Ch 12 CECs 010312

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							 1            CHAPTER 12 CONSTITUENTS OF EMERGING CONCERN
 2
 3
 4   Constituentstaminants of Emerging Concern (CECs) can be broadly defined as any chemicals not             Formatted: Justified
 5   commonly monitored but have the potential to cause adverse ecological or human health
 6   impacts. Due to rapid advances in analytical technology, the ability to detect infinitesimally
 7   small chemical concentrations has caused an “emergence” of chemicals previously undetectable
 8   such as caffeine, antibiotics, detergents, perfumes, disinfectants, insecticides, pain killers,
 9   steroids, other personal care products, drugs, and natural and synthetic hormones. Chemicals
10   known as endocrine disruptors are thought to be adversely affecting the reproductive systems of
11   fish that inhabit waters that also serve as drinking water sources. This chapter provides a brief
12   overview of the issues associated with these emerging contaminantsconstituents in regards to
13   occurrence, fate and transport, health effects, removal by wastewater and drinking water
14   treatment processes, and regulations.
15
16   Classes of Emerging ContaminantsConstituents

17   Pharmaceuticals or pharmaceutically active chemicals (PhACs) and personal care products
18   (PCPs) are often grouped together and called pharmaceuticals and personal care products
19   (PPCPs). PPCPs include a diverse group of thousands of chemicals that are ingested by humans
20   and animals or applied to the bodies of humans and animals. This wide-ranging class includes
21   prescription and non-prescription drugs (for both humans and animals), soaps, fragrances, insect
22   repellant and sunscreen, among others. These chemicals enter sewer systems when they are
23   excreted or washed off the body. Unused medications are also disposed of by flushing them
24   down the toilet or pouring them down the drain. Incomplete removal in wastewater treatment
25   plants results in numerous PPCPs being discharged to surface waters at very low (µg/L to ng/L)
26   concentrations. They can also enter surface waters from land application of organic materials and
27   by runoff contaminated by animal excrement.
28
29   In addition to PPCPs, other classes of emerging contaminantsconstituents include
30   polybrominated diphenyl ethers (PBDEs), pyrethroids, and PFCs. Recently, several other types
31   of high volume use chemicals have gained the attention of researchers and regulators which
32   include current-use flame retardants, antimicrobials, nanomaterials, cyclosiloxanes, and
33   quaternary ammonium compounds (QACs).
34
35   PFCs are chemicals used in non-stick cookware, stain-resistant fabrics, and food packaging. The
36   use of PFCs has been restricted over the past decade because of concerns with their potential
37   toxicity to humans and wildlife, but they are frequently detected in the environment worldwide.
38   Triclosan and triclocarban are antimicrobials found in many consumer products such as soaps,
39   toothpaste, and other personal care products. Concerns over these compounds include their
40   potential for endocrine disruption in wildlife, antibiotic resistance, and potential toxicity to algal
41   and microbial communities. Nanomaterials such as nanosilver, titanium dioxide, and carbon
42   nanotubes are used in commercial applications and are currently being studied to investigate
43   their environmental fate and potential toxicity. Cyclosiloxanes are persistent contaminants used
44   in a wide variety of personal care products, silicones, and in commercial applications as carriers,
45   lubricants, and solvents. Information on cyclosiloxanes such as Decamethylcyclopentasiloxane

     Draft Report                                    12-1                                     January 2012
     California State Water Project                                                             Chapter 12
     2011 Watershed Sanitary Survey Update                                Constituents of Emerging Concern

46   (D5) is limited due to the difficulty in measuring in environmental matrices. QACs are cationic
47   surfactants widely used in industrial applications and consumer products such as fabric softeners
48   and detergents.
49
50   Endocrine disrupting chemicals (EDCs) are chemicals that interfere with the normal functioning
51   of hormones in the bodies of humans and animals. It is debatable which compounds should be
52   considered as EDCs, as compounds not currently considered EDCs may be determined to have
53   endocrine disruptive effects after further screening. Modes of action of EDCs include mimicking
54   natural hormones, interfering with hormone function, and degrading hormones. Some PPCPs
55   such as phthalates, used in hair spray, fingernail polish, and cosmetics, and hormones contained
56   in oral contraceptives are EDCs but not all EDCs are PPCPs. For example, industrial waste
57   products such as dioxins (TCDD) and furans, industrial chemicals such as perchlorate, PCBs and
58   organometals (e.g. tributyltin, an anti-fouling agent in boat paint), organochlorine pesticides and
59   their degradation products, and flame retardants such as PDBEs are all endocrine disruptors. In
60   addition, potential EDCs are contained in natural products such as soybeans and alfalfa. EDCs
61   enter surface waters from a variety of sources including industrial and municipal wastewater
62   discharges and runoff from urban and agricultural areas. .
63
64   Pyrethroids are primarily used as an insectide. The usage of pyrethroids dramatically increased in
65   the early 2000s after the United States Environmental Protection Agency (USEPA) and
66   manufacturers withdrew diazinon and chloropyrifos products for residential use because of
67   health risks to users and their families (Aquatic Science Center, 2011). Pyrethroids have
68   endocrine disrupting properties and notably, bifenthrin stands out among the group for its
69   elevated concentration and frequency of detection in urban runoff, which originates from
70   pesticide use around homes and commercial establishments.
71
72   Nitrosamines are a class of organic CECs that are of particular concern to drinking water
73   agencies due to its carcinogenic nature. Nitrosamines can be formed as a byproduct of the
74   disinfection of some natural waters with chloramines. It is anticipated that certain nitrosamines
75   such as N-nitrosodimehtlyamine (NDMA), or a broader class of nitrosamines, may likely be the
76   next disinfection byproduct(s) regulated by the U.S. Environmental Protection Agency
77   (USEPA).
78
79   Occurrence in the Environment

80   EDCs and PPCPs were first recognized as potential contaminants when they were linked to
81   adverse impacts on aquatic organisms. Aquatic organisms, particularly freshwater and
82   anadromous fish, live in streams and lakes used as sources of drinking water so effects on fish
83   can be a first sign of the presence of these compounds in drinking water sources.
84
85   Effects on Aquatic Organisms

86
87   Aquatic organisms are sensitive to low levels of exposure and are particularly vulnerable when
88   exposure occurs during developmentally sensitive times such as before birth and during juvenile
89   stages of growth. There are a number of studies that have shown developmental and reproductive
90   effects on fish exposed to wastewater effluent, shellfish exposed to organotins, and alligators and

     Draft Report                                   12-2                                     January 2012
      California State Water Project                                                            Chapter 12
      2011 Watershed Sanitary Survey Update                               Constituents of Emerging Concern

 91   frogs exposed to pesticides. Exposure to estrogenic hormones can result in more females than
 92   males in a given fish population, the presence of both male and female reproductive organs
 93   within an individual organism, and reduced reproductive success. USGS has reported finding
 94   intersex or feminized male fish in many locations throughout the country. A nationwide USGS
 95   study that analyzed the concentrations of two hormones (17β-estradiol and 11-ketotestosterone)
 96   in the blood plasma of carp from 25 sites showed that fish from New Don Pedro Reservoir on the
 97   Tuolumne River had the highest concentrations (Goodbred et al, 1997). Fish collected from the
 98   San Joaquin River at two locations had lower concentrations of the two hormones.
 99
100   A study of Chinook salmon collected from 13 locations in the Sacramento and San Joaquin
101   watersheds indicated that up to 38 percent of the male fish exhibited complete sex reversal. The
102   highest percent was found in the Mokelumne River, which is generally considered to be a high
103   quality source of drinking water. The feminization of male salmon is potentially attributed to
104   steroid hormones in wastewater effluent, agricultural wastes, and fish hatchery discharges;
105   detergent metabolites used as carriers in pesticide formulations; and pyrethroid pesticides and
106   their metabolites (Sedlak, 2006).
107
108   Under the Surface Water Ambient Monitoring Program, the Central Valley Regional Water
109   Quality Control Board applied an estrogenic endocrine disrupting chemical (EEDC) screening
110   procedure with juvenile rainbow trout to surface freshwaters collected in the Central Valley and
111   northeastern California (Vlaming, 2006). The indicator used for this assessment was a juvenile
112   rainbow trout liver vitellogenin (Vtg) gene expression assay. Vtg is the liver-synthesized egg
113   yolk protein precursor and is usually silent or not expressed in male fish. The appearance of Vtg
114   in the plasma of adult male or juvenile fish is widely accepted as evidence of exposure to
115   estrogenic chemicals. Results showed that out of 113 samples, only six samples induced
116   marginal, but statistically significant estrogenic activity in the screening procedure. EEDC
117   concentrations in these six samples were low (at or near procedure threshold).
118
119   Since 2003, the U.S. Fish and Wildlife Service Environmental Contaminants Division have
120   periodically deployed water sampling devices to assess potential contaminant effects on special
121   status species in the Delta. In 2005, sampling frequency was increased to monthly, and extracts
122   collected from the sampling devices were injected into juvenile striped bass. Analytical results
123   showed numerous pesticides present at low levels in water. The laboratory tests demonstrated
124   that low level mixtures of contaminants in Delta water can set off responses that signal endocrine
125   disruption in fish (Aquatic Science Center, 2011). The results indicate a need for more
126   comprehensive assessment of endocrine disrupting chemicals in the Delta. Another study
127   conducted by Johnson et al 2010 was to: 1) determine the presence of vitellogenin in the
128   Sacramento splittail, a native fish of the Sacramento/San Joaquin River estuary and 2) to
129   determine the presence of trace levels of organic contaminants by using passive sampling
130   devices. Results showed that two male splittails out of 12 had extremely elevated vitellogenin.
131   Legacy organochlorines (DDT, DDE, dieldrin) were found at all sites during all seasons;
132   dieldrin, chlordane, and DDE were detected at 58.4 µg/L, 23.8 µg/L, and 61.2 µg/L, respectively.
133   Organophosphate pesticides chlorpyrifos and dioxathion were detected; chlorpyrifos was
134   detected at 154 µg/L in the False River site, a bend off the Sacramento River. Pyrethroids were
135   also detected; bifenthrin, cypermethrin and fenpropathrin were detected at much lower levels
136   than the organochlorines and organophosphates. Triazine herbicides such as atrazine, atroton,


      Draft Report                                   12-3                                    January 2012
      California State Water Project                                                             Chapter 12
      2011 Watershed Sanitary Survey Update                                Constituents of Emerging Concern

