Climate change will pose challenges to water quality management in the st. Croix River basin.

Responses of streamflow and nutrient export to changing climate conditions should be investigated for effective water quality management and pollution control. Using downscaled climate projections and the Soil and Water Assessment Tool (SWAT), we projected future streamflow, sediment export, and riverine nutrient export in the St. Croix River Basin (SCRB) during 2020-2099. Results show substantial increases in riverine water, sediment, and nutrient load under future climate conditions, particularly under the high greenhouse gas emission scenario. Intensified water cycling and enhanced nutrient export will pose challenges to water quality management and affect multiple Best Management Practices (BMPs) efforts, which are aimed at reducing nutrient loads in SCRB. In addition to the physical impacts of climate change on terrestrial hydrology, our analyses demonstrate significant reductions in ET under elevated atmospheric CO2 concentrations. Changes in plant physiology induced by climate change may markedly affect water cycling and associated sediment and nutrient export. Results of this study highlight the importance of examining climate change impacts on water and nutrient delivery for effective watershed management.

Use of the soil and water assessment tool to scale sediment delivery from field to watershed in an agricultural landscape with topographic depressions.

For two watersheds in the northern Midwest United States, we show that landscape depressions have a significant impact on watershed hydrology and sediment yields and that the Soil and Water Assessment Tool (SWAT) has appropriate features to simulate these depressions. In our SWAT models of the Willow River in Wisconsin and the Sunrise River in Minnesota, we used Pond and Wetland features to capture runoff from about 40% of the area in each watershed. These depressions trapped considerable sediment, yet further reductions in sediment yield were required for calibration and achieved by reducing the Universal Soil Loss Equation (USLE) cropping-practice (P) factor to 0.40 to 0.45. We suggest terminology to describe annual sediment yields at different conceptual spatial scales and show how SWAT output can be partitioned to extract data at each of these scales. These scales range from plot-scale yields calculated with the USLE to watershed-scale yields measured at the outlet. Intermediate scales include field, upland, pre-riverine, and riverine scales, in descending order along the conceptual flow path from plot to outlet. Sediment delivery ratios, when defined as watershed-scale yields as a percentage of plot-scale yields, ranged from 1% for the Willow watershed (717 km) to 7% for the Sunrise watershed (991 km). Sediment delivery ratios calculated from published relations based on watershed area alone were about 5 to 6%, closer to pre-riverine-scale yields in our watersheds.

Methylmercury declines in a boreal peatland when experimental sulfate deposition decreases.

Between 2001 and 2008 we experimentally manipulated atmospheric sulfate-loading to a small boreal peatland and monitored the resulting short and long-term changes in methylmercury (MeHg) production. MeHg concentrations and %MeHg (fraction of total-Hg (Hg(T)) present as MeHg) in the porewaters of the experimental treatment reached peak values within a week of sulfate addition and then declined as the added sulfate disappeared. MeHg increased cumulatively over time in the solid-phase peat, which acted as a sink for newly produced MeHg. In 2006 a "recovery" treatment was created by discontinuing sulfate addition to a portion of the experimentally treated section to assess how MeHg production might respond to decreased sulfate loads. Four years after sulfate additions ceased, MeHg concentrations and %MeHg had declined significantly from 2006 values in porewaters and peat, but remained elevated relative to control levels. Mosquito larvae collected from each treatment at the end of the experiment exhibited Hg(T) concentrations reflective of MeHg levels in the peat and porewaters where they were collected. The proportional responses of invertebrate Hg(T) to sulfate deposition rates demonstrate that further controls on sulfur emissions may represent an additional means of mitigating Hg contamination in fish and wildlife across low-sulfur landscapes.

Identifying pathways and processes affecting nitrate and orthophosphate inputs to streams in agricultural watersheds.

Understanding nutrient pathways to streams will improve nutrient management strategies and estimates of the time lag between when changes in land use practices occur and when water quality effects that result from these changes are observed. Nitrate and orthophosphate (OP) concentrations in several environmental compartments were examined in watersheds having a range of base flow index (BFI) values across the continental United States to determine the dominant pathways for water and nutrient inputs to streams. Estimates of the proportion of stream nitrate that was derived from groundwater increased as BFI increased. Nitrate concentration gradients between groundwater and surface water further supported the groundwater source of nitrate in these high BFI streams. However, nitrate concentrations in stream-bed pore water in all settings were typically lower than stream or upland groundwater concentrations, suggesting that nitrate discharge to streams was not uniform through the bed. Rather, preferential pathways (e.g., springs, seeps) may allow high nitrate groundwater to bypass sites of high biogeochemical transformation. Rapid pathway compartments (e.g., overland flow, tile drains) had OP concentrations that were typically higher than in streams and were important OP conveyers in most of these watersheds. In contrast to nitrate, the proportion of stream OP that is derived from ground water did not systematically increase as BFI increased. While typically not the dominant source of OP, groundwater discharge was an important pathway of OP transport to streams when BFI values were very high and when geochemical conditions favored OP mobility in groundwater.

Sulfate addition increases methylmercury production in an experimental wetland.

Atmospheric mercury is the dominant Hg source to fish in northern Minnesota and elsewhere. However, atmospherically derived Hg must be methylated prior to accumulating in fish. Sulfate-reducing bacteria are thought to be the primary methylators of Hg in the environment. Previous laboratory and field mesocosm studies have demonstrated an increase in methylmercury (MeHg) levels in sediment and peatland porewaters following additions of sulfate. In the current ecosystem-scale study, sulfate was added to half of an experimental wetland at the Marcell Experimental Forest located in northeastern Minnesota, increasing annual sulfate load by approximately four times relative to the control half of the wetland. Sulfate was added on four separate occasions during 2002 and delivered via a sprinkler system constructed on the southeast half (1.0 ha) of the S6 experimental wetland. MeHg levels were monitored in porewater and in outflow from the wetland. Prior to the first sulfate addition, MeHg concentrations (filtered, 0.7 microm) were not statistically different between the control (0.47 +/- 0.10 ng L(-1), n = 12; mean +/- one standard error) and experimental 0.52 +/- 0.05 ng L(-1), n = 18) halves. Following the first addition in May 2002, MeHg porewater concentrations increased to 1.63 +/- 0.27 ng L(-1) two weeks after the addition, a 3-fold increase. Subsequent additions in July and September 2002 did not raise porewater MeHg, but the applied sulfate was not observed in porewaters 24 h after addition. MeHg concentrations in outflow from the wetland also increased leading to an estimated 2.4x increase of MeHg flux from the wetland. Our results demonstrate enhanced methylation and increased MeHg concentrations within the wetland and in outflow from the wetland suggesting that decreasing sulfate deposition rates would lower MeHg export from wetlands.