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Evaluation of Exposure to and Human Health Risks
from PCPPs in Drinking Water from Lake Erie
FINAL REPORT
By:
Michelle Homan, Ph.D.
Hwidong Kim, Ph.D.
Department of Environmental Science and Engineering
Gannon University
November 14, 2018
Project Period: February 1, 2016 - September 30, 2018
i
TABLE OF CONTENTS
List of Figures ................................................................................................................................ iii
List of Tables ................................................................................................................................. iv
Executive Summary ........................................................................................................................ 1
Introduction ..................................................................................................................................... 3
Background ................................................................................................................................. 3
Project Goals and Objectives ...................................................................................................... 4
Methodology ................................................................................................................................... 5
OBJECTIVE 1: Determination of the concentrations of target PPCPs ...................................... 5
1. Sampling site .................................................................................................................... 6
2. Sampling methods ............................................................................................................ 8
3. Analytical methods ......................................................................................................... 13
4. Determination of PPCP concentration in water phase from POCIS analytical results .. 13
OBJECTIVE 2: Comparison of ELISA with Lab Analysis Results ......................................... 15
OBJECTIVE 3: Human Health Risk Assessment .................................................................... 17
Results and Discussion ................................................................................................................. 19
OBJECTIVE 1: Determination of the concentrations of target PPCPs .................................... 19
1. General water quality ..................................................................................................... 19
2. Sampling rates ................................................................................................................ 20
3. PPCPs in Grab samples .................................................................................................. 23
4. POCIS sampler results ................................................................................................... 25
Objective 2: ELISA versus Analytical Results ......................................................................... 30
Objective 3: Human Health Risk Assessment .......................................................................... 32
Conclusion .................................................................................................................................... 35
Future Research ........................................................................................................................ 35
ii
Citations ........................................................................................................................................ 37
Appendix A: Metrics..................................................................................................................... 40
Appendix B: Impact and/or Accomplishment Statement(s) ......................................................... 41
Appendix C: Raw Data ................................................................................................................. 43
iii
LIST OF FIGURES
Figure 1. (a) Location of the Wasielewski water treatment plant and (b) sampling points within
the Wasielewski water treatment plant ............................................................................... 7
Figure 2. (a) an assembly of membrane discs and holder (b) and (c) sampling canister with
POCIS membrane discs and holder .................................................................................... 9
Figure 3. A schematic of POCIS deployment setup (treated water) ............................................. 10
Figure 4. Sampling containers installed at (a) water treatment plant and (b) low duty pump
station ................................................................................................................................ 11
Figure 5. Sampling schedule for grab samples and POCIS sampler deployment ........................ 12
Figure 6. Temperature and dissolved oxygen concentrations of water samples over time .......... 19
Figure 7. Frequency of detection of PPCPs in raw and treated samples (grab samples) .............. 24
Figure 8. Frequency of detection of PPCPs in POCIS sampler .................................................... 27
Figure 9. Comparison of atrazine, caffeine and simazine concentrations in raw and treated water
samples (retrieved from POCIS sampler analytical results) ............................................. 29
Figure 10. Scatterplot and Bland-Altman plots from LC-MS/MS and ELISA test for Atrazine at
various dilutions (3 replicates) .......................................................................................... 30
Figure 11. Scatterplot and Bland-Altman plots from LC-MS/MS and ELISA test for Triclosan at
various dilutions (3 replicates) .......................................................................................... 31
Figure 12. Scatterplot of results from LC-MS/MS and ELISA test for caffeine at various
dilutions (3 replicates)....................................................................................................... 31
iv
LIST OF TABLES
Table 1. Summary of PPCPs Included in this Study ...................................................................... 5
Table 2. A summary of experimental setup for determination of sampling rates......................... 14
Table 3. Summary of Dilutions and Replicates for Validation Study .......................................... 15
Table 4. Summary of RfD values for Target PPCPs .................................................................... 18
Table 5. Analytical results of raw- and treated water samples for basic water quality parameters
(total number of samples = 45) ...................................................................................... 20
Table 6. POCIS sampling rates results estimated from analytes remained in the solution .......... 21
Table 7. A summary of PPCPs in grab samples .......................................................................... 25
Table 8. A summary of concentrations of PPCPs estimated based on POCIS analytical results . 28
Table 9. Summary of Risk Calculations using Maximum PPCP Values in Treated Drinking
Water .............................................................................................................................. 33
Table 10 (Appendix). PPCP concentrations in grab samples ....................................................... 43
Table 11 (Appendix). PPCP concentrations in POCIS samplers .................................................. 46
Table 12 (Appendix). Water quality data (raw water samples) .................................................... 52
Table 13 (Appendix). Water quality data (treated water samples) ............................................... 53
1
EXECUTIVE SUMMARY
The overall goal of this research project was to evaluate the exposure to and human health risks
associated with pharmaceuticals and personal care products (PPCPs) in drinking water
originating from Lake Erie. Three specific research objectives were identified and completed as
part of this project including:
● to determine the concentrations of 8 target PPCPs (acetaminophen, ampicillin, caffeine,
metformin, naproxen, sulfamethoxazole, triclosan, and trimethoprim) and an additional 10
analytes in raw and treated drinking water from Lake Erie;
● to evaluate whether the enzyme-linked immunosorbent assay (ELISA) is an effective
method for screening and characterizing PPCPs in drinking water; and
● to quantify the human health risks from exposure to trace levels of PPCPs in drinking water
from Lake Erie.
To achieve the first objective, raw and treated water samples were collected from the
Wasielewski Water Treatment Plant in Erie, Pennsylvania between October 2016 and August
2017. Along with grab samples, long-term samples were collected using Polar Organic
Chemical Integrative Samplers (POCIS). Samples were analyzed by liquid chromatography-
mass spectroscopy (LC-MS-MS) by an accredited laboratory. For short-term samples, six of
the 18 PPCPs were found at detectable levels in raw or treated drinking water including
atrazine, bisphenol-A, caffeine, ibuprofen, metformin and simazine. In the majority of cases,
analyte levels in treated water were lower compared to raw water samples. For long-term
samples, an additional four PPCPs (ten total) were found at detectable levels including
gemfibrozil, naproxen, sulfamethoxazole and trimethoprim. Aqueous phase concentrations of
PPCPs were estimated using sampling rates, deployment periods and analytical results of
POCIS samplers. Similar to the grab sample results, the concentration of all analytes in treated
water were lower than those in raw water samples.
A method comparison study was conducted to assess the agreement between the ELISA test
with that of LC-MS-MS for three analytes (atrazine, caffeine and triclosan). Spiked samples in
2
triplicate were prepared from certified standards to include concentrations of 0, 0.25, 0.5, 1.0
and 2.5 ng/mL. The spiked samples were split and analyzed separately using each method.
Analyte concentrations from each method were compared using Pearson product moment
correlations and the construction of Bland-Altman plots. Results across all three analytes
showed a moderate to high level of agreement between the two analytical methods. The
correlation coefficient (r) ranged between 0.96 and 0.99. The highest level of agreement was
observed with atrazine, followed by caffeine and triclosan, respectively.
The third objective was to calculate the human health risks from the PPCP concentrations
found in treated water samples. A literature review was conducted to find sources of average
daily intake (ADI) or reference dose (RfD) values needed to calculate a drinking water
exposure level (DWEL) for each analyte. The value of the DWEL was then compared to the
maximum measured value or the method detection limit for each of the 18 analytes to estimate
the risk quotient (RQ). A cumulative RQ was estimated at 0.003 for the 18 PPCPs included in
this study. This level is well below any level considered to pose a risk. A value approaching 1
would be considered significant.
The major public health finding was that the 18 PPCPs quantified in this study were found at
trace or non-detect levels and estimated to pose an insignificant health risk to the community.
Additional findings include that the long-term POCIS and ELISA methods were practical and
appropriate for measuring trace levels of PPCPs in source and treated water.
3
INTRODUCTION
BACKGROUND
Public concern and scientific interest in the potential health risks associated with PPCPs in
drinking water have recently increased as a result of studies documenting their presence in
surface, ground and treated drinking water (Henderson et al., 1999; Alliance for the Great
Lakes, 2010; Blair, et al., 2013). These compounds include a large variety of substances such
as prescription and over-the-counter drugs, antibiotics, fragrances, preservatives, disinfectants,
surfactants, among others. Drinking water that originates from a lake or river may contain
PPCPs when these products enter sewage systems and survive treatment at wastewater
treatment plants.
The presence and concentration of PPCPs in municipal drinking water from surface water
sources is not routinely monitored in the U.S. due to the expense necessary for complex
laboratory analysis and since most of these compounds are not currently regulated by the U.S.
Environmental Protection Agency (USEPA). While limited research studies have measured
PPCPs in trace levels (µg/L or ng/L) within raw or treated drinking water, few studies have
evaluated the comprehensive human health risks from exposure to trace PPCP mixtures in this
manner (Schwab, et al., 2005; Cunningham, et al. 2009; WHO, 2011; Leung, et al. 2013).
The City of Erie, Pennsylvania and several surrounding communities obtain their drinking
water directly from Lake Erie. In the City of Erie, lake water is treated at either one of two
treatment plants: the Wasielewski plant or the Chestnut Street plant. The Wasielewski plant is
the main treatment facility and has recently been upgraded with an ultrafiltration membrane
system replacing the previous sand filtration system. Although not required by law, Erie Water
Works tests its raw and finished water for a subset of PPCPs on a periodic basis. Most of the
PPCPs analyzed in the raw and treated water have been found in low or non-detect levels (Erie
Water Works, 2014).
