Emerging Contaminants Program: 2016 Annual Report · BT-UTD Big Thompson Downstream of Upper Thompson Sanitation District 40.3805 -105.4776 Y BT-DLU Big Thompson Upstream of Dille

Prepared by

Northern Water

Emerging Contaminants Program:

2016 Annual Report

Table of Contents

Monitoring Locations ........................................................................................................................... 1

Funding ............................................................................................................................................... 2

Sampling Frequency and Collection .................................................................................................... 3

Analysis and Parameters ..................................................................................................................... 5

2016 Results and Highlights ................................................................................................................ 8

Upper Big Thompson River Sites ..................................................................................................... 8

(AT-EP, BT-FRD, OLY, BT-UTD, BT-DLU and BB-LOV) ................................................................... 8

Horsetooth Reservoir Sites ............................................................................................................. 12

(HFC-HT, HT-SOL, HT-SPR) ........................................................................................................... 12

Upper Cache la Poudre River Sites.................................................................................................. 14

(NF-PRU, PR-NFU) ......................................................................................................................... 14

Carter Lake and Saint Vrain Supply Canal Sites (CL-DAM1, SVSC-SV) ........................................... 15

Nelson Flanders WTP and Saint Vrain River Sites ........................................................................... 16

(SV-LD, NFWTP-CL, NFWTP-SV, NFWTP-HD) ............................................................................... 16

Boulder Feeder Canal and Boulder Reservoir Sites ......................................................................... 17

(BFC, BR-SDT, BRWTF-BR, BRWTF-BFC, BRWTF-FIN) .................................................................. 17

Herbicide Applications in the Boulder Feeder Canal ....................................................................... 18

Betasso WTP Sites ........................................................................................................................ 24

(BET-BAR, BET-LAK, BET-FIN) ...................................................................................................... 24

Analyses for Endocrine Disruptors ................................................................................................. 25

2015 Quality Assurance and Quality Control ..................................................................................... 25

WWTP Analysis ................................................................................................................................. 26

Summary .......................................................................................................................................... 28

Works Cited .............................................................................................................................. 30

Appendix A - Map of Sampling Locations ............................................................................... A-1

Appendix B - CEMS Sampling Protocol................................................................................... B-1

Appendix C - Compounds Analyzed ........................................................................................ C-1

Appendix D - Graphs of Detected Compounds ....................................................................... D-1

Acronyms and Abbreviations BFC Boulder Feeder Canal

BRWTF Boulder Reservoir Water Treatment Facility

C-BT Colorado-Big Thompson

CEMS Center for Environmental Mass Spectrometry

EDC Endocrine Disrupting Compound

EPSD Estes Park Sanitation District

NFWTP Nelson Flanders Water Treatment Plant

PPCP Pharmaceuticals and Personal Care Products

UTSD Upper Thompson Sanitation District

WWTP Wastewater Treatment Plant

2016 Emerging Contaminants Annual Report Page 1

EMERGING CONTAMINANTS MONITORING PROGRAM Annual Report 2016

Emerging contaminants are a potential concern to human health and the environment, particularly in drinking water supplies. The laboratory analysis is costly and there is currently no clear standard list of parameters as analytical methods continue to develop. In 2009, Northern Water launched a collaborative Emerging Contaminants Monitoring Program, in cooperation with the cities of Boulder, Broomfield, Fort Collins, Greeley, Longmont, and Loveland, and the Town of Estes Park. The program is designed to take a pro-active approach to determine the presence of pharmaceuticals and personal care products (PPCPs), endocrine disrupting compounds (EDCs), and pesticides in the Colorado Big-Thompson (C-BT) and Windy Gap Projects and other source waters associated with drinking water supplies in Northern Colorado. The program develops a baseline of data for these compounds and allows assessment of changes in the future. The following is an annual report on the monitoring activities, changes to the monitoring program and an overview of the results for the 2016 cooperative Emerging Contaminants Monitoring Program.

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 in lakes, 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 Horsetooth Reservoir and Carter Lake, samples are collected at two depths: 1 meter from the surface 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. In previous years, an additional sample was collected in the metalimnion (the middle layer). As of 2016, the metalimnion is no longer sampled because the top and bottom samples sufficiently characterize concentrations in the two reservoirs. The bottom depth is of particular importance in these two reservoirs as releases to drinking water suppliers occur near the bottom. Samples from 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 2016, there were no sites added or removed from the monitoring program. All sites included in the 2016 monitoring program are listed in


Table 1 and a map of the sites can be found in Appendix A. 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/BFC1 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 1 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 2016, 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. All participants share costs 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

Fort Collins

Greeley Longmont 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

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. For funding purposes, the sampling schedule follows the Northern Water fiscal year: October 1 to September 30. The 2016 sampling schedule includes four sampling events: November, February, June, and August. The schedule is shown in Table 3. The participants of the monitoring program share the responsibility of sampling. Each participating entity is assigned a sampling site(s) that is of 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 – 2016 Sampling Schedule and Sampling Entity

Station Nov-15 Feb-16 Jun-16 Aug-16 Sampling Entity

AT-EP

X X X Northern Water

BT-FRD

X X X Estes Park

OLY


BT-UTD

X

X Northern Water

BT-DLU

X X X Loveland

HFC-HT


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

BR-SDT/BFC1

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

X2 X X Greeley

BET-FIN

X X X Boulder

BET-BAR

X X X Boulder

BET-LAK

X X X Boulder 1 Sample collected at the site that is not being used as the raw water source 2 Sample collected but not scheduled

