Photochemical reduction of hexavalent chromium in glycerol-containing solutions

Hexavalent chromium [Cr(VI)] in the form of potassium dichromate was photochemically reduced to trivalent chromium [Cr(III)] in aqueous solutions containing glycerol. This reaction occurred rapidly during irradiation with either unfiltered sunlight or a UVA-emitting light source. Photochemical reduction of Cr(VI) was pH-dependent and did not occur in dilute solutions of sodium hydroxide. In acidified solutions, the reduction occurred at elevated rates and at lower concentrations of glycerol. This reaction was found to be dependent on the unsubstituted alcohol groups of glycerol since alpha-phosphoglycerol and beta-phosphoglycerol did not support the photochemical reduction of Cr(VI). These findings suggest that glycerol or related polyols can be used for the remediation of hexavalent (toxic) chromium at contaminated environmental sites.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Modeling of flow and contaminant transport in coupled stream-aquifer systems

This paper describes an integrated approach for modeling flow and contaminant transport in hydraulically connected stream-aquifer systems. The code, FTSTREAM, extended the capabilities of the ground-water model, FTWORK, to incorporate chemical fate and transport in streams. Flow in the stream network is modeled as an unsteady, spatially varying flow, while transport modeling is based on a one-dimensional advection-dispersion equation. In addition to sorption and decay during transport in ground water, the model incorporates volatilization, settling and decay during transport in surface water. The interaction between surface water and ground water is accommodated by a leakage term and is implemented in the model using an iterative Picard-type procedure to ensure mass conservation across the interface between the two systems. The modeling approach is used to simulate contaminant transport in the Mad River, Ohio, which is hydraulically connected to a buried valley aquifer of sand and gravel outwash. The river is a receiving stream in the upstream part of the modeled area. Downstream, heavy pumping from a municipal well field causes the river to become a loosing stream. Induced infiltration from the river is responsible for a considerable portion of the well yield. The flow and transport model, developed for this study, simulates coupling between flow in the aquifer and the river. Hypothetical sources of contamination are introduced at selected locations in the upstream portion of the aquifer. The model is then used to simulate the expected transport in both the aquifer and the stream. A series of simulations elucidates the role of the river in facilitating the transport of the hypothetical contaminants in ground water and surface water. Effect of sorption, retardation and volatilization on contaminant transport is also examined for the case of the volatile organic compounds.     

Manganese toxicity thresholds for restoration grass species

Manganese toxicity thresholds for restoration plants have not been established. As a result, ecological risk assessments rely on toxicity thresholds for agronomic species, which may differ from those of restoration species. Our objective was to provide Mn toxicity thresholds for grasses commonly used in restoration. We used a greenhouse screening study where seedlings of redtop, slender wheatgrass, tufted hairgrass, big bluegrass, basin wildrye, and common wheat were grown in sand culture and exposed to increasing concentrations of Mn. The LC50, EC50-plant, EC50-shoot, EC50-root, PT50-shoot, and the PT50-root were then determined. Phytotoxicity thresholds and effective concentrations for the restoration species were generally higher than values reported for agronomic species. Our estimates of PT50-shoot for the five restoration grasses range from 41,528 to 120,082 mg Mn kg(-1). Measures of EC50-plant for these restoration grasses ranged from 877 to >6,000 mg Mn l(-1). These thresholds might be more useful for risk assessors than those based on crop plants that are widely used.     

Metal partitioning in products of incineration of municipal solid waste

Metals contained in the waste transfer to the waste incineration products, including flue gas, fly ash, and bottom ash, as different oxide, nitride, carbides, and other phases. Most of the metal-based phases formed in incineration are toxic and their emissions need to be strictly controlled. Therefore, behavior of metal species during incineration must be well understood. Such understanding is possible based on the experimental identification of the metal phases formed in the waste combustion and determination of their concentration in various incineration products. To avoid well-known experimental difficulties of the industrial waste incinerators associated with the poor fuel/conditions reproducibility and limited instrumentation, a 140,000 Btu/h pilot-scale, laboratory burner was constructed, characterized and operated at NJIT. A synthetic fuel representative of the municipal solid waste in the US was formulated and produced in 600-Lb batches. The solid fuel contained Fe and SiO2 as main constituents, and was doped with trace amounts of Al, Ni, Cr, Hg and PbO. Several experiments have been conducted on combustion of the synthetic fuel in the pilot-scale incinerator with varying fuel-air equivalence ratio. Both gaseous and condensed combustion products were sampled and analyzed. Atomic absorption spectroscopy and X-ray diffraction were used to analyze total metal contents and metal containing phases in the incineration products. Thermodynamic equilibrium computations were performed to obtain the adiabatic flame temperature and identify the phases of the metal-containing products formed at the equilibrium conditions. The results of the equilibrium computations performed at the varied fuel/air ratios were compared with the observed experimental results.     

