ABUNDANCE OF PHARMACEUTICALS AND PERSONAL CARE PRODUCTS
IN NEAR- SHORE HABITATS OF LAKE MICHIGAN
A THESIS
SUBMITTED TO THE GRADUATE SCHOOL
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE
MASTER OF SCIENCE
BY
PATRICK J. FERGUSON
DR. MELODY BERNOT, ADVISOR
DR. THOMAS LAUER, ADVISOR
BALL STATE UNIVERSITY
MUNCIE, INDIANA
MAY 2012
1
TABLE OF CONTENTS
Cover page
1
Table of contents
2
Project Abstract
3
Chapter 1: Abundance of pharmaceuticals and personal care products in near-shore
habitats of Lake Michigan
Abstract
4
Introduction
6
Materials and Methods
11
Results
15
Discussion
18
Acknowledgements
25
Tables
26
Figures
34
References
44
Appendix 1: Physiochemical data collected in near-shore
49
Lake Michigan sites.
Appendix 2: Pharmaceutical and personal care product data
50
collected in near-shore Lake Michigan sites.
Appendix 3: Cation and anion data collected in near-shore
51
Lake Michigan sites.
2
ABSTRACT
THESIS: Abundance of pharmaceuticals and personal care products in near-shore
habitats of Lake Michigan
STUDENT: Patrick Ferguson
DEGREE: Master of Science
COLLEGE: Sciences and Humanities
DATE: May, 2012
PAGES: 51
Pharmaceuticals and personal care products (PPCPs) enter aquatic ecosystems
through multiple pathways including human excretion into sewage systems, disposal of
surplus drugs, and the therapeutic treatment of livestock. Because PPCPs are designed to
have a physiological effect, it is likely that they may also influence aquatic organisms.
The objectives of this research were to quantify PPCP abundance in near-shore habitats
of Lake Michigan and identify factors related to PPCP abundance. Stratified sampling
was conducted seasonally at four southern Lake Michigan sites. All sites sampled had
measurable PPCP concentrations, but they varied significantly among time and location.
Concentrations of PPCPs did not differ with site or water depth. Multiple regression
analyses revealed that temperature, total carbon, total dissolved solids, dissolved oxygen,
and ammonium controlled total PPCP concentrations. These data indicate PPCPs are
ubiquitous in southern Lake Michigan with continued research needed to assess potential
effects on aquatic organisms and humans.
3
Chapter 1: Abundance of pharmaceuticals and personal care products in near-shore
habitats of Lake Michigan
Abstract
Pharmaceuticals and personal care products (PPCPs) enter aquatic ecosystems
from multiple sources, including human excretion into sewage systems, disposal of
surplus drugs, and the therapeutic treatment of livestock. In freshwaters, PPCPs have
been documented throughout the United States but research has focused largely on
streams and rivers with minimal assessments conducted in the Laurentian Great Lakes.
Because pharmaceuticals are designed to have a physiological effect, it is likely that they
may also influence aquatic organisms. Thus, concentrations of pharmaceuticals may
negatively impact the aquatic ecosystem. The objectives of this research were to quantify
PPCP abundance in near-shore habitats of Lake Michigan and identify factors related to
PPCP abundance. Stratified sampling was conducted seasonally at four southern Lake
Michigan sites (St. Joseph, Michigan City, East Chicago, Chicago). All sites and depths
had measurable PPCP concentrations, with individual compound ranges of
acetaminophen (2.5-17 ng/L), caffeine (18-100 ng/L), carbamazepine (0.5-10 ng/L),
cotinine (1-11 ng/L), gemfibrozil (1-49 ng/L), ibuprofen (1.5-84 ng/L), lincomycin (1.57.9 ng/L), naproxen (3.5-30 ng/L), paraxanthine 1,7-Dimethylxanthine (25-79 ng/L),
sulfadimethoxine (0.5-2.5 ng/L), sulfamerazine (0.5-1.6 ng/L), sulfamethazine (0.5-1.6
ng/L), sulfamethoxazole (1.5-220 ng/L), sulfathiazole (0.5-1.6 ng/L), triclocarban (2.5-14
4
ng/L), trimethoprim (1.5-18 ng/L), and tylosin (1.5-6.7 ng/L). Concentrations of PPCPs
varied significantly among sampling times and locations, with statistical interactions
between the main effects of site and time as well as time and location. Concentrations of
PPCPs did not differ with site or water depth. Temperature, total carbon, total dissolved
solids, dissolved oxygen, and ammonium concentrations were related to total
pharmaceutical concentrations. These data indicate PPCPs are ubiquitous in southern
Lake Michigan and may potentially pose harmful effects both to aquatic organisms as
well as to humans via indirect exposure.
5
Introduction
Pharmaceuticals and personal care products (PPCPs) in the environment are an
emerging concern in the scientific community (Daughton and Ternes, 1999; Jones et al.,
2001) and society (Jones et al., 2005). In the broadest sense, PPCPs consist of
prescription drugs, non-prescription drugs, and consumer chemicals including fragrances
and sun-screen agents (Daughton, 2001). When these compounds enter aquatic
ecosystems through human excretion into sewage systems (Daughton and Ternes, 1999),
improper disposal of surplus drugs (Bound and Voulvoulis, 2005), and agricultural runoff
associated with therapeutic treatment of livestock (Jorgensen and Halling-Sørensen,
2000), they potentially pose harmful effects both to aquatic organisms (Kolpin et al.,
2002; Bound and Voulvoulis, 2005) as well as to humans via indirect exposure (Jones et
al., 2004; Stackelberg et al., 2004; Jones et al., 2005).
Having been detected in numerous and diverse freshwater ecosystems, PPCPs are
regularly found across lotic (Kolpin et al., 2002; Bunch and Bernot 2010; Veach and
Bernot 2011) and lentic waterbodies (Metcalfe et al., 2003; Li et al., 2010), as well as in
effluent from wastewater treatment plants (Glassmeyer et al., 2005), groundwater (Barnes
et al., 2008), untreated sources of drinking water (Focazio et al., 2008) and finished-water
supplies (Stackelberg et al., 2004). Further, PPCPs have been detected in freshwater
ecosystems influenced by multiple surrounding land use types, including both urban and
agriculturally influenced streams (Bunch and Bernot, 2010; Veach and Bernot 2011). Not
only has the presence of PPCPs been well established in freshwater ecosystems of the
United States (Kolpin et al., 2002; Metcalfe et al., 2003; Glassmeyer et al., 2005; Barnes
et al., 2008; Focazio et al., 2008; Bunch and Bernot, 2010; Li et al., 2010; Veach and
6
Bernot 2011), but also worldwide (Sarmah et al., 2006; Voigt et al., 2008; Gros et al.,
2010).
Concentration and detection frequencies of PPCPs in freshwater vary among
individual compounds and ecosystems. For example, ranges of individual compound
concentrations vary dramatically including acetaminophen (0-10,000 ng/L) (Brun et al.,
2006; Kolpin et al., 2002), Ibuprofen (0-22,000 ng/L) (Brun et al., 2006), lincomycin (0730 ng/L) (Focazio et al., 2008; Kolpin et al., 2002), and carbamazepine (0- 650 ng/L)
(Brun et al., 2006; Metcalfe et al., 2003). Similarly, detection frequencies of individual
PPCPs vary from 0-84% for acetaminophen (Kolpin et al., 2004; Veach and Bernot,
2011) and ibuprofen (Glassmeyer et al., 2005; Ashton et al., 2004); 0-19.2% for
lincomycin (Focazio et al., 2008; Kolpin et al., 2002), and 4.3-82.5% for carbamazepine
(Kolpin et al., 2004; Glassmeyer et al., 2005). Such broad ranges in concentrations and
detection frequencies likely indicate variations in both input and fate of individual PPCP
compounds within aquatic ecosystems.
Concentrations of PPCPs are likely influenced by multiple controls including
surrounding land use (Bunch and Bernot, 2010), input rates (Vieno et al., 2005),
physicochemical characteristics of the ecosystem (Bunch and Bernot 2010; Veach and
Bernot, 2011), as well as individual PPCP compound characteristics (Jorgensen and
Halling-Sorensen, 2000). Once in the environment, individual PPCPs may be removed by
the processes of sorption (Castiglioni et al., 2006), biodegradation (Jones et al., 2004),
photodegradation (Buser et al., 1998), and hydrolysis (Kümmerer, 2010). Some PPCPs
are correlated with physiochemical characteristics of the water, including dissolved
7
oxygen, turbidity, chlorophyll a, and pH (Veach and Bernot, 2011). Additionally,
precipitation and discharge may be good predictors of PPCP abundance for select
compounds in lotic ecosystems (Kolpin et al., 2004; Veach and Bernot, 2011). Predictive
ability of compound fate in the environment is lacking, however, as there is limited
knowledge of mechanisms influencing PPCP abundance.
Previous studies investigating PPCPs have largely focused on lotic ecosystems
(e.g. Kolpin et al., 2002; Kolpin et al., 2004; Glassmeyer et. al., 2005; Bunch and Bernot
2010; Veach and Bernot 2011) with minimal assessment of large lentic systems (but see
Metcalfe et al., 2003; Li et al., 2010). Because lentic environments are physically distinct
from lotic environments, lentic systems may potentially exhibit differential patterns of
PPCP abundance and fate. For example, Kolpin et al., (2004) noted that PPCP
concentrations were higher in streams during low flow periods because of less dilution. In
large lakes, dilution may be continuous given higher water:PPCP ratios. Further, dilution
effects likely influence spatial distribution with higher PPCPs near-shore relative to
offshore locations. In lakes, photodegradation of PPCPs may also be greater than lotic
systems due to an increased water surface area. Buser et al., (1998) showed that 90% of
the pharmaceutical drug diclofenac was likely eliminated from a lake due to
photodegradation. Other hydrologic factors such as water circulation may also influence
PPCP occurrence throughout a lake as these events influence suspended materials
important in PPCP retention and degradation (Ji et al., 2002).
