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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
2
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.
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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.
4
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 (1.5-
7.9 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
5
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.
6
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
7
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 (0-
730 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
8
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
9
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
10
with water-column ammonium concentrations, following waste input, and negatively
correlated with temperature, following biotic degradation potential.
11
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 carry-
over 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
12
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.
13
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
14
regression analyses were performed using Minitab 16 (Minitab®
Inc. 2010, USA). Alpha
level was set at 0.05 for all statistical analyses.
15
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
16
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,
17
whereas ammonium concentrations influenced only 24% of individual PPCP compounds
measured.
18
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
19
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)
20
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
21
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
22
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
23
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
24
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.
25
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.
26
Table 1
Summary of pharmaceutical and personal care product concentrations measured in near-shore habitats of Lake
Michigan. N=64
PPCP Compound Common Use Chemical Structure
Detection
Limit
(ng/L)
Mean
Concentration
(ng/L)
Minimum
Concentration
(ng/L)
Maximum
Concentration
(ng/L)
Acetaminophen Antipyretic
5.00 5.36 2.50 17.0
Caffeine Stimulant
25.0 31.0 18.0 100
Carbamazepine Anticonvulsant
1.00 2.23 0.50 10.0
Cotinine Nicotine
metabolite2.00 4.03 1.50 11.0
Gemfibrozil Lipid regulator
1.00 7.03 1.00 49.0
Ibuprofen Anti-inflammatory
5.00 7.88 1.70 84.0
Lincomycin Antibiotic
2.50 4.28 1.50 7.6
Naproxen Anti-inflammatory
2.50 6.32 3.50 30.0
27
Table 1 (Continued)
PPCP Compound Common Use Chemical Structure
Detection
Limit
(ng/L)
Mean
Concentration
(ng/L)
Minimum
Concentration
(ng/L)
Maximum
Concentration
(ng/L)
Paraxanthine Caffeine metabolite
25.0 46.2 25.0 76.0
Sulfadimethoxine Antibiotic
0.50 0.94 0.50 2.50
Sulfamerazine Antibiotic
0.50 0.92 0.50 1.50
Sulfamethazine Antibiotic
0.50 0.92 0.50 1.50
Sulfamethoxazole Antibiotic
1.00 26.0 1.50 220
Sulfathiazole Antibiotic
0.50 0.92 0.50 1.50
Triclocarban Antimicrobial
2.50 5.72 2.50 14.0
Trimethoprim Antibiotic
2.50 5.15 1.50 18.0
Tylosin Antibiotic
2.00 3.75 1.50 6.70
28
Table 2
Sampling site characteristics. Values as a Range.
Site Location Sampling Depth
(m)
Temperature
(°C)
pH DO (%sat) DO (mg/L)
St. Joseph
Harbor1.0-1.0 6.1-26.4 8.4-9.4 108.8-115.0 9.2-17.8
5.4-7.6 6.1-26.3 8.5-9.6 108.4-114.4 9.1-17.7
Open Water1.0-1.0 2.7-26.1 8.6-10.1 108.9-134.0 10.8-19.4
3.7-4.2 4.5-25.6 8.7-10.1 109.4-128.4 10.5-19.0
Michigan City
Harbor1.0-1.0 6.3-26.1 8.7-9.1 103.1-132.6 10.7-17.2
3.3-4.0 6.2-26.0 8.5-9.3 104.0-127.2 10.3-17.2
Open Water1.0-1.0 4.6-26.3 8.6-10.0 113.8-130.0 10.5-19.3
3.8-5.5 4.5-25.5 8.7-10.0 114.3-129.1 10.6-20.0
East Chicago
Harbor1.0-1.0 13.2-26.3 8.9-9.7 90.0-110.6 8.9-12.6
5.7-9.8 10.2-16.4 9.2-9.9 92.4-144.4 11.7-14.9
Open Water1.0-1.0 3.7-24.8 9.4-10.0 108.6-140.0 11.6-18.9
5.0-6.4 3.6-17.3 9.5-10.0 111.2-150.8 13.1-19.4
Chicago
Harbor1.0-1.0 4.1-21.2 9.1-10.0 110.7-144.5 12.8-19.1
4.2-7.0 4.0-20.6 9.4-10.0 111.0-144.2 12.9-19.6
Open Water1.0-1.0 2.9-26.2 9.3-10.1 111.8-130.8 13.0-19.9
6.6-10.7 2.8-15.5 9.3-10.0 112.5-147.7 13.1-20.7
29
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
30
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 CAF CBZ COT GFB IBU LCM NAP PX
r P-Value r p-value r p-value r p-value r p-value r p-value r p-value r p-value r p-value
Temperature 0C -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
pH -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) 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
Dissolved oxygen
(% Sat) -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
Dissolved oxygen
(mg/L) -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
31
Table 4
(Continued)
SDM SMR SMT SMZ STZ TCC TMP TY TP
r p-value r p-value r p-value r p-value r p-value r p-value r p-value r p-value r p-value
Temperature 0C -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
pH -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) 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
Dissolved oxygen
(% Sat) -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
Dissolved oxygen
(mg/L) 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
Nitrate -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
32
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
R-SqS
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
33
Table 6
Comparison of pharmaceuticals and personal care products measured in this study relative to previous studies in the Laurentian Great Lakes. 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
Acetaminophen Caffeine Carbamazepine
Pharmaceutical concentration (ng/L) References
Gemfibrozil IbuprofenNaproxen Sulfamethoxazole Trimethoprim
Lake Michigan Harbor 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 Li et al., 2010 †
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 * * Metcalfe et al., 2003
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
34
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.
