Developing Nutrient Criteria for Streams: An Evaluation of the Frequency Distribution Method1

Abstract: The U.S. Environmental Protection Agency recommends two statistical methods to States and Tribes for developing nutrient criteria. One establishes a criterion as the 75th percentile of a reference‐population frequency distribution, the other uses the 25th percentile of a general‐population distribution; the U.S. Environmental Protection Agency suggests either method results in similar criteria. To evaluate each method, the Montana Department of Environmental Quality (MT DEQ) assembled data from STORET and other sources to create a nutrient general population. MT DEQ’s reference‐stream project provided reference population data. Data were partitioned by ecoregions, and by seasons (winter, runoff, and growing) defined for the project. For each ecoregion and season, nutrient concentrations at the 75th percentile of the reference population were matched to their corresponding concentrations in the general population. Additionally, nutrient concentrations from five regional scientific studies were matched to their corresponding reference population concentrations; each study linked nutrients to impacts on water uses. Reference‐to‐general population matches were highly variable between ecoregions, as nutrients at the 75th percentile of reference corresponded to percentiles ranging from the 4th to the 97th of the general population. In contrast, case studies‐to‐reference matches were more consistent, matching on average to the 86th percentile of reference, with a coefficient of variation of 13%.     

NUTRIENT LOADING ASSESSMENT IN THE ILLINOIS RIVER USING A SYNTHETIC APPROACH1

ABSTRACT: A synthetic relationship is developed between nutrient concentrations and discharge rates at two river gauging sites in the Illinois River Basin. Analysis is performed on data collected by the U.S. Geological Survey (USGS) on nutrients in 1990 through 1997 and 1999 and on discharge rates in 1988 through 1997 and 1999. The Illinois River Basin is in western Arkansas and northeastern Oklahoma and is designated as an Oklahoma Scenic River. Consistently high nutrient concentrations in the river and receiving water bodies conflict with recreational water use, leading to intense stakeholder debate on how best to manage water quality. Results show that the majority of annual phosphorus (P) loading is transported by direct runoff, with high concentrations transported by high discharge rates and low concentrations by low discharge rates. A synthetic relationship is derived and used to generate daily phosphorus concentrations, laying the foundation for analysis of annual loading and evaluation of alternative management practices. Total nitrogen (N) concentration does not have as clear a relationship with discharge. Using a simple regression relationship, annual P loadings are estimated as having a root mean squared error (RMSE) of 39.8 t/yr and 31.9 t/yr and mean absolute percentage errors of 19 percent and 28 percent at Watts and Tahlequah, respectively. P is the limiting nutrient over the full range of discharges. Given that the majority of P is derived from Arkansas, management practices that control P would have the most benefit if applied on the Arkansas side of the border.     

NUTRIENT CONCENTRATIONS IN WASTEWATER TREATMENT PLANT EFFLUENTS,SOUTH PLATTE RWER BASIN1

ABSTRACT: Accurate data about nutrient concentrations in wastewater treatment plant effluents are needed for river basin water-quality studies. As part of the U.S. Geological Survey's National Water-Quality Assessment Program in the South Platte River Basin, nutrient data were requested from 31 wastewater-treatment plants located in the basin. This article describes the types of nutrient data available from the plants, examines the variability of effluent nutrient concentrations, and discusses methods for estimation of nutrient concentrations where data are lacking. Ammonia was monitored at 88 percent of the plants, nitrite plus nitrate was monitored at 40 percent of the plants, and organic nitrogen and phosphorus were monitored at less than 25 percent of the plants. Median total nitrogen concentrations and median total phosphorus concentrations were small compared to typical literature estimates for wastewater-treatment plants with secondary treatment. Nutrient concentrations in effluent from wastewater-treatment plants varied widely between and within plants. For example, ammonia concentrations varied as much as 5 mg/L during a day, as much as 10 mg/L from day to day, and as much as 30 mg/L from summer to winter within a plant. In the South Platte River Basin, estimates of median annual ammonia and nitrite plus nitrate concentrations can be improved based on plant processes; and nitrite plus nitrate and organic nitrogen concentrations can be estimated based on ammonia concentrations. However, to avoid large estimation errors, more complete nutrient data from wastewater-treatment plants are needed for integration into river basin water quality studies. The paucity of data hinders attempts to evaluate the relative importance of point source and nonpoint source nutrient loadings to rivers.     

