Adsorption thermodynamics and kinetics of Advanced Green Environmental Media (AGEM) for nutrient removal and recovery in agricultural discharge and stormwater runoff.

Recycled materials were used in three types of green sorption media for nutrient removal and possible recovery in high nutrient-laden agricultural discharge and stormwater runoff. The three types of green sorption media included in this comparative study were two new aluminum-based green environmental media (AGEM) and one existing iron-filings based green environmental media (IFGEM). The corresponding adsorption isotherm, thermodynamics, and kinetics models were simulated based on isotherm studies to determine their removal efficiency and potential for recovery of nitrate, phosphate, and ammonia when used as a soil amendment in crop fields or in a filter for water treatment. AGEM-2 exhibited the shortest contact time required to achieve nutrient removal above 80% with an average of 7 h, followed by AGEM-1 and IFGEM with 10.6 and 28 h, respectively. Natural soil was included as a control and exhibited minimal nutrient removal. Ammonia, which may be recovered as fertilizer for drop fields in a soil-water-waste nexus, was generated by all three green sorption media mixes, therefore indicating their potential for use as soil amendments in agricultural and forested land after engineering filter applications. The kinetics analysis indicated that nitrate adsorption follows pseudo-first-order kinetics, while phosphate adsorption follows pseudo-second-order kinetics. The Gibbs free energy indicated that most of the adsorption reactions proceeded as exothermic. Lastly, a few equilibrium models, including the Langmuir, Freundlich, First Modified Langmuir, Temkin, Jovanovic, and Elovich models, were ranked and three were selected for use with IFGEM, AGEM-1, and AGEM-2, respectively, as below: (1) Langmuir, (2) Freundlich, and (3) First Modified Langmuir, according to three indices.

Assessing Nutrient Removal in Stormwater Runoff for Urban Farming with Iron filings-based Green Environmental Media.

Ensuring urban areas have access to clean drinking water, safe food supply, and uncontaminated water bodies is essential to the good health of millions of urban residents. This paper presents the functionality of Iron Filings-based Green Environmental Media (IFGEM) in terms of nutrient removal efficiencies to support water quality management and urban farming. IFGEM uses recycled materials such as tire crumb and iron filings to help remove nutrients with essential physicochemical properties. In this study, IFGEM were proven effective and sustainable through an isotherm study, a column study of reaction kinetics, and a microstructure examination under various inlet nutrient concentration levels. IFGEMs exhibited over 90% nitrate removal, as well as 50-70% total phosphorus removal, under most inlet conditions. These promising results make IFGEM suitable for treating stormwater runoff, wastewater effluent, and agricultural discharge via varying ex situ treatment units in flexible landscape environments. In addition, the byproduct of ammonia generation permits possible reuse of spent IFGEM as soil amendments in crop land, gardens and yards, and green roofs for urban farming. Findings may help secure urban food supply chains and harmonize nutrients, soil, water, and waste management in different urban environments.

The interaction of dissolved organic nitrogen removal and microbial abundance in iron-filings based green environmental media for stormwater treatment.

Nonpoint sources pollution from agricultural crop fields and urbanized regions oftentimes have elevated concentrations of dissolved organic nitrogen (DON) in stormwater runoff, which are difficult for microbial communities to decompose. The impact of elevated DON can be circumvented through the use of green sorption media, such as Biosorption Activated Media (BAM) and Iron-Filing Green Environmental Media (IFGEM), which, as integral parts of microbial ecology, can contribute to the decomposition of DON. To compare the fate, transport, and transformation of DON in green sorption media relative to natural soil (control), a series of fixed-bed columns, which contain natural soil, BAM, and two types of IFGEM, respectively, were constructed to compare nutrient removal efficiency under three distinct stormwater influent conditions containing nitrogen and phosphorus. The interactions among six microbial species, including ammonia-oxidizing bacteria, nitrite-oxidizing bacteria, complete ammonia oxidation (comammox) bacteria, anaerobic ammonium oxidation (anammox) bacteria, dissimilatory nitrate reduction to ammonium bacteria, and iron-reducing bacteria, were further analyzed from microbial ecology perspectives to determine the DON impact on nutrient removal in BAM and IFGEM. Natural soil was only able to achieve adequate DON transformation at the influent condition of lower nutrient concentration. However, the two types of IFGEM showed satisfactory nutrient removals and achieved greater transformation of DON relative to BAM when treating stormwater in all three influent conditions.