4
PROJECT GOALS AND OBJECTIVES
The overall goal of this research project was to evaluate the exposure to and human health risks
associated with pharmaceuticals and personal care products (PPCPs) in drinking water
originating from Lake Erie. Three specific research objectives were identified and completed as
part of this project including:
● to determine the concentrations of 8 target PPCPs (acetaminophen, ampicillin, caffeine,
metformin, naproxen, sulfamethoxazole, triclosan, and trimethoprim) and an additional ten
analytes in raw and treated drinking water from Lake Erie;
● to evaluate whether the enzyme-linked immunosorbent assay (ELISA) is an effective
method for screening and characterizing PPCPs in drinking water; and
● to quantify the human health risks from exposure to trace levels of PPCPs in drinking
water from Lake Erie.
5
METHODOLOGY
OBJECTIVE 1: DETERMINATION OF THE CONCENTRATIONS OF TARGET
PPCPS
In this study short and long-term samples were collected between October 2016 and August
2017 from the Erie Water Works plant located in Erie, Pennsylvania (refer to Table 1). A total
of eight target analytes and ten additional analytes were quantified in the raw and treated water
samples. Analysis of the 18 target analytes was conducted by an outside accredited laboratory.
Additional samples collected in high-density polyethylene (HDPE) bottles were analyzed for
basic water quality parameters such as free chlorine, solids (TSS and TDS), and organic matter
(BOD and COD).
Table 1. Summary of PPCPs Included in this Study
ANALYTE USE
Acetaminophen Analgesic
Ampicillin Antibiotic
Atrazine Herbicide
Bisphenol-A Plasticizer
Caffeine Found in beverages and pharmaceuticals
Carbamazepine Anticonvulsant
Cimetidine Acid reducer
Ciprofloxacin Antibiotic
Digoxin Heart medication
Gemfibrozil Lipid regulator
Ibuprofen Nonsteroidal anti-inflammatory
Metformin Anti-diabetic
Naproxen Nonsteroidal anti-inflammatory
Simazine Herbicide
6
Sulfamethoxazole Antibiotic
Sulfathiazole Antibiotic
Triclosan Anti-microbial
Trimethoprim Antibiotic
1. Sampling site
The raw and treated water samples were collected from the Wasielewski water treatment plant.
The Wasielewski water treatment plant was used to treat drinking water via conventional sand
filtration system for 80 years, but has recently been retrofitted with an ultrafiltration membrane
system with a capacity of treating over 45 million gallons of water per day. Lake water is being
drawn from approximately 14.5 miles away from the treatment facility via an intake pipe that
runs underneath the Presque Isle peninsula. To monitor water quality at the water intake point,
Erie Water Works installed an additional pipeline from the water intake point to the water
treatment plant. This pipeline is currently being used for collecting raw water samples. Since
access to the water intake source by boat is not permitted due to security restrictions, for this
research project, raw water samples were collected at the sampling point located within the
low-duty pump station located on Sommerheim Drive. Treated water samples were collected
directly from the main supply pipe. Sampling locations within the facility are illustrated in
Figure 1.
7
(a)
(b)
Figure 1. (a) Location of the Wasielewski water treatment plant and (b) sampling points within the
Wasielewski water treatment plant
8
2. Sampling methods
2.1. Grab sampling
Raw and treated water sampling were conducted using the grab water sampling technique.
Samples were collected in two 1-liter-amber bottles (Fisher Scientific, USA). Since both raw-
and treated water samples may contain 0.5 to 5.0 mg/L of chlorine for disinfection purposes, 50
mg/L of ascorbic acid was added to the sampling bottles prior to sampling to prevent PPCP
degradation during shipping to the analytical lab (Urbansky and Schenck, 2000; USDA, 2005).
The grab samples were shipped to the analytical laboratory by overnight delivery and
maintained at temperatures below 4 oC. Researchers visited the sampling site on a weekly basis
to monitor water flow, status of the sampler, temperature, dissolved oxygen, conductivity, and
pH. Additional water samples were collected in 500-mL HDPE bottles (Fisher Scientific,
USA). The samples collected in HDPE bottles were delivered to the water quality lab at
Gannon University and stored in a refrigerator until analysis. The water samples were analyzed
for basic water quality parameters such as residual chlorine, total suspended solids (TSS), total
dissolved solids (TDS), BOD, and COD. All parameters were analyzed on the day of sample
collection.
2.2. Polar Organic Chemical Integrative Sampler (POCIS)
In addition to grab sampling, PPCPs in raw and treated water were collected using the Polar
Organic Chemical Integrative Sampler (POCIS). Unlike conventional sampling methods, such
as grab or composite sampling, that are useful for measuring the presence of contaminants at a
sampling moment, the POCIS was developed to collect lipophilic organic compounds over a
long period of time (USGS, 2004; Alvarez, 2010; Kaserzon, et al., 2014). The sampler consists
of a sorbent material that is sandwiched between two microporous membranes and a metal ring
supporting membranes. Different types of sorbent materials can be utilized within the device to
target specific types of compounds; in this research, OASISTM
HLB sorbent was used. Typical
deployment time for the sampler is one month after which the sorbent material undergoes an
extraction procedure to desorb contaminants followed by an appropriate analytical technique.
9
Techniques such as gas chromatography (GC) and mass spectroscopy (MS) or liquid
chromatography followed by MS are employed. The assembly of the POCIS is presented in
Figure 2.
(a)
(b)
(c) Figure 2. (a) an assembly of membrane discs and holder (b) and (c) sampling canister with POCIS
membrane discs and holder
10
2.3. POCIS deployment
The schematic for the deployment of the POCIS sampler in the sampling container is presented
in Figure 3. Two stainless-steel 10-gallon brew kettles were purchased from an online store
(homebrewsupply.com) and modified for POCIS sampling (Figure 4). The flow rates of water
passing through the POCIS samplers were controlled by a valve at the bottom of the container.
To prevent contamination from airborne organic compounds during sampling, the container
was covered with lid during the period of deployment. After POCIS sampling was completed,
the POCIS canister was retrieved and membrane discs were removed from the holders and
wrapped in aluminum foil. The PPCP membranes were stored in a freezer (>-20 oC) prior to
shipment to the analytical laboratory. For shipment, membrane discs were wrapped in
aluminum foil, placed in labeled ZiplocTM
bags and shipped to the analytical laboratory by
overnight delivery while maintained at temperatures below 4 oC.
Figure 3. A schematic of POCIS deployment setup (treated water)
11
(a)
(b)
Figure 4. Sampling containers installed at (a) water treatment plant and (b) low duty pump station
12
2.4. Sampling schedule
The schedule for grab sampling and POCIS deployment period are presented in Figure 5.
During the monitoring period, a total of 9 grab samples from each sampling site were collected,
and 6 POCIS were deployed/retrieved. The grab samples were collected on a monthly basis,
but the period of POCIS deployment varied; an average period of POCIS deployment for the
first three POCIS (POCIS-1, 2, and 3) was 30 days, but extended to over 60 days for the rest of
three POCIS (POCIS-4, 5 and 6). Water samples had not been collected since September in
2017 as the Wasielewski plant was closed for several months for maintenance purposes.
Figure 5. Sampling schedule for grab samples and POCIS sampler deployment
13
3. Analytical methods
Analysis of grab water samples and POCIS membranes for target PPCPs was conducted using
EPA Method 1694 at Anatek Labs, Inc. (Moscow, ID). For QA/QC purpose, a duplicate of DI
water spiked with 7 analytes (acetaminophen, caffeine, sulfamethoxazole, trimethoprim,
ibuprofen, naproxen and triclosan) was analyzed and compared to a lab blank to estimate
recovery %. As described in the sampling methods, researchers visited the sampling site on a
weekly basis and monitored water samples for pH (Accumet AP110, Fisher Scientific, US),
dissolved oxygen, temperature (Orion, Fisher Scientific, US) and conductivity (Corning 311,
Corning, US). The analytical methods used for analyzing additional water samples collected
on a weekly basis were Standard Method 2540D (TSS), Standard Method 2540C (TDS),
Standard Method 5220 (COD), Standard Method 5210 (BOD) and HACH Method 8021 (Free
Chlorine).
4. Determination of PPCP concentration in water phase from POCIS analytical results
Additional steps were required to determine the mass concentrations (mg/L) of PPCPs in the
aqueous phase from POCIS analytical results (mg PPCP / mass adsorbent in POCIS) as follows
(MacLeod et al., 2007):
Cw = Cs * ms / (Rs * t)
Where,
Cw = PPCP concentrations in water phase (mg/L)
Cs = PPCP concentrations in solid phase (mg/g POCIS)
ms = mass of sorbent (g)
Rs = sampling rates
t = time for testing sampling rates
.
The sampling rates (Rs) for each target compound were determined by a laboratory test and
literature review. Prior to the test, all glassware was thoroughly rinsed with HPLC grade
deionized water (Fisher Scientific, US). To determine the sampling rates, six 2-liter glass
beakers (Fisher Scientific, US) were filled with 1 L of HPLC grade deionized water (Fisher
Scientific, US), and four of them were fortified by 100 ug/L of 9 target PPCPs. A POCIS
14
sampler was placed in four of the six vessels (Test-1, 2, 3 and 6) and the other two vessels were
used as negative controls to determine any potential contaminants within the water or POCIS.
