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In this Issue
2 Introduction -
Endocrine Disrupting Chemicals
and Pharmaceuticals and
Personal Care Products: A
Closer Look at Occurrence,
Relevance, and Treatment
3 Project Updates
6 Feature Story -
Occurrence and Impact of
Endocrine Disrupting Chemicals
in Water and Wastewater
12 What’s New
INTRODUCTION
March 9th, 2008 - The Associated Press and EDCs in Reclaimed Water,” pp. 5; and
reports that a vast array of pharmaceuticals “Carollo Studies the Fate of EDCs and
— including antibiotics, anti-convulsants, PPCPs Through Advanced Wastewater
mood stabilizers, and sex hormones Membrane Systems and the Biological
— have been detected in the drinking Impact of Effluent on Aquatic Organisms,”
water supplies of at least 41 million pp. 10) and an example of what one
Americans. wastewater utility is doing to manage
EDCs in their effluent (“Testing and
Recent press releases and media Design of Advanced Treatment Facilities
attention have raised substantial to Remove EDCs/PPCPs in Park City, UT,”
concerns among the public, politicians, pp. 3). Finally, our What’s New section
and regulators about the potential tackles the question all this new
implications of the presence of endocrine information raises: “What Does
disrupting chemicals (EDCs) and Our research team is investigating the It All Mean?,” pp. 12.
pharmaceuticals and personal care occurrence, fate, treatment, and significance of
products (PPCPs) in water for human trace organic compounds in water and wastewater. It is our intent
health and the environment. As a that this
result, the water and wastewater community related microcontaminants. Supplementing Special Edition
faces many questions, including: this overview of EDC occurrence and of Research
effects are four Project Updates highlighting Solutions provides
1. Are there potential human health and/ some current Carollo-led projects that are you with a snapshot of some of the latest
or aquatic impacts from these trace advancing our understanding of how best information on EDCs that may be useful for
contaminants? to mitigate EDCs in water, wastewater, water and wastewater utility managers as
2. What is the appropriate level of and reuse water. This includes both on- they go forward in assessing whether or not
treatment? going research into the efficacy of various this is an issue for your utility, and if so, how
3. What technologies can we use? treatment methods (“Removal of NDMA, you might approach managing it.
4. How much will it cost? EDCs, and PPCPs from South Delta Water,”
pp. 4; “Filtration and Destruction of PPCPs — Andrew Salveson, Special Editor
This special edition of Research Solutions
was put together by Carollo, working with
some of its research partners in emerging What are “pharmaceutically active compounds”?
contaminants, to provide water and
wastewater utility managers with up-to- Pharmaceuticals include human and veterinary drugs, both prescription and
date information on the important issues of over-the-counter medications. Examples of anthropogenic pharmaceuticals that
occurrence, impact, and treatment of these have been measured in the environment include antibiotics, antidepressants,
chemicals as it pertains to drinking water, heart medications, anti-convulsants, pain relievers, oral contraceptives, and x-ray
wastewater, and reclaimed water. contrast media. The term “pharmaceutically-active compounds” (PhACs) is
sometimes used in recognition of the fact that both the parent compounds and/or
In this issue’s Feature Story (“Occurrence their biologically active degradation products may be found in the environment.
and Impact of Endocrine Disrupting
re s e ar ch so l ut io n s
Chemicals in Water and Wastewater,” PhACs and personal care products (PCPs) are often grouped together under the
pp. 6), Dr. Shane Snyder distills and acronym “PPCPs.” Most PPCPs are active ingredients or preservatives in cosmetics,
simplifies the confusing mountain of data toiletries, fragrances, sunscreen lotions, and insect repellents. Endocrine disrupting
published on EDCs to help readers better chemicals (EDCs) are substances that can interfere with the actions of hormones
understand where they have been observed, in the body. Hundreds of chemicals have been identified to be EDCs or potential
2 what we know and don’t know about their EDCs, including industrial chemicals, pesticides, PPCPs, combustion byproducts
effects on the environment and in humans, (natural and anthropogenic), metals, inorganic ions, organic substances naturally
and how Federal and State regulators found in plants and fungi, and hormones excreted by humans and other animals.
currently approach managing EDCs and
PROJECTUPDATES
Testing and Design of Advanced Treatment
Facilities to Remove EDCs/PPCPs in Park City, UT
Background and Design Objectives Results KEY TEAm mEmbERS
For each removal technique, sampling
Snyderville Basin Water Reclamation and Project of treated and untreated effluent was
clint Rogers
District (SBWRD) in Park City, UT, designed to quantify and compare EDC
Direction (crogers@carollo.com)
concentrations, estrogenic activity (by
operates two wastewater treatment Bench- and craig Ashcroft, P.E.
facilities, East Canyon and Silver Creek. E-Screen bioassay), and water quality
pilot-scale
Measurable concentrations of EDCs and parameters (biological oxygen demand
testing of GAC contactors was conducted
PPCPs were found in both the influent and [BOD], total suspended solids [TSS],
at East Canyon using tertiary effluent from
effluent from these facilities; SBWRD is total organic carbon [TOC], ultraviolet
the existing granular media filters. Three
concerned about the potential hormonal transmittance at 254 nm [UVT], and/
GAC columns were dosed at a filter loading
impacts of treated effluent on sensitive fish or coliform counts). In an attempt to
rate of 3.5 gpm/ft2, which matches the rate
species. As part of a design project currently reduce the cost of analytical chemistry
of the full-scale filters, and sampled once a
underway to upgrade and expand both and focus on some of the EDC compounds
week over a 6-week study period. Samples
facilities, Carollo was asked to look for ways that may contribute most to the potential
were also sent to labs for bench-scale testing
to incorporate EDC/PPCP treatment. estrogenicity of fish, only the first phase of
of advanced oxidation processes (ozone,
an analytical quantification method (USGS
ozone/peroxide, UV, and UV/peroxide).
