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Evaluation of ultrafiltration for determining molecular weight of fulvic acid

Two commonly used ultrafiltration membranes are evaluated for the determination of molecular weights of humic substances. Polyacrylic acids of Mr 2000 and 5000 and two well-characterized fulvic acids are used as standards. Molecular size characteristics of standards, as determined by small-angle X-ray scattering, are presented. Great care in evaluating molecular weight data obtained by ultrafiltration is needed because of broad nominal cutoffs and membrane-solute interactions.

Environmental Science & Technology↗

Methyl-mercury degradation pathways: A comparison among three mercury impacted ecosystems

We examined microbial methylmercury (MeHg) degradation in sediment of the Florida Everglades, Carson River (NV), and San Carlos Creek (CA), three freshwater environments that differ in the extent and type of mercury contamination and sediment biogeochemistry. Degradation rate constant ( k deg ) values increased with total mercury (Hg t ) contamination both among and within ecosystems. The highest k deg 's (2.8−5.8 d - 1 ) were observed in San Carlos Creek, at acid mine drainage impacted sites immediately downstream of the former New Idria mercury mine, where Hg t ranged from 4.5 to 21.3 ppm (dry wt). A reductive degradation pathway (presumably mer -detoxification) dominated degradation at these sites, as indicated by the nearly exclusive production of 14 CH 4 from 14 C-MeHg, under both aerobic and anaerobic conditions. At the upstream control site, and in the less contaminated ecosystems (e.g. the Everglades), k deg 's were low (≤0.2 d - 1 ) and oxidative demethylation (OD) dominated degradation, as evident from 14 CO 2 production. k deg increased with microbial CH 4 production, organic content, and reduced sulfur in the Carson River system and increased with decreasing pH in San Carlos Creek. OD associated CO 2 production increased with pore-water SO 4 2- in Everglades samples but was not attributable to anaerobic methane oxidation, as has been previously proposed. This ecosystem comparison indicates that severely contaminated sediments tend to have microbial populations that actively degrade MeHg via mer -detoxification, whereas OD occurs in heavily contaminated sediments as well but dominates in those less contaminated.

Environmental Science & Technology↗

Partition coefficients of organic compounds in lipid-water systems and correlations with fish bioconcentration factors

Triolein-water partition coefficients (KtW) have been determined for 38 slightly water-soluble organic compounds, and their magnitudes have been compared with the corresponding octanol-water partition coefficients (KOW). In the absence of major solvent-solute interaction effects in the organic solvent phase, the conventional treatment (based on Raoult's law) predicts sharply lower partition coefficients for most of the solutes in triolein because of its considerably higher molecular weight, whereas the Flory-Huggins treatment predicts higher partition coefficients with triolein. The data are in much better agreement with the Flory-Huggins model. As expected from the similarity in the partition coefficients, the water solubility (which was previously found to be the major determinant of the KOW) is also the major determinant for the Ktw. When the published BCF values (bioconcentration factors) of organic compounds in fish are based on the lipid content rather than on total mass, they are approximately equal to the Ktw, which suggests at least near equilibrium for solute partitioning between water and fish lipid. The close correlation between Ktw and Kow suggests that Kow is also a good predictor for lipid-water partition coefficients and bioconcentration factors.

Environmental Science & Technology↗

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

The reductive dissolution of MnO 2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO 4 2 - ) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO 2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe 2 O 4 ), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

Environmental Science & Technology↗

In situ stimulation of groundwater denitrification with formate to remediate nitrate contamination

In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.

Environmental Science & Technology↗

Methyl tert-butyl ether biodegradation by indigenous aquifer microorganisms under natural and artificial oxic conditions

Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert -butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were >1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/L to a depth of 1.5 m, and MTBE concentrations decreased to <1 μg/L prior to discharge. MTBE mass flux calculations indicate that 96% of MTBE mass loss occurs in the relatively small oxic zone prior to discharge. Samples of a natural microbial biofilm present in the oxic zone beneath the ditch completely degraded [U- 14 C]MTBE to [ 14 C]CO 2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE- and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.

Environmental Science & Technology↗

Migration of wood-preserving chemicals in contaminated groundwater in a sand aquifer at Pensacola, Florida

Operation of a wood-preserving facility for nearly 80 years at Pensacola, FL, contaminated the near-surface groundwater with creosote and pentachlorophenol. The major source of aquifer contamination was unlined surface impoundments that were in direct hydraulic contact with the groundwater. Episodes of overtopping the impoundments and overland flow of treatment liquor and waste were also significant to the migration and contamination of the groundwater. Solutes contaminating the ground-water are mainly naphthalene and substituted phenols. Sorption did not influence retardation of solutes in transport in the groundwater. Phenol and the mono substituted methylphenols appear to be undergoing bio-transformation. Pentachlorophenol (PCP) was not found in significant concentrations in the groundwater possibly because the solubility of PCP is approximately 5 mg/L at pH 6, near the average acidity for the groundwater.

Florida↗

Snow chemistry of the Cascade-Sierra Nevada Mountains

This investigation assesses geographic variations in atmospheric deposition in Washington, Oregon, and California using snow cores from the Cascade-Sierra Nevada Mountains, collected from late February to mid-March 1983. A statistical analysis of the analytical and sampling precision was made. The snowpack in the higher Cascades and Sierra Nevada is not strongly influenced by anthropogenic activities at present. The pH of snow samples ranges from 5.11 to 5.88. Sulfate and nitrate correlate with H+ in some segments of the sample traverse. The SO4 data show apparent influence from major source areas in Washington and California; nitrate does not. An apparent decrease in NH4 in snow in Washington and California suggests atmospheric interactions resulting in the removal of NH4. The NH4 reduction raises questions about nutrient supply to the mountain vegetation. Heavy-metal correlations included Cd, Cu, and Fe with Pb, and Mn with K and DOC, among others. No correlation was found between constituents and snow-water content.

California, Oregon, Washington↗