The water/analyte mixture was stirred at a slow speed to keep the analytes mixed, and at a
consistent concentration within the vessel. Each vessel was wrapped with aluminum foil to
prevent photo-degradation of PPCPs during the testing period. The tests were performed for 23
hours. After the testing period, the fortified water in each vessel was immediately transferred to
clean amber HDPE bottles and shipped to the analytical laboratory for PPCP analysis. Based on
the PPCPs analyzed, the sampling rates (Rs) of each 9 target PPCPs were estimated as follows
(Morin et al., 2012):
Rs = (Ci – Ct)/Ct * Vt / t
where Ci and Ct represent initial and final PPCP concentrations at time t (µg/L); Ct is PPCP
concentration at time t (mg/L), and Vt is total water volume. The experimental setup for
determining sampling rates is summarized in Table 2.
Table 2. A summary of experimental setup for determination of sampling rates
Test Solutions Conditions
1. Standards at 0.1 ppm in pure water + 1
POCIS disk (24 hours) ● Stirred for 23 hours ● Beaker covered with aluminum to protect
from light
● Room temperature 2. Standards at 0.1 ppm in pure water + 1
POCIS disk (24 hours)
3. Standards at 0.1 ppm in pure water + 1
POCIS disk (24 hours)
4. Standards at 0.1 ppm in pure water Initial test solution. Immediately placed in sampling bottle and
stored in refrigerator.
5. Pure water used for dilution. Blank. Immediately placed in sampling bottle and
stored in refrigerator.
6. Pure water + POCIS disk (24 hours) Blank. ● Stirred for 23 hours ● Beaker covered with aluminum to protect
from light
15
OBJECTIVE 2: COMPARISON OF ELISA WITH LC-MS-MS RESULTS
For the validation study, a set of dilutions were prepared in the lab according to Table 3 for
atrazine, triclosan and caffeine. Each control and separate analyte dilution were prepared in
triplicate in 1 liter of HPLC-grade water. All glassware and items used were cleaned with 10%
hydrochloric acid followed by a triple rinse with deionized water and reagent grade acetone.
The solvent was removed by heating glassware to 300 OF for 3 hours and then rinsing with
purified water prior to use.
Table 3. Summary of Dilutions and Replicates for Validation Study
Caffeine
(ng/L)
Atrazine
(ng/L)
Triclosan
(ng/L)
TOTAL
VOLUME
Replicate 1
Control 0.000 0.000 0.000 1 Liter
Dilution 1 0.250 0.250 0.250 1 Liter
Dilution 2 0.500 0.500 0.500 1 Liter
Dilution 3 1.000 1.000 1.000 1 Liter
Dilution 4 2.500 2.500 2.500 1 Liter
Replicate 2
Control 0.000 0.000 0.000 1 Liter
Dilution 1 0.250 0.250 0.250 1 Liter
Dilution 2 0.500 0.500 0.500 1 Liter
Dilution 3 1.000 1.000 1.000 1 Liter
Dilution 4 2.500 2.500 2.500 1 Liter
Replicate 3
Control 0.000 0.000 0.000 1 Liter
Dilution 1 0.250 0.250 0.250 1 Liter
Dilution 2 0.500 0.500 0.500 1 Liter
Dilution 3 1.000 1.000 1.000 1 Liter
Dilution 4 2.500 2.500 2.500 1 Liter
Analytes were purchased from Absolute Standards, Inc. (Hamden, CT) in 1 mL aliquots at a
certified concentration of 1 mg/mL each. Dilutions were prepared using a Brand Handystep
electronic autopipette with disposable 1 mL pipette tips. Samples were prepared by a serial
dilution technique; 1:10 or 1:50 dilution was made by adding 1 part of stock solution to either 9
or 49 part of HPLC grade deionized water, and the same steps were repeated until target
dilution ratio reached. At every step, a solution mixture was mixed by mechanical stirrer for at
least 30 minutes.
16
Spiked one-liter samples for each dilution were split and analyzed separately for three PPCP
concentrations (atrazine, triclosan and caffeine) using both the ELISA test and LC-MS-MS. A
total of 100 mLs of each control and spiked sample were put into clean glass amber jars and
shipped overnight on ice to Anatek Labs (Moscow, ID). Samples were analyzed using EPA
method 1694 as previously described.
The ELISA test was performed according to the manufacturer’s instructions (Abraxis, 2008A,
2008B, 2010). The controls, samples and standards for atrazine, triclosan and caffeine were
added to the microplate wells, then followed by the relevant antibody and enzyme. After the
required incubation time, the microplate was rinsed with the washing buffer solution to remove
unreacted constituents. The color indicator (substrate) was then added to the rinsed plate to
estimate the total amount of target PPCP (analyte) bound to the conjugated enzyme by color
change. As a result, the concentrations of PPCP were determined by measuring the light
absorbance of individual wells using a Biotek Epoch microplate spectrophotometer. Standard
curves were constructed for each analyte by plotting the B/Bo for each standard on a vertical
logit (Y) axis versus the corresponding analyte concentration on a horizontal logarithmic (X)
axis. Data logging and analysis was performed using the Gen5TM
data analysis software,
version 3.022. Minimum detection limits for each respective ELISA kit are 0.04 ng/L for
atrazine, 0.02 ng/L for triclosan and 0.15 ng/L for caffeine (Abraxis, 2008A, 2008B, 2010).
Calibration linearity, bias, precision and method detection limits were determined using the
protocols outlined in EPA method validation guidelines (USEPA, 1999, 2014). Calibration
curve and linearity were assessed using the standards provided in each of the ELISA test kits
for atrazine, triclosan and caffeine respectively.
Agreement between ELISA and LC-MS-MS results was assessed with NCSS software, version
12 (NCSS, 2018) by utilizing correlation analysis (Pearson product moment) and the
construction of Bland-Altman plots.
17
OBJECTIVE 3: HUMAN HEALTH RISK ASSESSMENT
For those compounds that are found in detectable levels within drinking water, a cumulative
risk assessment was performed to estimate the long term human health risks from exposure to
these compounds. The process for determining the cumulative noncancer risk estimates from
exposure to PPCPs in drinking water begins with a determination of the Acceptable Daily
Intake (ADI) for each of the detected compounds. These values were obtained from a
comprehensive review of the literature (Schwab, et al., 2005; USEPA, 2008; Cunningham, et
al., 2009; Jeong, 2009; NACWA, 2010; Gaffney, et al., 2015; Minnesota DOH, 2017).
The most conservative ADI found for each PPCP was used to calculate a drinking water
exposure level (DWEL) representing an estimate of the PPCP dose that a person drinking tap
water with measured concentrations would be exposed to in µg/kg-day. DWELs are
determined by utilizing default values for exposure parameters such as daily water intake, body
weight, etc. per EPA guidance (USEPA, 2008; USEPA, 2011). The general formula is:
RSC represents the relative source contribution from tap water in which PPCPs were measured
(generally assumed to be 100%). A unit conversion of 1,000 is applied to convert
concentrations from micrograms to nanograms. BW represents body weight which is 70 Kg for
an average adult (USEPA, 2011). IR is 2 L/day representing the 90th
percentile ingestion rate
for drinking water for an average adult (USEPA, 2011).
Risk quotients (RQs) were calculated which represent the estimated noncancer risk for each
PPCP. These were calculated by dividing the maximum PPCP concentration measured in
treated water samples by the calculated DWEL. Compounds with risk quotients ≥1 are
considered to potentially affect human health. The combined risk for the PPCP mixture was
calculated by summing across the individual RQs for each PPCP.
An additional risk calculation included the use of the margin of exposure (MOE) approach to
calculate the number of glasses of water that would need to be consumed to exceed the drinking
water guideline value for each compound (Snyder, et al., 2003; NYC DEC, 2011).
18
Table 4. Summary of RfD values for Target PPCPs
19
RESULTS AND DISCUSSION
OBJECTIVE 1: DETERMINATION OF THE CONCENTRATIONS OF TARGET
PPCPS
1. General water quality
Water quality data are presented in Table 5 and Table 13 in Appendix. Since dissolved oxygen
(DO) concentrations are temperature dependent, DO results are presented separately in Figure 6.
As shown in Figure 6, both raw and treated water samples were nearly saturated with oxygen at
given temperatures across all sampling period. The pH, conductivity, TSS, TDS, BOD and
COD were not significantly different between raw and treated water samples according to the
analysis of variance (ANOVA) test results at the 0.05 level of significance. It is noted that a
low level of chlorine (approximately 0.1 mg/L) is added to the raw water intake for the purpose
of preventing the strainers from becoming clogged by mussels.
Figure 6. Temperature and dissolved oxygen concentrations of water samples over time
20
Table 5. Analytical results of raw- and treated water samples for basic water quality parameters (total
number of samples = 45)
Parameters Raw Treated
pH 8.12 +/- 0.22 8.08 +/- 0.14
Conductivity (µS/cm) 305.7 +/- 455.7 311.4 +/- 471.9
TSS (mg/L) 1.11E-04 +/- 1.65E-04 3.76E-05 +/- 7.97E-05
TDS (mg/L) 2.16E-04 +/- 5.54E-04 2.81E-04 +/-6.75E-04
Chlorine (mg/L) 0.14 +/- 0.18 1.32 +/- 0.22
BOD (mg/L) 1.50 +/- 1.14 1.51 +/- 1.12
COD (mg/L) 47.6 +/- 45.5 34.2 +/- 23.4
2. Sampling rates
The sampling rates obtained in the test are presented in Table 6. As outlined in the Method
Section, sampling rates were estimated by analytes removal rates, reaction time and volume of
water. The average values of sampling rates of triplicates (Std Mix #1, #2 and #3) were used
for estimating analytes concentrations in the water phase (Cw). The sampling rates obtained in
the test were compared to the values in literature for validation purpose; average sampling rates
were similar to those reported in the literature. It is noted that the average values of sampling
rates reported in Li et al (2010) (1.283 L/day) were adopted for triclosan because the
concentrations of the residual triclosan in the standard mix after reaction were all below
detection limits (< 10 ug/L).
