Mark A. Schlautman

Molecular weight fractionation of humic substances by adsorption onto minerals.

Molecular weight (MW) fractionation of Suwannee River fulvic acid (SRFA) and purified Aldrich humic acid (PAHA) by adsorption onto kaolinite and hematite was investigated in equilibrium and rate experiments with a size-exclusion chromatography system using ultraviolet (UV) light detection. The extent of adsorptive fractionation based on UV detection was positively correlated with the percent carbon adsorption for both humic substances (HS), although the specific fractionation pattern observed depended on the particular HS and mineral used. Higher MW fractions of SRFA, an aquatic HS, were preferentially adsorbed to both kaolinite and hematite whereas the fractionation trends for PAHA, a terrestrial peat HS, differed for the two minerals. The contrasting fractionation patterns for SRFA versus PAHA can be explained reasonably well by the different structural trends that occur in their respective MW fractions and the underlying adsorption processes. Rate studies of adsorptive fractionation revealed an initial rapid uptake of smaller HS molecules by the mineral surfaces, followed by their replacement at the surface by a much slower uptake of the larger HS molecules present in aqueous solution.

Effects of pH and dissolved oxygen on the reduction of hexavalent chromium by dissolved ferrous iron in poorly buffered aqueous systems

The effects of pH and dissolved oxygen (DO) on the reduction of Cr(VI) by dissolved Fe(II) were investigated for aqueous solutions having relatively low buffering capacities. All solutions were maintained at a constant ionic strength (generally 0.05 M) and temperature (23 +/- 2 degrees C). For the majority of the experiments conducted, initial concentrations of Fe(II) and Cr(VI) were 50 and 20 microM, respectively, representing a deficient amount of Fe(II) (i.e. nonstoichiometric conditions). Experiments conducted in the absence and presence of DO were performed in an anaerobic chamber and in vessels open to the atmosphere, respectively. Specific initial pH values were obtained by adjusting the pH of Cr(VI) and Fe(II) stock solutions prior to their mixing or by spiking Cr(VI)-Fe(II) systems with strong base to rapidly increase the pH in situ. Consistent with previous reports, Cr(VI) reduction rates for our systems increased with increasing pH (pH ranges of 3.5-6 and 3.5-7.2 for oxic and anoxic experiments, respectively). Because of our poorly buffered experimental systems, pH values decreased over the course of the reactions which, in turn, caused decreases in the reduction rates with time. Spiking some experimental systems with NaOH to rapidly raise the pH resulted in faster rates of Cr(VI) reduction than when the pH was adjusted prior to mixing the stock solutions together; this observation is likely due to the presence of microenvironments in the reactors for which local, short-term pH values greatly exceed the equilibrium value (i.e. mixing is slower than the reduction reaction in these high pH microenvironments). The molar ratios of Fe(II) oxidized to Cr(VI) reduced were close to the expected stoichiometric value of 3 for the majority of our experimental systems, which shows that DO will not cause a serious interference in most applications using Fe(II) to reduce Cr(VI).

Dynamic exchanges between DOM and POM pools in coastal and inland aquatic ecosystems: A review.

Dynamic exchanges between dissolved organic matter (DOM) and particulate organic matter (POM) plays a critical role in organic carbon cycling in coastal and inland aquatic ecosystems, interactions with aquatic organisms, mobility and bioavailability of pollutants, among many other ecological and geochemical phenomena. Although DOM-POM exchange processes have been widely studied from different aspects, little to no effort has been made to date to provide a comprehensive, mechanistic, and micro-spatial schema for understanding various exchange processes occurring in different aquatic ecosystems in a unified way. The phenomena occurring between DOM and POM were explained here with the homogeneous and heterogeneous mechanisms. In the homogeneous mechanism, the participating components are only organic matter (OM) constituents themselves with aggregation and dissolution involved, whereas OM is associated with other components such as minerals and particulate colloids in the heterogeneous counterpart. Besides the generally concerned processes of aggregation/dissolution and adsorption/desorption, other ecological factors such as sunlight and organisms can also participate in DOM-POM exchanges through altering the chemical nature of OM. Despite the limitation of current analytical technologies, many unknown and/or unquantified processes need to be identified to unravel the complicated exchanges of OM between its dissolved and particulate states. Based on the review of several previous mathematical models, we proposed a unified conceptual model to describe all major dynamic exchange mechanisms on the basis of exergy theory. More knowledge of dynamic DOM-POM exchanges is warranted to overcome the potential problems arising from a simple division of OM into dissolved versus particulate states and to further develop more sophisticated mathematic models.