137   prometon and simetryn were also observed. PCBs were detected at levels ranging from 32.3
138   µg/L to 73.4 µg/L.
139
140   Another study conducted by a university research team from UC Riverside and UC Berkeley
141   found further evidence regarding low level mixtures of contaminants in Delta water and signs of
142   endocrine disruption in fish (Lavado, 2009). This study evaluated the occurrence and sources of
143   compounds capable of feminizing fish in agriculturally impacted waterways in the Central
144   Valley. Out of 16 locations, estrogenic activity was repeatedly observed at six locations, with the
145   Sacramento River Delta location showing the highest estradiol equivalents. However, the
146   concentrations of compounds most frequently associated with feminization of fish (steroid
147   hormones, alkylphenol polyethoxylates, and alkylphenols) were well below the threshold values
148   for feminization of sensitive species, such as rainbow trout. The inconsistency between the water
149   sample and bioassay results was attributed to the possibility that other compounds could be
150   responsible for feminization of Delta fish species. Specifically, this study concluded that in
151   waters impacted by agricultural activities, estrogenic activity may result from the presence of
152   pesticide mixtures and/or their degradates as well as phytoestrogens, adjuvants, and other
153   compounds with multiple endocrine targets and modes of action. Subsequent work has shown
154   that there was a relationship between feminizing activity in fish and a mixture of alkylphenols
155   and alkyphenols ethoxylates (widely used as surfactants) and the pyrethoid bifenthrin.
156
157   Another recent study investigated the contribution of cattle-grazing rangelands to steroids in
158   surface waters (Kolodziej and Sedlak, 2007). Between April 2005 and March 2006, 30 sites were
159   sampled in Stanislaus, Marin, and Sonoma counties in central California. All of the steroid
160   analytes were detected in one or more of the 88 water samples. Estrone was detected more
161   frequently than the other steroids, with detectable concentrations in 78 percent of the samples at
162   concentrations as high as 38 ng/L. The estrogen 17α-estradiol was present in 31 percent of the
163   samples at concentrations up to 25 ng/L, while 17β-estradiol was present in 18 percent of the
164   samples at concentrations up to 1.7 ng/L. In approximately 10 to 20 percent of the samples,
165   steroid concentrations exceeded predicted no-effect concentrations (PNECs) for the feminization
166   of fish, indicating that allowing cattle direct access to surface waters may impact the health of
167   aquatic organisms in receiving waters.
168
169   In summary, studies conducted to date in the Bay-Delta system have pointed to adverse effects to
170   aquatic organisms from the presence of PPCPs, however more study is needed.
171
172   Occurrence in Surface Waters

173   PPCPs and EDCs have been detected in very small amounts in surface waters in the United
174   States and Europe. One of the first comprehensive studies conducted in the United States was
175   conducted by the United States Geological Survey (USGS) from 1999 to 2000. USGS sampled
176   139 streams in 30 states and found low levels of pharmaceuticals, antibiotics, and other organic
177   wastes (Barnes et al, 2002). Samples were collected from sites downstream of urban and
178   agricultural activities and analyzed for 95 chemicals. In 80 percent of the samples analyzed, one
179   or more chemicals were detected, typically at ng/L concentrations. Steroids, non-prescription
180   drugs (acetaminophen and ibuprofen), and insect repellants were the chemical groups most
181   frequently detected.
182

      Draft Report                                   12-4                                     January 2012
      California State Water Project                                                            Chapter 12
      2011 Watershed Sanitary Survey Update                               Constituents of Emerging Concern

183   Two subsequent USGS studies were conducted and results were published in 2008. The first
184   study evaluated 100 target chemicals (pharmaceuticals and organic wastewater compounds) in
185   25 groundwater and 49 surface waters sources (Focazio et al, 2008). Sites were chosen in areas
186   that were known or suspected to have at least some human and or animal wastewater sources in
187   upstream or upgradient areas. Sixty-three of the 100 targeted chemicals were detected in at least
188   one sample (Focazio et al, 2008). The five most frequently detected chemicals in surface water
189   were cholesterol, metolachlor, cotinine, β-sitosterol, and 1,7-dimethylxanthine. The second
190   USGS study reported on 63 different organic wastewater compounds in groundwater.
191
192   Synder et al 2008 also analyzed source waters, finished waters, and distribution system water
193   supplies for 62 EDCs and PPCPs for 18 drinking water utilities across the United States
194   (AWWAwwaRF 2008a). The suite of 62 chemicals included 20 pharmaceuticals, 26 potential
195   EDCs, five steroid hormones, and 11 phytoestrogens. Forty-one of the 62 targeted chemicals
196   were detected in at least one sample. Overall, pharmaceuticals were the most frequently detected
197   in raw waters. The five most frequently detected chemicals in raw waters were
198   sulfamethoxazole, carbamazepine, atrazine, phenytoin, and meprobamate. Both steroid hormones
199   and phytoestrogens had low frequency of detection in raw water.
200
201   Although the nationwide studies provide a baseline of knowledge for the occurrence of PPCPs, it
202   is important to note that occurrence patterns of PPCPs in wastewater effluent is region specific,
203   based on prescription practice and consumption practice,, and dependent on per-capita water
204   consumption (AWWAwwaRF 2008b). In addition, the occurrence of PPCPs in surface waters
205   highly depends on the degree of wastewater impact upon the source water. Therefore, it is
206   important to derive occurrence information based on studies which have occurred in the
207   watersheds draining to the State Water Project.
208
209   National Water Research Institute Study

210   In 2010, the National Water Research Institute (NWRI) completed a source, fate, and transport
211   study of endocrine disruptors, pharmaceuticals, and personal care products which contained
212   eleven sampling sites associated with the State Water Project (Guo et al, 2010). Sample
213   collection was conducted quarterly from April 2008 to April 2009. Table 3-E112-1 shows the
214   sampling locations and significance of the location. The treated effluents from the Sacramento
215   and Stockton WWTPs were not made available for sampling by the respective sanitation
216   districts. However, samples were collected upstream and downstream of both WWTPs.
217




      Draft Report                                  12-5                                     January 2012
      California State Water Project                                                             Chapter 12
      2011 Watershed Sanitary Survey Update                                Constituents of Emerging Concern

218        Table 3-E112-1. Sampling Locations Associated with the SWP, 2010 NWRI Study
219
                     Sampling Location                              Significance of the Location
      Natomas East Main drainage canal (NEMDC)           Urban Drainage
      American River at E.A. Fairbairn DWTP              Upstream of Sacramento WWTP
      Sacramento River at W. Sacramento DWTP             Upstream of Sacramento WWTP
      Sacramento River at Hood                           Downstream of Sacramento WWTP
      San Joaquin River at Mossdale Landing              Upstream of Stockton WWTP
      San Joaquin River at Holt Road                     Downstream of Stockton WWTP
      H.O. Banks Delta Pumping Plant                     Entry into State Water Project
      O’Neill Forebay (Check 13O’Neill Forebay Outlet)   Integration point of the Delta output
      Check 41                                           Entry point into Southern California; impact by
                                                         agricultural runoff from the Central Valley
      East Branch SWP at Devil Canyon                    Representing a terminal reservoir
      West Branch SWP at Foothill PCS                    Representing a terminal reservoir
220
221   A total of 43 samples were collected during four sample events. Detectable amounts of PPCPs
222   and organic wastewater compounds (OWCs) were found at all locations, except for the American
223   River at the Fairbairn WTP in April 2008, which had no detectable levels of any PPCPs or
224   OWCs. Of the 49 PPCPs and OWCs analyzed, 21 analytes were detected at or above the
225   minimum reporting level, whereas the other 28 were not detected at any locations with the
226   existing MRLs. The occurrence of PPCPs is shown in Table 3-E212-2, from the most to least
227   frequently detected.
228




      Draft Report                                   12-6                                     January 2012
      California State Water Project                                                          Chapter 12
      2011 Watershed Sanitary Survey Update                             Constituents of Emerging Concern

229       Table 3-E212-2. PPCPs and OWCs Detected in the State Water Project Watershed,                    Formatted: Font: 11 pt
230                                   NRWI 2010 Study                                                      Formatted: Font: 11 pt
231                                                                                                        Formatted: Font: (Default) Times New
                                                                                   Location                Roman, 11 pt
                                        Detection                                    where                 Formatted: Font: 11 pt
                                                  Minimum,    Median,    Maximum,
          Analyte             Use       Frequency                                  Maximum
                                                   (ng/L)     (ng/L)        (ng/L)                         Formatted: Font: 11 pt
                                          (n=40)                                      was
                                                                                                           Formatted: Font: 11 pt
                                                                                    detected
      Carbamazepine       Anti-         88%      <1          3           26        Holt Road               Formatted: Font: 11 pt
                          Convulsant                                                                       Formatted                              ...
      Diuron              Herbicide     88%      <5          81          873           O’Neill             Formatted                              ...
                                                                                       Forebay             Formatted Table
      Sulfamethoxazole Antibiotic       88%      <1          11          71            Holt Road
                                                                                                           Formatted: Font: 11 pt
      Caffeine                          83%      <5          8           67            Holt Road
      Primidone        Anti-            70%      <2          4           21            Holt Road           Formatted: Centered

                       Convulsant                                                                          Formatted                              ...
      TCEP                              70%      <5          7           34            Holt Road           Formatted: Font: 11 pt
      Gemfibrozil      Anti-            53%      <5          5           162           Hood                Formatted                              ...
                       Cholesterol
                                                                                                           Formatted                              ...
      Dilantin         Anti-            50%      <5          4           33            Holt
                                                                                                           Formatted                              ...
                       Convulsant
      Simazine         Herbicide        38%      <20         <20         408           Devil               Formatted                              ...
                                                                                       Canyon              Formatted: Font: 11 pt
      Atrazine            Herbicide     25%      <1          <1          2             Devil               Formatted                              ...
                                                                                       Canyon              Formatted                              ...
      O,p-DDD             Medicine      20%      <20         <20         82            Banks
                                                                                                           Formatted: Font: 11 pt
      Methoxychlor        Insecticide   18%      <20         <20         66            O’Neill
                                                                                                           Formatted: Font: 11 pt
      DEET                Insect        13%      <20         <20         35            Holt
                          Repellant                                                                        Formatted: Font: 11 pt
      Methylparaben       Anti-         10%      <20         <20         744           Check 41            Formatted: Font: 11 pt
                          fungal                                                                           Formatted: Font: 11 pt
                          agent                                                                            Formatted: Font: 11 pt
      Acetaminophen       Medicine      5%       <1          <1          28            Banks
                                                                                                           Formatted: Font: 11 pt
      Linuron             Pesticide     5%       <5          <5          5             Banks
      Bisphenol A         Plastics      3%       <30         <30         140           Check 41            Formatted: Font: 11 pt

      Desisopropyl-       Herbicide     3%       <20         <20         25                                Formatted: Font: 11 pt
      atrazine                                                                                             Formatted: Font: 11 pt
      Ibuprofen           Analgesic     3%       <10         <10         47            Holt                Formatted: Font: 11 pt
      Octylphenol         Rubber,       3%       <20         <20         68                                Formatted: Font: 11 pt
                          Pesticide,
                                                                                                           Formatted: Font: 11 pt
                          Paints
      Propylparaben       Cosmetic      3%       <20         <20         83            Check 41            Formatted: Font: 11 pt