21
Table 6. POCIS sampling rates results estimated from analytes remained in the solution Std Mix
#1
(ng/mL)
Sampling
rates
Std Mix
#2
(ng/mL)
Sampling
rates
Std Mix
#3
(ng/mL)
Sampling
rates
Sampling rates Sampling rates in literature
Acetaminophen 87.2 0.123 86.2 0.132 96.9 0.030 0.095 +/- 0.057 0.145 (±0.033)
0.139 (±0.011)
0.111 (±0.016)
Li et al
2010
Altrazine 34.3 0.630 45.7 0.520 43.9 0.538 0.563 +/- 0.059
Ampicillin 31 0.661 26.4 0.705 47.6 0.502 0.623 +/- 0.107
BPA 16.4 0.801 24.3 0.725 23.9 0.729 0.752 +/- 0.043 0.531±0.063
0.740±0.036
0.835±0.058
0.482±0.066
Li et al
Caffeine 76.9 0.221 83.4 0.159 81.6 0.176 0.186 +/- 0.032 0.127 (±0.021)
0.096 (±0.008)
0.151 (±0.018)
Li et al
2010
0.2±0.097 Brown et
al
0.27 Zenobio
et al
Carbamazepine
59.9 0.384 69.1 0.296 72.6 0.263 0.314 +/- 0.063 0.230±0.016
0.397±0.018
0.561±0.024
0.235±0.046
Li et al
0.112±0.023
0.348±0.116
Macleod
et al
0.227±0.045 Brown et
al
Cimetidine 19.9 0.768 20.6 0.761 24.4 0.725 0.751 +/- 0.023
Ciprofloxacin 22.3 0.745 37.4 0.600 32.8 0.644 0.663 +/- 0.074
Digoxin 79.7 0.195 79.5 0.196 90.6 0.090 0.16 +/- 0.061
Gemfimbrozil 33.7 0.635 47 0.508 42.5 0.551 0.565 +/- 0.065 0.257±0.005
0.306±0.031
0.350±0.012
0.222±0.014
Li et al
Ibuprofen 59.4 0.389 69.3 0.294 68 0.307 0.33 +/- 0.052 0.204±0.004 Li et al
22
0.254±0.019
0.348±0.052
0.197±0.013
Metformin 92.6 0.071 88.9 0.106 91.7 0.080 0.086 +/- 0.018
Naproxen 53.1 0.449 66 0.326 62.9 0.356 0.377 +/- 0.065 0.392 (±0.024)
0.298 (0.016)
0.239 (±0.009)
0.200 (±±0.037)
Li et al
Simazine 37.6 0.598 52.4 0.456 48.9 0.490 0.515 +/- 0.074 0.223
0.119
0.21
0.081
Harman
et al
Sulfathiazole 64 0.345 79.7 0.195 73.2 0.257 0.265 +/- 0.076 0.22
0.187
Harman
et al
Sulfamethoxazole 67.1 0.315 81.1 0.181 72.7 0.262 0.253 +/- 0.068 0.339 (±0.057)
0.348 (±0.049)
0.291 (±0.004)
0.202 (±0.019)
Li et al
Triclosan < 10 - < 10 - < 10 - - 1.929 (±0.232)
1.442 (±0.105)
1.006 (±0.037)
0.753 (±0.081)
Li et al
Trimethoprim 40.1 0.574 58.2 0.401 46.7 0.511 0.495 +/- 0.088 0.436 (±0.006)
0.411 (±0.073)
0.213 (±0.035)
0.215 (±0.003)
Li et al
23
3. PPCPs in Grab samples
The concentrations of the analytes found in individual grab samples are presented in Table 10
in the Appendix, and average concentrations and standard deviation of analytes found in grab
samples are summarized in Table 7. With the exception of a few analytes, concentrations of
most observed analytes were below detection limits. The frequencies of detection of individual
PPCPs in grab samples are illustrated in Figure 7. Among the18 analytes, atrazine was found
in all raw water samples and caffeine was found in all raw and treated water samples.
Metformin was detected in 6 raw water samples (67%), and simazine was detected in 5 raw
water samples (56%). On comparing PPCPs in raw and treated water samples, no detectable
levels of BPA, ibuprofen or metformin were detected in treated water samples although they
were detected in at least one raw sample. This suggests that these analytes were removed or
reduced in concentrations below detection limits by the water treatment system (ultrafiltration
membrane system). On the contrary, detectable concentrations of atrazine, caffeine and
simazine still remained in treated water samples. Comparing concentrations of atrazine,
caffeine and simazine in raw and treated water, approximately 31% and 36% of atrazine and
caffeine were removed by the water treatment system, respectively.
24
Figure 7. Frequency of detection of PPCPs in raw and treated samples (grab samples)
Frequency, % (total number of samples = 9)
0 20 40 60 80 100
Trimethoprim
Triclosan
Sulfathiazole
Sulfamethoxazole
Simazine
Naproxen
Metformin
Ibuprofen
Gemfibrozil
Digoxin
Ciprofloxacin
Cimetidine
Carbamazepine
Caffeine
Bisphenol-A
Atrazine
Ampicillin
Acetaminophen
Treated Water Raw Water
25
Table 7. A summary of PPCPs in grab samples
Analyte
Raw Water (ng/L)
Treated Water
(ng/L)
Avg St dev Avg St dev
Acetaminophen <MDL* <MDL <MDL <MDL
Ampicillin <MDL <MDL <MDL <MDL
Atrazine 50.34 31.99 41.26 34.52
Bisphenol-A 91.44 88.20 <MDL <MDL
Caffeine 124.97 207.90 39.88 59.68
Carbamazepine <MDL <MDL <MDL <MDL
Cimetidine <MDL <MDL <MDL <MDL
Ciprofloxacin <MDL <MDL <MDL <MDL
Digoxin <MDL <MDL <MDL <MDL
Gemfibrozil <MDL <MDL <MDL <MDL
Ibuprofen 1.13 <MDL <MDL <MDL
Metformin 58.15 62.75 <MDL <MDL
Naproxen <MDL <MDL <MDL <MDL
Simazine 4.01 2.07 3.74 2.61
Sulfamethoxazole <MDL <MDL <MDL <MDL
Sulfathiazole <MDL <MDL <MDL <MDL
Triclosan <MDL <MDL <MDL <MDL
Trimethoprim <MDL <MDL <MDL <MDL
* MDL (method detection limits): method detection limits varied depending on the types of analyte
4. POCIS sampler results
Figure 8 shows the frequencies of PPCP detection in the POCIS samplers. As described in the
Method Section, the POCIS samplers were deployed at the sampling sites for 1 to 2 months. In
addition to 6 PPCPs found in grab samples, a total of 10 analytes were found at detectable level
in the POCIS samplers. Unlike grab samples, however, metformin was not detected in any
26
POCIS samplers. Among 16 PPCPs of interest, metformin is the only aliphatic compound that
contains no benzene-ring; therefore, metformin would potentially be more susceptible to
biological and/or chemical decomposition. Analyte decomposition or modification cannot be
ruled out since deployment of the sampler was conducted within chlorinated water for 1 to 2
months. On comparing types of analytes at detectable levels found in grab samples and in
POCIS samplers, detectable levels of gemfibrozil, naproxen, sulfamethoxazole and
trimethoprim were found only in POCIS samplers. It is noted that these four PPCPs were
found only once when the deployment period was extended to 60 days. For 30-day deployment,
only atrazine, caffeine and simazine were found in detectable levels within the POCIS
samplers.
The average and standard deviation of concentrations of analytes estimated using analytical
results, sampling rates and deployment periods are summarized in Table 8. Analytical results
of individual POCIS samplers and analyte concentrations in the water phase are presented in
Table 11in Appendix. The analyte levels represent the average concentrations during the
period of deployment. Among 10 analytes found in the POCIS samplers, atrazine, caffeine and
simazine were found in all POCIS samplers. On comparing the concentrations of those analytes
in raw and treated waters (Figure 9), approximately 22%, 36% and 27% of atrazine, caffeine
and simazine, respectively, were potentially removed by the water treatment system.
