James N. Petersen

Development of analytical solutions for multispecies transport with serial and parallel reactions

A direct method for transforming multiple solute transport equations, coupled by linear, series, and/or parallel first-order, irreversible reactions, into a series of simple transport equations having known solutions is developed. Using this method, previously published analytical solutions to single-species transport problems, in which the transported species reacts with first-order kinetics, can be used to derive analytical solutions to multispecies transport systems with parallel, serial, and combined reaction networks. This new method overcomes many of the limitations that were implicit in previously published methods. In particular, the number of species that can be described is unlimited, and the reaction stoichiometry does not have to be unimolar. To illustrate the method, an analytical solution is derived for a five-species serial-parallel reactive transport system. The analytical solution obtained for this problem is compared with a numerical solution obtained with a previously developed code. This analytical method is applicable to the verification of new numerical codes.

Analytical solutions for multiple species reactive transport in multiple dimensions

Many numerical computer codes used to simulate multi-species reactive transport and biodegradation have been developed in recent years. Such numerical codes must be validated by comparison of the numerical solutions with an analytical solution. In this paper, a method for deriving analytical solutions of the partial differential equations describing multiple species multi-dimensional transport with first-order sequential reactions is presented. Although others have developed specific solutions of multi-species transport equations, here a more general analytical approach, capable of describing any number of reactive species in multiple dimensions is derived. A substitution method is used to transform the multi-species reactive transport problem to one that can be solved using previously published single-species solutions for various initial and boundary conditions. One- and three-dimensional examples are presented to illustrate the steps involved in extending single-species solutions to a four-species system with sequential first-order reactions.

A bacterial flavin reductase system reduces chromate to a soluble chromium(III)-NAD(+) complex.

Biological reduction of carcinogenic chromate has been extensively studied in eukaryotic cells partly because the reduction produces stable chromium(III)-DNA adducts, which are mutagenic. Microbial reduction of chromate has been studied for bioremediation purposes, but little is known about the reduction mechanism. In eukaryotic cells chromate is mainly reduced non-enzymatically by ascorbate, which is usually absent in bacterial cells. We have characterized the reduction of chromate by a flavin reductase (Fre) from Escherichia coli with flavins. The Fre-flavin system rapidly reduced chromate, whereas chemical reduction by NADH and glutathione was very slow. Thus, enzymatic chromate reduction is likely the dominant mechanism in bacterial cells. Furthermore, the end-product was a soluble and stable Cr(III)-NAD(+) complex, instead of Cr(III) precipitate. Since intracellularly generated Cr(III) forms adducts with DNA, protein, glutathione, and ascorbate in eukaryotic cells, we suggest that the produced Cr(III) is primarily complexed to NAD(+), DNA, and other cellular components inside bacteria.

Microbial growth and transport in porous media under denitrification conditions : experiments and simulations

Abstract Soil column experiments were conducted to study bacterial growth and transport in porous media under denitrifying conditions. The study used a denitrifying microbial consortium isolated from aquifer sediments sampled at the U.S. Department of Energys Hanford site. One-dimensional, packed-column transport studies were conducted under two substrate loading conditions. A detailed numerical model was developed to predict the measured effluent cell and substrate concentration profiles. First-order attachment and detachment models described the interphase exchange processes between suspended and attached biomass. Insignificantly different detachment coefficient values of 0.32 and 0.43 day−1, respectively, were estimated for the high and low nitrate loading conditions (48 and 5 mg l−1 NO3, respectively). Comparison of these values with those calculated from published data for aerobically growing organisms shows that the denitrifying consortium had lower detachment rate coefficients. This suggests that, similar to detachment rates in reactor-grown biofilms, detachment in porous media may increase with microbial growth rate. However, available literature data are not sufficient to confirm a specific analytical model for predicting this growth dependence.

Nitrate Reduction with Halomonas campisalis: Kinetics of Denitrification at pH 9 and 12.5% NaCl

Regeneration of ion exchange resins with NaCl produces brine containing high concentrations of nitrate that can be difficult to remove using standard biological, physical, or chemical technologies. In this study. Halomonas campisalis (ATCC #700597) (Mormile et al., 1999) was shown to completely reduce nitrate at 125 g/L NaCl and pH 9. This organism was also used in experiments to determine nitrate-reduction rates and biomass yields. Kinetic parameters were measured separately with glycerol, lactate. acetate, ethanol, and methanol. The specific nitrate-reduction rate coefficient was highest in cultures amended with acetate, while lactate and glycerol (a natural osmoticum in hypersaline environments) had lower reduction rates. No evidence of nitrate reduction was observed when ethanol or methanol was provided as an electron donor. Kinetic modeling provided values for nitrate and nitrite-reduction rate coefficients and for biomass yields. Measured rates and yields were similar to reported parameters obtained from non-halophilic nitrate-reducing cultures under low salt concentrations. Therefore, for highly saline solutions, the use of halophiles to selectively remove nitrate from these brines may represent a viable treatment option.

