emerging contaminants program: 2015 annual report · the emerging contaminants monitoring program...

Prepared by Northern Water

Emerging Contaminants Program:

2015 Annual Report

2015 Emerging Contaminants Annual Report Page 1

EMERGING CONTAMINANTS MONITORING PROGRAM Annual Report 2015

The following is an annual report on the monitoring activities, changes to the monitoring program and an overview of the results for the 2015 Cooperative Emerging Contaminants Monitoring Program. The objective of this program is to take a cost-effective and proactive approach to develop a baseline of data on pharmaceuticals, personal care products, hormones, and pesticides in the Colorado Big-Thompson (C-BT Project) and Windy Gap projects and other source waters associated with drinking water supplies in Northern Colorado. The program is a collaborative effort where the costs and sampling are shared by several municipalities on the Northern Front Range and with Northern Water. Monitoring Locations The Emerging Contaminants Monitoring Program includes monitoring sites in canals, streams, reservoirs, and water treatment plants (both raw and finished water) located in Northern Colorado. While most of the sites are within the C-BT Project, some sites in the program are located in rivers, tributaries or ditches outside of the C-BT Project that serve as drinking water sources for the municipalities that participate in the program. The monitoring sites in the streams and canals are strategically located to track the fate and transport of the chemicals as they move through the system. In the deeper reservoirs, Horsetooth Reservoir and Carter Lake, samples are collected at three depths: 1 meter, the metalimnion (the middle layer of the reservoir) and 1 meter from the bottom. Samples are collected at these depths to gain a better understanding of the spatial distribution of the chemicals in each reservoir, and the influences of thermal stratification and turnover on chemical concentrations and release from sediments. The bottom depth is of particular importance in these two reservoirs as releases to drinking water suppliers occur near the bottom. Samples from the shallower Boulder Reservoir are collected just below the surface. Each year, the participants review the monitoring locations and during this review sites can be added or discontinued from the program. In 2015, the site on Windy Gap Reservoir (WG-DAM) was discontinued from the monitoring program. This site is located on the West Slope and was originally sampled to see what effect effluent from upstream wastewater treatment plants (WWTP) had on the reservoir and potential impacts on East Slope water supplies. Water from Windy Gap Reservoir is not a constant source into the East Slope supply. In addition, it is significantly diluted before it is transported to the East Slope. Therefore, compounds detected at WG-DAM may not persist as water moves from the West Slope to the East Slope. A better indicator of West Slope water quality is the site at Adams Tunnel (AT-EP), which is monitored three times a year.


All sites included in the 2015 monitoring program are listed in Table 1 and a map of the sites can be found in Appendix 1.

Table 1 - Monitoring Locations

Station Description Latitude Longitude C-BT AT-EP Adams Tunnel at East Portal 40.3278 -105.5782 Y BT-FRD Big Thompson below confluence with Fall River 40.3757 -105.5212 Y OLY Olympus Tunnel below Lake Estes 40.3764 -105.4858 Y BT-UTD Big Thompson Downstream of Upper Thompson Sanitation District 40.3805 -105.4776 Y BT-DLU Big Thompson Upstream of Dille 40.4200 -105.2828 Y BB-LOV Big Barnes Ditch to Lake Loveland and Boyd Lake 40.4056 -105.1427 N HFC-HT Hansen Feeder Canal upstream of Horsetooth Reservoir 40.5056 -105.1970 Y CL-DAM1 Carter Lake at Dam #1 on south end of Reservoir 40.3253 -105.2152 Y HT-SPR Horsetooth Reservoir Spring Canyon Dam 40.5292 -105.1456 Y HT-SOL Horsetooth Reservoir Soldier Canyon Dam 40.5888 -105.1649 Y SVSC-SV Saint Vrain Supply Canal at Saint Vrain crossing 40.2220 -105.2483 Y SV-LD South Saint Vrain River at the Longmont Diversion 40.2139 -105.2772 N NFWTP-CL Nelson Flanders WTP at Carter Lake Connecting Pipeline 40.2142 -105.2289 Y NFWTP-SV Nelson Flanders WTP at North Saint Vrain 40.2142 -105.2289 N NFWTP-HD Nelson Flanders WTP at Highland Ditch 40.2144 -105.2283 N BR-SDT/BFC* Boulder Reservoir South Dam/Boulder Feeder Canal 40.0758 -105.2149 Y BRWTF-RAW Boulder Reservoir WTF Raw Water (BR-SDT or BFC is source water) 40.0768 -105.2087 Y BRWTF-FIN Boulder Reservoir WTF Finished Water 40.0768 -105.2087 Y NF-PRU North Fork of the Cache La Poudre River 40.7039 -105.2277 N PR-NFU Cache La Poudre River upstream of North Fork 40.7007 -105.2421 N BET-FIN Betasso Plant Finished Water 40.0118 -105.3348 N BET-BAR Betasso Plant Barker 40.0118 -105.3348 N BET-LAK Betasso Plant Lakewood 40.0118 -105.3348 N

* Sample collected at the site that is not being used as the raw water source

Funding The Emerging Contaminants Monitoring Program was launched as a collaborative effort in 2009 at which time interested parties were invited to contribute funding to the program. In 2015, there were eight participants: the cities of Boulder, Broomfield, Fort Collins, Greeley, Longmont, and Loveland, the Town of Estes Park, and Northern Water. Funding for the program is site specific; monitoring costs at a site are equally funded by the participant(s) that have a direct interest in the water quality at that site. Cost is shared by all participants at the sites that are located at the headwaters of the C-BT Project (AT-EP, BT-FRD, OLY and BT-UTD). Other sites may only be of interest to and funded by a few or only one participant(s). Table 2 lists the sampling sites and the funders of each site.


Table 2 - Funders for Monitoring Locations

Station Boulder Broom-field

Estes Park

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mont Loveland Northern Water

AT-EP X X X X X X X X BT-FRD X X X X X X X X OLY X X X X X X X X BT-UTD X X X X X X X X BT-DLU X X X X HFC-HT X X X NF-PRU X X PR-NFU X X SVSC-SV X X X SV-LD X NFWTP-CL X NFWTP-SV X NFWTP-HD X BFC X X BR-SDT/BFC X X BRWTF-RAW X X BRWTF-FIN X CL-DAM1 X X X X HT-SOL X X X HT-SPR X X X BB-LOV X X BET-FIN X BET-BAR X BET-LAK X

Sampling Frequency and Collection The sampling schedule has evolved since 2009 to include more sampling events in order to capture seasonal influences of spring runoff, recreational activities, herbicide applications, reservoir stratification and turnover, and fall/winter low stream flow conditions. The 2015 sampling schedule is shown in Table 3. For funding purposes, the sampling schedule follows the Northern Water fiscal year: October 1 to September 30. The participants of the monitoring program share the responsibility of sampling. Each participating entity is assigned a sampling site(s) that is of particular interest to them (Table 3). The sampling is coordinated to occur during the same week of the month so the data are comparable.