35
Figure 1:
36
Figure 2:
Time
August November March June
Tota
l pharm
aceuticals
(ng/L
)
0
100
200
300
400
500
St. Joseph
Michigan City
East Chicago
Chicago
37
Figure 3.
Time
August November March June
To
tal ph
arm
aceuticals
(n
g/L
)
0
100
200
300
400
500
Harbor
Open Water
38
Figure 4:
November
Caffeine
Gemfibrozil
Naproxen
Paraxanthine
Sulfamethoxazole
Other
August
0
100
200
300
400
500
Other
Sulfamethoxazole
Paraxanthine
Naproxen
Gemfibrozil
Caffeine
June
Harbor Open water
shallow deep shallow deep
March
Harbor Open water
shallow deep shallow deep
0
100
200
300
400
500
Tota
l pharm
aceuticals
(ng/L
)Tota
l pharm
aceuticals
(ng/L
)
39
Figure 5:
NovemberAugust
0
100
200
300
400
500
Caffeine Gemfibrozil
Naproxen
Paraxanthine
Sulfamethoxazole
Other
June
Harbor Open water
shallow deep shallow deep
March
Harbor Open water
shallow deep shallow deep
0
100
200
300
400
500
Tota
l pharm
aceuticals
(ng/L
)Tota
l pharm
aceuticals
(ng/L
)
40
Figure 6:
NovemberAugust
0
100
200
300
400
500
Caffeine
Naproxen
Paraxanthine
Sulfamethoxazole
Other
Gemfibrozil
June
Harbor Open water
shallow deep shallow deep
March
Harbor Open water
shallow deep shallow deep
0
100
200
300
400
500
Tota
l pharm
aceuticals
(ng/L
)Tota
l pharm
aceuticals
(ng/L
)
41
Figure 7:
November
June
Harbor Open water
shallow deep shallow deep
August
0
100
200
300
400
500
Caffeine Gemfibrozil
Naproxen Paraxanthine Sulfamethoxazole Other
March
Harbor Open water
shallow deep shallow deep
0
100
200
300
400
500
Tota
l pharm
aceuticals
(ng/L
)Tota
l pharm
aceuticals
(ng/L
)
42
Figure 8:
Dissolved oxygen (% saturation)
80 90 100 110 120 130 140 150 160
0
100
200
300
400
500
R = -0.242P = 0.054
Temperature (0C)
0 5 10 15 20 25 30
0
100
200
300
400
500
August
June
March
November
To
tal p
ha
rma
ce
utica
ls (n
g/L
)
43
Figure 9:
Total dissolved soilds (g/L)
0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
0
100
200
300
400
500
R = 0.7903P < 0.0001
Dissolved ammonium (mg NH4-N/L)
0.0 0.1 0.2 0.3 0.4 0.5 0.6
0
100
200
300
400
500
August
June
March
November
Total carbon (mg/L)
0 10 20 30 40 50
0
100
200
300
400
500
Tota
l pharm
aceuticals
(ng/L
)
44
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49
Appendix 1. Physiochemical data collected in near-shore Lake Michigan sites.