232                                                                                                        Formatted: Font: 11 pt
233   Overall, the median occurrence of targeted PPCPs was less than 30 ng/L, except for diuron (81        Formatted: Font: 11 pt
234   ng/L). Diuron is used extensively in California as a pre-emergent herbicide. Table 3-E2 also         Formatted: Font: 11 pt
235   shows the location of where the maximum concentrations were detected. It is interesting to note      Formatted: Font: 11 pt
236   that many of the maximums for the most frequently detected compounds were located at the San         Formatted: Font: 11 pt
237   Joaquin River at Holt Road, just downstream of the Stockton WWTP.                                    Formatted: Font: 11 pt
238
                                                                                                           Formatted: Font: 11 pt

      Draft Report                                    12-7                                 January 2012
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      2011 Watershed Sanitary Survey Update                               Constituents of Emerging Concern

239   Seasonal variations of PPCPs in wastewater effluent could not be determined, as the Sacramento
240   and Stockton WWTPs were not available for sampling. The seasonal variations of selected
241   PPCPs downstream of the Sacramento WWTP and the Stockton WTTP were evaluated as shown
242   in Figures 3-E112-1 and 3-E212-2. At both locations, caffeine was highest in winter (January
243   2009), possibly reflecting less biodegradation at the WWTPs or less biodegradation in the rivers
244   during this season. In addition, there might also be less photolysis in the winter. Concentrations
245   of PPCPs downstream of the Stockton WWTP were highest in January 2009. As stated in the
246   NRWI study, sSince WWTP discharge rates do not vary that much from season to season, the
247   flow in the San Joaquin River may have been lower than normal in January 2009.
248
249    Figure 3-E112-1. Concentrations of five representative PCCPs in the Sacramento River at
250             Hood (downstream of Sacramento WWTP), April 2008-January 2009*




251
252   *Adapted from Guo et al 2010 NWRI Study
253




      Draft Report                                   12-8                                    January 2012
      California State Water Project                                                            Chapter 12
      2011 Watershed Sanitary Survey Update                               Constituents of Emerging Concern

254   Figure #-12-2E2. Concentrations of five representative PCCPs in the San Joaquin River at
255            Holt Road (downstream of Stockton WWTP), April 2008-January 2009*




256
257   *Adapted from Guo et al 2010 NWRI Study
258
259   The NWRI study also provides an upstream to downstream comparison for selected PPCPs along
260   the State Water Project, beginning with sites just downstream of the Sacramento WWTP (Hood)
261   and downstream of the Stockton WWTP (Holt). Certain PPCPs (carbamazepine, primidone,
262   gemfibrozil, and sulfamethoxazole) are highly attenuated as shown in Figures 3-E312-3
263   through 312-E5        5. Since carbamazepine and primidone have been shown to be highly
264   recalcitrant (Loffler et al., 2005;Krasner et al., 2006), the attenuation of carbamazepine and
265   primidone can be attributed to dilution with non-wastewater-impacted water, such as
266   groundwater pumpins. Sulfamethoxazole has been shown to undergo biodegradation and
267   sorption to sediments or soils (Boxall, 2008; Radke et al., 2009) and gemfibrozil has been shown
268   to be attenuated by photolysis and biodegradation (Fono et al., 2006). Therefore, the attenuation
269   of gemfibrozil and sulfamethoxazole were most likely due to a combination of dilution and
270   natural degradation. However, detectable levels of some PPCPs were found at terminal reservoirs
271   in Southern California.
272




      Draft Report                                  12-9                                     January 2012
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      2011 Watershed Sanitary Survey Update                          Constituents of Emerging Concern

273   Figure 3-E312-3. Occurrence of carbamazepine Carbamazepine in the State Water Project
274                                            *




275
276   *Adapted from Guo et al 2010 NWRI Study
277
278       Figure 3-E412-4. Occurrence of gemfibrozil Gemfibrozil in the State Water Project*
                                                                                                        Formatted: Centered




279
280   *Adapted from Guo et al 2010 NWRI Study
281

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      2011 Watershed Sanitary Survey Update                            Constituents of Emerging Concern

282
283     Figure 3-E512-5. Occurrence of sulfamethoxazole Sulfamethoxazole in the State Water
284                                          Project*
285




286
287   *Adapted from Guo et al 2010 NWRI Study
288
289   The general conclusion from the Guo et al 2010 NWRI study is that there is no evidence of
290   human health risk from low levels of the commonly detected EDCs and PPCPs in drinking water
291   or drinking water supplies. However, more toxicological studies are needed.
292
293   University of California, Davis Aquatic Ecosystems Analysis Laboratory

294   A pilot study was conducted by the University of California Davis Aquatic Ecosystems Analysis
295   Laboratory to evaluate the presence of PPCPs in the Sacramento River (Schaefer et al, 2009).
296   This work was conducted for the State Water Resources Control Board. Four locations along the
297   Sacramento River were monitored using passive sampling devices: Freeport Marina
298   (approximately 100 meters upstream of the Sacramento Regional Wastewater Treatment plant
299   effluent discharge), West Bank (approximately 525 meters downstream of the effluent
300   discharge), Cliff’s Marina (approximately 1,180 meters downstream of the effluent discharge),
301   and a private dock approximately 1,900 meters downstream of the effluent discharge).
302   Deployment of sampling devices occurred on May 28, 2009 and was removed on June 29, 2009.
303   Table 3-E312-3 shows a summary of all detectable compounds during the study, as well as a
304   comparison to concentrations found at Hood during the NWRI Study. It should be noted that
305   none of the analytes were detected at the Freeport Marina site, which is upstream of the
306   Sacramento Regional Wastewater Treatment effluent discharge.

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307                                                                                                        Formatted Table                   ...
308    Table 3-E312-3. Detectable Results from 2009 PPCP Study of Sacramento River, Aquatic                Formatted                         ...
309                          Ecosystems Analysis Laboratory, UC Davis                                      Formatted                         ...
310                                                                                                        Formatted                         ...
                         Method                                                                Hood        Formatted                         ...
                                          Freeport      West      Cliff’s      Private
                        Detection                                                            (NRWI         Formatted
           Analyte                        Marina        Bank      Marina        Dock                                                         ...
                           Limit                                                              Study)
                                           (µg/L)      (µg/L)     (µg/L)       (µg/L)                      Formatted                         ...
                          (µg/L)                                                              (µg/L)
      Caffeine         0.020             ND          7.5        ND           ND            ND - 51         Formatted                         ...
      Trimethoprim     0.002             ND          2.00       28.3         26.3          NS              Formatted                         ...
      Sulfamethoxazole 0.005             ND          5.92       13.0         13.0          28-43           Formatted                         ...
      Gemfibrozil      0.002             ND          19.3       ND           214           83 - 162        Formatted                         ...
      Ibuprofen        0.02              ND          ND         182          ND            ND              Formatted                         ...
      Carbamazepine    0.005             ND          ND         45.6         43.2          3 - 11
                                                                                                           Formatted                         ...
      Fluoxetine       0.005             ND          17.6       20.8         20.8          NS
      Xylene           0.1               ND          1140       ND           100           NS              Formatted                         ...
      (polycyclic                                                                                          Formatted                         ...
      musk)                                                                                                Formatted                         ...
      Nonylphenol      0.5               ND          ND         160          68.5          NS              Formatted                         ...
      Nonylphenol      0.5               ND          ND         800          730           NS
                                                                                                           Formatted                         ...
      Ethoxylates
                                                                                                           Formatted                         ...
311   NS – Not sampled
                                                                                                           Formatted                         ...
312
313   California Department of Water Resources/Metropolitan Water District of Southern California          Formatted                         ...
314   (MWDSC) Joint Study                                                                                  Formatted                         ...
                                                                                                           Formatted                         ...
315                                                                                                        Formatted                         ...
316   MWDSC and the California Department of Water Resources (DWR) completed a two-year study              Formatted                         ...
317   in April 2010 of the sources and occurrence of NDMA, other nitrosamines, and their precursors        Formatted                         ...
318   in the Delta (DiGiorgio et al, 2010). Major conclusions from this study include:
                                                                                                           Formatted                         ...
319
                                                                                                           Formatted
320          To date, the onlyno instantaneous nitrosamines have been detected in sampling locations                                        ...
                                                                                                           Formatted                         ...
321           of the Sacramento-San Joaquin Delta was NDMA. . It was detected once at the Mossdale
322           sampling location at 4.2 ng/L, and also at the Vernalis sampling location at 2.5 ng/L.       Formatted                         ...
323           Photodegradation and/or dilution may be one explanation for nondetection.                    Formatted                         ...
324          N-nitrosodimethylamine formation potential concentrations were generally twohree to          Formatted                         ...
325           four times higher downstream of the wastewater treatment plants. Sacramento WWTP             Formatted                         ...
326           compared to upstream, and three times higher downstream of the Stockton WWTP                 Formatted                         ...
327           compared to upstream.                                                                        Formatted                         ...
328          Primidone concentrations were generally three times higher downstream of the                 Formatted                         ...
329           Sacramento WWTP compared to upstream, and three times higher downstream of the               Formatted                         ...
330           Stockton WWTP compared to upstream. These findings are generally similar to the
                                                                                                           Formatted                         ...
331           NRWI study above.
                                                                                                           Formatted                         ...
332          Diuron does not appear to be a major source of NDMA precursors.
                                                                                                           Formatted                         ...
333          Dissolved organic carbon (DOC), trihalomethane formation potential (THMFP), and
                                                                                                           Formatted                         ...
334           haloacetic acid formation potential (HAAFP) are not good predictors of NDMA
335           formation potential.                                                                         Comment [p1]: Row 414, line 955
                                                                                                           Comment [p2]: Row 415, line 958

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336
337   The second phase of this study began in early 2011 and will focus sampling efforts on the
338   Sacramento Regional Wastewater Treatment Plant and the City of Stockton Regional
339   Wastewater Control Facility. Unlike the previous study, this new study will collect samples by
340   boat to better quantify nitrosamines, their precursors and WWTP tracers (i.e., selected PPCPs) in
341   discharge effluent as well as continue to quantify WWTP impacts in the Sacramento and San
342   Joaquin Rivers. The City of Stockton has agreed to sampling of their treated effluent
343   immediately prior to discharge, but no agreement has been made with the Sacramento Regional
344   Wastewater Treatment Plant. Cryptosporidium and Giardia will also be assessed in the treated
345   effluent. The study will conclude at the end of 2012.
346
347   Central Valley Regional Water Quality Control Board

