Dissolved organic nitrogen regulation in freshwaters

Dissolved organic nitrogen (DON) has been hypothesized to play a major role in N cycling in a variety of ecosystems. Our aim was to assess the seasonal and concentration relationships between dissolved organic carbon (DOC), DON, and NO3- within 102 streams and 16 lakes within catchments of differing complexity situated in Wales. Further, we aimed to assess whether patterns of land use, soil type, and vegetation gave consistent trends in DON and dissolved inorganic nitrogen (DIN) relationships over a diverse range of catchments. Our results reinforce that DON constitutes a significant component of the total dissolved N pool typically representing 40 to 50% of the total N in streams and lakes but sometimes representing greater than 85% of the total dissolved N. Generally, the levels of DON were inversely correlated with the concentration of DIN. In contrast to DIN concentrations, which showed distinct seasonality, DON showed no consistent seasonal trend. We hypothesize that this reflects differences in the bioavailability of these two N types. The amount of DON, DOC, and DIN was significantly related to soil type with higher DON export from Histosol-dominated catchments in comparison with Spodosol-dominated watersheds. Vegetation cover also had a significant effect on DON concentrations independent of soil type with a nearly twofold decrease in DON export from forested catchments in comparison with nonforested watersheds. Due to the diversity in catchment DON behavior, we speculate that this will limit the adoption of DON as a broad-scale indicator of catchment condition for use in monitoring and assessment programs.     

Mitigating the Effects of Landscape Development on Streams in Urbanizing Watersheds

This collaborative study examined urbanization and impacts on area streams while using the best available sediment and erosion control (S&EC) practices in developing watersheds in Maryland, United States. During conversion of the agricultural and forested watersheds to urban land use, land surface topography was graded and vegetation was removed creating a high potential for sediment generation and release during storm events. The currently best available S&EC facilities were used during the development process to mitigate storm runoff water quality, quantity, and timing before entering area streams. Detailed Geographic Information System (GIS) maps were created to visualize changing land use and S&EC practices, five temporal collections of LiDAR (light detection and ranging) imagery were used to map the changing landscape topography, and streamflow, physical geomorphology, and habitat data were used to assess the ability of the S&EC facilities to protect receiving streams during development. Despite the use of the best available S&EC facilities, receiving streams experienced altered flow, geomorphology, and decreased biotic community health. These impacts on small streams during watershed development affect sediment and nutrient loads to larger downstream aquatic ecosystems such as the Chesapeake Bay.     

Denitrification potential in urban riparian zones

Denitrification, the anaerobic microbial conversion of nitrate (NO3-) to nitrogen (N) gases, is an important process contributing to the ability of riparian zones to function as "sinks" for NO3- in watersheds. There has been little analysis of riparian zones in urban watersheds despite concerns about high NO3- concentrations in many urban streams. Vegetation and soils in urban ecosystems are often highly disturbed, and few studies have examined microbial processes like denitrification in these ecosystems. In this study, we measured denitrification potential and a suite of related microbial parameters (microbial biomass carbon [C] and N content, potential net N mineralization and nitrification, soil inorganic N pools) in four rural and four urban riparian zones in the Baltimore, MD metropolitan area. Two of the riparian zones were forested and two had herbaceous vegetation in each land use context. There were few differences between urban and rural and herbaceous and forest riparian zones, but variability was much higher in urban than rural sites. There were strong positive relationships between soil moisture and organic matter content and denitrification potential. Given the importance of surface runoff in urban watersheds, the high denitrification potential of the surface soils that we observed suggests that if surface runoff can be channeled through areas with high denitrification potential (e.g., stormwater detention basins with wetland vegetation), these areas could function as important NO3- sinks in urban watersheds.     

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.     

