlcwww/ordmeth.htm).
Parker reviewed the occurrence of perchlorate in the environment and provided evidence of widespread natural occurrence.223
Furdui and Tomassini published a fascinating study of trends and
sources of perchlorate in Arctic snow.224 Samples from the
Devon Island ice cap in Canada were used to calculate the annual
input of atmospherically formed perchlorate. Ice cores were
dated between 1996 and 2005, and IC/ESI-MS/MS was used
for measurement. Concentrations varied between 1 and 18 ng/L
and were correlated with total ozone levels from this area. Data
suggested that perchlorate from the Arctic snow was formed in
the atmosphere by two dierent mechanisms: (1) Stratospheric
chlorine radicals reacted with ozone year-round, producing
concentrations of perchlorate correlated with the total ozone
level; (2) During the summer months, perchlorate was likely
formed in the troposphere. Interestingly, a deep ice core sample
revealed that perchlorate was present in precipitation at similar
concentrations more than 2000 years ago. The total estimated
amount that reached the Arctic in 2005 was 4186 t.
Jackson et al. evaluated the isotopic composition of natural
perchlorate indigenous to the southwestern U.S. to understand
its origins.225 Stable isotope ratios were measured for perchlorate
(18O, 17O, 37Cl) and associated nitrate in groundwater from
the southern High Plains of Texas and New Mexico and the
Middle Rio Grande Basin in New Mexico, unsaturated subsoil in
the southern High Plains, and nitrate-rich deposits near Death
Valley, California. Results showed that natural perchlorate in the
southwestern U.S. has a wide range of isotopic compositions that
are distinct from those reported previously from the Atacama
Desert of Chile, as well as for synthetic perchlorate. Results from
Death Valley samples indicated partial atmospheric formation via
reaction with ozone. In contract, perchlorate isotope ratios from
western Texas and New Mexico indicated that they were aected
by postdepositional oxygen isotope exchange. This study provides important new information on the possibility of divergent
perchlorate formation mechanisms and isotopic exchange in
biologically active environments.
Rao investigated perchlorate formation by ozone oxidation of
aqueous chlorine/oxy-chlorine species (Cl, OCl, ClO2,
ClO3, and ClO2).226 Higher reaction rates were observed for
higher oxidation states of chlorine, except for ClO3, which did
not react with ozone. The slow rate of perchlorate production
from Cl suggested minimal potential for perchlorate formation
in drinking water or wastewater systems that use ozone for
treatment. A potential formation pathway for perchlorate from
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Cl was proposed, which involved ClO2 and higher oxy-chlorine