Table 3 - 2015 Sampling Schedule and Sampling Entity

Station Nov-14 Feb-15 Jun-15 Aug-15 Sampling Entity

AT-EP X X X Northern Water BT-FRD X X X Estes Park OLY X X X Northern Water BT-UTD X X Northern Water BT-DLU X X X Loveland HFC-HT X X X Northern Water NF-PRU X X X Fort Collins PR-NFU X X X Fort Collins SVSC-SV X X Longmont SV-LD X X X Longmont NFWTP-CL X X X Longmont NFWTP-SV X X X Longmont NFWTP-HD X Longmont BFC X BR-SDT X X Boulder BRWTF-RAW X X X Boulder BRWTF-FIN X X X Boulder CL-DAM1 X X X Northern Water HT-SOL X X X Northern Water HT-SPR X X X Northern Water BB-LOV X X Greeley BET-FIN X X X Boulder BET-BAR X X Boulder BET-LAK X X X Boulder

Samples are collected according to guidelines provided by the Center for Environmental Mass Spectrometry at the University of Colorado (CEMS) standard operating procedure (SOP) dated January 1, 2010 found in Appendix 2. In general, all samples (except for the lake samples collected at a specific depth) are grab samples collected directly into a sampling bottle prepared by CEMS. Effort is made to collect the sample from a well-mixed portion of the water body. The lake samples collected at a specific depth are collected with a Kemmerer sampler and then transferred to a sampling bottle. Precautions taken during collection to prevent contamination of the sample include:

• Use of disposable gloves to prevent personal care products from contaminating the sample and sample bottle

• DEET should not be used by the sampler • Coffee should not be consumed during the sampling period • Cigarettes should not be used during the sampling period

For each scheduled sampling event, one blank sample is collected. There are two types of blank samples collected for this program. The “trip blank” involves filling a prepared sample bottle with de-ionized water, carrying it alongside the sampling container for the environmental sample and opening the bottle in the field when the environmental sample is


collected. The “equipment blank” is collected with the lake samples. This involves processing the de-ionized water through the equipment used to collect the lake samples at the various depths, the Kemmerer. Both help ensure that there is no contamination due to the sample collection processes. Blank sample collection is alternated between the sampling entities. Analysis and Parameters The Center for Environmental Mass Spectrometry at the University of Colorado does all of the laboratory analyses. Sample analysis is done by three methods: a presence/absence screening method (Liquid Chromatography/Time-Of-Flight Mass Spectrometry, LC/TOF-MS) and two low-level quantification methods (Liquid Chromatography/Mass Spectrometry/Mass Spectrometry, LC/MS/MS) for pharmaceuticals and endocrine disruptors. The presence/absence screening method using LC/TOF-MS allows detection of constituents above the method reporting limits and does allow a precise quantification of the concentration for a selected list for which there are standards. This includes all compounds from the low-level method plus the metabolites of several pharmaceuticals. The list of compounds tested with this method includes 104 compounds: 40 commonly used personal care products and pharmaceuticals and 64 herbicides/pesticides. The low-level method using LC/MS/MS began in 2010. This method allows quantification of the concentrations of the detected compounds and is used for a subset of compounds that are of particular interest. The list of compounds tested with this method is reviewed by the participants each year and compounds can be added or discontinued. The 2015 list of compounds analyzed by LC/MS/MS includes 29 herbicides/pesticides and personal care products/pharmaceuticals (subset from the LC/TOF-MS method), shown in Table 4. In addition, there are eight endocrine disrupting compounds (hormones and hormone-mimicking compounds) that are analyzed through a separate analytical procedure using LC/MS/MS: 17-alpha-ethinylestradiol (birth control pill), 17-beta-estradiol (natural feminine hormone), 4-androstene-3,17-dione (natural and synthetic hormone), Equilin (horse estrogen and synthetic hormone), Estriol (pregnancy hormone), Estrone (feminine hormone), progesterone (feminine hormone) and testosterone (male hormone). The full list of compounds for all methods and reporting limits can be found in Appendix 3.


Table 4 - Compounds analyzed with the low-level LC/MS/MS method

Compound Type Compound Detection Limit (ng/L) Classification Year

Added

Herbicides and Pesticides

2,4-D 5 Herbicide 2010 Atrazine 2 Herbicide 2012 Diazinon 1 Insecticide 2010 Diuron 5 Herbicide 2010

Fluridone 5 Herbicide 2010 Triclopyr 10 Herbicide 2013

Household Products Caffeine 10 Stimulant 2010

Sucralose 15 Artificial Sweetener 2011 Personal Care

Products DEET 20 Bug Repellant 2010

Triclosan 20 Antibacterial 2011 Endocrine Disruptor Bisphenol A 20 Plasticizer 2010

Pharmaceuticals

Acetaminophen 5 Pain Reliever 2010 Atenolol 5 Blood Pressure 2010

Bupropion 1 Antidepressant 2010 Carbamazepine 2 Antidepressant 2010 Clarithromycin 2 Antibiotic 2010

Cotinine 5 Stimulant 2010 Dextrorphan 5 Cough Suppressant 2014

Diltiazem 5 Blood Pressure 2010 Diphenhydramine 5 Antihistamine 2010

Erythromycin 10 Antibiotic 2010 Gabapentin 15 Antiepileptic 2014 Gemfibrozil 5 Analgesic 2010 Lamotrigine 5 Antidepressant 2011 Metoprolol 1 Blood Pressure 2010 Propranolol 1 Blood Pressure 2010

Sulfamethoxazole 5 Antibiotic 2010 Trimethoprim 5 Antibiotic 2010 Venlafaxine 1 Antidepressant 2010

2015 Results and Highlights The following discusses results from the low-level LC/MS/MS method in 2015. The discussion is sectioned by geographic location. Graphs of all compounds detected at all sites in 2015 can be found in Appendix 4. Upper Big Thompson River Sites (AT-EP, BT-FRD, OLY, BT-UTD, BT-DLU and BB-LOV) The Upper Big Thompson River sites geographically span from upstream of Estes Park to just downstream of the mouth of the Big Thompson Canyon upstream of the City of Loveland. The sites located on the mainstem of the Big Thompson River are BT-FRD, BT-UTD and BT-DLU. There are two sites located in tunnels that are part of the C-BT Project; AT-EP and OLY. There is one site located in the Big Barnes Ditch (BB-LOV) which receives Big Thompson River water and is part of the City of Greeley’s water supply system.


There are two WWTPs located in Estes Park that discharge into the Big Thompson River; Estes Park Sanitation District (EPSD) and Upper Thompson Sanitation District (UTSD). Figure 1 is a map of the area which includes the locations of the sampling sites and the WWTPs.

Figure 1 - Map of sampling sites and wastewater treatment plants in the Upper Big Thompson River. (Note: the locations of the wastewater plants are approximate)

The sites in the Upper Big Thompson River Basin upstream of Estes Park (AT-EP and BT-FRD) are fairly pristine and have fewer detected compounds compared to the other sites in the upper Big Thompson. AT-EP is located at the Adams Tunnel East Portal; this water is representative of the water that is pumped from the West Slope to the East Slope for the C-BT and Windy Gap Projects. BT-FRD is located downstream of the confluence of the Fall River; this water is subject to influences from septic systems and recreational activities. In 2015, there were no notable detections at these sites; the detected compounds were limited to sucralose and DEET at AT-EP in June and August respectively and caffeine at BT-FRD in February. The Big Thompson River sites downstream of Estes Park (BT-UTD, OLY, BT-DLU and BB-LOV) continue to have high detections of pharmaceuticals and personal care products (PPCP) due to their proximity to WWTP discharges. The site in the Big Thompson River just downstream of Lake Estes, BT-UTD is directly downstream from WWTP effluent from two sources; the Estes Park Sanitation District (EPSD) and Upper Thompson Sanitation District (UTSD) (Figure 1). This site consistently has the most detected PPCPs with the highest concentrations compared to all the sampling sites in the monitoring program. In total, 16 of the 29 compounds on the low-level analytical list were detected at BT-UTD in 2015, which is consistent with previous year’s results at this site.


