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Long-Term and Seasonal Trend Decomposition of Maumee River Nutrient Inputs to Western Lake Erie Craig A. Stow, YoonKyung Cha, Laura T. Johnson, Remegio Confesor, and R. Peter Richards Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/es5062648 • Publication Date (Web): 13 Feb 2015 Downloaded from http://pubs.acs.org on February 18, 2015

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Long-Term and Seasonal Trend Decomposition of Maumee River

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Nutrient Inputs to Western Lake Erie

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Craig A. Stow1, YoonKyung Cha2, Laura T. Johnson3, Remegio Confesor3, R. Peter Richards3 1

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Laboratory, 4840 South State Road, Ann Arbor, MI 48108, USA

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School of Natural Resources and Environment, University of Michigan, 440 Church Street, Ann Arbor, MI 48109, USA

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National Oceanic and Atmospheric Administration Great Lakes Environmental Research

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Heidelberg University, National Center for Water Quality Research, Tiffin, OH 44883 USA

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Keywords:Lake Erie, harmful algal blooms, Great Lakes Water Quality Agreement, phosphorus targets

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Abstract

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Cyanobacterial blooms in western Lake Erie have recently garnered widespread attention.

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Current evidence indicates that a major source of the nutrients that fuel these blooms is the

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Maumee River. We applied a seasonal trend decomposition technique to examine long-term

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and seasonal changes in Maumee River discharge, and nutrient concentrations and loads. Our

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results indicate similar long-term increases in both regional precipitation and Maumee River

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discharge (1975-2013), though changes in the seasonal cycles are less pronounced. Total and

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dissolved phosphorus concentrations declined from the 1970s into the 1990s; since then total

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phosphorus concentrations have been relatively stable while dissolved phosphorus

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concentrations have increased. However, both total and dissolved phosphorus loads have

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increased since the 1990s because of the Maumee River discharge increases. Total nitrogen and

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nitrate concentrations and loads exhibited patterns that were almost the reverse of those of

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phosphorus, with increases into the 1990s and decreases since then. Seasonal changes in

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concentrations and loads were also apparent with increases since approximately 1990 in March

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phosphorus concentrations and loads. These documented changes in phosphorus, nitrogen, and

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suspended solids likely reflect changing land-use practices. Knowledge of these patterns should

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facilitate efforts to better manage ongoing eutrophication problems in western Lake Erie.

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Introduction Eutrophication problems resulting from excessive nutrient inputs have plagued Lake

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Erie for many years. In 1965 an article in The Economist declared that Lake Erie was “literally

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dying” 1. To control eutrophication, the 1978 Great Lakes Water Quality Agreement

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established target total phosphorus (TP) loads for each of the Great Lakes, including an 11,000

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metric ton per year goal for Lake Erie 2. Following implementation of the 1978 Agreement,

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notable phosphorus reductions and corresponding water quality improvements were

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documented 3. However, the Lake Erie phosphorus target is still occasionally exceeded 4,5 and

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since the mid-late 1990s symptoms of “re-eutrophication” including increased phytoplankton

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biomass and a reappearance of widespread hypoxia have been documented6,7. In 2011, despite

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meeting the TP load target, Lake Erie experienced the most extensive algal bloom on record 8.

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In August 2014 the city of Toledo drinking water supply was temporally shut down due to high

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toxin levels resulting from a Microcystis bloom.

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The resurgence of eutrophication in Lake Erie have prompted the National Oceanic and

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Atmospheric Administration (NOAA) and partners to develop predictive models for harmful

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algal bloom occurrence 9-11 and issue regular bulletins for potentially affected stakeholders

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(http://www.glerl.noaa.gov/res/waterQuality/). Additionally, the updated 2012 Great Lakes

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Water Quality Agreement mandated a review of the existing total phosphorus target loads with

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a directive to update the Lake Erie target and develop numerical phosphorus concentration

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criteria within three years 12.

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Lake Erie’s most severe algal blooms originate in the western basin of the lake, where

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nutrient inputs from the Maumee River (Figure 1) drive algal growth 6,13. Unlike many Great

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Lakes tributaries where input data are sparse, making long-term estimation and inference

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uncertain 14, nearly continuous records of approximately daily concentration data are available

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for phosphorus, nitrogen, and other constituents in the Maumee River. These data are collected

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by Heidelberg University and, combined with available United States Geological Survey

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(USGS) discharge monitoring records, allow detailed analyses of changes in nutrient loads and

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concentrations since the late 1970s. Previous examination of long-term patterns in the annual

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phosphorus loads and flow-weighted mean concentrations from the Maumee River revealed

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substantial increases in bioavailable phosphorus forms since the early 1990s while total

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phosphorus changed little or decreased slightly 13.

