Highly selective molecular sieving of cis- over trans-1,2-dichloroethene isomers.

An intrinsically porous trianglimine macrocycle 1 is reported to display energy-efficient and cost-effective adsorptive properties by selectively separating cis-1,2-dichloroethene (cis-DCE) from an equimolar cis- and trans-DCE mixture with a purity of over 96%. The selectivity is enhanced by host/guest C-H⋯π intermolecular interactions. Moreover, the macrocycle can be reused many times without any decrease in performance, which further supports the sustainability of using molecular sieves in chemical separation.

Groundwater geochemical constituents controlling the reductive dechlorination of TCE by nZVI: Evidence from diverse anaerobic corrosion mechanisms of nZVI.

The corrosion mechanisms of nanoscale zero-valent iron (nZVI) vary with different geochemical constituents, which affect the reductive dechlorination process of trichloroethylene (TCE). In this study, the effect of nZVI anaerobic corrosion on the reductive dechlorination of TCE with different groundwater geochemical constituents (Ca2+-SO42-, Ca2+-HCO3-, Na+-NO3-) was investigated. Microscopic characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM) combined with pH, oxidation-reduction potential (ORP) and dissolved Fe2+ in solutions to illustrate the corrosion mechanism of nZVI. In the four systems including ultrapure water (UPW), the reduction of TCE conformed to pseudo-first-order kinetics, the generation of Cl- accorded with zero-order kinetics, and multi-step reaction kinetics was used to fit the generation and degradation of chlorinated byproducts (Dichloroethylene, DCEs). Compared with UPW system, the dissolution corrosion of Ca2+-HCO3- and Ca2+-SO42- promoted the reductive dechlorination of TCE (kobs, TCE = 0.658 ± 0.010 & 0.245 ± 0.028 d-1 and kobs, Cl- = 41.682 ± 1.016 & 20.623 ± 1.923 µM⋅d-1 for Ca2+-HCO3- & Ca2+-SO42-, respectively) and the degradation of DCEs (0.444 ± 0.036 & 0.244 ± 0.040 µM⋅d-1 for Ca2+-HCO3- & Ca2+-SO42-, respectively); redox-active NO3- competed for electrons and passivated the surface of nZVI, which limited the reductive dechlorination of TCE (kobs, TCE = 0.111 ± 0.025 d-1 & kobs, Cl- = 14.943 ± 0.664 µM⋅d-1) and the degradation of DCEs (0.078 ± 0.018 µM⋅d-1), and the passivation layer promoted the adsorption of TCE. This study from the perspective of nZVI corrosion provides a theoretical basis for the long-term application of nZVI technology in the remediation of TCE-contaminated sites with different groundwater geochemical types.

Impact of iron- and/or sulfate-reduction on a cis-1,2-dichloroethene and vinyl chloride respiring bacterial consortium: experiments and model-based interpretation.

Process understanding of microbial communities containing organohalide-respiring bacteria (OHRB) is important for effective bioremediation of chlorinated ethenes. The impact of iron and sulfate reduction on cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) dechlorination by a consortium containing the OHRB Dehalococcoides spp. was investigated using multiphase batch experiments. The OHRB consortium was found to contain endogenous iron- and sulfate-reducing bacteria (FeRB and SRB). A biogeochemical model was developed and used to quantify the mass transfer, aquatic geochemical, and microbial processes that occurred in the multiphase batch system. It was determined that the added SRB had the most significant impact on contaminant degradation. Addition of the SRB increased maximum specific substrate utilization rates, kmax, of cDCE and VC by 129% and 294%, respectively. The added FeRB had a slight stimulating effect on VC dechlorination when exogenous SRB were absent, but when cultured with the added SRB, FeRB moderated the SRB's stimulating effect. This study demonstrates that subsurface microbial community interactions are more complex than categorical, guild-based competition for resources such as electron donor.

Preparation of 4'-Spirocyclobutyl Nucleoside Analogues as Novel and Versatile Adenosine Scaffolds.