Lake Michigan is the sixth largest lake in the world and the third largest of the
Laurentian Great Lakes (Beeton, 1984). The lake provides numerous recreational
8
opportunities and serves as the primary source of drinking water for approximately 10
million people (USEPA, 2008). Lake Michigan is susceptible to anthropogenic
contaminants (Eadie, 1997) due to a highly urbanized lake basin (USEPA, 1995) and a
hydraulic residence time of 62 years (Quinn, 1992). Historically, polychlorinated
biphenyls (PCBs), DDT and mercury have been pervasive pollutants of Lake Michigan
(Evans et al., 1991; Mason and Sullivan, 1997). In addition to these legacy contaminants,
PPCP pollution in the Laurentian Great Lakes has become a growing concern (Metcalfe
et al., 2003; Li et al., 2010), with potential effects largely unknown (Stackelberg et al.,
2004). In Lake Michigan, PPCPs have been detected in lake trout tissue (Peck et al.,
2007) and in largemouth bass tissue from a Lake Michigan tributary (Ramirez et al.,
2009). Although PPCPs are present in Lake Michigan, limited data is available
quantifying their abundance. Further, there lacks an understanding of factors influencing
PPCP abundance and persistence to assess potential regulatory need.
The objectives of this study were to quantify the spatial and temporal variation of
PPCP abundance in near-shore habitats of Lake Michigan as well as to identify factors
related to and influencing abundance. We hypothesized that river discharges into Lake
Michigan are sources of PPCPs, with subsequent dilution of PPCPs off-shore resulting in
lower concentrations in open water locations relative to harbor locations. Additionally,
we hypothesized that PPCP concentrations would fluctuate through time, being greatest
in spring in conjunction with spring runoff and lower in summer as a result of increased
degradation potential. We further hypothesized that PPCPs would be positively correlated
9
with water-column ammonium concentrations, following waste input, and negatively
correlated with temperature, following biotic degradation potential.
10
Materials and Methods
Four near-shore sites in southern Lake Michigan near the cities of St. Joseph, MI;
Michigan City, IN; East Chicago, IN; and Chicago, IL were selected for study (Figure 1).
The rationale for site selection was based on areas expected to contain PPCPs;
specifically, river discharges into the lake of predominantly urban watersheds.
Pharmaceutical and personal care product sampling
As defined in this study, PPCPs comprise human and veterinary antibiotics,
prescription drugs, non-prescription drugs and their metabolites, and an antibacterial
additive. Sampling was conducted at each site seasonally (August, November, March,
June) beginning August 2010. At each site, water was collected at river mouth (harbor)
and off-shore (open water) locations at depths of 1 m below the surface and 1 m above
the bottom using a Van Dorn water sampler. Thus, four samples per site were collected
each season. After water was collected, the intake tubing of a GeoPump was placed
directly into the Van Dorn and rinsed with collected water for 30 s to ensure no carryover from previous sampling. Using forceps, a 47 mm Whatman glass fiber filter (GF/F,
nominal pore size 0.7 µm) was placed onto a filter screen. The filter was then closed and
placed on the outflow tubing of the GeoPump and rinsed for an additional 5 s. After
rinsing, water for PPCP analyses was directly filtered into a 1000 mL amber-baked glass
bottle containing sodium thiosulfate as a preservative; followed by direct filtration into a
separate 60 mL acid-washed Nalgene for analysis of nutrient concentrations. Control
field samples using ultra-pure deionized water as the filtrate were also collected at two
locations each season using the above procedure. Lake water was collected for matrix
analyses to ensure robust chemical analyses. All samples were immediately placed on ice
11
following the filtration. Individuals associated with the PPCP sampling were required to
wear neoprene gloves and did not ingest or use any PPCPs included in analyses 24 h prior
to sampling. Water samples for PPCP analyses were transported on ice to the Indiana
State Department of Health (ISDH) chemical laboratory, Indianapolis, within 24 h of
collection. Water samples for nutrient analyses were frozen within 24 h and stored for
subsequent analyses at Ball State University.
Sample analysis for 19 PPCP compounds was performed using an Applied
Biosystems triple quad API 4000 LC/MS/MS system equipped with an Agilent 1200 high
performance liquid chromatography (HPLC). PPCP measurements were determined via a
calibration curve constructed from the peak area response ratio of each compound to a
corresponding labeled internal standard. Compounds measured were acetaminophen,
caffeine, carbamazepine, cotinine, DEET, gemfibrozil, ibuprofen, lincomycin, naproxen,
paraxanthine 1,7-dimethylxanthine, sulfadimethoxine, sulfamerazine, sulfamethazine,
sulfamethoxazole, sulfathiazole, triclocarban, triclosan, trimethoprim, and tylosin with
variable detection limits (Table 1).
Measurement of independent variables
Physiochemical measurements (temperature, oxygen, pH, turbidity, conductivity)
were also measured at each site using a Hydrolab mini-sonde equipped with an LDO
sensor and Surveyor (Table 2). The Hydrolab mini-sonde was lowered, at each sample
location, to a depth of 1 m below the water surface and 1 m above the bottom,
corresponding with water sample locations. After ~ 60 s equilibration, data were
recorded.
12
Ion chromatography on a DIONEX ICS-3000 was performed for measurements of
nitrate, phosphate, fluoride, chloride, nitrite, sulfate, bromide, ammonium, potassium,
calcium, magnesium and total carbon following methods described by Eaton et al.,
(2005).
Statistical analyses
PPCP concentrations were analyzed both as individual compounds as well as total
pharmaceutical concentration, the sum of all PPCP compounds detected. Differences in
total pharmaceutical concentrations (response variable) with sampling site, time (season),
location (harbor; open water) and sample depth (1m below water surface; 1 m above the
bottom) (predictor variables) were assessed using a repeated measures analysis of
variance (ANOVA) followed by pairwise comparisons with time as the repeated factor
and site as the random factor with depth nested in location. Bonferroni-corrected Pearson
correlations coefficients were used to assess possible relationships between
physiochemical parameters and nutrient concentrations with individual and total PPCP
concentrations across all sites which comprise a total of sixty-four water samples
throughout the study (N = 64). Predictive models were developed using multiple
regression with backward elimination to assess factors controlling both individual and
total pharmaceutical concentration. Independent variables used in multiple regression
analyses were establish by Pearson correlations and included temperature, dissolved total
carbon, total dissolved solids, dissolved oxygen (% saturation), nitrate, phosphate, sulfate
and ammonium. Pearson correlation coefficients and ANOVA statistics were performed
using SAS statistical software (SAS Institute® 9.2, 2002-2008 Cary, NC, US). Multiple
13
regression analyses were performed using Minitab 16 (Minitab®Inc. 2010, USA). Alpha
level was set at 0.05 for all statistical analyses.
14
Results
Pharmaceutical concentrations
There were measurable concentrations of every PPCP compound sampled across
all sites, locations, and depths (Table 1). Concentrations varied considerably among
PPCPs, with maximum concentrations of some compounds found at ≥ 100 ng/L (caffeine,
sulfamethoxazole), where other compounds had maximum concentrations of  2 ng/L
(sulfamerazine, sulfamethazine, sulfathiazole) (Table 1). Further, concentration ranges of
individual compounds varied. For example, concentrations ranges of sulfamethoxazole
(1.5-220 ng/L) varied up to two orders of magnitude, where other compounds including
sulfamerazine (0.5-1.6 ng/L), sulfamethazine (0.5-1.6 ng/L), and sulfathiazole (0.5-1.6
ng/L) showed little variation in concentration range (Table 1).
Spatial and temporal variation of pharmaceuticals
Time (season) and location (harbor; open water) significantly influenced total
pharmaceutical concentrations (p ≤ 0.011; Table 3; Figs. 2, 3) in our models, with
significant interaction of main effects taking place between site and time (p = 0.009;
Table 3) and time and location (p = 0.002; Table 3). In contrast, sampling site and water
depth (1m below water surface; 1 m above the bottom) did not affect PPCP concentration
(p ≤ 0. 403; Table 3). East Chicago had ~4% higher total pharmaceutical concentrations
than St. Joseph, and ~40% higher total pharmaceutical concentrations than Chicago, but
was comparable to Michigan City (Fig. 2). The highest concentrations of total
pharmaceuticals for Michigan City (912.40 ng/L; Fig. 4) and East Chicago (1126.60
ng/L; Fig. 5) sites were measured in March; whereas, St. Joseph (978.20 ng/L; Fig. 6) had
the highest total pharmaceutical concentrations in November (Fig. 2) and Chicago
15
showed little temporal variation in total pharmaceutical concentrations (Fig. 7). River
mouths (harbor locations) had 56% higher total pharmaceutical concentrations than open
water locations (Fig. 3).