Assessment of chlorophyll-a as a criterion for establishing nutrient standards in the streams and rivers of Illinois

Nutrient enrichment is a frequently cited cause for biotic impairment of streams and rivers in the USA. Efforts are underway to develop nutrient standards in many states, but defensible nutrient standards require an empirical relationship between nitrogen (N) or phosphorus (P) concentrations and some criterion that relates nutrient levels to the attainment of designated uses. Algal biomass, measured as chlorophyll-a (chl-a), is a commonly proposed criterion, yet nutrient-chl-a relationships have not been well documented in Illinois at a state-wide scale. We used state-wide surveys of >100 stream and river sites to assess the applicability of chl-a as a criterion for establishing nutrient standards for Illinois. Among all sites, the median total P and total N concentrations were 0.185 and 5.6 mg L(-1), respectively, during high-discharge conditions. During low-discharge conditions, median total P concentration was 0.168 mg L(-1), with 25% of sites having a total P of > or =0.326 mg L(-1). Across the state, 90% of the sites had sestonic chl-a values of < or =35 microg L(-1), and watershed area was the best predictor of sestonic chl-a. During low discharge there was a significant correlation between sestonic chl-a and total P for those sites that had canopy cover < or =25% and total P of < or =0.2 mg L(-1). Results suggest sestonic chl-a may be an appropriate criterion for the larger rivers in Illinois but is inappropriate for small rivers and streams. Coarse substrate to support benthic chl-a occurred in <50% of the sites we examined; a study using artificial substrates did not reveal a relationship between chl-a accrual and N or P concentrations. For many streams and rivers in Illinois, nutrients may not be the limiting factor for algal biomass due to the generally high nutrient concentrations and the effects of other factors, such as substrate conditions and turbidity.     

Sources and Delivery of Nutrients to the Northwestern Gulf of Mexico from Streams in the South‐Central United States1

Rebich, Richard A., Natalie A. Houston, Scott V. Mize, Daniel K. Pearson, Patricia B. Ging, and C. Evan Hornig, 2011. Sources and Delivery of Nutrients to the Northwestern Gulf of Mexico From Streams in the South‐Central United States. Journal of the American Water Resources Association (JAWRA) 47(5):1061‐1086. DOI: 10.1111/j.1752‐1688.2011.00583.x Abstract: SPAtially Referenced Regressions On Watershed attributes (SPARROW) models were developed to estimate nutrient inputs [total nitrogen (TN) and total phosphorus (TP)] to the northwestern part of the Gulf of Mexico from streams in the South‐Central United States (U.S.). This area included drainages of the Lower Mississippi, Arkansas‐White‐Red, and Texas‐Gulf hydrologic regions. The models were standardized to reflect nutrient sources and stream conditions during 2002. Model predictions of nutrient loads (mass per time) and yields (mass per area per time) generally were greatest in streams in the eastern part of the region and along reaches near the Texas and Louisiana shoreline. The Mississippi River and Atchafalaya River watersheds, which drain nearly two‐thirds of the conterminous U.S., delivered the largest nutrient loads to the Gulf of Mexico, as expected. However, the three largest delivered TN yields were from the Trinity River/Galveston Bay, Calcasieu River, and Aransas River watersheds, while the three largest delivered TP yields were from the Calcasieu River, Mermentau River, and Trinity River/Galveston Bay watersheds. Model output indicated that the three largest sources of nitrogen from the region were atmospheric deposition (42%), commercial fertilizer (20%), and livestock manure (unconfined, 17%). The three largest sources of phosphorus were commercial fertilizer (28%), urban runoff (23%), and livestock manure (confined and unconfined, 23%).     