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In this analysis we build on previous work13 and use an approach to simultaneously

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examine both long-term and seasonal fluctuations in nutrient concentrations, loads, Maumee

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River discharge, and regional precipitation. Environmental trend analyses commonly employ

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linear regression or nonparametric methods based on order statistics, including Kendall’s tau

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test 15 and variations 16,17. However, these methods are most appropriate for linear or monotonic

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trends; assessments using them may be inaccurate when the supporting assumptions are not

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well met or when the data fluctuate with time. Polynomial regression is sometimes applied for

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nonlinear time-series analysis but this approach uses the entire time-range of observations to

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estimate nonlinear patterns, whereas nonlinearities are often temporally local features.

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Generalized additive modeling 18 is a graphical approach to highlight nonlinear patterns in data,

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based on various localized smoothing techniques (aka smoothers). To highlight seasonal and

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long-term patterns in Maumee River data we apply a form of generalized additive modeling:

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Seasonal Trend decomposition using Loess (STL) 19,20 which employs a locally-weighted

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running-line smoother, and has been previously used to analyze long-term nutrient

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concentration and river discharge data 21,22. Our results suggest that long-term precipitation

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increases are partially responsible for discharge and load increases since the mid-1990s, and

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that the seasonal timing of delivery has also changed for some constituents.

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Methods

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Water quality data were downloaded from the National Center for Water Quality

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Research website (http://www.heidelberg.edu/academiclife/distinctive/ncwqr/data). Data from

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the Maumee River were collected at the Bowling Green Water Treatment Plant, which is

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located 5.6 km upstream from the USGS stream gage in Waterville, Ohio (USGS #04193500).

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Samples were collected using an ISCO automated sampler that pulled water from a receiving

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basin continuously flushed with river water via a submersible pump in the river. Discrete

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samples were collected either 3 (1974-1988) or 4 (1988-present) times a day and all samples

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collected during high flow or with high turbidity were analyzed. Otherwise, one sample per day

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was analyzed. Samples were retrieved weekly and returned to the laboratory for analysis

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following standard EPA protocols. Dissolved reactive P and total P were both analyzed using

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molybdate blue colorimetry (EPA method 365.3); total P was pre-treated using persulfate

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digestion. Nitrate (NO3-N) was analyzed using ion chromatography (EPA method 300.1).

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Total Kjeldahl N (TKN) was analyzed using phenol colorimetry after pre-treatment with acid

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digestion (EPA method 351.2). Total N was calculated as the sum of NO3-N and TKN. Finally,

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total suspended solids (TSS) was analyzed by measuring dry weight after filtration through a

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glass fiber filter (EPA method 160.2). We downloaded average monthly precipitation data for Ohio region 1 from the National

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Oceanic and Atmospheric Administration (NOAA) National Climatic Data Center, Midwest

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Regional climate Center web site (http://mrcc.isws.illinois.edu/CLIMATE/index.jsp.).

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Before analyzing the data we first averaged the Maumee River concentration data by

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day (when multiple measurements were available) and then averaged the daily data by month to

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obtain monthly mean concentrations. We estimated loads first on a daily basis by multiplying

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the average daily concentration by average daily discharge from the USGS stream gage (USGS

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#04193500), and then on a monthly basis by summing the estimated daily loads. We then used

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the STL procedure on the average monthly concentrations and total monthly loads. Missing

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values early in the time series were imputed using long-term monthly means (Supplemental

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Information – Figure 1).

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STL applies repeated loess fitting 23 to decompose monthly time-series data into a

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smoothed trend, seasonal, and residual components. STL uses one continuous loess line for the

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smoothed long-term component and 12 month-specific loess lines for the seasonal component.

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Fitting is done on each component iteratively until the resulting trend and seasonal components

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no longer differ from those of the previous iterations. There are two smoothing parameters in

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the model, representing the window widths of the seasonal and long-term components. We

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chose window widths of 48 months and 250 months, respectively, to visually reveal trends.

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Generally, window-widths are selected to produce relatively smooth long-term patterns that

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highlight potentially important underlying changes, while simultaneously reducing the residuals

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to white noise. Attaining both of these goals is a balancing act; sometimes the residuals reveal

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noteworthy signals 24. However, in this analysis no signals were evident in the residuals, thus,

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our results focus on the smooth long-term and seasonal patterns.

