A new approach to generalizing riparian water and air quality function across regions.

There is growing interest in generalizing the impact of hydrogeomorphology and weather variables on riparian functions. Here, we used RZ-TRADEOFF to estimate nitrogen, phosphorus, water table (WT) depth, and greenhouse gas (GHG: N2O, CO2, CH4) functions for 80 riparian zones typical of the North American Midwest, Northeast (including Southern Ontario, Canada), and Mid-Atlantic. Sensitivity to weather perturbations was calculated for temperature and precipitation-dependent functions (CO2, phosphate concentration, and water table), and multivariate statistical analysis on model outputs was conducted to determine trade-offs between riparian functions. Mean model estimates were 93.10 cm for WT depth, 8.45 mg N L-1 for field edge nitrate concentration, 51.57% for nitrate removal, 0.45 mg PO43- L-1 for field edge phosphate concentration, 1.5% for subsurface phosphate removal, 91.24% for total overland phosphorus removal, 0.51 mg N m-2 day-1 for N2O flux, 5.5 g C m-2 day-1 for CO2 fluxes, and - 0.41 mg C m-2 day-1 and 621.51 mg C m-2 day-1 for CH4 fluxes in non-peat sites and peat sites, respectively. Sites in colder climates were most sensitive to weather perturbations for CO2, sites with deep water tables estimates had the highest sensitivity for WT, and sites in warm climates and/or with deep confining layers had the lowest sensitivity for phosphate concentration. Slope, confining layer depth, and temperature were the primary characteristics influencing similarities and trade-offs between sites. This research contributes to understanding how to optimize riparian restoration and protection in watersheds based on both water (nitrogen, phosphorus) and air quality (GHG) goals.

Watershed 'Chemical Cocktails': Forming Novel Elemental Combinations in Anthropocene Fresh Waters.

In the Anthropocene1, watershed chemical transport is increasingly dominated by novel combinations elements, which are hydrologically linked together as 'chemical cocktails.' Chemical cocktails are novel because human activities greatly enhance elemental concentrations and their probability for biogeochemical interactions and shared transport along hydrologic flowpaths. A new chemical cocktail approach advances our ability to: trace contaminant mixtures in watersheds, develop chemical proxies with high-resolution sensor data, and manage multiple water quality problems. We explore the following questions: (1) Can we classify elemental transport in watersheds as chemical cocktails using a new approach? (2) What is the role of climate and land use in enhancing the formation and transport of chemical cocktails in watersheds? To address these questions, we first analyze trends in concentrations of carbon, nutrients, metals, and salts in fresh waters over 100 years. Next, we explore how climate and land use enhance the probability of formation of chemical cocktails of carbon, nutrients, metals, and salts. Ultimately, we classify transport of chemical cocktails based on solubility, mobility, reactivity, and dominant phases: (1) sieved chemical cocktails (e.g., particulate forms of nutrients, metals and organic matter); (2) filtered chemical cocktails (e.g., dissolved organic matter and associated metal complexes); (3) chromatographic chemical cocktails (e.g., ions eluted from soil exchange sites); and (4) reactive chemical cocktails (e.g., limiting nutrients and redox sensitive elements). Typically, contaminants are regulated and managed one element at a time, even though combinations of elements interact to influence many water-quality problems such as toxicity to life, eutrophication, infrastructure and water treatment. A chemical cocktail approach significantly expands evaluations of water-quality signatures and impacts beyond single elements to mixtures. High-frequency sensor data (pH, specific conductance, turbidity, etc.) can serve as proxies for chemical cocktails and improve real-time analyses of water-quality violations, identify regulatory needs, and track water quality recovery following and extreme climate events. Ultimately, a watershed chemical cocktail approach is necessary for effectively co-managing groups of contaminants and provides a more holistic approach for studying, monitoring, and managing water quality in the Anthropocene.

Denitrifying Bioreactors for Nitrate Removal: A Meta-Analysis.

Meta-analysis approaches were used in this first quantitative synthesis of denitrifying woodchip bioreactors. Nitrate removal across environmental and design conditions was assessed from 26 published studies, representing 57 separate bioreactor units (i.e., walls, beds, and laboratory columns). Effect size calculations weighted the data based on variance and number of measurements for each bioreactor unit. Nitrate removal rates in bed and column studies were not significantly different, but both were significantly higher than wall studies. In denitrifying beds, wood source did not significantly affect nitrate removal rates. Nitrate removal (mass per volume) was significantly lower in beds with <6-h hydraulic retention times, which argues for ensuring that bed designs incorporate sufficient time for nitrate removal. Rates significantly declined after the first year of bed operation but then stabilized. Nitrogen limitation significantly affected bed nitrate removal. Categorical and linear assessments found significant nitrate removal effects with bed temperature; a of 2.15 was quite similar to other studies. Lessons from this meta-analysis can be incorporated into bed designs, especially extending hydraulic retention times to increase nitrate removal under low temperature and high flow conditions. Additional column studies are warranted for comparative assessments, as are field-based studies for assessing in situ conditions, especially in aging beds, with careful collection and reporting of design and environmental data. Future assessment of these systems might take a holistic view, reviewing nitrate removal in conjunction with other processes, including greenhouse gas and other unfavorable by-product production.

