Author: Stefan CretnikPublisher:
ISBN:
Category : Carbon
Languages : en
Pages :
Book Description
Mechanistic Investigation of Chlorinated Ethylene Degradation Using Chlorine and Carbon Isotope Fractionation
Author: Stefan CretnikInvestigating Mechanisms of Chlorinated Ethane Biotransformation Using Compound Specific Carbon Isotope Analysis
Author: Sarah Kathleen HirschornPublisher:
ISBN:
Category :
Languages : en
Pages : 340
Book Description
Stable carbon isotope fractionation during biotransformation of the chlorinated ethanes 1,2-dichloroethane (1,2-DCA), 1,1,1-trichloroethane (1,1,1-TCA) and 1,1-dichloroethane (1,1-DCA) was investigated. Isotopic fractionation during aerobic 1,2-DCA biotransformation in microcosms, enrichment cultures and pure microbial cultures was measured and was found to be pathway dependent. Biodegradation of 1,2-DCA under aerobic conditions produced a consistent bimodal distribution of enrichment factors (s) with one mean c centered on --3.9 +/- 0.6 and the other on --29.2 +/- 1.9. Reevaluation of epsilon in terms of kinetic isotope effects 12k/ 13k, gave values of 12k/13k = 1.01 and 1.06, which are typical of oxidation and hydrolytic dehalogenation (S N2) reactions, respectively. The relationship between degradation pathway and measured carbon isotope fractionation was applied to constrain the degradation pathway of 1,2-DCA in a microbial enrichment culture capable of degrading 1,2-DCA under both O2 and NO3-reducing conditions, but where the degradation pathway was previously uncharacterized. delta 13C values indicated biodegradation in the enrichment culture under both O2 and NO3-reducing conditions likely proceeded via a hydrolytic dehalogenase enzyme. Stable carbon isotope analysis during biotransformation of other chlorinated ethanes was then investigated. Isotopic enrichment factors of -1.9 and -10.4 were measured during reductive dechlorination of 1,1,1-trichloroethane (1,1,1-TCA) and 1,1-dichloroethane (1,1-DCA), respectively. These are the first reported isotopic enrichment factors for microbial biotransformation of these compounds, which can now potentially be applied to investigate and quantify biodegradation of 1,1,1-TCA and 1,1-DCA in the field. Stable carbon isotope analysis was used to provide a conservative estimate of the extent of 1,2-DCA and trichloroethene (TCE) biodegradation in a biostimulation field study. Isotope analysis was able to confirm that 1,2-DCA degradation, rather than degradation of vinyl chloride, was the primary mechanism of ethene production at the site. This thesis not only advances the application of compound specific carbon isotope fractionation to identify and quantify biodegradation of chlorinated ethanes in groundwater, but in particular progresses our understanding of the relationship between the enzymatic mechanisms of contaminant degradation and isotopic fractionation, and the ability to use that knowledge to predict degradation mechanisms for previously unconstrained pathways of contaminant remediation.
The Geochemistry of Stable Chlorine and Bromine Isotopes
Author: Hans EggenkampPublisher: Springer
ISBN: 3642285066
Category : Science
Languages : en
Pages : 174
Book Description
This book provides detailed information on the history, analysis and applications of chlorine and bromine isotope geochemistry. Chlorine and bromine are geochemically unique as they prefer to exist as single charged negative ions. For this reason isotope fractionation reflects mostly processes that are not related to changes in the redox state and this fractionation is generally modest. The book will describe the processes that are most easily detected using these isotopes. Also isotope variations, and processes that cause them, measured in oxidised species such as perchlorates and in organic molecules will be described in this book.
Investigations of Reductive Dechlorination Reactions of Chlorinated Ethenes and Ethanes on Zero-valent Metals Using Compound Specific Isotopic Analysis
Author: Nancy Anne VanStonePublisher:
ISBN: 9780494157541
Category :
Languages : en
Pages : 426
Book Description
Reductive dechlorination reactions occurring on zero-valent metal surfaces for chlorinated ethenes and chlorinated ethanes are investigated using compound specific isotopic analysis (CSIA) to measure carbon isotopic fractionation and carbon kinetic isotope effects (KIE). Reductive dechlorination of chlorinated contaminants on zero-valent iron (Fe0) is used for remediation purposes at over 100 sites worldwide employing permeable reactive barrier (PRB) technology. Degradation can occur via 3 main pathways: (1) alpha-elimination, (2) beta-elimination and (3) hydrogenolysis. Experiments documenting carbon isotopic fractionation observed during degradation of a suite of chlorinated ethenes are described, and it is demonstrated that reproducible carbon isotopic fractionation occurs for perchloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinyl chloride (VC). The results for Fe0 from two different sources show distinct differences in both rates of reaction and isotopic fractionation factors (epsilon), particularly for the cis-DCE and VC. Using ground water samples from pre- and post-treatment of a Fe0 PRB at F.E. Warren Air Force Base, it is established that carbon isotopic fractionation of chlorinated ethenes follows the same principles under field conditions, and it is shown that CSIA, in combination with traditional compositional analysis, can help to resolve complex performance-related problems for PRBs. Finally, it is demonstrated that reaction pathways and mechanisms can be investigated using CSIA and ranges of epsilon and KIE are established for the investigated reactions on different zero-valent metals. In batch experiments monitoring dichloroethane (DCA) degradation on Zn0, CSIA was used to determine that a common rate limiting step occurs for hydrogenolysis and alpha-elimination reactions of 1,1-DCA. As well, overall epsilon and KIE are greater for beta-elimination of 1,2-DCA than for hydrogenolysis and alpha-elimination of 1,1-DCA. The degradation of a chlorinated ethene, cis-DCE, was investigated on Fe0. Direct measurements of epsilon and KIE for hydrogenolysis and beta-elimination were measured using CSIA. It is established that these reactions do not share a rate limiting step, and unique and reproducible carbon isotopic fractionation is associated with each reaction pathway. CSIA has been shown to be a versatile tool, aiding research as both a reliable diagnostic (i.e. identification of degradation) and as a valuable analytical instrument for mechanistic studies.