Toxic Effects of Chromium(VI) on Anaerobic and Aerobic Growth of Shewanella oneidensis MR‐1

Cr(VI) was added to early‐ and mid‐log‐phase Shewanella oneidensis ( S. oneidensis) MR‐1 cultures to study the physiological state‐dependent toxicity of Cr(VI). Cr(VI) reduction and culture growth were measured during and after Cr(VI) reduction. Inhibition of growth was observed when Cr(VI) was added to cultures of MR‐1 growing aerobically or anaerobically with fumarate as the terminal electron acceptor. Under anaerobic conditions, there was immediate cessation of growth upon addition of Cr(VI) in early‐ and mid‐log‐phase cultures. However, once Cr(VI) was reduced below detection limits (0.002 mM), the cultures resumed growth with normal cell yield values observed. In contrast to anaerobic MR‐1 cultures, addition of Cr(VI) to aerobically growing cultures resulted in a gradual decrease of the growth rate. In addition, under aerobic conditions, lower cell yields were also observed with Cr(VI)‐treated cultures when compared to cultures that were not exposed to Cr(VI). Differences in response to Cr(VI) between aerobically and anaerobically growing cultures indicate that Cr(VI) toxicity in MR‐1 is dependent on the physiological growth condition of the culture. Cr(VI) reduction has been previously studied in Shewanella spp., and it has been proposed that Shewanella spp.may be used in Cr(VI) bioremediation systems. Studies of Shewanella spp. provide valuable information on the microbial physiology of dissimilatory metal reducing bacteria; however, our study indicates that S. oneidensis MR‐1 is highly susceptible to growth inhibition by Cr(VI) toxicity, even at low concentrations [0.015 mM Cr(VI)].

Effect of Carbon and Energy Source on Bacterial Chromate Reduction

Studies were conducted to evaluate carbon and energy sources suitable to support hexavalent chromium (Cr(VI)) reduction by a bacterial consortium enriched from dichromate-contaminated aquifer sediments. The consortium was cultured under denitrifying conditions in a minimal, synthetic groundwater medium that was amended with various individual potential carbon and energy sources. The effects of these individual carbon and energy sources on Cr(VI) reduction and growth were measured. The consortium was found to readily reduce Cr(VI) with sucrose, acetate, L-asparagine, hydrogen plus carbon dioxide, ethanol, glycerol, glycolate, propylene glycol, or D-xylose as a carbon and energy source. Minimal Cr(VI) reduction was observed when the consortium was cultured with citrate, 2-ketoglutarate, L-lactate, pyruvate, succinate, or thiosulfate plus carbon dioxide as a carbon and energy source when compared with abiotic controls. The consortium grew on all of the above carbon and energy sources, with the highest cell densities reached using D-xylose and sucrose, demonstrating that the consortium is metabolically diverse and can reduce Cr(VI) using a variety of different carbon and energy sources. The results suggest that the potential exists for the enrichment of Cr(VI)-reducing microbial populations in situ by the addition of a sucrose-containing feedstock such as molasses, which is an economical and readily available carbon and energy source.

Chromate reduction in Shewanella oneidensis MR-1 is an inducible process associated with anaerobic growth

Cr(VI) reduction was observed during tests with Shewanella oneidensis MR‐1 (previously named S. putrefaciens MR‐1) while being grown with nitrate or fumarate as electron acceptor and lactate as electron donor. From the onset of anoxic growth on fumarate, we measured a gradual and progressive increase in the specific Cr(VI) reduction rate with incubation time until a maximum was reached at late exponential/early stationary phase. Under denitrifying conditions, the specific Cr(VI) reduction rate was inhibited by nitrite, which is produced during nitrate reduction. However, once nitrite was consumed, the specific reduction rate increased until a maximum was reached, again during the late exponential/early stationary phase. Thus, under both fumarate‐ and nitrate‐reducing conditions, an increase in the specific Cr(VI) reduction rate was observed as the microorganisms transition from oxic to anoxic growth conditions, presumably as a result of induction of enzyme systems capable of reducing Cr(VI). Although Cr(VI) reduction has been studied in MR‐1 and in other facultative bacteria under both oxic and anoxic conditions, a transition in specific reduction rates based on physiological conditions during growth is a novel finding. Such physiological responses provide information required for optimizing the operation of in situ systems for remediating groundwater contaminated with heavy metals and radionuclides, especially those that are characterized by temporal variations in oxygen content. Moreover, such information may point the way to a better understanding of the cellular processes used by soil bacteria to accomplish Cr(VI) reduction.

Sorption of heavy metals by untreated red fir sawdust

Equilibrium and rate relationships have been determined for the sorption of divalent copper (Cu2+) and hexavalent chromium (Cr6+) onto untreated Red Fir sawdust. For both ions, the equilibrium sorption levels were determined to be a function of the solution pH and temperature. The equilibrium adsorption capacity of the sawdust for Cu2+ was found to increase with increasing pH. However, for Cr6+ the sorption capacity increased with decreasing pH. For both ions, the rate of adsorption and the equilibrium adsorption capacity increased with temperature. The sorption capacity of α-cellulose was at least an order of magnitude less than the untreated sawdust.

Bacterial reduction of hexavalent chromium by Enterobacter cloacae strain HO1 grown on sucrose

Chromium(VI) was reduced by Enterobacter cloacae strain HO1 grown with sucrose as a carbon source and nitrate as the initial terminal electron acceptor. Under excess substrate conditions, the Cr(VI) concentration, initially at 5 and 10 mg/l, was reduced to less than 100 mg/l.