Carollo conducted bench- and pilot-scale Method 2, LC/MS APCI positive-ion mode
Applied Process Technology, Inc. (Pleasant
studies of three EDC/PPCP treatment only) was used for pilot and bench-scale
Hill, CA) performed testing on the plant
technologies: granular activated carbon analyticals. This narrowed the spectrum
effluents using three different ozone doses
(GAC) adsorption, ozone/peroxide of possible EDC/PPCP tests to just six
(5, 10, 15 ppm) and two ozone/peroxide
advanced oxidation, and ultraviolet light compounds: Carbamazepine, Estrone,
doses (peroxide:ozone molar ratios of 0.35
(UV)/peroxide advanced oxidation. Estradiol, Ethinyl Estradiol-17 alpha,
and 0.70 at an ozone dose of 5 ppm). UV
Reverse osmosis membranes were not Progesterone, and Testosterone. Results are
and UV/peroxide testing was performed
considered due to budget and concentrate summarized as follows:
by Dr. Karl Linden at Duke University
disposal limitations. Carollo evaluated the (Durham, NC) [he is now at University
treatment effectiveness of each technology • Plant effluent concentrations for the six
of Colorado-Boulder]. Plant effluent was
and estimated the cost of full-scale EDCs of interest ranged from 146 to
treated at a UV fluence of 80, 200, and
implementation. <1 ng/L.
400 mJ/cm2 and for each fluence three
• Estrogenic activity of the plant effluent
different doses of peroxide (2, 5, 10 ppm)
Expansion plans for East Canyon are to as measured by E-screen is typically
were added.
increase plant capacity from 4 to 7.2 mgd. 1 ng/L of estradiol equivalents.
The plant currently uses both biological • EDCs and estrogenic activity in GAC
and chemical processes to meet a total treated effluent were below detection or
phosphorous limit of 0.1 mg/L. Chemical were reduced by an order of magnitude.
phosphorous removal is accomplished by • The lowest ozone dose of 5 ppm,
dosing coagulant upstream of a tertiary without any peroxide addition, reduced
filter. In order to improve the reliability estrogenic activity below the detection
of this filtration process and treat to the limit.
eventual total maximum daily load (TMDL) • Although there were some
target of 0.05 mg/L, MF membranes will inconsistencies in the data, a trend of
replace the existing granular media filters. estrogenic activity removal was seen at a
Rather than demolishing the existing filters, UV fluence of 400 mJ/cm2 with peroxide
Carollo proposed replacing filter media with addition.
GAC and converting them to contactors for
re s e arc h so l ut io n s
EDC/PPCP removal. This method, coupled Ozone oxidation was recommended as the
with the membrane filtration and existing best EDC treatment technology based on
UV disinfection, may be the most cost life-cycle cost, even though it required the
effective means of incorporating EDC/PPCP highest initial capital investment. However,
treatment into the current project. Silver given the results for GAC that show it is an
Creek will be expanded from 2 to 3.7 mgd effective treatment method and the ability 3
and upgraded to match the process used at to use existing infrastructure, SBWRD has
East Canyon. indicated that they will exchange filter
Pilot-scale carbon filters for EDC/PPCP media and begin treating for EDCs/PPCPs
removal. at the completion of the expansion project.
PROJECTUPDATES Costa Water District’s Bollman Water
Treatment Plant. The evaluation of ozone
followed by BAF will provide a baseline
understanding of the effectiveness of the
existing full-scale treatment processes
(Phase 1). Then the effectiveness of
advanced oxidation with ozonation and
peroxide will be investigated (Phase 2).
Finally, NF following full-scale ozonation
and BAF will be evaluated (Phase 3). In
all test phases EDCs, PPCPs, and salts
(bromide, iodide, sulfate, and chloride) will
be added to the pilot feed water. Removal
efficiencies for target EDCs and PPCPs
will be quantified in the various treatment
trains. Subsequent tests for DBP formation
will be performed in bench-scale reactors
for various ultraviolet (UV) treatment and
chlorination schemes (dosing free chlorine
or chloramines).
NF pilot skid at Contra Costa Water District, CA.
Results and Implications
Removal of NDMA, EDCs, and PPCPs from Pilot testing was completed in July 2008.
The data gathered from this study will
South Delta Water provide information on the effectiveness of
the various treatment trains for removing
Background observed, as well as contaminants of select trace organic compounds from Delta
KEY TEAm mEmbERS
and Research emerging concern (e.g., EDCs and PPCPs). water. Results from the bench-scale DBP
cari Ishida, Ph.D., P.E.
An additional concern with treatment tests will provide side-by-side comparisons
Objectives (cishida@carollo.com)
of Delta waters is the formation of of expected DBP formation from different
Various Elisa Garvey, Ph.D., P .E.
disinfection byproducts (DBPs) including combinations of UV, free chlorine, and
trace organic Tom Patten, P .E.
trihalomethanes (THMs), haloacetic chloramination treatments. These results
compounds are Kimberly Lin, P.E.
[ccWD] acids (HAAs), N-Nitrosodimethylamine will be used for planning, design, and
finding their way
(NDMA), and other nitrosamines. Delta operation of existing and future disinfection
into the nation’s
utilities need to understand the treatment systems.
water supply. The Sacramento-San Joaquin
effectiveness of existing processes as well as
River Delta System (Delta) is one example
advanced treatment processes that may be
where the presence of these compounds
implemented in the future to remove these
is of growing concern. The Delta is a vital
chemicals. To meet this need, a diverse
source of drinking water for more than
research team, including: the Contra Costa
23 million Californians. Supplies from the
Water District, Carollo Engineers, Trent
south Delta are conveyed through the
University, the University of Colorado at
South Bay Aqueduct and the Contra Costa
Boulder, and the University of Toronto, as
Canal, serving more than 2.5 million people
well as numerous specialists, is evaluating
in the Bay Area, much of the time as an
the performance of advanced water
unblended source of drinking water.
treatment technologies with respect to
the destruction/removal of trace organic
Deterioration of the Delta source water
compounds and the formation of DBPs.
quality due to xenobiotic inputs (e.g.,
The California Department of Public
agricultural drains and wastewater
Health and the California Department of
effluents), and increased freshwater
Water Resources are providing funding and
re s e ar ch so l ut io n s
diversions is a growing concern for drinking
oversight for the project.
water users. In particular, users must
consider the possibility of significantly
The treatment technology combinations
deteriorated water quality during severe
under investigation include: ozone/
drought events. As such, Delta water
biologically active filtration (BAF)
4 utilities must be prepared for both the
[biologically active sand and granular
presence of existing contaminants (e.g.,
activated carbon media], ozone/peroxide/
pesticides and nutrients) at significantly Ozone pilot skid at Contra Costa Water
BAF, and nanofiltration (NF) at Contra
greater concentrations than currently District, CA.