NITROGEN AND PHOSPHORUS CONCENTRATIONS IN FOREST STREAMS OF THE UNITED STATES1

ABSTRACT: Seventy to eighty percent of the water flowing in rivers in the United States originates as precipitation in forests. This project developed a synoptic picture of the patterns in water chemistry for over 300 streams in small, forested watersheds across the United States. Nitrate (NO₃^?) concentrations averaged 0.31 mg N/L, with some streams averaging ten times this level. Nitrate concentrations tended to be higher in the northeastern United States in watersheds dominated by hardwood forests (especially hardwoods other than oaks) and in recently harvested watersheds. Concentrations of dissolved organic N (mean 0.32 mg N/L) were similar to those of NO₃～, whereas ammonium (NH₄⁺) concentrations were much lower (mean 0.05 mg N/L). Nitrate dominated the N loads of streams draining hardwood forests, whereas dissolved organic N dominated the streams in coniferous forests. Concentrations of inorganic phosphate were typically much lower (mean 12 mg P/L) than dissolved organic phosphate (mean 84 mg P/L). The frequencies of chemical concentrations in streams in small, forested watersheds showed more streams with higher NO₃^? concentrations than the streams used in national monitoring programs of larger, mostly forested watersheds. At a local scale, no trend in nitrate concentration with stream order or basin size was consistent across studies.     

Non-Point-Source Impacts on Stream Nutrient Concentrations Along a Forest to Urban Gradient

We conducted statistical analyses of a 10-year record of stream nutrient and sediment concentrations for 17 streams in the greater Seattle region to determine the impact of urban non-point-source pollutants on stream water quality. These catchments are dominated by either urban (22–87%) or forest (6–73%) land cover, with no major nutrient point sources. Stream water phosphorus concentrations were moderately strongly (r²=0.58) correlated with catchment land-cover type, whereas nitrogen concentrations were weakly (r²=0.19) and nonsignificantly (at < 0.05) correlated with land cover. The most urban streams had, on average, 95% higher total phosphorus (TP) and 122% higher soluble reactive phosphorus (SRP) and 71% higher turbidity than the most forested streams. Nitrate (NO₃), ammonium (NH₄), and total suspended solids (TSS) concentrations did not vary significantly with land cover. These results suggest that urbanization markedly increased stream phosphorus concentrations and modestly increased nitrogen concentrations. However, nutrient concentrations in Seattle region urban streams are significantly less than those previously reported for agricultural area streams.     

Chloride effects on nitrogen dynamics in forested and suburban stream debris dams

Organic debris dams (accumulations of organic material) can function as "hotspots" of nitrogen (N) processing in streams. Suburban streams are often characterized by high flows that prevent the accumulation of organic debris and by elevated concentrations of solutes, especially nitrate (NO(3)(-)) and chloride (Cl(-)). In this study we (1) studied the effects of urbanization on the extent and characteristics of debris dams in large and small streams and (2) evaluated the effects of NO(3)(-) and Cl(-) on rates of N cycle processes in these debris dams. In some suburban streams debris dams were small and rare, but in others factors that reduce the effects of high stream flows fostered the maintenance of debris dams. Ambient denitrification enzyme activity (DEA) in these suburban and forested streams was positively correlated with stream NO(3)(-) concentrations. In laboratory microcosms, DEA in debris dam material from a forested reference stream was increased by NO(3)(-) additions. Chloride additions constrained the response of DEA to NO(3)(-) additions in material from the forested stream, but had no effect on DEA in material from streams with a history of high Cl(-) levels. Chloride additions changed the sign of net N mineralization from negative (consumption of inorganic N) to positive in debris dam material from the forested reference stream, but had no effect on net mineralization in material from streams with a history of exposure to Cl(-). Understanding the factors regulating the maintenance and N cycling activity of organic debris, and incorporating them into urban stream management plans could have important effects on N dynamics in suburban watersheds.     