Evaluation of green sorption media blanket filters for nitrogen removal in a stormwater retention basin at varying groundwater conditions in a karst environment.

Removing excess nutrient from stormwater runoffs is necessary to protect the water quality of receiving water bodies such as rivers, lakes, springs, and groundwater aquifers. Silver Springs Springshed, located in the vicinity of Ocala, Florida, has received widespread attention from the local government and residents due to its long-term nutrient impact, which has resulted in eutrophication. Blanket filters containing Bio-sorption Activated Media (BAM) were implemented with different depths of the vadose zone in a stormwater retention basin. The design combined the interaction with groundwater as an innovative Best Management Practice can potentially boost the performance of nutrient removal. Selected storm runoffs were collected at multiple points that cover the runoff timeframe to determine the pollutant load. Infiltrating water samples were collected at various depths within BAM using lysimeters to validate the treatment effectiveness. Significant pollutant load reduction of nutrients was confirmed with highest 99% and 91% removal of nitrate and nitrite (NOx) and total nitrogen (TN) at the deep blanket filter (with more groundwater intrusion impacts) due to more effective denitrification and longer contact time. Yet the highest pollutant load reduction of 93% and 84% removal of NOx and TN was also observed at the shallow blanket filter (with less groundwater intrusion impacts). On the other hand, better pollutant load reduction of ammonia in the BAM layer was found at the shallow blanket filter presumably due to more available oxygen for nitrification.

Comparative copper toxicity impact and enzymatic cascade effect on Biosorption Activated Media and woodchips for nutrient removal in stormwater treatment.

Copper, a commonly occurring heavy metal in stormwater runoff, was tested for its inhibitory effects on key nitrogen cycle bacteria in Biosorption Activated Media (BAM) and woodchip. The information in this paper is used to show that copper can enhance the denitrification process through enzyme cascade reactions since nitrous reductase is the enzyme responsible for the last step of denitrification and is largely dependent on copper as its cofactor. However, media characteristics are critical for assessing multi-enzymatic cascade reactions from the microbial ecology point of view. Moreover, both media showed significant copper removal through various mechanisms at 30 cm depth. The bioactivity evaluation indicates that other bacteria (fermentative bacteria, etc.) can be largely depressed with the presence of copper, hence the biofilm structure would be more vulnerable under shearing effects, which may result in holistic depression on the microbial community.

The Impact of Carbon Source as Electron Donor on Composition and Concentration of Dissolved Organic Nitrogen in Biosorption-Activated Media for Stormwater and Groundwater Co-Treatment.

Eutrophication has been a long-term issue in aquatic environments, where dissolved organic nitrogen (DON) recalcitrance is important. Bioavailable nitrogen qualification and quantification for effluents from stormwater and wastewater are always a challenge. The information in this study deepens the understanding of the interactions between carbon addition and DON decomposition through linear-ditch best management practices for stormwater and groundwater cotreatment. By running a laboratory-scale column study for nitrogen removal using green sorption media, the variation in composition and concentration of DON can be further linked to the population dynamics of microbial species that dominate the nitrification and denitrification processes. With the varying levels of influent total nitrogen concentration, the efficacy of nitrogen removal via biosorption activated media may be realized at the molecular level with ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry.

Reliability analysis of nutrient removal from stormwater runoff with green sorption media under varying influent conditions.