RELATING TRENDS OF PRINCIPAL COMPONENTS TO TRENDS OF WATER-QUALITY CONSTITUENTS1

ABSTRACT: The seasonal Kendall test is used for detecting water-quality trend or lack of trend for monthly data of 15 water-quality constituents at 15 sampling stations in the Arkansas River, the Neosho River, and the Verdigris River basins. Trends of individual constituents and the trends of the first four principal components for the correlation matrix of water-quality data at each station are determined, and the relationships between the trends of constituents and the trends of principal components are established. Using the principal components not only reduces the high dimensionality of the original data to a few principal components, but also presents an overall picture of water-quality trend of these river basins.     

Relationships among nutrients, chlorophyll-a, and dissolved oxygen in agricultural streams in Illinois

A better understanding of the controls on algae and dissolved O2 in agricultural streams of Illinois is needed to aid in development of nutrient standards. We investigated the relationships between dissolved nutrients, algal abundance, and dissolved O2 in five streams in east-central Illinois from March through November 2004. The streams drained watersheds from 25 to 777 km2 that were dominated by row crop agriculture. Three sites had open canopies and two were bordered by a narrow forest of deciduous trees. Algal abundance was measured as chlorophyll-a (chl-a) concentration in the water column (sestonic) and on the streambed (periphytic). Mean NO3-N concentrations ranged from 5.5 to 8.8 mg N L(-1) and did not relate to algal abundance. Sestonic chl-a values ranged from nearly zero to >15 mg m(-3) with no differences between open and shaded streams and only a weak correlation with dissolved reactive P (mean concentrations were 44-479 microg L(-1)). The results suggest that sestonic chl-a is a poor criterion for assessing nutrient-related problems in these streams. Greatest periphytic chl-a occurred during low flow from August through October, but periphyton occurred consistently in only two of the five streams. The abundance of filamentous algae explained 64% of the variation in diel O2 saturation, but was not correlated with nutrients. Currently it appears that hydrology and light, rather than nutrients, control algal abundance in these streams, and in the agricultural landscape of east-central Illinois, it may not be possible to reduce nutrient concentrations sufficiently to limit filamentous algal blooms.     

NITROGEN AND PHOSPHORUS IN SURFACE WATERS OF THE UPPER COLORADO RWER BASIN1

ABSTRACT: As part of a basinwide water-quality study, nitrogen and phosphorus data for the Upper Colorado River Basin from the Colorado-Utah State line to the Continental Divide were analyzed for spatial distributions, concentrations associated with various land uses, and temporal trends. Nitrogen and phosphorus concentrations generally increased in a downstream direction. Some nutrient concentrations were elevated at some sites in the upper parts of the basin in areas influenced by increasing urbanization. Sites were grouped according to land use and site type, and median nutrient concentrations were compared among groups. Sites within the agricultural areas of the basin generally had the highest concentrations of nitrogen and phosphorus; concentrations for main-stem, tributary, and urbanization sites were slightly lower than for the agricultural sites. Background sites, or sites with minimal land-use impacts, had very low median nutrient concentrations. Several sites with long-term data were analyzed for temporal trends in concentrations. Several statistically significant downward trends of low and moderate magnitude were observed for nitrogen and phosphorus species. No upward trends were observed in the data at any site.     

EVALUATION OF NITRATE DATA IN THE OCKLAWAHA RIVER BASIN,FLORIDA (1953–2002)1

ABSTRACT: Nitrate levels in the Ocklawaha River Basin in north central Florida were reviewed over a 50‐year period. Data were obtained from the literature, U.S. Environmental Protection Agency (USEPA) STOrage and RETrieval (STORET), and U.S. Geological Survey (USGS) databases. The study objective was to determine whether nitrate concentrations are increasing and if so, whether this increase is linked to land use changes. Increasing nitrate levels were seen at 5 of the 14 stations, while other stations showed no trend or a decreasing trend. Median nitrate concentrations in the Ocklawaha River increased from 0.07 mg‐N/L to 0.78 mg‐N/L at sites downstream from the Silver River. Throughout the Rodman Reservoir, median nitrate concentrations decreased from 0.48 mg‐N/L to 0.01 mg‐N/L and increased to 0.04 mg‐N/L after the Kirkpatrick Dam. Flow and concentration relationships were correlated for five stations. At four of the five stations nitrate concentrations decreased in response to increasing flow, likely the result of dilution with nitrate poor water. Changes in land use over a 20‐ year period (1970 to 1990) also were monitored. Sources of nitrate have been linked by isotopic analysis to organic and inorganic fertilizers, which appear to be related to increased urbanization and an increase in lawns that require nutrient fertilization.     