348   Under the Central Valley Water Board’s Surface Water Ambient Monitoring Program, a special
349   study was conducted to assess the potential for aquatic life impairment in the Sacramento-San
350   Joaquin River Delta due to the occurrence and toxicity of pyrethroid pesticides in the water
351   column. The current use of pyrethroids in California is 50 percent greater than what it was just
352   five years ago (CDPR, 2007). Samples were collected for the eight commonly used pyrethroid
353   pesticides: bifenthrin, cyfluthrin, cypermethrin, esfenvalerate, lambda-cyhalothrin, deltamethrin,
354   fenpropathrin, and permethrin. Water toxicity testing was done with a native crustacean,
355   Hyalella azteca. Major conclusions from this study include:
356
357          For several of the pyrethroids, threshold for water toxicity was as low as 2 parts per
358           trillion.
359          Virtually all urban runoff contained pyrethroids, typically at about four times the
360           concentration that would paralyze Hyalella.
361          Bifenthrin and cyfluthrin are the pyrethroids of greatest toxicological concern in urban
362           runoff.
363          Pyrethroids were present in 66 percent of the final effluent samples from wastewater
364           treatment plants. They were found most often, and in highest concentration at the
365           Sacramento WWTP, followed by the Vacaville WWTP, and then the Stockton WWTP.
366           The typical wastewater treatment plant effluent contains pyrethroids at about 1 to 1.5
367           times the concentrations that would paralyze Hyalella.
368          Pyrethroids were present in 30 percent of agricultural discharges.
369          Pyrethroids (most often bifenthrin) were found in the Sacramento River as it passed
370           through the City of Sacramento. Concentrations peaked near the threshold of causing
371           toxicity.
372
373   United States Geological Survey

374   After the national reconnaissance study was conducted by USGS from 1999 to 2000, there have
375   been no USGS CEC follow-up studies for surface water within the Central Valley. The national
376   reconnaissance study conducted by USGS from 1999 to 2000 included six sites within or
377   tributary to the Delta: the Sacramento River at Freeport; the San Joaquin River near Vernalis;
378   Mud Slough and Orestimba Creek, west-side tributaries to the San Joaquin River that are
379   dominated by agricultural drainage; Turlock Irrigation District (TID) Lateral 5, a canal that

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      2011 Watershed Sanitary Survey Update                              Constituents of Emerging Concern

380   receives agricultural drainage and municipal wastewater effluent and drains to the San Joaquin
381   River; and French Camp Slough, a tributary to the San Joaquin River that is dominated by urban
382   runoff. The key findings for this study were summarized in the previous watershed sanitary
383   survey. The key findings for the Central Valley sites are:
384
385          Steroid and Hormone Compounds – Samples were collected from the Sacramento River
386           at Freeport and TID Lateral 5 and analyzed for seven steroid and hormone compounds.
387           Cholesterol was detected at 0.383 µg/L in the Sacramento River and at 1.11 µg/L in TID
388           Lateral 5. Coprostanol was found at 0.624 µg/L in TID Lateral 5.
389
390          Pharmaceuticals – The samples were analyzed for ten pharmaceuticals. None of the
391           pharmaceuticals was detected in the Sacramento River at Freeport, Mud Slough, and
392           French Camp Slough. Acetaminophen was estimated to be 0.004 µg/L in Orestimba
393           Creek and the San Joaquin River at Vernalis. Five pharmaceuticals were detected in TID
394           Lateral 5; acetaminophen at 0.39 µg/L, caffeine at 0.68 µg/L, diltiazem at 0.017 µg/L,
395           1,7-Dimethylxanthine at 0.21 µg/L and codeine was estimated at 0.019 µg/L.
396
397          Antibiotics – The USGS study reported that the antibiotic data were not yet analyzed for
398           the sites in the Central Valley. The data are not available through the USGS National
399           Water Information System (NWIS) database.
400
401          Selected Organic Wastewater Contaminants – The samples were analyzed for eight
402           organics that the USGS has identified as being present in wastewater. TID Lateral 5 was
403           estimated to contain 0.01 µg/L of 1,4-dichlorobenzene and 0.04 µg/L of 2,6-di-tert-p-
404           benzoquinone. None of the organics was detected at the other five sites.
405
406   These data indicate that TID Lateral 5, which receives municipal wastewater from the City of
407   Turlock contained a number of compounds associated with human wastewater at low
408   concentrations. Although the Freeport site on the Sacramento River is downstream of the
409   Sacramento urban area, it is upstream of the discharge from the Sacramento Regional
410   Wastewater Treatment Plant (SRWTP). Due to tidal influence in the Sacramento River, the
411   Freeport site can be influenced by the discharge from the treatment plant but these data do not
412   adequately characterize the quality of water downstream from the discharge.
413
414   USGS also sampled for 63 organic wastewater compounds at the intake to West Sacramento’s
415   Bryte Bend WTP on the Sacramento River just upstream from the confluence with the American
416   River. This location is upstream of the urban Sacramento area and downstream of a number of
417   large agricultural drains. Eleven samples were collected between October 2004 and June 2005.
418   Nine pesticides were detected and nine organics were verified but not quantified in the samples,
419   including caffeine, cholesterol, and the insect repellant, DEET. The Bryte Bend site does not
420   adequately characterize the quality of water entering the Delta because the largest wastewater
421   discharger in the watershed (SRWTP) is downstream of this site.
422
423



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424   Occurrence in Drinking Water

425
426   In general, the occurrence of PPCPs is more frequent and at higher median concentrations in
427   source waters than in finished drinking water. The occurrencepersistence of these contaminants
428   in finished drinking waters depends on their occurrence in source waters, the drinking water
429   treatment processes, and the analytical detection limit.        Some pharmaceuticals and their
430   metabolites have been reported to occur at very low concentrations in some finished drinking
431   water samples in the U.S. A recent, comprehensive study of source, raw and finished waters for
432   EDCs and pharmaceuticals was conducted for the AWWARF study “Toxicological Relevance of
433   EDCs and Pharmaceuticals in Drinking Water”. In this study, finished drinking water samples
434   were collected from 18 water utilities across the United States. The five most frequently detected
435   PPCPs were atrazine, meprobamate, phenytoin, atenolol, and carbamazepine, with median
436   concentrations less than 10 ng/L, with the exception of atrazine at median 49 ng/L (Benotti et
437   al., 2009 and Synder et al, 2008). Atrazine exhibited the highest frequency of occurrence (83%),
438   followed by meprobamate (78%), phenytoin (56%), atenolol (44%), carbamazepine (44%), and
439   gemfibrozil (39%).
440
441   Fate and Transport

442   As presented in the 2008 AWWAwwaRF Study (AWWAwwaRF 2008b), concentrations of
443   PPCPs in surface waters can be potentially reduced due to phase partitioning and abiotic and
444   biotic transformation processes. Trace organic wastewater compounds, such as fragrances
445   galaxolide and tonalide, have high octanol-water partition coefficients and can absorb onto river-
446   bed sediments (Rimkus 1999). However, most pharmaceuticals have low sorption potential and
447   volatility, thus sorption and volatilization removal mechanisms are negligible. Abiotic
448   transformation processes include hydrolysis and photolysis. Photolysis can occur either by direct
449   absorption of light or indirectly by photosensitizers, such as nitrate and humic acids. Several
450   pharmaceuticals such as diclofenac, triclosan, sulfamethoxazole and propranolol have been
451   found to be amenable to photolytic decay in surface waters (AWWAwwaRF, 2008b).
452   Biotransformation mechanisms become more important for hydraulic travel times on the order of
453   weeks. Ibuprofen, gemfibrozil, caffeine, and naproxen have been shown to be transformed via
454   biotransformation processes.
455
456   As discussed earlier, the Guo et al 2010 NWRI Study presents fate and transport information on
457   three selected PPCPs through the State Water Project.
458
459   Analytical Methods

460   One of the major challenges in evaluating CECs in water is that there are no national or
461   international standardized methods. Currently the Water Research Foundation is sponsoring a
462   project entitled “Evaluation of Analytical Methods for EDCs and PPCPs via Interlaboratory
463   Comparison #4167”. This project will evaluate current methodology commonly used for the
464   analysis of EDCs and PPCPs by multiple laboratories in various water matrices.
465
466   The goal of the project is to provide guidelines to drinking water utilities on optimizing data
467   quality for EDCs and PPCPs. The study will determine which factors are most important in

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      2011 Watershed Sanitary Survey Update                                 Constituents of Emerging Concern

468   determining the performance of a method at environmentally relevant (ng/L) concentrations. To
469   accomplish this goal, a literature review and single-blind, multi-round interlaboratory studies
470   will be carried out. Using statistical analysis and expert review of results from the interlaboratory
471   studies, major factors that have the most important role in determining the performance of a
472   method will be identified. After testing and evaluating various sample collection related
473   parameters such as bottle type and preservation and quenching agents, the optimized method(s)
474   will be implemented in several laboratories and further tested in a variety of matrices to ensure
475   widespread applicability of the technique(s). This project will provide reliable data on the
476   capabilities of both analytical methods and laboratories for measuring EDCs/PPCPs in typical
477   drinking water related matrices. More importantly, the product of this research will provide the
478   foundation for the establishment of standardized protocols for a representative target list of
479   EDCs/PPCPs with supportable reporting levels. The final report should be completed by the end
480   of 2011.
481
482   Health Effects

483   The initial concerns when EDCs and PPCPs were first reported in surface waters were focused
484   on increased bacterial resistance to antibiotics and interference with growth and reproduction of
485   aquatic organisms. More recently, concerns for human health due to exposure in drinking water
486   have been expressed. Cause-effect relationships between low-level environmental exposures to
487   specific EDCs and human health have not been established. Although no known health effects
488   have been linked to exposure to drinking water with EDCs and PPCPs at trace levels, drinking
489   water providers are concerned about potential effects and their consumers’ perception of the
490   safety of drinking water. Human and animal studies of the effects of continual, long-term
491   exposure to environmentally relevant doses are lacking for most known or potential EDCs, but
492   results of some animal studies indicate that certain EDCs can produce effects at low doses. There
493   is sufficient evidence to conclude that adverse endocrine-mediated effects have occurred in some
494   wildlife species. However, to date there is little evidence that levels of EDCs found in source
495   waters have produced adverse endocrine effects in humans (Snyder et al, 2005). Studies
496   examining EDC-induced effects in humans have yielded inconsistent and inconclusive results,
497   highlighting the need for more rigorous studies.
498
499   An AWWAwwaRF study titled “Toxicological Relevance of EDCs and Pharmaceuticals in
500   Drinking Water” evaluated health effects by comparing levels of 16 pharmaceuticals, ten EDCs
501   and three steroid hormones in drinking water to calculated health risk thresholds such as
502   acceptable daily intakes (ADIs) and drinking water equivalent levels (DWELs) (AWWAwwaRF,
503   2008a). Water samples were collected from 20 geographically diverse sites within the United
504   States. ADIs are defined as the amount of a chemical to which a person can be exposed on a
505   daily basis over an extended period of time (usually a lifetime) without suffering deleterious
506   effect. ADIs were calculated using methods consistent with USEPA approaches for determining
507   levels of exposure to environmental contaminants that are not likely to be associated with
508   adverse health effects. A cautious, conservative approach was taken in developing the ADI
509   values. ADIs can be converted to DWELs by multiplying the ADI by an assumed body weight
510   and dividing by an average daily drinking water ingestion rate. Estradiol equivalents (EEq) were
511   also used as another approach to evaluate health effects.
512


