Experimental and Computational Study of Pyrogenic Carbonaceous Matter Facilitated Hydrolysis of 2,4-Dinitroanisole (DNAN).

This study investigated the reaction pathway of 2,4-dinitroanisole (DNAN) on the pyrogenic carbonaceous matter (PCM) to assess the scope and mechanism of PCM-facilitated surface hydrolysis. DNAN degradation was observed at pH 11.5 and 25 °C with a model PCM, graphite, whereas no significant decay occurred without graphite. Experiments were performed at pH 11.5 due to the lack of DNAN decay at pH below 11.0, which was consistent with previous studies. Graphite exhibited a 1.78-fold enhancement toward DNAN decay at 65 °C and pH 11.5 relative to homogeneous solution by lowering the activation energy for DNAN hydrolysis by 54.3 ± 3.9%. This is supported by our results from the computational modeling using Car-Parrinello simulations by ab initio molecular dynamics/molecular mechanics (AIMD/MM) and DFT free energy simulations, which suggest that PCM effectively lowered the reaction barriers by approximately 8 kcal mol-1 compared to a homogeneous solution. Quaternary ammonium (QA)-modified activated carbon performed the best among several PCMs by reducing DNAN half-life from 185 to 2.5 days at pH 11.5 and 25 °C while maintaining its reactivity over 10 consecutive additions of DNAN. We propose that PCM can affect the thermodynamics and kinetics of hydrolysis reactions by confining the reaction species near PCM surfaces, thus making them less accessible to solvent molecules and creating an environment with a weaker dielectric constant that favors nucleophilic substitution reactions. Nitrite formation during DNAN decay confirmed a denitration pathway, whereas demethylation, the preferred pathway in homogeneous solution, produces 2,4-dinitrophenol (DNP). Denitration catalyzed by PCM is advantageous to demethylation because nitrite is less toxic than DNAN and DNP. These findings provide critical insights for reactive adsorbent design that has broad implications for catalyst design and pollutant abatement.

Effect of Interfacial Action on the Generation and Transformation of Reactive Oxygen Species in Tripolyphosphate-Enhanced Heterogeneous Fe3O4/O2 Systems.

It has been reported that tripolyphosphate (TPP) can enhance the oxygenation of natural Fe(II)-containing minerals to produce reactive oxygen species (ROS). However, the molecular structure of the TPP-Fe(II) mineral surface complex and the role of this complex in the generation and transformation of ROS have not been fully characterized. In the present study, a heterogeneous magnetite (Fe3O4)/O2/TPP system was developed for the degradation of p-nitrophenol (PNP). The results showed that the addition of TPP significantly accelerated the removal of PNP in the Fe3O4/O2 system and extended the range of effective pH to neutral. Experiments combined with density functional theory calculations revealed that the activation of O2 mainly occurs on the surface of Fe3O4 induced by a structural Fe(II)-TPP complex, where the generated O2•- (intermediate active species) can be rapidly converted into H2O2, and then the •OH generated by the Fenton reaction is released into the solution. This increases the concentration of •OH produced and the efficiency of •OH produced relative to Fe(II) consumed, compared with the homogeneous system. Furthermore, the binding of TPP to the surface of Fe3O4 led to stretching and even cleavage of the Fe-O bonds. Consequently, more Fe(II)/(III) atoms are exposed to the solvation environment and are available for the binding of active O2 and O2•-. This study demonstrates how common iron minerals and O2 in the natural environment can be combined to yield a green remediation technology.

Modeling the Role in pH on Contaminant Sequestration by Zerovalent Metals: Chromate Reduction by Zerovalent Magnesium.

