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Bioremediation of 1,1,1-trichloroethane (TCA) is more challenging than bioremediation of other chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). TCA transformation often occurs under methanogenic and sulfate-reducing conditions and is mediated by Dehalobacter. The source area at the project site contains moderately permeable medium sand with a low hydraulic gradient and is approximately 0.5 acre. TCA contamination generally extended to 35 feet, with the highest concentrations at approximately 20 feet. The concentrations then decreased with depth; several wells contained 300 to 600 mg/L of TCA prior to bioremediation. The area of treatment also contained 2 to 30 mg/L of TCE from an upgradient source. Initial site groundwater conditions indicated minimal biotic dechlorination and the presence of up to 20 mg/L of nitrate and 90 mg/L of sulfate. Microcosm testing indicated that TCA dechlorination was inhibited by the site's relatively low pH (5 to 5.5) and high TCA concentration. After the pH was adjusted and TCA concentrations were reduced to less than 35 mg/L (by dilution with site water), dechlorination proceeded rapidly using whey (or slower with sodium lactate) as an electron donor. Throughout the remediation program, increased resistance to TCA inhibition (from 35 to 200 mg/L) was observed as the microbes adapted to the elevated TCA concentrations. The article presents the results of a full-scale enhanced anaerobic dechlorination recirculation system and the successful efforts to eliminate TCA- and pH-related inhibition. © 2012 Wiley Periodicals, Inc.

Enhanced anaerobic dechlorination is being conducted to remediate a 50-acre groundwater area impacted with chlorinated volatile organic compounds (CVOCs). The plume, which is over 3,000 feet (ft) long, initially contained tetrachloroethene and breakdown products at concentrations of 2 to 3 milligrams per liter. The site's high groundwater flow velocity (greater than 1,000 ft per year) was incorporated into the design to help with amendment distribution. Bioaugmentation was conducted using a mixed culture containing Dehalococcoides ethenogenes. There is evidence that it has migrated to distances exceeding 600 ft. The major benefit of the high groundwater flow velocity is greater areal coverage by the remediation system, but the downside is the difficulty in delivering sufficient donor to create the required anaerobic conditions. Overall performance has been excellent with total CVOC reductions and conversion to ethene of 98 percent within a 25-acre area downgradient of the treatment transect that has operated the longest. © 2011 Wiley Periodicals, Inc.

Kinetic studies reported here have shown that acetylene is a potent reversible inhibitor of reductive dehalogenation of trichloroethene (TCE) and vinyl chloride (VC) by a mixed dehalogenating anaerobic culture. The mixed culture was enriched from a contaminated site in Corvallis, OR, and exhibited methanogenic, acetogenic, and reductive dehalogenation activities. The H2-fed culture transformed TCE to ethene via cis-dichloroethene (c-DCE) and VC as intermediates. Batch kinetic studies showed acetylene reversibly inhibited reduction of both TCE and VC, and the levels of inhibition were strongly dependent on acetylene concentrations in both cases. Acetylene concentrations of 192 and 12 microM, respectively, were required to achieve 90% inhibition in rates of TCE and VC transformation at an aqueous concentration of 400 microM. Acetylene also inhibited methane production (90% inhibition at 48 microM) but did not inhibit H2-dependent acetate production. Mass balances conducted during the studies of VC inhibition showed that acetogenesis, VC transformation to ethene, and methane production were responsible for 52%, 47%, and 1% of the H2 consumption, respectively. The results indicate that halorespiration is the dominant process responsible for VC and TCE transformation and that dehalorespiring organisms are the target of acetylene inhibition. Acetylene has potential use as a reversible inhibitor to probe the biological activities of reductive dechlorination and methanogenesis. It can be added to inhibit reactions and then removed to permit reactions to proceed. Thus, it can be a powerful tool for investigating intrinsic and enhanced anaerobic remediation of chloroethenes at contaminated sites. The results also suggest that acetylene produced abiotically by reactions of chlorinated ethenes with zero-valent iron could inhibit the biological transformation of VC to ethene.

CuCl2(NH2CH2CH2OH) is monoclinic, space group C2/c, witha+11.092(2),b+10.012(2),c+6.401(1) A, β=121.71(1)°, andV=604.8(2)A3 withZ+4. The structure was refined to a final value ofR+0.27 for 518 unique observed reflections with |F|>3σ. The ethanolamine and halide ions coordinate to the copper(II) ion forming a pseudoplanar four-coordinate monomeric CuCl2L2 complex (L2+bidentate ligand). The copper ion also interacts with the halides of neighboring complexes through the formation of semi-coordinate Cu-Cl linkages (2.926(1) A) between oligomers. The copper thus attains a 4+2 elongated octahedral coordination geometry. In this space group, the ligand is statisticallydisordered The Cu-Cl distance is 2.267(1)A while the Cu-N/O distances are 2.025(2)A. The dibromide structure is isomorphous with the dichloride structure, with space group C2/c, anda+11.285(2),b+10.218(2),c+6.715(1) A, β=121.65(1)°, andV=659.2(2)A3.