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Results

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To illustrate the STL approach we first applied it to the entire available period (1895-

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2013) of monthly average precipitation data (Figure 2). Over this time-span the monthly data

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appeared noisy with no obvious visual pattern (Figure 2a). The STL procedure breaks the time-

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series into three components, a long-term, smoothed trend (Figure 2b, left), a seasonal pattern

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that changes with time (Figure 2b, middle), and residuals (Figure 2b, right).

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On the scale of the original monthly variability the long-term, smoothed pattern was

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almost linear with no obvious trend (Figure 2b, left). Superimposed over the original monthly

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time-series, the long-term, smoothed pattern went approximately through the middle of the

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observations, and captured the subtle fluctuations in the data (Figure 2a). When resolution on

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the vertical scale was expanded an overall increasing pattern was apparent, which deviated

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from a least squares linear fit through the data (Figure 2c). Through the 1900s a periodicity of

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approximately 30 years was distinguishable, similar in timing to a corresponding cycle

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previously reported in Great Lakes water levels 24. A comparison with the least squares line

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emphasizes an uptick in precipitation beginning in the early 1990s.

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A view of the seasonal periodicity over the entire period of record was not of sufficient

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resolution to highlight clear patterns; however, this depiction did indicate that amplitude

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fluctuations in the cycle have occurred over this time (Figure 2b, middle). When the resolution

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was increased, and seasonal patterns were depicted by month, several changes became more

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apparent (Figure 2d). The overall seasonal pattern displayed a minimum in February and a peak

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in June, and most months display only slight trends or apparent random fluctuations about the

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overall monthly average. January and March are exceptions, with both months showing a

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decrease over the period of record.

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When we focus on data from 1975-2013, the period for which nutrients and sediment

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measurements are available for the Maumee River, the long-term, smoothed patterns for

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precipitation and Maumee River discharge were similar. Both precipitation and discharge

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were relatively stable from approximately 1975 to the late 1980s, declined slightly into the

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early 1990s, and steadily increased since the early to mid-1990s, with overall increases of

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approximately 12-16% (Figure 3a,c). By contrast, the seasonal patterns for precipitation and

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discharge differed (Figure 3b,d). Highest precipitation was from April-August and minimum

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from January-February, whereas maximum discharge was in March and minimum from

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August-October (Figure 3b,d). Changes in the seasonal pattern over time were not pronounced,

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except in March where precipitation and discharge have increased since about 1990, a time

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approximately coincident with the increase in the long-term, smoothed precipitation and flow

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(Figure 3a,c).

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Long-term, smoothed total phosphorus (TP) concentrations declined steadily from 1975

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until the late 1990s, and since that time have been relatively stable or slightly increasing

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(Figure 4a). The long-term, smoothed TP load declined similarly to TP concentrations through

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the late 1990s, but has risen steadily since approximately 2000, reflecting the concurrent

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increase in discharge, and is currently at levels comparable to those of the mid-1970s (Figure

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4b). Long-term, smoothed dissolved reactive phosphorus (DRP) concentrations also declined

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from 1975 until approximately the early 1990s but have increased since then (Figure 4c). The

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long-term, smoothed DRP load decline from 1975 until approximately 1990 tracked that of the

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DRP concentration, but since approximately 1990 DRP loads have increased more rapidly than

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concentrations, with current levels slightly exceeding those of 1975 (Figure 4d).

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Long-term, smoothed Maumee River nitrogen trajectories were almost the reverse of

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the phosphorus trends, with increases from 1975 until the early to mid-1990s and declines since

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that time (Figure 4e,f,g,h). Long-term, smoothed total nitrogen (TN) concentrations increased

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from 1975 until the early 1990s and have decreased steadily since then (Figure 4d) while the

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long-term, smoothed TN load increased and remained fairly stable until the early 2000s, but has

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decreased slightly since then (Figure 4f). Long-term, smoothed nitrate concentration and load

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patterns over time were similar to that of TN, nitrate being a substantial proportion of total

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nitrogen (Figure 4g,h).

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Long-term, smoothed suspended solids (SS) concentrations were relatively stable or

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slowly declining from 1975 until approximately 1990 and have declined continuously since the

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early 1990s, though the rate of decline has been relatively slow since approximately 2000

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(Figure 4i). The overall long-term, smoothed SS load pattern was similar to the concentration

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pattern except that the load has increased slightly since 2000 (Figure 4j).

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Phosphorus, nitrogen and suspended solids all followed regular seasonal patterns,

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although their seasonal concentration cycles differed from one-another (Figure 5a,c,e,g,i). TP

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concentrations were generally lowest in August-November, rising in December and remaining

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at relatively high levels into July (Figure 5a). DRP concentrations tended to drop earlier than

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TP, declining in March and remaining at seasonal lows through November (Figure 5c). Total

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nitrogen and nitrate both followed a well-defined seasonal pattern with the lowest

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concentrations in August and September and high, relatively steady concentrations from

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December-June (Figure 5d,e). Suspended solids concentrations generally peaked in March-

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April and drop to seasonal lows in August-November (Figure 5f).