Site LOC Date DEPTHTemperature
(°C)pH
TC
(mg/L)
Specific
Conductivity
(mS/cm)
Total
Dissolved
Solids
(g/L)
DO
(%sat)
DO
(mg/L)
Salinity
(ppt)
STJOE HARB AUG SHAL 26.42 9.4 26.98 597.8 0.3832 115 9.21 0.31
STJOE HARB AUG DEEP 26.31 9.39 29.08 597.7 0.3825 113.4 9.13 0.31
STJOE OPEN AUG SHAL 26.06 9.5 17.86 357.4 0.2289 133.6 10.8 0.18
STJOE OPEN AUG DEEP 25.59 9.5 12.05 358.9 0.2313 128.4 10.48 0.18
MICH HARB AUG SHAL 26.1 9.12 11.16 567 0.3608 132.6 10.72 0.29
MICH HARB AUG DEEP 25.9 9.02 15.86 609.7 0.3811 127.2 10.34 0.3
MICH OPEN AUG SHAL 26.3 9.19 13.45 323.5 0.2072 130 10.48 0.16
MICH OPEN AUG DEEP 25.49 9.07 11.99 320.2 0.205 129.1 10.56 0.16
ECHIC HARB AUG SHAL 26.25 9.27 11.86 525.9 0.3343 110.6 8.9 0.27
ECHIC HARB AUG DEEP 15.76 9.35 14.1 312.7 0.1984 144.4 14.4 0.15
ECHIC OPEN AUG SHAL 24.81 9.56 14.5 316.1 0.2021 140 11.59 0.15
ECHIC OPEN AUG DEEP 17.32 9.45 12.46 304.6 0.1945 150.8 14.44 0.15
CHICA HARB AUG SHAL 21.15 9.67 12.74 310.1 0.1981 144.5 12.83 0.15
CHICA HARB AUG DEEP 20.57 9.47 11.91 308.7 0.1975 144.2 12.96 0.15
CHICA OPEN AUG SHAL 26.21 9.49 12.77 317.3 0.2032 130.8 10.56 0.15
CHICA OPEN AUG DEEP 13.58 9.34 15.01 299.3 0.193 147.7 15.51 0.15
STJOE HARB NOV SHAL 7.93 9.37 33.83 644.4 0.4122 114.1 13.5 0.33
STJOE HARB NOV DEEP 7.75 9.62 43.43 652.8 0.4181 114.4 13.59 0.34
STJOE OPEN NOV SHAL 10.03 10.06 21.19 316.8 0.2029 115.4 12.99 0.15
STJOE OPEN NOV DEEP 10.19 10.09 20.96 316.5 0.2033 115.2 12.91 0.15
MICH HARB NOV SHAL 8.16 9.14 26.5 603.1 0.3815 109.1 12.84 0.31
MICH HARB NOV DEEP 7.92 9.34 23.19 600.1 0.3874 107.7 12.74 0.31
MICH OPEN NOV SHAL 10.25 9.95 18.9 315.3 0.2021 114.4 12.82 0.15
MICH OPEN NOV DEEP 10.19 9.96 22.64 320 0.2048 114.3 12.84 0.16
ECHIC HARB NOV SHAL 13.2 9.67 21.17 402.9 0.2588 103.5 10.89 0.2
ECHIC HARB NOV DEEP 10.62 9.85 20.36 371.1 0.2363 106.5 11.74 0.18
ECHIC OPEN NOV SHAL 9.57 9.94 22.17 319.9 0.2048 114.8 13.19 0.16
ECHIC OPEN NOV DEEP 8.98 9.9 22.22 316.2 0.2024 113.3 13.09 0.15
CHICA HARB NOV SHAL 8.97 10.04 21.15 312.5 0.1998 112.1 12.97 0.15
CHICA HARB NOV DEEP 8.48 9.96 16.15 312.1 0.1999 111 12.94 0.15
CHICA OPEN NOV SHAL 9.37 10.06 21.91 309.9 0.1981 114.1 13.04 0.15
CHICA OPEN NOV DEEP 8.63 10 20.68 310.3 0.1987 112.5 13.11 0.15