PROJECTUPDATES
Filtration and Destruction of PPCPs • The TiO2/UV (Photo-Cat) process
and EDCs in Reclaimed Water in the range of power tested (0.1 to
0.6 kW per gpm) effectively oxidized
dissolved organic compounds, provided
Background and Research reclaimed
KEY TEAm mEmbERS
complete disinfection of coliforms
Objectives water for (~5-log removal) and MS-2 virus
Andrew Salveson, P .E.
Although some microconstituents can various (asalveson@carollo.com) (>6-log reduction), destroyed trace
persist through wastewater treatment states Karl Linden, Ph.D. organic chemicals such as triclosan
(Stackelberg et al., 2004; Gomez et al., (e.g., Tavy Wade and carbamazepine, and substantially
2007), current research suggests that CA). Keith bourgeous, Ph.D., P .E. reduced estradiol activity in the water
advanced treatment technologies can • Peracetic Vincent hart, P .E. based upon in-vitro bioassays.
effectively remove a range of PPCPs (Tang acid Jess brown, Ph.D., P .E. • The TiO2/UV process effluent had a
et al., 2006) to concentrations below human (PAA), particle count equivalent to distilled
health risk levels (Snyder et. al, 2007). when combined with medium-pressure water and a UV transmittance at
In addition, some research shows that UV, demonstrated robust removal of 254 nm (UVT) of nearly 90%
advanced treatment technologies following many trace organic compounds. (increasing from an influent of 67%).
conventional wastewater treatment can • UV disinfection at doses of 80 to • Most compelling, this work
significantly reduce the risk to aquatic 100 mJ/cm2, when combined with demonstrated that the use of MF or
organisms (Schwatter et al., 2007). hydrogen peroxide, showed ≥50% UF membranes with low-dose ozone
reduction of many of the target
To better understand the most efficient ways compounds. Continued on page 12
to destroy EDCs and PPCPs in wastewater
effluent, the WateReuse Foundation, the 250 240 UV Reactor Flow Rate ~ 355 gpm
Southwest Florida Water Management UVT ~ 63%
District (SWFWMD), and the U.S. REDMS2 ~ 89 mJ/cm2
200 190
NDMA Concentration (ng/L)
Bureau of Reclamation funded a research
team from Carollo, Duke University, and
the U.S. Department of Agriculture to 150
conduct WRF 02-009, Innovative Treatment
Technologies for Reclaimed Water. The project
100
included detailed bench- and pilot-scale
investigations to find and demonstrate 63
emerging (market-ready) reclaimed water 48 55
50
treatment technologies that could robustly
destroy pathogens and PPCPs at a cost
substantially below that of reverse osmosis 0
UV Reactor UV Reactor UV Reactor UV Reactor UV Reactor
(RO) (Wade et al., 2008). Technologies Influent, Effluent, Effluent, 5 mg/L Effluent, 10 mg/L Effluent, 15 mg/L
investigated included media and membrane Flow No Peroxide Peroxide Peroxide Peroxide
filtration, ozone, ozone/peroxide, peracetic
acid/ultraviolet light (UV), hydrogen
NDMA destruction by MP UV with hydrogen peroxide.
peroxide/UV, and titanium dioxide/UV. 200
180 EEQ - MF Eff. No Peroxide
Results and Implications
160 EEQ - Sand Eff. No Peroxide
Significant results include:
Estradiol Equivalents (EEQ)
EEQ - Sand Eff. ~0.50 to 0.65 Peroxide/Ozone MF
140
• Substantial removal of EDCs and PPCPs EEQ - Sand Eff. 2.2 Peroxide/Ozone MF
by full-scale microfiltration (MF) and 120
sand filtration, including 50 to 80% (or 100
re s e ar ch so l ut io n s
greater) reduction of 4-nonylphenol,
80
bisphenol-A, and triclosan, and limited
removal of DEET. 60
• Ozone after media filtration and after 40
MF provided ≥90% destruction of the
majority of the target compounds and 20
hormonal activity (as measured by
5
0
estradiol equivalency [EEQ]) at low 0 1 2 3 4 5 6 7
ozone doses (<6 mg/L), while meeting Applied Ozone Dose
the stringent disinfection criteria for
Destruction of hormonal equivalency by different treatment process combinations.
FEaTuRESTORY processing of forest products (MacLatchy et
al., 1997; Mellanen et al., 1996). Synthetic
Occurrence and Impact of EDCs include certain biocides and their
degradates (pesticides, herbicides, and
fungicides), PPCPs including veterinary
Endocrine Disrupting Chemicals and human drugs, industrial chemicals
and intermediates or byproducts from
in Water and Wastewater their production and their environmental
degradates, and combustion byproducts
from human activities such as burning of
By Shane A. Snyder, Ph.D. [Total been tested for endocrine activity by any
fossil fuels and incineration of industrial and
Environmental Solutions, Inc.] means.
municipal waste (Institute for Environment
and Health, 2005; Myers, 2008; World
Endocrine Disrupting Chemicals The U.S. Environmental Protection Agency
Health Organization, 2002).
EDCs are substances that interfere with (USEPA) established the Endocrine
the functioning of the endocrine system in Disruptor Screening Program (EDSP) to
EDCs can originate from numerous sources
humans or other animals. Alternative terms develop a battery of standardized toxicity
and enter the environment by many routes.
used to describe these chemicals include: tests that can be used to determine
Effluents from municipal wastewater
‘endocrine disruptors,’ ‘hormonally active whether a particular chemical is an EDC
treatment plants (WWTPs) have been
agents,’ and ‘endocrine-active substances.’ by USEPA’s definition. The program
implicated as major contributors of EDCs to
Currently, there is no consensus among focuses exclusively on chemicals that act
surface waters (Anderson, 2005). WWTPs
experts regarding the definition of an by interfering with estrogen, androgen, or
receive EDCs from sources including plant
EDC or the criteria that should be used to ,
thyroid action (USEPA-EDSP 2008); these
material, plastics, items treated with fire
determine whether a chemical is or is not are the best-characterized modes of action.