Despite the large variety of modified nucleosides that have been reported, the preparation of constrained 4'-spirocyclic adenosine analogues has received very little attention. We discovered that the [2+2]-cycloaddition of dichloroketene on readily available 4'-exo-methylene furanose sugars efficiently results in the diastereoselective formation of novel 4'-spirocyclobutanones. The reaction mechanism was investigated via density functional theory (DFT) and found to proceed either via a non-synchronous or stepwise reaction sequence, controlled by the stereochemistry at the 3'-position of the sugar substrate. The obtained dichlorocyclobutanones were converted into nucleoside analogues, providing access to a novel class of chiral 4'-spirocyclobutyl adenosine mimetics in eight steps from commercially available sugars. Assessment of the biological activity of designed 4'-spirocyclic adenosine analogues identified potent inhibitors for protein methyltransferase target PRMT5.

Characterization of hydrosoluble fraction and oligomers in poly(vinylidene chloride) latexes by capillary electrophoresis using electrophoretic mobility modeling.

The characterization of hydrosoluble oligomers in latexes is an important topic in emulsion polymerization since oligomers are suspected to be responsible for latex destabilization. In this work, the hydrosoluble fraction of poly(vinylidene chloride) latexes synthesized by emulsion polymerization of three monomers (acrylic acid, methyl acrylate, vinylidene chloride) was characterized by capillary electrophoresis (CE). CE using direct UV detection permitted to estimate residual monomers and surfactants concentrations contained in the latexes serums. Water soluble oligomers, polymerization initiator (persulfate) and other inorganic anions were detected by indirect UV detection. The oligomers content in the dry extract of serum was estimated to be about 6% (% m/m) represented mainly by 9 different compounds belonging to 3 different families. Using a semi-empirical electrophoretic mobility modeling, the charge number of these oligomers was estimated to be -2 and the molar masses were estimated in the range of ∼300-550 g.mol-1. Oligomer samples obtained by surfactant-free polymerization, with different initial monomers proportions, provided qualitatively 14 different oligomers, including the 9 oligomers previously detected in the serums. Finally, the latex was characterized (electrophoretic mobility and zeta potential) using its serum as a background electrolyte. This approach could be very useful to study the behavior of the latexes, and possibly destabilization effect, in analytical conditions very close to its real environment / applications.

Photoionization dynamics of cis-dichloroethene from investigation of vibrationally resolved photoelectron spectra and angular distributions.

The influence of vibronic coupling on the outer valence ionic states of cis-dichloroethene has been investigated by recording photoelectron spectra over the excitation range 19-90 eV using plane polarized synchrotron radiation, for two polarization orientations. The photoelectron anisotropy parameters and electronic state branching ratios derived from these spectra have been compared to theoretical predictions obtained with the continuum multiple scattering approach. This comparison shows that the photoionization dynamics of the Ã2B2, B̃2A1, C̃2A2, and D̃2B1 states, all of which are formed through the ejection of an electron from a nominally chlorine lone-pair orbital, exhibit distinct evidence of the Cooper minimum associated with the halogen atom. While retaining a high degree of atomic character, these orbital ionizations nevertheless display clear distinctions. Simulations, assuming the validity of the Born-Oppenheimer and the Franck-Condon approximations, of the X̃2B1, Ã2B2, and D̃2B1 state photoelectron bands have allowed some of the vibrational structure observed in the experimental spectra to be assigned. The simulations provide a very satisfactory interpretation for the X̃2B1 state band but appear less successful for the Ã2B2 and D̃2B1 states, with irregularities appearing in both. The B̃2A1 and C̃2A2 state photoelectron bands exhibit very diffuse and erratic profiles that cannot be reproduced at this level. Photoelectron anisotropy parameters, ß, have been evaluated as a function of binding energy across the studied photon energy range. There is a clear step change in the ß values of the Ã2B2 band at the onset of the perturbed peak intensities, with ß evidently adopting the value of the B̃2A1 band ß. The D̃2B1 band ß values also display an unexpected vibrational level dependence, contradicting Franck-Condon expectations. These various behaviors are inferred to be a consequence of vibronic coupling in this system.