STJOE HARB MAR SHAL 6.11 8.59 33.55 549.3 0.3521 109 17.81 0.28
STJOE HARB MAR DEEP 6.12 9.56 20.7 550 0.352 108.4 17.74 0.28
STJOE OPEN MAR SHAL 2.74 9.77 15.88 329.8 0.2114 108.9 19.43 0.16
STJOE OPEN MAR DEEP 4.53 9.76 15.7 397.6 0.2461 109.4 18.91 0.19
MICH HARB MAR SHAL 6.25 9.02 18.17 725.5 0.4651 106 17.21 0.37
MICH HARB MAR DEEP 6.18 9.07 18.71 727.6 0.4663 105.6 17.18 0.38
MICH OPEN MAR SHAL 4.56 9.44 15.14 352 0.2255 113.8 19.31 0.17
MICH OPEN MAR DEEP 4.5 9.59 20.7 353.3 0.2272 117 19.92 0.17
ECHIC HARB MAR SHAL 12.92 8.99 31.8 630.3 0.4037 90 12.58 0.32
ECHIC HARB MAR DEEP 10.16 9.2 27.8 585.1 0.3754 92.4 13.71 0.3
ECHIC OPEN MAR SHAL 3.68 9.45 12.97 308.9 0.1979 108.6 18.9 0.15
ECHIC OPEN MAR DEEP 3.63 9.56 17.65 309.2 0.1979 111.2 19.36 0.15
CHICA HARB MAR SHAL 4.1 9.92 10.89 316.9 0.2028 110.7 19.1 0.15
CHICA HARB MAR DEEP 3.98 10.02 13.23 317.2 0.2031 114 19.63 0.15
CHICA OPEN MAR SHAL 2.86 9.53 12.97 291.1 0.1869 111.8 19.87 0.14
CHICA OPEN MAR DEEP 2.81 9.61 14.51 293 0.1874 117 20.72 0.14
STJOE HARB JUN SHAL 21.83 8.38 24.26 575.8 0.3684 108.8 12.6 0.29
STJOE HARB JUN DEEP 21.82 8.54 26.05 580.3 0.3714 109.3 12.68 0.3
STJOE OPEN JUN SHAL 19.69 8.57 14.86 298 0.1909 112.9 13.64 0.14
STJOE OPEN JUN DEEP 19.23 8.65 20.26 296.8 0.19 115.2 14.04 0.14
MICH HARB JUN SHAL 20.29 8.69 27.94 533.2 0.3374 103.1 12.35 0.26
MICH HARB JUN DEEP 19.32 8.49 26.82 463.9 0.3003 103.9 12.63 0.23
MICH OPEN JUN SHAL 17.94 8.59 16.26 304.6 0.1948 117.9 14.74 0.15
MICH OPEN JUN DEEP 17.61 8.68 14.86 301 0.1923 120.7 15.17 0.15
ECHIC HARB JUN SHAL 21.22 8.92 16.95 481.5 0.3079 98.4 11.47 0.24
ECHIC HARB JUN DEEP 16.38 9.24 15.47 311.9 0.2024 115.4 14.87 0.15
ECHIC OPEN JUN SHAL 18.7 9.41 16.46 292.1 0.1875 121.2 14.88 0.14
ECHIC OPEN JUN DEEP 15.9 9.56 12.58 286.3 0.1832 129.8 16.91 0.14
CHICA HARB JUN SHAL 17.64 9.1 19.25 283 0.1813 124.6 15.72 0.14
CHICA HARB JUN DEEP 16.55 9.38 13.17 283.8 0.1816 129.8 16.76 0.14
CHICA OPEN JUN SHAL 17.8 9.25 17.99 285.5 0.183 119.2 14.97 0.14
CHICA OPEN JUN DEEP 15.46 9.43 19.36 283.3 0.1812 131 17.19 0.14
50
Appendix 2. Pharmaceutical and personal care product data collected in near-shore Lake Michigan sites.