retardants, cleaning products, pesticides,
an EDC. Some definitions require that an However, EDCs may also interfere with
other household chemicals and consumer
effect must be demonstrated in vivo (i.e., in a the functions of other hormones (World
products, hormones excreted by humans,
live animal), while others stipulate only that Health Organization, 2002). The EDSP
and PPCPs excreted or washed from the
the potential for an effect be demonstrated, will use a two-tiered testing strategy, with
body and flushed to the sanitary sewer.
such as through in vitro receptor binding Tier 1 consisting of screening-level tests
WWTPs might also receive industrial or
(binding of test chemicals with estrogen and Tier 2 consisting of in vivo bioassays
hospital effluents and stormwater runoff
receptors) or structure-activity relationships that will generate data suitable for use in
streams that contain EDCs. Although
([SARs] predictable impact based upon ,
risk assessments (USEPA-EDSP 2008).
wastewater treatment processes can remove
molecular structure). Other definitions seek This process is not yet complete, but Tier
some EDCs, recalcitrant chemicals may
to distinguish adverse effects from merely 1 screening of an initial set of chemicals is
remain at detectable levels in effluents
compensatory responses (non-adverse but expected in Fall 2008 (USEPA, 2007).
discharged to surface water or in reclaimed
measurable effects) (USEPA-EDSTAC, water used for groundwater recharge. These
1998; World Health Organization, 2002). Sources and Occurrence in the contaminants may be diluted, sequestered
This has also been a source of controversy. Water Cycle (e.g., in sediment), or degraded by physical
Known and potential EDCs encompass a or biological processes, but some are
Hundreds of chemicals have been wide variety of chemicals and a diversity detected in the environment due to their
implicated as potential EDCs based on a of structures. They include both natural persistence or relatively constant loading.
variety of criteria (Institute for Environment and synthetic chemicals (Table 1). EDCs
and Health, 2005). While screening-level arising from natural sources include WWTP effluents and reclaimed water
evidence such as SARs, in vitro receptor hormones excreted by humans and other are not the only sources of EDCs to the
binding activity, and certain short-term in animals, substances found in plants environment. Other potential sources
vivo tests might suggest the potential for (phytoestrogens, phytosterols) or fungi include private septic systems (Swartz et
endocrine disruption, such effects are often (mycoestrogens), metals, inorganic ions, al., 2006), untreated stormwater flows and
not demonstrated in the more definitive and byproducts of natural combustion urban runoff (Boyd et al., 2004), industrial
in vivo tests, (e.g., tests conducted on processes (e.g., volcanic activity, forest effluents (Kosaka et al., 2007), landfill
intact animals or on multiple generations fires) (Institute for Environment and leachate (Coors et al., 2003), discharges
of exposed animals). Standardized test Health, 2005; Myers, 2008; World Health from fish hatcheries and dairy facilities
re s ea rc h s o lu ti o n s
methods are generally unavailable. At Organization, 2002). Some of these EDCs (Kolodziej et al., 2004), fish spawning in
this time, only certain in vivo bioassays occur normally in the environment or in natural waters (Kolodziej et al., 2004),
conducted with intact animals and using dietary items, but their concentrations runoff from agricultural fields and livestock
appropriate protocols (e.g., encompassing may be elevated due to human activities. enclosures (Orlando et al., 2004), and
susceptible life stages) provide data that are For example, metals may be mobilized in land amended with biosolids or manure
6 useful for risk assessment. Few chemicals the environment during mining (Wilkin, (Hanselman et al., 2003; Khanal et al.,
have been subjected to this type of testing 2007), and endocrine-active phytosterols 2006).
due to the cost and time required to may be released to water in effluents from
conduct them. Most chemicals have not
Table 1. Examples of Known or Potential Endocrine Woodling et al., 2006), and elsewhere where
Disrupting Chemicals WWTP effluents have been implicated in
endocrine-related effects on fish.
Chemical Class Representative Chemicals
Naturally-occurring EDCs WWTP effluents contain a mixture of
known or potential EDCs. In most cases
Hormones Estradiol, estrone researchers have been unable to pinpoint
Phytoestrogens and plant sterols Genistein, ß-sitosterol the specific chemicals responsible for effects
Mycoestrogens Zearalenone indicating endocrine disruption in exposed
Metals Arsenic, cadmium, lead, mercury fish. Estradiol, estrone, ethynylestradiol,
nonylphenol, octylphenol, alkylphenol
Inorganic ions Perchlorate, thiocyanate ethoxylates, and bisphenol A have been
Combustion byproducts Dioxins, certain PAHs identified as likely causes (Purdom et al.,
Synthetic EDCs 1994; World Health Organization, 2002)
Biocides or their degradates Atrazine, DDT (or DDE), tributyltin based on their concentrations in wastewater
effluents and their potency in laboratory
PPCPs Ethynylestradiol, trenbolone studies. Natural hormones produced in
Industrial chemicals, intermediates, and degradates PCBs, bisphenol-A, octylphenol the bodies of humans and other animals
Combustion byproducts Dioxins, certain PAHs (e.g., estradiol and estrone) and synthetic
EDCs, endocrine disrupting chemicals; PAHs, polycyclic aromatic hydrocarbons; PCBs, polychlorinated hormones intended to mimic the actions
biphenyls; PPCPs, pharmaceuticals and personal care products. of endogenous hormones (e.g., the oral
contraceptive ingredient ethynylestradiol)
Various EDCs have been reported to is a symptom of exposure to estrogens are of particular concern because they are
occur in WWTP effluents, surface water, from external sources but generally is not potent at very small concentrations and are
groundwater, reclaimed water, and drinking considered to be an adverse effect. Later commonly detected in WWTP effluents.
water, usually at concentrations in the ng/L studies suggested a link between exposure to
(0.000000001 g/L) range. In general, EDCs WWTP effluents and adverse or potentially While hormonal disruption of aquatic life
are reported to occur with greater frequency harmful effects on the reproductive organs by wastewater-derived EDCs has clearly
and at higher levels in WWTP effluents and fertility of fish (Jobling et al., 2002; been demonstrated, limited information
than in reclaimed water or drinking water. Jobling and Tyler, 2003). The findings in exists on the possibility of long-term effects
Dilution and environmental degradation are the U.K. studies spurred research in other on aquatic life populations. This is an area
responsible for smaller concentrations and European countries (Petrovic et al., 2002; for further research.