The role of pH in sequestration of Cr(VI) by zerovalent magnesium (ZVMg) was characterized by global fitting of a kinetic model to time-series data from unbuffered batch experiments with varying initial pH values. At initial pH values ranging from 2.0 to 6.8, ZVMg (0.5 g/L) completely reduced Cr(VI) (18.1 µM) within 24 h, during which time pH rapidly increased to a plateau value of ∼10. Time-series correlation analysis of the pH and aqueous Cr(VI), Cr(III), and Mg(II) concentration data suggested that these conditions are controlled by combinations of reactions (involving Mg0 oxidative dissolution and Cr(VI) sequestration) that evolve over the time course of each experiment. Since this is also likely to occur during any engineering applications of ZVMg for remediation, we developed a kinetic model for dynamic pH changes coupled with ZVMg corrosion processes. Using this model, the synchronous changes in Cr(VI) and Mg(II) concentrations were fully predicted based on the Langmuir-Hinshelwood kinetics and transition-state theory, respectively. The reactivity of ZVMg was different in two pH regimes that were pH-dependent at pH < 4 and pH-independent at the higher pH. This contrasting pH effect could be ascribed to the shift of the primary oxidant of ZVMg from H+ to H2O at the lower and higher pH regimes, respectively.

pKa prediction of per- and polyfluoroalkyl acids in water using in silico gas phase stretching vibrational frequencies and infrared intensities.

To successfully understand and model the environmental fate of per- and polyfluoroalkyl substances (PFAS), it is necessary to know key physicochemical properties (PChPs) such as pKa; however, measured PChPs of PFAS are scarce and of uncertain reliability. In this study, quantitative structure-activity relationships (QSARs) were developed by correlating calculated (M062-X/aug-cc-pVDZ) vibrational frequencies (VF) and corresponding infrared intensities (IRInt) to the pKa of carboxylic acids, sulfonic acids, phosphonic acids, sulfonamides, betaines, and alcohols. Antisymmetric stretching VF of the anionic species were used for all subclasses except for alcohols where the OH stretching VF performed better. The individual QSARs predicted the pKa for each subclass mostly within 0.5 pKa units from the experimental values. The inclusion of IRInt as a pKa predictor for carboxylic acids improved the results by decreasing the root-mean-square error from 0.35 to 0.25 (n > 100). Application of the developed QSARs to estimate the pKa of PFAS within each subclass revealed that the length of the perfluoroalkyl chain has minimal effect on the pKa, consistent with other models but in stark contrast with the limited experimental data available.

Modeling the Partitioning of Anionic Carboxylic and Perfluoroalkyl Carboxylic and Sulfonic Acids to Octanol and Membrane Lipid.

Perfluoroalkyl carboxylic and sulfonic acids (PFCAs and PFSAs, respectively) have low acid dissociation constant values and are, therefore, deprotonated under most experimental and environmental conditions. Hence, the anionic species dominate their partitioning between water and organic phases, including octanol and phospholipid bilayers which are often used as model systems for environmental and biological matrices. However, data for solvent-water (SW) and membrane-water partition coefficients of the anion species are only available for a few per- and polyfluoroalkyl substances (PFAS). In the present study, an equation is derived using a Born-Haber cycle that relates the partition coefficients of the anions to those of the corresponding neutral species. It is shown via a thermodynamic analysis that for carboxylic acids (CAs), PFCAs, and PFSAs, the log of the solvent-water partition coefficient of the anion, log KSW (A- ), is linearly related to the log of the solvent-water partition coefficient of the neutral acid, log KSW (HA), with a unity slope and a solvent-dependent but solute-independent intercept within a PFAS (or CA) family. This finding provides a method for estimating the partition coefficients of PFCAs and PFSAs anions using the partition coefficients of the neutral species, which can be reliably predicted using quantum chemical methods. In addition, we have found that the neutral octanol-water partition coefficient, log KOW , is linearly correlated to the neutral membrane-water partition coefficient, log KMW ; therefore, log KOW , being a much easier property to estimate and/or measure, can be used to predict the neutral log KMW . Application of this approach to KOW and KMW for PFCAs and PFSAs demonstrates the utility of this methodology for evaluating reported experimental data and extending anion property data for chain lengths that are unavailable. Environ Toxicol Chem 2023;42:2317-2328. © 2023 SETAC.

Degradation of Chloroform by Zerovalent Iron: Effects of Mechanochemical Sulfidation and Nitridation on the Kinetics and Mechanism.