Site LOC Date DEPTHAcetaminophen
(ng/L)
Caffeine
(ng/L)
Carbamazepine
(ng/L)
Cotinine
(ng/L)
Gemfibrozil
(ng/L)
Ibuprofen
(ng/L)
Lincomycin
(ng/L)
Naproxen
(ng/L)
Paraxanthine (1,7-
Dimethylxanthine
(ng/L)
Sulfadimethoxine
(ng/L)
Sulfamerazine
(ng/L)
Sulfamethazine
(ng/L)
Sulfamethoxazole
(ng/L)
Sulfathiazole
(ng/L)
Triclocarban
(ng/L)
Trimethoprim
(ng/L)
Tylosin
(ng/L)
TOT
PHARM
STJOE HARB AUG SHAL 3.2 32 2.4 3.1 9.3 5.1 1.9 6.4 32 0.6 0.6 0.6 21 0.6 6.4 2.5 5.4 133.1
STJOE HARB AUG DEEP 3.4 34 2.1 3.2 10 2 2 6.8 34 0.7 0.7 0.7 19 0.7 6.8 2.4 3 131.5
STJOE OPEN AUG SHAL 3.3 34 0.7 2.1 1.6 2.9 2 6.7 34 0.7 0.7 0.7 4.9 0.7 6.7 2 2 105.7
STJOE OPEN AUG DEEP 3.6 36 0.9 1.7 1.9 3.1 2.2 7.3 36 0.7 0.7 0.7 6.4 0.7 7.3 2.2 4.5 115.9
MICH HARB AUG SHAL 4.5 56 5.9 4.7 3.7 6.9 2.7 6.4 32 0.6 0.6 0.6 5.9 0.6 6.4 1.9 1.9 141.3
MICH HARB AUG DEEP 3.1 42 5.5 4.2 5.1 4.7 1.6 5.4 27 0.5 0.5 0.5 5.2 0.5 5.4 1.6 1.6 114.4
MICH OPEN AUG SHAL 4.6 46 0.9 2.7 1.9 2.8 2.8 9.3 46 0.9 0.9 0.9 2.8 0.9 9.3 2.8 2.8 138.3
MICH OPEN AUG DEEP 3.1 31 0.6 1.7 1.2 2.4 1.9 6.2 31 0.6 0.6 0.6 1.9 0.9 6.2 1.9 1.9 93.7
ECHIC HARB AUG SHAL 3.3 33 3.9 3.9 1.7 2 2 6.7 33 0.7 0.7 0.7 12 0.7 7.6 2 2 115.9
ECHIC HARB AUG DEEP 2.8 28 0.6 1.5 1.1 1.7 1.7 5.6 28 0.6 0.6 0.6 1.7 0.6 5.6 1.7 1.7 84.1
ECHIC OPEN AUG SHAL 3.4 34 0.7 2.1 1.4 2.1 2.1 6.8 34 0.7 0.7 0.7 2.1 0.7 6.8 2.1 2.1 102.5
ECHIC OPEN AUG DEEP 3.7 38 0.7 1.9 1.5 2.2 2.2 7.5 38 0.7 0.7 0.7 2.2 0.7 7.5 2.2 6.7 117.1
CHICA HARB AUG SHAL 5.1 52 1 3.6 2 3.1 3.1 10 51 1 1 1 3.1 1 10 3.1 3.1 154.2
CHICA HARB AUG DEEP 2.5 25 0.5 1.8 1 3.3 1.5 5 25 0.5 0.5 0.5 1.5 0.5 2.5 1.5 1.5 74.6
CHICA OPEN AUG SHAL 4.8 49 1 2.5 1.9 2.9 2.9 9.7 49 1 1 1 2.9 1 9.7 2.9 2.9 146.1
CHICA OPEN AUG DEEP 3.4 34 0.7 1.7 2 2 2 6.8 34 0.7 0.7 0.7 2 0.7 6.8 2 2 102.2
STJOE HARB NOV SHAL 13 100 1.7 5.5 25 28 4.2 25 42 0.8 0.8 0.8 70 0.8 4.2 6.1 3.4 331.3
STJOE HARB NOV DEEP 17 97 2 5 49 30 5.1 30 51 1 1 1 68 1 5.1 6 4 373.2
STJOE OPEN NOV SHAL 7.6 38 1.5 6 3 7.6 7.6 7.6 76 1.5 1.5 1.5 4.9 1.5 7.6 7.6 6 187
STJOE OPEN NOV DEEP 3.5 18 0.7 2.8 1.4 3.5 3.5 3.5 35 0.7 0.7 0.7 2.2 0.7 3.5 3.5 2.8 86.7
MICH HARB NOV SHAL 15 36 10 6.1 22 5.2 5.2 5.2 52 1 1 1 88 1 5.2 5.2 4.2 263.3
MICH HARB NOV DEEP 7.3 24 9.8 5.3 25 6.2 4.8 4.8 48 1 1 1 97 1 5.5 4.8 3.8 250.3
