Donald L. Macalady

Abiotic reduction reactions of anthropogenic organic chemicals in anaerobic systems: a critical review

Abstract This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several difficulties (both semantic and experimental) that recur in the studies reviewed are discussed. The subtle effects of various sterilization techniques on extracellular biochemicals and complex chemical reducing agents in sediment have stifled attempts to separate abiotic from biological degradation reactions. The characterization of redox conditions in a natural system is still problematic since measured redox potential is not adequate. Suggestions for future research toward a process-level understanding of abiotic chemical reductions are made.

Identification of persistent anionic surfactant-derived chemicals in sewage effluent and groundwater

Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3–10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F300-50 groundwater have a minimum residence time in the range of 2.7–4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50–500 half lives.

New perspectives in aquatic redox chemistry: Abiotic transformations of pollutants in groundwater and sediments☆

Abstract Presented is a review of recent advances in the chemistry of abiotic redox transformations of organic pollutants in anaerobic ecosystems. The goal is to provide an indication of the state of knowledge and the remaining difficulties, rather than an exhaustive review of the existing literature. Particular attention is given to the types of functional groups that undergo reaction and the findings concerning physical and chemical parameters of ecosystems that govern the rates and products of redox transformations. Classes of compounds and structural features within these classes of compounds provide information about the intrinsic nature of the natural reductants. Further information is provided by studies which consider system variables such as sediment concentrations, organic carbon levels, pH, Eh and temperature. While the identity of reducing agents that transform organic pollutants in anaerobic systems remains elusive, the reactivities of these agents are being characterized and compared with surrogate (model) reductants. It is apparent that chemical and biological reduction processes are strongly coupled, and there is increasing evidence for widespread mediation of reductive reactions by bio-organic molecules.

The Interaction of Natural Organic Matter with Iron in a Wetland (Tennessee Park, Colorado) Receiving Acid Mine Drainage

Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

Chapter 24 – Predictive Double-Layer Modeling of Metal Sorption in Mine-Drainage Systems

Previous comparison of predictive double-layer modeling and empirically derived metal-partitioning data has validated the use of the double-layer model to predict metal sorption reactions in iron-rich mine-drainage systems. The double-layer model subsequently has been used to model data collected from several mine-drainage sites in Colorado with diverse geochemistry and geology. This work demonstrates that metal partitioning between dissolved and sediment phases can be predictively modeled simply by knowing the water chemistry and the amount of suspended iron-rich particulates present in the system. Sorption on such iron-rich suspended sediments appears to control metal and arsenic partitioning between dissolved and sediment phases, with sorption on bed sediment playing a limited role. At pH > 5, Pb and As are largely sorbed by iron-rich suspended sediments and Cu is partially sorbed; Zn, Cd, and Ni usually remain dissolved throughout the pH range of 3 to 8.

Electrode measurement of redox potential in anaerobic ferric/ferrous chloride systems

The behaviour of two inert redox electrodes (Pt and wax-impregnated graphite) was investigated in anaerobic ferrous and ferric chloride solutions in order to establish if these electrodes respond to the Fe3+/Fe2+ couple in a Nernstian manner. A new method for determining dissolved ferric iron at any point in time was used which permitted the calculation of Eh values that are independent of variations in the solubility of ferric oxyhydroxides. This method is applicable to simple iron solution at pH levels of 4 or less. In solutions of ironic strength greater than 0.005 M, both electrodes yielded measured potentials that correspond to the value calculated by the Nernst equation. In solutions of ionic strength less than 0.005 M, electrode response became non-Nernstian. Low exchange current densities did not appear to be responsible for the non-Nernstian behaviour.

New light on a dark subject: On the use of fluorescence data to deduce redox states of natural organic matter (NOM)

Abstract.This paper reports the use of excitation-emission matrix fluorescence spectroscopy (EEMS), parallel factor statistical analysis (PARAFAC), and oxidation-reduction experiments to examine the effect of redox conditions on PARAFAC model results for aqueous samples rich in natural organic matter. Fifty-four aqueous samples from 11 different geographic locations and two plant extracts were analyzed untreated and after chemical treatments or irradiation were used in attempts to change the redox status of the natural organic matter. The EEMS spectra were generated and modeled using a PARAFAC package developed by Cory and McKnight (2005). The PARAFAC model output was examined for consistency with previously reported relations and with changes expected to occur upon experimental oxidation and reduction of aqueous samples. Results indicate the implied fraction of total sample fluorescence attributed to quinone-like moieties was consistent (0.64 to 0.78) and greater than that observed by Cory and McKnight (2005). The fraction of the quinone-like moieties that was reduced (the reducing index, RI) showed relatively little variation (0.46 to 0.71) despite attempts to alter the redox status of the natural organic matter. The RI changed little after reducing samples using zinc metal, oxidizing at high pH with air, or irradiating with a Xenon lamp. Our results, however, are consistent with the correlations between the fluorescence indices (FI) of samples and the ratio of PARAFAC fitting parameters suggested by Cory and McKnight (2005), though we used samples with a much narrower range of FI values.

Measuring the saturation limit of low-volatility organic compounds in soils: implications for estimates of dermal absorption.

Estimating dermal absorption from contaminated soils typically requires extrapolations from measurements obtained on soils artificially contaminated at much larger concentrations. Such extrapolations should be constrained by the fact that maximum absorption will occur for the largest possible concentration of chemical on the soil without neat chemical being present; i.e., at the soil saturation limit (S(soil)). Saturation limits of two low-volatility model compounds (4-cyanophenol and methyl paraben) were determined on the 38-63μm sieve fraction of four soils with different fractions of organic carbon (f(oc)=0.015-0.45) and specific surface areas (σ(soil)=4-34m(2) g(-1)) using two methods: equilibrium uptake into silicone rubber membranes and differential scanning calorimetry. Except for Pahokee peat, which had the largest f(oc), a model assuming contributions from both surface adsorption and organic carbon absorption provided excellent predictions of S(soil). In all soils, the surface saturation concentration of both chemicals was estimated at 2.2mg m(-2). The saturation concentration of 4-cyanophenol in the soil organic carbon was 1.7-fold higher than methyl paraben, which is consistent with the estimated solubility limits of these two chemicals in octanol.