Factors influencing pharmaceutical abundance
Total pharmaceutical concentration, across all sampling events, were negatively
correlated with temperature (r = -0.242; p ≤ 0.054) and percent oxygen saturation (r = 0.538; p ≤ 0.001) (Fig. 8). Total dissolved solids (r = 0.716; p ≤ 0.001), total carbon (r =
0.615; p ≤ 0.001), dissolved ammonium (r = 0.790; p ≤ 0.001) (Fig. 9), specific
conductivity (r = 0.711; p ≤ 0.001), salinity (r = 0.712; p ≤ 0.001), phosphate (r = 0.428;
p ≤ 0.001), and sulfate (r = 0.682; p ≤ 0.001) were positively correlated with total
pharmaceutical concentration across every sampling event (Table 4). Overall, dissolved
ammonium, total dissolved solids, salinity, and specific conductivity explained the most
variation in total pharmaceutical concentrations (Table 4). Dissolved nitrate, pH, and
dissolved oxygen concentration were not correlated to total pharmaceutical
concentrations (Table 4).
Temperature, total carbon, total dissolved solids, percent oxygen saturation, and
ammonium influenced total pharmaceutical concentrations in multiple regression
analyses (Table 5), although factors influencing individual compound concentrations
varied. For example, the lipid regulator gemfibrozil was influenced by all variables
measured in contrast to tylosin, which was influenced only by temperature and phosphate
concentrations (Table 5). Across all PPCP compounds, temperature influenced the
greatest number of individual PPCP compounds (76%) in multiple regression analyses,
16
whereas ammonium concentrations influenced only 24% of individual PPCP compounds
measured.
17
Discussion
Pharmaceutical concentrations
All sites, locations, and depths sampled had measurable concentrations of PPCPs,
with concentrations varying significantly among the main factors of time (season) and
location (harbor; open water) and no significant difference observed among site and
depth. Significant interactions occurred between the main effects of site and time,
indicating site differences in total PPCP concentrations are dependent on time. Similarly,
significant interactions were identified between location and time, signifying that
differences in total PPCP concentrations between locations are also dependent on time. In
addition, multiple regression analyses identify considerable variation in abiotic factors
influencing total and individual PPCP compounds (Table 5). Such variability in PPCP
concentrations across temporal and spatial dimensions, in addition to differing abiotic
factors influencing total pharmaceuticals and individual compounds, is likely an outcome
of numerous linked controls, including unique characteristics of each sampling site,
hydrology, physiochemical distinction and complex biogeochemical interactions
involving structurally diverse compounds.
In this study, individual PPCP compounds were found in ng/L concentrations and
were comparable to individual PPCP compound concentrations found previously in Lake
Ontario (Metcalfe et al., 2003; Li et al., 2010) (Table 6). For example, mean
concentrations of gemfibrozil, ibuprofen, and naproxen measured were all within the
same order of magnitude between studies and showed similarities in locality, with higher
concentrations of individual compounds in harbor locations relative to open water
locations (Metcalfe et al., 2003; Li et al., 2010) (Table 6). Differences in individual PPCP
18
concentrations observed between studies, mainly carbamazepine concentrations, were
likely influenced by specific site characteristics (e.g. surrounding land-use, wastewater
treatment plant proximity, input rates) and corresponding hydrology (e.g. dilution effects,
proximity to river runoff), highlighting the complexity of factors influencing PPCP
concentrations within lentic systems. Further, when comparing sampling methods
between studies, four sampling events (August, November, March, June) using water
grab methods, provided assessment of temporal variation in PPCP abundance in our
study that were generally comparable in magnitude (ng/L concentrations) and locality
(i.e. harbors having higher PPCP concentrations relative to open water locations) to
investigations using passive polar organic chemical sampler (POCIS) methodologies (Li
et al., 2010) (Table 6). Concentrations of individual PPCP compounds in this study were,
however, lower than those measured in wastewater treatment plant effluent (Glassmeyer
et al., 2005; Brun et al., 2006) and U.S. streams and rivers (Kolpin et al., 2002; Kolpin et
al., 2004; Bunch and Bernot, 2010; Veach and Bernot, 2011). Lower concentrations of
PPCPs in lentic waterbodies compared to lotic waterbodies were likely due to the dilution
effect of PPCPs found in large volumes of water, such as Lake Michigan (Buerge et al.,
2003; Kolpin et al., 2004).
Spatial variation of pharmaceuticals
Although all PPCPs sampled for were detected at every site, East Chicago and
Michigan City had higher PPCP concentrations when compared to St. Joseph and
Chicago (Fig. 2), possibly due to variability in land-use between sites (Bunch and Bernot,
2010; Glassmeyer et al., 2005). While all sites were developed urban regions, the Little
Calumet and Grand Calumet watersheds (containing Michigan City and East Chicago)
19
together have 18 % developed land; whereas, the St. Joseph River Watershed (containing
St. Joseph) is 3.5 % developed (USEPA, 2006). Because higher PPCP concentrations
have been associated with increased population densities within a drainage basin (Buerge
et al., 2003), variability in population densities and percent developed land among sites
(Glassmeyer et al., 2005) may explain increased abundance of PPCP compounds
occurring in the more developed and densely populated Little Calumet and Grand
Calumet watersheds with 511,797 people per 706 square miles, compared to the less
developed and less densely populated St. Joseph River Watershed with 944,771 people
per 4,670 square miles (Mills and Sharp, 2010).
Our hypothesis that harbor locations would have higher PPCP concentrations
when compared to open water locations due to river discharges into Lake Michigan was
supported (Fig. 3), with river discharges potentially serving as sources of PPCPs coupled
with dilution of PPCPs at off-shore locations. Higher concentrations of PPCPs occurring
at river mouths (harbor locations) were not unexpected as PPCPs are regularly found
within lotic waterbodies (Kolpin et al., 2002; Kolpin et al., 2004; Glassmeyer et. al.,
2005; Bunch and Bernot 2010; Veach and Bernot 2011), with dilution of PPCPs taking
place in large volumes of water (Buerge et al., 2003; Kolpin et al., 2004). In contrast,
sample depth was not a significant factor in determining PPCP concentration, suggesting
hydrologic mixing of compounds in the water-column.
Lake hydrology may have influenced PPCP abundance between sampling sites.
For instance, the direction of flow of the Chicago River (Lake Michigan flows inland to
the Chicago River) at the Chicago site likely negates any PPCPs entering the lake via
river discharge. In contrast, St. Joseph, Michigan City, and East Chicago sites are
20
characterized by river mouths that each drain entire watersheds influenced by
anthropogenic stressors (e.g. combined sewer overflow, municipal and industrial effluent
outlets) into Lake Michigan (USEPA, 2006). The Chicago River therefore, likely acted as
a buffer to sources of PPCPs to the lake, possibly explaining the lower PPCP
concentrations and uniformity of concentrations between locations (harbor; open water)
observed at the Chicago site despite Chicago being a more developed and densely
populated region.
Temporal variation of pharmaceuticals
Our hypothesis that total PPCP concentrations would be higher in spring in
conjunction with spring runoff was consistent with results found in Michigan City and
East Chicago (Fig. 2). Higher PPCP concentrations at Michigan City and East Chicago
sites during March sampling may be explained by increased runoff of land surfaces
associated with amplified spring precipitation and snowmelt at those sites, increasing the
rate of PPCPs entering surface water (Kümmerer, 2010) and draining to Lake Michigan.
Increased runoff can also result in more combined sewer overflow (CSO) discharging
raw sewage into surface water, contributing to higher total PPCPs abundance (Buerge et
al., 2006). Ammonium, suspended solids, and total carbon concentrations are typically
correlated with urban waterbodies due to waste water treatment plant effluent and non–
point source runoff (Paul and Meyer, 2001). Our hypothesis that total pharmaceuticals
would be positively correlated with water-column ammonium concentrations following
waste input, was also supported (Fig 9). Additionally, total pharmaceuticals were
positively correlated with total dissolved solids, and total carbon (Fig 9). Significant
correlations among these constituents and total pharmaceutical concentrations coupled
21
with multiple regression analyses, suggest that ammonium, total dissolved solids, and
total carbon are likely good indicators of PPCPs following urban waste runoff.
Seasonal maximums of total PPCP concentrations at the St. Joseph site during
November sampling, together with heightened total PPCP concentrations observed at
Michigan City and East Chicago sites relative to summer samplings, are likely a result of
decreasing November temperatures and reduced solar radiation. Lower temperatures may
reduce the rate of biodegradation of PPCPs in surface water and sewage treatment plants,
allowing for further transport of PPCPs to the lake (Vieno et al., 2005). Because
temperature influences biodegradation rates (Veach et al., 2012), it was hypothesized that
temperature would be negatively correlated with total pharmaceutical concentration
following biotic degradation potential. Consistent with this hypothesis, there was a
negative correlation between temperature and total pharmaceutical abundance (Fig. 8).
Similarly, aerobic conditions may also foster biodegradation of PPCPs (Carr et al., 2011).
Increasing biodegradation due to greater oxygen availability may therefore explain
negative correlations between percent oxygen saturation and total pharmaceutical
abundance (Fig. 8). In addition to changing temperatures and oxygen availability,
shortening daylight hours during November likely reduced the amount of solar radiation
to the lake, decreasing the rate of photodegradation of PPCPs, resulting in higher
November concentrations (Vieno et al., 2005; Veach et al., 2012).