Samples are collected per 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 B. Most samples are grab samples collected directly into a sampling bottle prepared by CEMS. Effort is made to collect the grab sample from a well-mixed portion of the water body. Samples at Horsetooth Reservoir and Carter Lake taken at the top and bottom depth are collected with a Kemmerer sampler and then transferred into a prepared sampling bottle. To prevent sample contamination, field personnel take several precautions including:

• Using disposable gloves

• Fully rinsing the sample bottle and cap with site water before collecting the sample

• Avoiding consumption of caffeinated drinks before or during sampling

• Avoiding the use of products that contain DEET (insect repellent) before or during sampling

• Avoiding the use of products that contain nicotine before or during sampling


For each of the four scheduled sampling events, one blank sample is collected. There are two types of blank samples collected for this program: Trip blank – A prepared sample bottle is filled with de-ionized water and carried into the field alongside the sampling container for the environmental sample. The bottle with the de-ionized water is opened in the field when the environmental sample is collected. Equipment blank – De-ionized water is processed in the field through the equipment used to collect lake samples at

depth, the Kemmerer. The equipment blank is only collected with the Horsetooth Reservoir and Carter Lake samples.

Both types of blank samples help to ensure that there is no contamination due to the sample collection processes or atmospheric influences. Blank sample collection is alternated between the sampling entities and utilizes de-ionized water from the sampling entity’s water quality laboratory.

Analysis and Parameters Research scientists Imma Ferrer and Michael Thurman with CEMS conduct the laboratory analysis and data interpretation for the program. Both are actively involved in emerging contaminants research through development of methods for analysis of PPCPs, EDCs, and pesticides in water. There are three methods of analysis used in this program:

• Liquid Chromatography/Quadrupole-Time-Of-Flight Mass Spectrometry (LC/Q-TOF-MS) – a presence/absence screening method used as a precursor to select compounds analyzed with the low-level quantification method.

• Liquid Chromatography/Mass Spectrometry/Mass Spectrometry (LC/MS/MS) – a low-level quantification method used for analysis of PPCPs and pesticides.

• Liquid Chromatography/Mass Spectrometry/Mass Spectrometry (LC/MS/MS) – a low-level quantification method specific for endocrine disrupting compounds.

Analysis using the LC/QTOF-MS method indicates whether a compound is present or absent in a sample. Precise quantification of concentrations can be determined for many of the compounds analyzed by this method as there is a standard available that has been used to

Figure 1 - Sample collection using a Kemmerer sampler


refine the methodology. The list of compounds tested with the LC/QTOF-MS method includes 104 compounds: 40 commonly used PPCPs and 64 herbicides/pesticides. Analysis using the low-level LC/MS/MS method began in 2010. This method provides precise, low-level quantification of concentrations. The list of compounds analyzed by this method are those that have consistently been present in the screening analyses by LC/QTOF-MS or those that are of specific interest to the study area (i.e. herbicides used locally). The participants review the list of parameters tested with this method each year and compounds can be added or removed. The 2016 list of compounds analyzed by LC/MS/MS includes 32 herbicides/ pesticides and PPCPs (subset from the LC/QTOF-MS method), shown in Table 4. 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

Imazamox 5 Herbicide 2016

Penoxsulam 10 Herbicide 2016

Topramezone 20 Herbicide 2016

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


In 2016, three herbicides were added to both the LC/QTOF-MS and LC/MS/MS method compound lists: imazamox, topramezone, and penoxsulam. Northern Water maintains the East Slope C-BT canal systems, which includes control of nuisance and invasive weed species. The Boulder Feeder Canal, which runs south from Carter Lake to Boulder Reservoir, is an earthen lined canal that is prone to excessive weed growth. Northern Water added herbicides containing these three compounds to their 2016 Pesticide Discharge Management Plan (PDMP) to help control weed growth in this section of the canal system. The City of Boulder’s Boulder Reservoir Water Treatment Facility (BRWTF) and Left Hand Water District use water that comes from the canal for a drinking water source. Monitoring for these compounds will allow for detection of any changes or affects herbicide applications may have on the water supply. There is detailed discussion regarding these applications in the ‘Herbicide Applications in the Boulder Feeder Canal’ section of this report. 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 – found in birth control pills

• 17-beta-estradiol – natural feminine hormone

• 4-androstene-3,17-dione – a natural and synthetic hormone

• Equilin – horse estrogen and a synthetic hormone

• Estriol – pregnancy hormone

• Estrone – natural feminine hormone

• Progesterone – natural feminine hormone

• Testosterone – natural male hormone Analytical costs increased in 2016. In an effort to offset the increase, the participants opted to reduce the frequency of analysis for the suite of the eight EDCs. Outside of estrone, these compounds are generally not detected above the method detection limit, especially during the high flows that occur during runoff. Beginning in 2016, the full suite of the eight EDCs is only included during the August sampling event; all the sites in the program are sampled in August and it has low flow conditions where dilution is less apparent. For the remaining sampling events (November, February, and June), analysis will only be done for estrone. If estrone is detected, follow-up analyses will be done on the full suite of EDCs for that sample. The full list of compounds for all methods and reporting limits can be found in Appendix C.