Organohalide-Respiring Bacteria
Author: Lorenz AdrianPublisher: Springer
ISBN: 3662498758
Category : Science
Languages : en
Pages : 620
Book Description
This book summarizes the current state of knowledge concerning bacteria that use halogenated organic compounds as respiratory electron acceptors. The discovery of organohalide-respiring bacteria has expanded the range of electron acceptors used for energy conservation, and serves as a prime example of how scientific discoveries are enabling innovative engineering solutions that have transformed remediation practice. Individual chapters provide in-depth background information on the discovery, isolation, phylogeny, biochemistry, genomic features, and ecology of individual organohalide-respiring genera, including Dehalococcoides, Dehalogenimonas, Dehalobacter, Desulfitobacterium and Sulfurospirillum, as well as organohalide-respiring members of the Deltaproteobacteria. The book introduces readers to the fascinating biology of organohalide-respiring bacteria, offering a valuable resource for students, engineers and practitioners alike.
Selected Water Resources Abstracts
Author: Compound-specific Stable Isotope Analysis
Author: Maik A JochmannPublisher: Royal Society of Chemistry
ISBN: 1782626107
Category : Science
Languages : en
Pages : 306
Book Description
The use of Compound-specific Stable Isotope Analysis (CSIA) is increasing in many areas of science and technology for source allocation, authentication, and characterization of transformation reactions. Until now, there have been no textbooks available for students with an analytical chemical background or basic introductory books emphasising the instrumentation and theory. This book is the first to focus solely on stable isotope analysis of individual compounds in sometimes complex mixtures. It acts as both a lecture companion for students and a consultant for advanced scientists in fields including forensic and environmental science. The book starts with a brief history of the field before going on to explain stable isotopes from scratch. The different ways to express isotope abundances are introduced together with isotope effects and isotopic fractionation. A detailed account of the required technical equipment and general procedures for CSIA is provided. This includes sections on derivatization and the use of microextraction techniques in GC-IRMS. The very important topic of referencing and calibration in CSIA is clearly described. This differs from approaches used in quantitative analysis and is often difficult for the newcomer to comprehend. Examples of successful applications of CSIA in food authenticity, forensics, archaeology, doping control, environmental science, and extraterrestrial materials are included. Applications in isotope data treatment and presentation are also discussed and emphasis is placed on the general conclusions that can be drawn from the uses of CSIA. Further instrumental developments in the field are highlighted and selected experiments are introduced that may act as a basis for a short practical course at graduate level.
Isotope Effects In Chemistry and Biology
Author: Amnon KohenPublisher: CRC Press
ISBN: 1420028022
Category : Medical
Languages : en
Pages : 1092
Book Description
The field of isotope effects has expanded exponentially in the last decade, and researchers are finding isotopes increasingly useful in their studies. Bringing literature on the subject up to date, Isotope Effects in Chemistry and Biology covers current principles, methods, and a broad range of applications of isotope effects in the physical, biolo
In Situ Remediation of Chlorinated Solvent Plumes
Author: Hans F. StrooPublisher: Springer Science & Business Media
ISBN: 1441914013
Category : Technology & Engineering
Languages : en
Pages : 807
Book Description
In the late 1970s and early 1980s, our nation began to grapple with the legacy of past disposal practices for toxic chemicals. With the passage in 1980 of the Comprehensive Envir- mental Response, Compensation, and Liability Act (CERCLA), commonly known as Sup- fund, it became the law of the land to remediate these sites. The U. S. Department of Defense (DoD), the nation’s largest industrial organization, also recognized that it too had a legacy of contaminated sites. Historic operations at Army, Navy, Air Force, and Marine Corps facilities, ranges, manufacturing sites, shipyards, and depots had resulted in widespread contamination of soil, groundwater, and sediment. While Superfund began in 1980 to focus on remediation of heavily contaminated sites largely abandoned or neglected by the private sector, the DoD had already initiated its Installation Restoration Program in the mid-1970s. In 1984, the DoD began the Defense Environmental Restoration Program (DERP) for contaminated site assessment and remediation. Two years later, the U. S. Congress codified the DERP and directed the Secretary of Defense to carry out a concurrent program of research, development, and demonstration of innovative remediation technologies. As chronicled in the 1994 National Research Council report, “Ranking Hazardous-Waste Sites for Remedial Action,” our early estimates on the cost and suitability of existing techn- ogies for cleaning up contaminated sites were wildly optimistic. Original estimates, in 1980, projected an average Superfund cleanup cost of a mere $3.
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