Chloroform (CF) is a widely used chemical reagent and disinfectant and a probable human carcinogen. The extensive literature on halocarbon reduction with zerovalent iron (ZVI) shows that transformation of CF is slow, even with nano, bimetallic, sulfidated, and other modified forms of ZVI. In this study, an alternative method of ZVI modification─involving simultaneous sulfidation and nitridation through mechanochemical ball milling─was developed and shown to give improved degradation of CF (i.e., higher degradation rate and inhibited H2 evolution reaction). The composite material (denoted as S-N(C)-ZVI) gave synergistic effects of nitridation and sulfidation on CF degradation. A complete chemical reaction network (CRN) analysis of CF degradation suggests that O-nucleophile-mediated transformation pathways may be the main route for the formation of the terminal nonchlorinated products (formate, CO, and glycolic polymers) that have been used to explain the undetected products needed for mass balance. Material characterizations of the ZVI recovered after batch experiments showed that sulfidation and nitridation promoted the formation of Fe3O4 on the S-N(C)-ZVI particles, and the effect of aging on CF degradation rates was minor for S-N(C)-ZVI. The synergistic benefits of sulfidation and nitridation on CF degradation were also observed in experiments performed with groundwater.

Electron exchange capacity of pyrogenic dissolved organic matter (pyDOM): complementarity of square-wave voltammetry in DMSO and mediated chronoamperometry in water.

Pyrogenic dissolved organic matter (pyDOM) is derived from black carbon, which is important in the global carbon cycle and other biogeochemical redox processes. The electron-exchange capacity (EEC) of pyDOM has been characterized in water using mediated chronoamperometry (MCA), which gives precise results under specific operational conditions, but the broader significance of these EECs is less clear. In this study, we described a novel but complementary electrochemical approach to quantify EECs of pyDOM without mediation using square-wave voltammetry (SWV) in dimethyl sulfoxide (DMSO). Using both the SWV and MCA methods, we determined EECs for 10 pyDOMs, 6 natural organic matter (NOM) samples, and 2 model quinones. The two methods gave similar EECs for model quinones, but SWV gave larger EECs than MCA for NOM and pyDOM (by several-fold and 1-2 orders of magnitude, respectively). The differences in the EECs obtained by SWV and MCA likely are due to multiple factors, including the potential range of electrons sampled, kinetics of electron transfer from (macro)molecular structures, and coupling of electron and proton transfer steps. Comparison of the results obtained by these two methods should provide new insights into important environmental processes such as carbon-cycling, wildfire recovery, and contaminant mitigation using carbon-based amendments.

Computational Predictions of the Hydrolysis of 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN).

Hydrolysis is a common transformation reaction that can affect the environmental fate of many organic compounds. In this study, three proposed mechanisms of alkaline hydrolysis of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroaniline (DNAN) were investigated with plane-wave density functional theory (DFT) combined with ab initio and classical molecular dynamics (AIMD/MM) free energy simulations, Gaussian basis set DFT calculations, and correlated molecular orbital theory calculations. Most of the computations in this study were carried out using the Arrows web-based tools. For each mechanism, Meisenheimer complex formation, nucleophilic aromatic substitution, and proton abstraction reaction energies and activation barriers were calculated for the reaction at each relevant site. For TNT, it was found that the most kinetically favorable first hydrolysis steps involve Meisenheimer complex formation by attachment of OH- at the C1 and C3 arene carbons and proton abstraction from the methyl group. The nucleophilic aromatic substitution reactions at the C2 and C4 arene carbons were found to be thermodynamically favorable. However, the calculated activation barriers were slightly lower than in previous studies, but still found to be ΔG‡ ≈ 18 kcal/mol using PBE0 AIMD/MM free energy simulations, suggesting that the reactions are not kinetically significant. For DNAN, the barriers of nucleophilic aromatic substitution were even greater (ΔG‡ > 29 kcal/mol PBE0 AIMD/MM). The most favorable hydrolysis reaction for DNAN was found to be a two-step process in which the hydroxyl first attacks the C1 carbon to form a Meisenheimer complex at the C1 arene carbon C1-(OCH3)OH-, and subsequently, the methoxy anion (-OCH3) at the C1 arene carbon dissociates and the proton shuttles from the C1-OH to the dissociated methoxy group, resulting in methanol and an aryloxy anion.