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513   The AWWAwwaRF report showed that none of the EDCs and PPCPs detected in their drinking
514   water samples exceeded the ADIs and DWELs, therefore none occurred at concentrations
515   predicted to be of relevance to human health. Additionally, EEqs in the drinking water were
516   either not detected or extremely low, much lower than some common food and beverage items
517   like vegetable juice, coffee and soy milk. The evaluation indicates that although some
518   pharmaceuticals and EDCs were detected in U.S. drinking waters, there is no evidence of human
519   health risk from consumption of these waters. Furthermore, the exposure through water is
520   expected to be small compared to medications, food and beverages, occupational exposures, and
521   residential activities.
522
523   Similarly, the AWWAwwaRF study titled “State of Knowledge of Endocrine Disruptors and
524   Pharmaceuticals in Drinking Water” evaluated health effects by comparing maximum levels of
525   pharmaceuticals in source and raw waters, to the lowest therapeutic dosage (i.e. the lowest
526   recommended dosage level indicated on the package labeling, assumed to be the lowest exposure
527   level at which the chemical produces the desired pharmacologic effect). The therapeutic dose
528   was translated into a water concentration, assuming that a person drinks two liters of water at this
529   concentration every day. To provide an additional margin of safety, the lowest therapeutic dose
530   was divided by 1,000. For each pharmaceutical, the highest detected concentration in source or
531   raw water was well below the concentration based on the lowest therapeutic dose divided by
532   1,000. (TABLE 6.2 can be put in as an appendix). Furthermore, the maximum detected
533   concentrations in drinking water were a factor of 5 to 12,000 lower than the therapeutic dose
534   divided by 1,000.
535
536   Removal in Wastewater Treatment Plants

537   Although PPCPs and EDCs can potentially originate from numerous sources and enter the
538   environment by many routes, numerous studies have reported the occurrence of CECs in effluent
539   from municipal wastewater treatment plants. EDCs and PCPPs are biologically active
540   compounds. These compounds and their metabolites are not completely removed by current
541   wastewater treatment technologies and are often found in treated effluents. As discussed in
542   Chapter 4, approximately 350 mgd of treated wastewater is discharged to surface waters in the
543   Sacramento, San Joaquin and Delta watersheds. There have been a number of studies to address
544   removal of CECs using conventional wastewater treatment processes, with some of the larger
545   studies as cited below. It is difficult to draw absolute conclusions regarding removal as there are
546   numerous CECs, and removal studies tend to focus on a small group of
547   contaminantsconstituents.
548
549   Conventional wastewater treatment facilities are not specifically designed to remove EDCs, and
550   the degree with which they are removed varies from nearly complete to very little during primary
551   and secondary treatment. Overall, biological treatment (namely activated sludge) is the most
552   effective treatment process for CEC removal when conventional wastewater processes are
553   employed.
554
555   AWWARF Study # 2617 Occurrence Survey of Pharmaceutically Active Compounds

556   This study focused on PhACs likely to be present in wastewater at 18 wastewater treatment
557   plants (AWWAwwaRF, 2006). The key findings from that study are:

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558
559          PhACs are detectable in the effluent of conventional wastewater treatment plants.
560           Diclofenac, gemfibrozil, metoprolol, naproxen, sulfamethoxazole, and trimethoprim were
561           detected in almost all of the wastewater effluent samples. The median concentrations of
562           the PhACs in effluent ranged from less than 10 to 1,400 ng/L.
563
564          Reverse osmosis treatment plants remove most PhACs however metoproiol and
565           propranolol were detected in the effluent from one reverse osmosis plant.
566
567   Some preliminary work by researchers at U.C. Berkeley indicates that hormones such as
568   estradiol are not transformed or removed by secondary treatment and that more advanced
569   treatment is required before significant removals are observed. Others have reported similar
570   results on a range of pharmaceutical compounds (Sakaji, 2004).
571
572   Water Environmental Research Foundation (WERF) Study 01-HHE-20T Removal of
573   Endocrine Disrupting Compounds in Water Reclamation Processes

574   A WERF study conducted by Drewes et al 2006 assessed conventional water reclamation trains
575   and advanced treatment processes to determine their ability to reduce concentrations of
576   endocrine disrupting compounds and activity. Studies were conducted at seven full-scale water
577   reclamation facilities located in California, Arizona, Florida, Virginia, and Wisconsin. The target
578   compounds included several steroid hormones (testosterone, 17β-estradiol, 17α-ethinylestradiol,
579   estrone, estriol) and phenolic compounds (bisphenol A, 4-t-octylphenol, nonylphenol). In
580   addition to chemical measurements, estrogenic activity was evaluated. Removal efficiencies after
581   secondary treatment for total estrogenic activity, 17β-estradiol, estriol, and bisphenol A were at
582   90 percent or greater, while estrone, 4-nonylphenol, 4-t-octylphenol, and 17α-ethinylestradiol
583   had lower removals of 48, 61, 80, and 71 percent respectively. This study also concluded that
584   estrogenic activity in the influent correlated strongly with BOD loading, as well as BOD
585   removal. Other findings included:
586
587          High removal of EDCs and activity was achieved at solid retention times (SRT)
588           exceeding two days.
589          Additional removal of steroid hormones was achieved during chlorination, but only
590           partial oxidation occurred for phenolic compounds.
591          UV using low pressure, high intensity radiation had no effect on EDCs.
592          Small amounts of activated carbon (10 mg/L) were required to remove steroid hormones
593           to below detection limits and significantly reduce phenolic compounds.
594          Microfiltration followed by reverse osmosis was proven to remove EDCs and biological
595           activity to no detection levels.
596
597   WERF Study 03-CTS-22UR Fate of Pharmaceuticals and PCP Through Municipal
598   Wastewater Treatment Processes

599   A study conducted by Stephenson et al 2007 evaluated the passage of personal care products
600   through full-scale wastewater facilities located in the Southwestern United States. The focus of
601   the study was to evaluate the impact of SRT on personal care product removal through secondary

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      2011 Watershed Sanitary Survey Update                              Constituents of Emerging Concern

602   treatment, as well as media filtration. As shown in Table 3-E412-4, the study concluded that for
603   the target list of 20 personal care product compounds, half of the compounds were well removed
604   (greater than 80 percent) at SRTs equal to or less than 5 days. DEET required a longer SRT of
605   greater than 13 days and TCEP, musk ketone, and galaxolide required greater than 25 days.
606   Media filtration offered little additional removal of these compounds.
607
608   Table 3-E412-4. Percent Removals for Personal Care Products and Minimum Solids
609   Retention Times Needed to Consistently Achieve Over 80 Percent Removal
610
                                                                                SRT80 (Minimum
                                                                                 Solids Retention
                                     Median Percent                              Time Required to           Formatted: Centered
             Removal Bin                                      Compound
                                       Removal                                 Consistently Achieve         Formatted Table
                                                                                 Removal greater
                                                                                 than 80%), days
                                  Greater   than   80 Methyl-3-                0-5
         Excellent Removal        Percent Removal      phenylpropionate
                                                       Caffeine                5
                                                       Ibuprofen               5
                                                       Oxybenzone              5
                                                       Chloroxylenol           5
                                                       Methylparaben           0-5
                                                       Benzyl Salicylate       5
                                                       3-Phenylpropionate      0-5
                                                       Butylbenzyl Phthalate   5
                                                       Octylmethoxycinnamate   5
                                                       Benzophenone            13
         Moderate Removal         Greater   than   50 Octylphenol              5-28
                                  Percent Removal but Ethyl-3-                 >5
                                  less than 80 Percent phenylproprionate
                                  Removal              Triclosan               10
         Poor Removal             Less than 50 Percent TCEP                    >25
                                  Removal              Triphenylphosphate      >5
                                                       BHA                     >8
                                                       DEET                    >13
                                                       Musk Ketone             >25
                                                       Galaxolide              >25
611
612   Source: WERF 2007
613
614   In 2003, the USGS and Metcalf and Eddy devised a multi-disciplinary collaborative research
615   program to investigate concentrations of 63 trace contaminants at four wastewater treatment
616   plants in New York. Samples were collected after the primary, secondary, tertiary and
617   disinfection stages at each plant. A comparison of removal percentages among plants indicated
618   that in general, the plants operating with activated sludge processes (plants A, B, C) were
619   consistently capable of effecting greater emerging contaminant removal than the plant operating
620   with the trickling filter process (plant D). Table 3-E512-5 shows results for seven of the 63
621   compounds, as these compounds are among the most frequently detected. The wastewater
622   treatment plants examined were effective in removing significant amounts of emerging

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      2011 Watershed Sanitary Survey Update                                               Constituents of Emerging Concern

623   contaminantsconstituents using conventional wastewater treatment processes. Similar to the
624   Stephenson study, biological treatment was the most important process for the reduction of the
625   studied compounds, as compared to the filtration or disinfection processes. The median removals
626   observed through the filtration and disinfection processes were less than ten percent at all plants,
627   except for plant D.
628
629   Table 3-E512-5. Median Influent and Effluent Concentration (µg/l) of Selected Emerging
630   Contaminants and percent removals (from influent to effluent)
631
        Analyte
                      Plant    Plant    %     Plant    Plant      %     Plant    Plant    %     Plant    Plant    %
                      A inf.   A eff.   rem   B inf.   B eff.     rem   C inf.   C eff.   rem   D inf.   D eff.   rem
                      3.7      2.1      44    1.0      0.48       53    3.3      1.8      41    2.3      1.8      21
        AHTN
        Caffeine      130      0.075    >99   51       0.056      >99   70       0.11     >99   41       20       39
        Cholesterol   11       ND       100   17       ND         100   21       0.88     96    9.0      1.7      66
        DEET          0.94     ND       100   0.56     ND         100   2.1      ND       98    1.6      1.3      24
        Para-         13       ND       100   4.3      1.1        75    59       0.93     98    18       18       8.1
        nonylpheno
        l
        Triclosan     2.6      0.13     94    2.8      0.13       94    2.4      0.12     94    1.8      1.0      36
        TBEP          14       0.15     99    3.1      ND         100   140      ND       100   12       11       15
632
633   % rem. = percent removal
634
635   Source: Esposito et al. 2006
636
637   AWWA Research Foundation Study #3012 Comparing Nanofiltration and Reverse Osmosis
638   for Treating Recycled Water

639   Today, the industry standard for subsurface injection of treated wastewater for groundwater
640   recharge or for surface water augmentation projects is to have an integrated membrane system
641   such as microfiltration pretreatment followed by reverse osmosis. In this study, nanofiltration
642   and ultra-low pressure RO (ULPRO) membranes were compared to conventional RO membranes
643   with respect to removing TOC, total nitrogen, and both regulated and unregulated trace organic
644   compounds. The findings of this study reveal that ULPRO membranes can “consistently meet
645   potable water quality requirements for treating source water of impaired quality with respect to
646   TOC, total nitrogen, and both regulated and unregulated trace organic compounds.” ULPRO
647   membranes potentially offer lower operating expenses than conventional RO. Certain low
648   fouling loose NF membranes were tested, and although they demonstrated effluent rejection of
649   TOC and a high selectivity for a wide range of trace organics, they resulted in lowered permeate
650   water quality for ammonia and nitrate.
651
652
653   Removal in Water Treatment Plants