Competition between kaolinite flocculation and stabilization in divalent cation solutions dosed with anionic polyacrylamides

Divalent cations have been reported to develop bridges between anionic polyelectrolytes and negatively-charged colloidal particles, thereby enhancing particle flocculation. However, results from this study of kaolinite suspensions dosed with various anionic polyacrylamides (PAMs) reveal that Ca(2+) and Mg(2+) can lead to colloid stabilization under some conditions. To explain the opposite but coexisting processes of flocculation and stabilization with divalent cations, a conceptual flocculation model with (1) particle-binding divalent cationic bridges between PAM molecules and kaolinite particles and (2) polymer-binding divalent cationic bridges between PAM molecules is proposed. The particle-binding bridges enhanced flocculation and aggregated kaolinite particles in large, easily-settleable flocs whereas the polymer-binding bridges increased steric stabilization by developing polymer layers covering the kaolinite surface. Both the particle-binding and polymer-binding divalent cationic bridges coexist in anionic PAM- and kaolinite-containing suspensions and thus induce the counteracting processes of particle flocculation and stabilization. Therefore, anionic polyelectrolytes in divalent cation-enriched aqueous solutions can sometimes lead to the stabilization of colloidal particles due to the polymer-binding divalent cationic bridges.

Reductive Capacity of Soils for Chromium

A standard batch procedure was developed to measure soil reductive capacity (SRC) based on the ability of soil to reduce Cr(VI). Parameters that were investigated and optimized included extractant (sulfate) concentration, reaction temperature, types of reductants, reductant contact time and Cr(VI) contact time. 0.1 M sulfate was used as the extracting solution as a measure of safety. Reaction temperature did not have a significant influence on the reduction kinetics of Cr(VI). Dithionite was selected as a standard reductant due to its efficiency in increasing SRC by reducing labile soil components in the soil itself. A time period of 2 days was optimum contact time to achieve full reduction and oxidation. Soil treated with Fe(II) and the combination of Fe(II) and dithionite showed a constant SRC regardless of the frequency of reduction/oxidation cycle, whereas the intrinsic reductive capacity and total reductive capacity of the soil treated with dithionite were exhausted within several cycles. Column tests were conducted using soil with measured intrinsic and total reductive capacities. Differences observed between Cr(VI) breakthrough and that predicted from batch studies are likely to have benn caused by slow Cr(VI) reduction kinetics and heterogeneity of the soil. The relative behavior of the column tests agreed with observations of the reactants in the batch experiments. The tests demonstrate that soils can be used to develop an in situ treatment process in which soils are reduced by the addition of reductants and groundwater contaminated with Cr(VI) is passed through the reduced soil zone.

Effects of ferrous iron and molecular oxygen on chromium(VI) redox kinetics in the presence of aquifer solids

The kinetics and stoichiometry of the reduction of hexavalent chromium (Cr(VI)) with ferrous iron (Fe(II)) were examined in systems with and without aquifer solids. Cr(VI) reduction was rapid in the absence of solids, but demonstrated slower and more complex kinetics in the presence of aquifer solids. The aquifer solids removed Fe(II) from solution and a portion of the reducing capacity of Fe(II) was transferred to the aquifer solids. The solid phases were then able to continue to remove Cr(VI). This suggests in situ treatment of Cr(VI) by Fe(II) injection would be feasible in the aquifer environment. In general, re-oxidation of reduced chromium by molecular oxygen was not observed in our systems over time periods of nearly 1 year, suggesting that the potential for chromium solubilization under these oxidizing conditions will be low. An empirical model was developed to describe the reduction kinetics of Cr(VI) in the presence of solids. The model assumes that the reaction is brought about by pseudo-species of iron that react instantaneously, rapidly and slowly with Cr(VI). A fourth pseudo-species is assumed to be non-reactive. Model coefficients were determined by non-linear regression. The model was able to describe observed concentrations of chromium well, but analysis of model errors indicated the potential existence of a distribution of species with different reaction rates rather than just three distinct species. Another model was developed to predict concentrations of different pseudo-species depending on the total amount of Fe(II) added and the amount of aquifer solids present. This model assumed that pseudo-species could result from intrinsic characteristics of the aquifer solids as well as being formed by addition of Fe(II), which could sorb to the aquifer solids.

Does current management of storm water runoff adequately protect water resources in developing catchments

The effectiveness of best management practices (BMPs) at preventing erosion and controlling storm water and sediment runoff in developing catchments in the Reedy River (South Carolina) watershed was evaluated from 2004 to 2005. Catchment-normalized storm water runoff and event mean concentrations and cumulative mass loads of selected pollutants were compared among four catchments exhibiting similar rainfall, soil, and geographic characteristics but undergoing varying degrees of development. Despite the implementation of BMPs, streams below catchments undergoing active development exhibited patterns characteristic of urbanized watersheds, namely, storm hydrographs characterized by steep rising and descending limbs due to accelerated storm water runoff. In contrast with the developing catchments, streams below relatively undisturbed catchments exhibited more gradual rising and descending limbs on their hydrographs, presumably due to enhanced infiltration and interflow and less direct surface runoff. A comparison of surface runoff depths and runoff ratios confirmed more direct surface runoff was generated from rainfall in the developing catchments versus the undisturbed catchments despite the use of BMPs. In addition, area-normalized maximum stream discharges during storm events were generally higher for the developing versus undisturbed catchments. Similarly, mean concentrations and mass loads of total suspended solids were consistently higher for the developing versus undisturbed catchments. In many cases, mean concentrations for total suspended solids and other selected pollutants in storm water runoff from the developing catchments exceeded recognized water quality criteria. Taken together, the quantity and quality of storm water runoff from the developing catchments indicate that the overall protective goals of erosion prevention and sediment control regulations are not being met. Possible explanations for this include BMPs that have not been properly designed or located, are not the correct type, are insufficiently numerous, and/or have not been adequately maintained to control the increased surface runoff and/or soil erosion due to land disturbance. Alternatively, the failure may reflect shortcomings in the regulations themselves.