MICH OPEN NOV SHAL 4 20 0.8 3.2 1.6 4 4 4 40 0.8 0.8 0.8 2.4 0.8 4 4 3.2 98.4
MICH OPEN NOV DEEP 4.7 23 0.9 3.8 1.9 4.7 4.7 4.7 47 0.9 0.9 0.9 3 0.9 4.7 4.7 3.8 115.2
ECHIC HARB NOV SHAL 7.1 28 4.5 5.7 25 5.6 5.6 5.6 56 1.1 1.1 1.1 89 1.1 5.6 10 4.4 256.5
ECHIC HARB NOV DEEP 4 20 1.3 3.2 5.2 5.7 4 4 40 0.8 0.8 0.8 32 0.8 4 4 3.2 133.8
ECHIC OPEN NOV SHAL 5.7 29 1.1 4.6 2.3 5.7 5.7 5.7 57 1.1 1.1 1.1 5.9 1.1 5.7 5.7 4.6 143.1
ECHIC OPEN NOV DEEP 4.8 24 1 3.8 1.9 4.8 4.8 4.8 48 1 1 1 3.2 1 4.8 4.8 3.8 118.5
CHICA HARB NOV SHAL 4.1 20 0.8 3.3 1.6 4.1 4.1 4.1 41 0.8 0.8 0.8 2.5 0.8 4.1 4.1 3.3 100.3
CHICA HARB NOV DEEP 4.4 22 0.9 3.5 1.8 4.4 4.4 4.4 44 0.9 0.9 0.9 2.6 0.9 4.4 4.4 3.5 108.3
CHICA OPEN NOV SHAL 4.7 23 0.9 3.7 1.9 4.7 4.7 4.7 47 0.9 0.9 0.9 2.8 0.9 4.7 4.7 3.7 114.8
CHICA OPEN NOV DEEP 5.7 29 1.1 4.6 2.3 5.7 5.7 5.7 57 1.1 1.1 1.1 3.4 1.1 5.7 5.7 4.6 140.6
STJOE HARB MAR SHAL 5 25 1 4 13 5 5 5 50 1 1 1 40 1 5 5 4 171
STJOE HARB MAR DEEP 4.9 25 1.1 4 15 4.9 4.9 4.9 49 1 1 1 38 1 4.9 4.9 4 169.5
STJOE OPEN MAR SHAL 4.8 24 1 3.9 5.1 4.8 4.8 4.8 48 1 1 1 8.3 1 4.8 4.8 3.9 127
STJOE OPEN MAR DEEP 5 25 1 4 5.8 5 5 5 50 1 1 1 12 1 5 5 4 135.8
MICH HARB MAR SHAL 5 25 9.9 4 11 5 5 5 50 1 1 1 170 1 5 18 6.1 323
MICH HARB MAR DEEP 5 25 8.7 4 5.1 5 5 5 50 1 1 1 180 1 5 18 4 323.8
MICH OPEN MAR SHAL 4.9 25 1 3.9 4.7 4.9 4.9 4.9 49 1 1 1 11 1 4.9 4.9 3.9 131.9
MICH OPEN MAR DEEP 5 25 1 4 4.7 5 5 5 50 1 1 1 11 1 5 5 4 133.7
ECHIC HARB MAR SHAL 5 25 4.3 4 19 84 5 5 50 1 1 1 200 1 5 15 4 429.3
ECHIC HARB MAR DEEP 5 25 4.7 4 16 84 5 5 50 1 1 1 220 1 5 15 5.9 448.6
ECHIC OPEN MAR SHAL 4.8 24 1 3.9 4.1 4.8 4.8 4.8 48 1 1 1 5.8 1 4.8 4.8 3.9 123.5
ECHIC OPEN MAR DEEP 4.9 24 1 3.9 3.6 4.9 4.9 4.9 49 1 1 1 6.4 1 4.9 4.9 3.9 125.2
CHICA HARB MAR SHAL 5 25 1 4 4.6 5 5 5 50 1 1 1 8.7 1 5 5 4 131.3
CHICA HARB MAR DEEP 4.9 24 1 3.9 5.6 4.9 4.9 4.9 49 1 1 1 23 1 4.9 4.9 3.9 143.8
CHICA OPEN MAR SHAL 5.1 25 1 4 2.7 5.1 5.1 5.1 51 1 1 1 4.4 1 5.1 5.1 4 126.7
CHICA OPEN MAR DEEP 4.9 25 1 3.9 2.4 4.9 4.9 4.9 49 1 1 1 4.1 1 4.9 4.9 3.9 122.7
STJOE HARB JUN SHAL 5 25 * 4.4 7.4 5 5 6.6 50 2.5 1 1 19 1 5 5.4 4 147.3
STJOE HARB JUN DEEP 5.7 29 * 4.6 14 5.7 5.7 8.3 57 1.1 1.1 1.1 24 1.1 5.7 5.7 4.6 174.4
STJOE OPEN JUN SHAL 5 25 * 4 4.3 5 5 5 50 1 1 1 3.7 1 5 5 4 125
