Elevated concentrations of nutrients, particularly nitrate, in groundwater and springs in Florida are a growing resource management concern. Stormwater infiltration basins, which are a common stormwater management practice in the well-drained karst terrain areas of Florida, are a potentially important source of nutrients to the groundwater system because stormwater exits the basin by only evaporation or infiltration. To better understand the biogeochemical processes integrating stormwater infiltration impacts on groundwater resources in a field-scale setting, a combination of hydrologic, soil chemistry, water chemistry, dissolved and soil gas, isotope, and microbiological data was collected from 2007 through 2010 at two stormwater infiltration basins receiving runoff from predominantly residential watersheds in north-central Florida. Substantially different biogeochemical processes affecting nitrogen fate and transport were observed beneath the two stormwater infiltration basins. Differences are related to soil textural properties that deeply link hydroclimatic conditions with soil moisture variations in a humid, subtropical climate. During 2008, shallow groundwater beneath the basin with predominantly clayey soils (median 41% silt+clay content) exhibited decreases in dissolved oxygen from 3.8 to 0.1 mg/L and decreases in nitrate-nitrogen from 2.7 mg/L to less than 0.016 mg/L, followed by manganese and iron reduction, sulfate reduction, and methanogenesis. In contrast, beneath the basin with predominantly sandy soils (median 2% silt+clay content), aerobic conditions persisted from 2007 through 2009 (dissolved oxygen of 5.0â€"7.8 mg/L), resulting in nitrate-nitrogen of 1.3â€"3.3 mg/L in shallow groundwater. Soil extractable nitrate-nitrogen was significantly lower and the copper-containing nitrite reductase gene density was significantly higher beneath the clayey basin. Differences in moisture retention capacity between fine- and coarse-textured soils resulted in median volumetric gas-phase contents of 0.04 beneath the clayey basin and 0.19 beneath the sandy basin, inhibiting surface/subsurface oxygen exchange beneath the clayey basin. Subsurface biogeochemical processes at the clayey stormwater infiltration basin were further analyzed to better understand the effects of the highly variable hydrologic conditions common in humid, subtropical climates. Cyclic variations in biogeochemical processes generally coincided with wet and dry hydroclimatic conditions. Oxidizing conditions in the subsurface persisted for about one month or less at the beginning of wet periods with dissolved oxygen and nitrate showing similar temporal patterns. Reducing conditions in the subsurface evolved during prolonged flooding of the basin. At about the same time oxygen and nitrate reduction concluded, manganese, iron, and sulfate reduction began, with the onset of methanogenesis one month later. Reducing conditions persisted up to six months, continuing into subsequent dry periods until the next major oxidizing infiltration event. Evidence of denitrification in shallow groundwater at the site is supported by median nitrate-nitrogen less than 0.016 mg/L, excess nitrogen gas up to 3 mg/L progressively enriched in delta-15N during prolonged basin flooding, and isotopically heavy delta-15N and delta-18O of nitrate (up to 25 and 15 per mil, respectively). Isotopic enrichment of newly infiltrated stormwater suggests denitrification was partially completed within two days. Soil and water chemistry data suggest a biogeochemically active zone exists in the upper 1.4 m of soil, where organic carbon was the likely electron donor supplied by organic matter in soil solids or dissolved in infiltrating stormwater. The cyclic nature of reducing conditions effectively controlled the nitrogen cycle, switching nitrogen fate beneath the basin from nitrate leaching to reduction in the shallow saturated zone. Soil beneath the sandy stormwater infiltration basin was amended using biosorption activated media (BAM) to study the effectiveness of this technology in reducing inputs of nitrogen and phosphorus to groundwater. The functionalized soil amendment BAM consists of a 1.0:1.9:4.1 mixture (by volume) of tire crumb (to increase sorption capacity), silt and clay (to increase soil moisture retention), and sand (to promote sufficient infiltration), which was applied to develop an innovative best management practice (BMP) utilizing nutrient reduction and flood control sub-basins. Construction and materials costs, excluding profit and permit fees, for the