An experimental and theoretical study of the photoelectron spectra of cis-dichloroethene: Valence shell vertical ionization and vibronic coupling in the low-lying cationic states.

The valence shell photoelectron spectrum of cis-dichloroethene has been studied both experimentally and theoretically. Photoelectron spectra have been recorded with horizontally and vertically plane polarized synchrotron radiation, thereby allowing the anisotropy parameters, characterizing the angular distributions, to be determined. The third-order algebraic-diagrammatic construction approximation scheme for the one-particle Green's function has been employed to compute the complete valence shell ionization spectrum. In addition, the vertical ionization energies have been calculated using the outer valence Green's function (OVGF) method and the equation-of-motion coupled-cluster, with single and double substitutions for calculating ionization potentials (EOM-IP-CCSD) model. The theoretical results have enabled assignments to be proposed for most of the structure observed in the experimental spectra, including the inner-valence regions dominated by satellite states. The linear vibronic coupling model has been employed to study the vibrational structure of the lowest photoelectron bands, using parameters obtained from ab initio calculations. The ground state optimized geometries and vibrational frequencies have been computed at the level of the second-order Møller-Plesset perturbation theory, and the dependence of the ionization energies on the nuclear configuration has been evaluated using the OVGF method. While the adiabatic approximation holds for the X̃2B1 state photoelectron band, the Ã2B2, B̃2A1, and C̃2A2 states interact vibronically and form a complex photoelectron band system with four distinct maxima. The D̃2B1 and Ẽ2B2 states also interact vibronically with each other. The potential energy surface of the D̃2B1 state is predicted to have a double-minimum shape with respect to the out-of-plane a2 deformations of the molecular structure. The single photoelectron band resulting from this interaction is characterized by a highly irregular structure, reflecting the non-adiabatic nuclear dynamics occurring on the two coupled potential energy surfaces forming a conical intersection close to the minimum of the Ẽ2B2 state.

Evidence of rock matrix back-diffusion and abiotic dechlorination using a field testing approach.

An in situ field demonstration was performed in fractured rock impacted with trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) to assess the impacts of contaminant rebound after removing dissolved contaminants within hydraulically conductive fractures. Using a bedrock well pair spaced 2.4m apart, TCE and DCE were first flushed with water to create a decrease in dissolved contaminant concentrations. While hydraulically isolating the well pair from upgradient contaminant impacts, contaminant rebound then was observed between the well pair over 151days. The magnitude, but not trend, of TCE rebound was reasonably described by a matrix back-diffusion screening model that employed an effective diffusion coefficient and first-order abiotic TCE dechlorination rate constant that was based on bench-scale testing. Furthermore, a shift in the TCE:DCE ratio and carbon isotopic enrichment was observed during the rebound, suggesting that both biotic and abiotic dechlorination were occurring within the rock matrix. The isotopic data and back-diffusion model together served as a convincing argument that matrix back-diffusion was the mechanism responsible for the observed contaminant rebound. Results of this field demonstration highlight the importance and applicability of rock matrix parameters determined at the bench-scale, and suggest that carbon isotopic enrichment can be used as a line of evidence for abiotic dechlorination within rock matrices.

Enhanced reductive de-chlorination of a solvent contaminated aquifer through addition and apparent fermentation of cyclodextrin.