Generation of Reactive Oxygen Species and Degradation of Pollutants in the Fe2+/O2/Tripolyphosphate System: Regulated by the Concentration Ratio of Fe2+ and Tripolyphosphate.

Tripolyphosphate (TPP) has many advantages as a ligand for the optimization of the Fe2+/O2 system in environmental remediation applications. However, the relationship between remediation performance and the Fe2+/TPP ratio in the system has not been previously described. In this study, we report that the degradation mechanism of p-nitrophenol (PNP) in Fe2+/O2 systems is regulated by the Fe2+/TPP ratio under neutral conditions. The results showed that although PNP was effectively degraded at different Fe2+/TPP ratios, the results of specific reactive oxygen species (ROS) scavenging experiments and the determination of PNP degradation products showed that the mechanism of PNP degradation varies with the Fe2+/TPP ratio. When CFe2+ ≥ CTPP, the initially formed O2•- is converted to •OH and the •OH degrades PNP by oxidation. However, when CFe2+ < CTPP, the O2•- persists long enough to degrade PNP by reduction. Density functional theory (DFT) calculations revealed that the main reactive species of Fe2+ in the system include [Fe(TPP)(H2O)3]- and [Fe(TPP)2]4-, whose content in the solution is the key to achieve system regulation. Consequently, by controlling the Fe2+/TPP ratio in the solution, the degradation pathways of PNP can be selected. Our study proposed a new strategy to regulate the oxidation/reduction removal of pollutants by simply varying the Fe2+/TPP ratio of the Fe2+/O2 system.

Fe(II) Redox Chemistry in the Environment.

Iron (Fe) is the fourth most abundant element in the earth's crust and plays important roles in both biological and chemical processes. The redox reactivity of various Fe(II) forms has gained increasing attention over recent decades in the areas of (bio) geochemistry, environmental chemistry and engineering, and material sciences. The goal of this paper is to review these recent advances and the current state of knowledge of Fe(II) redox chemistry in the environment. Specifically, this comprehensive review focuses on the redox reactivity of four types of Fe(II) species including aqueous Fe(II), Fe(II) complexed with ligands, minerals bearing structural Fe(II), and sorbed Fe(II) on mineral oxide surfaces. The formation pathways, factors governing the reactivity, insights into potential mechanisms, reactivity comparison, and characterization techniques are discussed with reference to the most recent breakthroughs in this field where possible. We also cover the roles of these Fe(II) species in environmental applications of zerovalent iron, microbial processes, biogeochemical cycling of carbon and nutrients, and their abiotic oxidation related processes in natural and engineered systems.

Advances in metal(loid) oxyanion removal by zerovalent iron: Kinetics, pathways, and mechanisms.

Metal(loid) oxyanions in groundwater, surface water, and wastewater can have harmful effects on human or ecological health due to their high toxicity, mobility, and lack of degradation. In recent years, the removal of metal(loid) oxyanions using zerovalent iron (ZVI) has been the subject of many studies, but the full scope of this literature has not been systematically reviewed. The main elements that form metal(loid) oxyanions under environmental conditions are Cr(VI), As(V and III), Sb(V and III), Tc(VII), Re(VII), Mo(VI), V(V), etc. The removal mechanisms of metal(loid) oxyanions by ZVI may involve redox reactions, adsorption, precipitation, and coprecipitation, usually with one of these mechanisms being the main reaction pathway and the other playing auxiliary roles. However, the removal mechanisms are coupled to the reactions involved in corrosion of Fe(0) and reaction conditions. The layer of iron oxyhydroxides that forms on ZVI during corrosion mediates the sequestration of metal(loid) oxyanions. This review summarizes most of the currently available data on mechanisms and performance (e.g., kinetics) of removal of the most widely studies metal(loid) oxyanion contaminants (Cr, As, Sb) by different types of ZVI typically used in wastewater treatment, as well as ZVI that has been sulfidated or combination with catalytic bimetals.

