Reductive dechlorination

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In organochlorine chemistry, reductive dechlorination describes any chemical reaction which cleaves the covalent bond between carbon and chlorine via reductants, to release chloride ions. Many modalities have been implemented, depending on the application. Reductive dechlorination is often applied to remediation of chlorinated pesticides or dry cleaning solvents. It is also used occasionally in the synthesis of organic compounds, e.g. as pharmaceuticals.

Contents

Chemical

Dechlorination is a well-researched reaction in organic synthesis, although it is not often used. Usually stoichiometric amounts of dechlorinating agent are required. In one classic application, the Ullmann reaction, chloroarenes are coupled to biphenyl]]s. For example, the activated substrate 2-chloronitrobenzene is converted into 2,2'-dinitrobiphenyl with a copper - bronze alloy. [1] [2]

Ullmann reaction. UllmannReaction.svg
Ullmann reaction.

Zerovalent iron effects similar reactions. Organophosphorus(III) compounds effect gentle dechlorinations. The products are alkenes and phosphorus(V). [3]

Biological

Vicinal reduction involves the removal of two halogen atoms that are adjacent on the same alkane or alkene, leading to the formation of an additional carbon-carbon bond. [5]

Biological reductive dechlorination is often effected by certain species of bacteria. Sometimes the bacterial species are highly specialized for organochlorine respiration and even a particular electron donor, as in the case of Dehalococcoides and Dehalobacter . In other examples, such as Anaeromyxobacter , bacteria have been isolated that are capable of using a variety of electron donors and acceptors, with a subset of possible electron acceptors being organochlorines. [6] These reactions depend on a molecule which tends to be very aggressively sought after by some microbes, vitamin B12. [7]

Bioremediation using reductive dechlorination

Reductive dechlorination of chlorinated organic molecules is relevant to bioremediation of polluted groundwater. [8] [9] One example [10] is the organochloride respiration of the dry-cleaning solvent, tetrachloroethylene, and the engine degreasing solvent trichloroethylene by anaerobic bacteria, often members of the candidate genera Dehalococcoides. Bioremediation of these chloroethenes can occur when other microorganisms at the contaminated site provide H2 as a natural byproduct of various fermentation reactions. The dechlorinating bacteria use this H2 as their electron donor, ultimately replacing chlorine atoms in the chloroethenes with hydrogen atoms via hydrogenolytic reductive dechlorination. This process can proceed in the soil provided the availability of organic electron donors and the appropriate strains of Dehalococcoides. Trichloroethylene is dechlorinated via dichloroethene and vinyl chloride to ethylene. [11]

A chloroform-degrading reductive dehalogenase enzyme has been reported in a Dehalobacter member. The chloroform reductive dehalogenase, termed TmrA, was found to be transcriptional up-regulated in response to chloroform respiration [12] and the enzyme can be obtained both in native [13] and recombinant forms. [14]

Reductive dechlorination has been investigated for bioremediation of polychlorinated biphenyls (PCB) and chlorofluorocarbons (CFC). The reductive dechlorination of PCBs is performed by anaerobic microorganisms that utilize the PCB as an electron sink. The result of this is the reduction of the "meta" site, followed by the "para" site, and finally the "ortho" site, leading to a dechlorinated product. [15] [16] [17] In the Hudson River, microorganisms effect dechlorination over the course of weeks. The resulting monochlorobiphenyls and dichlorobiphenyls are less toxic and more easily degradable by aerobic organisms compared to their chlorinated counterparts. [17] The prominent drawback that has prevented the widespread use of reductive dechlorination for PCB detoxification and has decreased its feasibility is the issue of the slower than desired dechlorination rates. [16] It has been suggested that bioaugmentation with DF-1 can lead to enhanced reductive dechlorination rates of PCBs through stimulation of dechlorination. Additionally, high inorganic carbon levels do not affect dechlorination rates in low PCB concentration environments. [15]

The reductive dechlorination applies to CFCs. [18] Reductive dechlorination of CFCs including CFC-11, CFC-113, chlorotrifluoroethene, CFC-12, HCFC-141b, and tetrachloroethene occur through hydrogenolysis. Reduction rates of CFC mirror theoretical rates calculated based on the Marcus theory of electron transfer rate. [19]

Electrochemical

The electrochemical reduction of chlorinated chemicals such as chlorinated hydrocarbons and chlorofluorocarbons can be carried out by electrolysis in appropriate solvents, such as mixtures of water and alcohol. Some of the key components of an electrolytic cell are types of electrodes, electrolyte mediums, and use of mediators. The cathode transfers electrons to the molecule, which decomposes to produce the corresponding hydrocarbon (hydrogen atoms substitute the original chlorine atoms) and free chloride ions. For instance, the reductive dechlorination of CFCs is complete and produces several hydrofluorocarbons (HFC) plus chloride.

Hydrodechlorination (HDC) is a type of reductive dechlorination that is useful due to its high reaction rate. It uses H2 as the reducing agent over a range of potential electrode reactors and catalysts. [20] Amongst the types of catalysts studied such as precious metals (platinum, palladium, rhodium), transition metals (niobium and molybdenum), and metal oxides, a preference for precious metals overrides the others. As an example, palladium often adopts a lattice formation which can easily embed hydrogen gas making it more accessible to be readily oxidized. [21] However a common issue for HDC is catalyst deactivation and regeneration. As catalysts are depleted, chlorine poisoning on surfaces can sometimes be observed, and on rare occasions, metal sintering and leaching occurs as a result. [22]

Electrochemical reduction can be performed at ambient pressure and temperature. [23] This will not disrupt microbial environments or raise extra cost for remediation. The process of dechlorination can be highly controlled to avoid toxic chlorinated intermediates and byproducts such as dioxins from incineration. Trichloroethylene and perchloroethylene are common targets of treatment which are directly converted to environmentally benign products. Chlorinated alkenes and alkanes are converted to hydrogen chloride which is then neutralized with a base. [22] However, even though there are many potential benefits to adopting this method, research have mainly been conducted in a laboratory setting with a few cases of field studies making it not yet well established.