radicals and intermediates (e.g., Cl2O6) in its formation.
Recent studies have addressed perchlorate occurrence in drinking
water. For example, Brandhuber et al. compiled data from the
rst UCMR, as well as from state surveys carried out in Arizona,
California, Massachusetts, and Texas.227 Perchlorate was detected
in 26 states, including 5% of the large public drinking water
systems (serving >10 000 people each). Due to perchlorate
contamination, many potable water systems have been taken
o-line (estimated at 50 mgd). When detected, perchlorate was
generally present at <12 g/L levels. In another study, Blount
et al. investigated perchlorate, nitrate, and iodide intake through
direct and indirect consumption of tap water.228 Median perchlorate levels measured in tap water were 1.16 g/L, which were
below the U.S. EPAs drinking water equivalent level of 24.5 g/L.
Signicant correlations were found between perchlorate and
nitrate. Using individual tap water consumption data and body
weight, the median perchlorate dose attributable to tap water was
9.11 ng/kg-day.
New methods for perchlorate include a creative one by
Gertsch et al., who developed a microchip electrophoresis system
to measure perchlorate in drinking water at ppb levels.229 This
system was inexpensive and rapid, oering portability, high
selectivity, minimal sample pretreatment, and reduced analysis
time relative to IC methods. In tap water, detection limits of 5.6
g/L were reported. Finally, Sturchio et al. explored the use of
36
Cl measurements for improving the discrimination of perchlorate sources.230 Stable chlorine and oxygen isotope ratios had
been used previously to distinguish sources of perchlorate, but
the additional use of 36Cl data from accelerator mass spectrometry measurements was able to provide a clear distinction
among the 3 principal perchlorate source types in the environment: synthetic perchlorate, natural perchlorate from soils and
groundwater of the Atacama Desert, and natural perchlorate
from the southwestern U.S.
ALGAL TOXINS
Algal toxins (mostly cyanobacterial toxins produced from
blue-green algae) continue to be of increasing interest in the
United States and in other countries around the world. Increased
discharges of nutrients (from agricultural runo and from wastewater discharges) have led to increased algal blooms and an
accompanying increased incidence of shellsh poisoning, large
sh kills, and deaths of livestock and wildlife, as well as illness and
death in humans. Toxins produced by these algae have been
implicated in the adverse eects. There was even a recent report
of the death of rhinoceros and other large animals in a national
park in South Africa, where microcystin-LR was responsible.231
An unusually high hippopotamus density had led to high urine
and fecal loadings, which caused an increased growth of Microcystis aeruginosa and subsequent release of extraordinarily high
levels of microcystins.
The most commonly occurring algal toxins are microcystins,
nodularins, anatoxins, cylindrospermopsin, and saxitoxins. Red
tide toxins are also often found in coastal waters. Microcystins and nodularins are hepatotoxic high molecular weight,
cyclic peptide structures. Anatoxins, cylindrospermopsin, and
saxitoxins are heterocyclic alkaloids; anatoxins and saxitoxins are
neurotoxic, and cylindrospermopsin is hepatotoxic. Red tide
toxins include brevetoxins, which have heterocyclic polyether
structures and are neurotoxic. Microcystins (of which, more than
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70 dierent variants have been isolated and characterized) are the
most frequently reported of the algal toxins.
The most common microcystins are cyclic heptapeptides that
contain the amino acids leucine and arginine in their structures.
Nearly every part of the world that uses surface water as a drinking
water source has encountered problems with cyanobacteria and
their toxins. Algal toxins were on the U.S. EPAs previous CCLs
(CCL-1 and CCL-2) in a general way, cyanobacteria (bluegreen algae, other freshwater algae, and their toxins, and now,
the CCL-3 has specically named three cyanobacterial toxins:
anatoxin-a, microcystin-LR, and cylindrospermopsin for the new
list (http://water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.
cfm). Several countries, including Australia, Brazil, Canada,
France, and New Zealand, have guideline values for microcystins,
anatoxin-a, and cylindrospermopsin (ranging from 1.0 to
1.5 g/L). Many of these toxins have relatively high molecular
weights and are highly polar. New methods for algal toxins
include those using UPLC/MS, IR-MALDI-TOF-MS, and uorescent immunochromatography, as well as new sensors.
In 2010, a special issue of the journal Toxicon, on Harmful
Algal Blooms and Natural Toxins in Fresh and Marine Waters,
included 14 papers on the exposure, occurrence, detection,
toxicity, control, management, and policy.232 This issue is a mustread for the latest state-of-the science for algae and their toxins.
New methods include a particularly clever one from Morais
et al., who created a new microsensor array on the polycarbonate
side of ordinary compact discs (CDs) to measure microcystins in
water.233 The method was based on the principle of indirect
competitive microimmunoassay, where free microcystin-LR
competes with immobilized conjugate for a specic monoclonal
antibody. Each disk surface was designed with 48 arrays; the
hydrophobic nature of the polycarbonate side of the disk, along
with the array distance and low sample volume used, prevented
cross-contamination of samples. The article includes nice photos
showing the arrays on the CDs. Immunoreactions were detected
with a DVD drive, which displayed the readouts in minutes.
Detection limits of 1.04 g/L could be achieved over a linear
range of 0.12 to 2.0 g/L, which encompasses the WHO upper
limit in drinking water and is comparable to other screening
methods. This method was simple, sensitive, and rapid and could
be used in a high-throughput capacity for eld use. Precoated
discs were stable for at least 7 weeks without losing their
analytical performance. The assay also showed high congener
reactivity to microcystin-LY, -LA, -LF, -LW, -YR, and nodularin.
The applicability of this method was tested on 42 samples of river
water, where the eect of the water matrix was found to be
negligible.
Another clever method involved the use of carbon nanohorns
in electrochemical immunosensors for rapid detection of microcystin-LR in water.234 The single-walled carbon nanohorns
(SWNHs) were functionalized by covalently binding microcystinLR to the carboxylic groups on the cone-shaped tips of the SWNHs
in the presence of linkage reagents. They were characterized using
Raman spectroscopy, X-ray photoelectron spectroscopy, scanning
electron microscopy, and transmission electron microscopy.
SWNHs were determined to be more sensitive than singlewalled carbon nanotubes, and a detection limit of 0.03 g/L
could be achieved, with a linear response of 0.05 to 20 g/L.
Good agreement was shown with reference values.
UPLC/MS/MS was used in a method by Oehrie et al. to
improve chromatographic resolution and increase the speed of
analysis for cyanotoxins.235 With UPLC, the cyanotoxins,
REVIEW