less frequent detections in surface water. Diniz et al., 2005), North America (Bevans
The limited data available to date indicate et al., 1996; Folmar et al., 1996, 2001; Implications for Human
that EDCs originating from municipal Giesy et al., 2003; Hemming et al., 2004; Health
WWTPs generally occur infrequently and at Nichols et al., 1999; Patiño et al., 2003; Although there are well substantiated
exceedingly small levels in finished drinking Schoenfuss et al., 2002; Snyder et al., 2004; links between environmental exposure
water because they are diluted and undergo to EDCs and effects in fish and wildlife,
degradation in the environment and then there is little evidence to suggest that
must survive drinking water treatment typical low-level environmental exposures
processes and distribution to remain in to EDCs (including EDCs in WWTP
potable water at the tap. effluent, reclaimed water, and drinking
water) have had any adverse effects on
Implications for Aquatic Life human health (World Health Organization,
There is a substantial and growing body 2002). However, the science of endocrine
of evidence indicating that EDCs at disruption is relatively new, as is research
levels found in some WWTP effluents into exposure to EDCs and the potential
can cause endocrine disruption in fish human health consequences.
and other aquatic life, with the literature
suggesting that some EDCs at or above Reports of endocrine disruption in fish
0.1 ng/L can induce endocrine-mediated
re s ea rc h s o lu ti o n s
collected from source waters for drinking
changes in aquatic life (Purdom et al., water treatment plants (e.g., Blazer et
1994; Vanderford et al., 2003). This issue al., 2007) and detection of wastewater-
first gained public attention when male associated EDCs in these waters commonly
fish collected downstream of WWTPs in trigger consumer concern. However, there
the United Kingdom (U.K.) were found are important differences in exposure to
to have elevated levels of vitellogenin, a Outfall from a wastewater treatment wastewater contaminants between fish and 7
female-specific egg yolk protein, in their plant can be a source of EDCs to the humans. Fish may be immersed in effluents
blood. Vitellogenin induction in male fish environment.
Continued on page 8
FEaTuRESTORY technology is capable of identifying and
quantifying sub-ng/L levels of organic
Exposed to Treated Sewage Effluent.”
Ecotoxicology and Environmental Safety,
Continued from page 7 contaminants, it is prudent to determine 62(3):427-435.
the toxicological relevance of these
at their point of entry into surface water, emerging contaminants in order to establish Folmar, L.C., N.D. Denslow, K.J. Kroll, E.F.
where concentrations are greatest. They can meaningful treatment goals. Orlando, J. Enblom, J. Marcino,
take up contaminants directly across their C. Metcalfe, and L.J.J. Guillette. 2001.
body surfaces, particularly the gills. Fish can References “Altered serum sex steroids and vitellogenin
also be exposed to EDCs and other effluent Anderson, P 2005. Technical Brief:
.D. induction in walleye (Stizostedion vitreum)
contaminants that accumulate in their Endocrine Disrupting Compounds and collected near a metropolitan sewage
food or that are associated with particulate Implications for Wastewater Treatment. treatment plant.” Archives of Environmental
material and sediments. In contrast, people Alexandria, VA: Water Environment Contamination and Toxicology, 40:392-398.
tend to receive little direct exposure to Research Foundation (WERF).
EDCs in WWTP effluent, so concerns Folmar, L.C., N.D. Denslow, V. Rao,
related to potential human health effects Bevans, H.E., S.L. Goodbred, J.F. Miesner, M. Chow, D.A. Crain, J. Enblom,
generally center around drinking water S.A. Watkins, T.S. Gross, N.D. Denslow, J. Marcino, and L.J. Guillette, Jr. 1996.
contamination. EDCs discharged in WWTP and T. Schoeb. 1996. “Synthetic Organic “Vitellogenin Induction and Reduced
effluents or reclaimed water undergo Compounds and Carp Endocrinology Serum Testosterone Concentrations in Feral
dilution, environmental degradation, and Histology in Las Vegas Wash and Las Male Carp Cyprinus carpio Captured Near
and water treatment processes that can Vegas and Callville Bays of Lake Mead, a Major Metropolitan Sewage Treatment
substantially reduce their concentrations Nevada, 1992 and 1995.” Water-Resources Plant.” Environmental Health Perspectives,
before they reach the tap. Investigations Report 96-4266. Carson City, 104(10):1096-1101.
NV: United States Geological Survey.
Regulations http://pubs.er.usgs.gov/pubs/wri/wri964266 .,
Giesy, J.P E.M. Snyder, K.M. Nichols,
Although some chemicals that might be .D.
S.A. Snyder, S.A. Villalobos, P Jones,
considered to be EDCs are regulated in Blazer, V.S., L.R. Iwanowicz, D.D. and S.D. Fitzgerald. 2003. “Examination
WWTP effluent for the protection of Iwanowicz, D.R. Smith, J.A. Young, J.D. of Reproductive Endpoints in Goldfish
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based on endocrine modes of action except “Intersex (testicular oocytes) in Smallmouth Municipal Sewage Treatment Plant
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might be classified as EDCs are federally Boyd, G.R., J.M. Palmeri, S. Zhang, and Hanselman, T.A., D.A. Graetz, and A.C.
regulated in drinking water, but not on the D.A. Grimm. 2004. “Pharmaceuticals Wilkie. 2003. “Manure-borne Estrogens as
basis of their potential to cause endocrine and Personal Care Products (PPCPs) and Potential Environmental Contaminants: A
disruption. In Massachusetts, the level of Endocrine Disrupting Chemicals (EDCs) in Review.” Environ. Sci. Technol., 37(24):5471-
perchlorate in drinking water is regulated Stormwater Canals and Bayou St. John in 5478.
on the basis of its potential to act as an New Orleans, Louisiana, USA.” Science of
EDC (by interfering with thyroid function) the Total Environment, 333(1-3):137-148. Hemming, J.M., H.J. Allen, K.A. Thuesen,
(Massachusetts DEP 2006), but to date
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P Turner, W.T. Waller, J.M. Lazorchak,
no other state has regulated any drinking California Department of Public Health. D. Lattier, M. Chow, N. Denslow, and
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(CDPH) has mandated monitoring and Health; Chapter 3. Recycling Criteria.” Ecotoxicology and Environmental Safety,
reporting of EDCs and pharmaceuticals, but (Draft - January 4, 2007, most recently 57(3):303-310.
not their removal (California Department updated August 5, 2008). http://www.cdph.