Integrating Bioassessment and Ecological Risk Assessment: An Approach to Developing Numerical Water-Quality Criteria

Bioassessment is used worldwide to monitor aquatic health but is infrequently used with risk-assessment objectives, such as supporting the development of defensible, numerical water-quality criteria. To this end, we present a generalized approach for detecting potential ecological thresholds using assemblage-level attributes and a multimetric index (Index of Biological Integrity—IBI) as endpoints in response to numerical changes in water quality. To illustrate the approach, we used existing macroinvertebrate and surface-water total phosphorus (TP) datasets from an observed P gradient and a P-dosing experiment in wetlands of the south Florida coastal plain nutrient ecoregion. Ten assemblage attributes were identified as potential metrics using the observational data, and five were validated in the experiment. These five core metrics were subjected individually and as an aggregated Nutrient–IBI to nonparametric changepoint analysis (nCPA) to estimate cumulative probabilities of a threshold response to TP. Threshold responses were evident for all metrics and the IBI, and were repeatable through time. Results from the observed gradient indicated that a threshold was 50% probable between 12.6 and 19.4 g/L TP for individual metrics and 14.8 g/L TP for the IBI. Results from the P-dosing experiment revealed 50% probability of a response between 11.2 and 13.0 g/L TP for the metrics and 12.3 g/L TP for the IBI. Uncertainty analysis indicated a low (typically 5%) probability that an IBI threshold occurred at 10 g/L TP, while there was 95% certainty that the threshold was 17 g/L TP. The weight-of-evidence produced from these analyses implies that a TP concentration > 12–15 g/L is likely to cause degradation of macroinvertebrate assemblage structure and function, a reflection of biological integrity, in the study area. This finding may assist in the development of a numerical water-quality criterion for TP in this ecoregion, and illustrates the utility of bioassessment to environmental decision-making.     

The opportunity cost of regulating phosphorus from broiler production in the Illinois River Basin

The Illinois River Basin in eastern Oklahoma and northwest Arkansas is an example of a region where significant growth in poultry production has been accompanied by water quality problems. The primary concern in the basin is the problem of phosphorus in runoff that is associated with application of litter to crops. Existing data suggest that there has been a continuing decline in the quality of water in the Illinois River, and discussions have focused on developing and implementing a phosphorus standard. The specific objectives of this study are to estimate the reduction in poultry production necessary to achieve the reduction in phosphorus runoff under a set of phosphorus constraints, including soil test phosphorus, and to estimate the opportunity costs of reducing poultry production in the basin under each phosphorus constraint on the economic activity in the watershed. A mathematical programming model that incorporates poultry production and cropping decisions is developed. The parameters for the model are identified and then it is solved to provide a base solution. Model solutions are then developed for the different policy target levels of phosphorus. The model structure is modified to account for the presence of soil test phosphorus levels and the corresponding limits on soil test phosphorus throughout the basin. This formulation includes current soil test phosphorus throughout the basin. All of the applications assume that the only disposal option for poultry litter is land application within the basin. An economic impact assessment of the effects of phosphorus limitations in the basin is also conducted for Arkansas counties only, Oklahoma counties only, and all five affected counties combined.     