Primary Factors influencing pharmaceutical abundance
Although multiple regression analyses indicated temperature, total carbon, total
dissolved solids, dissolved oxygen, and ammonium as primary factors influencing total
PPCP concentrations, there was considerable variation in factors influencing individual
22
compounds (Table 5). Such variability in factors influencing individual compounds is
likely an outcome of structurally diverse compounds and complex biogeochemical
interactions involving PPCPs within lentic waterbodies. For example, caffeine was
influenced by total carbon, nitrate, total dissolved solids, and dissolved oxygen, in
contrast to paraxanthine (1, 7-Dimethylxanthine) a caffeine metabolite, which was
influenced by temperature, pH, total dissolved solids, and dissolved oxygen; despite
caffeine and paraxanthine being two structurally similar compounds, differing only by a
methyl group. Notable difference (i.e. total carbon, nitrate, temperature, pH) in factors
influencing caffeine and paraxanthine abundance is possibly a consequence of these
subtle structural differences. Individuality of PPCP compounds also likely results in
altered responses to biogeochemical processes, changing individual PPCPs subsequent
fate in the environment (Lam et al., 2004; Sarmah et al., 2006; Lorphensri et al., 2007;
Yamamoto et al., 2009) with degradation of individual PPCPs likely a function of the
compound chemical structure (Daughton, 2001). For instance, the lack of double
aromatic rings likely makes ibuprofen more easily degraded than naproxen, a more
structurally complex compound that possesses double aromatic rings (Kimura et al.,
2005). Predicting compound fate based on its chemical structure alone however, is
inherently difficult due to the complexity of physiochemical interactions and
biogeochemical processes affecting PPCPs within lentic ecosystems.
Relevance
Results from this study indicate that PPCPs are ubiquitous in southern Lake
Michigan, with numerous abiotic controls on concentrations. Because PPCPs are
designed to have a physiological effect in target organisms, it is possible that they may
23
also influence non-target, aquatic organisms (Halling-Sørensen et al., 1998). Previous
research has shown the accumulation of PPCPs in fishes (Peck et al., 2007; Ramirez et
al., 2009), causing reproductive failure when exposed to chronic ng/L concentrations of
select pharmaceuticals (e.g., ethynylestradiol) (Nash et al, 2004). Although acute
exposure to trace concentrations of PPCPs on aquatic organisms will not likely cause
lethal effects, chronic exposure to PPCPs (e.g. ibuprofen) at ng/L concentrations have
resulted in sub-lethal behavioral effects in benthic invertebrates (De Lange et al., 2006;
Brown et al., In Press). In addition to PPCPs posing a possible threat to aquatic
organisms, PPCPs (e.g. caffeine, carbamazepine, cotinine) have also been shown to
endure conventional water treatment processes, thus occurring in finished drinking water
supplies (Stackelburg et al., 2004). Most PPCPs lack any drinking water standards or
health advisories (Stackelberg et al., 2004). Consequently, trace concentrations of PPCPs
in southern Lake Michigan may pose potential harmful effects to both aquatic organisms
as well as to humans via indirect exposure. More comprehensive investigation into PPCP
abundance and persistence in Lake Michigan are needed to fully identify potential
threats, with models generated from this study potentially helping to assess regulatory
need.
24
Acknowledgements
This work was supported by an Illinois-Indiana Sea Grant and Ball State
University. We thank Robin Bruner and the Indiana State Department of Health for
pharmaceutical analyses, Kip Rounds and the Indiana Department of Natural Resources
for field assistance, Ann Raffel, Carrie Olinger and Lindy Caffo for laboratory assistance
and Angela Gibson for GIS assistance.
25
Table 1
Summary of pharmaceutical and personal care product concentrations measured in near-shore habitats of Lake
Michigan. N=64
Detection Mean
Maximum
Minimum
Concentration Concentration Concentration
PPCP Compound Common Use
Chemical Structure Limit
(ng/L) (ng/L)
(ng/L)
(ng/L)
Acetaminophen Antipyretic
Caffeine
Carbamazepine
Cotinine
Gemfibrozil
Ibuprofen
Lincomycin
Naproxen
5.00
5.36
2.50
17.0
25.0
31.0
18.0
100
1.00
2.23
0.50
10.0
2.00
4.03
1.50
11.0
1.00
7.03
1.00
49.0
5.00
7.88
1.70
84.0
2.50
4.28
1.50
7.6
2.50
6.32
3.50
30.0
Stimulant
Anticonvulsant
Nicotine
metabolite
Lipid regulator
Anti-inflammatory
Antibiotic
Anti-inflammatory
26
Table 1 (Continued)
PPCP Compound
Common Use
Paraxanthine
Caffeine metabolite
Sulfadimethoxine
Sulfamerazine
Sulfamethazine
Sulfamethoxazole
Sulfathiazole
Triclocarban
Trimethoprim
Tylosin
Detection
Chemical Structure Limit
(ng/L)
Mean
Maximum
Minimum
Concentration Concentration Concentration
(ng/L)
(ng/L)
(ng/L)
25.0
46.2
25.0
76.0
0.50
0.94
0.50
2.50
0.50
0.92
0.50
1.50
0.50
0.92
0.50
1.50
1.00
26.0
1.50
220
0.50
0.92
0.50
1.50
2.50
5.72
2.50
14.0
2.50
5.15
1.50
18.0
2.00
3.75
1.50
6.70
Antibiotic
Antibiotic
Antibiotic
Antibiotic
Antibiotic
Antimicrobial
Antibiotic
Antibiotic
27
Table 2
Sampling site characteristics. Values as a Range.
Site
Location
Sampling Depth
(m)
1.0-1.0
Harbor
5.4-7.6
St. Joseph
1.0-1.0
Open Water
3.7-4.2
1.0-1.0
Harbor
3.3-4.0
Michigan City
1.0-1.0
Open Water
3.8-5.5
1.0-1.0
Harbor
5.7-9.8
East Chicago
1.0-1.0
Open Water
5.0-6.4
1.0-1.0
Harbor
4.2-7.0
Chicago
1.0-1.0
Open Water
6.6-10.7
Temperature
(°C)
6.1-26.4
6.1-26.3
2.7-26.1
4.5-25.6
6.3-26.1
6.2-26.0
4.6-26.3
4.5-25.5
13.2-26.3
10.2-16.4
3.7-24.8
3.6-17.3
4.1-21.2
4.0-20.6
2.9-26.2
2.8-15.5
pH
DO (%sat)
DO (mg/L)
8.4-9.4
8.5-9.6
8.6-10.1
8.7-10.1
8.7-9.1
8.5-9.3
8.6-10.0
8.7-10.0
8.9-9.7
9.2-9.9
9.4-10.0
9.5-10.0
9.1-10.0
9.4-10.0
9.3-10.1
9.3-10.0
108.8-115.0
108.4-114.4
108.9-134.0
109.4-128.4
103.1-132.6
104.0-127.2
113.8-130.0
114.3-129.1
90.0-110.6
92.4-144.4
108.6-140.0
111.2-150.8
110.7-144.5
111.0-144.2
111.8-130.8
112.5-147.7
9.2-17.8
9.1-17.7
10.8-19.4
10.5-19.0
10.7-17.2
10.3-17.2
10.5-19.3
10.6-20.0
8.9-12.6
11.7-14.9
11.6-18.9
13.1-19.4
12.8-19.1
12.9-19.6
13.0-19.9
13.1-20.7
28
Table 3
ANOVA table showing main factors influencing total pharmaceutical
concentrations and interactions among factors. * = significant effect.
Factor
df
F
P
Site
3
3.71
0.155
Time
3
8.51
<0.001 *
Location
1
31.3
0.011 *
Depth
1
0.94
0.403
Site*Time
9
3.08
0.009 *
Site*Location
3
4.32
0.130
Site*Depth
3
0.20
0.894
Time*Location
3
6.33
0.002 *
Time*Depth
3
0.32
0.814
Location*Depth
1
0.07
0.804
29
Table 4
Pearson correlation coefficient assessing relationships between pharmaceuticals and personal care products (PPCP) in Lake Michigan and physiochemical
parameters. Acronyms represent the following PPCPs: ACT (acetaminophen), CAF (caffeine), CBZ (carbamazepine), COT (cotinine), GFB (gemfibrozil), IBU
(ibuprofen), LCM (lincomycin), NAP (naproxen), PX (paraxanthine 1,7-dimethylxanthine), SDM (sulfadimethoxine), SMR (sulfamerazine), SMT
(sulfamethazine), SMZ (sulfamethoxazole), STZ (sulfathiazole), TCC (triclocarban), TMP (trimethoprim), TY (tylosin), TP (total pharmaceuticals).