To support nutrient removal, various stormwater treatment technologies have been developed via the use of green materials, such as sawdust, tire crumbs, sand, clay, sulfur, and limestone, as typical constituents of filter media mixes. These materials aid in the physiochemical sorption and precipitation of orthophosphates as well as in the biological transformation of ammonia, nitrates and nitrites. However, these processes are dependent upon influent conditions such as hydraulic residence time, influent orthophosphate concentrations, and other chemical species present in the inflow. This study aims to compare the physiochemical removal of orthophosphate by isotherm and column tests under differing influent conditions to realize the reliability of orthophosphate removal process with the aid of green sorption media. The green sorption media of interest in this study is composed of a 5:2:2:1 (by volume) mixture of cement sand, tire crumb, fine expanded clay, and limestone. Scenarios of manipulating the hydraulic residence time of the water from 18 min and 60 min, the influent dissolved phosphorus concentrations of 1.0 mg·L(-1) and 0.5 mg·L(-1), and influent water types of distilled and pond water, were all investigated in the column tests. Experimental data were compared with the outputs from the Thomas Model based on orthophosphate removal to shed light on the equilibrium condition versus kinetic situation. With ANOVA tests, significant differences were confirmed between the experimental data sets of the breakthrough curves in the column tests. SEM imaging analysis helps to deepen the understanding of pore structures and pore networks of meta-materials being used in the green sorption media. Life expectancy curves derived from the output of Thomas Model may be applicable for future system design of engineering processes.

System dynamics modeling of nitrogen removal in a stormwater infiltration basin with biosorption-activated media.

Stormwater infiltration basins, one of the typical stormwater best management practices, are commonly constructed for surface water pollution control, flood mitigation, and groundwater restoration in rural or residential areas. These basins have soils with better infiltration capacity than the native soil; however, the ever-increasing contribution of nutrients to groundwater from stormwater due to urban expansion makes existing infiltration basins unable to meet groundwater quality criteria related to environmental sustainability and public health. This issue requires retrofitting current infiltration basins for flood control as well as nutrient control before the stormwater enters the groundwater. An existing stormwater infiltration basin in north-central Florida was selected, retrofitted, and monitored to identify subsurface physiochemical and biological processes during 2007-2010 to investigate nutrient control processes. This implementation in the nexus of contaminant hydrology and ecological engineering adopted amended soil layers packed with biosorption activated media (BAM; tire crumb, silt, clay, and sand) to perform nutrient removal in a partitioned forebay using a berm. This study presents an infiltration basin-nitrogen removal (IBNR) model, a system dynamics model that simulates nitrogen cycling in this BAM-based stormwater infiltration basin with respect to changing hydrologic conditions and varying dissolved nitrogen concentrations. Modeling outputs of IBNR indicate that denitrification is the biogeochemical indicator in the BAM layer that accounted for a loss of about one third of the total dissolved nitrogen mass input.

Nutrient removal using biosorption activated media: preliminary biogeochemical assessment of an innovative stormwater infiltration basin.

Soil beneath a stormwater infiltration basin receiving runoff from a 23 ha predominantly residential watershed in north-central Florida, USA, 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 stormwater infiltration basin utilizing nutrient reduction and flood control sub-basins. Comparison of nitrate/chloride (NO(3)(-)/Cl(-)) ratios for the shallow groundwater indicates that prior to using BAM, NO(3)(-) concentrations were substantially influenced by nitrification or variations in NO(3)(-) input. In contrast, for the new basin utilizing BAM, NO(3)(-)/Cl(-) ratios indicate minor nitrification and NO(3)(-) 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 that NO(3)(-) losses are primarily attributable to denitrification, whereas dissimilatory nitrate reduction to ammonium is a minor process. Denitrification was likely occurring intermittently in anoxic microsites in the unsaturated zone, which was enhanced by the 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 (PO(4)(3-)) 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 PO(4)(3-)/Cl(-) ratios for shallow groundwater indicate predominantly minor increases and decreases in PO(4)(3-) 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. Observed nitrogen and phosphorus losses demonstrate the potential, as well as the future research needs to improve performance, of the innovative stormwater infiltration basin using BAM for providing passive, economical, stormwater nutrient-treatment technology to support green infrastructure.

Assessing biological and chemical signatures related to nutrient removal by floating islands in stormwater mesocosms.