Water Quality Model Uncertainty Analysis of a Point‐Point Source Phosphorus Trading Program1

Kardos, Josef S. and Christopher C. Obropta, 2011. Water Quality Model Uncertainty Analysis of a Point‐Point Source Phosphorus Trading Program. Journal of the American Water Resources Association (JAWRA) 47(6):1317–1337. DOI: 10.1111/j.1752‐1688.2011.00591.x Abstract: Water quality modeling is a major source of scientific uncertainty in the Total Maximum Daily Load (TMDL) process. The effects of these uncertainties extend to water quality trading programs designed to implement TMDLs. This study examines the effects of water quality model uncertainty on a nutrient trading program. The study builds on previous work to design a phosphorus trading program for the Nontidal Passaic River Basin in New Jersey that would implement the watershed TMDL for total phosphorus (TP). The study identified how water quality model uncertainty affects outcomes of potential trades of TP between wastewater treatment plants. The uncertainty analysis found no evidence to suggest that the outcome of trades between wastewater treatment plants, as compared with command and control regulation, will significantly increase uncertainty in the attainment of dissolved oxygen surface water quality standards, site‐specific chlorophyll a criteria, and reduction targets for diverted TP load at potential hot spots in the watershed. Each simulated trading scenario demonstrated parity with or improvement from the command and control approach at the TMDL critical locations, and low risk of hot spots elsewhere.     

Nitrogen and phosphorus leaching from growing season versus year-round application of wastewater on seasonally frozen lands

Land application of wastewater has become an important disposal option for food-processing plants operating year-round. However, there are concerns about nutrient leaching from winter wastewater application on frozen soils. In this study, P and N leaching were compared between nongrowing season application of tertiary-treated wastewater plus growing season application of partially treated wastewater (NGS) vs. growing season application of partially treated wastewater (GS) containing high levels of soil P. As required by the Minnesota Pollution Control Agency (MPCA), the wastewater applied to the NGS fields during October through March was treated such that it contained < or =6 mg L(-1) total phosphorus (TP), < or =10 mg L(-1) NO3-N, and < or =20 mg L(-1) total Kjeldahl nitrogen (TKN). The only regulation for wastewater application during the growing season (April through September) was that cumulatively it did not exceed the agronomic N requirements of the crop in any sprayfield. Application of tertiary-treated wastewater during the nongrowing season plus partially treated wastewater during the growing season did not significantly increase NO3-N leaching compared with growing season application of nonregulated wastewater. However, median TP concentration in leachate was significantly higher from the NGS (3.56 mg L(-1)) than from the GS sprayfields (0.52 mg L(-1)) or nonirrigated sites (0.52 mg L(-1)). Median TP leaching loss was also significantly higher from the NGS sprayfields (57 kg ha(-1)) than from the GS (7.4 kg ha(-1)) or control sites (6.9 kg ha(-1)). This was mainly due to higher hydraulic loading from winter wastewater application and limited or no crop P uptake during winter. Results from this study indicate that winter application of even low P potato-processing wastewater to high P soils can accelerate P leaching. We conclude that the regulation of winter wastewater application on frozen soils should be based on wastewater P concentration and permissible loading. We also recommend that winter irrigation should take soil P saturation into consideration.     

Rethinking the contribution of drained and undrained grasslands to sediment-related water quality problems

Grass vegetation has been recommended for use in the prevention and control of soil erosion because of its dense sward characteristics and stabilizing effect on the soil. A general assumption is that grassland environments suffer from minimal soil erosion and therefore present little threat to the water quality of surface waters in terms of sediment and sorbed contaminant pollution. Our data question this assumption, reporting results from one hydrological year of observations on a field-experiment monitoring overland flow, drain flow, fluxes of suspended solids, total phosphorus (TP), and molybdate-reactive phosphorus (<0.45 mum) in response to natural rainfall events. During individual rainfall events, 1-ha grassland lysimeters yield up to 15 kg of suspended solids, with concentrations in runoff waters of up to 400 mg L(-1). These concentrations exceed the water quality standards recommended by the European Freshwater Fisheries Directive (25 mg L(-1)) and the USEPA (80 mg L(-1)) and are beyond those reported to have caused chronic effects on freshwater aquatic organisms. Furthermore, TP concentrations in runoff waters from these field lysimeters exceeded 800 mug L(-1). These concentrations are in excess of those reported to cause eutrophication problems in rivers and lakes and contravene the ecoregional nutrient criteria in all of the USA ecoregions. This paper also examines how subsurface drainage, a common agricultural practice in intensively managed grasslands, influences the hydrology and export of sediment and nutrients from grasslands. This dataset suggests that we need to rethink the conceptual understanding of grasslands as non-erosive landscapes. Failure to acknowledge this will result in the noncompliance of surface waters to water quality standards.     