ACT
r
Temperature
0C
CAF
P-Value r
p-value
CBZ
r
p-value
COT
r
p-value
GFB
r
p-value
IBU
r
p-value
LCM
r
p-value
NAP
r
p-value
PX
r
p-value
-0.24 0.06
0.19 0.13
-0.03 0.85
-0.11 0.39
-0.16 0.20
-0.13 0.31
-0.58 0.01
0.05 0.68
-0.42 0.01
-0.13 0.29
-0.06 0.65
-0.49 0.01
-0.32 0.01
-0.25 0.05
-0.11 0.38
-0.02 0.89
-0.01 0.91
-0.03 0.84
SPC (mS/cm)
0.39 0.01
0.36 0.01
0.75 0.01
0.33 0.01
0.65 0.01
0.38 0.01
0.01 0.99
0.33 0.01
-0.04 0.74
TDS (g/L)
Dissolved oxygen
(% Sat)
Dissolved oxygen
(mg/L)
0.39 0.01
0.36 0.01
0.75 0.01
0.33 0.01
0.65 0.01
0.38 0.01
0.01 0.97
0.34 0.01
-0.04 0.77
-0.32 0.01
0.20 0.11
-0.35 0.02
-0.56 0.01
-0.44 0.01
-0.43 0.01
-0.64 0.01
0.09 0.47
-0.49 0.01
-0.01 0.99
-0.28 0.02
0.12 0.41
-0.01 0.98
-0.10 0.43
-0.06 0.66
0.46 0.01
-0.18 0.16
0.36 0.01
Salinity (ppt)
0.39 0.01
0.37 0.01
0.75 0.01
0.32 0.01
0.65 0.01
0.38 0.01
-0.01 0.96
0.34 0.01
-0.05 0.71
Total carbon
0.63 0.01
0.38 0.01
0.19 0.19
0.41 0.01
0.77 0.01
0.47 0.01
0.31 0.01
0.49 0.01
0.24 0.06
Nitrate
0.29 0.02
0.20 0.11
0.37 0.01
0.20 0.12
0.33 0.01
0.01 0.98
-0.03 0.81
0.18 0.16
-0.06 0.63
Phosphate
0.22 0.08
-0.10 0.41
0.45 0.01
0.65 0.01
0.30 0.02
0.32 0.01
0.32 0.01
-0.12 0.36
0.29 0.02
Sulfate
0.25 0.05
0.04 0.78
0.60 0.01
0.28 0.02
0.44 0.01
0.50 0.01
0.19 0.13
0.08 0.54
0.12 0.35
Ammonium
0.18 0.16
0.06 0.63
0.31 0.03
0.20 0.11
0.41 0.01
0.92 0.01
0.21 0.09
0.09 0.49
0.19 0.14
pH
30
Table 4
(Continued)
SDM
r
Temperature
0C
SMR
p-value r
SMT
p-value r
SMZ
p-value r
STZ
p-value r
TCC
p-value r
TMP
p-value r
TY
p-value r
TP
p-value r
p-value
-0.21 0.09
-0.45 0.01
-0.44 0.01
-0.25 0.05
-0.42 0.01
-0.50 0.01
-0.40 0.01
-0.35 0.01
-0.24 0.05
-0.21 0.09
-0.01 0.91
-0.02 0.86
-0.20 0.11
-0.03 0.79
-0.22 0.08
-0.16 0.21
-0.03 0.79
-0.21 0.09
SPC (mS/cm)
0.07 0.57
-0.06 0.61
-0.06 0.64
0.69 0.01
-0.08 0.51
0.07 0.58
0.47 0.01
0.14 0.28
0.71 0.01
TDS (g/L)
Dissolved oxygen
(% Sat)
Dissolved oxygen
(mg/L)
0.08 0.55
-0.06 0.63
-0.05 0.67
0.70 0.01
-0.08 0.54
0.07 0.58
0.48 0.01
0.14 0.26
0.72 0.01
-0.39 0.01
-0.50 0.01
-0.51 0.01
-0.53 0.01
-0.49 0.01
0.13 0.32
-0.60 0.01
-0.43 0.01
-0.54 0.01
0.22 0.08
0.40 0.01
0.39 0.01
0.01 0.98
0.38 0.01
-0.39 0.01
0.23 0.07
0.27 0.03
-0.03 0.83
Salinity (ppt)
0.07 0.61
-0.07 0.58
-0.06 0.62
0.70 0.01
-0.09 0.50
0.07 0.59
0.47 0.01
0.14 0.27
0.71 0.01
Total carbon
0.21 0.10
0.20 0.10
0.20 0.11
0.44 0.01
0.18 0.16
-0.12 0.36
0.32 0.01
0.28 0.03
0.61 0.01
-0.08 0.53
-0.05 0.70
-0.05 0.72
0.15 0.25
-0.06 0.62
0.02 0.89
-0.05 0.70
-0.13 0.29
0.19 0.14
Phosphate
0.23 0.06
0.28 0.02
0.31 0.01
0.43 0.01
0.28 0.03
0.36 0.01
0.53 0.01
0.32 0.01
0.43 0.01
Sulfate
0.09 0.50
0.14 0.26
0.14 0.26
0.74 0.01
0.13 0.32
-0.05 0.70
0.62 0.01
0.14 0.26
0.68 0.01
Ammonium
0.08 0.51
0.19 0.13
0.20 0.11
0.79 0.01
0.18 0.17
0.04 0.74
0.64 0.01
0.26 0.04
0.79 0.01
pH
Nitrate
31
Table 5
Summary of Multiple Regression results assessing factors influencing pharmaceutical concentrations in Lake Michigan. TEMP = temperature; PH = dissolved pH; TC = total carbon; TDS = total
dissolved solids; DO = dissolved oxygen % saturation; NO3 = nitrate; PO4 = phosphate; SO4 = sulfate; NH4 = ammonium
Compound
Regression Equation
Variables Removed
Adjusted
S
R-Sq
Mallows
Cp
Acetaminophen
6.377 + -0.14(TEMP) + -1.25(PH) + 0.28(TC) + 0.06(DO) + 1.02(NO3) + 137(PO4) + -0.05(SO4)
TDS, NH4
58.0
1.70 6.40
Caffeine
-91.85 + 1.14(TC) + 47(TDS) + 0.74(DO) + 1.94(NO3)
TEMP, PH, PO4, SO4, NH4
43.5
10.8 5.40
Carbamazepine
-1.958 + -0.05(TEMP) + -0.15(TC) + 28(TDS) + 0.21(NO3)
PH, DO, PO4, SO4, NH4
67.6
1.49 1.70
Cotinine
11.52 + -0.04(TEMP) + -0.56(PH) + 0.06(TC) + -0.02(DO) + 0.69(NO3) + 164(PO4) + -0.04(SO4)
TDS, NH4
75.4
0.789 7.40
Gemfibrozil
6.484 + -0.35(TEMP) + -4(PH) + 0.79(TC) + 32(TDS) + 0.17(DO) + 2.69(NO3) + 279(PO4) + -0.16(SO4) +
20.2(NH4)
73.9
4.48 10.0
Ibuprofen
24.03 + -2.8(PH) + 0.287(TC) + -1.68(NO3) + -352(PO4) + 161.8(NH4)
TEMP, TDS, DO, SO4
90.1
4.56 3.30
Lincomycin
21.32 + -0.08(TEMP) + -0.90(PH) + 0.04(TC) + -7.1(TDS) + -0.06(DO)
NO3, PO4, SO4, NH4
61.7
0.834 4.90
Naproxen
-23.22 + 0.46(TC) + 0.17(DO) + 0.56(NO3)
TEMP, PH, PO4, SO4, NH4
42.8
3.08 0.40
Paraxanthine
144.6 + -0.34(TEMP) + -4.70(PH) + -36(TDS) + -0.34(DO)
TC, NO3, PO4, SO4, NH4
34.4
7.17 3.70
Sulfadimethoxine
3.441 + -0.12(PH) + -0.01(DO) + -0.003(SO4)
TEMP, TC, TDS, NO3, PO4,NH4
19.0
0.238 1.10
Sulfamerazine
2.960 + -0.01(TEMP) + -0.10(PH) + -0.77(TDS) + -0.01(DO)
TC, NO3, PO4, SO4, NH4
38.8
0.137 2.40
Sulfamethazine
3.004 + -0.01(TEMP) + -0.10(PH) + -0.78(TDS) + -0.01(DO)
TC, NO3, PO4, SO4, NH4
38.7
0.139 2.80
Sulfamethoxazole
-34.43 + -1.10(TEMP) + -1.08(TC) +280(TDS) + -6.3(NO3) + 0.44(SO4) +270(NH4)
PH, DO, PO4,
84.3
19.4 7.10
Sulfathiazole
3.012 + -0.01(TEMP) + -0.10(PH) + -0.81(TDS) + -0.01(DO)
TC, NO3, PO4, SO4, NH4
38.3
0.134 1.80
Triclocarban
-4.753 + 0.12(TEMP) + 0.90(PH) + 0.40(NO3) + 140(PO4) + -0.02(SO4)
TC, TDS, DO, NH4
43.8
1.33 4.80
Trimethoprim
10.679 + -0.10(TEMP) + -0.09(TC) + 8.3(TDS) + -0.05(DO) + -0.97(NO3) + 0.06(SO4) + 8.9 (NH4)
PH, PO4
71.6
1.80 6.10
Tylosin
4.237 + -0.05(TEMP) + 40(PO4)
PH, TC, TDS, DO,NO3, SO4, NH4
20.5
0.937 2.10
Total Pharmaceuticals
-78.40 + -2.00(TEMP) + 1.82(TC) + 414(TDS) + 0.81(DO) + 519(NH4)
PH, NO3, PO4, SO4
82.9
32.9 4.80
32
Table 6
Comparison of pharmaceuticals and personal care products measured in this study relative to previous studies in the Laurentian Great Lak es. Reported concentrations are mean values.
Sampling method used are grab samples. * = compounds not included in study; ** = median values; <DL = below detection limit, † = passive polar organic chemical sampler.