Aquatic floating plants on BioHaven mats were tested for their potential use as a Best Management Practice to be incorporated within existing stormwater detention ponds. Plants were analyzed for their capability to remove nutrient-pollution in parallel with the study of ecological dynamics. Experiments were carried out in cylindrical mesocosms of 5 m diameter and 1.2 m height, above-ground pools with a water volume of 14 m(3). The design parameters tested were for 5% and 10% vegetated floating island coverage of the mesocosm, both with and without shoreline plants called littoral zone. This littoral shelf was 0.5 m thick, graded at a downward slope of 1:5 toward the center using loamy soil with low organic matter content, excavated from below turf grass. Endemic plant species were chosen for the experimental location in central Florida based on a wetland identification manual by the Florida Department of Environmental Protection to ensure the study was not compromised by unique climate requirements of the plants. Nutrient and aquatic chemical conditions such as pH, dissolved oxygen, temperature, turbidity, and chlorophyll a were monitored to understand their relationships to the general wetland ecosystem. Real-time polymerase chain reaction analysis identified the microbial activity near the rhizospheric zone. Logistical placement considerations were made using spatial sampling across the horizontal plane of the mesocosms, beneath and around the root zone, to determine if nutrients tend to aggregate around the floating island. This study concluded that the application of floating islands as a stormwater technology can remove nutrients through plant uptake and biological activity. The most cost-effective size in the outdoor mesocosms was 5% surface area coverage of the mat.

Cyclic biogeochemical processes and nitrogen fate beneath a subtropical stormwater infiltration basin.

A stormwater infiltration basin in north-central Florida, USA, was monitored from 2007 through 2008 to identify subsurface biogeochemical processes, with emphasis on N cycling, under the highly variable hydrologic conditions common in humid, subtropical climates. Cyclic variations in biogeochemical processes generally coincided with wet and dry hydrologic conditions. Oxidizing conditions in the subsurface persisted for about one month or less at the beginning of wet periods with dissolved O(2) and NO(3)(-) showing similar temporal patterns. Reducing conditions in the subsurface evolved during prolonged flooding of the basin. At about the same time O(2) and NO(3)(-) reduction concluded, Mn, Fe and SO(4)(2-) 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 NO(3)(-)-N less than 0.016 mg L(-1), excess N(2) up to 3 mg L(-1) progressively enriched in δ(15)N during prolonged basin flooding, and isotopically heavy δ(15)N and δ(18)O of NO(3)(-) (up to 25‰ and 15‰, respectively). Isotopic enrichment of newly infiltrated stormwater suggests denitrification was partially completed within two days. Soil and water chemistry data suggest that a biogeochemically active zone exists in the upper 1.4m 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 N cycle, switching N fate beneath the basin from NO(3)(-) leaching to reduction in the shallow saturated zone. Results can inform design of functionalized soil amendments that could replace the native soil in a stormwater infiltration basin and mitigate potential NO(3)(-) leaching to groundwater by replicating the biogeochemical conditions under the observed basin.

Soil property control of biogeochemical processes beneath two subtropical stormwater infiltration basins.

Substantially different biogeochemical processes affecting nitrogen fate and transport were observed beneath two stormwater infiltration basins in north-central Florida. 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) exhibited decreases in dissolved oxygen from 3.8 to 0.1 mg L and decreases in nitrate nitrogen (NO-N) from 2.7 mg L to <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), aerobic conditions persisted from 2007 through 2009 (dissolved oxygen, 5.0-7.8 mg L), resulting in NO-N of 1.3 to 3.3 mg L in shallow groundwater. Enrichment of δN and δO of NO combined with water chemistry data indicates denitrification beneath the clayey basin and relatively conservative NO transport beneath the sandy basin. Soil-extractable NO-N 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. Results can inform development of soil amendments to maintain elevated moisture content in shallow soils of stormwater infiltration basins, which can be incorporated in improved best management practices to mitigate NO impacts.

A tracer study for assessing the interactions between hydraulic retention time and transport processes in a wetland system for nutrient removal.

In this study, a new-generation subsurface upflow wetland (SUW) system packed with the unique sorption media was introduced for nutrient removal. To explore the interface between hydraulic and environmental performance, a tracer study was carried out in concert with a transport model to collectively provide hydraulic retention time (7.1 days) and compelling evidence of pollutant fate and transport processes. Research findings indicate that our pollution-control media demonstrate smooth nutrient removal efficiencies across different sampling port locations given the appropriate size distribution conversant with the anticipated hydraulic patterns and layered structure among the sorption media components. The sizable capacity for nutrient removal in this bioprocess confirms that SUW is a promising substitute for an extension of traditional on-site wastewater treatment systems.