Stream Discharge and Riparian Land Use Influence In-Stream Concentrations and Loads of Phosphorus from Central Plains Watersheds

Total annual nutrient loads are a function of both watershed characteristics and the magnitude of nutrient mobilizing events. We investigated linkages among land cover, discharge and total phosphorus (TP) concentrations, and loads in 25 Kansas streams. Stream monitoring locations were selected from the Kansas Department of Health and Environment stream chemistry long-term monitoring network sites at or near U.S. Geological Survey stream gauges. We linked each sample with concurrent discharge data to improve our ability to estimate TP concentrations and loads across the full range of possible flow conditions. Median TP concentration was strongly linked (R ² = 76%) to the presence of cropland in the riparian zones of the mostly perennial streams. At baseflow, discharge data did not improve prediction of TP, but at high flows discharge was strongly linked to concentration (a threshold response occurred). Our data suggest that on average 88% of the total load occurred during the 10% of the time with the greatest discharge. Modeled reductions in peak discharges, representing increased hydrologic retention, predicted greater decreases in total annual loads than reductions of ambient concentrations because high discharge and elevated phosphorus concentrations had multiplicative effects. No measure of land use provided significant predictive power for concentrations when discharge was elevated or for concentration rise rates under increasing discharge. These results suggest that reductions of baseflow concentrations of TP in streams without wastewater dischargers may be managed by reductions of cropland uses in the riparian corridor. Additional measures may be needed to manage TP annual loads, due to the large percentage of the TP load occurring during a few high-flow events each year.     

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%).     

NUTRIENTS DISCHARGED TO THE MISSISSIPPI RIVER FROM EASTERN IOWA WATERSHEDS, 1996.19971

ABSTRACT: The introduction of nutrients from chemical fertilizer, animal manure, wastewater, and atmospheric deposition to the eastern Iowa environment creates a large potential for nutrient transport in watersheds. Agriculture constitutes 93 percent of all land use in eastern Iowa. As part of the U.S. Geological Survey National Water Quality Assessment Program, water samples were collected (typically monthly) from six small and six large watersheds in eastern Iowa between March 1996 and September 1997. A Geographic Information System (GIS) was used to determine land use and quantify inputs of nitrogen and phosphorus within the study area. Streamliow from the watersheds is to the Mississippi River. Chemical fertilizer and animal manure account for 92 percent of the estimated total nitrogen and 99.9 percent of the estimated total phosphorus input in the study area. Total nitrogen and total phosphorus loads for 1996 were estimated for nine of the 12 rivers and creeks using a minimum variance unbiased estimator model. A seasonal pattern of concentrations and loads was observed. The greatest concentrations and loads occur in the late spring to early summer in conjunction with row‐crop fertilizer applications and spring nmoff and again in the late fall to early winter as vegetation goes into dormancy and additional fertilizer is applied to row‐crop fields. The three largest rivers in eastern Iowa transported an estimated total of 79,000 metric tons of total nitrogen and 6,800 metric tons of total phosphorus to the Mississippi River in 1996. The estimated mass of total nitrogen and total phosphorus transported to the Mississippi River represents about 19 percent of all estimated nitrogen and 9 percent of all estimated phosphorus input to the study area.     

Denitrification in alluvial wetlands in an urban landscape

Riparian wetlands have been shown to be effective "sinks" for nitrate N (NO3-), minimizing the downstream export of N to streams and coastal water bodies. However, the vast majority of riparian denitrification research has been in agricultural and forested watersheds, with relatively little work on riparian wetland function in urban watersheds. We investigated the variation and magnitude of denitrification in three constructed and two relict oxbow urban wetlands, and in two forested reference wetlands in the Baltimore metropolitan area. Denitrification rates in wetland sediments were measured with a 15N-enriched NO3- "push-pull" groundwater tracer method during the summer and winter of 2008. Mean denitrification rates did not differ among the wetland types and ranged from 147 +/- 29 microg N kg soil(-1) d(-1) in constructed stormwater wetlands to 100 +/- 11 microg N kg soil(-1) d(-1) in relict oxbows to 106 +/- 32 microg N kg soil(-1) d(-1) in forested reference wetlands. High denitrification rates were observed in both summer and winter, suggesting that these wetlands are sinks for NO3- year round. Comparison of denitrification rates with NO3- standing stocks in the wetland water column and stream NO3- loads indicated that mass removal of NO3- in urban wetland sediments by denitrification could be substantial. Our results suggest that urban wetlands have the potential to reduce NO3- in urban landscapes and should be considered as a means to manage N in urban watersheds.     