Abiotic Transformation of Nitrobenzene by Zero Valent Iron under Aerobic Conditions: Relative Contributions of Reduction and Oxidation in the Presence of Ethylene Diamine Tetraacetic Acid.

Zero valent iron (ZVI) applications to remediation of shallow groundwaters can be affected by dissolved oxygen (DO) and organic ligands. To explore the intersection between these complicating factors, this study thoroughly characterized the reactions of nitrobenzene (NB) with ZVI in the presence DO and the model ligand ethylene diamine tetraacetic acid (EDTA). The results showed that NB is degraded by both ZVI reduction and ZVI-induced advanced oxidation under oxygen-limited conditions. The contribution of ·OH to the degradation of NB increased with time so that nearly 39% of NB was oxidized by ·OH at 15 min (pH = 3), but reduction was still the main pathway of NB transformation throughout. NB reduction products, such as aniline (AN), were also oxidized by ·OH. The lower the pH, the greater the contribution of advanced oxidation, but DO was the limiting factor for ·OH generation. Only 4.7% NB was fully degraded by ring opening and/or mineralization because the production of •OH was limited by low DO. After the transformation of NB and AN, other benzene ring and nitrogen-containing intermediates were identified (e.g., p-nitrophenol, p-aminophenol, hydroquinone, and p-benzoquinone). The removal of total organic carbon and total organic nitrogen was minimal. The results suggested that the relative doses of ZVI, DO, and iron-complexing ligands can be balanced for the optimal (rapid and deep) removal of organic contaminants.

FeNX(C)-Coated Microscale Zero-Valent Iron for Fast and Stable Trichloroethylene Dechlorination in both Acidic and Basic pH Conditions.

FeNX in Fe single-atom catalysts can be the active site for adsorption and activation of reactants. In addition, FeNX species have been shown to facilitate electron transfer between Fe and the carbon supports used in newly developed metal-air batteries. We hypothesized that the combination of FeNX species with granular zero-valent iron (ZVI) might result in catalyzed reductive decontamination of groundwater contaminants such as trichloroethylene (TCE). Here, such materials synthesized by ball milling microscale ZVI with melamine and the resulting N species were mainly in the form of pyridinic, pyrrolic, and graphitic N. This new material (abbreviated as N-C-mZVIbm) dechlorinated TCE at higher rates than bare mZVIbm (about 3.5-fold) due to facilitated electron transfer through (or around) the surface layer of iron oxides by the newly formed Fe-NX(C). N-C-mZVIbm gave higher kTCE (0.4-1.14 day-1) than mZVIbm (0-0.4 day-1) over a wide range of pH values (4-11). Unlike most ZVI systems, kTCE for N-C-mZVIbm increased with increasing pH values. This is because the oxide layer that passivates Fe0 at a high pH is disrupted by Fe-NX(C) formed on N-C-mZVIbm, thereby allowing TCE dechlorination and HER under basic conditions. Serial respike experiments gave no evidence of decreased performance of N-C-mZVIbm, showing that the advantages of this material might remain under field applications.

Quantitative structure activity relationships (QSARs) and machine learning models for abiotic reduction of organic compounds by an aqueous Fe(II) complex.