Beaver Ponds: Resurgent Nitrogen Sinks for Rural Watersheds in the Northeastern United States.

Beaver-created ponds and dams, on the rise in the northeastern United States, reshape headwater stream networks from extensive, free-flowing reaches to complexes of ponds, wetlands, and connecting streams. We examined seasonal and annual rates of nitrate transformations in three beaver ponds in Rhode Island under enriched nitrate-nitrogen (N) conditions through the use of N mass balance techniques on soil core mesocosm incubations. We recovered approximately 93% of the nitrate N from our mesocosm incubations. Of the added nitrate N, 22 to 39% was transformed during the course of the incubation. Denitrification had the highest rates of transformation (97-236 mg N m d), followed by assimilation into the organic soil N pool (41-93 mg N m d) and ammonium generation (11-14 mg N m d). Our denitrification rates exceeded those in several studies of freshwater ponds and wetlands; however, rates in those ecosystems may have been limited by low concentrations of nitrate. Assuming a density of 0.7 beaver ponds km of catchment area, we estimated that in nitrate-enriched watersheds, beaver pond denitrification can remove approximately 50 to 450 kg nitrate N km catchment area. In rural watersheds of southern New England with high N loading (i.e., 1000 kg km), denitrification from beaver ponds may remove 5 to 45% of watershed nitrate N loading. Beaver ponds represent a relatively new and substantial sink for watershed N if current beaver populations persist.

Resurgent beaver ponds in the northeastern United States: implications for greenhouse gas emissions.

Beaver ponds, a wetland type of increasing density in the northeastern United States, vary spatially and temporally, creating high uncertainty in their impact to greenhouse gas (GHG) emissions. We used floating static gas chambers to assess diffusive fluxes of methane (CH), carbon dioxide (CO), and nitrous oxide (NO) from the air-water interface of three beaver ponds (0.05-8 ha) in Rhode Island from fall 2012 to summer 2013. Gas flux was based on linear changes of gas concentrations in chambers over 1 h. Our results show that these beaver ponds generated considerable CH and CO emissions. Methane flux (18-556 mg m d) showed no significant seasonal differences, but the shallowest pond generated significantly higher CH flux than the other ponds. Carbon dioxide flux (0.5-22.0 g m d) was not significantly different between sites, but it was significantly higher in the fall, possibly due to the degradation of fresh leaves. Nitrous oxide flux was low (0-2.4 mg m d). Overall, CH and CO comprised most of the global warming potential, 61 and 38%, respectively. The shallowness of the beaver ponds may have limited the time needed for CH oxidation to CO before CH escaped to the atmosphere. Beaver dams also increase the aerial extent of hydric soils, which may transform riparian areas from upland GHG sinks to wetland GHG sources thereby changing the net global warming potential. Further studies tracking the pattern and conditions of beaver pond creation and abandonment will be essential to understanding their role as GHG sources.

In situ push-pull method to determine ground water denitrification in riparian zones.

To quantify ground water denitrification in discrete locations of riparian aquifers, we modified and evaluated an in situ method based on conservative tracers and 15N-enriched nitrate. Ground water was "pushed" (i.e., injected) into a mini-piezometer and then "pulled" (i.e., extracted) from the same mini-piezometer after an incubation period. This push-pull method was applied in replicate mini-piezometers at two Rhode Island riparian sites, one fresh water and one brackish water. Conservative tracer pretests were conducted to determine incubation periods, ranging from 5 to 120 h, to optimize recovery of introduced plumes. For nitrate push-pull tests, we used two conservative tracers, sulfur hexafluoride and bromide, to provide insight into plume recovery. The two conservative tracers behaved similarly. The dosing solutions were amended with 15N-enriched nitrate that enabled us to quantify the mass of denitrification gases generated during the incubation period. The in situ push-pull method detected substantial denitrification rates at a site where we had previously observed high denitrification rates. At our brackish site, we found high rates of ground water denitrification in marsh locations and minimal denitrification in soils fringing the marsh. The push-pull method can provide useful insights into spatial and temporal patterns of denitrification in riparian zones. The method is robust and results are not seriously affected by dilution or degassing from ground water to soil air. In conjunction with measurements of ground water flow-paths, this method holds promise for evaluating the influence of site and management factors on the ground water nitrate removal capacity of riparian zones.