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Conclusion/Summary Disruptors: A Compilation of Published
re s e ar ch so l ut io n s
Trace levels of EDCs and pharmaceuticals . .
Coors, A., P D. Jones, J.P Giesy, and H.T. Lists (Web Report W20). Institute for
are ubiquitous in municipal wastewater Ratte. 2003. “Removal of Estrogenic Environment and Health (IEH). Leicester,
effluents. In some cases, steroid hormones Activity From Municipal Waste Landfill United Kingdom. http://www.silsoe.
have been implicated as the primary source Leachate Assessed with a Bioassay Based cranfield.ac.uk/ieh/pdf/w20.pdf
of estrogenicity in effluents; however, on Reporter Gene Expression.” Environ. Sci.
8 some synthetic organic chemicals have the Technol., 37(15):3430-3434. Jobling, S., S. Coey, J.G. Whitmore,
ability to mimic endogenous hormones. D.E. Kime, K.J.W. Van Look, B.G.
Advanced water treatment processes can Diniz, M.S., I. Peres, I. Magalhaes-Antoine, McAllister, N. Beresford, A. C. Henshaw,
greatly reduce the concentration of organic J. Falla, and J.C. Pihan. 2005. “Estrogenic .
G. Brighty, C.R. Tyler, and J.P Sumpter.
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rutilus) Have Reduced Fertility.” Biology of L.E. Gray, Jr., A.M. Soto, and L.J. Guillette, http://www.epa.gov/waterscience/criteria/
Reproduction, 67(2):515-524. Jr. 2004. “Endocrine-Disrupting Effects nonylphenol/final-doc.pdf
of Cattle Feedlot Effluent on an Aquatic
Jobling, S. and C.R.Tyler. 2003. “Endocrine Sentinel Species, the Fathead Minnow.” USEPA. 2007. “Draft List of Initial Pesticide
Disruption in Wild Freshwater Fish.” Pure Environ. Health Perspectives, 112(3):353-358. Active Ingredients and Pesticide Inerts
& Applied Chemistry, 75(11):2219-2234. to be Considered for Screening under the
Patiño, R., S.L. Goodbred, R. Draugelis- Federal Food, Drug, and Cosmetic Act.”
Khanal, S.K., B. Xie, M.L. Thompson, Dale, C.E. Barry, J.S. Foott, M.R. Wainscott, Federal Register, 72 (116):33486-33503.
S. Sung, S.K. Ong, and J. vanLeeuwen. T.S. Gross, and K.J. Covay. 2003.
2006. “Fate, Transport, and Biodegradation “Morphometric and Histopathological .
USEPA-EDSP 2008. Endocrine Disruptor
of Natural Estrogens in the Environment Parameters of Gonadal Development in Screening Program (EDSP) [Website]. Last
and Engineered Systems.” Environ. Sci. Adult Common Carp from Contaminated updated March 24, 2008. Washington,
Technol., 40(21):6537-6546. and Reference Sites in Lake Mead, D.C.: United States Environmental
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Kolodziej, E.P T. Harter, and D.L. Sedlak. 15:55-68. Screening Program (USEPA-EDSP). http://
2004. “Dairy Wastewater, Aquaculture, www.epa.gov/endo/
and Spawning Fish as Sources of Steroid Petrovic, M., M. Solé, M.J. López de
Hormones in the Aquatic Environment.” Alda, and D. Barceló. 2002. “Endocrine USEPA-EDSTAC. 1998. Endocrine
Environ. Sci. Technol., 38(23):6377-6384. Disruptors in Sewage Treatment Plants, Disruptor Screening and Testing Advisory
Receiving Waters, and Sediments: Committee (EDSTAC) Final Report.
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M. Kamoshita, and S. Kunikane. 2007. Biological Effects on Feral Carp.” Environ. Environmental Protection Agency,
“Occurrence of Perchlorate in Drinking Toxicology and Chemistry, 21(10):2146-2156. Endocrine Disruptor Screening and
Water Sources of Metropolitan Area in Testing Advisory Committee (U.S. EPA-
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b-Sitosterol Alters the Endocrine Status of Ecology, 8:275-285. Rexing, and S.A. Snyder. 2003. “Analysis
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Snyder, E.M., S.A. Snyder, K.L. Kelly, Environmental Protection Agency, National
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“Wood-derived Estrogens: Studies in Vitro Carp (Cyprinus carpio) Exposed in Cages
with Breast Cancer Cell Lines and in Vivo in to Influent of the Las Vegas Wash in Lake Woodling, J.D., E.M. Lopez, T.A.
Trout.” Toxicology and Applied Pharmacology, Mead, Nevada, from Late Winter to Early Maldonado, D.O. Norris, and A.M. Vajda.
136:381-388. Spring.” Environ. Sci. Technol., 38(23):6385- 2006. “Intersex and Other Reproductive
6395. Disruption of Fish in Wastewater Effluent
Myers, J.P 2008. Our Stolen Future
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[Website]. http://ourstolenfuture.org/ Swartz, C.H., S. Reddy, M.J. Benotti, Biochemistry and Physiology Part C: Toxicology
H. Yin, L.B. Barber, B.J. Brownawell, and & Pharmacology, 144(1):10-15.
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of Exposure to Municipal Wastewater in and Other Wastewater Contaminants in Assessment of the State-of-the-Science of
Situ on the Reproductive Physiology of the Groundwater Affected by a Residential Endocrine Disruptors. WHO/PCS/EDC/02.2.
Fathead Minnow (Pimephales promelas).” Septic System on Cape Cod, MA.” Environ. Edited by Damstra, T.; S. Barlow,
Environ. Toxicology and Chemistry, 18(9): Sci. Technol., 40(16):4894-4902. A. Bergman, R. Kavlock, G. Van Der
2001-2012. Kraak. Geneva, Switzerland: World Health 9
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EPA), Office of Water. EPA-822-R-05-005. disruptors/en/print.html
PROJECTUPDATES
Carollo Studies the Fate of EDCs and PPCPs Through
Advanced Wastewater Membrane Systems and the
Biological Impact of Effluent on Aquatic Organisms
Background and Research Results and KEY TEAm mEmbERS
Objectives Implications George Zhou, Ph.D.