654   There has been a number of research projects conducted to evaluate specific water treatment
655   processes in removing pharmaceuticals, and both regulated and unregulated trace organic
656   compounds. Relevant information from four research projects is discussed below. The projects
657   studied removal by potassium permanganate and potassium ferrate salts, ozonation, conventional


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      2011 Watershed Sanitary Survey Update                               Constituents of Emerging Concern

658   water treatment processes (coagulation, sedimentation), chlorine, chloramines, UV, activated
659   carbon, and membranes.
660
661   AWWA Research Foundation Study #2758 Removal of EDCs and Pharmaceuticals in
662   Drinking in Drinking and Reuse Treatment Processes

663   This study evaluated various physical, chemical, and biological drinking water treatment plant
664   processes on the removal/transformation efficiencies of EDCs and PPCPs in natural waters
665   (AWWAwwaRF, 2007). The key findings from this study are:
666
667          Conventional Processes - Coagulation, flocculation, and sedimentation are ineffective for
668           removing the majority of EDCs and PPCPs that were evaluated.
669
670          Disinfectants - Free chlorine disinfection can remove many target compounds depending
671           on the structure of the contaminant. Chloramines are less effective than free chlorine at
672           removing EDCs and PPCPs. Ozone is more effective than chlorine, and is able to
673           significantly remove the majority of target analytes. Ozone is likely the most cost
674           effective measure for removing the majority of EDCs and PPCPs for water treatment. UV
675           irradiation at typical disinfection doses is ineffective for removing most EDCs and PCPs;
676           however, high energy UV at oxidative doses can be effective, and the combination of UV
677           and hydrogen peroxide can achieve removal rates similar to ozone. As adapted from the
678           NWRI study, Table 3-E6 summarizes the findings from the various disinfection
679           processes.
680
681          Activated Carbon – Activated carbon is highly effective, although exhausted activated
682           carbon is ineffective.
683
684          Magnetic Ion Exchange – Magnetic ion exchange processes are ineffective.
685
686          Membranes – Reverse osmosis and nanofiltration are highly effective while ultrafiltration
687           and microfiltration are largely ineffective.
688
689




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690
691    Table 3-E612-6. PPCP Removal/Transformation Efficiencies in Selected Drinking Water
692                                 Treatment Processes #




693
694
695   Little is known about the occurrence and potential toxicity of degradation products of EDCs and
696   PCPPs that might result from treatment processes such as oxidation that alter chemical structures
697   rather than removing chemicals from water. UV and ozone are possible treatment schemes but
698   they create numerous oxidation products, thereby increasing the number of chemicals present
699   (Daughton, 2006b).
700




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701   AWWA Research Foundation Study #3033 State of Knowledge of Endocrine Disruptors and
702   Pharmaceuticals in Drinking Water

703   As this project was developed to provide the water industry with a current status of science
704   available on EDCs and PPCPs, much of the information presented in AWWAwwaRF project
705   #2758 is repeated in this report. Therefore, only additional findings on water treatment will be
706   presented.
707
708          Chlorine dioxide is generally a stronger oxidant than free chlorine.
709          Chlorine and chlorine dioxide react primarily with electron functional groups like amines
710           and phenols. Ozone also attacks carbon-carbon double bonds and activate benzene rings.
711          Advanced oxidation processes such as UV/hydrogen peroxide, ozone/hydrogen peroxide,
712           and UV/ozone are very effective in oxidizing EDCs and PPCPs, however they provide
713           only a small increase in removal efficiency compared to ozone.
714          High-pressure membranes such as NF or RO can remove a wide range of EDCs and
715           PPCPs. However, low-molecular weight organics, such as N-nitrosamines or certain
716           pharmaceuticals (acetaminophen, phenacetine) can be problematic.
717
718   Water Research Foundation Study #4066 Oxidation of Pharmaceutically Active Compounds
719   During Water Treatment

720
721   One of the major objectives of this study was to identify pharmaceutically active compounds that
722   are susceptible to rapid oxidation by permanganate and ferrate salts. Results from the initial
723   bench-scale experiments indicated that permanganate and ferrate are selective oxidants that can
724   be expected to oxidize only a fraction of pharmaceutically active compounds present in source
725   waters. Of the eighteen compounds studied, only ten showed high or moderate activity with
726   permanganate, and only eight showed high or moderate activity with ferrate. It is important to
727   note that carbamazepine, one of the compounds with the highest (88%) detection frequency in
728   the 2010 NWRI study, and resistant to oxidation by chlorine, is rapidly oxidized by
729   permanganate and ferrate.
730
731   Water Research Foundation Study #3071 PPCPs and EDCs – Occurrence in the Detroit River
732   and Their Removal by Ozonation

733   The efficiency of ozonation in removing PPCPs and EDCs at the bench and pilot-scale was
734   studied, and the effects of operating parameters including ozone dose, contact time, pH and
735   temperature on process efficiency were investigated. In general, ozone dose, contact time and
736   DOC loading were the governing factors in contaminant removal, while temperature and pH
737   played secondary roles. The experiments which had the lowest removal rates had low ozone dose
738   (0.8 mg/L) and high DOC loading (4.5 mg/L).
739
740   Results indicated that under optimized water quality and operating conditions, close to complete
741   transformation of 12 (bisphenol A, carbamazepine, erythromycin, gemfibrozil, indomethacin,
742   lincomycin, naproxen, sulfachloropyradizine, sulfamethazin, sulfamethoxazol, tetracycline,
743   tylosin) of the 16 target substances is possible. Ibuprofen and clofibric acid were found to be
744   most difficult to transform, as removal was limited to an average of 50 percent. Bezafibrate

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745   removal increased from 50 percent to 90 percent when ozone dose increased from 0.3 to 1.5
746   mg/L. Experiments with monensin were not conclusive.
747
748   AWWA Research Foundation Study #3012 Comparing Nanofiltration and Reverse Osmosis
749   for Treating Recycled Water

750   Today, the industry standard for subsurface injection of treated wastewater for groundwater
751   recharge or for surface water augmentation projects is to have an integrated membrane system
752   such as microfiltration pretreatment followed by reverse osmosis. In this study, nanofiltration
753   and ultra-low pressure RO (ULPRO) membranes were compared to conventional RO membranes
754   with respect to removing TOC, total nitrogen, and both regulated and unregulated trace organic
755   compounds. The findings of this study reveal that ULPRO membranes can “consistently meet
756   potable water quality requirements for treating source water of impaired quality with respect to
757   TOC, total nitrogen, and both regulated and unregulated trace organic compounds.” ULPRO
758   membranes potentially offer lower operating expenses than conventional RO. Certain low
759   fouling loose NF membranes were tested, and although they demonstrated effluent rejection of
760   TOC and a high selectivity for a wide range of trace organics, they resulted in lowered permeate
761   water quality for ammonia and nitrate.
762
763   Regulations

764   The chemicals that are regulated in source waters and in treated drinking water by USEPA and
765   the State of California represent a minor subset of chemicals that are potentially present due to
766   natural occurrence and human actions. Regulatory programs are only just beginning to address
767   these emerging contaminantsconstituents.
768
769   Drinking Water Regulations

770   The concentrations of most PPCPs and EDCs are not regulated in drinking waters in the U.S.
771   From USEPA’s perspective, CECs remain something to be watched rather than actively pursued
772   for regulation (Water Education Foundation, 2011). Some chemicals (e.g. several pesticides,
773   PCBs) that are regulated in drinking water are not currently regulated based on their potential
774   endocrine disrupting effects. One exception is perchlorate. Please refer to the Regulatory
775   Environment Section for regulatory information regarding perchlorate.
776
777   MCLs are generally developed following detection of contaminantsconstituents in drinking water
778   sources at levels that are thought to potentially have an impact on human health. The
779   development of MCLs also requires identification of best available technologies for contaminant
780   removal and the ability to monitor and detect the contaminantsconstituents at levels of concern.
781   The analytical methods for many EDCs and PCPPs are still being developed and most
782   commercial laboratories are not capable of measuring these contaminantsconstituents at the
783   levels found in source waters and treated drinking water.
784
785   Based on the large number of potential endocrine disruptors, new regulations could shift towards
786   regulating compounds as a class based on a common mechanism for toxicity (e.g. endocrine
787   disruption) or similar chemical structure rather than by individual compound. Regulating
788   compounds by class will be an effective technique for regulating due to the growing number of

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789   CECs being identified (Water Education Foundation, 2011). Another possible regulatory
790   approach could require a specific treatment technology (e.g. granular activated carbon) for an
791   array of chemicals, instead of setting standards for a class of chemicals or a proliferation of
792   specific MCLs (AWWAwwaRF, 2005).
793
794   Wastewater Effluent Limitations

795   The concentrations of most PPCPs and EDCs are not regulated in wastewater discharge permits.
796   As with drinking water standards, a few chemicals that have been found or suspected to be
797   EDCs, are regulated based on other effects such as acute and chronic toxicity to aquatic
798   organisms. Currently wastewater is primarily regulated on a chemical by chemical basis. It is not
799   possible to test all chemicals and possible combinations of chemicals that may occur in
800   wastewater effluent. As a result, National Pollutant Discharge Elimination System (NPDES)
801   permits include a requirement for Whole Effluent Toxicity (WET) testing to determine the
802   aggregate toxicity of an effluent in the aquatic environment. WET testing exposes laboratory
803   populations of aquatic organisms (fish, invertebrates, and algae) to diluted and undiluted effluent
804   samples to determine environmental toxicity of that sample. Acute and chronic tests focus on
805   how well an organism survives, grows, and reproduces. However, current toxicity tests do not
806   screen for endocrine disrupting effects. Daughton (2006a) advocates that a more accurate
807   assessment of risks is needed; measuring and assigning toxicity based on the total amount of
808   chemicals in wastewater that share the same mode of action or way of working.
809
810   Groundwater Recharge Regulations

811   CDPH has addressed monitoring for pharmaceuticals and EDCs in the August 2008 Draft
812   Groundwater Recharge Reuse Regulations. The draft regulations specify monitoring for
813   regulated contaminants, contaminants with drinking water notification levels, and priority
814   pollutants, but they do not recommend monitoring specific CECs. CDPH mentions chromium 6,
815   diazinon, and nitrosamines for monitoring. However, the draft regulations state that groundwater
816   water recharge reuse projects should develop their own CEC monitoring program and conduct
817   ongoing monitoring to address public concerns. Depending on the results of analyses and the
818   consistency of the monitoring, subsequent monitoring may be reduced (i.e. twice a year for two
819   or three years). As stated in the draft regulation, a monitoring program could include analysis for
820   representatives of these categories of contaminants:
821
822          Hormones – representing both male and female hormones, or surrogates to represent
823           both.
824          Industrial EDCs - bisphenol A, nonylphenol and nonylphenol polyethoxylates,
825           octylphenol, octylphenol polyethoxylates, and polybrominated diphenyl ethers, or
826           surrogates that could represent one or more industrial EDCs.
827          Pharmaceuticals - acetaminophen, amoxicillin, azithromycin, carbamazepine,
828           ciprofloxacin, dilantin, gemfibrozil, ibuprofen, lipitor, meprobamate, sulfamethoxazole,
829           trimethoprin, and salicylic acid or surrogates.
830          Personal care products – triclosan and DEET, or surrogates.
831          Other chemicals – caffeine, iodinated contrast media, fire retardants.
832

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833   Senate Bill 918, signed by the Governor and filed on Sept 30, 2010 states that CDPH must adopt
834   uniform water recycling criteria for groundwater recharge by December 31, 2013 and must adopt
835   uniform water recycling criteria for surface water augmentation by December 31, 2016. CDPH is
836   targeting to release another revised draft for criteria governing groundwater recharge by the end
837   of 2011. In addition, CDPH must investigate the feasibility of developing uniform water
838   recycling criteria for direct potable re-use and provide a report by December 31, 2016.
839
840   The State Water Resources Control Board convened a CEC Science Advisory Panel to develop
841   guidance for the establishment of monitoring programs to assess potential CEC threats from
842   water recycling activities. The final report was completed in June 2010 which was followed by a
843   Staff Report. The Staff Report provides recommendations for monitoring CECs in municipal
844   recycled water used for groundwater recharge/reuse and landscape irrigation. The Staff Report
845   also presents recommendations for additional research on CEC monitoring. A public hearing was
846   held on December 15, 2010 to accept comments on the Staff Report. The State Water Resources
847   Control Board is currently considering comments received on the Staff Report.

