Nucleophilic aliphatic substitution reactions of propachlor, alachlor, and metolachlor with bisulfide (HS-) and polysulfides (Sn2-).

Reactions of bisulfide and polysulfides with alachlor, propachlor, and metolachlor were examined in aqueous solution to investigate the role reduced sulfur species could play in effecting abiotic transformations of chloroacetanilide herbicides. Experiments at 25 degrees C demonstrated that reactions were approximately first-order in HS- concentration and revealed that polysulfides are considerably more reactive than HS-. delta H not equal to values for reactions of the three chloroacetanilides with HS- are statistically indistinguishable at the 95% confidence level, as are delta S not equal to values, despite significant differences in second-order rate constants (kHS-). Transformation products were characterized by GC/MS (in some cases following methylation) and were found to be consistent with substitution of chlorine by the sulfur nucleophile. Products containing multiple sulfur atoms were observed for the reactions of chloroacetanilides with polysulfides, while products resulting from reaction with HS- only possessed a single sulfur atom. When second-order rate constants at 25 degrees C are multiplied by HS- and polysulfide concentrations reported in salt marsh porewaters, predicted half-lives range from minutes to hours. HS- and especially polysulfides could thus exert a substantial influence on the fate of chloroacetanilide herbicides in aquatic environments. Oxidation of the resulting sulfur-substituted products could generate ethane sulfonic acid derivatives, previously reported as prevalent chloroacetanilide degradates.

Pb(II) distributions at biofilm-metal oxide interfaces.

The distribution of aqueous Pb(II) sorbed at the interface between Burkholderia cepacia biofilms and hematite (alpha-Fe(2)O(3)) or corundum (alpha-Al(2)O(3)) surfaces has been probed by using an application of the long-period x-ray standing wave technique. Attached bacteria and adsorbed organic matter may interfere with sorption processes on metal oxide surfaces by changing the characteristics of the electrical double layer at the solid-solution interface, blocking surface sites, or providing a variety of new sites for metal binding. In this work, Pb L(alpha) fluorescence yield profiles for samples equilibrated with 10(-7) to 10(-3.8) M Pb(II) were measured and modeled to determine quantitatively the partitioning of Pb(II) at the biofilm-metal oxide interface. Our data show that the reactive sites on the metal oxide surfaces were not passivated by the formation of a monolayer biofilm. Instead, high-energy surface sites on the metal oxides form the dominant sink for Pb(II) at submicromolar concentrations, following the trend alpha-Fe(2)O(3) (0001) > alpha-Al(2)O(3) (1102) > alpha-Al(2)O(3) (0001), despite the greater site density within the overlying biofilms. At [Pb] > 10(-6) M, significant Pb uptake by the biofilms was observed.

Effect of flue gas desulfurization (FGD) by-product on water quality at an underground coal mine.

In this paper, a field study was carried out to examine the effect of flue gas desulfurization (FGD) by-product on water quality at an underground coal mine in central-eastern Ohio. Flue gas desulfurizalion by-product was injected into the down-dip portions of the Robert-Dawson mine in an attempt to seal major seeps exiting the mine and to coat exposed pyritic surfaces. Immediately following grout injection, significant increases in acidity, iron, aluminum, sulfur, and calcium were observed at most surface and ground water locations near where grouting was carried out. Following this initial flush of elements, concentrations of most constituents have decreased to near pre-grouting levels. Data from the site and geochemical modeling suggest that an increase in water level or rerouting of drainage flow resulted in the dissolution of iron and aluminum sulfate salts and ferrihydrite. Dissolution of the FGD grout material resulted in increases in calcium and sulfate concentrations in the drainage waters. Water within the mine voids was saturated with respect to calcium sulfate and gypsum immediately following grout injection. Based on an analysis of core samples obtained from the site, acid mine drainage (AMD) was in contact with at least some portions of the grout and this resulted in grout weathering. Subsequent transport of calcium and sulfate to the underclay, perhaps by fracture flow, has resulted in the deposition of gypsum and calcium sulfate solids.

