Bruce M. Thomson

Reduction of Cr, Mo, Se and U by Desulfovibrio desulfuricans immobilized in polyacrylamide gels

Intact cells of Desulfovibrio desulfuricans, immobilized in polyacrylamide gel, removed Cr, Mo, Se and U from solution by enzymatic-mediated reduction reactions. Lactate or H2 served as the electron donor and the oxidized Cr(VI), Mo(VI), Se(VI) and U(VI) served as electron acceptors. Reduction of the oxidized metal species resulted in the precipitation of solid phases of the metals. Metal removal efficiencies of 86–96% were achieved for initial concentrations of 1 mM Mo, Se, and U and 0.5 mM Cr. Insoluble metal phases accumulated on both the surface and the interior of the polyacrylamide gel. In column tests conducted for U removal, effluent concentrations less than 20 μg L−1 were achieved with initial concentrations of 5 mg L−1 and 20 mg L−1 U and residence times from 25–37 h. The enzymatic reduction of Cr, Mo, Se, and U by immobilized cells of D. desulfuricans may be a practical method for removing these metals from solution in a biological reactor.

Permanganate oxidation of sorbed polycyclic aromatic hydrocarbons.

The polycyclic aromatic hydrocarbons (PAH) that contaminate soils at many industrial and government sites are resistant to natural biotic and abiotic degradation processes. The recalcitrant nature of these compounds may require aggressive chemical treatment to effectively remediate these sites. This study was conducted to assess the viability of permanganate oxidative treatment as a method to reduce PAH concentration in contaminated soils. Study results demonstrated a reduction in soil sorbed concentration for a mixture of six PAHs that included anthracene, benzo(a)pyrene, chrysene, fluoranthene, phenanthrene, and pyrene by potassium permanganate (KMnO4) oxidative treatment. The greatest reduction in soil concentration was observed for benzo(a)pyrene, pyrene, phenanthrene, and anthracene at 72.1, 64.2, 56.2, and 53.8%, respectively, in 30 min at a KMnO4 concentration of 160 mM. Minimal reductions in fluoranthene and chrysene concentration were observed at 13.4 and 7.8%, respectively, under the same conditions. A relative chemical reactivity order of benzo(a)pyrene>pyrene>phenanthrene>anthracene>fluoranthene>chrysene towards permanganate ion was observed. Aromatic sextet theory was applied to the degradation results to explain the highly variable and compound-specific chemical reactivity order.

Ozone and biofiltration as an alternative to reverse osmosis for removing PPCPs and micropollutants from treated wastewater

This pilot-scale research project investigated and compared the removal of pharmaceuticals and personal care products (PPCPs) and other micropollutants from treated wastewater by ozone/biofiltration and reverse osmosis (RO). The reduction in UV254 absorbance as a function of ozone dose correlated well with the reduction in nonbiodegradable dissolved organic carbon and simultaneous production of biodegradable dissolved organic carbon (BDOC). BDOC analyses demonstrated that ozone does not mineralize organics in treated wastewater and that biofiltration can remove the organic oxidation products of ozonation. Biofiltration is recommended for treatment of ozone contactor effluent to minimize the presence of unknown micropollutant oxidation products in the treated water. Ozone/biofiltration and RO were compared on the basis of micropollutant removal efficiency, energy consumption, and waste production. Ozone doses of 4-8 mg/L were nearly as effective as RO for removing micropollutants. When wider environmental impacts such as energy consumption, water recovery, and waste production are considered, ozone/biofiltration may be a more desirable process than RO for removing PPCPs and other trace organics from treated wastewater.