Reaction Of Cu(ClO4)2 with 2,3-dimethylpyrazine (2,3-dmpz) in aqueous solution yields the bright yellow, air-stable, crystalline complex Cu2(2,3-dmpz)3(ClO4)2 (1) in 40% yield. The single-crystal X-ray structure reveals a two-dimensional polymeric lattice of tricoordinate copper(I) atoms bridged by 2,3-dimethylpyrazine ligands.

The crystal structures of two hydrated copper(II) chloride salts are reported: N,N'-dimethylpiperazinium bis(aquotrichlorocuprate(II)), C 6 H 20 N 2 O 2 Cu 2 Cl 6 , monoclinic, P2 1 /n, a=6.714 (2) A, b=6.215 (2) A, c=19.545 (6) A, β=92.24 (6)°, Z=2, and R=0.041, and 2-aminopyrimidinium aquotrichlorocuprate(II), C 4 H 8 N 3 OCuCl 3 , monoclinic, Cc, a=3.9025 (6) A, b=13.788 (3) A, c=16.826 (3) A, β=93.99 (1)°, Z=4, and R=0.030. In addition, the crystal parameters of the anhydrous analogue of the latter, bis(2-aminopyrimidinium) hexachlorodicuprate(II), C 8 H 12 N 6 Cu 2 Cl 6 are triclinic, a=3.902 (1) A, b=10.850 (3) A, c=11.129 (3) A, α=62.82 (2)°, β=84.84 (3)°, γ=82.69 (2)°, Z=1, and R=0.0252

The reaction of 4,4'-dimethyl-2,2-bipyridine (henceforth dmbp) with copper(I) and/or copper(II) bromide under a wide variety of conditions has led to the isolation of 10 different crystalline materials. These include one Cu(I) salt, [Cu(dmbp)(2)]Br (a distorted tetrahedral Cu species and a lattice Br(-) ion); two mixed valence Cu(I,II) compounds, [Cu(dmbp)(2)Br][CuBr(2)] (discrete 5-coordinated Cu(II) and linear Cu(I) species) and Cu(dmbp)(2)BrCu(2)Br(3) (linked 5-coordinate Cu(II) and trigonal planar Cu(I) species); and seven Cu(II) compounds, (dmbp)CuBr(2) (stacked planar monomers), [(dmbp)CuBr(2)](2)(five coordinate bibridged dimers), (dmbp)Cu(2)Br(4) (stacked planar bibridged dimers), (dmbp)CuBr(2)(DMSO) (five coordinate monomers), [Cu(dmbp)(2)Br]OH.5(1)/(2)H(2)O and [Cu(dmbp)(2)Br](Br/OH).5(1)/(2)H(2)O (five coordinate monomers), and (dmbpH(2))CuBr(4).H(2)O (distorted tetrahedral monomers). The crystal structure determinations of these materials are reported. A common thread in their structural chemistry is the supramolecular architecture developed through interdigitation of the dmbp rings on neighboring molecular species. The interdigitation leads to layer structures in many of the materials. The distances between the interdigitated dmbp rings are in the range 3.4-3.7 A. The Cu(dmbp)(2)Br(+) species exhibits an exceptionally large distortion from tetrahedral geometry due to deviation of the dihedral angle between the mean planes of the Cu(dmbp) fragments from 90 degrees. The Cu(dmbp)(2)Br(+) cations have distorted trigonal bipyramidal geometry, the Br(-) ion occupying an equatorial position. The length of the Cu-Br bond in the Cu(dmbp)(2)Br(+) species is correlated with the change in dihedral angle between the planes of the two dmbp ligands. The mono-dmbp complexes show a greater variation in coordination geometry for the Cu(II) species, including distorted trigonal bipyramidal and augmented square planar 4 + 1 and 4 + 2 coordination.

Reaction of Cu(ClO4)2 with 2-methylpyrazine (mepz), 2,5-dimethylpyrazine (2,5-dmpz) or 2,6-dimethylpyrazine (2,6-dmpz) in aqueous solution yields the corresponding CuLn(ClO4)2(H2O)m (n = 2,4; m = 1,2,4). Single-crystal X-ray diffraction of Cu(mepz)2(ClO4)2(H2O)2 (1) reveals a roughly octahedral geometry with all ligands trans. Similarly, Cu(mepz)4(ClO4)2(H2O) (2) is pseudo-octahedral with one coordinated perchlorate and one H2O in the axial sites. The pyrazines are coordinated through the N(4) nitrogen atom in both 1 and 2. The magnetic susceptibilities of these compounds have been measured in the range 2–300 K. All the compounds behave as paramagnets. Conversely, reaction of Cu(ClO4)2 with 2,3-dimethylpyrazine in aqueous solution, or with mepz, 2,3-dmpz or 2,5-dmpz and NaBH4 or NaSCN in aqueous solution yields complexes of the type Cu2(L)3(ClO)4)2 or Cu2(L)(SCN)2, respectively. IR analysis suggests that the complexes are polymeric lattices of tri-coordinate copper(I) atoms bridged by the pyrazine ligands or the pyrazine and thiocyanate ligands, similar to the known structure of Cu2(2,3-dimethylpyrazine)3(ClO4)2.