Biodegradation of 2-methyl, 2-ethyl, and 2-hydroxypyridine by an Arthrobacter sp. isolated from subsurface sediment.

A bacterium capable of degrading 2-methylpyridine was isolated by enrichment techniques from subsurface sediments collected from an aquifer located at an industrial site that had been contaminated with pyridine and pyridine derivatives. The isolate, identified as an Arthrobacter sp., was capable of utilizing 2-methylpyridine, 2-ethylpyridine, and 2-hydroxypyridine as primary C, N, and energy sources. The isolate was also able to utilize 2-, 3-, and 4-hydroxybenzoate, gentisic acid, protocatechuic acid and catechol, suggesting that it possesses a number of enzymatic pathways for the degradation of aromatic compounds. Degradation of 2-methylpyridine, 2-ethylpyridine, and 2-hydroxypyridine was accompanied by growth of the isolate and release of ammonium into the medium. Degradation of 2-methylpyridine was accompanied by overproduction of riboflavin. A soluble blue pigment was produced by the isolate during the degradation of 2-hydroxypyridine, and may be related to the diazadiphenoquinones reportedly produced by other Arthrobacter spp. when grown on 2-hydroxypyridine. When provided with 2-methylpyridine, 2-ethylpyridine, and 2-hydroxypyridine simultaneously, 2-hydroxypyridine was rapidly and preferentially degraded; however there was no apparent biodegradation of either 2-methylpyridine or 2-ethylpyridine until after a seven day lag. The data suggest that there are differences between the pathway for 2-hydroxypyridine degradation and the pathways(s) for 2-methylpyridine and 2-ethylpyridine.

Contaminant bioavailability in soils, sediments, and aquatic environments.

The aqueous concentrations of heavy metals in soils, sediments, and aquatic environments frequently are controlled by the dissolution and precipitation of discrete mineral phases. Contaminant uptake by organisms as well as contaminant transport in natural systems typically occurs through the solution phase. Thus, the thermodynamic solubility of contaminant-containing minerals in these environments can directly influence the chemical reactivity, transport, and ecotoxicity of their constituent ions. In many cases, Pb-contaminated soils and sediments contain the minerals anglesite (PbSO4), cerussite (PbCO3), and various lead oxides (e.g., litharge, PbO) as well as Pb2+ adsorbed to Fe and Mn (hydr)oxides. Whereas adsorbed Pb can be comparatively inert, the lead oxides, sulfates, and carbonates are all highly soluble in acidic to circumneutral environments, and soil Pb in these forms can pose a significant environmental risk. In contrast, the lead phosphates [e.g., pyromorphite, Pb5(PO4)3Cl] are much less soluble and geochemically stable over a wide pH range. Application of soluble or solid-phase phosphates (i.e., apatites) to contaminated soils and sediments induces the dissolution of the "native" Pb minerals, the desorption of Pb adsorbed by hydrous metal oxides, and the subsequent formation of pyromorphites in situ. This process results in decreases in the chemical lability and bioavailability of the Pb without its removal from the contaminated media. This and analogous approaches may be useful strategies for remediating contaminated soils and sediments.

A Fourier-transform infrared spectroscopic analysis of organic matter degradation in a bench-scale solid substrate fermentation (composting) system.

The degradation of organic matter was evaluated by a quantitative Fourier transform infrared spectroscopy (FTIR) analysis technique. The degradation process was conducted in a bench-scale reactor under controlled operational conditions of 50 degrees C, with 50-60% moisture content, and subjected to uniform aeration for 325 h. During the composting process, ATP concentration increased from 0.1 to 8 mug/g and the maximum CO(2) evolution and O(2) consumption rates reached 0.04 and 0.085 mmol/g-h, respectively. Polysaccharide content decreased approximately 50% while lignin content remained unchanged. Three regions of the FTIR spectra were used for quantification: 1070-974, 1705-1614, and 2995-2887 cm(-1), which correspond to polysaccharides and aromatic and aliphatic compounds, respectively. The actual spectra quantification consisted of peak identification using a second derivative and curve fitting technique, followed by normalization using the internal standard CaCO(3). The results obtained with the spectra quantification technique was then compared to commonly used wet chemistry extraction procedures. Reasonable correlation between the two techniques was obtained. (c) 1996 John Wiley & Sons, Inc.