Sample Site
Sample Location
Pharmaceutical concentration (ng/L)
References
Lake Michigan
Harbor
Acetaminophen Caffeine Carbamazepine Gemfibrozil IbuprofenNaproxen Sulfamethoxazole Trimethoprim
6.03
33.75
3.53
11.21
11.37
7.00
47.48
5.97
This Study
Lake Michigan
Open Water
4.70
28.28
0.93
2.85
4.40
5.65
4.45
4.33
Lake Ontario
Hamilton Harbour
17.10
20.30
16.30
14.10
34.60
6.64
1.40
5.51
Lake Ontario
Open Water
<DL
8.00
1.37
<DL
1.12
<DL
0.05
0.26
Lake Ontario
Hamilton Harbour (2000)** *
*
120.00
12.00
64.00
94.00
*
*
Lake Ontario
Open Water (2000)
*
*
20.00
<DL
<DL
<DL
*
*
Lake Ontario
Hamilton Harbour (2002)
*
33.00
23.00
38.00
27.00
39.00
*
43.00
Li et al., 2010 †
Metcalfe et al., 2003
33
Figure 1. Sampling locations in near-shore sites of southern Lake Michigan.
Figure 2. Difference in total pharmaceutical concentrations (sum of all compounds
measured) of near-shore (harbor) samples among Lake Michigan sites over time.
Symbols are mean values (N = 4) SE.
Figure 3. Differences in total pharmaceutical concentrations (sum of all compounds
measured) between near-shore (harbor) and off-shore (open water) sampling locations in
Lake Michigan. Symbols are mean values (N = 4) SE.
Figure 4. Total pharmaceutical concentrations of near-shore (harbor) and off-shore (open
water) sampling locations at the Michigan City site in Lake Michigan. The “Other”
category represents the sum concentration of all PPCP compounds not listed.
Figure 5. Total pharmaceutical concentrations of near-shore (harbor) and off-shore (open
water) sampling locations at the East Chicago site in Lake Michigan. The “Other”
category represents the sum concentration of all PPCP compounds not listed.
Figure 6. Total pharmaceutical concentrations of near-shore (harbor) and off-shore (open
water) sampling locations at the St. Joseph site in Lake Michigan. The “Other” category
represents the sum concentration of all PPCP compounds not listed.
Figure 7. Total pharmaceutical concentrations of near-shore (harbor) and off-shore (open
water) sampling locations at the Chicago site in Lake Michigan. The “Other” category
represents the sum concentration of all PPCP compounds not listed.
Figure 8. Correlation between physical factors (dissolved oxygen and temperature) and
total pharmaceutical concentration in near-shore southern Lake Michigan sites. Total
pharmaceutical concentration is equal to the sum of all pharmaceuticals detected. Data
separated by month.
Figure 9. Correlations of nutrient (dissolved ammonium, total carbon and total dissolved
solids) and pharmaceutical compounds in Lake Michigan. Total pharmaceuticals equal to
sum of all pharmaceuticals detected. Data separated by month.
34
Figure 1:
35
Figure 2:
Total pharmaceuticals (ng/L)
500
St. Joseph
Michigan City
East Chicago
Chicago
400
300
200
100
0
August
November
March
June
Time
36
Figure 3.
Total pharmaceuticals (ng/L)
500
Harbor
Open Water
400
300
200
100
0
August
November
March
June
Time
37
Total pharmaceuticals (ng/L) Total pharmaceuticals (ng/L)
Figure 4:
500
August
November
Other
Other
Sulfamethoxazole
Sulfamethoxazole
Paraxanthine
Paraxanthine
Naproxen
Naproxen
Gemfibrozil
Gemfibrozil
Caffeine
Caffeine
400
300
200
100
0
500
March
June
400
300
200
100
0
shallow
deep
Harbor
shallow
deep
Open water
shallow
deep
Harbor
shallow
deep
Open water
38
Total pharmaceuticals (ng/L) Total pharmaceuticals (ng/L)
Figure 5:
500
August
November
Other
Sulfamethoxazole
Paraxanthine
Naproxen
Gemfibrozil
Caffeine
400
300
200
100
0
500
March
June
400
300
200
100
0
shallow
deep
Harbor
shallow
deep
Open water
shallow
deep
Harbor
shallow
deep
Open water
39
Total pharmaceuticals (ng/L) Total pharmaceuticals (ng/L)
Figure 6:
500
August
400
November
Other
Sulfamethoxazole
Paraxanthine
Naproxen
Gemfibrozil
Caffeine
300
200
100
0
500
June
March
400
300
200
100
0
shallow
deep
Harbor
shallow
deep
Open water
shallow
deep
Harbor
shallow
deep
Open water
40
Total pharmaceuticals (ng/L) Total pharmaceuticals (ng/L)
Figure 7:
500
November
August
400
Other
Sulfamethoxazole
Paraxanthine
Naproxen
Gemfibrozil
Caffeine
300
200
100
0
500
March
June
400
300
200
100
0
shallow
deep
Harbor
shallow
deep
Open water
shallow
deep
Harbor
shallow
deep
Open water
41
Figure 8:
500
August
June
March
November
400
R = -0.242
P = 0.054
Total pharmaceuticals (ng/L)
300
200
100
0
0
5
10
15
20
25
30
Temperature (0C)
500
400
300
200
100
0
80
90
100
110
120
130
140
150
160
Dissolved oxygen (% saturation)
42
Figure 9:
500
400
R = 0.7903
P < 0.0001
300
200
August
June
March
November
100
0
Total pharmaceuticals (ng/L)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Dissolved ammonium (mg NH4-N/L)
500
400
300
200
100
0
0
10
20
30
40
50
Total carbon (mg/L)
500
400
300
200
100
0
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
Total dissolved soilds (g/L)
43
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200.
Beeton, A.M., 1984. The world's great lakes. J. Great Lakes Res. 10, 106-113
Bound, J. P., Voulvoulis, N., 2005. Household Disposal of Pharmaceuticals as a Pathway
for Aquatic Contamination in the United Kingdom. Environ. Health Perspect.
113, 1705-1711.
Brown, J., Bernot, M.J., Bernot, R.J., In press. The influence of TCS on the growth and
behavior of the freshwater snail, Physa acuta. J. Environ. Safety Health Part B.
Brun, G.L., Bernier, M., Losier, R., Doe, K., Jackman, P., Lee, H.B., 2006.
Pharmaceutically active compounds in Atlantic Canadian sewage treatment plant
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by acute and chronic aquatic toxicity. Environ. Toxicol. Chem. 25, 2163-2176.
Buerge, I.J., Buser, H., Müller, M.D., Poiger, T., 2003. Behavior of the polycyclic musks
HHCB and AHTN in lakes, two potential anthropogenic markers for domestic
wastewater in surface waters. Environ. Sci. Technol. 37, 5636-5644.
Buerge, I.J., Poiger, T., Müller, M.D., Buser, H., 2006. Combined sewer overflows to
surface water detected by the anthropogenic marker caffeine. Environ. Sci.
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Bunch, A.R., Bernot, M.J., 2010. Distribution of nonprescription pharmaceuticals in
central Indiana streams and effects on sediment microbial activity. Ecotoxicology.
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Buser, H., Poiger, T., Müller, M.D., 1998. Occurrence and fate of the pharmaceutical
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44
Carr, D.L., Morse, A.N., Zak, J.C., Anderson, T.A., 2011. Microbially mediated
degradation of common pharmaceuticals and personal care products in soil under
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Castiglioni, S., Bagnati, R., Fanelli, R., Pomati, F., Calamari, D., Zuccato, E., 2006.
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Daughton, C.G., 2001. “Emerging” pollutants, and communicating the science of
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concentrations of pharmaceuticals. Aquat. Toxicol. 78, 209–216.
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Eaton, A.D., Clesceri, L.S., Rice, W. E.,Greenberg, A.E., 2005. Standard methods for the
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Evans, M.S., Noguchi, G.E., Rice, C.P., 1991. The biomagnification of polychlorinated
biphenyls, toxaphene, and DDT compounds in a Lake Michigan offshore food
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Barber, L.B., Thurman, M.E., 2008. A national reconnaissance for
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Glassmeyer, S.T., Furlong, E.T., Kolpin, D.W., Cahill, J.D., Zaugg, S.D., Werner, S.L.,
Meyer, M. T., Kryak, D.D., 2005. Transport of chemical and microbial
compounds from known wastewater discharges: potential for use as indicators of
human fecal contamination. Environ. Sci. Technol. 39, 5157-5169.
Gros, M., Petrovic, M., Ginebreda, A., Barceló, D., 2010. Sources, occurrence, and
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Env. Chem. 13, 209-237.
45
Halling-Sørensen, B., Nors Nielsen, S. Lanzky, P.F., Ingerslev, F., Holten Lützhøft, H.C.,
Jørgensen, S.E., 1998. Occurrence, fate and effects of pharmaceutical substances
in the environment – a review. Chemosphere. 36, 357-393.
Ji, R., Chen, C., Budd, J.W., Schwab, D.J., Beletsky, D., Fahnenstiel, G.L., Johengen,
T.H., Vanderploeg, H., Eadie, B., Cotner, J., Gardner, W., Bundy, M., 2002.
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Jones, O.A.H., Voulvoulis, N., Lester, J.N., 2001. Human pharmaceuticals in the aquatic
environment a review. Environmental Technology. 22, 1383-1394.
Jones, O.A.H., Voulvoulis, N., Lester, J.N., 2004. Potential ecological and human health
risks associated with the presence of pharmaceutically active compounds in the
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Jørgensen, S.E., Halling-Sørensen, B., 2000. Drugs in the environment. Chemosphere.
40, 691-699.
Kimura, K., Hara, H., Watanabe, Y., 2005. Removal of pharmaceutical compounds by
submerged membrane bioreactors (MBRs). Desalination. 178, 135-140.