including cylindrospermopsin, anatoxin-a, nodularin, and microcystin-LR, -RR, -YR, -LA, -LY, -LW, and -LF, could be resolved
and analyzed in <8 min. Without sample enrichment, analytes
could be detected at 0.5 ppb levels. Another method developed
by Meisen et al. coupled thin layer chromatography (TLC) and
UV spectroscopy with IR-MALDI-TOF-MS to measure microcystin-LR and nodularin.236 Detection limits were 5 ng for UV
detection and 3 ng for MS. Mekebri et al. developed a LC/ESIMS/MS method to measure 6 microcystins in water, bivalves,
and sh, providing improved detection limits from other methods in the literature.237 Detection limits between 0.2 and 1 pg oncolumn (0.010.03 g/L in water) were possible. Further, this
method allowed the detection of microcystin metabolites,
desmethyl-LR and desmethyl-RR, which were subsequently identied and measured in real lake samples, along with the parent
microcystins. Microcystin-RR, -LR, and -YR were found at averages
of 68.2, 76.5, and 1.68 g/L in lake water samples impacted by a
natural algal bloom of Microcystis aeruginosa. Desmethyl-RR and
desmethyl-LR were found at averages of 70.2 and 66.5 g/L,
respectively. Finally, uorescent immunochromatography was used
in a new method by Khreich et al. for measuring microcystins and
nodularins.238 Monoclonal antibodies labeled with uorescent
liposomes (called immunoliposomes) were developed as tracers
to allow the detection of a large number of microcystins and
nodularin variants in water samples. The uorescent signal
generated by these immunoliposomes can be measured and
quantied using a small transportable, easy-to-use uorometer.
This method proved to be 10 more sensitive than a previous
immunochromatographic test using colloidal gold for labeling.
Detection limits of 0.06 g/L for microcystin-LR were achieved.
Several good fate studies have been published recently. For
example, Wormer et al. investigated the natural photodegradation of
microcystins (-LR, -RR, and -YR) and cylindrospermopsin.239
LC with photodiode array detection was used to measure the
microcystins; UPLC/MS/MS was used to measure cylindrospermopsin. Photodegradation of cylindrospermopsin was highly
dependent on UV-A and was very low under natural conditions.
Microcystin photodegradation was higher at all 3 radiation bands
tested (photosynthetic active radiation [PAR], UV-A, and UV-B),
with UV-A and PAR being more pronounced. Results showed
that photodegradation can play an important role in the fate of
microcystins in some situations, including shallow waters or thin
mixed layers in deep, stratied systems.
Studies continue to investigate the oxidation of algal toxins. For
example, as mentioned earlier in the DBPs of Pollutants Section, 8
new chlorination byproducts of microcystin-LR and cylindrospermopsin were identied: chloro-microcystin, chloro-dihydroxy-microcystin, dichloro-dihydroxy-microcystin, trichlorohydroxy-microcystin, and several dihydroxy-microcystins.171 In
a follow-up review article, Merel et al. discussed the chlorination
of cylindrospermopsin, saxitoxins, and nodularin, as well as
microcystins.240 All algal toxins were eciently transformed by
chlorine and showed a resulting loss in acute toxicity. DBPs
were identied for microcystins and cylindrospermopsin. In
contrast, anatoxin-a exhibited slow reaction kinetics, suggesting that it is resistant to chlorination.
MICROORGANISMS
Outbreaks of waterborne illness in the United States and other
parts of the world have necessitated improved analytical methods
for detecting and identifying microorganisms in water and other
4642
environmental samples. Several microorganisms are included on
the new CCL-3 (http://water.epa.gov/scitech/drinkingwater/
dws/ccl/ccl3.cfm) (Table 4). The U.S. EPAs National Exposure Research Laboratory in Cincinnati has developed several
methods for measuring microorganisms in water (www.epa.gov/
nerlcwww). These include methods for Cryptosporidium, Giardia,
E. coli, Aeromonas, coliphages, viruses, total coliforms, and
enterococci. E. coli O157:H7 and H1N1 (swine u) have
captured a lot of attention recently because they have caused a
number of outbreaks and deaths around the world. Traditional
biological methods are often used for detection of microorganisms, including cell culture, immunological methods, polymerase
chain reaction (PCR), and microscopic identication, but ESI
and MALDI-MS methods are also often used.
In a new review article, Vikesland and Wigginton discussed a
promising but currently underdeveloped area for the future of
drinking water pathogen monitoring: nanomaterial-enabled
biosensors.241 The authors summarize the state-of-thescience for nanoenabled biosensors but highlight the fact that
only a few studies have focused on detection of whole cells and
waterborne pathogens, suggesting this as a signicant opportunity for environmental monitoring. While a wide variety of
nanomaterial-enabled bioassays have been developed for
pathogens, their suitability under environmental conditions
has not been established. Problems, such as nonspecic
binding, particle size variation, nanoparticle aggregation, and
nanoparticle stability, must be addressed to make these
techniques useful for environmental monitoring. In addition,
the dierentiation of viable from nonviable cells and the
detection of viable but noncultural organisms is not yet
possible with these techniques.
In another review, Girones et al. discuss the pros and cons of
molecular techniques for detection of pathogens in water.242
They discuss the fact that the range of methods has increased,
which has facilitated the identication, genotyping, enumeration, viability assessment, and source-tracking of human and
animal contamination. Also, recent improvements have allowed
the simultaneous detection of multiple targets in a single assay.
However, the authors discuss the need for yet improved
methods that can be applied to diverse matrixes, including
disinfected waters, which may aect the viability of pathogens,
whose numbers can be overestimated by molecular techniques.
Jofre and Blanch published a review outlining the feasibility of
methods based on nucleic acid amplication techniques for
analysis of microorganisms.243 Positive aspects of nucleic acid
methods include the potential for identifying isolates from
conventional culture methods, providing data on culturable
and nonculturable microorganisms, information on the presence of pathogens in waters, determining the causes of waterborne outbreaks, and in some cases, detecting emerging
pathogens. Challenges discussed include the varied composition
of water samples, low numbers of target microorganisms, varied
water quality required for dierent uses, and the physiological
state of the microorganisms, as well as the need for standardized
molecular techniques.
New microorganism methods include one by Wildeboer et al.
that uses a hand-held uorescence detector for the rapid detection of E. coli in water.244 This method is based on the use of
4-methyl-umbelliferone--D-glucuronide as a substrate. Results
obtained with the hand-held device compared favorably to those
obtained with an established uorescent substrate assay and by
quantifying microbial growth on a chromogenic medium. This
REVIEW
method was used to analyze samples obtained from the River