Population growth in South Florida has The removal (gzhou@carollo.com)
put pressure on valuable fresh water of select EDCs/ Jose Lopez, P.E.
resources. Various utilities are investigating PPCPs was Jess brown, Ph.D., P.E.
the use of advanced wastewater treatment tracked across Andrew Salveson, P .E.
processes to indirectly supplement existing two treatment This Advanced Membrane Pilot was used
potable water supplies. However, concerns trains: Train 1: membrane bioreactor for the WRF project in Plantation, FL.
have been raised by the public regarding (MBR) + reverse osmosis (RO); Train 2:
presence of EDCs and PPCPs in wastewater activated sludge(AS) + denitrifying other compounds added or generated
effluents and the potential impact of these filtration (DNF) + ultrafiltration (UF) in the RO permeate. These included
compounds on aquatic life and human + and RO. Removal of EDCs/PPCPs by ammonia, chloramine, and anti-scalant
health. MBRs and UF processes was demonstrated. (used for maintaining the membrane
Significant removal of EDCs/PPCPs by system). Dechlorination (quenching)
In response to some of these concerns, the RO was observed for all compounds, with of chloramine with sodium thiosulfate
WateReuse Foundation (WRF) and the most removed to levels below the analytical reduced and delayed toxicity effects.
South Florida Water Management District detection limits (1-25 ng/L). The RO Further experiments without ammonia,
(SFWMD) funded WRF 06-019, Monitoring performance data were in accordance with chloramine, and antiscalant eliminated
for Microconstituents in an Advanced other published data (Drewes et al., 2006). the toxic effects in the RO permeate and
Wastewater Treatment (AWT) Facility and significantly increased the survival of
Modeling Discharge of Reclaimed Water to Furthermore, the concentrations of PPCPs .
P promelas and C. dubia. Similar results
Surface Canals for Indirect Potable Use. This were correlated with toxicity tests and both were found for the test with antiscalant
research, led by Carollo and SFWMD, tissue culture and live fish bioassays. The alone, suggesting that antiscalant did
with help from the University of Florida results indicated that the EDCs and PPCPs not exert toxic effects on C. dubia. These
at Gainesville, the City of Plantation, FL, in the RO permeate caused no toxicity. results indicate that dechlorination or
Hazen and Sawyer, and others, monitored Detailed results include: other quenching methods should be
and evaluated water quality through used to remove chloramines or ammonia
advanced wastewater treatment facilities • The toxicity tests were chronic definitive in these AWT facilities to minimize their
and modeled the fate and transport of tests on the waterflea Ceriodaphnia dubia toxic effects.
various compounds through a canal system and the fathead minnow Pimephales • In vitro estrogen screen (E-Screen)
and into groundwater supply wells. promelas following EPA 821-R-02-013 bioassays were conducted to evaluate
Test Method 1002.0 and 1000.0, the endocrine disrupting potential of the
respectively. The results of tests on MBR treated permeate. In these bioassays, the
and UF permeate indicated that there estradiol equivalents (a measure of the
were no significant survival differences hormone-inducing activity of a given
between the control (deionized water) solution) in all the RO permeate were
.
and the treated samples for P promelas below the detection limit (0.03 ng/L),
and C. dubia, except that the although they were detected in
survivability of C. dubia was low in MBR secondary effluent (0.11 ng/L), DNF
permeate in one of the five sampling filtrate (0.12-0.23 ng/L), MBR permeate
events. These results suggest that the (0.12-0.18 ng/L), and UF permeate
MBR permeate and UF permeate did (0.14-0.21 ng/L). The results of the
not have significant toxic effects on the E-Screen bioassay indicated that the
re s e arc h so l ut io n s
.
survival of P promelas and C. dubia. permeate did not produce a significant
• Some toxic effects were observed in estrogenic response in MCF-7 cells, a
the RO permeate, but they did not breast cancer cell line that proliferates in
appear to have been caused by PPCPs. response to estrogenic activity.
The survival of P promelas and C. dubia
. • The in vitro yeast estrogen screen (YES)
10 in the RO permeate was poor for one bioassay was conducted to evaluate the
sampling event. Because PPCPs in the endocrine disrupting potential in the
RO permeate were all non-detectable treated effluents. In the YES bioassay,
Fish biossays at the University of Florida (<1 ng/L in most cases), the observed yeast cells are transformed to contain
at Gainesville. toxic effects were likely caused by human estrogen receptors. The results
showed that estradiol equivalents were
not detected in MBR permeate, UF
MBR and UF could partially remove
microconstituents, only RO completely
PROJECTUPDATES
permeate, and RO permeate, although removed microconstituents from advanced treatment facilities for future
they were detected in the secondary wastewater. In addition, no hormonal indirect potable use of reclaimed water.
effluent (0.22 ng/L) and DNF filtrate threats were found in RO permeate to tissue
(0.23 ng/L). The results suggest that cultures and live fish, while some hormonal References
MBR permeate and RO permeate responses were detected in MBR permeate Drewes, J.E., J.D.C. Hemming, J.J. Schauer,
may not possess endocrine disrupting and UF permeate. and W.C. Sonzogni. 2006. Removal of
potential, though in vivo assays provide a Endocrine Disrupting Compounds in Water
higher measure of confidence for such a The observed toxicity due to membranes Reclamation Processes. Alexandria, VA:
conclusion compared to in vitro assays. pretreated with chemicals suggests that Water Environment Research Foundation
• In vivo assays, such as fathead minnow dechlorination equipment may be necessary Report 01-HHE-20T.
vitellogenin assays and steroid to minimize the impact on aquatic
immunoassays, were conducted to organisms if similar RO processes are Zhou, Z., A. Salveson, J. Brown, and J.
measure the estrogenic activity of the designed and operated. Lopez. 2008. “Water Quality Through
treated effluents. There was no plasma Advanced Wastewater Treatment
vitellogenin induction in fish exposed to Hydrodynamic and water quality models (AWT) Facilities and Recharge Modeling
the MBR permeate and RO permeate, can help us evaluate the fate and transport (WateReuse Foundation Project 06-019).”
suggesting that the MBR permeate and of microconstituents in reclaimed water 2008 California Section Annual Conference.