Kolpin, D.W., Furlong, E.T., Meyer, M.T., Thurman, E.M., Zaugg, S.D., Barber, L.B.,
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Kümmerer, K., 2010. Pharmaceuticals in the environment. Annu. Rev. Environ. Resour.
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pharmaceuticals, personal care products, and the endocrine-disrupting substance
46
using the passive polar organic chemical integrative sampler. Environ. Toxicol.
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48
Appendix 1. Physiochemical data collected in near-shore Lake Michigan sites.
Site
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
LOC
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
Date
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
DEPTH
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
Temperature
(°C)
pH
26.42
26.31
26.06
25.59
26.1
25.9
26.3
25.49
26.25
15.76
24.81
17.32
21.15
20.57
26.21
13.58
7.93
7.75
10.03
10.19
8.16
7.92
10.25
10.19
13.2
10.62
9.57
8.98
8.97
8.48
9.37
8.63
6.11
6.12
2.74
4.53
6.25
6.18
4.56
4.5
12.92
10.16
3.68
3.63
4.1
3.98
2.86
2.81
21.83
21.82
19.69
19.23
20.29
19.32
17.94
17.61
21.22
16.38
18.7
15.9
17.64
16.55
17.8
15.46
9.4
9.39
9.5
9.5
9.12
9.02
9.19
9.07
9.27
9.35
9.56
9.45
9.67
9.47
9.49
9.34
9.37
9.62
10.06
10.09
9.14
9.34
9.95
9.96
9.67
9.85
9.94
9.9
10.04
9.96
10.06
10
8.59
9.56
9.77
9.76
9.02
9.07
9.44
9.59
8.99
9.2
9.45
9.56
9.92
10.02
9.53
9.61
8.38
8.54
8.57
8.65
8.69
8.49
8.59
8.68
8.92
9.24
9.41
9.56
9.1
9.38
9.25
9.43
TC
(mg/L)
26.98
29.08
17.86
12.05
11.16
15.86
13.45
11.99
11.86
14.1
14.5
12.46
12.74
11.91
12.77
15.01
33.83
43.43
21.19
20.96
26.5
23.19
18.9
22.64
21.17
20.36
22.17
22.22
21.15
16.15
21.91
20.68
33.55
20.7
15.88
15.7
18.17
18.71
15.14
20.7
31.8
27.8
12.97
17.65
10.89
13.23
12.97
14.51
24.26
26.05
14.86
20.26
27.94
26.82
16.26
14.86
16.95
15.47
16.46
12.58
19.25
13.17
17.99
19.36
Total
Specific
Dissolved
Conductivity
Solids
(mS/cm)
(g/L)
597.8
0.3832
597.7
0.3825
357.4
0.2289
358.9
0.2313
567
0.3608
609.7
0.3811
323.5
0.2072
320.2
0.205
525.9
0.3343
312.7
0.1984
316.1
0.2021
304.6
0.1945
310.1
0.1981
308.7
0.1975
317.3
0.2032
299.3
0.193
644.4
0.4122
652.8
0.4181
316.8
0.2029
316.5
0.2033
603.1
0.3815
600.1
0.3874
315.3
0.2021
320
0.2048
402.9
0.2588
371.1
0.2363
319.9
0.2048
316.2
0.2024
312.5
0.1998
312.1
0.1999
309.9
0.1981
310.3
0.1987
549.3
0.3521
550
0.352
329.8
0.2114
397.6
0.2461
725.5
0.4651
727.6
0.4663
352
0.2255
353.3
0.2272
630.3
0.4037
585.1
0.3754
308.9
0.1979
309.2
0.1979
316.9
0.2028
317.2
0.2031
291.1
0.1869
293
0.1874
575.8
0.3684
580.3
0.3714
298
0.1909
296.8
0.19
533.2
0.3374
463.9
0.3003
304.6
0.1948
301
0.1923
481.5
0.3079
311.9
0.2024
292.1
0.1875
286.3
0.1832
283
0.1813
283.8
0.1816
285.5
0.183
283.3
0.1812
DO
(%sat)
DO
(mg/L)
Salinity
(ppt)
115
113.4
133.6
128.4
132.6
127.2
130
129.1
110.6
144.4
140
150.8
144.5
144.2
130.8
147.7
114.1
114.4
115.4
115.2
109.1
107.7
114.4
114.3
103.5
106.5
114.8
113.3
112.1
111
114.1
112.5
109
108.4
108.9
109.4
106
105.6
113.8
117
90
92.4
108.6
111.2
110.7
114
111.8
117
108.8
109.3
112.9
115.2
103.1
103.9
117.9
120.7
98.4
115.4
121.2
129.8
124.6
129.8
119.2
131
9.21
9.13
10.8
10.48
10.72
10.34
10.48
10.56
8.9
14.4
11.59
14.44
12.83
12.96
10.56
15.51
13.5
13.59
12.99
12.91
12.84
12.74
12.82
12.84
10.89
11.74
13.19
13.09
12.97
12.94
13.04
13.11
17.81
17.74
19.43
18.91
17.21
17.18
19.31
19.92
12.58
13.71
18.9
19.36
19.1
19.63
19.87
20.72
12.6
12.68
13.64
14.04
12.35
12.63
14.74
15.17
11.47
14.87
14.88
16.91
15.72
16.76
14.97
17.19
0.31
0.31
0.18
0.18
0.29
0.3
0.16
0.16
0.27
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.33
0.34
0.15
0.15
0.31
0.31
0.15
0.16
0.2
0.18
0.16
0.15
0.15
0.15
0.15
0.15
0.28
0.28
0.16
0.19
0.37
0.38
0.17
0.17
0.32
0.3
0.15
0.15
0.15
0.15
0.14
0.14
0.29
0.3
0.14
0.14
0.26
0.23
0.15
0.15
0.24
0.15
0.14
0.14
0.14
0.14
0.14
0.14
49
Appendix 2. Pharmaceutical and personal care product data collected in near-shore Lake Michigan sites.
Site
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
LOC
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
Date
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
DEPTH
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
Paraxanthine (1,7Acetaminophen Caffeine Carbamazepine Cotinine Gemfibrozil Ibuprofen Lincomycin Naproxen
Sulfadimethoxine Sulfamerazine Sulfamethazine Sulfamethoxazole Sulfathiazole Triclocarban Trimethoprim Tylosin
Dimethylxanthine
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
(ng/L)
3.2
3.4
3.3
3.6
4.5
3.1
4.6
3.1
3.3
2.8
3.4
3.7
5.1
2.5
4.8
3.4
13
17
7.6
3.5
15
7.3
4
4.7
7.1
4
5.7
4.8
4.1
4.4
4.7
5.7
5
4.9
4.8
5
5
5
4.9
5
5
5
4.8
4.9
5
4.9
5.1
4.9
5
5.7
5
5
11
11
5
5
5.6
4.9
5
5
5
5
5.2
5.1
32
34
34
36
56
42
46
31
33
28
34
38
52
25
49
34
100
97
38
18
36
24
20
23
28
20
29
24
20
22
23
29
25
25
24
25
25
25
25
25
25
25
24
24
25
24
25
25
25
29
25
25
39
36
25
25
28
25
25
25
25
25
26
26
2.4
2.1
0.7
0.9
5.9
5.5
0.9
0.6
3.9
0.6
0.7
0.7
1
0.5
1
0.7
1.7
2
1.5
0.7
10
9.8
0.8
0.9
4.5
1.3
1.1
1
0.8
0.9
0.9
1.1
1
1.1
1
1
9.9
8.7
1
1
4.3
4.7
1
1
1
1
1
1
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
3.1
3.2
2.1
1.7
4.7
4.2
2.7
1.7
3.9
1.5
2.1
1.9
3.6
1.8
2.5
1.7
5.5
5
6
2.8
6.1
5.3
3.2
3.8
5.7
3.2
4.6
3.8
3.3
3.5
3.7
4.6
4
4
3.9
4
4
4
3.9
4
4
4
3.9
3.9
4
3.9
4
3.9
4.4
4.6
4
4
9.4
11
4.6
4
7.9
3.9
4
4
4
4
4.1
4.1
9.3
10
1.6
1.9
3.7
5.1
1.9
1.2
1.7
1.1
1.4
1.5
2
1
1.9
2
25
49
3
1.4
22
25
1.6
1.9
25
5.2
2.3
1.9
1.6
1.8
1.9
2.3
13
15
5.1
5.8
11
5.1
4.7
4.7
19
16
4.1
3.6
4.6
5.6
2.7
2.4
7.4
14
4.3
5.2
22
26
4.6
4.1
4
2.4
2.1
3.2
2.7
2.4
2.3
2.6
5.1
2
2.9
3.1
6.9
4.7
2.8
2.4
2
1.7
2.1
2.2
3.1
3.3
2.9
2
28
30
7.6
3.5