Thames. The miniaturized uorescence detector allowed reduced incubation times, making the device portable and rapid.
E. coli levels as low as 7 cfu/mL could be detected in a river
sample. It was pointed out that this technique can be used in
conjunction with dierent uorescent substrates to target other
organisms.
A real-time PCR assay was developed by Yanez et al. to
measure Helicobacter pylori in water.245 This method is based on
the amplication of a fragment of a gene specic to H. pylori and
the use of an external standard for quantication. Linearity and
specicity of the method were excellent, and quantication limits
were 607 genomic copies. This method was demonstrated using
69 water samples, including drinking water, surface water, and
wastewater. Three wastewater samples were found to be positive
for H. pylori; all other samples were negative.
Gold nanoparticle labeling was used with ICP-MS in a new
method by Li et al. to measure E. coli O157:H7 in water.246
This method took advantage of the signal amplication
property of gold nanoparticles, monoclonal antibody recognition, and the high sensitivity of ICP-MS, which enabled the
detection of as few as 500 E. coli O157:H7 cells in a 1 mL
sample. Specicity was excellent, as nonpathogenic forms of
E. coli did not bind or adsorb to the antibody-conjugated gold
nanoparticles, and tests with these showed only background
signals equivalent to the blanks. The specicity of this assay is
due to the specic antibodies used for E. coli O157:H7. The assay
was also very rapid, requiring only 40 min. Because of the ability
of ICP-MS to detect a wide range of elements, the applicability of
this technique could be extended to other nanoparticles (including
silver and rare earth nanoparticles), and potentially be used in a
high throughput capacity to enable multiple bacterial cells to be
measured simultaneously, through the use of dierent antibodies
for dierent cells.
Quantication of viable but nonculturable (VBNC) E. coli
O157:H7 was the focus of a new method by Liu et al.247 This onestep quantication method combined reverse transcription and
real-time quantitative PCR and was capable of quantifying as few
as 7 E. coli O157:H7 cells in pure culture, 9 culturable cells in tap
water and river water, and 23 VBNC cells in river water, which are
the best quantication limits to-date for environmental waters.
Measurement of a selective marker in VBNC E. coli O157:H7
that was not present in dead cells or the negative controls serves
as the basis for this method, which showed a linear dynamic range
>6 orders of magnitude and >90% amplication eciency for
tap and river water samples. This technique is important because
E. coli O157:H7 easily becomes VBNC under environmental
stresses (including disinfection) and escapes detection by current
methods. An earlier paper by Liu previously demonstrated
how E. coli O157:H7 could enter a VBNC state following
chloramination in tap water but could resuscitate themselves
back into an infective form.248 As a result, it is important to be
able to detect these VBNC forms that can remain a potential
health risk.
CONTAMINANTS ON THE HORIZON: IONIC LIQUIDS