Due to the increasing diversity of organic contaminants discharged into anoxic water environments, reactivity prediction is necessary for chemical persistence evaluation for water treatment and risk assessment purposes. Almost all quantitative structure activity relationships (QSARs) that describe rates of contaminant transformation apply only to narrowly-defined, relatively homogenous families of reactants (e.g., dechlorination of alkyl halides). In this work, we develop predictive models for abiotic reduction of 60 organic compounds with diverse reducible functional groups, including nitroaromatic compounds (NACs), aliphatic nitro-compounds (ANCs), aromatic N-oxides (ANOs), isoxazoles (ISXs), polyhalogenated alkanes (PHAs), sulfoxides and sulfones (SOs), and others. Rate constants for their reduction were measured using a model reductant system, Fe(II)-tiron. Qualitatively, the rates followed the order NACs > ANOs ≈ ISXs ≈ PHAs > ANCs > SOs. To develop QSARs, both conventional chemical descriptor-based and machine learning (ML)-based approaches were investigated. Conventional univariate QSARs based on a molecular descriptor ELUMO (energy of the lowest-unoccupied molecular orbital) gave good correlations within classes. Multivariate QSARs combining ELUMO with Abraham descriptors for physico-chemical properties gave slightly improved correlations within classes for NCs and NACs, but little improvement in correlation within other classes or among classes. The ML model obtained covers reduction rates for all classes of compounds and all of the conditions studied with the prediction accuracy similar to those of the conventional QSARs for individual classes (r2 = 0.41-0.98 for univariate QSARs, 0.71-0.94 for multivariate QSARs, and 0.83 for the ML model). Both approaches required a scheme for a priori classification of the compounds for model training. This work offers two alternative modeling approaches to comprehensive abiotic reactivity prediction for persistence evaluation of organic compounds in anoxic water environments.

Sulfidation of Zero-Valent Iron by Direct Reaction with Elemental Sulfur in Water: Efficiencies, Mechanism, and Dechlorination of Trichloroethylene.

Sulfidation can enhance both the reactivity and selectivity (i.e., electron efficiency, εe) of zero-valent iron (ZVI) in contaminant removal, which may make this technology cost-effective for a wider range of water treatment applications. However, current sulfidation methods involve either hazardous or unstable sulfidation agents (e.g., Na2S, Na2S2O3, and Na2S2O4) or energy-intensive preparations (e.g., mechanochemical sulfidation with elemental sulfur). In this study, we demonstrate that very efficient sulfidation of microscale ZVI (mZVI) can be achieved at all S/Fe molar ratios (∼100% sulfidation efficiency, εs) simply by direct reaction between elemental sulfur (S0) and ZVI in an aqueous suspension at ambient temperature. In comparison, the εs values obtained using Na2S, Na2S2O3, or Na2S2O4 as the sulfidation agents were only ∼23, ∼75, and ∼38%, respectively. The sulfidated mZVI produced using the new method reacts with trichloroethylene (TCE) with very high rates and electron efficiencies: rate constants and electron efficiencies were 800- and 79-fold higher than those of the unsulfidated mZVI. The enhanced performance of this material, together with the operational advantages of S0 for sulfidation (including safety, stability, and cost), may make it a desirable product for full-scale engineering applications.

Role of complexation in the photochemical reduction of chromate by acetylacetone.

Organic ligands can alter the redox behavior of metal species through the generation of metal-ligand complexes. Photo-induced complexation between ligands and metals is an important, but under-appreciated, aspect of process. Acetylacetone (AA) is a good chelating agent due to keto-enol tautomerization. In the presence of AA, photoreduction of Cr(VI) is accelerated; however, it is unclear exactly how complexation is involved in UV/AA mediated Cr(VI) reduction. On the basis of spectral and kinetic analyses, this study shows that the formation of {Cr(VI)-AA}* complexes is the main mechanism of Cr(VI) reduction by UV/AA. Evidence for this includes (1) the formation rate constant of Cr(III)-AA complexes in the UV system was 2-3 orders of magnitude greater than that in the thermal system; (2) there was a linear relationship between the photons absorbed by AA and the reduction rate constants of Cr(VI); and (3) the reaction appeared initially zero-order in Cr(VI) and turned to first-order as the pool of available Cr(VI) ran out. The results presented here are not only important for the better understanding of the complexation effects in the reduction of Cr(VI), but also crucial for the possible application of the UV/AA process in many other scenarios.

Quantifying the efficiency and selectivity of organohalide dechlorination by zerovalent iron.