Figure 2 and Figure 3 show concentrations of the PPCPs detected at BT-UTD during the scheduled sampling months of February and August from 2011-2015. The figures show that generally the same compounds are consistently detected and in most cases, the concentrations are similar every year. Typically, the concentrations are higher in February compared to August due to low winter flows and lack of dilution of the WWTP effluents in February. (Note: Analysis for the compounds dextrorphan and gabapentin began in 2014.)

Figure 2 - Concentrations of PPCPs detected during the month of February at BT-UTD from 2011-2015

Figure 3 - Concentrations of PPCPs detected during the month of August at BT-UTD from 2011-2015

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PPCPs in February at BT-UTD 20112012201320142015

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It should be noted that in the 2014 Emerging Contaminants Monitoring Program Annual Report, it was reported that diphenhydramine (an antihistamine found in Benadryl and other over-the-counter allergy medications) was detected in February 2014 at BT-UTD for the first time. As shown in Figure 2 and Figure 3, this statement was incorrect; diphenhydramine has been regularly detected at this site. The sites further downstream in the Big Thompson River (BT-DLU and BB-LOV) show impact from the WWTP discharges. Generally, at both of these sites, the same PPCPs are detected as those detected at BT-UTD but the concentrations are lower due to dilution as the water moves downstream. In 2015, the detected PPCPs at BT-DLU and BB-LOV were consistent both with previous years and with those detected upstream at BT-UTD.

In general, 2,4-D is the only herbicide that is detected with a significant concentration at the sites in the Big Thompson River below Lake Estes. Historically, 2,4-D has been detected at these sites every year with peak concentrations occurring in August. This is likely a result of herbicide applications on personal properties and parks that are adjacent to the Big Thompson River. However, in 2014 and 2015, there were no detections of 2,4-D in August in the Big Thompson River sites below Lake Estes as shown in Figure 4. Most of the homes, parks and other developments that are directly alongside the upper portion of the Big Thompson River (where the sampling sites are) were destroyed in the September 2013 flood. Therefore, there have likely been less applications of 2,4-D. Detections of 2,4-D are expected in future years as homes and parks are re-established.

The OLY site is directly below Lake Estes and is representative of the water that moves from Lake Estes through the Olympus Tunnel to Carter Lake. This site is subject to WWTP effluent from the EPSD (Figure 1). The EPSD discharges into the Big Thompson River directly upstream of Lake Estes. This discharge is diluted in Lake Estes but the effects are still apparent at the OLY site. Figure 5

Figure 4 - 2,4-D concentrations for the month of August in the Big Thompson River below Lake Estes from 2010-2015

Figure 5 - Pharmaceuticals detected at OLY and BT-UTD in August 2015

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OLY vs BT-UTD Detected Pharmaceuticals - August 2015

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shows the concentrations of the compounds that were detected in August 2015 at the OLY site compared to the BT-UTD site. In general, the same compounds are detected at OLY as those detected at BT-UTD, but the concentrations are lower at OLY due to the dilution in Lake Estes paired with only receiving effluent from one source compared to the two sources at BT-UTD. Horsetooth Reservoir Sites (HFC-HT, HT-SOL, HT-SPR) Horsetooth Reservoir is one of the terminal reservoirs in the C-BT Project. The source water for Horsetooth Reservoir is primarily from the West Slope which is moved through the C-BT Project canal/tunnel system (Adam and Olympus Tunnels) but can also receive water from the Big Thompson River below Lake Estes. The Hansen Feeder Canal supplies the source water for Horsetooth Reservoir. The Horsetooth Reservoir sites include two sites in Horsetooth Reservoir (HT-SPR and HT-SOL) and one site in the Hansen Feeder Canal just above the inlet to the reservoir (HFC-HT) (Figure 6). Horsetooth Reservoir shows some impact from WWTP effluent via the Big Thompson River. The PPCPs that are detected at the Horsetooth Reservoir sites are consistent with those detected in the Big Thompson River. Figure 7 shows the concentrations of PPCPs at the inlet site located in the Hansen Feeder Canal, HFC-HT, in August from 2011-2015. The compounds detected at HFC-HT are consistent with those that are detected at the sites located in the reservoir, HT-SPR and HT-SOL. The concentrations in the reservoir are lower due to dilution and mixing with the cleaner water in the upper Big Thompson River.

Figure 7 - Concentrations of PPCPs detected during the month of August at HFC-HT from 2011-2015

Figure 6 - Map of sampling sites in and surrounding Horsetooth Reservoir


The flood in September 2013 resulted in structural damage to the conveyance system, the Dille Tunnel, which moves water from the Lower Big Thompson River to the Hansen Feeder Canal. In 2014 and 2015, the Dille Tunnel was not operational and no water from the lower portion of the Big Thompson River was moved into Horsetooth Reservoir during this time, except for a small amount in early spring 2014. The 2014 and 2015 data at the Horsetooth Reservoir sites reflect this. As shown in Figure 7, there were less detected PPCPs in the source water in 2014 and 2015 compared to previous years and those that were detected typically had a lower concentration (Note: gabapentin was added to the compound list in 2014). There were no detections for carbamazepine, gemfibrozil in either 2014 or 2015, both which have been detected in past years. This indicates that these compounds are only present when there is a regular influx of WWTP-impacted waters into the system. The herbicides detected in 2015 were 2,4-D in the reservoir and canal, and atrazine in the reservoir. The concentrations are fairly evenly distributed throughout the reservoir, with minor evidence of degradation or dilution within the reservoir at depth, which is consistent with these compounds and compares well with data from previous years. There is evidence of recreational influences in Horsetooth Reservoir as there were detections for DEET, caffeine and sucralose during the summer. Upper Cache la Poudre River Sites (NF-PRU, PR-NFU) The sites located in the Upper Poudre River are upstream of Fort Collins in the Poudre Canyon. One site is located on the North Fork of the Poudre River (NF-PRU) and the other site is on the Poudre River directly upstream of the confluence with the North Fork (PR-NFU) (Figure 8). The Poudre River is a drinking water source for the Cities of Fort Collins and Greeley. The North Fork of the Poudre River is a drinking water source for the City of Greeley. The upper portion of the Poudre River is fairly pristine; compounds detected can be linked to recreation and/or landscaping along the river. In general, these sites are among the most pristine sites in the monitoring program with very few detected compounds. Since monitoring began at these sites in 2009 only five compounds have been detected: 2,4-D, atrazine, caffeine, DEET and triclosan. In 2015, the only compound that was detected was 2,4-D in August at the site on the North Fork of the Poudre.

Figure 8 - Map of sampling sites in the Upper Poudre River


Carter Lake and Saint Vrain Supply Canal Sites (CL-DAM1, SVSC-SV) Carter Lake’s source water comes from the Olympus Tunnel via Flatiron Reservoir. The water from Carter Lake is released into the Saint Vrain Supply Canal which eventually makes its way south into Boulder Reservoir. Water from Carter Lake and the Saint Vrain Supply Canal is a drinking water source for several municipalities including three monitoring program participants: Boulder, Broomfield and Longmont. There are canal releases into tributaries to the South Platte River as the water moves south to Boulder Reservoir. These sites include one site in Carter Lake (CL-DAM) and one site in the Saint Vrain Supply Canal upstream of the Saint Vrain River (SVSC-SV) (Figure 9).