Model‐Based Nitrogen and Phosphorus (Nutrient) Criteria for Large Temperate Rivers: 2. Criteria Derivation

Nitrogen and phosphorus criteria were developed for 233 km of the Yellowstone River, one of the first cases where a mechanistic model has been used to derive large river numeric nutrient criteria. A water quality model and a companion model which simulates lateral algal biomass across transects were used to simulate effects of increasing nutrients on five variables (dissolved oxygen, total organic carbon, total dissolved gas, pH, and benthic algal biomass in depths ≤1 m). Incremental increases in nutrients were evaluated relative to their impact on predefined thresholds for each variable; the first variable to exceed a threshold set the nutrient criteria. Simulations were made at a low flow, the 14Q5 (lowest average 14 consecutive day flow, July‐September, recurring one in five years), which was derived using benthic algae growth curves and EPA guidance on excursion frequency. An extant climate dataset with an annual recurrence was used, and tributary water quality and flows were coincident with the river's 10 lowest flow years. The river had different sensitivities to nutrients longitudinally, pH being the most sensitive variable in the upstream reach and algal biomass in the lower. Model‐based criteria for the Yellowstone River are as follows: between the Bighorn and Powder river confluences, 55 μg TP/l and 655 μg TN/l; from the Powder River confluence to Montana state line, 95 μg TP/l and 815 μg TN/l. Pros and cons of using steady‐state models to derive river nutrient criteria are discussed.     

Defining Nutrient and Biochemical Oxygen Demand Baselines for Tropical Rivers and Streams in São Paulo State (Brazil): A Comparison Between Reference and Impacted Sites

Determining reference concentrations in rivers and streams is an important tool for environmental management. Reference conditions for eutrophication-related water variables are unavailable for Brazilian freshwaters. We aimed to establish reference baselines for São Paulo State tropical rivers and streams for total phosphorus (TP) and nitrogen (TN), nitrogen-ammonia (NH₄ ⁺) and Biochemical Oxygen Demand (BOD) through the best professional judgment and the trisection methods. Data from 319 sites monitored by the São Paulo State Environmental Company (2005 to 2009) and from the 22 Water Resources Management Units in São Paulo State were assessed (N = 27,131). We verified that data from different management units dominated by similar land cover could be analyzed together (Analysis of Variance, P = 0.504). Cumulative frequency diagrams showed that industrialized management units were characterized by the worst water quality (e.g. average TP of 0.51 mg/L), followed by agricultural watersheds. TN and NH₄ ⁺ were associated with urban percentages and population density (Spearman Rank Correlation Test, P < 0.05). Best professional judgment and trisection (median of lower third of all sites) methods for determining reference concentrations showed agreement: 0.03 &; 0.04 mg/L (TP), 0.31 &; 0.34 mg/L (TN), 0.06 &; 0.10 mg-N/L (NH₄ ⁺) and 2 &; 2 mg/L (BOD), respectively. Our reference concentrations were similar to TP and TN reference values proposed for temperate water bodies. These baselines can help with water management in São Paulo State, as well as providing some of the first such information for tropical ecosystems.     