2016 Results and Highlights The following discusses results from the low-level LC/MS/MS method in 2016. The discussion is sectioned by geographic location. Graphs of all compounds detected at all sites in 2016 are in Appendix D.

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 (Figure 2). 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.

Figure 2 - 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 this basin. 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 2016, there were no notable detections at these sites; DEET was detected at AT-EP in February and August and there were no detected compounds at BT-FRD.


The Big Thompson River sites downstream of Estes Park (BT-UTD, OLY, BT-DLU and BB-LOV) have a high number of detected PPCPs with elevated concentrations compared to the other sites in the program 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 two WWTP effluent discharges; the Estes Park Sanitation District (EPSD) and Upper Thompson Sanitation District (UTSD) (Figure 2). This site consistently has the most detected PPCPs with the highest concentrations compared to all the sampling sites in the monitoring program. In total, 17 of the 32 PPCPs on the low-level analytical list were detected at BT-UTD in 2016, which is consistent with previous year’s results at this site. Figure 3 and Figure 4 compare the concentrations of the PPCPs detected at BT-UTD in February and August 2016 to data collected in previous years; 2011-2015. (Note: Analysis for the compounds dextrorphan and gabapentin began in 2014.)

Figure 3 - Concentrations of PPCPs detected during the month of February at BT-UTD from 2011-2016 (concentrations above 200 ng/L not shown: Atenolol 2011 – 755; Gabapentin 2014 – 834, 2015 – 1310, 2016 – 3619; Gemfibrozil 2011 – 769)


Figure 4 - Concentrations of PPCPs detected during the month of August at BT-UTD from 2011-2016 (concentrations above 200 ng/L not shown: Gabapentin 2015 – 392)

The figures show that generally the same compounds are consistently detected and in most cases, the concentrations are similar year-to-year. Typically, the concentrations are higher in February compared to August due to low winter flows and minimal WWTP effluent dilution. In 2016, DEET was not detected in February but was detected in August, which is likely due to the seasonal use of the product. The pharmaceutical diltiazem (found in blood pressure medications) and the anti-bacterial compound triclosan had not been detected for several years but were detected in both February and August in 2016. The sites further downstream in the Big Thompson River, BT-DLU and BB-LOV, show impact from the WWTP discharges consistent with the upstream site, BT-UTD. Generally, the same PPCPs are detected at the sites further downstream but the concentrations are lower due to dilution and degradation. Often, compounds that were detected at BT-UTD are no longer present at the site that is the furthest downstream, BB-LOV. Figure 5 shows the PPCP’s that were detected and how the concentrations decrease from the samples collected in August 2016. The exception is sulfamethoxazole, an antibiotic, where concentrations increase at the mid-site, BT-DLU. This is not an isolated occurrence; data from previous years and different months often show an increase of sulfamethoxazole at the BT-DLU site compared to the BT-UTD site.


Figure 5 - PPCPs detected in August 2016 at the sites in the Big Thompson River below Lake Estes

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. In 2016, 2,4-D was only detected at the furthest downstream site, BB-LOV as shown in Figure 6. 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. The BB-LOV site is further downstream and is less effected by flood destruction and restoration efforts; the detection of 2,4-D in 2016 may indicate the area is becoming more representative of pre-flood conditions. Detections of 2,4-D are expected in future years in the upstream sites as homes and parks are re-established.

Figure 6 - 2,4-D concentrations for the month of August at the Big Thompson River sites below Lake Estes from 2010-2016


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 2). 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 7 shows the concentrations of the compounds that were detected in August 2016 at the OLY site compared to the BT-UTD site. Typically, when there are detections at OLY, they are for the same compounds as those detected at BT-UTD. The concentrations are significantly 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 it also receives water from the Big Thompson River above and below Lake Estes. The Hansen Feeder Canal supplies the source water for Horsetooth Reservoir. Sampling for Horsetooth Reservoir includes two sites in the reservoir (HT-SPR and HT-SOL) and one site in the Hansen Feeder Canal just above the inlet to the reservoir (HFC-HT) (Figure 8).

Figure 7 - PPCPs detected at OLY and BT-UTD in August 2016

Figure 8 - Map of sampling sites in and surrounding Horsetooth Reservoir


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 9 shows the concentrations of PPCPs at the inlet site located in the Hansen Feeder Canal, HFC-HT, in August (generally the month with the highest occurrence of PPCPs) from 2011-2016.

Figure 9 - Concentrations of PPCPs detected during the month of August at HFC-HT from 2011-2016

Figure 10 shows the concentrations of all the detected compounds in the Hansen Feeder Canal and at both the top and bottom depths at the sites in Horsetooth Reservoir for August 2016.