GROUNDWATER DISCHARGE AND ITS IMPACT ON SURFACE WATER QUALITY IN A CHESAPEAKE BAY INLET1

ABSTRACT: Surface water, groundwater, and groundwater discharge quality surveys were conducted in Cherrystone Inlet, on Virginia's Eastern Shore. Shallow groundwater below agricultural fields had nitrate concentrations significantly higher than inlet surface waters and shallow groundwater underlying forested land. This elevated nitrate groundwater discharged to adjacent surface waters. Nearshore discharge rates of water across the sediment-water interface ranged from 0.02 to 3.69 liters·m^?2·hr^?1 during the surveys. The discharge was greatest nearshore at low tide periods, and decreased markedly with increasing distance offshore. Vertical hydraulic heads, E_h, and inorganic nitrogen flux in the sediments followed similar patterns. Nitrate was the predominant nitrogen species discharged nearshore adjacent to agricultural land use, changing to ammonium farther offshore. Sediment nitrogen fluxes were sufficient to cause observable impacts on surface water quality; nitrate concentrations were up to 20 times greater in areas of groundwater discharge than in the main stem inlet water. Based on DIN:DIP ratios, nitrogen contributions from direct groundwater discharge and tidal creek inputs appear to be of significant ecological importance. This groundwater discharge links land use activity and the quality of surface water, and therefore must be considered in selection of best management practices and water quality management strategies.     

Long-Term Effects of Changing Land Use Practices on Surface Water Quality in a Coastal River and Lagoonal Estuary

The watershed of the Neuse River, a major tributary of the largest lagoonal estuary on the U.S. mainland, has sustained rapid growth of human and swine populations. This study integrated a decade of available land cover and water quality data to examine relationships between land use changes and surface water quality. Geographic Information Systems (GIS) analysis was used to characterize 26 subbasins throughout the watershed for changes in land use during 1992–2001, considering urban, agricultural (cropland, animal as pasture, and densities of confined animal feed operations [CAFOs]), forested, grassland, and wetland categories and numbers of wastewater treatment plants (WWTPs). GIS was also used together with longitudinal regression analysis to identify specific land use characteristics that influenced surface water quality. Total phosphorus concentrations were significantly higher during summer in subbasins with high densities of WWTPs and CAFOs. Nitrate was significantly higher during winter in subbasins with high numbers of WWTPs, and organic nitrogen was higher in subbasins with higher agricultural coverage, especially with high coverage of pastures fertilized with animal manure. Ammonium concentrations were elevated after high precipitation. Overall, wastewater discharges in the upper, increasingly urbanized Neuse basin and intensive swine agriculture in the lower basin have been the highest contributors of nitrogen and phosphorus to receiving surface waters. Although nonpoint sources have been emphasized in the eutrophication of rivers and estuaries such as the Neuse, point sources continue to be major nutrient contributors in watersheds sustaining increasing human population growth. The described correlation and regression analyses represent a rapid, reliable method to relate land use patterns to water quality, and they can be adapted to watersheds in any region.     

DROUGHT EFFECTS ON WATER QUALITY IN THE SOUTH PLATTE RIVER BASIN,COLORADO1

ABSTRACT: Twenty‐three stream sites representing a range of forested, agricultural, and urban land uses were sampled in the South Platte River Basin of Colorado from July through September 2002 to characterize water quality during drought conditions. With a few exceptions, dissolved ammonia, Kjeldahl nitrogen, total phosphorus, and dissolved orthophosphate concentrations were similar to seasonal historical levels in all land use areas during the drought. At some agricultural sites, decreased dilution of irrigation return flow may have contributed to higher concentrations of some nutrient species, increased primary productivity, and higher dissolved oxygen concentrations. At some urban sites, decreased dilution of base flow and wastewater treatment plant effluent may have contributed to higher dissolved nitrite‐plus‐nitrate concentrations, increased primary productivity, and higher dissolved oxygen concentrations. Total pesticide concentrations in urban and agricultural areas were not consistently higher or lower during the drought. At most forested sites, decreased dilution of ground water‐derived calcium bicarbonate type base flow likely led to elevated pH and specific‐conductance values. Water temperatures at many of the forested sites also were higher, contributing to lower dissolved oxygen concentrations during the drought.     