STJOE OPEN JUN DEEP 5 25 * 4 5.2 5 5 5 50 1 1 1 3.3 1 5 5 4 125.5
MICH HARB JUN SHAL 11 39 * 9.4 22 5.2 5.2 7.9 52 1 1 1 11 1 9.4 5.2 4.1 185.4
MICH HARB JUN DEEP 11 36 * 11 26 5.2 5.1 5.4 51 1 1 1 13 1 8 5.1 4.1 184.9
MICH OPEN JUN SHAL 5 25 * 4.6 4.6 5 5 5 50 1 1 1 3.7 1 5 5 4 125.9
MICH OPEN JUN DEEP 5 25 * 4 4.1 5 5 5 50 1 1 1 3.5 1 5 5 4 124.6
ECHIC HARB JUN SHAL 5.6 28 * 7.9 4 12 5.6 5.6 56 1.1 1.1 1.2 44 1.1 14 7.7 4.5 199.4
ECHIC HARB JUN DEEP 4.9 25 * 3.9 2.4 4.9 4.9 4.9 49 1 1 1 4.3 1 4.9 4.9 3.9 121.9
ECHIC OPEN JUN SHAL 5 25 * 4 2.1 5 5 5 50 1 1 1 3 1 5 5 4 122.1
ECHIC OPEN JUN DEEP 5 25 * 4 3.2 5 5 5 50 1 1 1 3 1 5 5 4 123.2
CHICA HARB JUN SHAL 5 25 * 4 2.7 5 5 5 50 1 1 1 3 1 5 5 4 122.7
CHICA HARB JUN DEEP 5 25 * 4 2.4 5 5 5 50 1 1 1 3 1 5 5 4 122.4
CHICA OPEN JUN SHAL 5.2 26 * 4.1 2.3 5.2 5.2 5.2 52 1 1 1 3.1 1 5.2 5.2 4.1 126.8
CHICA OPEN JUN DEEP 5.1 26 * 4.1 2.6 5.1 5.1 5.1 51 1 1 1 3.1 1 5.1 5.1 4.1 125.5
51
Appendix 3. Cation and anion data collected in near-shore Lake Michigan sites.
Site LOC Date DEPTH Sulfate Sodium Ammonium Potassium Magnesium Calcium
STJOE HARB AUG SHAL 21.78 18.20 0.03 3.16 23.14 28.63
STJOE HARB AUG DEEP 14.78 18.61 0.02 2.52 23.87 34.16
STJOE OPEN AUG SHAL 21.97 9.17 0.01 1.59 14.19 19.19
STJOE OPEN AUG DEEP 15.27 9.72 0.01 1.69 14.60 9.25
MICH HARB AUG SHAL 22.73 21.60 0.03 2.51 16.11 12.36
MICH HARB AUG DEEP 50.02 29.53 0.02 3.02 18.70 18.69
MICH OPEN AUG SHAL 30.20 7.55 0.01 1.56 12.22 12.16
MICH OPEN AUG DEEP 24.58 7.78 0.00 1.43 12.57 12.51
ECHIC HARB AUG SHAL 157.80 24.25 0.08 3.79 13.84 13.89
ECHIC HARB AUG DEEP 27.34 8.78 0.03 1.67 12.62 13.52
ECHIC OPEN AUG SHAL 14.29 8.83 0.01 2.04 13.01 14.54
ECHIC OPEN AUG DEEP 14.98 8.48 0.03 1.73 13.44 15.39
CHICA HARB AUG SHAL 6.07 8.76 0.03 1.51 13.43 10.60
CHICA HARB AUG DEEP 24.28 7.87 0.03 1.74 12.08 11.16
CHICA OPEN AUG SHAL 18.49 7.86 0.02 1.44 12.58 10.67
CHICA OPEN AUG DEEP 28.24 6.38 0.02 1.26 11.18 14.77
STJOE HARB NOV SHAL 63.97 19.44 0.13 2.38 24.25 45.85
STJOE HARB NOV DEEP 63.61 19.55 0.11 2.42 24.33 46.88
STJOE OPEN NOV SHAL 35.33 8.53 0.07 2.33 13.61 33.08
STJOE OPEN NOV DEEP 33.69 7.50 0.01 1.39 12.29 30.80
MICH HARB NOV SHAL 70.44 27.27 0.08 3.67 20.46 53.97