Figure 10 - Concentrations of detected compounds in the Hansen Feeder Canal and Horsetooth Reservoir in August 2016


The PPCP’s detected at HFC-HT are consistent with those that are detected at the sites located in the reservoir, HT-SPR and HT-SOL. Generally, the concentrations for PPCP’s in the reservoir are lower due to dilution, mixing, and degradation. The compounds caffeine and DEET are usually only present in the sample collected at the top depth, and when they are detected at the bottom depth the concentrations are significantly lower. This may be due to inputs of these compounds through recreational uses, as they are not always present in the source water, HFC-HT. The herbicides detected in August 2016 were 2,4-D and atrazine at the reservoir sites only, shown in Figure 10. In June 2016 2,4-D was detected in both the reservoir and in the Hansen Feeder Canal. Low levels of atrazine are evenly distributed throughout the reservoir, with minor evidence of degradation or dilution within the reservoir at depth, which is consistent with data from previous years. In 2016, the concentrations for 2,4-D were higher at the top depth compared to the bottom depth.

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 11). 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 2016, 2,4-D was detected in August at the site on the North Fork of the Poudre. Caffeine, DEET and sucralose were also detected in August at the site in the Poudre River, PR-NFU.

Figure 11 - 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 flows south into the Boulder Feeder Canal. The Boulder Feeder Canal flows into and ends at Boulder Reservoir. Water from Carter Lake and the Saint Vrain Supply Canal is treated for drinking water by several municipalities including three monitoring program participants: Boulder, Broomfield and Longmont. There are canal releases into several tributaries to the South Platte River as the water moves south to Boulder Reservoir. There are two monitoring

sites in this section; 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 12). The source water for Carter Lake is the Olympus Tunnel; therefore, these sites are subject to WWTP influences from EPSD (Figure 7). The same PPCPs can be detected in Carter Lake as at OLY but with lower concentrations due to dilution and degradation processes. Figure 13 shows all the detected PPCPs in Carter Lake at the one-meter depth, CL-DAM, and in the Saint Vrain Supply Canal, SVSC-SV, in August (typically the month with the highest occurrence of PPCPs) from 2011 – 2016. Generally, the same compounds are detected at SVSC-SV as at CL-DAM. In 2016, gabapentin and DEET were the only PPCP’s detected at CL-DAM and only gabapentin was detected at SVSC-SV.

Figure 12 - Map of sampling sites in Carter Lake and the Saint Vrain Supply Canal

Figure 13 – August concentrations of PPCPs detected in Carter Lake at the 1-meter depth and in the Saint Vrain

Supply Canal in August from 2011-2016


The herbicides 2,4-D and atrazine are routinely detected in Carter Lake and the Saint Vrain Supply Canal. In 2016, 2,4-D and atrazine were only detected at the CL-DAM site and not in the Saint Vrain Supply Canal. In addition, the herbicide triclopyr (related to Northern Water’s use of Renovate® to control terrestrial weeds along the canal) was detected at the SVSC-SV site in both 2014 and 2015 but was not detected in 2016. Figure 14 shows the concentrations for all detected herbicides in Carter Lake at the one-meter depth, CL-DAM, and in the Saint Vrain Supply Canal, SVSC-SV, in August from 2011 – 2016.

Although not shown, caffeine and sucralose were also detected at these sites in 2016 which 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: North Saint Vrain River (NFWTP-SV), Carter Lake (NFWTP-CL) and 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 2016, NFWTP-HD had the most detected compounds. Figure 15 shows all the detected compounds at this site for sampling in August (generally the month with the highest occurrence of PPCPs) from 2013-2016. Though the concentrations are low, the detections of PPCPs show some influence of WWTP or septic inputs.

Figure 14 – August concentrations of herbicides detected in Carter Lake at the 1-meter depth and the Saint Vrain Supply Canal from 2011-2016


Figure 15 - Concentrations of compounds detected during the month of August at NFWTP-HD from 2013-2016 (note: graph does not include sucralose which is consistently detected often with concentrations greater than 100 ng/L every year)

As in previous years, in 2016 the detected compounds at NFWTP-CL were consistent with the compounds detected in the source water, Carter Lake (CL-DAM). At the site in the Saint Vrain River, SV-LD, sucralose was detected in February. There were no detected compounds in 2016 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. Carter Lake delivers water to Boulder Reservoir through the Saint Vrain Supply Canal to the BFC. The canal’s terminus is Boulder Reservoir. The City of Boulder’s Boulder Reservoir Water Treatment Facility (BRWTF) can use either Boulder Reservoir or the BFC as the source drinking water supply depending on the season. Generally, samples are collected at three sites during each sampling event (Figure 16). A sample of the raw water going into the water treatment plant is collected. These sites are either BRWTF-BR or BRWTF-BFC. The name indicates what source water is being used at the time of sampling; BRWTF-BR indicates Boulder Reservoir is the source and BRWTF-BFC indicates the source water is the Boulder Feeder Canal. The second sample is a finished, or treated, drinking water sample collected, BRWTF-FIN. The third sample is a sample of the

Figure 16 - Map of Sampling Sites in and near Boulder Reservoir


alternate source water not being used as the raw water supply: Boulder Reservoir at the South Dam surface (BR-SDT) and the BFC. The PPCPs detected at these sites are similar to those detected upstream 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. Figure 17 shows the concentrations of all the PPCPs detected in August (generally the month with the highest occurrence of PPCPs) at the source water sites for the BRWTF from 2011-2016. In the figure, BRWTF-RAW represents the source water being treated, either BRWTF-BFC or BRWTF-BR, and BFC/BR represents the alternate source water, either BFC or BR-SDT. DEET and gabapentin are the compounds consistently detected in most every year during the period of record. (Note: Analysis for the compound gabapentin began in 2014.)