In a field study, aqueous cyclodextrin (CD) was investigated for its ability to extract chlorinated volatile organic compounds (cVOC), such as trichloroethylene (TCE), 1,1,1-trichloroethane (TCA), and dichloroethene (DCE) through in-situ flushing of a sandy aquifer. After cessation of aquifer flushing, a plume of CD was left. Changes in CD, cVOC, and inorganic terminal electron acceptors (TEAs) (DO, nitrate, sulfate, iron) were monitored in four rounds of wellwater sampling (20, 210, 342, and 425days after cessation of active pumping). Post-CD flushing VOC levels rebounded (850% for TCE, 190% for TCA, and 53% for DCE) between the first two sampling rounds, apparently due to rate-limited desorption from aquifer media and dissolution from remaining NAPL. However, substantial reduction in the mass of TCE (6.3 to 0.11mol: 98%) and TCA (2.8 to 0.73mol: 74%) in groundwater was observed between 210 and 425days. DCE should primarily be produced from the degradation of TCE and is expected to subsequently degrade to chloroethene. Since DCE levels decreased only slightly (0.23 to 0.17mol: 26%), its degradation rate should be similar to that produced from the decaying TCE. Cyclodextrin was monitored starting from day 210. The mass of residual CD (as measured by Total Organic Carbon) decreased from 150mol (day 210) to 66 (day 425) (56% decrease). The naturally anaerobic zone within the aquifer where residual CD mass decreased coincided with a loss of other major potential TEAs: nitrate (97% loss), sulfate (31%) and iron (31%). In other studies, TCE and 1,1,1-TCA have been found to be more energetically favorable TEAs than sulfate and iron and their degradation via reductive dechlorination has been found to be enhanced by the fermentation of carbohydrates. Such processes can explain these observations, but more investigation is needed to evaluate whether residual levels of CD can facilitate the anaerobic degradation of chlorinated VOCs.

Predictive QSAR Models for the Toxicity of Disinfection Byproducts.

Several hundred disinfection byproducts (DBPs) in drinking water have been identified, and are known to have potentially adverse health effects. There are toxicological data gaps for most DBPs, and the predictive method may provide an effective way to address this. The development of an in-silico model of toxicology endpoints of DBPs is rarely studied. The main aim of the present study is to develop predictive quantitative structure-activity relationship (QSAR) models for the reactive toxicities of 50 DBPs in the five bioassays of X-Microtox, GSH+, GSH-, DNA+ and DNA-. All-subset regression was used to select the optimal descriptors, and multiple linear-regression models were built. The developed QSAR models for five endpoints satisfied the internal and external validation criteria: coefficient of determination (R²) > 0.7, explained variance in leave-one-out prediction (Q²LOO) and in leave-many-out prediction (Q²LMO) > 0.6, variance explained in external prediction (Q²F1, Q²F2, and Q²F3) > 0.7, and concordance correlation coefficient (CCC) > 0.85. The application domains and the meaning of the selective descriptors for the QSAR models were discussed. The obtained QSAR models can be used in predicting the toxicities of the 50 DBPs.

Synthesis and Evaluation of Molybdenum and Tungsten Monoaryloxide Halide Alkylidene Complexes for Z-Selective Cross-Metathesis of Cyclooctene and Z-1,2-Dichloroethylene.

Molybdenum complexes with the general formula Mo(NR)(CHR')(OR″)(Cl)(MeCN) (R = t-Bu or 1-adamantyl; OR″ = a 2,6-terphenoxide) recently have been found to be highly active catalysts for cross-metathesis reactions between Z-internal olefins and Z-1,2-dichloroethylene or Z-(CF3)CH═CH(CF3). In this paper we report methods of synthesizing new potential catalysts with the general formula M(NR)(CHR')(OR″)(Cl)(L) in which M = Mo or W, NR = N-2,6-diisopropylphenyl or NC6F5, and L is a phosphine, a pyridine, or a nitrile. We also test and compare all catalysts in the cross-metathesis of Z-1,2-dichloroethylene and cyclooctene. Our investigations indicate that tungsten complexes are inactive in the test reaction either because the donor is bound too strongly or because acetonitrile inserts into a W═C bond. The acetonitrile or pivalonitrile Mo(NR)(CHR')(OR″)(Cl)(L) complexes are found to be especially reactive because the 14e Mo(NR)(CHR')(OR″)Cl core is accessible through dissociation of the nitrile to a significant extent. Pivalonitrile can be removed (>95%) from Mo(NAr)(CHCMe2Ph)(OHMT)(Cl)(t-BuCN) (Ar = 2,6-diisopropylphenyl; OHMT = 2,6-dimesitylphenoxide) to give 14e Mo(NAr)(CHCMe2Ph)(OHMT)Cl in solution as a mixture of syn and anti (60:40 at 0.015 M) nitrile-free isomers, but these 14e complexes have not yet been isolated in pure form. The syn isomer of Mo(NAr)(CHCMe2Ph)(OHMT)Cl binds pivalonitrile most strongly. Other Mo(NR)(CHR')(OR″)(Cl)(L) complexes can be activated through addition of B(C6F5)3. High stereoselectivities (>98% Z,Z) of ClCH═CH(CH2)6CH═CHCl are not restricted to tert-butylimido or adamantylimido complexes; 96.2% Z selectivity is observed with boron-activated Mo(NC6F5)(CHR')(OHIPT)(Cl)(PPhMe2). So far no Mo═CHCl complexes, which are required intermediates in the test reaction, have been observed in NMR studies at room temperature.