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While these seasonal concentration patterns have been relatively stable over time there

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are a few changes that, in the context of the ongoing problems in Lake Erie, are worth noting.

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Both TP and DRP have increased since the 1990s from approximately December-March, the

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period in which vegetative ground cover is minimal. During much of the rest of the year slight

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decreases have occurred over this time period (Figure 5a,c). The biggest observable change in

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the seasonal pattern of total nitrogen and nitrate concentrations was a steady decrease in July

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(Figure 5e,g). July SS concentrations also steadily declined, while January concentrations have

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steadily increased and March concentrations have increased since the 1990s, approximately

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consistent with the patterns for TP (Figure 5i).

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Constituent load seasonal patterns tracked the discharge seasonal pattern with peaks in

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March and minima running from roughly July-October (Figures 3d and 5b,d,f,h,j right).

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Notably, all loads decreased during March until ~1990 and have since increased (Figure

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5b,d,f,h,j) approximately matching the March discharge trajectory (Figure 3d). This decline

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and reversal was particularly pronounced for TP, DRP, and SS, all of which also exhibit similar

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curves in their respective concentrations (Figure 5a,c,i).

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In addition to changes in both concentrations and loads, we examined differences in

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DRP:TP and TN:TP ratios over time and seasonally (Figures 6 and 7). The long-term,

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smoothed DRP:TP ratio declined from 1975 through the early 1990s, and subsequently

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increased since then (Figure 6a), similar to both the TP and DRP long-term, smoothed

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concentration patterns (Figure 4a,c). However, the most recent DRP:TP ratio was currently

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somewhat below that of the beginning of the time-series. Seasonally, this ratio was lowest

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from March-October and somewhat higher from November – February (Figure 6b). Changes

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over time during March-October have been minimal or more recently slightly declining, while

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during November-February the ratio has been recently increasing.

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The long-term, smoothed TN:TP ratio pattern was nearly the reverse of the DRP:TP

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pattern. The long-term, smoothed pattern increased through the late 1990s and decreased since

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then (Figure 7a). Seasonally, this ratio was highest from December-June and lowest in August-

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October (Figure 7b). In contrast to the DRP:TP ratio, the TN:TP ratio has recently been steady

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or slightly declining during the seasonal high period (December-June), and increasing during

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the seasonal low period (August-October) (Figure 7b).

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Discussion Establishing the causes of recurring HABs in western Lake Erie is essential to develop

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effective management strategies. While it would be misleading to ascribe too much meaning to

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every wiggle in the long-term or seasonal STL results a few signals seem noteworthy. Our

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results reaffirm previously documented concentration and load increases in the more

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bioavailable phosphorus fraction 13, but also indicate that discharge increases associated with

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increased regional precipitation are influencing loads of other important constituents. The

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contrasts between long-term, smoothed concentration and load patterns revealed by our results

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underscore the influence of a long-term discharge increase (Figure 3c) on differences in

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Maumee River loads. For example, smoothed, long-term TP concentrations show a slight

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increase since the late 1990s, whereas the smoothed, long-term TP load increase since then has

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been more pronounced, returning approximately to late 1970s levels (Figure 4a,b). Similarly,

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the recent smoothed, long-term DRP load increase exceeds the corresponding concentration

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increase (Figure 4d and c, respectively), while smoothed, long-term nitrogen concentration

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decreases are more pronounced than the corresponding load decreases (Figure 4e,f,g,h).

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Concurrently, the smoothed, long-term SS concentration decrease since approximately 2000

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corresponds to a load increase (Figure 4i,j); in this instance the discharge increase has more

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than offset the concentration decrease.

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Increases in March river discharge (Figure 3d) and both TP and DRP concentrations

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and load (Figure 5a,b,c,d) since approximately 1990 may be important factors promoting

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increased cyanobacterial blooms. Recent studies have suggested that March-June phosphorus

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inputs are most strongly related to cyanobacterial bloom size in Lake Erie 10,11. The observation

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that peak seasonal discharge (March) generally precedes peak precipitation (~April-August),

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suggests that the March discharge is attributable to runoff from melting snowpack and high

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antecedent soil moisture conditions. Thus, the runoff in March probably reflects activities on

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the land that have occurred during the preceding winter. Investigating whether increasing

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phosphorus concentrations during March can be attributed to changing land-uses during the

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winter months may offer clues for more effective phosphorus management.