Ionic liquids are organic salts with a low melting point
(<100 C) that are being promoted as green chemistry
replacements to traditional solvents used in industry.249,250 They
are currently one of the hottest areas in chemistry, with many
papers and reviews highlighting ionic liquids as a state-of-the-art,
4643
innovative approach to sustainable chemistry, due to their low
vapor pressures and ammability. However, there is limited
toxicity and environmental data for these new green solvents,
and there is the potential that they may pose a threat to
aquatic and terrestrial ecosystems. While not volatile, most ionic
liquids are highly water-soluble and chemically and thermally
stable, creating the potential for entry and persistence in the
environment. Ionic liquids have unique properties including
tunable viscosity, miscibility, and electrolytic conductivity, which
make them useful for many applications, including organic
synthesis and catalysis, production of fuel cells, batteries, coatings, oils, and nanoparticles, as well as other chemical engineering
and biotechnology applications. Their chemical structures typically
involve a cationic or anionic polar headgroup with accompanying
alkyl side chains. Cationic head groups include imidazolium,
pyridinium, pyrrolidinium, morpholinium, piperidium, quinolinium, quaternary ammonium, and quaternary phosphonium
moieties; anionic head groups include tetrauoroborate
(BF4), hexauorophosphate (PF6), bis(triuoromethylsulfonyl)imide [(CF3SO2)2N], dicyanamide [(CN)2N], chloride, and
bromide.249 Pham et al. wrote an excellent, thought-provoking
review on the environmental fate and toxicity of ionic liquids,
outlining these concerns and summarizing the toxicity
data, antibacterial activity, chemical and biodegradation, and
sorption in environmental systems.249 Current data show that
ionic liquids are toxic in nature and that their toxicities vary
considerably across organisms and trophic levels. Introduction of
polar groups to the alkyl chains has been shown to decrease their
toxicity and increase biodegradation, suggesting the possibility of
tailoring the chemical structures to produce more environmentally friendly compounds. A recent review by Sun and Armstrong
summarizes recent analytical chemistry papers devoted to ionic
liquids, including those covering extractions, GC, LC, CE, MS,
electrochemistry, sensors, and spectroscopy.250
BIOGRAPHIES
Susan D. Richardson is a research chemist at the U.S.
Environmental Protection Agencys National Exposure Research
Laboratory in Athens, GA. She received her B.S. degree in
Chemistry and Mathematics from Georgia College in 1984 and
her Ph.D. degree in Chemistry from Emory University in 1989.
Her research has focused on the identication, characterization,
and quantication of new toxicologically important disinfection
byproducts (DBPs), with special emphasis on alternative disinfectants and polar byproducts. She is particularly interested in
promoting new health eects research so that the risks of DBPs
can be determined and minimized.
Thomas A. Ternes graduated with an undergraduate degree in
Chemistry from the University of Mainz (Germany) in 1989. In
1993, he completed his Ph.D. at the University of Mainz in
Analytical Chemistry. In January 2001, he completed his
habilitation and became an ocial lecturer at the University
of Mainz. Since 1995, his research has focused on the analysis
and fate of organic pollutants, such as pharmaceuticals and
personal care products (PPCPs), in various kinds of environmental matrixes. Dr. Ternes was the coordinator of the Pharmacluster project POSEIDON (http//www.eu-poseidon.com)
dealing with the removal of PPCPs in wastewater and drinking
water treatment, soil aquifer treatment, and environmental
risk assessment. Since May 2003, he has been at the Federal
REVIEW
Institute of Hydrology (BfG) in Koblenz, Germany, where he is