RO permeate were not estrogenic as discharged to surface canals and therefore Newport Beach, CA.
assessed in this bioassay. are useful tools for designing or upgrading
All of these results suggested that RO Table 1. Concentrations of Microconstituents
permeate did not exert endocrine disrupting
Treatment Trains
potential to tissue cultures or live fish (Zhou
MBR/RO AS/DNF/UF/RO
et al., 2008). Microconstituents (ng/L)
RO Permeate Sampling Dates
A hydrodynamic and water quality model 10/29/07 11/26/07 1/14/08 1/31/08 2/21/08
was also developed to track the fate and 2,6-di-tert-butylphenol <10 <10 <10 <10 <10
transport of a range of potential PPCPs 4-Methylphenol <25 <25 <25 <25 <25
from a surface water discharge point to 4-Nonyl Phenol <25 <25 <25 <25 <25
groundwater supply wells. The Plantation Acetaminophen <1 <1 <1 <1 <1
sub-model was extracted from the Broward Alpha Chlordane <10 <10 <10 <10 <10
County model including the surface and Bisphenol A (BPA) <25 <25 <25 <25 57
groundwater features since they have a
Caffeine <25 <25 <25 <25 <25
direct hydraulic connection to the proposed
Carbamazepine <5 <5 <5 <5 <5
discharge location, the East Holloway
Canal. The model area was determined Carbaryl <50 <50 <50 <50 <50
with both the surface water basin divides Chlorpyrifos <25 <25 <25 <25 <25
and the groundwater capture areas. N,N-diethyl-m-toluamide <25 <25 <25 <25 <25
Boundary conditions for the model area Diazinon <25 <25 <25 <25 <25
were extracted from the Broward model Dieldrin <25 <25 <25 <25 <25
results for all of the groundwater and the Estradiol <1 <1 <1 <1 <1
surface water boundaries in the Plantation Estrone <1 <1 <1 <1 <1
sub-model. In general, the groundwater Ethinyl Estradiol -17 alpha <1 <5 <5 <5 <5
results followed the observed data closely Fluoxetine <1 <1 <1 <1 <1
while the surface water results deviated Gemfibrozil NA <1 <1 NA <1
somewhat from the observed data. Three Ibuprofen <1 3.1 <1 <1 <1
representative PPCPs (sulfamethoxazole, Iopromide <5 <5 <5 <5 <5
phenol, triclosan) were selected for Methyl Parathion <25 <25 <25 <25 <25
the water quality model based on their
re s e ar ch so l ut io n s
Phenol <100 <100 <100 <100 <100
susceptibility to photodegradation, sorption,
Progesterone <1 <1 <1 <1 <1
and biodegradation, as well as their
Sulfamethoxazole <1 <1 <1 <1 <1
occurrence.
Testosterone <1 <1 <1 <1 <1
Triclosan <50 <50 <50 <50 <50
Conclusions
Trimethoprim <1 <1 <1 <1 <1 11
The results suggest that RO is most
effective among membrane technologies Triphenylphosphate <25 <25 <25 <25 <25
if utilities plan to reach maximum Tris(1,3-dichloro-2-propyl) phosphate <25 NA <25 NA <25
removal of microconstituents and their Tris(2-butoxyethyl) phosphate <100 <100 <100 <100 <100
endocrine disrupting potential. Although Tris(2-chloroethyl) phosphate <25 <25 <25 <25 <25
WhaT’sNEW
What Does It All Mean? Phoenix, Arizona
Yuma, Arizona
Concentrations of EDCs in reclaimed water The solution to dealing with EDCs and Bakersfield, California
and surface water do not appear to pose a PPCPs must be multi-faceted. Public
public health threat, but wastewater effluent health is paramount, but enhancing water Fresno, California
can cause detrimental effects like endocrine treatment to eliminate very small amounts Inland Empire, California
disruption in aquatic life. of EDCs and PPCPs will result in substantial
cost and energy use. Increased levels of Orange County, California
Economic analyses associated with the treatment must be scientifically and fiscally Pasadena, California
projects described in this publication show based. Balancing the improvement of water
that advanced treatment technologies quality with the generation of greenhouse Sacramento, California
can be cost-effective for reducing EDCs gases (due to energy-intensive advanced San Diego, California
and PPCPs in wastewater. Similar results treatment) must be considered as must
are expected for drinking water. The public concerns. Walnut Creek, California
larger problem is that of perception. Public Denver (Broomfield), Colorado
concerns jumped after the recent U.S. The technical work presented here is
Senate hearings on PhACs in water. Recent part of the solution, detailing EDC/PPCP Denver (Littleton), Colorado
Associated Press articles led the general occurrence, risk, and treatment. Integrating Broward County, Florida
public to believe that ANY amount of this knowledge base with a proactive public
pharmaceuticals in the water is toxic. “The relations program is recommended. Miami, Florida
dose makes the poison” logic goes unheard. Orlando, Florida
Palm Beach County, Florida
PROJECTUPDATES
Sarasota, Florida
Filtration and Destruction Boise, Idaho
Continued from page 5 Overland Park, Kansas
or UV (when combined with hydrogen Snyder, S., H. Lei, J. Hemming, J. Zeigler- Las Vegas, Nevada
peroxide, PAA, or TiO2) can provide Holiday, and R. Trenholm. 2007. Relative Reno, Nevada
90-99% reduction/destruction of various Risk Assessment of Estrogens in Reuse
EDCs and PPCPs at a cost near that of Water. 22nd Annual WateReuse Association Charlotte, North Carolina
conventional reclaimed water filtration Symposium, September 2007 in Tampa, FL. Portland, Oregon
and disinfection. Further, it showed that
particle removal could result in removal Stackelberg, P E.T. Furlong, M.T.
.E., Austin, Texas
of substantial amounts of particle- Meyer, S.D. Zaugg, A.K. Henderson, Dallas, Texas
associated PhACs. Thus, optimizing and D.B. Reissman. 2004. Persistence of
the performance of sand filtration Pharmaceutical Compounds and Other Fort Worth, Texas
for particle removal can provide a Organic Wastewater Contaminants in a San Antonio, Texas
significant barrier to EDCs and PPCPs Conventional Drinking-Water-Treatment
without substantial capital cost. Plant. Sci. Total Environ, 329(1-3), 99-113. Salt Lake City, Utah
Seattle, Washington
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