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Baker et al. 13 emphasized the importance of increasing bioavailable P inputs, and while

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our results confirm recent DRP increases (Figure 4c,d) we also note that during the March-June

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critical period, both the DRP concentrations (Figure 5c) and DRP:TP concentration ratios

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(Figure 6b) are at seasonal lows. These seasonal dips likely reflect the observation that SS

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concentrations are generally highest from March-June (Figure 5i), thus the spring phosphorus

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pulse includes a relatively high proportion of particulate-associated phosphorus.

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DRP load has been increasing since the early 1990s (Figure 4d) because both

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components of load, discharge and concentration, have been rising (Figure 3c and Figure 4c,

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respectively). We suggest that both of these factors may be contributing to recent increases in

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HAB occurrence. Baker et al. 25 observed that storm-related discharge pulses pushed DRP

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further offshore than particulate phosphorus. Similarly, long-term discharge increases may be

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expanding phosphorus distribution over a larger portion of the lake than would occur by

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concentration increases alone. Higher discharge can lower hydraulic residence time, and

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modify local circulation patterns, possibly increasing both TP and DRP delivery efficiency over

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a broader area. Further investigation using fine-scale hydrodynamic models may be useful to

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evaluate the extent to which increased discharge is influencing phosphorus availability and

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resultant primary productivity 26.

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Our results indicate, over approximately the same period that phosphorus has been

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increasing, nitrogen has been decreasing (Figure 4e,f,g,h). Thus the TN:TP ratio has also been

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decreasing (Figure 7a). Reavie et al. 27 reported a decline in the N:P ratio in the western and

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central basins of Lake Erie, possibly reflecting this trend in the river. The TN:TP ratio is lowest

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during the summer (Figure 7b) and may underlie reported summer nitrogen limitation in

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portions of the western Lake Erie basin 28-30, though the overall decline has probably not been

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sufficient, so far, to effect changes in the dominant phytoplankton species or a shift to nitrogen

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limitation. We note that the early 1990s onset of the long-term nitrogen decline is

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approximately coincident with nitrogen drops reported in rivers in the eastern United States,

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which have been attributed to reduced atmospheric nitrogen deposition resulting from various

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emission control programs 31. From our results the cause of the decline cannot be ascertained.

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Because previous studies have implicated changing agricultural practices13,32 as the main cause

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of the observed phosphorus increase, it seems plausible that regional changes in agriculture

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might also be responsible for the simultaneous nitrogen decline. However, the possibility that

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larger-scale processes may also be influencing the observed nitrogen patterns invites further

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exploration.

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Declining nitrogen inputs may also influence the toxicity of blooms in Lake Erie; recent

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studies have highlighted a positive relationship between nitrogen and microcystin

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production33,34. The influence of the changing ratio of phosphorus and nitrogen on the relative

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toxicity of Microcystis in western Lake Erie may also be important. Davis et al. 35 reported that

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toxic Microcystis strains have a greater need for both nitrogen and phosphorus than non-toxic

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strains, and that toxic strains are preferentially stimulated by inorganic forms of both nutrients.

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The effect of concurrent phosphorus increases and nitrogen declines is unclear, but merits

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additional research.

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The 1978 GLWQA established the use of annual target loads as an accounting

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procedure to evaluate the effectiveness of actions taken to reduce nutrient pollution. This

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approach has been widely adopted under the United States Clean Water Act for a range of

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pollutants under the Total Maximum Daily Load (TMDL) program. While it is generally

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acknowledged that targets may be exceeded during years of unusually high precipitation and

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tributary discharge, the use of load targets remains a common management tool. However

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Milly et al. 36 highlighted the growing recognition that, for variables such as tributary

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discharge, the assumption of stationarity, in an era of uncertain climate change, poses

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management challenges. Our results, indicating progressive precipitation and discharge

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increases in the Maumee River basin (Figure 3) and concurrent phosphorus input increases to

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Lake Erie (Figure 4a, b, c, d) suggest that imposing fixed load targets may require phosphorus

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concentrations to be persistently lowered to compensate for increasing discharge, if the targets

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are to be achieved. As phosphorus load targets are re-evaluated pursuant to the updated 2012

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GLWQA, it may be appropriate to address the possibility that continued discharge increases

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into the future may affect target attainment even if phosphorus reduction strategies are

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successful. Establishing phosphorus “substance objectives” (concentration targets) as required

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by the 2012 GLWQA37 may be useful to complement load targets as a means to evaluate the

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effectiveness of phosphorus reduction management actions in the watershed.