Since the source water for Carter Lake is the Olympus Tunnel, these sites are subject to WWTP influences from EPSD. In general, the same PPCPs can be detected in Carter Lake as at OLY but the concentrations are lower due to dilution and other degradation processes. Figure 10 shows all the detected PPCPs in Carter Lake in June and August at the one-meter depth from 2010 – 2015. Similarly, the same compounds can be detected at SV-SVSC as at CL-DAM but with yet lower concentrations. In 2015, gabapentin and DEET were the only PPCP’s detected; both were detected in Carter Lake but not in the Saint Vrain Supply Canal, SVSC-SV.

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Figure 10 - Concentrations of PPCPs detected in Carter Lake at the 1-meter depth from 2010-2015

Figure 9 - Map of sampling sites in Carter Lake and the Saint Vrain Supply Canal


The herbicides 2,4-D and atrazine are routinely detected at both sites. The herbicide triclopyr was detected at the SVSC-SV site in August 2014 and again in August 2015. This is likely related to Northern Water’s use of Renovate®, whose active ingredient is triclopyr, to control terrestrial weeds along the canal which began in 2014. Figure 11 shows the concentrations for all detected herbicides in August at these two sites from 2010-2015.

Caffeine and sucralose were detected at both sites in 2015. This is consistent with data from previous years. Nelson Flanders WTP and Saint Vrain River Sites (SV-LD, NFWTP-CL, NFWTP-SV, NFWTP-HD) The Nelson Flanders Water Treatment Plant (NFWTP) is the City of Longmont’s drinking water treatment facility. The treatment plant receives water from and monitors three different sources: the North Saint Vrain River (NFWTP-SV), Carter Lake (NFWTP-CL) and the Highland Ditch (NFWTP-HD). SV-LD is a site located in the South Saint Vrain River upstream of the confluence with the North Saint Vrain River. Sampling at these sites began in 2013. In 2015, NFWTP-CL and NFWTP-HD had the most detected compounds. The detections at NFWTP-CL were consistent with compounds that are detected in the source water, Carter Lake. At the site in the Saint Vrain River, SV-LD, sucralose was detected in February. There were no detected compounds in 2015 at the NFWTP-SV site. Boulder Feeder Canal and Boulder Reservoir Sites (BFC, BR-SDT, BRWTF-BR, BRWTF-BFC, BRWTF-FIN) The Boulder Feeder Canal (BFC) is part of the C-BT Project. It receives water from the Saint Vrain Supply Canal whose source water is Carter Lake. The canal’s terminus is Boulder Reservoir. The City of Boulder’s Boulder Reservoir Water Treatment Facility (BRWTF) is located at Boulder Reservoir. This facility can use either Boulder Reservoir or the BFC as the source drinking water supply. Generally, samples are collected at three sites during each sampling event (Figure 12). A sample of the raw water going into the water treatment plant is collected. These sites are either BRWTP-BR or BRWTP-BFC. The name indicates what source water is being used at the time of sampling; BRWTP-BR indicates Boulder Reservoir is the source and BRWTP-BFC indicates the source water is the Boulder Feeder Canal. The second sample is a finished, or

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Figure 11 - Concentrations of herbicides detected in Carter Lake and the Saint Vrain Supply Canal from 2010-2015


treated, drinking water sample collected, BRWTP-FIN. The third sample is a sample of the alternate source water not being used as the raw water supply: the Boulder Reservoir at the South Dam surface sample (BR-SDT) and the Boulder Feeder Canal (BFC). The PPCPs detected at these sites are similar to those detected in Carter Lake and the Saint Vrain Supply Canal. Given dilution and the distance the water travels from Carter Lake to Boulder Reservoir, the compounds are detected

at lower concentrations which vary from year to year. In some years, such as 2010, no PPCPs were detected at these sites. Figure 13 shows the concentrations of all the PPCPs detected in August (which generally has the highest occurrence of PPCPs) at the source water sites (both the source water being used at the time of the sampling and the alternate source water not being used) for the BRWTF from 2010-2015. DEET is the only compound consistently detected in most every year during the period of record. (Note: Analysis for the compounds dextrorphan and gabapentin began in 2014.)

Figure 13 - Concentrations of PPCPs detected at the Boulder source water sites from 2010-2015

The Boulder Feeder Canal is earth-lined which contributes to ongoing issues with aquatic and riparian weeds. The other canals in the monitoring program are concrete lined; therefore growth of weeds in the channel is not an issue. Northern Water maintains the canals in the C-BT Project, which includes the BFC. Maintenance includes occasional use of herbicides next to the canals in the prism (or adjacent to the water) in order to control nuisance (noxious) weeds. These applications can occur during times when the canal is delivering water. Other applications are made in the canal itself during the fall and winter when no water is being

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PPCPs in August in Boulder Reservoir and Boulder Feeder Canal 2011

2012

2013

2014

2015

Figure 12 - Map of Sampling Sites in and near Boulder Reservoir


delivered. These applications are made when the canal is dewatered onto sections that still contain pooled water due to groundwater seepage. There is also agriculture in the area. These factors have led to several herbicides being consistently detected with elevated

concentrations at the sites on the BFC compared to other sites in the monitoring program. Figure 14 shows the concentrations of all herbicides detected in August (which generally has the highest occurrence of herbicides) for the source water being used at the time of the sampling and the alternate source water not being used for the BRWTF from 2010-2015.

The results for detected herbicides in 2015 were consistent with previous years with the exception of fluridone which was detected in June at the BFC site. Fluridone had been detected at high concentrations in 2010 and 2011 due to use of the herbicide Sonar® in the canal, whose active ingredient is fluridone. Northern Water stopped using Sonar® in 2011 which resulted in no detections for fluridone at these sites until the flood in September 2013. Fluridone was detected at a high concentration in the post-flood sampling and again during June 2014 and 2015. Fluridone is bound to sediment so the detections are likely due to sediment transport and may still be flood related. In many of the instances where herbicides were detected in the source/raw water, they were also detected in the finished water. Figure 15 shows the concentrations of all herbicides detected in August at the raw and finished water sites. The concentrations in the finished

water were very low and well below any applicable maximum contaminant levels for drinking water. Nonetheless, efforts are being made to reduce the herbicides and/or use more environmentally friendly products to control the weeds in this area. Herbicide concentrations will continue to be closely monitored at these sites.

Figure 14 - Concentrations of herbicides detected at the Boulder source water sites from 2010-2015

Figure 15 - Concentrations of herbicides detected at the Boulder raw and finished water sites from 2010-2015

0

20

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BFC/

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BR

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BR

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RAW

2,4-D Atrazine Diuron Fluridone Triclopyr

Conc

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Herbicides in August in Boulder Reservoir and Boulder Feeder Canal

201020112012201320142015

320

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2,4-D Atrazine Fluridone Triclopyr

Conc

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n (n

g/L)