Transformation of mackinawite to greigite by trichloroethylene and tetrachloroethylene.

Trichloroethylene (TCE) and tetrachloroethylene (PCE) are common ground water contaminants susceptible to reductive dechlorination by FeS (mackinawite) in anaerobic environments. The objective of this study was to characterize the mineral-associated products that form when mackinawite reacts with TCE and PCE. The dissolved products of the reaction included Cl- and Fe2+, and trace amounts of cis 1,2-dichloroethylene (for TCE) and TCE (for PCE). Selected area electron diffraction (SAED) analysis identified greigite as a mackinawite oxidation product formed after reaction between TCE or PCE and FeS over seven weeks. Release of Fe2+ is consistent with the solid state transformation of mackinawite to greigite, resulting in depletion of the solid with Fe. X-ray photoelectron spectroscopy of the sulfur 2p peak showed a shift to a higher binding energy after FeS reacted with TCE or PCE, also observed in other studies of mackinawite oxidation to greigite. The results may help efforts to maintain the reactivity of FeS generated to remediate chlorinated aliphatic contaminants in ground water.

Unraveling the Mechanism and Regioselectivity of the B12-Dependent Reductive Dehalogenase PceA.

PceA is a cobalamin-dependent reductive dehalogenase that catalyzes the dechlorination of perchloroethylene to trichloroethylene and then to cis-dichloroethylene as the sole final product. The reaction mechanism and the regioselectivity of this enzyme are investigated by using density functional calculations. Four different substrates, namely, perchloroethylene, trichloroethylene, cis-dichloroethylene, and chlorotheylene, have been considered and were found to follow the same reaction mechanism pattern. The reaction starts with the reduction of Co(II) to Co(I) through a proton-coupled electron transfer process, with the proton delivered to a Tyr246 anion. This is followed by concerted C-Cl bond heterolytic cleavage and proton transfer from Tyr246 to the substrate carbon atom, generating a Co(III) -Cl intermediate. Subsequently, a one-electron transfer leads to the formation of the Co(II) -Cl product, from which the chloride and the dehalogenated product can be released from the active site. The substrate reactivity follows the trend perchloroethylene>trichloroethylene≫cis-dichloroethylene≫chlorotheylene. The barriers for the latter two substrates are significantly higher compared with those for perchloroethylene and trichloroethylene, implying that PceA does not catalyze their degradation. In addition, the formation of cis-dichloroethylene has a lower barrier by 3.8 kcal mol(-1) than the formation of trans-dichloroethylene and 1,1-dichloroethylene, reproducing the regioselectivity. These results agree quite well with the experimental findings, which show cis-dichloroethylene as the sole product in the PceA-catalyzed dechlorination of perchloethylene and trichloroethylene.

[Sorption Characteristics of Phenanthrene and 1, 1-Dichloroethene onto Reed Straw Biochar in Aquatic Solutions].