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Acknowledgments

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This work was supported, in part, by a grant from the Great Lakes Restoration Initiative. Cathy Darnell provided assistance with graphics. GLERL contribution number 1746.

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References

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1. The Economist. Goodbye to Lake Erie? 1965, 216: 782.

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2. International Joint Commission, 1978. Great Lakes Water Quality Agreement of 1978, with

321

Annexes and Terms of Reference Between the United States and Canada, Signed at Ottawa,

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November 22, 1978, Windsor, Ontario, Canada.

323

3. DePinto, J. V.; Young, T. C.; Mcilroy, L. M., Great-Lakes Water-Quality Improvement - the

324

Strategy of Phosphorus Discharge Control Is Evaluated. Environ Sci Technol 1986, 20, (8),

325

752-759.

326 327 328 329 330

4. Dolan, D. M.; McGunagle, K. P., Lake Erie total phosphorus loading analysis and update: 1996-2002. J Great Lakes Res 2005, 31, 11-22. 5. Dolan, D. M.; Chapra, S. C., Great Lakes total phosphorus revisited: 1. Loading analysis and update (1994-2008). J Great Lakes Res 2012, 38, (4), 730-740. 6. Kane, D. D.; Conroy, J. D.; Richards, R. P.; Baker, D. B.; Culver, D. A., Re-eutrophication

331

of Lake Erie: Correlations between tributary nutrient loads and phytoplankton biomass. J

332

Great Lakes Res 2014, 40, (3), 496-501.

333

7. Scavia, D.; Allan, J. D.; Arend, K. K.; Bartell, S.; Beletsky, D.; Bosch, N. S.; Brandt, S. B.;

334

Briland, R. D.; Daloglu, I.; DePinto, J. V.; Dolan, D. M.; Evans, M. A.; Farmer, T. M.; Goto,

335

D.; Han, H. J.; Hook, T. O.; Knight, R.; Ludsin, S. A.; Mason, D.; Michalak, A. M.;

336

Richards, R. P.; Roberts, J. J.; Rucinski, D. K.; Rutherford, E.; Schwab, D. J.; Sesterhenn, T.

337

M.; Zhang, H. Y.; Zhou, Y. T., Assessing and addressing the re-eutrophication of Lake Erie:

338

Central basin hypoxia. J Great Lakes Res 2014, 40, (2), 226-246.

339 340

8. Michalak, A. M.; Anderson, E. J.; Beletsky, D.; Boland, S.; Bosch, N. S.; Bridgeman, T. B.; Chaffin, J. D.; Cho, K.; Confesor, R.; Daloglu, I.; DePinto, J. V.; Evans, M. A.; Fahnenstiel,

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G. L.; He, L. L.; Ho, J. C.; Jenkins, L.; Johengen, T. H.; Kuo, K. C.; LaPorte, E.; Liu, X. J.;

342

McWilliams, M. R.; Moore, M. R.; Posselt, D. J.; Richards, R. P.; Scavia, D.; Steiner, A. L.;

343

Verhamme, E.; Wright, D. M.; Zagorski, M. A., Record-setting algal bloom in Lake Erie

344

caused by agricultural and meteorological trends consistent with expected future conditions.

345

P Natl Acad Sci USA 2013, 110, (16), 6448-6452.

346

9. Wynne, T. T.; Stumpf, R. P.; Tomlinson, M. C.; Schwab, D. J.; Watabayashi, G. Y.;

347

Christensen, J. D., Estimating cyanobacterial bloom transport by coupling remotely sensed

348

imagery and a hydrodynamic model. Ecol Appl 2011, 21, (7), 2709-2721.

349 350 351

10. Stumpf, R. P.; Wynne, T. T.; Baker, D. B.; Fahnenstiel, G. L., Interannual Variability of Cyanobacterial Blooms in Lake Erie. Plos One 2012, 7, (8). 11. Obenour, D.R.; Gronewold, A.D.; Stow, C.A.; Scavia, D., Using a Bayesian hierarchical

352

model with a gamma error distribution to improve Lake Erie cyanobacteria bloom forecasts.

353

Water Resources Research 2014, 50, 7847-7860.

354

12. Great Lakes Water Quality Protocol. 2012. Protocol Amending the Agreement between

355

Canada and the United States of America on Great Lakes Water Quality. Signed at

356

Washington, D.C. September 7, 2012.

357

13. Baker, D. B.; Confesor, R.; Ewing, D. E.; Johnson, L. T.; Kramer, J. W.; Merryfield, B. J.,

358

Phosphorus loading to Lake Erie from the Maumee, Sandusky and Cuyahoga rivers: The

359

importance of bioavailability. J Great Lakes Res 2014, 40, (3), 502-517.