Herbicides in August in Boulder Reservoir WTF Raw and Finished Water

201020112012201320142015


Betasso WTP Sites (BET-BAR, BET-LAK, BET-FIN) The Betasso sites are located at the Betasso Water Treatment Facility which is the City of Boulder’s primary water treatment plant. The WTP is west of Boulder. The Betasso plant receives its raw water from Barker (BET-BAR) and Lakewood Reservoirs (BET-LAK). The Nederland WWTP discharges into Barker Reservoir. Lakewood Reservoir is located downstream of a small WWTP that discharges intermittently to North Boulder Creek; the influence of this WWTP on Lakewood Reservoir is therefore very minimal. The sites monitored include the two source waters, BET-BAR and BET-LAK, and the finished water, BET-FIN. Detections at the BET-BAR site in 2015 included caffeine, gabapentin, lamotrigine, sucralose, and venlafaxine, all of which were detected in February. Sucralose was also detected in August. This is consistent with the compounds that have been detected in previous years and shows the influence of the Nederland WWTP. Sucralose was the only compound detected at the BET-FIN water site in February 2015. The BET-LAK site had no detections of any compounds in 2015 which is consistent with previous years. The BET-LAK site continues to have the cleanest water in terms of emerging contaminants in the monitoring program. Triclopyr in the Saint Vrain Supply Canal and Boulder Feeder Canal Northern Water maintains the canals in the C-BT Project. This includes occasional use of herbicides next to the canals in the prism (or adjacent to the water) in order to control nuisance (noxious) weeds. In the past, the treatments have used products that contain 2,4-D. Previous years data collected in the Boulder Feeder Canal and at the BRWTF have shown that 2,4-D concentrations were elevated in this area compared to other places within the study area. In an effort to address this, beginning in 2013, Northern Water started using Renovate® which contains triclopyr as the active ingredient instead of products with 2,4-D. Renovate® is used in the canal prism on the Hansen Feeder Canal, the Saint Vrain Supply Canal and the Boulder Feeder Canal.

Northern Water selected Renovate® specifically based on the fact that triclopyr is the active ingredient. The half-life of triclopyr is short and it is soluble; therefore in water it should degrade quickly, ideally before it reaches the BRWTF. Triclopyr also contains functional groups that might allow it to be sorbed to sediments and then slowly released over time. Triclopyr is reported to have a half-life of 30-90 days in soil (microbial decomposition) and 1-10 days in water (photochemical degradation). In reality half-life is dependent on many factors including temperature, UV light and bacterial activity.

Location Date Gallons Applied

Boul

der F

eede

r Can

al

4/15/2015 1.5 4/20/2015 1.5 4/21/2015 2 4/22/2015 1 4/23/2015 2.5 4/24/2015 1 5/11/2015 0.5 5/13/2015 1 7/13/2015 1.5 7/23/2015 2 8/4/2015 3

Sain

t Vr

ain

Supp

ly

Cana

l 4/24/2015 1.5 5/13/2015 4 5/14/2015 8 5/15/2015 4

Table 5 – 2015 Renovate Application Log for the BFC and Saint Vrain Supply Canal


Triclopyr was detected in June in the source, raw and finished water samples and in August in the source and raw water at the Boulder Reservoir sites. It was also detected in the Saint Vrain Supply Canal (SVSC-CL) in August. There were no detections north of Carter Lake in the Hansen Feeder Canal. The variability in the half-life and the ability for triclopyr to sorb to sediments may be factors in the detections of triclopyr as the detections do not necessarily correspond to when Renovate applications occurred as shown in Table 5 and Table 6. Triclopyr will continue to be closely monitored in the future. Hormone Analyses Analysis included eight hormones. The only detection for a hormone in 2015 occurred in June; estrone was detected with a reported concentration of 7.4 (ng/L) in the Boulder Feeder Canal at the Boulder Reservoir WTP intake (BFC). 2015 Quality Assurance and Quality Control Non Target and Unknown Analysis with LC/TOF-MS The LC/TOF-MS results are in agreement with the LC/MS/MS analyses and indicate the importance of taking winter, spring, and summer samples when investigating water quality impacts from PPCPs and herbicides/pesticides. Quality Assurance and Quality Control One blank sample was submitted for each of the four scheduled sampling events. In 2015, the following blank samples were submitted:

• November: Field Equipment Blank, Northern Water • February: Field Trip Blank, City of Longmont • June: Field Trip Blank, City of Greeley • August: Field Equipment Blank, City of Loveland

The blank samples submitted in November, February and June did not show detections for any of the compounds included in the analysis. Cotinine and DEET were both detected in the blank sample submitted in August. These detections were verified by the LC/TOF-MS method.

Location Site Sampled Date

Concen-tration (ng/L)

Boul

der F

eede

r Ca

nal

BRWTF-BR 6/18/2015 56.9

BRWTF-FIN 6/18/2015 67.5 BFC 6/24/2015 28.7

BR-SDT 8/4/2015 13.3 BRWTF-BFC 8/12/2015 25.5

Sain

t Vr

ain

Supp

ly

Cana

l

SVSC-SV 8/12/2015 13.9

Table 6 – 2015 Detections for Triclopyr


Environmental Protection Agency Replicate Analysis In August, a replicate sample was submitted to the U.S. Environmental Protection Agency (EPA) Region 8 Laboratory for in-kind analysis of PPCPs. The EPA has different compounds included in their analysis and the monitoring program participants wanted to see if there were any detected compounds outside of what ones are currently included in the analysis that is done by CEMS. The site in the Big Thomson River below Lake Estes (BT-UTD) was chosen for the duplicate analysis due to its proximity to WWTPs resulting in elevated detections of PPCPs. The results for the compounds that are included in both CEMS (LC/MS/MS and LC/TOF-MS analytical lists) and EPA analyses are shown in Table 7.

The positive detections from CEMS and EPA are comparable in concentrations. The differences are not significant, especially given that the laboratories use different methods of extraction and detection (CEMS uses the LC/MS/MS or LC/TOF-MS method; EPA uses analytical method EPA 1694). These differences would be the same results obtained when performing triplicate analyses (up to 25% relative standard deviation), therefore, the results from CEMS and EPA fall inside this analytical relative error. The only exception is for a venlafaxine metabolite, norvenlafaxine, which CEMS detected at a higher concentration than EPA. By comparing the signals with the parent compound (venlafaxine) the CEMS values were verified for the LC/TOF-MS analytical methodology. At these trace levels of pharmaceuticals (i.e., 5-20 ng/L) it is possible to have variations in the water samples themselves. Although the samples submitted to each lab were collected at approximately the same time and at the same location, CEMS and EPA analyzed different water bottles, which could result in slight variations at the detection limits. This could explain the results obtained for some of the metabolites, such as carbamazepine and bupropion metabolites. Instances where EPA did not detect and CEMS did detect the compound were due to lower limits of detections for the CEMS analysis. Generally when this occurred, CEMS detected the compound below