848   According to State Water Resources Control Board staff, an amendment will be written for the
849   existing Recycled Water Policy developed in 2009. This amendment will address what
850   constituents should be monitored for groundwater recharge/reuse projects. The amendment
851   would then be peer-reviewed, and then open for public comment before final adoption, likely
852   sometime in 2012.

853   The CEC Science Advisory Panel identified four indicator compounds based on their
854   toxicological relevance for groundwater recharge projects: NDMA, 17beta-estadiol, caffeine,
855   and triclosan. Four additional CECs were identified as viable performance indicators (N,N-
856   Diethyl-meta-toluamide (DEET), gemfibrozil, iopromide, and sucralose), along with certain
857   surrogate parameters. Surrogates for groundwater recharge projects by surface spreading are
858   ammonia, nitrate, DOC, and UVA. Surrogates for groundwater recharge by injection are
859   conductivity and DOC, and surrogates for landscape irrigation are turbidity, chlorine residual,
860   and total coliform. CDPH recommended monitoring for certain additional CECs (bisphenyl A,
861   boron, carbamazepine, chlorate, chromium 6, diazinon, 1,4-dioxane, naphthalene, N-
862   nitrosodiethyamine (NDEA), N-nitrosodi-n-propylamine (NDPA), N-nitrosodiphenylamine, N-
863   nitrosopyrrolidine (NPYR), 1,2,3-Trichloropropane, Tris(2-carboxyethyl)phosphate, and
864   vanadium) which have been incorporated into the final Staff Report.

865   Numerous State Water Project contractors and their member agencies submitted comments on
866   the Staff Report including Alameda County Water District, Zone 7 Water Agency, Coachella
867   Valley Water District, Las Virgenes Municipal Water District, Metropolitan Water District of
868   Southern California, San Bernardino Valley Municipal Water District, and the San Diego County
869   Water Authority. The main comments submitted to the State Water Resources Control Board
870   were: 1) to not add the 13 additional constituents for baseline CEC monitoring for groundwater
871   recharge spreading projects, as specified in a comment letter from the CDPH, as the letter
872   provided no scientific or technical basis, 2) the Regional Boards should not have the authority to
873   select and add CECs to be monitored to individual permits, even if the CECs identified by the
874   Panel are included as a minimum, and 3) the State Water Board should adopt the Panel’s
875   recommendation to conduct a one-year study of a particular class of CECs for which the Panel

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876   felt it had insufficient occurrence information (Table 8.4 in Panel Report). A few of the letters
877   also recommended a clearer distinction for the monitoring requirements for irrigation projects
878   from those applied to groundwater recharge. No additional monitoring of CECs is necessary for
879   irrigation project beyond the monitoring specified in Title 22. The Los Angeles Regional Water
880   Quality Control Board commented that although the Panel chose to focus its recommendations
881   on toxicological relevance of CECs to human health, they believe that this focus was too narrow,
882   given that in the Los Angeles Region, most dischargers that recycle treated wastewater also
883   discharge directly to surface waters where resident aquatic life is exposed to nearly 100 percent
884   effluent. The Los Angeles Regional Water Quality Control Board believes it is imperative to
885   consider toxicological impacts on ecological receptors in developing a monitoring strategy for
886   CECs.

887   The Los Angeles Regional Water Quality Control Board is currently developing salt and nutrient
888   management plans for groundwater basins within its region. Suggested elements of a salt/nutrient
889   management plan include a placeholder for CECs. Requirements for monitoring CECs will be
890   based on adoption of policy currently being developed by the State Water Resources Control
891   Board.
892
893   Environmental Risk Assessments

894   The U.S. Food and Drug Administration requires environmental risk assessments for new
895   pharmaceuticals with predicted environmental concentrations greater than 1 µg/L (Snyder et al,
896   2005). Daughton (2006b) points out that the conventional toxicological procedures used in these
897   risk assessments may not screen for the types of subtle effects that could occur from exposure to
898   the low-levels found in surface waters.
899
900   Endocrine Disruptor Screening Program

901   This is a monitoring program through the USEPA Office of Science that was finalized in April
902   2009. This program only applies to pesticide manufacturers, importers, and potentially users. The
903   USEPA developed criteria for screening endocrine disrupters to identify priority chemicals.
904   USEPA will implement the workplan by using assays in a two-tiered screening and testing
905   process (Endocrine Disrupters Screening Program):
906
907            Through Tier 1 screening, USEPA hopes to identify chemicals that have the potential
908           to interact with the endocrine system.
909            Through Tier 2 testing, USEPA will determine the endocrine-related effects caused
910           by each chemical and obtain information about effects at various doses.
911
912   USEPA will use this two-tiered approach to gather information needed to identify endocrine-
913   active substances and take appropriate action. The initial list of 67 chemicals considered for Tier
914   1 screening is primarily pesticides – both active ingredients and inerts. In December 2007,
915   USEPA issued draft procedures for the initial screening. For active ingredients, test orders will
916   be sent to technical registrants and for inert ingredients, test orders will be sent to manufacturers,
917   importers, and potentially users of chemicals on the list. . Some of these constituents are already
918   regulated in drinking water and some are on the Contaminant Candidate List 3.
919
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      2011 Watershed Sanitary Survey Update                                Constituents of Emerging Concern

920   A second list of chemicals for Tier 1 screening was published in November 2010. The list of 134
921   chemicals includes a large number of pesticides, two perfluorocarbon compounds (PFCs), and
922   three pharmaceuticals (erythromycin, nitroglycerin, and quinoline). This list also contains other
923   chemicals, such as those used for industrial manufacturing processes, plasticizers, or in the
924   production of pharmaceutical and personal care products (PPCPs).
925
926   Mandatory Control Programs

927   There are three main types of programs that collect home-generated pharmaceuticals in
928   California: continuous collection programs, events, or mail-back programs. The primary
929   locations for continuous collection programs are pharmacies, law enforcement sites, and
930   household hazardous waste collection sites. Mail-back collection programs are defined as
931   programs that transport drug waste through the U.S. Postal Service to an appropriate disposal
932   location. The three mail-back programs all began in the Bay Area in 2009: the City of San
933   Francisco, Teleosis (non-profit), and Santa Cruz County. CalRecycle has a directory that lists
934   facilities in California that collect pharmaceuticals for disposal.
935   http://www.calrecycle.ca.gov/HomeHazWaste/HealthCare/Collection/Default.aspx
936
937   Based on information available to CalRecycle, collection programs in California currently collect
938   approximately 200,000 pounds of home-generated pharmaceutical waste per year. However,
939   several sources suggest that a very large amount is sold and that a significant percentage
940   becomes waste. The Associated Press estimated that Americans generate at least 250 million
941   pounds of pharmaceuticals and contaminated packaging in medical facilities each year. Relative
942   to California population, that would be approximately 30 million pounds in California hospitals
943   alone (CalRecycle, 2010).

944   The disposal of pharmaceutical waste is governed by provisions of SB 966 (Simitian, Chapter
945   542, Statutes of 2007). It requires the California Department of Resources Recycling and                Formatted: No underline
946   Recovery (CalRecycle) to develop, in consultation with appropriate government agencies,
947   criteria and procedures for model programs for the collection and proper disposal of
948   pharmaceutical waste. Provisions of SB 966 remain in effect until January 1, 2013. The goal is to
949   provide local jurisdictions in California with the tools to implement collection programs as well
950   as work with manufacturers, retailers, pharmacies, hospitals, and other health-related constituents
951   for the proper disposition of medication and sharps in a single location.

952   As directed by SB 966, CalRecycle formed a working group that consisted of representatives
953   from the Pharmacy Board, State Water Resources Control Board, California Department of
954   Public Health (CDPH), and the Department of Toxic Substances Control. CalRecycle staff
955   convened the working group and conducted four workshops during 2008 to facilitate comments
956   and suggestions from stakeholders representing local government, pharmaceutical companies,
957   medical and hazardous waste haulers, for-profit and non-profit health care providers, and other
958   interested parties. As a result of this collaboration, criteria and procedures are available for
959   facilities willing to become model programs for the collection and proper disposal of
960   pharmaceutical waste.

961   SB 1305 revised a section of the State of California Medical Waste Management Act to make it a
962   violation of state law for home-generated sharps waste to be placed in solid waste collection
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       2011 Watershed Sanitary Survey Update                                 Constituents of Emerging Concern

 963   containers, including recycling and green waste containers. SB 1305 also require sharps waste to
 964   be transported in an approved sharps containers and managed by a specified facility (i.e.,
 965   household hazardous waste facility, medical waste generator facility, or a facility managed as
 966   part of a mail back program). SB 1305 was approved by Gov. Schwarzenegger on July 12, 2006
 967   and took effect on September 1, 2008.
 968
 969   Voluntary Control Programs

 970   The United States Department of Justice Drug Enforcement Agency, in conjunction with state
 971   and local law enforcement throughout the United States, conducted the first ever National
 972   Prescription Take Back Day on September 25, 2010. Due to the overwhelming success of the
 973   first event, the Second National Prescription Take Back Day was held on April 30, 2011.