27
Figure 8. Frequency of detection of PPCPs in POCIS samplers
Frequency, % (total number of samples = 6)
0 20 40 60 80 100
Trimethoprim
Triclosan
Sulfathiazole
Sulfamethoxazole
Simazine
Naproxen
Metformin
Ibuprofen
Gemfibrozil
Digoxin
Ciprofloxacin
Cimetidine
Carbamazepine
Caffeine
Bisphenol-A
Atrazine
Ampicillin
Acetaminophen
Treated Water Raw Water
28
Table 8. A summary of concentrations of PPCPs estimated based on POCIS analytical results
Analytes Raw water (ng/L) Treated water (ng/L)
average std average std
Acetaminophen <MDL <MDL <MDL <MDL
Ampicillin <MDL <MDL <MDL <MDL
Atrazine 12.97 6.34 10.41 5.51
Bisphenol-A 0.31 <MDL <MDL <MDL
Caffeine 2.21 2.39 0.98 0.49
Carbamazepine 1.41 0.32 0.34 0.10
Cimetidine <MDL <MDL <MDL <MDL
Ciprofloxacin <MDL <MDL <MDL <MDL
Digoxin <MDL <MDL <MDL <MDL
Gemfibrozil 0.69 1.00 0.22 <MDL
Ibuprofen 0.63 <MDL <MDL <MDL
Metformin <MDL <MDL <MDL <MDL
Naproxen 0.36 <MDL <MDL <MDL
Simazine 1.18 0.46 0.82 0.26
Sulfamethoxazole 0.38 <MDL <MDL <MDL
Sulfathiazole <MDL <MDL <MDL <MDL
Triclosan <MDL <MDL <MDL <MDL
Trimethoprim 0.19 1E<MDL05 <MDL <MDL
29
Figure 9. Comparison of atrazine, caffeine and simazine concentrations in raw and treated water
samples (retrieved from POCIS sampler analytical results)
30
OBJECTIVE 2: ELISA VERSUS ANALYTICAL RESULTS
The agreement between ELISA and LC-MS-MS results show comparable results for the three
analytes. Figures 10 through 12 show the scatter and Bland-Altman plots to compare the
results obtained between the two methods. The analyte showing the most consistent and
accurate results between the ELISA test and analytical results is atrazine, with a correlation
coefficient of 0.99 (p<0.001) and a bias of 0.23. This value indicates that the ELISA test was
biased in the positive direction as concentrations were consistently higher than that from LC-
MS-MS. The correlation between the two methods for triclosan resulted in a correlation
coefficient of 0.96 (p<0.001) and a bias of 0.21. The results of the method comparison for
caffeine showed a relatively high correlation coefficient (r) with values of 0.984 and a bias of -
0.59. This latter result indicates that ELISA concentrations were consistently lower (negatively
biased) by 0.59 compared to LC-MS-MS.
Figure 10. Scatterplot and Bland-Altman plots from LC-MS/MS and ELISA test for atrazine at various
dilutions (3 replicates)
31
Figure 11. Scatterplot and Bland-Altman plots from LC-MS/MS and ELISA test for triclosan at various
dilutions (3 replicates)
Figure 12. Scatterplot of results from LC-MS/MS and ELISA test for caffeine at various dilutions (3
replicates)
32
OBJECTIVE 3: HUMAN HEALTH RISK ASSESSMENT
Table 9 summarizes the results of the health risk assessment. The maximum measured value of
each PPCP from grab sampling was compared with that of the DWEL and the more
conservative screening values. Only three (atrazine, caffeine and simazine) of the 18 PPCPs
measured in the grab samples had values above the method detection limit (MDL). All
measured PPCP concentrations were below both the DWELs and screening values. The
cumulative non-cancer risk calculation (risk quotient = measured concentration divided by the
DWEL) was found to be negligible and less than 0.003. This risk estimate includes the MDL
in the calculation for all 15 PPCPs that were found in concentrations below its respective MDL.
A risk quotient approaching 1 and greater would be of concern.
33
Table 9. Summary of Risk Calculations using Maximum PPCP Values in Treated Drinking Water
Analyte ADI/RfD
(µg/kg-dy)
DWEL
(µg/L)
SCREENING
VALUE or
HEALTH RISK
LEVEL
(µg/L)
MAX
VALUE
treated water
sample
(µg/L)
Risk Quotient
(RQ)
Source of ADI/RfD
Acetaminophen 250 8750 2002
<.0025 2.9E-07 Minnesota Dept. of
Health, 2015a
Ampicillin 1.6 56 101
<.0025 4.5E-05 WHO, 2017
Atrazine 3.5 123 32
0.118 9.6E-04 EPA, 1993a
Bisphenol-A 50 1750 201
<.0025 1.4E-06 EPA, 1988
Caffeine 150 5250 .197 3.8E-05 Gaffney, et al, 2015
Carbamazepine 0.34 11.9 402
<.0025 2.1E-04 NACWA, 2010
Cimetidine 28.6 1001 301
<.0025 2.5E-06 Cunningham et al,
2009
Ciprofloxacin 0.15 5.25 61
<.0025 4.8E-04 Jeong et al, 2009
Digoxin 0.071 2.485 0.00041
<.0025 1.0E-03 Cunningham et al,
2009
Gemfibrozil 1.3 45.5 101
<.0025 5.5E-05 NACWA, 2010
Ibuprofen 6.7 234.5 51
<.001 4.3E-06 Minnesota Dept. of
Health, 2017
Metformin 79.4 2779 41
<.0025 9.0E-07 Cunningham et al,
2009
Naproxen 46 1610 201
<.001 6.2E-07 Gaffney, et al 2015
Simazine 5 175 42
.0071 4.1E-05 EPA, 1993b
34
Sulfamethoxazole 510 17850 1002
<.0025 1.4E-07 NACWA, 2010
Sulfathiazole 130 4550 11
<.0025 5.5E-07 Gaffney, et al, 2015
Triclosan 67 2345 502
<.0025 1.1E-06 Minnesota Dept. of
Health, 2015b
Trimethoprim 190 6650 41
<.0025 3.8E-07 NACWA, 2010
Cumulative RQ
2.8E-03
1 Minnesota Department of Health (2018), Pharmaceutical Water Screening Values Report. 2 Minnesota Department of Health Human Health-based Water Guidance Table, Accessed on 9/18/18 at http://www.health.state.mn.us/divs/eh/risk/guidance/gw/table.html
35
CONCLUSION
The results of this project have benefits to a broad audience that includes the general
public, water quality officials and the scientific community. The monitoring component
provided meaningful results about the quality of the drinking water as it relates to the analytes
assessed in this study. The 18 analytes were all found at very low or non-detect levels. In a
majority of cases, analyte concentrations were lower in treated water compared to raw water
from Lake Erie showing the effectiveness of the ultrafiltration membrane system. The results
of the human health risk assessment component confirm that the level of the 18 PPCPs
measured within the treated water pose an insignificant risk to the community.
The method evaluation component yielded practical information about the comparability
between ELISA testing and laboratory analysis using LC-MS-MS for PPCP quantification.
The two methods show moderate to high comparability for atrazine, triclosan and caffeine as
shown in the results section. ELISA testing is a much faster and cheaper test allowing for rapid
testing of water samples and may be useful for screening specific target analytes.
The development of a methodology for evaluating the human health risks of these
compounds in drinking water will offer a model for water quality officials to assess the human
health risks of multiple compounds. It is anticipated that the risk assessment spreadsheet could
be used to help guide risk management decisions. Additionally, this project offers benefits to
the scientific community by adding additional sampling rate values for the POCIS sampler; a
method evaluation study of ELISA results to that of analytical lab techniques (i.e., GC-MS);
and methods for determining the human health risks from PPCPs in drinking water.
FUTURE RESEARCH
The major conclusion from this study is that the water used for drinking water for the City of
Erie has low or below detectable levels of certain PPCPs that pose insignificant known human
health risks. As a result of this conclusion, several additional lines of inquiry in future studies
include:
36
● To quantify the levels of other PPCPs that were not included in this study (i.e.,
opioids, pesticides, personal care products and other emerging contaminants of
concern)
● To evaluate the levels of PPCPs within both the influent and effluent of the waste
water treatment plant.
● To evaluate the levels of PPCPs in tributaries to and in Presque Isle Bay and Lake
Erie.
37
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Water Samples (Microtiter plate). Abraxis, Inc, Warminster, PA.
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Water Samples (Microtiter plate). Abraxis, Inc, Warminster, PA.
Abraxis (2010). User Instructions for Enzyme-Linked Immunosorbent Assay for the Determination of Atrazine in
Water Samples (Microtiter plate). Abraxis, Inc, Warminster, PA.
Alliance for the Great Lakes (2010). Protecting the Great Lakes from Pharmaceutical Pollution, Accessed 9/12/17 at
https://cdn.ymaws.com/www.productstewardship.us/resource/resmgr/imported/GLAReport2010.pdf
Alvarez, D.A. (2010). Guidelines for the use of the semipermeable membrane device (SPMD) and the polar organic
chemical integrative sampler (POCIS) in environmental monitoring studies: U.S. Geological Survey,
Techniques and Methods 1–D4, 28 p.
Blair B.D., Crago J.P., Hedman C.J., and Klaper R.D. (2013). Pharmaceuticals and personal care products found in
the Great Lakes above concentrations of environmental concern. Chemosphere 93(9): 2116-2123.
Brown, DelShawn. "Use of Passive Samplers to Evaluate Pharmaceutical Fate in Surface Waters." N.p., 1 May 2010.
Cunningham V.L., Binks S.P., Olson M.J. (2009). Human health risk assessment from the presence of human
pharmaceuticals in the aquatic environment. Regul Toxicol Pharmacol. 53(1):39-45.
Erie Waters Works (2014). Laboratory Report: Pharmaceutical Testing Group Report No. 494880 (9/21/2014).
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health risk assessment. Water Res. 72:199-208.
Harman, C., Allan, I. J., & Vermeirssen, E. L. M. (2012). Calibration and use of the polar organic chemical
integrative sampler-a critical review. Environmental Toxicology and Chemistry, 31(12): 2724-2738.