Compound CEMS EPA Acetaminophen <5 <10

Albuterol <10 <10 Atenolol 15.6 19.6 Atrazine <2 <10

Bupropion 7.2 <25 Bupropion Metabolite 10 16

Caffeine <10 <25 Carbamazepine 8.3 <10

Carbamazepine Metabolite 10 24 Cotinine <5 <10

DEET 20 17.6 Dextromethorphan <10 <10

Dextrorphan 13.3 <10 Diclofenac <20 <10 Diltiazem <5 <10

Diphenhydramine <5 <10 Erythromycin <10 <10

Erythromycin Anhydrate <5 <25 Fluoxetine <10 <25

Gabapentin 392 306 Gemfibrozil 39.4 24.7 Ibuprofen <50 <10

Lamotrigine 60.6 44.8 Metformin <50 48.6 Metoprolol 23.1 <10 Naproxen <50 <10

Norvenlafaxine Metabolite 126 51 Oxycodone <20 <10 Propranolol 3.6 <10

Sulfamethoxazole 20.6 12.5 Thiabendazole <5 <10

Triclosan <20 <10 Trimethoprim 18.6 14.7 Venlafaxine 18.2 14.4

Warfarin <10 <10 Table 7 - EPA and CEMS Results for QAQC Sample


the EPA detection limit. There were several compounds that were not detected by either CEMS or EPA, which reassures the capability of the method for negative and positive detections. The EPA detected five compounds that are not included in the CEMS list of compounds: furosemide, hydrochlorothiazide, oxcarbazepine, tramadol and triamterene. Three of these compounds (oxcarbazepine, tramadol and triamterene) could be included in the LC/TOF-MS list of compounds in the future. WWTP Analysis Wastewater effluent is the main source of pharmaceuticals and personal care products, and a major contributor of endocrine disrupting compounds, into natural water systems. The type of wastewater treatment process utilized impacts the percent removal of PPCPs in the effluent. Although there is not any one treatment process that is 100% effective, some processes have been shown to work better than others (Rosal, et al., 2010; Snyder, et al., 2007; Writer, 2013). Conventional (and the most common) wastewater treatment processes that use activated sludge are more effective than those that utilize biological filters. But, the effectiveness of the activated sludge process is highly dependent on several things including sludge age, temperature and retention time (Rosal, et al., 2010; Bolonga, Ismail, Salim, & Matsuura, 2009; World Health Organization, 2011). Advanced wastewater treatment processes such as ozonation and membrane treatment are more effective than conventional processes but are expensive and less commonly used (World Health Organization, 2011; Bolonga, Ismail, Salim, & Matsuura, 2009; Rosal, et al., 2010; Snyder, et al., 2007). Often, removal rates depend on the compound. Different chemical structures react differently during the treatment process; some are easily broken down while others persist. Pharmaceuticals that are classified as antidepressants and beta-blockers are a few that have been shown to persist through the treatment process (World Health Organization, 2011; Rosal, et al., 2010). In addition, all of these treatment processes can transform some of the compounds, thus generating degradation products that can have similar physicochemical properties to their parent compounds (Snyder, Lei, & Wert, 2008; Weinberg, Pereira, & Ye, 2008). In some cases, the degradation products can be endocrine disruptors. Some of the degradation products have been shown to be present at higher concentrations than the parent compounds in wastewater and surface water (Writer, 2013). In 2015, a program participant submitted one-time samples of WWTP influent and stream water upstream and downstream of the WWTP discharge point. The WWTP is downstream of all sampling sites included in this monitoring program. The percent removal was calculated for each compound as shown in Table 8.


Compound Type Compound % Removal Classification

Herbicides and Pesticides

2,4-D 92% Herbicide Atrazine 100% Herbicide Diazinon 52% Insecticide Diuron 19% Herbicide

Fluridone NA Herbicide Triclopyr NA Herbicide

Household Products Caffeine 100% Stimulant Sucralose 65% Artificial Sweetener

Personal Care Products DEET 100% Bug Repellant Triclosan 61% Antibacterial

Endocrine Disruptor

17-a-Ethinylestradiol NA Ovulation Inhibitor 17-b-Estradiol NA Reproductive Hormone

4-Androstene-3,17-dione 98% Reproductive Hormone Bisphenol A 81% Plasticizer

Equilin NA Reproductive Hormone Estriol 100% Reproductive Hormone

Estrone 100% Reproductive Hormone Progesterone 65% Reproductive Hormone Testosterone 100% Reproductive Hormone

Pharmaceuticals

Acetaminophen 100% Pain Reliever Atenolol 59% Blood Pressure

Bupropion 0% Antidepressant Carbamazepine 15% Antidepressant Clarithromycin 99% Antibiotic

Cotinine 98% Stimulant Dextrorphan 1% Cough Suppressant

Diltiazem 96% Blood Pressure Diphenhydramine 96% Antihistamine

Erythromycin 90% Antibiotic Gabapentin 98% Antiepileptic Gemfibrozil 100% Analgesic Lamotrigine 0% Antidepressant Metoprolol 36% Blood Pressure Propranolol 0% Blood Pressure

Sulfamethoxazole 0% Antibiotic Trimethoprim 66% Antibiotic Venlafaxine 0% Antidepressant

Table 8 - Percent removal of compounds at a WWTP. The percent removal rates highlighted in red indicate less than 50% removal. The percent removal rates noted with a ‘NA’ indicate the compound was not detected in the WWTP influent.

The data from this particular WWTP support the data collected for the Emerging Contaminants Monitoring Program. Pharmaceuticals that were shown to have little to no removal/degradation are consistent with the ones that are routinely detected at sites in the monitoring program that are influenced by other wastewater facilities. In addition, in support of the literature that is available, the compounds that are classified as antidepressants and beta-blockers showed little to no removal/degradation (0 – 15% removal). These compounds include: bupropion, carbamazepine, lamotrigine, metoprolol, propranolol and venlafaxine.


These data show that the endocrine disrupting compounds are removed at a fairly high percentage, ranging from 65-100%. There were three EDCs that are included on the analytical list that were not detected in the influent: 17-a-Ethinylestradiol, 17-b-Estradiol and equilin. Caffeine and the pharmaceuticals gabapentin and gemfibrozil showed high removal rates: 98-100%. This is unexpected since these compounds, especially caffeine and gabapentin, are detected in the surface waters of the study area, often with elevated concentrations. Caffeine may have an alternate source as it can also be introduced into the water through recreational activities or could come from a natural source, such as plant material that enters the aquatic environment. On the other hand, gabapentin and gemfibrozil are taken in high doses (grams and milligrams respectively). Even though they have a high removal percentage at the WWTP, the compounds may still be detected surface water at the nanogram concentration range. Summary In general, the drinking water sources in the study area have very clean water, free of most of the compounds included in the analysis. Only a handful of compounds were detected and the detections were at very low concentrations. In addition, the detected compounds are ubiquitous in water resources throughout the country and are not unique to our system. Detection limits are in the nanogram per liter range, which is low enough to detect very minute concentrations of the compounds. These low concentration levels do not present a known health hazard for drinking water and are well below any drinking water standards that may apply. The 2015 data are fairly consistent with data collected in previous years. As in previous years, there were a few compounds that were more commonly detected and were found to persist throughout the study area. The PPCPs, whose source is primarily from WWTP effluent, that were consistently detected were: carbamazepine, gemfibrozil, lamotrigine, metoprolol, sulfamethoxazole and venlafaxine. Gabapentin, which was a compound added in 2014, was detected frequently with elevated concentrations. Gabapentin is taken in large doses for many illnesses, up to 1.8 grams per day. This dose is 10 to 100 times greater than some of the other pharmaceuticals, which may explain the frequent detections. 2,4-D and atrazine were the most common herbicides detected in the study area. Triclopyr was detected in the south part of the study area in the Saint Vrain Supply and Boulder Feeder Canals. Caffeine, DEET, sucralose and triclosan whose source may be from WWTP effluent and/or recreational activities, were also detected on a regular basis throughout the study area. The study includes the sampling of treated (or finished) drinking water from two separate treatment plants. 2015 data from these samples showed very low detections for 2,4-D, atrazine, caffeine, sucralose and triclopyr. This is consistent with data from previous years and leads to the conclusion that these compounds persist through the water treatment process.


The influence of WWTPs in the study area is apparent but dilution is significant and only low concentrations were detected at sites downstream of the sources. Monitoring at BT-UTD, downstream of two WWTPs discharges, has provided a good baseline of compounds to look for throughout the study area, even in those places not influenced by this discharge but by other WWTPs. Monitoring at BT-UTD will continue as it provides key information for data interpretation and to support the evolving list of compounds.


Works Cited Bolonga, N., Ismail, A., Salim, M., & Matsuura, T. (2009). A review of the effects of emerging

contaminants in wastewater and options for their removal. Science Direct, 239, 229-246.