Figure 17 – August concentrations of PPCPs detected at the Boulder source water sites from 2011-2016

Herbicide Applications in the Boulder Feeder Canal 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, weed growth in these canals is not problematic. Northern Water maintains the canals in the C-BT Project, including the BFC. Canal maintenance includes occasional use of herbicides to control nuisance (noxious) weeds. Herbicides can be applied in the canal prism below the high-water level, in the canal prism above the high-water level, and on the areas adjacent to the canal but outside of the prism (Figure 18). Applications that occur when the canal is delivering

Figure 18 - Schematic of canal herbicide applications


water are generally outside of the prism or above the high-water level. Applications can be made in the canal prism during the fall and winter when no water is being delivered. The fall applications are made after the canal is dewatered, often onto sections that still contain pooled water due to groundwater seepage. In addition, there is agriculture in the area that may contribute to herbicides found in the BFC. The use of herbicides in this area has 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 19 shows the concentrations of all herbicides detected in August (which generally has the highest occurrence of herbicides) for the source water sites for the BRWTF from 2010-2016. In the figure, BRWTF-RAW represents the source water being treated, either BRWTF-BFC or BRWTF-BR, and BFC/BR represents the alternate source water, either BFC or BR-SDT. The results for detected herbicides are consistent with what have been detected in previous years.

Figure 19 – August concentrations of herbicides detected at the Boulder source water sites from 2010-2016

In many of the instances where herbicides were detected in the source/raw water, they were also detected in the finished water. Figure 20 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.


Triclopyr in the Boulder Feeder Canal The Boulder Feeder Canal is earth-lined which contributes to ongoing issues with aquatic and terrestrial weeds within the canal prism. Historically, Northern Water has used aquatic-labeled herbicides (products formulated, approved, and registered by the EPA for application in and adjacent to water) that contain 2,4-D for the treatment of terrestrial weeds in the canal prism. Previous years data collected in the Boulder Feeder Canal and at the BRWTF have shown that 2,4-D concentrations were elevated compared to other places within the study area. To address this, beginning in 2013, Northern Water started using aquatic-labeled Renovate® 3 which contains triclopyr (triclopyr triethylamine (TEA) salt) as the active ingredient, instead of products with 2,4-D, for treatment of terrestrial weeds in the canal prism. Northern Water selected Renovate® 3 specifically because 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 is reported to have a half-life of 30-90 days in soil (microbial decomposition) and 1-10 days in water (photochemical degradation). When

used in natural environments, many additional factors can affect half-life including temperature, dissolved oxygen levels, pH, UV light and bacterial activity. Triclopyr was primarily applied to the BFC in April and May, with one application in August as shown in Table 5 (applications in the Saint Vrain Supply Canal are included in the table since it is upstream of the BFC). Triclopyr was detected in both the June and August samples for the alternate source water and the raw and finished BRWTF sites as shown in Table 6. The concentrations in the raw and finished water were

Canal Date Gallons Applied

Boulder Feeder Canal

4/12/2016 2.5

4/13/2016 11.5

4/19/2016 4.5

5/10/2016 2.5

5/11/2016 2

5/13/2016 2

8/8/2016 3.5

Saint Vrain Supply Canal

4/21/2016 6

5/25/2016 5

Table 5 – 2016 Renovate Applications on the Boulder Feeder and Saint Vrain Supply Canals

Figure 20 – August concentrations of herbicides detected at the Boulder raw and finished water sites from 2010-2016


particularly high in August; an application of Renovate® was made on a section of the BFC closest to the BRWTF on August 8, 2016, the same day the sample was collected. The variability in the triclopyr half-life (due to the influence of various environmental factors) likely impacts the observed detections of triclopyr, with concentrations not necessarily corresponding to when Renovate applications occurred. The data show that triclopyr was detected during the June sampling event,

with a fairly high concentration at the BFC site. The last application of Renovate® prior to this sampling event was made on May 13th in the BFC and May 25th further upstream in the Saint Vrain Supply Canal. The June sample was collected on June 14th, well after triclopyr’s reported 1-10 day half-life in water. Some of the triclopyr detected in the water samples may have been present in the soil of the canal banks (with a longer half-life) and subsequently washed into the canal during rain events. Figure 21 shows how the concentrations for 2,4-D and triclopyr have changed from 2011-2016 for the months of June and August. In the BFC, the highest 2,4-D concentrations were in 2011-2012; which is consistent with and shows the effect of applications of products containing 2,4-D made in the canal prism. Concentrations for 2,4-D are low, less than 20 ng/L, in the BFC from 2013-2016, after 2,4-D products were no longer applied in the prism. The 2,4-D concentrations in samples collected in the Boulder Reservoir do not show the same decrease; it is unknown if applications of 2,4-D occur in areas surrounding the reservoir or if the concentrations are related to a longer residence time in the reservoir. The concentrations in the finished water (BRWTF-FIN) vary and are dependent on if the source water is from the BFC or Boulder Reservoir.