Henderson A.K., et al. (1999). Presence of Wastewater Tracers and Endocrine Disrupting Chemicals in Treated
Wastewater Effluent and in Municipal Drinking Water, Metropolitan Atlanta, 1999. Accessed 9/12/15 at
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Jeong SH, Song YK, Cho JH (2009). Risk assessment of ciprofloxacin, flavomycin, olaquindox and colistin sulfate
based on microbiological impact on human gut biota. Regul Toxicol Pharmacol. Apr;53(3)
Kaserzon, S.L.; Hawker, D.W.; Kennedy, K.; Bartkow, M.; Carter, S.; Booij, K.; Mueller, J.F. (2014).
Characterization and comparison of the uptake of ionizable and polar pesticides, pharmaceuticals and personal
care products by POCIS and Chemcatchers. Environ Sci-Proc Imp. 16: 2517-2526.
Leung H.W., Ling J., Wei, S., et al. (2013). Pharmaceuticals in Tap Water: Human Health Risk Assessment and
Proposed Monitoring Framework in China. Environ Health Perspectives 121(7): 839-846.
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Li, H.X., Helm, P.A., Metcalfe, C.D. (2010). Sampling in the Great Lakes for Pharmaceuticals, Personal Care
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Environ Toxicol Chem. 29:751-762.
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Environ Toxicol Chem. 26:2517-2529.
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http://www.health.state.mn.us/divs/eh/risk/guidance/dwec/sumacetamin.pdf.
Minnesota Department of Health (2015b). Toxicological Summary for Triclosan. Accessed 9/1/18 at:
http://www.health.state.mn.us/divs/eh/risk/guidance/gw/triclosan.pdf.
Minnesota Department of Health (2017). Pharmaceutical Water Screening Values Report Methods and Results of
Rapid Assessments for Pharmaceuticals. Accessed on 9/8/18 at:
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applications of the polar organic chemical integrative sampler (POCIS) in aquatic environments. Trac-Trend
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Schwab B., Hayes E.P., Fiori J.M., Frank J. Mastrocco F.J.,Roden N.M., Cragin D., Meyerhoff R.D., D’Aco V.J.
and Anderson P. (2005). Human pharmaceuticals in US surface waters: A human health risk assessment.
Regulatory Toxicology and Pharmacology 42, 296–312.
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and Anderson P. (2005). Human pharmaceuticals in US surface waters: A human health risk assessment.
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(IRIS) Chemical Assessment Summary.
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(IRIS) Chemical Assessment Summary.
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(IRIS) Chemical Assessment Summary.
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U.S. Environmental Protection Agency (2007), Method 1694: Pharmaceuticals and Personal Care Products in Water,
Soil, Sediment, and Biosolids by HPLC/MS/MS, EPA 821-R-08-002, Office of Water, Washington DC.
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Protection Agency, Washington, DC, SW-846 Chapter 1.
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Center. Accessed 9/12/15 at: http://www.cerc.usgs.gov/pubs/center/pdfDocs/POCIS.pdf
Urbansky, E. T., & Schenck, K. M. (2000). Ascorbic acid reduction of active chlorine prior to determining Ames
mutagenicity of chlorinated natural organic matter (NOM). Journal of Environmental Monitoring, 2(2): 161-
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Zenobio, J. E., Sanchez, B. C., Leet, J. K., Archuleta, L. C., & Sepulveda, M. S. (2015). Presence and effects of
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750-755
40
APPENDIX A: METRICS
UNDERGRADUATE AND GRADUATE STUDENT SUPPORT:
Student Degree Job upon graduation Emily Hesch MS in Environmental Health &
Engineering, December 2017 Chemist, Erie Wastewater
Treatment Plant Colleen Lawrence MS in Environmental Health &
Engineering, May 2018 not currently employed
Matthew Loughner MS in Environmental Health &
Engineering, in progress (May
2019 graduation date)
currently employed at
Gannon university as a
Graduate Research
Assistant and at Lord
Corporation in
Environmental Health &
Safety Internship.
FACULTY AND STAFF SUPPORT:
Faculty Title FTE
Michelle Homan, Ph.D. Professor and Chair 0.79
Hwidong Kim, Ph.D. Associate Professor 0.94
PUBLICATIONS:
Hesch, Emily (2017). “Pharmaceuticals and Personal Care Products (PPCPs) within
Wastewater Effluent and Lake Erie in the Erie, Pennsylvania Area.” Research project report
submitted in fulfillment of the requirements for the M.S. degree in Environmental Health &
Engineering, Gannon University, December 2017.
PUBLIC AND PROFESSIONAL PRESENTATIONS, AND ATTENDEES:
No presentations to-date. Two presentations are planned for 2018 to present the ELISA
validation study and the results of the PPCP concentrations in raw and treated water.
PROJECT COLLABORATORS:
o Erie Water Works
o Erie Wastewater Treatment Plant
41
APPENDIX B: IMPACT AND/OR ACCOMPLISHMENT
STATEMENT(S)
IMPACT STATEMENTS
o The sampling results for this study demonstrate the effectiveness of the current drinking
water system in Erie, PA in reducing the amount of PPCPs in City’s drinking water.
o The results of the method comparison evaluation show good agreement between the ELISA
test and laboratory analysis. These results suggest that the ELISA could be a practical,
relatively low-cost screening test to determine the presence of selected PPCPs in drinking
water.
o The levels of the 18 PPCPs measured in the City of Erie’s drinking water pose minimal
risks to the community. All measured concentrations were orders of magnitude below
minimum risk values.
ACCOMPLISHMENT STATEMENTS
This study used procedures to evaluate the human health risks from trace levels of PPCPs
in drinking water. These same procedures can be used by water quality managers to
evaluate risks by entering future PPCP monitoring results into the risk spreadsheet. This
spreadsheet may need to be updated to include emerging PPCPs and changes in toxicity
values used to calculate risks.
STATEMENT FORMAT
o Title: Evaluation of Exposure to and Human Health Risks from PCPPs in Drinking Water
from Lake Erie.
o Collaborators: Gannon University and Erie Water Works
o Recap: This research project evaluated the levels of 18 pharmaceuticals and personal care
products (PPCPs) in raw and drinking water from Lake Erie as well as estimating human
health risks.
42
o Relevance: Public concern of the potential health risks associated with PPCPs in drinking
water have recently increased as a result of studies documenting their presence in surface,
ground and treated drinking water. This study looks at whether there are human health
risks from exposure to PPCPs from drinking water from Lake Erie for residents of the City
of Erie, PA.
o Response: Researchers from Gannon University collected raw and treated water samples
from the Wasielewski Treatment Facility which supplies drinking water for the City of
Erie, PA. Both grab and long-term samples were analyzed for the presence of 20 PPCPs.
PPCP concentrations were then used to estimate human health risks from exposure to these
chemicals within the drinking water.
o Results: The results comparing raw and treated water samples show a decline in almost all
analytes upon treatment demonstrating the effectiveness of the ultrafiltration membrane
system. The levels of PPCPs found were low in source waters and were reduced to lower
levels upon water treatment. This study suggests that there are low human health risks
from exposure to the 18 PPCPs included in this study.
