Production of biogas from different organic materials is a most interesting source of renewable energy.The biomethane potential (BMP) of these materials has to be determined to get insight in design parameters for anaerobic digesters. Although several norms and guidelines for BMP tests exist, inter-laboratory tests regularly show high variability of BMPs for the same substrate. A workshop was held in June 2015, in Leysin, Switzerland, with over 40 attendees from 30 laboratories around the world, to agree on common solutions to the conundrum of inconsistent BMP test results. This paper presents the consensus of the intense roundtable discussions and cross-comparison of methodologies used in respective laboratories. Compulsory elements for the validation of BMP results were defined. They include the minimal number of replicates, the request to carry out blank and positive control assays, a criterion for the test duration, details on BMP calculation, and last but not least criteria for rejection of the BMP tests. Finally, recommendations on items that strongly influence the outcome of BMP tests such as inoculum characteristics, substrate preparation, test setup, and data analysis are presented to increase the probability of obtaining validated and reproducible results.
Contamination of soils and aquifers with (poly)nitroaromatic compounds ((P)NACs) is a widespread problem. This work demonstrates that (P)NACs such as the explosive 2,4,6-trinitrotoluene (TNT) can be completely reduced to the corresponding aromatic polyamines by Fe(II) present at the surface of Fe(III)(hydr)oxides or, less efficiently, by hydroquinone moieties of (natural) organic matter in the presence of H2S. The reduction kinetics of (P)NACs were investigated in sterile batch systems as well as in columns containing either FeOOH-coated sand and a pure culture of the iron-reducing bacterium Geobacter metallireducens or ferrogenic consortia in aquifer sediments. The relative reactivities as well as the competition behavior of (P)NACs in batch and column systems, respectively, correlated well with their one-electron reduction potentials, ‘, which we determined for TNT and its aminonitrotoluene transformation products. A similar reactivity pattern of (P)NACs was found irrespective of the processes that (re)generated the surface-bound Fe(II), i.e., adsorption of Fe(II) from aqueous solution or microbial reduction of Fe(III)(hydr)oxides. The apparent stability of the toxic arylamine products under ferrogenic conditions may compromise intrinsic attenuation as an acceptable remediation option for (P)NAC contaminated anoxic aquifers. Iron-reducing conditions would, however, be favorable as a first step in a two-stage anaerobic/aerobic treatment of PNAC contaminated sediments since aromatic polyamines are biodegradable and/or bind irreversibly to the solid matrix under oxic conditions.
SUMMARY Lindane, the γ-isomer of hexachlorocyclohexane (HCH), is a potent insecticide. Purified lindane or unpurified mixtures of this and α-, β-, and δ-isomers of HCH were widely used as commercial insecticides in the last half of the 20th century. Large dumps of unused HCH isomers now constitute a major hazard because of their long residence times in soil and high nontarget toxicities. The major pathway for the aerobic degradation of HCH isomers in soil is the Lin pathway, and variants of this pathway will degrade all four of the HCH isomers although only slowly. Sequence differences in the primary LinA and LinB enzymes in the pathway play a key role in determining their ability to degrade the different isomers. LinA is a dehydrochlorinase, but little is known of its biochemistry. LinB is a hydrolytic dechlorinase that has been heterologously expressed and crystallized, and there is some understanding of the sequence-structure-function relationships underlying its substrate specificity and kinetics, although there are also some significant anomalies. The kinetics of some LinB variants are reported to be slow even for their preferred isomers. It is important to develop a better understanding of the biochemistries of the LinA and LinB variants and to use that knowledge to build better variants, because field trials of some bioremediation strategies based on the Lin pathway have yielded promising results but would not yet achieve economic levels of remediation.
Within the last few decades, several anaerobic bacteria have been isolated which are able to reductively dechlorinate chlorinated aliphatic and aromatic compounds at catabolic rates. For some of these bacteria, it has been shown that the reductive dechlorination is coupled to energy conservation, a process designated as`dehalorespiration'. Somewhat simple respiratory chains seem to be involved that utilize the free energy that could be gained from the exergonic dechlorination reaction quite inefficiently. With one exception, all reductive dehalogenases isolated to date contain a corrinoid and iron^sulfur clusters as cofactors. During the course of the catalytic reaction cycle, the cobalt of the corrinoid is subjected to a change in its redox state. Hence, reductive dechlorination represents a new type of biochemical reaction. z
It is shown that in homogeneous aqueous solution containing titanium(III) citrate or titanium(III)-NTA as bulk electron donor, cobalamin, cobinamide, and cobamide are effective electron transfer mediators for the reduction of tetrachloroethene (PCE), trichloroethene (TCE), and trichlorofluoroethene (TCFE). For a given chlorinated ethene, the reaction rate varied only slightly with pH and type of corrinoid present and was about 5 and 50 times faster for PCE as compared to TCFE and TCE, respectively. Evidence is presented that the first and rate-limiting step of the reduction of PCE, TCE, and TCFE by super-reduced corrinoids is a dissociative one-electron transfer yielding the corresponding vinyl radicals. Furthermore, the elimination of a chloride radical from the 1,1-dichlorovinyl radical yielding chloroacetylene and subsequently acetylene is proposed to account for the direct formation of acetylene out of TCE. Finally, it is demonstrated that at higher reduction potentials the corrinoid mediators may be blocked by the formation of addition products.
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