Lead removal from synthetic leachate matrices by a novel ion-exchange material

This paper discusses the application of a novel polyacrylate-based ion-exchange material for the removal of Pb ions from water. Preliminary testing includes the establishment of the operating pH range, capacity information, and the effect of Ca2+ and anions in the matrix. Batch testing with powder indicates slightly different optimal operational conditions from those used for column testing. The ion-exchanger is excellent for removing Pb from aqueous solutions.     

PAH deposition to snow surface

The urban snowpack effectively acts as a collection device for atmospheric-deposited PAHs. When these PAHs are flushed out in a short time interval along with springtime snowmelt, these cause shockloading to receiving waters. In order to assess the PAH deposition and accumulation in urban snowpacks, a deposition survey of PAH for the winter months of 1991-92 from the city of Sault Ste. Marie, Ontario, Canada was undertaken. The results of the survey are interpreted in view of prevailing meteorology and various emission sources in the study area. The relative PAH deposition levels (to BaP) are compared with relative source emission fingerprints to examine consistency in sampling and analysis. While analyzing the PAH samples using the ASTM (1987) method, the problem of concentration levels being below the detection level was encountered. The ASTM method for PAH analysis was modified to enhance the detection limit of the PAHs by concentrating the PAH extract to very low volumes, on the order of 200-300 microL.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

Floodplain Trapping and Cycling Compared to Streambank Erosion of Sediment and Nutrients in an Agricultural Watershed

Floodplains and streambanks can positively and negatively influence downstream water quality through interacting geomorphic and biogeochemical processes. Few studies have measured those processes in agricultural watersheds. We measured inputs (floodplain sedimentation and dissolved inorganic loading), cycling (floodplain soil nitrogen [N] and phosphorus [P] mineralization), and losses (bank erosion) of sediment, N, and P longitudinally in stream reaches of Smith Creek, an agricultural watershed in the Valley and Ridge physiographic province. All study reaches were net depositional (floodplain deposition > bank erosion), had high N and P sedimentation and loading rates to the floodplain, high soil concentrations of N and P, and high rates of floodplain soil N and P mineralization. High sediment, N, and P inputs to floodplains are attributed to agricultural activity in the region. Rates of P mineralization were much greater than those measured in other studies of nontidal floodplains that used the same method. Floodplain connectivity and sediment deposition decreased longitudinally, contrary to patterns in most watersheds. The net trapping function of Smith Creek floodplains indicates a benefit to water quality. Further research is needed to determine if future decreases in floodplain deposition, continued bank erosion, and the potential for nitrate leaching from nutrient‐enriched floodplain soils could pose a long‐term source of sediment and nutrients to downstream rivers.     

A CALIBRATION PROCEDURE USING TOPMODEL TO DETERMINE SUITABILITY FOR EVALUATING POTENTIAL CLIMATE CHANGE EFFECTS ON WATER YIELD1

ABSTRACT: An evaluation was conducted on three forested upland watersheds in the northeastern U.S. to test the suitability of TOPMODEL for predicting water yield over a wide range of climatic scenarios. The analysis provides insight of the usefulness of TOPMODEL as a predictive tool for future assessments of potential long-term changes in water yield as a result of changes in global climate. The evaluation was conducted by developing a calibration procedure to simulate a range of climatic extremes using historical temperature, precipitation, and streamfiow records for years having wet, average, and dry precipitation amounts from the Leading Ridge (Pennsylvania), Fernow (West Virginia), and Hubbard Brook (New Hampshire) Experimental Watersheds. This strategy was chosen to determine whether the model could be successfully calibrated over a broad range of soil moisture conditions with the assumption that this would be representative of the sensitivity necessary to predict changes in streamfiow under a variety of climate change scenarios. The model calibration was limited to a daily time step, yet performed reasonably well for each watershed. Model efficiency, a least squares measure of how well a model performs, averaged between 0.64 and 0.78. A simple test of the model whereby daily temperatures were increased by 1.7°C, resulted in annual water yield decreases of 4 to 15 percent on the three watersheds. Although these results makes the assumption that the model components adequately describe the system, this version of TOPMODEL is capable to predict water yield impacts given subtle changes in the temperature regime. This suggests that adequate representations of the effects of climate change on water yield for regional assessment purposes can be expected using the TOPMODEL concept.