innovative BMP were about $US 65 per square meter of basin bottom. Comparison of nitrate/chloride ratios for the shallow groundwater indicate that prior to using BAM, nitrate concentrations were substantially influenced by nitrification or variations in nitrate input. In contrast, for the new basin utilizing BAM, nitrate/chloride ratios indicate minor nitrification and nitrate losses with the exception of one summer sample that indicated a 45% loss. Biogeochemical indicators (denitrifier activity derived from real-time polymerase chain reaction and variations in major ions, nutrients, dissolved and soil gases, and stable isotopes) suggest nitrate losses are primarily attributable to denitrification, whereas dissimilatory nitrate reduction to ammonium and plant uptake are minor processes. Denitrification was likely occurring intermittently in anoxic microsites in the unsaturated zone, which was enhanced by increased soil moisture within the BAM layer and resultant reductions in surface/subsurface oxygen exchange that produced conditions conducive to increased denitrifier activity. Concentrations of total dissolved phosphorus and orthophosphate were reduced by more than 70% in unsaturated zone soil water, with the largest decreases in the BAM layer where sorption was the most likely mechanism for removal. Post-BAM orthophosphate/chloride ratios for shallow groundwater indicate predominantly minor increases and decreases in orthophosphate with the exception of one summer sample that indicated a 50% loss. Differences in nutrient variations between the unsaturated zone and shallow groundwater may be the result of the intensity and duration of nutrient removal processes and mixing ratios with water that had undergone little biogeochemical transformation. In order to quantify potential processes leading to observed nitrogen losses beneath the innovative BMP, an integrated infiltration basinâ€"nitrogen reduction (IBNR) system dynamics model was developed. Based on two simulation periods, the IBNR model indicated denitrification accounted for a loss of about one-third of the total dissolved nitrogen mass inflow and was occurring predominantly in the BAM layer. The IBNR model results in combination with the field-based biogeochemical assessment demonstrated that the innovative BMP using the functionalized soil amendment BAM is a promising passive, economical, stormwater nutrient-treatment technology. Further field- and laboratory-scale research on the long-term sustainability of nutrient losses and further elucidation of causative physicochemical and biogeochemical mechanisms would contribute to improved BAM performance and green infrastructure development in the future.

Many Best Management Practices (BMPs) have been developed to reduce excessive nutrients in stormwater runoff and mitigate harmful algal blooms in downstream receiving water bodies. This study demonstrates a new BMP by comparing two green sorption media (i.e., specialty adsorbents) for nutrient removal in cascade upflow biofiltration systems operated in parallel. The proposed filtration technology can control hydraulic gradients, prevent clogging and settlements, and increase hydraulic loading while removing more nutrients in an integrated physicochemical and microbiological treatment process. The two green sorption media being tested in this study include zero-valent-iron and perlite-based green sorption media (ZIPGEM) and biochar, iron, and perlite-integrated green sorption media (BIPGEM). BIPGEM or ZIPGEM was installed in two identical upflow bioreactors operated in sequence within each biofiltration system compared mainly for nitrate removal at three influent conditions for process reliability assessment. In addition, kinetics studies were conducted and analyzed to improve the understanding of reactor design. Dissolved organic nitrogen was monitored by using FT-ICR MS (Fourier transform ion cyclotron resonance mass spectrometer) whereas population dynamics of nitrifiers and denitrifiers were quantified by using RT-PCR (real time polymerase chain reaction). The process reliability was compared and confirmed based on the nitrate removal efficiencies, microbial population, and oxidation-reduction potential variations across the two biofiltration systems with different green sorption media. Results indicated that ZIPGEM performed slightly better than BIPGEM and the two identical upflow bioreactors operated in sequence within each biofiltration system exhibited steady operation with higher hydraulic loading relative to the downflow settings in the literature.