Figure 21 – 2,4-D and Triclopyr concentrations at the Boulder Feeder Canal sites in June and August from 2011-2016

Sampled Date

Site Concentration

(ng/L)

6/14/2016 BR-SDT 31.5

BRWTF-BFC 187.9

BRWTF-FIN 82.6

8/8/2016

BR-SDT 11.7

BRWTF-BFC 816

BRWTF-FIN 628 Table 6 – 2016 Detections for Triclopyr at the Boulder Feeder Canal sites


Analysis for triclopyr did not begin until 2013, so it is unknown if it was present in the BFC and at what concentrations prior to that. Since adding triclopyr to the program in 2013, the BFC is the only place in the monitoring area where triclopyr is routinely detected. In contrast, 2,4-D is commonly detected at most all the sites in the program. Therefore, it is concluded that most of the triclopyr detected in the BFC is related to Northern’s Renovate® applications. Triclopyr has been detected in June and August at most of the BFC sites from 2014-2016 ( Figure 21). In 2013, there was only one instance where it was detected; in August in the finished water (BRWTF-FIN). From 2014-2016 there were more frequent detections for triclopyr in the finished water, and when detected the concentrations can be higher than those typically seen for 2,4-D in the finished water. This is contradictory to what was expected given the 1-10 day reported half-life in water. Triclopyr is also found in Boulder Reservoir; it is unknown if the BFC is the only source or if there may be other sources of triclopyr to the reservoir. Triclopyr will continue to be closely monitored in the future. Fluridone and Imazamox in the Boulder Feeder Canal Significant problems with aquatic vascular plants occur within the Boulder Feeder Canal since this canal is entirely earth lined. The growth of vascular plants in the canals can significantly reduce canal capacity and restrict the amount of water that can be delivered. Specific problem sections of the Boulder Feeder Canal are downstream of seeps/springs that provide a continuous supply of moisture such that they never dry out, even after the canal has been dewatered for the winter. Prior to November 2015, aquatic-labeled herbicides containing endothall, Teton® and Cascade®, were applied to the BFC when the canal was dewatered in the winter. These applications began in 2011 and initially proved to be effective; the aquatic weed population was manageable for the first few years after endothall was used. Aquatic and terrestrial weeds can become resistant to herbicides over time when the same herbicide is used year after year. This proved to be the case with the continual use of products containing endothall. Figure 22 shows thick vascular plant growth in the BFC in November 2015 which were no longer affected by applications of endothall. To address this problem, Northern elected to try a combination of herbicides that would be rotated annually to keep targeted weeds species from becoming resistant to herbicides.

Figure 22 - Vascular plant growth in the Boulder Feeder Canal November 2015


In 2016, Northern Water used two new aquatic-labeled herbicides to control weeds in the canal; Sonar Genesis® and Clear Cast® whose active ingredients are fluridone and imazamox respectively. The herbicides were applied in November 2015 after the BFC was dewatered for the season. Applications were made on almost the entire length of the canal, from Lyons to just upstream of Boulder Reservoir shown in Figure 23. In an effort to monitor the fate and transport of these compounds, imazamox was added to the low-level compound list. Fluridone did not need to be added; it was already on the low-level list since Northern had previously used it for weed control. A sampling site downstream of where the applications ended was established, BFC-STAR (Figure 23). Intensive monitoring was done at this site in April and May of 2016 when the canal started delivering water for the season. Figure 24 shows how the concentrations decreased over time. The detected concentrations for fluridone were significantly higher than those for imazamox. By the end of May, both compounds had decreased to concentrations less than 150 ng/L.

Figure 24 Concentrations of fluridone and imazamox in the Boulder Feeder Canal at BFC-STAR, Spring 2016

Figure 23 - Map of where herbicides were applied in November 2015 in the Boulder Feeder Canal


Figure 25 shows the concentrations of fluridone and imazamox from 2010-2016 at the BFC sites. Since imazamox was just added to the compound list in 2016, there is not a baseline of data to compare to. There was one detection for imazamox in June of 2016 in the BRWTF finished water sample. 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, at lower concentrations, 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 2016, fluridone was detected at all the sites in both June and August, with lower concentrations in August.

Figure 25 - Fluridone and imazamox concentrations at the Boulder Feeder Canal sites in June and August from 2010-2016

Betasso WTP Sites

(BET-BAR, BET-LAK, BET-FIN) The City of Boulder samples raw and finished water at the Betasso Water Treatment Plant. The Betasso plant receives its raw water from Barker Reservoir (BET-BAR) and Lakewood Reservoir (BET-LAK) in the upper Boulder Creek watershed. Finished water can be either source or a mix, (BET-FIN). Barker Reservoir receives effluent discharges from the Nederland WWTP. The primary tributary to the reservoir, Middle Boulder Creek, may be influenced by septic systems and also indirectly receives discharges from the Eldora Mountain Resort WWTP lagoons. Boating and aquatic recreation are prohibited on Barker Reservoir.


Lakewood Reservoir is minimally impacted by anthropogenic influences since there is only one ranch and a few houses with septic systems in the watershed. During certain times of the year there are cattle on the ranch. In 2016, the BET-BAR site had the most detected compounds compared to the other Betasso sites, which is consistent with previous years. Figure 26 shows all the detected compounds at this site for sampling in February (generally the month with the highest occurrence of PPCPs) from 2014-2016. Though the concentrations are low, the detections of PPCPs show some influence of the Nederland WWTP and septic systems.