the head of the water chemistry department and is responsible
for the coordination and management of research projects in
the eld of organic pollutants and their removal during wastewater treatment and drinking water treatment.
ACKNOWLEDGMENT
S.R. would like to thank Jody Shoemaker and Jean Munch of
the U.S. EPA for information on new EPA methods (they have
developed many for EPA), Shay Fout of the U.S. EPA for
information on the new EPA Method 1615, Stig Regli of the U.S.
EPAs Oce of Water for helpful information on the new
proposed perchlorate regulation, Jon Martin of the University
of Alberta, Mary Kaiser of DuPont, and Tom Jenkins of the U.S.
EPA for helpful information on PFCs, John Sumpter of Brunel
University for the incredible presentation he gave recently that
alerted me to the issue with the vultures and diclofenac, Robert
Loos of the European Commission's Joint Research Centre
Institute for Environment and Sustainability for helpful information on algal toxins, Jim Evans of SRA International for designing
our nice TOC art, and David Humphries of the Alberta Research
Council for daily inspiration. This paper has been reviewed in
accordance with the U.S. EPAs peer and administrative review
policies and approved for publication. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use by the U.S. EPA.
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Emerging Contaminants and Current Issues

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Water Analysis: Emerging Contaminants and Current Issues

dx.doi.org/10.1021/ac200915r | Anal. Chem. 2011, 83, 46144648

atmospheric pressure chemical ionization

atmospheric pressure photoionization

Contaminant Candidate List

electron capture detection

endocrine disrupting compounds

enzyme-linked immunosorbent assay

ethane sulfonic acid

uorinated telomer alcohols

hypercrosslinked polymer resin

inductively coupled plasma

matrix-assisted laser desorption ionization

maximum contaminant level

membrane introduction mass spectrometry

negative chemical ionization

nuclear magnetic resonance

N-ethyl peruorooctane sulfonamide acetate

polybrominated diphenyl ethers

Registration, Evaluation, and Authorization of Chemicals

solid phase extraction

solid phase microextraction

the third Unregulated Contaminants Monitoring Rule

wastewater treatment plant

references and to mainly focus on new trends. Even with a more

dx.doi.org/10.1021/ac200915r |Anal. Chem. 2011, 83, 46144648

dx.doi.org/10.1021/ac200915r |Anal. Chem. 2011, 83, 46144648

Table 2. Useful Websites

U.S. EPA approved methods for drinking water compliance monitoring

link to Standard Methods Online

link to ASTM International methods

and microorganisms. These continue to be intense areas of

environment.9 Contaminants included stimulants, fragrances,

NEW REGULATIONS/REGULATORY METHODS

dx.doi.org/10.1021/ac200915r |Anal. Chem. 2011, 83, 46144648

Table 3. Recent U.S. Rules/Regulations

Stage 2 D/DBP Rule

Contaminant Candidate List (CCL)-3

Draft Third Unregulated Contaminants Monitoring

UCMR-2 national occurrence data

Protection Agency (EPA) has decided to regulate perchlorate

dx.doi.org/10.1021/ac200915r |Anal. Chem. 2011, 83, 46144648

Methyl bromide (Bromomethane)

Methyl tert-butyl ether

Metolachlor ethanesulfonic acid (ESA)

Metolachlor oxanilic acid (OA)

Acetochlor oxanilic acid (OA)

Alachlor ethanesulfonic acid (ESA)

Alachlor oxanilic acid (OA)

Peruorooctane sulfonic acid (PFOS)

Chloromethane (Methyl chloride)

Triphenyltin hydroxide (TPTH)

Ethinyl estradiol (17R-ethinyl estradiol)

Halon 1011 (bromochloromethane)

dx.doi.org/10.1021/ac200915r |Anal. Chem. 2011, 83, 46144648

Table 5. Draft Unregulated Contaminants Monitoring Rule

List 1. Assessment Monitoring

EPA Method 539

EPA Method 539

(Table 6): Method 539 (hormones), 538 (pesticides, quinoline,

EPA Method 539

EPA Method 539

EPA Method 539