Removal of U and Mo from water by immobilized Desulfovibrio desulfuricans in column reactors

Intact cells of Desulfovibrio desulfuricans were immobilized in polyacrylamide gel and used to remove soluble U and Mo from water by enzymatically mediated reduction reactions in column reactors. Formate or lactate served as the electron donor and oxidized U(VI) and Mo(VI) species served as electron acceptors. Greater than 99% removal efficiencies were achieved for both metals with initial concentrations of 5 mg/L U and 10 mg/L Mo. Hydraulic residence times in the columns were between 24 and 36 h. Sulfate concentrations as high as 2000 mg/L did not inhibit reduction of U or Mo in the columns. However, nitrate inhibited uranium reduction at concentrations near 50 mg/L and inhibited molybdenum reduction at concentrations near 150 mg/L. The results indicate that enzymatic reduction of U and Mo by immobilized cells of D. desulfuricans may be a practical method for removing these contaminants from solution in continuous-flow reactors.

Treatment of waste containing EDTA by chemical oxidation

Abstract Ethylenediaminetetraacetic acid (EDTA) is a chelating agent that has been extensively used to enhance the solubilization of heavy metal cations and release of EDTA contributes to environmental problems. EDTA is recalcitrant to microbial metabolism and chemical oxidation is considered a possible method of remedial treatment. The use of the commercially available process of MIOX Corporation generates mixed oxidants on site and this solution is markedly effective in the destruction of the chelating characteristic and the decarboxylation of EDTA. When measuring the release of C-14 from carboxyl labeled EDTA, the mixed oxidant solution was comparable to the Fentons reaction over a broad pH range. The presence of Mn 2+ , Cr 3+ , or Fe 3+ at levels equal to that of EDTA stimulated the rate of EDTA decomposition; however, the rate of EDTA breakdown was inhibited when the concentration of Cr 3+ or Mn 2+ exceeded the concentration of EDTA. The treatment of Co 2+ –EDTA or Cu 2+ –EDTA with mixed oxidants in the presence of ultra violet light resulted in the loss of chelation ability of EDTA. In the absence of chelated metals, over 75% of the chelation property of a 70 mM EDTA solution was destroyed in 45 min. The reaction products resulting from the use of mixed oxidants added to EDTA were non-toxic to bacteria and should not contribute to additional environmental problems.

Kinetic coefficients for simultaneous reduction of sulfate and uranium by Desulfovibrio desulfuricans

Abstract Previously it was demonstrated that bacteria are capable of transforming soluble uranyl ion, U(VI), to insoluble uraninite, U(IV); however, the rate for this transformation has not been determined. We report the kinetic coefficients for Desulfovibrio desulfuricans DSM 1924 grown in a continuous-flow chemostat where pyruvate was the electron donor and sulfate was the electron acceptor. The medium was supplemented with 1 mM uranyl nitrate, and the chemostat flow rate ranged from 1.12 ml/h to 4.75 ml/h with incubation at 28°C. The maximum rate of pyruvate utilization (k) was determined to be 4.7 days-1, while the half-velocity constant (Ks) was 127 mg/l. The yield coefficient (Y) of cells per mole of pyruvate oxidized was calculated to be 0.021 g, while the endogenous decay coefficient (kd) was determined to be 0.072 days-1. More than 90% of U(VI) was transformed to U(VI) in the chemostat under the conditions employed.

Identifying US populations for the study of health effects related to drinking water arsenic.

The US Environmental Protection Agency recently set a new maximum contaminant level (MCL) for arsenic in drinking water of 10 μg/l. In this paper, we review the completeness and accuracy of drinking water arsenic occurrence data in the United States and identify populations exposed to elevated arsenic concentrations that would be suitable for epidemiological studies of arsenic health effects. Using existing data from the Environmental Protection Agency Arsenic Occurrence and Exposure Database and additional data from state health and environment departments and water utilities, we identified 33 counties in 11 states with an estimated mean drinking water arsenic concentration of 10 μg/l or greater. A total of 11 of these ‘confirmed’ counties had an estimated mean arsenic concentration of 20 μg/l or more and two had an estimated mean arsenic concentration 50 μg/l or more. Based on census data, between 1950 and 1999 there were approximately 51.1 million person-years of exposure to drinking water arsenic at levels of 10 μg/l or more, 8.2 million at levels of 20 μg/l or more arsenic and 0.9 million at levels of 50 μg/l or more. Mortality and incidence of diseases known to be associated with arsenic exposure can and should be examined in these counties as part of a comprehensive assessment of arsenic health effects in US populations.