Metalloporphyrin solubility: A trigger for catalyzing reductive dechlorination of tetrachloroethylene

Metalloporphyrins are well known for their electron-transfer roles in many natural redox systems. In addition, several metalloporphyrins and related tetrapyrrole macrocycles complexed with various core metals have been shown to catalyze the reductive dechlorination of certain organic compounds, thus demonstrating the potential for using naturally occurring metalloporphyrins to attenuate toxic and persistent chlorinated organic pollutants in the environment. However, despite the great interest in reductive dechlorination reactions and the wide variety of natural and synthetic porphyrins currently available, only soluble porphyrins, which comprise a small fraction of this particular family of organic macrocycles, have been used as electron-transfer shuttles in these reactions. Results from the present study clearly demonstrate that metalloporphyrin solubility is a key factor in their ability to catalyze the reductive dechlorination of tetrachloroethylene and its daughter compounds. Additionally, we show that certain insoluble and nonreactive metalloporphyrins can be activated as catalysts merely by changing solution conditions to bring about their dissolution. Furthermore, once a metalloporphyrin is fully dissolved and activated, tetrachloroethylene transformation proceeds rapidly, giving nonchlorinated and less toxic alkenes as the major reaction products. Results from the present study suggest that if the right environmental conditions exist or can be created, specific metalloporphyrins may provide a solution for cleaning up sites that are contaminated with chlorinated organic pollutants.

Copper leaching from brake wear debris in standard extraction solutionsElectronic supplementary information (ESI) available: thermodynamic equilibrium speciation results from the geochemical model MINTEQ. See http://www.rsc.org/suppdata/em/b3/b303820c/

Quantification of the copper content of and copper leaching from a disc brake wear debris sample was performed using microwave-assisted acid digestion, the Federal Toxicity Characteristic Leaching Procedure (TCLP), and the State of California Waste Extraction Test (WET). The brake wear debris tested was a composite sample obtained from a brake dynamometer test of one brake pad source material. Comparative digestion studies demonstrated that a modified aqua regia matrix (HNO3:HCl:H2O2 = 1:3:0.5) optimized the digestion effectiveness for determining the total copper content in the brake wear debris. No significant sample heterogeneity within the brake wear debris was observed, based on statistically indistinguishable total copper content results for subsamples with a wide range of sample masses. Upon pooling all subsample results, an overall total copper content for the composite brake wear debris sample was determined to be 10.8% (g/g), with a 95% confidence limit of +/- 0.5% (g/g). Copper leaching increased with decreasing solid-to-liquid ratios in TCLP tests, but was unaffected by the solid-to-liquid ratio in the WET. For a 1:10(4) (g/g) solid-to-liquid ratio, 85% and 99% of the total mass of copper present in the composite brake wear debris sample was leached into solution during the TCLP and WET, respectively. Rate studies also demonstrated that the WET resulted in a faster rate and higher extent of copper leaching relative to the TCLP. Compared to reference copper-containing materials, the composite brake wear debris sample exhibited relatively higher TCLP and WET copper leaching characteristics. The higher copper leaching exhibited by the brake wear debris sample may have resulted from its higher specific surface area and/or from changes in the chemical form of copper that occurred during the braking process.

Effects of organic ligands and pH on the leaching of copper from brake wear debris in model environmental solutions

Copper leaching from a disc brake wear debris sample was examined in a variety of aqueous solutions to simulate potential leaching processes during rain events and in surface waters. Synthetic rainwater leached 40% of the total copper present in the brake wear debris into solution after 18 h in batch reactors, which was approximately three times more copper than that extracted by the US Environmental Protection Agencys Synthetic Precipitation Leaching Procedure. Formate and acetate were responsible for the enhanced copper leaching, as demonstrated by higher average amounts of leached copper in synthetic rainwater with- versus without the organic acids (40 versus 31% recovery). This observation suggests leaching tests that do not incorporate the appropriate types and concentrations of organic ligands present in rainwater will likely underestimate copper mobilization from brake wear debris during rain events. Leaching of copper from the brake wear debris ranged from 23 to 40% in solutions containing 3 to 15 mg C L(-1) dissolved humic substances, and was higher still in solutions containing relatively high concentrations of the synthetic metal chelating agent ethylenediaminetetraacetic acid. Static pH tests demonstrated that copper leaching from brake wear debris is highly pH dependent, with more leaching occurring at lower solution pH values. Leaching rate studies revealed that equilibrium generally was not attained within 48 h in the model solutions, indicating that additional copper can be expected to be released in environments where brake wear debris is exposed to long-term leaching processes.