Weighted Regressions on Time,Discharge, and Season (WRTDS), with an Application to Chesapeake Bay River Inputs1

Hirsch, Robert M., Douglas L. Moyer, and Stacey A. Archfield, 2010. Weighted Regressions on Time, Discharge, and Season (WRTDS), With an Application to Chesapeake Bay River Inputs. Journal of the American Water Resources Association (JAWRA) 46(5):857-880. DOI: 10.1111/j.1752-1688.2010.00482.x Abstract: A new approach to the analysis of long-term surface water-quality data is proposed and implemented. The goal of this approach is to increase the amount of information that is extracted from the types of rich water-quality datasets that now exist. The method is formulated to allow for maximum flexibility in representations of the long-term trend, seasonal components, and discharge-related components of the behavior of the water-quality variable of interest. It is designed to provide internally consistent estimates of the actual history of concentrations and fluxes as well as histories that eliminate the influence of year-to-year variations in streamflow. The method employs the use of weighted regressions of concentrations on time, discharge, and season. Finally, the method is designed to be useful as a diagnostic tool regarding the kinds of changes that are taking place in the watershed related to point sources, groundwater sources, and surface-water nonpoint sources. The method is applied to datasets for the nine large tributaries of Chesapeake Bay from 1978 to 2008. The results show a wide range of patterns of change in total phosphorus and in dissolved nitrate plus nitrite. These results should prove useful in further examination of the causes of changes, or lack of changes, and may help inform decisions about future actions to reduce nutrient enrichment in the Chesapeake Bay and its watershed.     

NUTRIENTS IN STREAMS DURING BASEFLOW IN SELECTED ENVIRONMENTAL SEVFINGS OF THE POTOMAC RiVER BASIN1

ABSTRACT: A regional assessment of water quality in small streams was conducted within four areas of distinct physiography and lithology in the upper Potomac River Basin. The Potomac River is a major tributary to the Chesapeake Bay, and this study provides new insight on the relationships between nutrient concentrations in small streams and watershed characteristics within this river basin. Nutrient concentrations were compared to land-use data including categories for agriculture (cropland and pasture), urban areas, and forests. Among agricultural areas, streams draining areas of intense row cropping typically contained higher nitrate concentrations than did those draining pastures. Streams draining forested areas typically had the lowest nutrient concentrations. Streams in areas underlain by carbonate bedrock were more likely to contain elevated concentrations of inorganic nitrogen and potassium than did streams in areas underlain by fractured siliciclastic or crystalline rocks, and we suggest that this is a physical phenomenon related to high hydraulic conductivities in carbonate ground-water systems. The median nitrate concentrations were highest in the Great Valley portion of the Valley and Ridge physiographic province, particularly in watersheds that have both carbonate bedrock and intensive row cropping. Values of nitrate in these streams ranged up to 8.99 mg/L as nitrogen. The soluble phosphorus concentrations during baseflow were generally low in all sub-units, even in some settings with potential for high phosphorus inputs such as urban areas with municipal point sources or agricultural areas. The mobility of phosphorus in these environments may be hindered by adsorption and geochemical reactions.     

Wetland Flowpaths Mediate Nitrogen and Phosphorus Concentrations across the Upper Mississippi River Basin

Eutrophication, harmful algal blooms, and human health impacts are critical environmental challenges resulting from excess nitrogen and phosphorus in surface waters. Yet we have limited information regarding how wetland characteristics mediate water quality across watershed scales. We developed a large, novel set of spatial variables characterizing hydrological flowpaths from wetlands to streams, that is, “wetland hydrological transport variables,” to explore how wetlands statistically explain the variability in total nitrogen (TN) and total phosphorus (TP) concentrations across the Upper Mississippi River Basin (UMRB) in the United States. We found that wetland flowpath variables improved landscape-to-aquatic nutrient multilinear regression models (from R² = 0.89 to 0.91 for TN; R² = 0.53 to 0.84 for TP) and provided insights into potential processes governing how wetlands influence watershed-scale TN and TP concentrations. Specifically, flowpath variables describing flow-attenuating environments, for example, subsurface transport compared to overland flowpaths, were related to lower TN and TP concentrations. Frequent hydrological connections from wetlands to streams were also linked to low TP concentrations, which likely suggests a nutrient source limitation in some areas of the UMRB. Consideration of wetland flowpaths could inform management and conservation activities designed to reduce nutrient export to downstream waters.