Rosal, R., Rodríguez, A., Perdigón-Melón, J. A., Petre, A., García-Calvo, E., Gómez, M. J., et al. (2010, January). Occurrence of Emerging Pollutants in Urban Wastewater and Their Removal Through Biological Treatment Followed by Ozonation. Water Research, 44(2), 578-588.

Snyder, S. A., Adham, S., Redding, A. M., Cannon, F. S., DeCarolis, J., Oppenheimer, J., et al. (2007). Role of membranes and activated carbon in the removal of endocrine disruptors and pharmaceuticals. Science Direct, 156-181.

Snyder, S., Lei, H., & Wert, E. (2008). Removal of endocrine disruptors and pharmaceuticals during water treatment. In D. S. Aga (Ed.), Fate of Pharmaceuticals in the Environment and in Water Treatment Systems (pp. 229-259). Boca Raton, Florida: CRC Press.

Weinberg, H., Pereira, V., & Ye, Z. (2008). Treatment of Pharmaceuticals in Drinking Water and Wastewater Drugs in Drinking Water : Treatment Options. In D. S. Aga (Ed.), Fate of Pharmaceuticals in the Environment and in Water Treatment Systems (pp. 217-228). Boca Raton, Florida: CRC Press.

World Health Organization. (2011). Phamaceuticals in Drinking-water. Geneva: WHO Press. Writer, J. F. (2013). Widespread Occurrence of Neuro-active Pharmaceuticals and Metabolites

in 24 Minnesota Rivers and Wastewaters. Science of the Total Environment, 461-462, 519-527.

2015 Emerging Contaminants Annual Report

1 Appendix

Map of Sampling Locations The map below shows the location of the sites as well as the year they were added to the program.

Note on Map NFWTP is the location of three sampling sites: NFWTP-CL, NFWTP-HD, and NFWTP-SV BRWTF is the location of three sampling sites: BRWTF-BFC, BRWTF-BR, and BRWTF-FIN BETWTP is the location of three sampling sites: BET-BAR, BET-LAK and BET-FIN


2 Appendix

CEMS Sampling Protocol January 1, 2010

The University of Colorado, Center for Environmental Mass Spectrometry, CEMS, is committed to a rigorous program of quality assurance and quality control for all phases of research and analysis, including sample collection, sample storage, physical and chemical analyses, and evaluation of the resulting data. The following sampling procedures are taken from our most recent SOP Manual, dated January 1, 2010. Sampling Procedures for Water Samples: All samples will be collected in baked, glass, 1-liter, amber bottles complete with Teflon lined caps to ensure sample integrity. In addition, a concerted effort will be made to keep bottle head space to a minimum by filling the bottles to the top. The bottles will be rinsed in the field three times with sample and filled to the top on the fourth sampling. Disposable gloves will be used by the sampler to prevent any personal care products from contaminating the sample bottles. No use of insect repellent (i.e. DEET) is allowed, and no smoking or coffee should be consumed during the sampling period. Any unusual conditions concerning each sample will be noted in a field notebook and copies of these field notes will be sent along with the samples in a waterproof envelope. All samples will be kept refrigerated at ≤4°C from the time of collection until sample extraction has taken place. This is accomplished by placing all samples in an appropriate ice-chest filled with blue ice packets or regular ice. The sample bottles will be labeled clearly with an indelible black pen and covered with cellophane tape for name protection. The bottle will be wrapped with bubble wrap and taped to prevent banging and breakage of the bottles. Finally, All details related to sample collection and preservation will be recorded in a notebook. This notebook will contain all relevant information including time and date of sampling, retrieval method, initials of sampler, sample identification number, and any other data deemed necessary. This notebook will also contain any deviations that may occur during the sampling process. River and Lake Water Sampling: Proper integrated sampling of river and water is necessary for quantitative results. This may follow standard USGS protocol and be taken by integrating sampling across the river or profile depth sampling of a lake. If this is not available, a grab sample may be taken. Grab samples are not quantitative but may be useful for early surveys. Grab samples should be taken from the rapid area of the stream or river where the majority of flow is occurring. Care is taken that the sample is not contaminated by the sampler during this process.


3 Appendix

Pesticides Suite (LC/TOF-MS) PPCPs Suite (LC/TOF-MS) Low Level Suite (LC/MS-MS)Compound MRL (ng/L) Compound MRL (ng/L) Compound MRL (ng/L)Acetamiprid 3 1,7 Dimethylxanthine 100 2,4-D 5Acetochlor 2 Acetaminophen 50 Acetaminophen 5Alachlor 3 Albuterol 10 Atenolol 5Aldicarb 5 Atenolol 5 Atrazine 2Atrazine 5 Azithromycin 10 Bisphenol A 20Azoxystrobin 1 Bupropion 10 Bupropion 1Bromacil 5 Bupropion Metabolite 10 Caffeine 10Bromoxynil 20 Caffeine 20 Carbamazepine 2Bromuconazole 1 Carbamazepine 5 Clarithromycin 2Buprofezin 1 Carbamazepine Metabolite 5 Cotinine 5Captan 15 Cimetidine 10 DEET 20Carbaryl 3 Ciprofloxacin 5 Dextrorphan 5Carbendazim 1 Clarithromycin 10 Diazinon 1Carbofuran 4 Cotinine 20 Diltiazem 5Chlorpyrifos methyl 30 DEET 20 Diphenhydramine 5Cyanazine 2 Dehydronifedipine 2 Diuron 5Cyproconazole 1 Dextromethorphan 10 Erythromycin 10Cyromazine 9 Dextrorphan 10 Fluridone 5Deethylatrazine 2 Diclofenac 20 Gabapentin 15Deisopropylatrazine 2 Diltiazem 15 Gemfibrozil 5Diazinon 1 Diphenhydramine 2 Lamotrigine 5Dichlorvos 1 Erthyromycin 5 Metoprolol 1Difenoconazole 1 Erthyromycin Anhydrate 5 Propranolol 1Diflubenzuron 12 Fluoxetine 10 Sucralose 15Dimethenamide 1 Ibuprofen 50 Sulfamethoxazole 5Dimethoate 1.5 Lamotrigine 5 Triclopyr 10Dimethomorph 4 Lamotrigine Glucuronide 10 Triclosan 20Diuron 15 Metformin 50 Trimethoprim 5Flufenacet 3 Metoprolol 5 Venlafaxine 1Fluridone 5 Naproxen 50 # of Low Level 29Fluroxypyr 45 Norvenlafaxine Metabolite 20Hexaflumuron 8 Oxycodone 20Hydroxyatrazine 1 Propranolol 5 Hormone Suite (LC/MS-MS)Imazalil 1 Ranitidine 10 Compound MRL (ng/L)Imazapyr 5 Sulfadimethoxine 5 17-a-Ethinylestradiol 10Imidacloprid 2 Sulfamethoxazole 50 17-b-Estradiol 5Iprodione 4 Triclocarban 20 4-Androstene-3,17-dione 2Isoxaben 5 Trimethoprim 5 Equilin 5Isoxaflutole 5 Venlafaxine 10 Estriol 10Malathion 1.5 Warfarin 10 Estrone 5Metalaxyl 1 # of PPCPs 40 Progesterone 1Methidathion 15 Testosterone 1Methiocarb 1 # of Hormones 8Methiocarb sulfone 9Methomyl 2Metolachlor 1Metribuzin 1Nicosulfuron 1Parathion-methyl 17Pendimethalin 11Phosmet 1Prometon 1Propachlor 1Propazine 1Propiconazole 1Propoxur 5Prosulfuron 5Simazine 5Spinosyn A 1Spinosyn D 6Terbuthylazine 5Thiabendazole 5Thiacloprid 1.5Triflumizole 3# of Pesticides 64