The purpose of this study was to investigate the sorption characteristics of phenanthrene (PHE) and 1, 1-dichloroethene (1, 1-DCE) onto reed straw biochar at 500 degrees C in aquatic solutions. The sorption mechanisms and effects of solution pH and biochar mass on sorption intensity were discussed. The results showed that the time required to reach sorption equilibrium was 60 min and 480 min for PHE and 1, 1-DCE, respectively, with maximum removal rates of 81, 87% and 90.18%. The sorption kinetics of both PHE and 1, 1-DCE fitted the pseudo-second-order model well, but the pseudo-second-order reaction rate of PHE was higher than that of 1, 1-DCE. Furthermore, the sorption processes were controlled by both membrane diffusion and intra-particle diffusion, and the latter was found to be the rate-controlling step. Sorption isotherms of the two organic pollutants fitted well with the Freundlich equation, and the sorption affinity of 1, 1-DCE onto biochar was greater than that of PHE. The total sorption mechanism of biochar was the combination of partition and adsorption, and dominated by adsorption. The adsorption capacity of 1, 1-DCE was greater than that of PHE, but its partition capacity was much smaller, indicating that pollutants' molecular volume and relative polarity would mainly affect the total sorption. Analysis of Fourier transform infrared spectroscopy (FTIR) demonstrated that oxygen- and hydrogen-containing functional groups and pi--pi interaction were important for PHE and 1, 1-DCE sorption onto biochar. The solution pH value had no significant effect on the sorption intensity of PHE and 1, 1-DCE, however, with biochar mass increasing from 5 mg to 50 mg, the equilibrium sorption amount of PHE and 1, 1-DCE decreased by 6.78 times and 2.18 times, and the removal rate increased by 20.21% and 15.78%, respectively.

Hydrogen Isotope Exchange of Chlorinated Ethylenes in Aqueous Solution: Possibly a Termolecular Liquid Phase Reaction.

This work reports an experimental study of the hydrogen/deuterium exchange in the basic aqueous solutions of trichloroethylene, trans-1,2-dichloroethylene, and cis-1,2-dichloroethylene using (1)H NMR as a monitoring method. 1,1-Dichlorethylene was also investigated but found not to exchange hydrogen isotopes with water. The kinetics of isotope exchange features two different pathways, the first is first order with respect to hydroxide ion, whereas the second is second order. The first pathway is interpreted as a straightforward bimolecular reaction between chloroethylene and hydroxide ion, which leads to the deprotonation of chloroethylene. The second pathway involves a transition state with the association of one molecule of the chloroethylene and two hydroxide ions. It is shown that the second pathway could involve the formation of a precursor complex composed of one chloroethylene molecule and one hydroxide ion, but a direct termolecular elementary reaction is also feasible, which is shown by deriving a theoretical highest limit for the rate constants of termolecular reactions in solution.

Biodegradation of cis-1,2-Dichloroethene in Simulated Underground Thermal Energy Storage Systems.

Underground thermal energy storage (UTES) use has showed a sharp rise in numbers in the last decades, with aquifer thermal energy storage (ATES) and borehole thermal energy storage (BTES) most widely used. In many urban areas with contaminated aquifers, there exists a desire for sustainable heating and cooling with UTES and a need for remediation. We investigated the potential synergy between UTES and bioremediation with batch experiments to simulate the effects of changing temperature and liquid exchange that occur in ATES systems, and of only temperature change occurring in BTES systems on cis-DCE reductive dechlorination. Compared to the natural situation (NS) at a constant temperature of 10 °C, both UTES systems with 25/5 °C for warm and cold well performed significantly better in cis-DCE (cis-1,2-dichloroethene) removal. The overall removal efficiency under mimicked ATES and BTES conditions were respectively 13 and 8.6 times higher than in NS. Inoculation with Dehalococcoides revealed that their initial presence is a determining factor for the dechlorination process. Temperature was the dominating factor when Dehalococcoides abundance was sufficient. Stimulated biodegradation was shown to be most effective in the mimicked ATES warm well because of the combined effect of suitable temperature, sustaining biomass growth, and regular cis-DCE supply.

Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

Development of KMnO(4)-releasing composites for in situ chemical oxidation of TCE-contaminated groundwater.