43
APPENDIX C: RAW DATA
Table 10 (Appendix). PPCP concentrations in grab samples
Sampling date 10/31/2016 11/30/2016 1/17/2017
Analytes
Treated
Water
(ng/L)
Raw Water
(ng/L)
Treated
Water
(ng/L)
Raw Water
(ng/L)
Treated
Water
(ng/L)
Raw Water
(ng/L)
Acetaminophen < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ampicillin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Atrazine 50.7 50.4 < 1.0 52.4 37.7 53
Bisphenol-A < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Caffeine 18.1 16.7 4.48 20.2 9.64 30.6
Carbamazepine < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Cimetidine < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ciprofloxacin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Digoxin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Gemfibrozil < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ibuprofen < 1.0 < 1.0 < 1.0 1.13 < 1.0 < 1.0
Metformin < 2.5 < 2.5 < 2.5 19.8 < 2.5 < 2.5
Naproxen < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0
Simazine < 1.0 < 1.0 < 1.0 <1.0 2.08 1.48
Sulfamethoxazole < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Sulfathiazole < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Triclosan < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Trimethoprim < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
44
Table 10 (Appendix). PPCP concentrations in grab samples (continued)
Sampling date 2/27/2017 3/28/2017 5/3/2017
Analytes
Treated
Water
(ng/L)
Raw Water
(ng/L) Treated
Water
(ng/L)
Raw Water
(ng/L) Treated
Water
(ng/L)
Raw Water
(ng/L)
Acetaminophen < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ampicillin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Atrazine 19.3 25.6 19.9 23.7 8.01 35.2
Bisphenol-A < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Caffeine 22.2 16.9 27.3 26.7 29.3 30.6
Carbamazepine < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Cimetidine < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ciprofloxacin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Digoxin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Gemfibrozil < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ibuprofen < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0
Metformin < 2.5 0.0585 < 2.5 < 2.5 < 2.5 0.0585
Naproxen < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0
Simazine < 1.0 < 1.0 4.48 3.4 < 1.0 6.31
Sulfamethoxazole < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Sulfathiazole < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Triclosan < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Trimethoprim < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
45
Table 10 (Appendix). PPCP concentrations in grab samples (continued)
Sampling date 6/8/2017 7/13/2017 8/23/2017
Analytes
Treated
Water
(ng/L)
Raw Water
(ng/L) Treated
Water
(ng/L)
Raw Water
(ng/L) Treated
Water
(ng/L)
Raw Water
(ng/L)
Acetaminophen < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ampicillin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Atrazine 26.2 33.7 118 130 50.3 49.1
Bisphenol-A < 2.5 0.0055 < 2.5 98.3 < 2.5 176
Caffeine 197 196 34.5 134 16.4 653
Carbamazepine < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Cimetidine < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ciprofloxacin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Digoxin < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Gemfibrozil < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Ibuprofen < 1.0 < 1.0 < 1.0 < 2.5 < 1.0 < 2.5
Metformin < 2.5 116 < 2.5 148 < 2.5 65
Naproxen < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0
Simazine < 1.0 <1.0 7.09 5.96 1.32 2.89
Sulfamethoxazole < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Sulfathiazole < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Triclosan < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
Trimethoprim < 2.5 < 2.5 < 2.5 < 2.5 < 2.5 < 2.5
46
Table 11 (Appendix). PPCP concentrations in POCIS samplers
Sampling Date 11/30/2016
Analytes Treated
(ug/pocis) Cw (ng/L)
Raw
(ug/pocis) Cw (ng/L)
Acetaminophen < 0.005 <MDL < 0.005 <MDL
Ampicillin < 0.010 <MDL < 0.010 <MDL
Atrazine 0.69 15.279 0.919 20.350
Bisphenol-A < 0.010 <MDL < 0.010 <MDL
Caffeine 0.00756 0.510 0.0136 0.918
Carbamazepine < 0.005 <MDL < 0.005 <MDL
Cimetidine < 0.005 <MDL < 0.005 <MDL
Ciprofloxacin < 0.005 <MDL < 0.005 <MDL
Digoxin < 0.010 <MDL < 0.010 <MDL
Gemfibrozil < 0.005 <MDL < 0.005 <MDL
Ibuprofen < 0.005 <MDL < 0.005 <MDL
Metformin < 0.005 <MDL < 0.005 <MDL
Naproxen < 0.005 <MDL < 0.005 <MDL
Simazine 0.045 1.094 0.0655 1.592
Sulfamethoxazole < 0.005 <MDL < 0.005 <MDL
Sulfathiazole < 0.005 <MDL < 0.005 <MDL
Triclosan < 0.005 <MDL < 0.005 <MDL
Trimethoprim < 0.005 <MDL < 0.005 <MDL
47
Table 11 (Appendix). PPCP concentrations in POCIS samplers
Sampling Date 1/17/2017
Analytes Treated (ug/pocis) Cw
(ng/L)
Raw
(ug/pocis)
Cw
(ng/L)
Acetaminophen < 0.005 <MDL < 0.005 <MDL
Ampicillin < 0.010 <MDL < 0.010 <MDL
Atrazine 0.681 13.195 0.891 17.263
Bisphenol-A < 0.010 <MDL < 0.010 <MDL
Caffeine 0.0194 1.146 0.034 2.009
Carbamazepine < 0.005 <MDL < 0.005 <MDL
Cimetidine < 0.005 <MDL < 0.005 <MDL
Ciprofloxacin < 0.005 <MDL < 0.005 <MDL
Digoxin < 0.010 <MDL < 0.010 <MDL
Gemfibrozil < 0.005 <MDL < 0.005 <MDL
Ibuprofen < 0.005 <MDL < 0.005 <MDL
Metformin < 0.005 <MDL < 0.005 <MDL
Naproxen < 0.005 <MDL < 0.005 <MDL
Simazine 0.046 0.978 0.0618 1.315
Sulfamethoxazole < 0.005 <MDL < 0.005 <MDL
Sulfathiazole < 0.005 <MDL < 0.005 <MDL
Triclosan < 0.005 <MDL < 0.005 <MDL
Trimethoprim < 0.005 <MDL < 0.005 <MDL
48
Table 11 (Appendix). PPCP concentrations in POCIS samplers
Sampling Date 2/27/2017
Analytes Treated
(ug/pocis)
Cw
(ng/L)
Raw
(ug/pocis) Cw (ng/L)
Acetaminophen < 0.005 <MDL < 0.005 <MDL
Ampicillin < 0.010 <MDL < 0.010 <MDL
Atrazine 0.424 9.065 0.498 10.647
Bisphenol-A < 0.010 <MDL < 0.010 <MDL
Caffeine 0.0241 1.571 0.0306 1.995
Carbamazepine < 0.005 <MDL < 0.005 <MDL
Cimetidine < 0.005 <MDL < 0.005 <MDL
Ciprofloxacin < 0.005 <MDL < 0.005 <MDL
Digoxin < 0.010 <MDL < 0.010 <MDL
Gemfibrozil < 0.005 <MDL < 0.005 <MDL
Ibuprofen < 0.005 <MDL < 0.005 <MDL
Metformin < 0.005 <MDL < 0.005 <MDL
Naproxen < 0.005 <MDL < 0.005 <MDL
Simazine 0.0264 0.620 0.0301 0.706
Sulfamethoxazole < 0.005 <MDL < 0.005 <MDL
Sulfathiazole < 0.005 <MDL < 0.005 <MDL
Triclosan < 0.005 <MDL < 0.005 <MDL
Trimethoprim < 0.005 <MDL < 0.005 <MDL
49
Table 11 (Appendix). PPCP concentrations in POCIS samplers
Sampling Date 5/3/2017
Analytes Treated
(ug/pocis) Cw (ng/L)
Raw
(ug/pocis) Cw (ng/L)
Acetaminophen < 0.005 <MDL < 0.005 <MDL
Ampicillin < 0.010 <MDL < 0.010 <MDL
Atrazine 0.272 2.858 0.39 4.098
Bisphenol-A < 0.010 <MDL < 0.010 <MDL
Caffeine 0.0089 0.285 0.0148 0.474
Carbamazepine < 0.005 <MDL < 0.005 <MDL
Cimetidine < 0.005 <MDL < 0.005 <MDL
Ciprofloxacin < 0.005 <MDL < 0.005 <MDL
Digoxin < 0.010 <MDL < 0.010 <MDL
Gemfibrozil < 0.005 <MDL 0.0114 0.117
Ibuprofen < 0.005 <MDL < 0.005 <MDL
Metformin < 0.005 <MDL < 0.005 <MDL
Naproxen < 0.005 <MDL < 0.005 <MDL
Simazine 0.0347 0.400 0.0434 0.501