AUTUMN CHEMISTRY OF OREGON COAST RANGE STREAMS1

ABSTRACT: During an autumn runoff event we sampled 48 streams with predominantly forested watersheds and igneous bedrock in the Oregon Coast Range. The streams had acid neutralizing capacities (ANC) > 90 μeq/L and pH > 6.4. Streamwater Na ⁺, Ca^{2 +}, and Mg^{2 +} concentrations were greater than K ⁺ concentrations. Anion concentrations generally followed the order of Cl^- > NO₃^- > SO₄^2-. Chloride and Na ⁺ concentrations were highest in samples collected in streams near the Pacific Ocean and decreased markedly as distance from the coast increased. Sea salt exerted no discernible influence on stream water acid-base status during the sampling period. Nitrate concentrations in the study streams were remarkably variable, ranging from below detection to 172 μeq/L. We hypothesize that forest vegetation is the primary control of spatial variability of the NO₃^- concentrations in Oregon Coast Range streams. We believe that symbiotic N fixation by red alder in pure or mixed stands is the primary source of N to forested watersheds in the Oregon Coast Range.     

Boosted Regression Tree Models to Explain Watershed Nutrient Concentrations and Biological Condition

Boosted regression tree (BRT) models were developed to quantify the nonlinear relationships between landscape variables and nutrient concentrations in a mesoscale mixed land cover watershed during base‐flow conditions. Factors that affect instream biological components, based on the Index of Biotic Integrity (IBI), were also analyzed. Seasonal BRT models at two spatial scales (watershed and riparian buffered area [RBA]) for nitrite‐nitrate (NO₂‐NO₃), total Kjeldahl nitrogen, and total phosphorus (TP) and annual models for the IBI score were developed. Two primary factors — location within the watershed (i.e., geographic position, stream order, and distance to a downstream confluence) and percentage of urban land cover (both scales) — emerged as important predictor variables. Latitude and longitude interacted with other factors to explain the variability in summer NO₂‐NO₃ concentrations and IBI scores. BRT results also suggested that location might be associated with indicators of sources (e.g., land cover), runoff potential (e.g., soil and topographic factors), and processes not easily represented by spatial data indicators. Runoff indicators (e.g., Hydrological Soil Group D and Topographic Wetness Indices) explained a substantial portion of the variability in nutrient concentrations as did point sources for TP in the summer months. The results from our BRT approach can help prioritize areas for nutrient management in mixed‐use and heavily impacted watersheds.     

Detecting Temporal Change in Watershed Nutrient Yields

Meta-analyses reveal that nutrient yields tend to be higher for watersheds dominated by anthropogenic uses (e.g., urban, agriculture) and lower for watersheds dominated by natural vegetation. One implication of this pattern is that loss of natural vegetation will produce increases in watershed nutrient yields. Yet, the same meta-analyses also reveal that, absent land-cover change, watershed nutrient yields vary from one year to the next due to many exogenous factors. The interacting effects of land cover and exogenous factors suggest nutrient yields should be treated as distributions, and the effect of land-cover change should be examined by looking for significant changes in the distributions. We compiled nutrient yield distributions from published data. The published data included watersheds with homogeneous land cover that typically reported two or more years of annual nutrient yields for the same watershed. These data were used to construct statistical models, and the models were used to estimate changes in the nutrient yield distributions as a result of land-cover change. Land-cover changes were derived from the National Land Cover Database (NLCD). Total nitrogen (TN) yield distributions increased significantly for 35 of 1550 watersheds and decreased significantly for 51. Total phosphorus (TP) yield distributions increased significantly for 142 watersheds and decreased significantly for 17. The amount of land-cover change required to produce significant shifts in nutrient yield distributions was not constant. Small land-cover changes led to significant shifts in nutrient yield distributions when watersheds were dominated by natural vegetation, whereas much larger land-cover changes were needed to produce significant shifts when watersheds were dominated by urban or agriculture. We discuss our results in the context of the Clean Water Act.     