Compounds Analyzed in 2015


4 Appendix

0

10

20

30

40

50

60

70

80

90

100At

enol

ol

Bupr

opio

n

Caffe

ine

Carb

a-m

azep

ine

Clar

ithr-

omyc

in

Dext

rorp

han

Diph

en-

hydr

amin

e

Gab

apen

tin

Gem

fibro

zil

Lam

otrig

ine

Met

opro

lol

Prop

rano

lol

Sucr

alos

e

Sulfa

met

h-ox

azol

eTr

ime-

thop

rim

Venl

afax

ine

Feb-15

Conc

entr

atio

n (n

g/L)

Detections at Upper Big Thompson SitesFebruary 2015

BT-FRDOLYBT-UTDBT-DLU

127 1444; 9811310; 969 157

0

10

20

30

40

50

60

70

80

90

100

2,4-

D

Gab

apen

tin

Gem

fibro

zil

Lam

otrig

ine

Met

opro

lol

Sucr

alos

e

Tric

losa

n

Venl

afax

ine

Jun-15

Conc

entr

atio

n (n

g/L)

Detections at Upper Big Thompson SitesJune 2015

AT-EPOLYBT-DLUBB-LOV

108121

0

10

20

30

40

50

60

70

80

90

100

Aten

olol

Bupr

opio

n

Carb

a-m

azep

ine

Clar

ithr-

omyc

in

DEET

Dext

rorp

han

Gab

apen

tin

Gem

fibro

zil

Lam

otrig

ine

Met

opro

lol

Prop

rano

lol

Sucr

alos

e

Sulfa

met

h-ox

azol

e

Trim

e-th

oprim

Venl

afax

ine

Aug-15

Conc

entr

atio

n (n

g/L)

Detections at Upper Big Thompson SitesAugust 2015

AT-EPOLYBT-UTDBT-DLUBB-LOV

207; 1095; 596; 347

392; 164


4 Appendix

0

10

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30

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50

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90

100

2,4-

D

Atra

zine

Caffe

ine

Gab

apen

tin

Sucr

alos

e

Nov-14

Conc

entr

atio

n (n

g/L)

Detections at Horsetooth Reservoir SitesNovember 2014

HT-SOL-1HT-SOL-mHT-SOL-bHT-SPR-1HT-SPR-mHT-SPR-b

0

10

20

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90

100

2,4-

D

Atra

zine

Caffe

ine

DEET

Gab

apen

tin

Sucr

alos

e

Jun-15

Conc

entr

atio

n (n

g/L)

Detections at Horsetooth Reservoir SitesJune 2015

HFC-HTHT-SOL-1HT-SOL-mHT-SOL-bHT-SPR-1HT-SPR-mHT-SPR-b

0

10

20

30

40

50

60

70

80

90

100

2,4-

D

Acet

amin

-op

hen

Atra

zine

Caffe

ine

DEET

Gab

apen

tin

Lam

otrig

ine

Met

opro

lol

Sucr

alos

e

Sulfa

met

h-ox

azol

e

Venl

afax

ine

Aug-15

Conc

entr

atio

n (n

g/L)

Detections at Horsetooth Reservoir SitesAugust 2015

HFC-HTHT-SOL-1HT-SOL-mHT-SOL-bHT-SPR-1HT-SPR-mHT-SPR-b

142 119


4 Appendix

0

10

20

30

40

50

60

70

80

90

100

2,4-D

Aug-15

Conc

entr

atio

n (n

g/L)

Detections at Upper Poudre River Sites2015 NF-PRU

0

10

20

30

40

50

60

70

80

90

100

2,4-D Atrazine Gabapentin Sucralose

Nov-14

Conc

entr

atio

n (n

g/L)

Detections at Carter Lake and Saint Vrain Supply Canal SitesNovember 2014 CL-DAM1-1

CL-DAM1-m

CL-DAM1-b

0

10

20

30

40

50

60

70

80

90

100

2,4-D Atrazine Gabapentin Sucralose

Jun-15

Conc

entr

atio

n (n

g/L)

Detections at Carter Lake and Saint Vrain Supply Canal SitesJune 2015 CL-DAM1-1

CL-DAM1-m

CL-DAM1-b

0

10

20

30

40

50

60

70

80

90

100

2,4-D Atrazine Caffeine DEET Gabapentin Sucralose Triclopyr

Aug-15

Conc

entr

atio

n (n

g/L)

Detections at Carter Lake and Saint Vrain Supply Canal SitesAugust 2015 CL-DAM1-1

CL-DAM1-mCL-DAM1-bSVSC-SV


4 Appendix

0

10

20

30

40

50

60

70

80

90

100

Atrazine Caffeine Gabapentin Sucralose Venlafaxine

Feb-15

Conc

entr

atio

n (n

g/L)

Detections at Nelson Flanders WTP and Saint Vrain River SitesFebruary 2015 NFWTP-CL

SV-LD

0

10

20

30

40

50

60

70

80

90

100

Gabapentin Sucralose

Jun-15

Conc

entr

atio

n (n

g/L)

Detections at Nelson Flanders WTP and Saint Vrain River SitesJune 2015

NFWTP-CL

0

10

20

30

40

50

60

70

80

90

100

2,4-D Caffeine Gabapentin Lamo-trigine

Sucralose Venlafaxine

Aug-15

Conc

entr

atio

n (n

g/L)

Detections at Nelson Flanders WTP and Saint Vrain River SitesAugust 2015

NFWTP-CL

NFWTP-HD


4 Appendix

0

10

20

30

40

50

60

70

80

90

100

2,4-D Atrazine DEET Sucralose

Nov-14

Conc

entr

atio

n (n

g/L)

Detections at Boulder Reservoir SitesNovember 2014

BRWTF-BR

BRWTF-FIN

0

10

20

30

40

50

60

70

80

90

100

2,4-D Atrazine Caffeine Gabapentin Sucralose

Feb-15

Conc

entr

atio

n (n

g/L)

Detections at Boulder Reservoir SitesFebruary 2015

BR-SDT-S

130

0

10

20

30

40

50

60

70

80

90

100

2,4-D Atrazine Caffeine Diuron Estrone Fluridone Gaba-pentin

Lamo-trigine

Sucralose Triclopyr Triclosan

Jun-15

Conc

entr

atio

n (n

g/L)

Detections at Boulder Reservoir SitesJune 2015

BFCBRWTF-BRBRWTF-FIN

182103

0

10

20

30

40

50

60

70

80

90

100

2,4-D Atrazine Caffeine DEET Diuron Gaba-pentin

Lamo-trigine

Sucralose Triclopyr

Aug-15

Conc

entr

atio

n (n

g/L)

Detections at Boulder Reservoir SitesAugust 2015

BR-SDT-S

BRWTF-BFC

150


4 Appendix

0

10

20

30

40

50

60

70

80

90

100

Caffeine Gabapentin Lamotrigine Sucralose Venlafaxine

Feb-15

Conc

entr

atio

n (n

g/L)

Detections at Betasso WTP SitesFebruary 2015 BET-BAR

BET-FIN155; 186

0

10

20

30

40

50

60

70

80

90

100

Sucralose

Aug-15

Conc

entr

atio

n (n

g/L)

Detections at Betasso WTP SitesAugust 2015 BET-BAR

emerging contaminants program: 2015 annual report · the emerging contaminants monitoring program...

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