Figure 26 - Concentrations of compounds detected during the month of February at BET-BAR from 2014-2016 (note: graph does not include sucralose which is consistently detected at concentrations greater than 100 ng/L every year)

Sucralose (not shown) was the only compound detected at the BET-FIN water site in February and June of 2016. The BET-LAK site had no detections of any compounds in 2016 which is consistent with previous years, and reflects minimal impacts to the system. The BET-LAK site continues to have the cleanest water in terms of emerging contaminants in the monitoring program.

Analyses for Endocrine Disruptors Analysis included eight hormones or EDCs. There were no detections for any EDCs in 2016.

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 three of the four scheduled sampling events (there was not a blank submitted for the November event). In 2016, the following blank samples were submitted:

• February: Field Trip Blank, City of Fort Collins

• June: Field Trip Blank, City of Boulder

• August: Field Trip Blank, Town of Estes Park There were no detected compounds in any of the blank samples submitted in 2016.

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 (or degradation of the parent compound) 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 and degradation 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 2016, a program participant submitted samples in August of WWTP influent and stream water upstream and downstream of the WWTP discharge point. The same WWTP also collected samples at these locations in August 2015. The WWTP is downstream of all sampling


sites included in this monitoring program. The percent removal was calculated for each compound for 2015 and 2016 and is shown in Table 7.

Compound Type Compound 2015 %

Removal 2016 %

Removal Classification

Herbicides and Pesticides

2,4-D 92% 8% Herbicide

Atrazine 100% 0% Herbicide

Diazinon 52% 0% Insecticide

Diuron 19% 0% Herbicide

Fluridone NA NA Herbicide

Triclopyr NA 0% Herbicide

Household Products Caffeine 100% 100% Stimulant

Sucralose 65% 0% Artificial Sweetener

Personal Care Products DEET 100% 92% Bug Repellant

Triclosan 61% 80% Antibacterial

Endocrine Disruptor

17-a-Ethinylestradiol NA NA Ovulation Inhibitor

17-b-Estradiol NA NA Reproductive Hormone

4-Androstene-3,17-dione 98% 98% Reproductive Hormone

Bisphenol A 81% NA Plasticizer

Equilin NA NA Reproductive Hormone

Estriol 100% 100% Reproductive Hormone

Estrone 100% 62% Reproductive Hormone

Progesterone 65% 100% Reproductive Hormone

Testosterone 100% 100% Reproductive Hormone

Pharmaceuticals

Acetaminophen 100% 100% Pain Reliever

Atenolol 59% 16% Blood Pressure

Bupropion 0% 0% Antidepressant

Carbamazepine 15% 0% Antidepressant

Clarithromycin 99% 0% Antibiotic

Cotinine 98% 98% Stimulant

Dextrorphan 1% 0% Cough Suppressant

Diltiazem 96% 0% Blood Pressure

Diphenhydramine 96% 0% Antihistamine

Erythromycin 90% 0% Antibiotic

Gabapentin 98% 94% Antiepileptic

Gemfibrozil 100% 99% Analgesic

Lamotrigine 0% 0% Antidepressant

Metoprolol 36% 0% Blood Pressure

Propranolol 0% 0% Blood Pressure

Sulfamethoxazole 0% 0% Antibiotic

Trimethoprim 66% 0% Antibiotic

Venlafaxine 0% 0% Antidepressant

Table 7 - 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 for both 2015 and 2016 show that pharmaceuticals which show little to no removal/degradation during treatment are the same pharmaceuticals that are routinely detected at other sites in the monitoring program that are influenced by WWTPs. In addition, 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 or degraded at a high percentage. Three EDCs included on the analytical list were not detected in the influent in either 2015 or 2016: 17-a-Ethinylestradiol, 17-b-Estradiol and equilin. Caffeine and the pharmaceuticals gabapentin and gemfibrozil showed high removal rates for both 2015 and 2016: 94-100%. 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 be introduced into the water through recreational activities (i.e., dumping a caffeinated beverage into the water) or could come from a natural source, such as plant material that enters the aquatic environment. Gabapentin and gemfibrozil are taken in high doses compared to other pharmaceuticals. Gabapentin is taken in doses up to 1.8 grams per day which is 10 to 100 times greater than some of the other pharmaceuticals. Therefore, even though there is a high removal percentage at the WWTP, the compounds may still be detected in surface water at the nanogram concentration range. There were some differences in the percent removal when comparing the data collected from 2015 and 2016. There are several possible explanations for the differences: how the plant is operating, the concentration of the compound, and timing of sample collection. For these samples, the influent samples were collected at the same time as the effluent samples. The calculated RPD is an estimate based on the assumption that concentrations coming into the plant and leaving the plant were measured on the same unit volume of water that has traveled through the treatment process, which was not the case since the influent and effluent samples were collected at essentially the same time. A more accurate RPD would be obtained if the effluent sample is collected at a later time (equal to the plant hydraulic detention time), after the water has made its way through the treatment process.