360

14. Cha, Y.; Stow, C. A.; Reckhow, K. H.; DeMarchi, C.; Johengen, T. H., Phosphorus load

361

estimation in the Saginaw River, MI using a Bayesian hierarchical/multilevel model. Water

362

Res 2010, 44, (10), 3270-3282.

363

15. Kendall, M. G. Rank Correlation Methods; Charles Griffin:London, 1975.

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Page 19 of 33

364 365 366 367 368 369

Environmental Science & Technology

16. Sen, P. K., Estimates of Regression Coefficient Based on Kendalls Tau. J Am Stat Assoc 1968, 63, (324), 1379-1389. 17. Hirsch, R. M.; Slack, J. R.; Smith, R. A., Techniques of Trend Analysis for Monthly WaterQuality Data. Water Resour Res 1982, 18, (1), 107-121. 18. Hastie, T. J.; Tibshirani, R. J. Generalized Additive Models;Chapman and Hall: London, 1993.

370

19. Cleveland, R. B.; Cleveland, W. S.; McRae, J. E.; Terpenning, I., STL: A seasonal-trend

371

decomposition procedure based on loess. Journal of Official Statistics 1990, 6, (1), 3-33.

372

20. Cleveland, W. S. Visualizing Data; Hobart Press: Summit, NJ, 1993.

373

21. Qian, S. S.; Borsuk, M. E.; Stow, C. A., Seasonal and long-term nutrient trend decomposition

374

along a spatial gradient in the Neuse River watershed. Environ Sci Technol 2000, 34, (21),

375

4474-4482.

376

22. Stow, C. A.; Dyble, J.; Kashian, D. R.; Johengen, T. H.; Winslow, K. P.; Peacor, S. D.;

377

Francoeur, S. N.; Burtner, A. M.; Palladino, D.; Morehead, N.; Gossiaux, D.; Cha, Y.; Qian,

378

S. S.; Miller, D., Phosphorus targets and eutrophication objectives in Saginaw Bay: A 35

379

year assessment. J Great Lakes Res 2014, 40, 4-10.

380 381 382 383 384 385

23. Cleveland, W. S., Robust Locally Weighted Regression and Smoothing Scatterplots. J Am Stat Assoc 1979, 74, (368), 829-836. 24. Sellinger, C. E.; Stow, C. A.; Lamon, E. C.; Qian, S. S., Recent water level declines in the Lake Michigan-Huron system. Environ Sci Technol 2008, 42, (2), 367-373. 25. Baker, D. B.; Ewing, D. E.; Johnson, L. T.; Kramer, J. W.; Merryfield, B. J.; Confesor, R. B.; Richards, R. P.; Roerdink, A. A., Lagrangian analysis of the transport and processing of

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Environmental Science & Technology

386

agricultural runoff in the lower Maumee River and Maumee Bay. J Great Lakes Res 2014,

387

40, (3), 479-495.

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26. Schwab, D. J.; Beletsky, D.; DePinto, J.; Dolan, D. M., A hydrodynamic approach to modeling phosphorus distribution in Lake Erie. J Great Lakes Res 2009, 35, (1), 50-60. 27. Reavie, E. D.; Barbiero, R. P.; Allinger, L. E.; Warren, G. J., Phytoplankton trends in the Great Lakes, 2001-2011. J Great Lakes Res 2014, 40, (3), 618-639. 28. Chaffin, J. D.; Bridgeman, T. B.; Bade, D. L., Nitrogen constrains the growth of late summer cyanobacterial blooms in Lake Erie. Advances in Microbiology 2013, 3, 16-26. 29. Chaffin, J. D.; Bridgeman, T. B., Organic and inorganic nitrogen utilization by nitrogen-

395

stressed cyanobacteria during bloom conditions. Journal of Applied Phycology 2014, 26, (1),

396

299-309.

397

30. Chaffin, J. D.; Bridgeman, T. B.; Bade, D. L.; Mobilian, C. N., Summer phytoplankton

398

nutrient limitation in Maumee Bay of Lake Erie during high-flow and low-flow years. J

399

Great Lakes Res 2014, 40, (3), 524-531.

400 401 402

31. Eshleman, K. N.; Sabo, R. D.; Kline, K. M., Surface Water Quality Is Improving due to Declining Atmospheric N Deposition. Environ Sci Technol 2013, 47, (21), 12193-12200. 32. Daloglu, I.; Cho, K. H.; Scavia, D., Evaluating Causes of Trends in Long-Term Dissolved

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Reactive Phosphorus Loads to Lake Erie. Environ Sci Technol 2012, 46, (19), 10660-10666.