Sulfamethoxazole < 0.005 <MDL < 0.005 <MDL
Sulfathiazole < 0.005 <MDL < 0.005 <MDL
Triclosan < 0.005 <MDL < 0.005 <MDL
Trimethoprim < 0.005 <MDL < 0.005 <MDL
50
Table 11 (Appendix). PPCP concentrations in POCIS samplers
Sampling Date 6/8/2017
Analytes Treated
(ug/pocis) Cw (ng/L)
Raw
(ug/pocis) Cw (ng/L)
Acetaminophen < 0.005 <MDL < 0.005 <MDL
Ampicillin < 0.010 <MDL < 0.010 <MDL
Atrazine 0.553 5.530 0.805 8.050
Bisphenol-A < 0.010 <MDL 0.0423 0.312
Caffeine 0.0424 1.293 0.227 6.921
Carbamazepine 0.0202 0.414 0.08 1.638
Cimetidine < 0.005 <MDL < 0.005 <MDL
Ciprofloxacin < 0.005 <MDL < 0.005 <MDL
Digoxin < 0.010 <MDL < 0.010 <MDL
Gemfibrozil 0.0223 0.218 0.189 1.844
Ibuprofen < 0.005 <MDL 0.0362 0.635
Metformin < 0.005 <MDL < 0.005 <MDL
Naproxen < 0.005 <MDL 0.0238 0.360
Simazine 0.0832 0.913 0.145 1.592
Sulfamethoxazole < 0.005 <MDL 0.0185 0.380
Sulfathiazole < 0.005 <MDL < 0.005 <MDL
Triclosan < 0.005 <MDL < 0.005 <MDL
Trimethoprim < 0.005 <MDL 0.0183 0.193
51
Table 11 (Appendix). PPCP concentrations in POCIS samplers
Sampling Date 8/23/2017
Analytes Treated
(ug/pocis) Cw (ng/L)
Raw
(ug/pocis) Cw (ng/L)
Acetaminophen < 0.005 <MDL < 0.005 <MDL
Ampicillin < 0.010 <MDL < 0.010 <MDL
Atrazine 1.84 16.534 1.94 17.432
Bisphenol-A < 0.010 <MDL < 0.010 <MDL
Caffeine 0.0393 1.077 0.0353 0.967
Carbamazepine 0.0147 0.270 0.0646 1.188
Cimetidine < 0.005 <MDL < 0.005 <MDL
Ciprofloxacin < 0.005 <MDL < 0.005 <MDL
Digoxin < 0.010 <MDL < 0.010 <MDL
Gemfibrozil < 0.005 <MDL 0.0114 0.100
Ibuprofen < 0.005 <MDL < 0.005 <MDL
Metformin < 0.005 <MDL < 0.005 <MDL
Naproxen < 0.005 <MDL < 0.005 <MDL
Simazine 0.0931 0.918 0.137 1.351
Sulfamethoxazole < 0.005 <MDL < 0.005 <MDL
Sulfathiazole < 0.005 <MDL < 0.005 <MDL
Triclosan < 0.005 <MDL < 0.005 <MDL
Trimethoprim < 0.005 <MDL 0.0188 0.178
52
Table 12 (Appendix). Water quality data (raw water samples)
DATE temp (oC)
DO (mg/L)
pH
Conductivity uS/m
TSS (mg/L)
Chlorine (mg/L)
BOD (mg/L)
TDS (mg/L)
COD (mg/L)
7/29/16
7.85 3250 1.80E-06
1.81E-05
9/13/16 23.9 10.57 8.36 278 6.25E-07
1.85E-04 22.5
9/20/16 23.5 6.63 8.33 254 bdl
bdl 5
9/27/16 21.2 6.59 8.25 258 2.94E-05
1.75E-04 40
10/4/16 20 7.15 8.29 256 6.25E-07
1.50E-04 32.5
10/18/16 18.8 8.38 8.37 238 bdl
2.04E-04 16.25
10/25/16 15.9 9.1 8.04 249 1.25E-06
1.1 1.43E-04 26.67
11/1/16 16.6 10.34 8.38 245 1.00E-04 0.225 1.22 9.31E-05 34.17
11/8/16 21.7 9.14 8.27 261 bdl 0.025 1.58 1.63E-04 22.22
11/15/16 14.5 10.09 8.32 235 2.00E-04 0.045 1.17 1.19E-04 24.17
11/29/16 10 10.89 8.29 222 4.00E-04 0.235 0.14 1.38E-04 52.5
12/6/16 9.1 10.94 8.25 238 1.13E-05 0.32 0.52 1.78E-04 14.03
12/14/16 5.6 12.19 8.14 228 4.18E-04 0.04 3.88 1.36E-04 30.83
12/21/16 2.9 11.03 8.03 212 1.36E-04 0.09 0.83 1.85E-04 16.67
12/28/16 6.1 9.8 8.17 214 1.29E-04 0.12 2.13 5.10E-05 24.7
1/4/17 4.9 11.03 8.1 236 1.02E-04 0.14 2.87 9.13E-05 23.33
1/17/17 3.5 12.19 8.06 229 1.35E-04 0.3 1.55 bdl 14.44
1/24/17 4.7 12.11 8.04 252 bdl 0.22 3.09 1.26E-04 6.66
1/31/17 3.3 12.75 8.06 162 3.38E-05 0.34 2.41 8.13E-06 10
2/8/17 2.6 12.5 8.01 241 1.38E-04 0.42 4.03 1.10E-04 74.08
2/14/17 2.7 12.8 8.06 222 2.81E-05 0.26 3.42 4.13E-05 55.83
2/21/17 4.3 13.17 8.03 144 8.13E-06 0.4 1.36 8.13E-06
2/27/17 4 9.87 7.08 134 1.89E-04 0.4 0.98 1.74E-04 27.42
3/7/17 10.2 11.86 7.97 213 5.17E-04 0.47 1 2.77E-04 56.65
3/14/17 2.7 11.26 8.04 188 1.00E-05 0.49 1.37 9.61E-05 26.65
3/21/17 3.1 13.65 8.17 147 bdl 0.52 3.65 1.34E-04 33.34
3/28/17 4.6 13.83 8.24
7.50E-06 0.43 0.55 1.53E-04 11.66
4/4/17 6.7 13.21 8.11 248 1.38E-05
1.3 2.38E-04 111.67
4/11/17 8.7 12.47 8.04 346 7.26E-04
1.14E-04 2.5
4/25/17 9.1 13.34 8.13 251 1.45E-04
2.58 1.68E-04 30
5/5/17 11.7 10.99 8.05 247 4.70E-05
1.11 8.63E-05 39.17
5/10/17 11.1 10.51 7.99 248 bdl
0.07 1.66E-04 150.83
5/18/17 14.4
8.3 252 8.50E-05
1.08 3.66E-03 46.67
5/25/17 14.2 8.54 8.16 253 bdl
1.11 bdl 62.5
6/1/17 16.5 9.54 8.19 255 bdl
0.57 1.04E-04 39.17
6/8/17 16.5 9.61 8.12 225 bdl
1.38 bdl 23.33
6/15/17 19.1 9.66 8.23 250 8.75E-06
0.12 1.81E-04 100
6/22/17 22.1 8.73 8.17 243 3.75E-06
0.02 1.05E-04
6/29/17 24.9 8.66 8.19 268 1.50E-05
1.89E-04 81.67
7/6/17 24.9 7.94 8.18 257 bdl
0.2175 1.98E-04 50.83
7/13/17 26.2 7.29 8.09 277 5.06E-05
2.87 9.44E-05 81.67
7/20/17 26.2 8.2 8.22 260 2.62E-05
1.11 7.69E-05 126.67
7/27/17 24.9 7.59 7.57 257 1.31E-04
bdl 1.36E-04 245
8/10/17 24.8 10.01 8.29 261 1.94E-05
1.53 7.50E-05 41.67
8/17/17 25.3 7.7 8.35 248 1.06E-05
0.13 1.14E-04 63.33
53
Table 13 (Appendix). Water quality data (treated water samples)
DATE temp (oC)
DO (mg/L)
pH
Conductivity
S/m TSS
(mg/L) Chlorine (mg/L)
BOD (mg/L)
TDS (mg/L)
COD (mg/L)
7/29/16
8.09 3330 6.90E-06
4.69E-05
9/13/16 24 12.01 8.39 260 bdl
1.87E-04 5.83
9/20/16 23.3 8.06 8.35 256 bdl
n/a 15.83
9/27/16 21.5 8.54 8.36 252 bdl
3.34E-04 22.49
10/4/16 19.9 9.05 8.37 247 1.25E-06
1.56E-04 19.37
10/18/16 18.2 9.47 7.99 254 bdl
1.88E-04 10.62
10/25/16 15.8 9.94 8.1 244 bdl
1.44 1.55E-04 16.67
11/1/16 14.3 10.08 8.15 237 bdl 1.375 1.07 3.63E-05 30
11/8/16 14.4 9.96 8.21 239 6.25E-05 1.5 0.655 1.66E-04 28.33
11/15/16 12.6 10.35 8.2 246 3.00E-04 1.52 0.948 2.50E-03 43.33
11/29/16 9.5 11.08 8.14 232 bdl 1.52 0.583 1.53E-04 36.42
12/6/16 8.4 11.52 8.12 232 bdl 1.64 0.21 1.85E-04 16.66
12/14/16 5.7 11.35 8.01 243 bdl 1.48 2.97 1.36E-04 12.5
12/21/16 3.2 11.01 8.06
1.26E-05 1.35 0.53 1.74E-04 13.33
12/28/16 3.7 11.96 8.02 216 1.28E-06 1.21 2.23 4.88E-05 15
1/4/17 3.3 12.25 7.91 203 4.83E-06 1.31 1.49 1.74E-04 26.66
1/17/17 2.8 12.62 7.94 229 1.25E-05 1.37 1.76 bdl 21.11
1/24/17 3 12.4 7.94 244 bdl 1.56 3.72 9.75E-05 bdl
1/31/17 2.3 12.77 7.99 208 bdl
2.25 8.13E-06 13.33
2/8/17 2.2 12.8 7.89 239 bdl 1.35 4.26 5.19E-05 84.17
2/14/17 1.6 12.52 7.91 224 3.75E-06 1.5 3.6 1.15E-04 50.83
2/21/17 2.6 13.63 7.86 175 2.50E-06 1.56 1.85 9.13E-05
2/27/17 3.7 13.12 8.07 173 2.50E-04
0.97 2.50E-04 25
3/7/17 4.4 11.51 8.07 213 bdl 1.41 1.55 2.63E-04 80.83
3/14/17 2.7 11.26 8.04 188 1.13E-05 1.5 1.61 9.74E-05 26.6
3/21/17 2.5 12.7 8.02 204 5.63E-06 1.45 2.85 1.50E-04 10
3/28/17 4.6 13.83 8.24
bdl 1.48 1.49 2.22E-04 86.6
4/4/17 5.5 12.46 7.88 235 bdl 1.47 1.09 2.34E-04 89.17
4/11/17 7.2 11.7 8.01 244 2.97E-05 1.48
1.14E-05 17.5
4/25/17 10.6 12.4 8.05 253 bdl 1.51 3 1.82E-04 60
5/5/17 12.1 10.2 8.04 243 bdl 1.14 0.01 6.06E-05 11.67
5/10/17 11.6 11.4 7.95 247 3.75E-06 1.08 0.67 bdl 44.17
5/18/17 14.4
8.07 260 8.06E-05 1.24 0.74 3.65E-03 35.83
5/25/17 14.9 8.79 8.05 260 bdl 1.13 1.53 bdl 56.67
6/1/17 16.7 9.61 7.98 254 bdl 1.52 0.58 9.31E-05 50
6/8/17 16.9 10.55 8.01 255 bdl 1.42 0.83 bdl 21.67
6/15/17 19.1 10.4 8.02 262 bdl 1.25 bdl 1.48E-04 67.5
6/22/17 22.4 8.08 7.93 260 bdl 1.26 bdl 9.69E-05
6/29/17 24.9 8.66 8.03 270 1.25E-06 1.11
2.33E-05 47.5
7/6/17 24.9 8.44 8.07 261 1.56E-05 1.09 0.1 1.48E-04 24.17
7/13/17 24.3 9.03 8.23 260 2.50E-06 1.01 bdl bdl 36.67
7/20/17 25.7 8.52 8.12 267 6.25E-06 1.03 0.24 2.75E-05 33.33
7/27/17 24.9 8.28 8.21 263 1.06E-05 0.93 bdl 1.36E-04 65.83
8/10/17 24.8 8.94 8.29 261 2.50E-06 0.88 bdl 6.44E-05 12.5
8/17/17 25.5 8.13 8.35 248 bdl 0.83 bdl 1.11E-04 16.67