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 the waterbodies sampled in this program. Detection limits are in the nanogram per liter range, which is low enough to detect very minute concentrations of the compounds. These low concentrations do not present a known health hazard for drinking water and are well below any drinking water standards that may apply ( (World Heath Organization, 2011). The 2016 data are 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 and septic systems, 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. 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 Boulder Feeder Canal. 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 water treatment plants. 2016 data from these samples showed very low detections for 2,4-D, atrazine, fluridone, imazamox, sucralose and triclopyr. This is consistent with data from previous years and/or herbicides that were used in close proximity to the drinking water source and leads to the conclusion that these compounds persist through the water treatment process. The influence of WWTPs and septic systems in the study area is apparent given that some PPCPs are detected. However, the concentrations are very low, suggesting dilution and degradation of the parent compounds. 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 and septic systems. 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.

2016 Emerging Contaminants Annual Report

Appendix A Map of Sampling Locations


Appendix A – Map of Sampling Locations

2016 Emerging Contaminants Annual Report A - 1

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



Appendix B CEMS Sampling Protocol


Appendix B – Sampling Protocol

2016 Emerging Contaminants Annual Report B - 1

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 4C 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.



Appendix C Compounds Analyzed


Appendix C – Compounds Analyzed

2016 Emerging Contaminants Annual Report C - 1

Pesticides - LC/TOF-MS PPCPs - LC/TOF-MS Low Level Compounds - LC/MS-MS

Compound MRL (ng/L) Compound MRL (ng/L) Compound MRL (ng/L)

Acetamiprid 3 1,7 Dimethylxanthine 100 2,4-D 5

Acetochlor 2 Acetaminophen 50 Acetaminophen 5

Alachlor 3 Albuterol 10 Atenolol 5

Aldicarb 5 Atenolol 5 Atrazine 2

Atrazine 5 Azithromycin 10 Bisphenol A 20

Azoxystrobin 1 Bupropion 10 Bupropion 1

Bromacil 5 Bupropion Metabolite 10 Caffeine 10

Bromoxynil 20 Caffeine 20 Carbamazepine 2

Bromuconazole 1 Carbamazepine 5 Clarithromycin 2

Buprofezin 1 Carbamazepine Metabolite 5 Cotinine 5

Captan 15 Cimetidine 10 DEET 20

Carbaryl 3 Ciprofloxacin 5 Dextrorphan 5

Carbendazim 1 Clarithromycin 10 Diazinon 1

Carbofuran 4 Cotinine 20 Diltiazem 5

Chlorpyrifos methyl 30 DEET 20 Diphenhydramine 5

Cyanazine 2 Dehydronifedipine 2 Diuron 5

Cyproconazole 1 Dextromethorphan 10 Erythromycin 10

Cyromazine 9 Dextrorphan 10 Fluridone 5

Deethylatrazine 2 Diclofenac 20 Gabapentin 15

Deisopropylatrazine 2 Diltiazem 15 Gemfibrozil 5

Diazinon 1 Diphenhydramine 2 Imazamox 5

Dichlorvos 1 Erthyromycin 5 Lamotrigine 5

Difenoconazole 1 Erthyromycin Anhydrate 5 Metoprolol 1

Diflubenzuron 12 Fluoxetine 10 Penoxsulam 10

Dimethenamide 1 Ibuprofen 50 Propranolol 1

Dimethoate 1.5 Lamotrigine 5 Sucralose 15

Dimethomorph 4 Lamotrigine Glucuronide 10 Sulfamethoxazole 5

Diuron 15 Metformin 50 Topramezone 20

Flufenacet 3 Metoprolol 5 Triclopyr 10

Fluridone 5 Naproxen 50 Triclosan 20

Fluroxypyr 45 Norvenlafaxine Metabolite 20 Trimethoprim 5

Hexaflumuron 8 Oxycodone 20 Venlafaxine 1

Hydroxyatrazine 1 Propranolol 5 # of Low Level 32

Imazalil 1 Ranitidine 10

Imazapyr 5 Sulfadimethoxine 5

Imidacloprid 2 Sulfamethoxazole 50 EDCs - LC/MS-MS

Iprodione 4 Triclocarban 20 Compound MRL (ng/L)

Isoxaben 5 Trimethoprim 5 17-a-Ethinylestradiol 10

Isoxaflutole 5 Venlafaxine 10 17-b-Estradiol 5

Malathion 1.5 Warfarin 10 4-Androstene-3,17-dione 2

Metalaxyl 1 # of PPCPs 40 Equilin 5

Methidathion 15 Estriol 10

Methiocarb 1 Estrone 5

Methiocarb sulfone 9 Progesterone 1

Methomyl 2 Testosterone 1

Metolachlor 1 # of Hormones 8

Metribuzin 1

Nicosulfuron 1

Parathion-methyl 17

Pendimethalin 11

Phosmet 1

Prometon 1

Propachlor 1

Propazine 1

Propiconazole 1

Propoxur 5

Prosulfuron 5

Simazine 5

Spinosyn A 1

Spinosyn D 6

Terbuthylazine 5

Thiabendazole 5

Thiacloprid 1.5

Triflumizole 3

# of Pesticides 64



Appendix D Graphs of Detected Compounds


Appendix D – Detected Compounds

2016 Emerging Contaminants Annual Report D - 1

Only sampling dates where compounds were detected are shown in the graphs. All sampling dates are in Table 3 – 2016 Sampling Schedule and Sampling Entity.




























Documents

Emerging Contaminants Program: 2016 Annual Report · BT-UTD Big Thompson Downstream of Upper Thompson Sanitation District 40.3805 -105.4776 Y BT-DLU Big Thompson Upstream of Dille