 974   Some communities have taken a proactive approach and started to educate their customers on
 975   proper disposal practices for unused pharmaceuticals. One example is the “No Drugs Down the
 976   Drain” Program sponsored by the City of Los Angeles, Sanitation Districts of Los Angeles
 977   County, County of Los Angeles, Orange County Sanitation District, and the Cities of Riverside
 978   of San Diego. The No Drugs Down the Drain program is a public outreach program to provide
 979   California residents living in specific regions with available, safe and proper disposal choices.
 980   These agencies have a web page that discusses how to dispose of drugs depending on your
 981   geographical location Generally, the two recommended options are 1) take to a household
 982   hazardous waste collection center and 2) put in a sturdy and sealed container and then in the
 983   trash. In limited cases, unused or expired pharmaceuticals can be returned to pharmacies for
 984   "take-back" programs. Chemotherapy pharmaceuticals need to be returned to the clinic that
 985   dispensed them.

 986   In addition, the Los Angeles County Sheriff’s Department in conjunction with the Los Angeles
 987   County Department of Public Health and Public Works have developed a “Safe Drug Drop-Off
 988   Program”. The program provides an opportunity for residents to safely and anonymously
 989   surrender any unused or expired prescriptions, over the counter medications, needles or other
 990   controlled substances. Controlled substances cannot be taken to a household hazardous waste
 991   collection center.

 992   Websites for the cities of Sacramento and Stockton and the counties of Sacramento and San
 993   Joaquin were searched for information on disposal of PPCPs. The City of Sacramento and
 994   Sacramento County provide information on disposal of household hazardous waste (which
 995   includes sharps), electronic wastes, paints, and universal wastes (e.g. batteries, fluorescent light
 996   bulbs), but no information could be located on disposal of medications. The City of Stockton and
 997   San Joaquin County lists prescription medicines as an example of household hazardous waste,
 998   and also lists one location where home generated sharps (needles) and medications can be
 999   disposed of.
1000
1001   The Sacramento Regional County Sanitation District has a “Don’t Flush Your Meds” website
1002   where locations are given for disposal of both prescription and over the counter medications, as
1003   well as controlled substances.
1004


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1005                                           REFERENCES
1006
1007
1008   Aquatic Science Center, 2011. The Pulse of the Delta: Monitoring and Managing Water Quality
1009   in the Sacramento-San Joaquin Delta. Re-thinking Water Quality Monitoring. Contribution 630.
1010   Aquatic Science Center, Oakland, CA.
1011
1012   AwwaRF. 2005. AwwaRF Featured Topic: EDCs, PhACs, and PCPs. Accessed by internet at:
1013   www.awwarf.org/research/TopicsAndProjects/topicSnapshot.aspx?topic=EDCS.
1014
1015   AwwaRF. 2006. Project Abstract and Executive Summary Occurrence Survey of
1016   Pharmaceutically Active Compounds #2617.
1017
1018   AwwaRF. 2007. Removal of EDCs and Pharmaceuticals in Drinking and Reuse Treatment
1019   Processes. #2758.
1020
1021   AwwaRF. 2008a. Toxicological Relevance of Endocrine Disruptors and Pharmaceuticals in
1022   Drinking Water. #3085.
1023
1024   AwwaRF. 2008b. State of Knowledge of Endocrine Disruptors and Pharmaceuticals in Drinking
1025   Water. #3033.
1026
1027   AwwaRF. 2008c. Comparing Nanofiltration and Reverse Osmosis for Treating Recycled Water.
1028   #3012.
1029
1030   Barnes, K.K, D.W. Kolpin, M.T. Meyer, E.M. Thurman, E.T. Furlong, S.D. Zaugg, and L.B.
1031   Barber. 2002. Water-Quality Data for Pharmaceuticals, Hormones, and Other Organic
1032   Wastewater Contaminants in U.S. Streams, 1999-2000.U.S. Geological Survey Open-File Report
1033   02-94.
1034
1035   Benotti, M. J., Trenholm, R. A., Vanderford, B.J., Holady, J.C., Stanford, B.D., and Synder, S.A.
1036   2009. Pharmaceuticals and Endocrine Disrupting Compounds in U.S. Drinking Water.
1037   Environmental Science and Technology, 43, 597-603.
1038
1039   Boxall, A.B.A. Fate and Transport of Veterinary Medicines in the Soil Environment. In Fate of
1040   Pharmaceuticals in the Environment and in Water Treatment Systems. Aga, D.S., Ed. CRC
1041   Press: Boca Raton, FL, 2008;123-137.
1042
1043   CalRecycle. 2010. Evaluation of Home-Generated Pharmaceutical Programs in California.
1044   Background Paper for July 20, 2010 Workshop.
1045
1046   Daughton, C.G. 2006a. Pharmaceuticals and Personal Care Products in the Environment:
1047   Overarching Issues and Overview.Accessed by internet at:
1048   www.EPA.gov/esd/chemistry/pharma/book-summary.htm.
1049



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       2011 Watershed Sanitary Survey Update                                Constituents of Emerging Concern

1050   Daughton, C.G. 2006b. Pharmaceuticals and Personal Care Products in the Environment.
1051   Accessed by internet at: www.EPA.gov/nerlesd1/chemistry/pharma/faq.htm.
1052   DiGiorgio, C.L., Krasner, S.W., Guo, Y.C., Dale, M.S., Sclimenti, M.J., and MWQI Field Unit.
1053   2010. Investigation into the Sources of Nitrosamines and Their Precursors in the Sacramento-
1054   San Joaquin Delta, California.
1055
1056   Esposito, K.M., P.J. Phillips, B.M. Stinson, R. Tsuchihashi, J. Anderson. 2005. “The Implication
1057   of Emerging Contaminants in the Future of Water Reuse.” WateReuse 2005 Symposium
1058   Proceedings.
1059
1060   Focazio, M.J., Kolpin, D.W., Barnes, K.K., Furlong, E.T., Meyer, M.T., Zaugg, S.D., Barber,
1061   L.B., Thurman, M.E. 2008. A national reconnaissance for pharmaceuticals and other organic
1062   wastewater contaminants in the United States- II) Untreated drinking water sources, Science of
1063   the Total Environment, 402, 201-216.
1064
1065   Fono, L.J., Kolodziej, E.P., Sedlak, D.L. 2006. Attenuation of Wastewater-Derived
1066   Contaminants in an Effluent-Dominated River. Environmental Science and Technology. 40,
1067   7257-7262.
1068
1069   Goodbred, S.L, R.J Gilliom, T.S. Gross, N.P. Denslow, W.L Bryant, and T.R. Schoeb. 1997.
1070   Reconnaissance of 17B-Estradiol, 11-Ketotestosterone, Vitellogenin, and Gonad Histopathology
1071   in Common Carp of United States Streams: Potential for Contaminant-Introduced Endocrine
1072   Disruption. U.S. Geological Survey Open-File Report 96-627.
1073
1074   Guo, Y. C.; Krasner, S. W.; Fitzsimmons, S.; Woodside, G.; Yamachika, N. 2010. Source, Fate
1075   and Transport of Endocrine Disruptors, Pharmaceuticals, and Personal Care Products in
1076   Drinking Water Sources in California. National Water Research Institute, 2010.
1077   http://www.nwri-usa.org/CECs.htm
1078
1079   Johnson, C.S., Kroll, K., Denslow, N., and K. Aceituno. “Evaluation of Contaminants and
1080   Endocrine Disruption in Sacramento-San Joaquin Estuary”, poster at 2010 Bay Delta
1081   Conference.
1082
1083   Kolodziej, E.P. and Sedlak, D.L. 2007. Rangeland Grazing as a Source of Steroid Hormones to
1084   Surface Waters. Environ. Sci. Tech. 41(10):3514-3520.
1085
1086   Krasner, S.W., Pastor, S.J., Garcia, E.A. 2006. Measurement of the Pharmaceutical Primidone
1087   as a Conservative Tracer of Wastewater Influences in Drinking Water Supplies. Proc. 2006
1088   American Water Works Association Water Quality Technology Conference, Denver, CO, 2006.
1089
1090   Lavado, R., Loyo-Rosales, J.E., Floyd, E., Kolodziej, E.P., Snyder, S.A., Sedlak, D.L. and D.
1091   Schlenk. Site-Specific Profiles of Estrogenic Activity in Agricultural Areas of California’s Inland
1092   Waters. Environ. Sci. Tech. 43:9110-9116.
1093




       Draft Report                                   12-31                                    January 2012
       California State Water Project                                                            Chapter 12
       2011 Watershed Sanitary Survey Update                               Constituents of Emerging Concern

1094   Loffler, D., Rombke, J., Meller, M., and Ternes, T.A. 2005. Environmental Fate of
1095   Pharmaceuticals in Water/Sediment Systems. Environmental Science and Technology, 39, 5209-
1096   5218.
1097
1098   Radke, M., Lauwigi, C., Heinkele, G., Murdter, T.E., and Letzel, M. 2009. Fate of the Antibiotic
1099   Sulfamethoxazole and Its Two Major Human Metabolites in a Water Sediment Test.
1100   Environmental Science and Technology, 43, 3135-3141.
1101
1102   Rimkus, G.G. 1999. Polycyclic Musk Fragrances in the Aquatic Environment. Toxicology
1103   Letters 111 (1-2): 37-56.
1104
1105   Sakaji, R.H, S. Book, R. Hultquist, and R. Haberman. 2004. Xenobiotics: What Are They and
1106   Why Are We So Concerned About Them? Jour. AWWA 96:5:58.
1107
1108   Schaefer, M. and M.L. Johnson. 2009. Pharmaceuticals and Personal Care Products in the
1109   Sacramento River. Final Report: Activities from May-June 2008. Prepared for the State Water
1110   Resources Control Board. October 2009.
1111
1112   Sedlak, D.L. 2006. Identifying the Causes of Feminization of Chinook Salmon in the Sacramento
1113   and San JoaquinRiver System. Accessed by internet at: www.ce.berkeley.edu/~sedlak.
1114
1115   Snyder, E.C, R.C. Pleus, and S.A. Snyder. 2005. Pharmaceuticals and EDCS in the US Water
1116   Industry-An Update. Jour. AWWA 97:11:32.
1117
1118   Vlaming, V., A. Biales, D. Riordan, D. Markiewicz, R. Holmes, P. Otis, C. Leutenegger, R.
1119   Zander, and J. Lazorchak. 2006. Screening California Surface Waters for Estrogenic Endocrine
1120   Disrupting Chemicals (EEDC) with a Juvenile Rainbow Trout Liver Vitellogenin mRNA
1121   Procedure.
1122
1123   Water Education Foundation. Pervasive and Persistent: Constituents of Emerging Concern.
1124   Western Water, January/February 2011.
1125
1126   Water Research Foundation Study. 2010. Oxidation of Pharmaceutically Active Compounds
1127   During Water Treatment. #4066.
1128
1129   Water Research Foundation Study. 2009. PPCPs and EDCs – Occurrence in the Detroit River
1130   and Their Removal by Ozonation. #3071.
1131
1132   WERF. 2006. Removal of Endocrine Disrupting Compounds in Water Reclamation Processes.
1133
1134   WERF. 2007. Fate of Pharmaceuticals and Personal Care Products Through Municipal
1135   Wastewater Treatment Processes
1136




       Draft Report                                  12-32                                    January 2012

						
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