404

33. Horst, G. P.; Sarnelle, O.; White, J. D.; Hamilton, S. K.; Kaul, R. B.; Bressie, J. D., Nitrogen

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availability increases the toxin quota of a harmful cyanobacterium, Microcystis aeruginosa.

406

Water Res 2014, 54, 188-198.

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Environmental Science & Technology

407

34. Yuan, L. L.; Pollard, A. I.; Pather, S.; Oliver, J. L.; D'Anglada, L., Managing microcystin:

408

identifying national-scale thresholds for total nitrogen and chlorophyll a. Freshwater Biol

409

2014, 59, (9), 1970-1981.

410

35. Davis, T. W.; Harke, M. J.; Marcoval, M. A.; Goleski, J.; Orano-Dawson, C.; Berry, D. L.;

411

Gobler, C. J., Effects of nitrogenous compounds and phosphorus on the growth of toxic and

412

non-toxic strains of Microcystis during cyanobacterial blooms. Aquatic Microbial Ecology

413

2010, 61, (2), 149-162.

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36. Milly, P. C. D.; Betancourt, J.; Falkenmark, M.; Hirsch, R. M.; Kundzewicz, Z. W.;

415

Lettenmaier, D. P.; Stouffer, R. J., Climate change - Stationarity is dead: Whither water

416

management? Science 2008, 319, (5863), 573-574.

417

37. Stow, C.A.; Cha, Y.; Qian, SS., A Bayesian hierarchical model to guide development and

418

evaluation of substance objectives under the 2012 GLWQA. J Great Lakes Res 2014, 40

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Supplement 3, 49-55.

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Figure Captions

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Figure 1

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Lake Erie Map. Upper right inset depicts all five Laurentian Great Lakes with Erie enclosed in

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rectangle. Upper left inset shows mouth of Maumee River in the western Lake Erie Basin.

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Orange area indicates Ohio region 1, the area represented by the precipitation data.

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Figure 2

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Panel a - Ohio climate region 1 monthly average precipitation data (1895-2013) with STL long-

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term trend line (blue) and least squares line (red). Panel b – STL long-term trend centered at

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zero (left), seasonal pattern (center), and residuals. Seasonal pattern and residuals are shown as

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deviations from the long-term trend. Panel c – enhanced resolution depiction of STL long-term

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trend (blue) and least squares line (red). Panel d – STL seasonal patterns depicted by month (blue

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curves) with corresponding long-term monthly averages (black horizontal lines), shown as

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deviations from the smoothed long-term trend.

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Figure 3

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Panels a and b show enhanced temporal resolution (1975-2013) depiction of Ohio climate region

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1 monthly average precipitation STL results for comparison with Maumee River discharge STL

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results over the same period. Panel a shows STL long-term trend line, and panel b shows STL

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seasonal patterns by month as deviations from the smoothed long-term trend (blue curves), with

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corresponding long-term monthly averages (black horizontal lines). Panels c and d show

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analogous Maumee River average monthly discharge STL results for the same period of record.

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Figure 4

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STL long-term trend lines (blue) for monthly average Maumee River constituent concentrations

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(left panels) and corresponding monthly average loads (right panels).

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Figure 5

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STL seasonal patterns (blue) and long-term monthly averages (horizontal black lines) for

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Maumee River constituent concentrations (left panels) and corresponding monthly average loads

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(right panels). Seasonal patterns shown as deviations from the smoothed long-term trends.

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Figure 6

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STL smoothed long-term trend for the DRP:TP concentration ratio (panel a), and the STL

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seasonal pattern for the DRP:TP concentration ratio (panel b). Seasonal patterns shown as

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deviation from the smoothed long-term trend.

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Figure 7

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STL smoothed long-term trend for the molar TN:TP concentration ratio (panel a), and the STL

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seasonal pattern for the molar TN:TP concentration ratio (panel b). Seasonal patterns shown as

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deviation from the smoothed long-term trend.

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Figure 1

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Supporting Information Figure Caption

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Monthly time-series of the Maumee River constituent concentrations and loads. Imputed values

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are depicted in yellow. Red line denotes a least squares linear fit among the data, blue line

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depicts the STL smoothed, long-term trend.

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Supporting Information Figure

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Table of Contents Art

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MODIS satellite image of Lake Erie showing harmful algal bloom in the western basin that

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shut down the Toledo drinking water supply. August 4, 2014. Credit: NOAA Great Lakes

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CoastWatch

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