Biodegradation of atrazine in surface soils and subsurface sediments collected from an agricultural research farm.

The purpose of the present study was to assess atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) mineralization by indigenous microbial communities and to investigate constraints associated with atrazine biodegradation in environmental samples collected from surface soil and subsurface zones at an agricultural site in Ohio. Atrazine mineralization in soil and sediment samples was monitored as 14CO2 evolution in biometers which were amended with 14C-labeled atrazine. Variables of interest were the position of the label ([U-14C-ring]-atrazine and [2-14C-ethyl]-atrazine), incubation temperature (25 degrees C and 10 degrees C), inoculation with a previously characterized atrazine-mineralizing bacterial isolate (M91-3), and the effect of sterilization prior to inoculation. In uninoculated biometers, mineralization rate constants declined with increasing sample depth. First-order mineralization rate constants were somewhat lower for [2-14C-ethyl]-atrazine when compared to those of [U-14C-ring]-atrazine. Moreover, the total amount of 14CO2 released was less with [2-14C-ethyl]-atrazine. Mineralization at 10 degrees C was slow and linear. In inoculated biometers, less 14CO2 was released in [2-14C-ethyl]-atrazine experiments as compared with [U-14C-ring]-atrazine probably as a result of assimilatory incorporation of 14C into biomass. The mineralization rate constants (k) and overall extents of mineralization (Pmax) were higher in biometers that were not sterilized prior to inoculation, suggesting that the native microbial populations in the sediments were contributing to the overall release of 14CO2 from [U-14C-ring]-atrazine and [2-14C-ethyl]-atrazine. A positive correlation between k and aqueous phase atrazine concentrations (Ceq) in the biometers was observed at 25 degrees C, suggesting that sorption of atrazine influenced mineralization rates. The sorption effect on atrazine mineralization was greatly diminished at 10 degrees C. It was concluded that sorption can limit biodegradation rates of weakly-sorbing solutes at high solid-to-solution ratios and at ambient surface temperatures if an active degrading population is present. Under vadose zone and subsurface aquifer conditions, however, low temperatures and the lack of degrading organisms are likely to be primary factors limiting the biodegradation of atrazine.

Degradation and mineralization of atrazine by a soil bacterial isolate.

An atrazine-degrading bacterial culture was isolated from an agricultural soil previously impacted by herbicide spills. The organism was capable of using atrazine under aerobic conditions as the sole source of C and N. Cyanuric acid could replace atrazine as the sole source of N, indicating that the organism was capable of ring cleavage. Ring cleavage was confirmed in 14CO2 evolution experiments with [U-14C-ring]atrazine. Between 40 and 50% of ring-14C was mineralized to 14CO2. [14C]biuret and [14C]urea were detected in spent culture media. Cellular assimilation of 14C was negligible, in keeping with the fully oxidized valence of the ring carbon. Chloride release was stoichiometric. The formation of ammonium during atrazine degradation was below the stoichiometric amount, suggesting a deficit due to cellular assimilation and metabolite-N accumulation. With excess glucose and with atrazine as the sole N source, free ammonium was not detected, suggesting assimilation into biomass. The organism degraded atrazine anaerobically in media which contained (i) atrazine only, (ii) atrazine and glucose, and (iii) atrazine, glucose, and nitrate. To date, this is the first report of a pure bacterial isolate with the ability to cleave the s-triazine ring structure of atrazine. It was also concluded that this bacterium was capable of dealkylation, dechlorination, and deamination in addition to ring cleavage.