5.2
6.2
4
4.7
5.6
5.7
5.7
4.8
4.1
4.4
4.7
5.7
5
4.9
4.8
5
5
5
4.9
5
84
84
4.8
4.9
5
4.9
5.1
4.9
5
5.7
5
5
5.2
5.2
5
5
12
4.9
5
5
5
5
5.2
5.1
1.9
2
2
2.2
2.7
1.6
2.8
1.9
2
1.7
2.1
2.2
3.1
1.5
2.9
2
4.2
5.1
7.6
3.5
5.2
4.8
4
4.7
5.6
4
5.7
4.8
4.1
4.4
4.7
5.7
5
4.9
4.8
5
5
5
4.9
5
5
5
4.8
4.9
5
4.9
5.1
4.9
5
5.7
5
5
5.2
5.1
5
5
5.6
4.9
5
5
5
5
5.2
5.1
6.4
6.8
6.7
7.3
6.4
5.4
9.3
6.2
6.7
5.6
6.8
7.5
10
5
9.7
6.8
25
30
7.6
3.5
5.2
4.8
4
4.7
5.6
4
5.7
4.8
4.1
4.4
4.7
5.7
5
4.9
4.8
5
5
5
4.9
5
5
5
4.8
4.9
5
4.9
5.1
4.9
6.6
8.3
5
5
7.9
5.4
5
5
5.6
4.9
5
5
5
5
5.2
5.1
32
34
34
36
32
27
46
31
33
28
34
38
51
25
49
34
42
51
76
35
52
48
40
47
56
40
57
48
41
44
47
57
50
49
48
50
50
50
49
50
50
50
48
49
50
49
51
49
50
57
50
50
52
51
50
50
56
49
50
50
50
50
52
51
0.6
0.7
0.7
0.7
0.6
0.5
0.9
0.6
0.7
0.6
0.7
0.7
1
0.5
1
0.7
0.8
1
1.5
0.7
1
1
0.8
0.9
1.1
0.8
1.1
1
0.8
0.9
0.9
1.1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2.5
1.1
1
1
1
1
1
1
1.1
1
1
1
1
1
1
1
0.6
0.7
0.7
0.7
0.6
0.5
0.9
0.6
0.7
0.6
0.7
0.7
1
0.5
1
0.7
0.8
1
1.5
0.7
1
1
0.8
0.9
1.1
0.8
1.1
1
0.8
0.9
0.9
1.1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1.1
1
1
1
1
1
1
1.1
1
1
1
1
1
1
1
0.6
0.7
0.7
0.7
0.6
0.5
0.9
0.6
0.7
0.6
0.7
0.7
1
0.5
1
0.7
0.8
1
1.5
0.7
1
1
0.8
0.9
1.1
0.8
1.1
1
0.8
0.9
0.9
1.1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1.1
1
1
1
1
1
1
1.2
1
1
1
1
1
1
1
21
19
4.9
6.4
5.9
5.2
2.8
1.9
12
1.7
2.1
2.2
3.1
1.5
2.9
2
70
68
4.9
2.2
88
97
2.4
3
89
32
5.9
3.2
2.5
2.6
2.8
3.4
40
38
8.3
12
170
180
11
11
200
220
5.8
6.4
8.7
23
4.4
4.1
19
24
3.7
3.3
11
13
3.7
3.5
44
4.3
3
3
3
3
3.1
3.1
0.6
0.7
0.7
0.7
0.6
0.5
0.9
0.9
0.7
0.6
0.7
0.7
1
0.5
1
0.7
0.8
1
1.5
0.7
1
1
0.8
0.9
1.1
0.8
1.1
1
0.8
0.9
0.9
1.1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1.1
1
1
1
1
1
1
1.1
1
1
1
1
1
1
1
6.4
6.8
6.7
7.3
6.4
5.4
9.3
6.2
7.6
5.6
6.8
7.5
10
2.5
9.7
6.8
4.2
5.1
7.6
3.5
5.2
5.5
4
4.7
5.6
4
5.7
4.8
4.1
4.4
4.7
5.7
5
4.9
4.8
5
5
5
4.9
5
5
5
4.8
4.9
5
4.9
5.1
4.9
5
5.7
5
5
9.4
8
5
5
14
4.9
5
5
5
5
5.2
5.1
2.5
2.4
2
2.2
1.9
1.6
2.8
1.9
2
1.7
2.1
2.2
3.1
1.5
2.9
2
6.1
6
7.6
3.5
5.2
4.8
4
4.7
10
4
5.7
4.8
4.1
4.4
4.7
5.7
5
4.9
4.8
5
18
18
4.9
5
15
15
4.8
4.9
5
4.9
5.1
4.9
5.4
5.7
5
5
5.2
5.1
5
5
7.7
4.9
5
5
5
5
5.2
5.1
5.4
3
2
4.5
1.9
1.6
2.8
1.9
2
1.7
2.1
6.7
3.1
1.5
2.9
2
3.4
4
6
2.8
4.2
3.8
3.2
3.8
4.4
3.2
4.6
3.8
3.3
3.5
3.7
4.6
4
4
3.9
4
6.1
4
3.9
4
4
5.9
3.9
3.9
4
3.9
4
3.9
4
4.6
4
4
4.1
4.1
4
4
4.5
3.9
4
4
4
4
4.1
4.1
TOT
PHARM
133.1
131.5
105.7
115.9
141.3
114.4
138.3
93.7
115.9
84.1
102.5
117.1
154.2
74.6
146.1
102.2
331.3
373.2
187
86.7
263.3
250.3
98.4
115.2
256.5
133.8
143.1
118.5
100.3
108.3
114.8
140.6
171
169.5
127
135.8
323
323.8
131.9
133.7
429.3
448.6
123.5
125.2
131.3
143.8
126.7
122.7
147.3
174.4
125
125.5
185.4
184.9
125.9
124.6
199.4
121.9
122.1
123.2
122.7
122.4
126.8
125.5
50
Appendix 3. Cation and anion data collected in near-shore Lake Michigan sites.
Site
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
STJOE
STJOE
STJOE
STJOE
MICH
MICH
MICH
MICH
ECHIC
ECHIC
ECHIC
ECHIC
CHICA
CHICA
CHICA
CHICA
LOC
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
HARB
HARB
OPEN
OPEN
Date
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
AUG
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
NOV
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
MAR
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
JUN
DEPTH
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
SHAL
DEEP
Sulfate
21.78
14.78
21.97
15.27
22.73
50.02
30.20
24.58
157.80
27.34
14.29
14.98
6.07
24.28
18.49
28.24
63.97
63.61
35.33
33.69
70.44
70.42
33.36
35.51
69.97
49.36
36.30
35.49
33.34
35.59
34.75
33.94
67.39
67.51
39.98
44.25
99.86
101.36
41.34
42.95
113.52
105.99
35.52
35.98
36.87
37.28
33.92
35.08
39.87
40.66
23.50
23.00
46.67
49.21
23.65
23.72
56.93
28.77
24.14
22.94
22.77
22.59
22.46
23.02
Sodium Ammonium Potassium Magnesium Calcium
18.20
18.61
9.17
9.72
21.60
29.53
7.55
7.78
24.25
8.78
8.83
8.48
8.76
7.87
7.86
6.38
19.44
19.55
8.53
7.50
27.27
28.70
7.45
8.55
23.27
13.71
8.50
8.22
7.33
8.38
8.14
7.35
15.09
14.80
9.38
10.34
42.51
44.88
9.22
9.71
43.75
39.01
9.84
9.81
11.16
15.71
8.17
8.33
14.94
15.16
7.88
7.83
32.22
33.25
8.30
8.57
28.97
10.71
7.98
7.37
7.15
7.07
7.03
7.16
0.03
0.02
0.01
0.01
0.03
0.02
0.01
0.00
0.08
0.03
0.01
0.03
0.03
0.03
0.02
0.02
0.13
0.11
0.07
0.01
0.08
0.06
0.01
0.04
0.18
0.09
0.04
0.03
0.03
0.05
0.03
0.05
0.05
0.06
0.02
0.01
0.08
0.09
0.02
0.00
0.54
0.45
0.07
0.05
0.05
0.07
0.04
0.04
0.02
0.02
0.01
0.01
0.04
0.05
0.01
0.01
0.20
0.03
0.01
0.01
0.01
0.00
0.02
0.02
3.16
2.52
1.59
1.69
2.51
3.02
1.56
1.43
3.79
1.67
2.04
1.73
1.51
1.74
1.44
1.26
2.38
2.42
2.33
1.39
3.67
3.52
1.49
2.60
3.37
2.68
1.64
1.93
1.53
1.83
1.85
2.97
2.16
2.12
1.55
1.61
3.14
3.18
1.58
1.59
4.76
4.83
1.35
1.37
1.32
1.48
1.31
1.33
1.91
1.92
1.34
1.37
2.73
2.83
1.35
1.42
3.31
1.75
1.33
1.60
1.29
1.28
1.29
1.52
23.14
23.87
14.19
14.60
16.11
18.70
12.22
12.57
13.84
12.62
13.01
13.44
13.43
12.08
12.58
11.18
24.25
24.33
13.61
12.29
20.46
20.10
11.89
13.46
15.34
14.59
11.99
11.95
11.81
13.40
13.24
11.85
21.31
20.83
13.33
14.59
22.57
22.63
13.70
14.53
19.38
18.74
12.18
12.26
12.23
12.60
11.87
11.92
21.84
21.78
12.05
11.97
19.48
21.08
12.05
12.09
16.69
12.43
11.84
11.82
11.89
11.77
11.76
11.83
28.63
34.16
19.19
9.25
12.36
18.69
12.16
12.51
13.89
13.52
14.54
15.39
10.60
11.16
10.67
14.77
45.85
46.88
33.08
30.80
53.97
49.95
21.71
34.06
37.19
31.71
28.58
28.81
26.08
29.06
32.60
28.93
52.65
27.76
27.41
24.64
33.03
36.50
20.04
28.52
29.45
32.02
17.63
22.57
16.93
18.11
15.11
21.18
43.24
37.54
25.09
26.61
45.96
53.64
23.60
21.59
29.94
23.83
21.24
22.84
27.07
21.65
23.54
23.25
51