The objective of this study was to develop a controlled-oxidant-release technology combining in situ chemical oxidation (ISCO) and permeable reactive barrier (PRB) concepts to remediate trichloroethene (TCE)-contaminated groundwater. In this study, a potassium permanganate (KMnO4)-releasing composite (PRC) was designed for KMnO4 release. The components of this PRC included polycaprolactone (PCL), KMnO4, and starch with a weight ratio of 1.14:2:0.96. Approximately 64% (w/w) of the KMnO4 was released from the PRC after 76 days of operation in a batch system. The results indicate that the released KMnO4 could oxidize TCE effectively. The results from a column study show that the KMnO4 released from 200 g of PRC could effectively remediate 101 pore volumes (PV) of TCE-contaminated groundwater (initial TCE concentration = 0.5 mg/L) and achieve up to 95% TCE removal. The effectiveness of the PRC system was verified by the following characteristics of the effluents collected after the PRC columns (barrier): (1) decreased TCE concentrations, (2) increased ORP and pH values, and (3) increased MnO2 and KMnO4 concentrations. The results of environmental scanning electron microscope (ESEM) analysis show that the PCL and starch completely filled up the pore spaces of the PRC, creating a composite with low porosity. Secondary micro-scale capillary permeability causes the KMnO4 release, mainly through a reaction-diffusion mechanism. The PRC developed could be used as an ISCO-based passive barrier system for plume control, and it has the potential to become a cost-effective alternative for the remediation of chlorinated solvent-contaminated groundwater.

Reactions of aromatic S- and O-enynes with two methyl substituents on the olefinic unit assisted by a ruthenium complex: tandem cyclization and product selectivity.

Ruthenium-assisted cyclizations of two enynes, HC≡CCH(OH)(C6H4)X-CH2CH=CMe2 (X=S (1a), O (1b)), each of which contains two terminal methyl substituents on the olefinic parts, are explored. The reaction of 1a in CH2Cl2 gives the vinylidene complex 2a from the first cyclization and two side products, 3a and the carbene complex 4a with a benzothiophene ligand. The same reaction in the presence of HBF4 affords 4a exclusively. Air oxidation of 4a in the presence of Et3N readily gives an aldehyde product. In MeOH, tandem cyclizations of 1a generate a mixture of the benzothiochromene compound 10a and the carbene complex 7a also with a benzothiochromene ligand. First, cyclization of 1b likewise proceeds in CH2Cl2 to give 2b. Tandem cyclization of 1b in MeOH yields comparable products 10b and 7b with benzochromene moieties, yet with no other side product. The reaction of [Ru]Cl with HC≡CCH(OH)(C6H4)S-CH2CH=CH2 (1c), which contains no methyl substituent in the olefinic part, in MeOH gives the carbene complex 15c with an unsubstituted thiochromene by means of a C-S bond formation. Structures of 3a and 15c are confirmed by X-ray diffraction analysis. The presence of methyl groups of enynes 1a and 1b promotes sequential cyclization reactions that involve C-C bond formation through carbocationic species.

pH impact on reductive dechlorination of cis-dichloroethylene by Fe precipitates: an X-ray absorption spectroscopy study.

The pH impact on reductive dechlorination of cis-dichloroethylene (cis-DCE) was investigated using in situ Fe precipitates formed under iron-rich sulfate-reducing conditions. The dechlorination rate of cis-DCE increased with pH, which was attributed to changes in the solid-phase Fe concentration, the composition of Fe minerals, and the surface speciation of Fe minerals. With increasing pH, larger quantities of Fe minerals, having much greater reactivity than dissolved Fe(II), were produced. Fe-K edge X-ray absorption spectroscopy (XAS) analysis of Fe precipitates revealed the presence of multiple Fe phases with their composition varying with pH. Correlation analyses were performed to examine how the solid-phase Fe concentration, the composition of Fe minerals, and their surface speciation were linked with the cis-DCE dechlorination rate. Such analyses revealed that neither mackinawite (FeS) nor magnetite (Fe3O4) was reactive with cis-DCE dechlorination, but that Fe (oxyhydr)oxides including green rusts and Fe(OH)2 were reactive. Based on a proposed model of the surface acidity of Fe minerals, the increasing deprotonated surface Fe(II) groups with pH correlated well with the enhanced cis-DCE dechlorination.