The efficiency and selectivity of zerovalent iron-based treatments for organohalide contaminated groundwater can be quantified by accounting for redistribution of electrons derived from oxidation of Fe0. Several types of efficiency are reviewed, including (i) the efficiency of Fe(0) utilization, εFe(0), (ii) the electron efficiency of target contaminant reduction, εe, and (iii) the electron efficiency of natural reductant demand (NRD) involving H2O, O2, and co-contaminants such as nitrate, εNRD. Selectivity can then be calculated by using εe/εNRD. Of particular interest is εe and the key to its determination is measuring the total quantity of electrons provided by Fe0 oxidation, which can be based on either the loss of Fe(0), the formation of Fe(ii)/Fe(iii), or the composition of the total reaction products. Recently, many data have accumulated on εe for the treatment of various chlorinated solvents (esp. trichloroethylene, TCE) by zerovalent iron (ZVI), and analysis of these data shows that ZVI particle properties (e.g., stabilization with polymers, bimetallic modification, sulfidation, etc.) and other operational factors have variable effects on εe. Of particular interest is that pre-exposure of ZVI to reduced sulfur species (i.e., sulfidation) consistently improves the εe of contaminant reduction, mainly by suppressing the reduction of water.

Reduction of 1,2,3-trichloropropane (TCP): pathways and mechanisms from computational chemistry calculations.

The characteristic pathway for degradation of halogenated aliphatic compounds in groundwater or other environments with relatively anoxic and/or reducing conditions is reductive dechlorination. For 1,2-dihalocarbons, reductive dechlorination can include hydrogenolysis and dehydrohalogenation, the relative significance of which depends on various structural and energetic factors. To better understand how these factors influence the degradation rates and products of the lesser halogenated hydrocarbons (in contrast to the widely studied per-halogenated hydrocarbons, like trichloroethylene and carbon tetrachloride), density functional theory calculations were performed to compare all of the possible pathways for reduction and elimination of 1,2,3-trichloropropane (TCP). The results showed that free energies of each species and reaction step are similar for all levels of theory, although B3LYP differed from the others. In all cases, the reaction coordinate diagrams suggest that ß-elimination of TCP to allyl chloride followed by hydrogenolysis to propene is the thermodynamically favored pathway. This result is consistent with experimental results obtained using TCP, 1,2-dichloropropane, and 1,3-dichloropropane in batch experiments with zerovalent zinc (Zn0, ZVI) as a reductant.

Electrochemical characterization of natural organic matter by direct voltammetry in an aprotic solvent.

The complex and indeterminant composition of NOM makes characterization of its redox properties challenging. Approaches that have been taken to address this challenge include chemical probe reactions, potentiometric titrations, chronocoulometry, and voltammetry. In this study, we revisit the use of direct voltammetric methods in aprotic solvents by applying an expanded and refined suite of methods to a large set of NOM samples and model compounds (54 NOM samples from 10 different sources, 7 NOM model compounds, and 2 fresh extracts of plant materials that are high in redox-active quinonoid model compounds dissolved in DMSO). Refinements in the methods of fitting the data obtained by staircase cyclic voltammetry (SCV) provided improved definition of peaks, and square wave voltammetry (SWV), performed under the same conditions as SCV, provided even more reliable identification and quantitation of peaks. Further evidence is provided that DMSO improves the electrode response by unfolding some of the tertiary structure of NOM polymers, thereby allowing greater contact between redox active functional groups and the electrode surface. We averaged experimental peak potentials for all NOM compounds and calculated potentials in water. Average values for Epa1, Epc1, and Ep1 in DMSO were -0.866 ± 0.069, -1.35 ± 0.071, and -0.831 ± 0.051 V vs. Ag/Ag+, and -0.128, -0.613, and -0.0930 V vs. SHE in water. In addition to peak potentials, the breadth of SCV peaks was quantified as a way to characterize the degree to which the redox activity of NOM is due to a continuum of contributing functional groups. The average breadth values were 1.63 ± 0.24, 1.28 ± 0.34, and 0.648 ± 0.15 V for Epa1, Epc1, and Ep1 respectively. Comparative analysis of the overall dataset-from SCV and SWV on all NOMs and model compounds-revealed that NOM redox properties vary over a narrower range than expected based on model compound properties. This lack of diversity in redox properties of NOM is similar to conclusions from other recent work on the molecular structure of NOM, all of which could be the result of selectivity in the common extraction methods used to obtain the materials.