AGRICULTURE LAND‐USE EFFECTS ON NUTRIENT LOSSES IN WEST TIAOXI WATERSHED,CHINA1

ABSTRACT: Five types of land use/land covers in the West Tiaoxi watershed of China were studied for nutrient losses in artificial rainstorm runoff. A self‐designed rainfall simulator was used. In situ rainfall simulations were used to: (1) compare the concentrations of nitrogen and phosphorous in different land use/land covers and (2) evaluate the flux of nitrogen and phosphorous export from runoff and sediment in various types of land use/land covers. Three duplicated experiments were carried out under rain intensity of 2 mm/min, each lasting 32 minutes on a 3 m² plot. Characteristics of various species of nitrogen and phosphorous in runoff and sediment were investigated. The results showed that the concentrations of total nitrogen (TN) and total phosphorous (TP) were greatest in runoff from mulberry trees and smallest from pine forest. The TN and TP export was mainly from suspended particulate in runoff. TN and TP exports from the top 10 cm layer of five types of land use/land covers were estimated as high as 4.66 to 9.40 g/m² and 2.57 to 4.89 g/m², respectively, of which exports through sediment of runoff accounted for more than 90 percent and 97 percent. The rate of TN and TP exports ranged from 2.68 to approximately 14.48 and 0.45 to approximately 4.11 mg/m²/min in runoff; these rates were much lower than those of 100.01 to approximately 172.67 and 72.82 to approximately 135.96 mg/m²/min in the runoff sediment.     

A Daily Time Series Analysis of StreamWater Phosphorus Concentrations Along an Urban to Forest Gradient

During a 1-year period, we sampled stream water total phosphorus (TP) concentrations daily and soluble reactive phosphorus (SRP) concentrations weekly in four Seattle area streams spanning a gradient of forested to urban-dominated land cover. The objective of this study was to develop time series models describing stream water phosphorus concentration dependence on seasonal variation in stream base flows, short-term flow fluctuations, antecedent flow conditions, and rainfall. Stream water SRP concentrations varied on average by ±18% or ±5.7 μg/L from one week to another, whereas TP varied ±48% or ±32.5 μg/L from one week to another. On average, SRP constituted about 47% of TP. Stream water SRP concentrations followed a simple sine-wave annual cycle with high concentrations during the low-flow summer period and low concentrations during the high-flow winter period in three of the four study sites. These trends are probably due to seasonal variation in the relative contributions of groundwater and subsurface flows to stream flow. In forested Issaquah Creek, SRP concentrations were relatively constant throughout the year except during the fall, when a major salmon spawning run occurred in the stream and SRP concentrations increased markedly. Stream water SRP concentrations were statistically unrelated to short-term flow fluctuations, antecedent flow conditions, or rainfall in each of the study streams. Stream water TP concentrations are highly variable and strongly influenced by short-term flow fluctuations. Each of the processes assessed had statistically significant correlations with TP concentrations, with seasonal base flow being the strongest, followed by antecedent flow conditions, short-term flow fluctuations, and rainfall. Times series models for each individual stream were able to predict ∼70% of the variability in the SRP annual cycle in three of the four streams (r² = 0.57–0.81), whereas individual TP models explained ∼50% of the annual cycle in all streams (r² = 0.39–0.59). Overall, time series models for SRP and TP dynamics explained 82% and 76% of the variability for these variables, respectively. Our results indicate that SRP, the most biologically available and therefore most important phosphorus fraction, has simpler and easier-to-predict seasonal and weekly dynamics.     

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.