Effect of membrane bioreactor solids retention time on reverse osmosis membrane fouling for wastewater reuse.

The effect of the solids retention time (SRT) in a membrane bioreactor (MBR) on the fouling of the membranes in a subsequent reverse osmosis (RO) process used for wastewater reuse was studied experimentally using a pilot-scale treatment system. The MBR-RO pilot system was fed effluent from the primary clarifiers at a large municipal wastewater treatment plant. The SRT in the MBRs was adjusted to approximately 2, 10, and 20 days in three experiments. The normalized specific flux through the MBR and RO membranes was evaluated along with inorganic and organic constituents in the influent and effluent of each process. Increasing the SRT in the MBR led to an increase in the removal of bulk DOC, protein, and carbohydrates, as has been observed in previous studies. Increasing the SRT led to a decrease in the fouling of the MBR membranes, which is consistent with previous studies. However, the opposite trend was observed for fouling of the RO membranes; increasing the SRT of the MBR resulted in increased fouling of the RO membranes. These results indicate that the constituents that foul MBR membranes are not the same as those that foul RO membranes; to be an RO membrane foulant in a MBR-RO system, the constituents must first pass through the MBR membranes without being retained. Thus, an intermediate value of SRT may be best choice of operating conditions in an MBR when the MBR is followed by RO for wastewater reuse.

Geochemical constraints on underground disposal of uranium mill tailings

Abstract A three phase investigation has been conducted on groundwater quality impacts of the underground disposal of tailings from acid-leach milling of uranium ores. These phases included field collection and analysis of samples obtained during backfilling of mill tailings in empty underground mine stopes, collection of soil samples from mill tailings piles and previously backfilled stopes, and evaluation of thermodynamic constraints on possible geochemical transformations. Contaminants of principal concern include As, Mo, Se, U, V and Ra-226. The investigation has shown that short-term degradation of groundwater due to backfill disposal of the sand fraction of uranium tailings is negligible. Long-term effects, defined as those occurring after mining operations cease and the mine fills with water, are predicted to also be very small. This is attributed to immobilization of pollutants through chemical reduction and precipitation, as well as adsorption onto aquifer materials. This conclusion is substantiated, in part, by observation of high concentrations of most of the contaminants on the silt and clay fraction of the soil samples collected, in contrast to the concentrations found on the sand fraction.

Spatial and temporal evolution of organic foulant layers on reverse osmosis membranes in wastewater reuse applications.

Advanced treatment to remove trace constituents and emerging contaminants is an important consideration for wastewater treatment for potable reuse, and reverse osmosis (RO) can be a suitable technology to provide the necessary level of treatment. However, membrane fouling by biological and organic matter is a concern. This research examined the development of the RO membrane fouling layer using a bench-scale membrane bioreactor operating at different solids retention times (SRTs), followed by a custom-designed RO test cell. The RO test cell contained stacked plates that sandwich five sheets of RO membrane material, which can be extracted for autopsy at separate times over the course of an experiment without disturbing the remaining membranes. The MBR-RO system was run continuously for 2 weeks at each SRT. The RO membranes were stained for live and dead cells, protein, and carbohydrate-like materials, and visualized using confocal laser scanning microscopy. Images of the stained foulant layers were obtained at different depths within the foulant layer at each time point for all SRT conditions. As the RO foulant layer developed, changes occurred in the distribution and morphology of the live cells and carbohydrates, but not the proteins. These trends were similar for all three SRT conditions tested. RO membrane fouling increased with increased MBR SRT, and the highest SRT had the highest ratios of live to dead cells and carbohydrate-like material to dead cells. The autopsied membranes were also analyzed for protein and carbohydrate content, and it was found that the carbohydrate concentration on the membranes after 14 days increased as the SRT increased.