MICH HARB NOV DEEP 70.42 28.70 0.06 3.52 20.10 49.95
MICH OPEN NOV SHAL 33.36 7.45 0.01 1.49 11.89 21.71
MICH OPEN NOV DEEP 35.51 8.55 0.04 2.60 13.46 34.06
ECHIC HARB NOV SHAL 69.97 23.27 0.18 3.37 15.34 37.19
ECHIC HARB NOV DEEP 49.36 13.71 0.09 2.68 14.59 31.71
ECHIC OPEN NOV SHAL 36.30 8.50 0.04 1.64 11.99 28.58
ECHIC OPEN NOV DEEP 35.49 8.22 0.03 1.93 11.95 28.81
CHICA HARB NOV SHAL 33.34 7.33 0.03 1.53 11.81 26.08
CHICA HARB NOV DEEP 35.59 8.38 0.05 1.83 13.40 29.06
CHICA OPEN NOV SHAL 34.75 8.14 0.03 1.85 13.24 32.60
CHICA OPEN NOV DEEP 33.94 7.35 0.05 2.97 11.85 28.93
STJOE HARB MAR SHAL 67.39 15.09 0.05 2.16 21.31 52.65
STJOE HARB MAR DEEP 67.51 14.80 0.06 2.12 20.83 27.76
STJOE OPEN MAR SHAL 39.98 9.38 0.02 1.55 13.33 27.41
STJOE OPEN MAR DEEP 44.25 10.34 0.01 1.61 14.59 24.64
MICH HARB MAR SHAL 99.86 42.51 0.08 3.14 22.57 33.03
MICH HARB MAR DEEP 101.36 44.88 0.09 3.18 22.63 36.50
MICH OPEN MAR SHAL 41.34 9.22 0.02 1.58 13.70 20.04
MICH OPEN MAR DEEP 42.95 9.71 0.00 1.59 14.53 28.52
ECHIC HARB MAR SHAL 113.52 43.75 0.54 4.76 19.38 29.45
ECHIC HARB MAR DEEP 105.99 39.01 0.45 4.83 18.74 32.02
ECHIC OPEN MAR SHAL 35.52 9.84 0.07 1.35 12.18 17.63
ECHIC OPEN MAR DEEP 35.98 9.81 0.05 1.37 12.26 22.57
CHICA HARB MAR SHAL 36.87 11.16 0.05 1.32 12.23 16.93
CHICA HARB MAR DEEP 37.28 15.71 0.07 1.48 12.60 18.11
CHICA OPEN MAR SHAL 33.92 8.17 0.04 1.31 11.87 15.11
CHICA OPEN MAR DEEP 35.08 8.33 0.04 1.33 11.92 21.18
STJOE HARB JUN SHAL 39.87 14.94 0.02 1.91 21.84 43.24
STJOE HARB JUN DEEP 40.66 15.16 0.02 1.92 21.78 37.54
STJOE OPEN JUN SHAL 23.50 7.88 0.01 1.34 12.05 25.09
STJOE OPEN JUN DEEP 23.00 7.83 0.01 1.37 11.97 26.61
MICH HARB JUN SHAL 46.67 32.22 0.04 2.73 19.48 45.96
MICH HARB JUN DEEP 49.21 33.25 0.05 2.83 21.08 53.64
MICH OPEN JUN SHAL 23.65 8.30 0.01 1.35 12.05 23.60
MICH OPEN JUN DEEP 23.72 8.57 0.01 1.42 12.09 21.59
ECHIC HARB JUN SHAL 56.93 28.97 0.20 3.31 16.69 29.94
ECHIC HARB JUN DEEP 28.77 10.71 0.03 1.75 12.43 23.83
ECHIC OPEN JUN SHAL 24.14 7.98 0.01 1.33 11.84 21.24
ECHIC OPEN JUN DEEP 22.94 7.37 0.01 1.60 11.82 22.84
CHICA HARB JUN SHAL 22.77 7.15 0.01 1.29 11.89 27.07
CHICA HARB JUN DEEP 22.59 7.07 0.00 1.28 11.77 21.65
CHICA OPEN JUN SHAL 22.46 7.03 0.02 1.29 11.76 23.54
CHICA OPEN JUN DEEP 23.02 7.16 0.02 1.52 11.83 23.25