Related Research Articles

<span class="mw-page-title-main">Tetrachloroethylene</span> Chemical compound in very wide use

Tetrachloroethylene, also known under the systematic name tetrachloroethene, or perchloroethylene, and abbreviations such as "perc" (or "PERC"), and "PCE", is a chlorocarbon with the formula Cl2C=CCl2. It is a colorless liquid widely used for dry cleaning of fabrics, hence it is sometimes called "dry-cleaning fluid". It also has its uses as an effective automotive brake cleaner. It has a mild sweet odor, similar to the smell of chloroform, detectable by most people at a concentration of 1 part per million (1 ppm).

<span class="mw-page-title-main">Trichloroethylene</span> Chemical compound

Trichloroethylene (TCE) is a halocarbon with the formula C2HCl3, commonly used as an industrial degreasing solvent. It is a clear, colourless non-flammable liquid with a chloroform-like pleasant and pungent smell. The IUPAC name is trichloroethene. Industrial abbreviations include TCE, trichlor, Trike, Tricky and tri. It should not be confused with the similar 1,1,1-trichloroethane, which is commonly known as chlorothene. It has been sold under a variety of trade names. Under the trade names Trimar and Trilene, trichloroethylene was used as a volatile anesthetic and as an inhaled obstetrical analgesic in millions of patients.

Halocarbon compounds are chemicals in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms resulting in the formation of organofluorine compounds, organochlorine compounds, organobromine compounds, and organoiodine compounds. Chlorine halocarbons are the most common and are called organochlorides.

Biological augmentation is the addition of archaea or bacterial cultures required to speed up the rate of degradation of a contaminant. Organisms that originate from contaminated areas may already be able to break down waste, but perhaps inefficiently and slowly.

Organohalide respiration (OHR) (previously named halorespiration or dehalorespiration) is the use of halogenated compounds as terminal electron acceptors in anaerobic respiration. Organohalide respiration can play a part in microbial biodegradation. The most common substrates are chlorinated aliphatics (PCE, TCE, chloroform) and chlorinated phenols. Organohalide-respiring bacteria are highly diverse. This trait is found in some Campylobacterota, Thermodesulfobacteriota, Chloroflexota (green nonsulfur bacteria), low G+C gram positive Clostridia, and ultramicrobacteria.

Dehalococcoides is a genus of bacteria within class Dehalococcoidia that obtain energy via the oxidation of hydrogen and subsequent reductive dehalogenation of halogenated organic compounds in a mode of anaerobic respiration called organohalide respiration. They are well known for their great potential to remediate halogenated ethenes and aromatics. They are the only bacteria known to transform highly chlorinated dioxins, PCBs. In addition, they are the only known bacteria to transform tetrachloroethene to ethene.

Microbial biodegradation is the use of bioremediation and biotransformation methods to harness the naturally occurring ability of microbial xenobiotic metabolism to degrade, transform or accumulate environmental pollutants, including hydrocarbons, polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), heterocyclic compounds, pharmaceutical substances, radionuclides and metals.

In enzymology, a tetrachloroethene reductive dehalogenase is an enzyme that catalyzes the chemical reaction. This is a member of reductive dehalogenase enzyme family.

A dehalogenase is a type of enzyme that catalyzes the removal of a halogen atom from a substrate.

In situ chemical reduction (ISCR) is a type of environmental remediation technique used for soil and/or groundwater remediation to reduce the concentrations of targeted environmental contaminants to acceptable levels. It is the mirror process of In Situ Chemical Oxidation (ISCO). ISCR is usually applied in the environment by injecting chemically reductive additives in liquid form into the contaminated area or placing a solid medium of chemical reductants in the path of a contaminant plume. It can be used to remediate a variety of organic compounds, including some that are resistant to natural degradation.

Dehalobacter is a genus in the phylum Bacillota (Bacteria).

Dehalococcoidia is a class of Chloroflexota, a phylum of Bacteria. It is also known as the DHC group.

Desulfitobacterium dehalogenans is a species of bacteria. They are facultative organohalide respiring bacteria capable of reductively dechlorinating chlorophenolic compounds and tetrachloroethene. They are anaerobic, motile, Gram-positive and rod-shaped bacteria capable of utilizing a wide range of electron donors and acceptors. The type strain JW/IU-DCT, DSM 9161, NCBi taxonomy ID 756499.

Desulfitobacterium hafniense is a species of gram positive bacteria, its type strain is DCB-2T..

Dehalogenimonas lykanthroporepellens is an anaerobic, Gram-negative bacteria in the phylum Chloroflexota isolated from a Superfund site in Baton Rouge, Louisiana. It is useful in bioremediation for its ability to reductively dehalogenate chlorinated alkanes.

Adsorbable Organic Halides (AOX) is a measure of the organic halogen load at a sampling site such as soil from a land fill, water, or sewage waste. The procedure measures chlorine, bromine, and iodine as equivalent halogens, but does not measure fluorine levels in the sample.

Polychorinated biphenyls, or PCBs, are a type of chemical that was widely used in the 1960s and 1970s, and which are a contamination source of soil and water. They are fairly stable and therefore persistent in the environment. Bioremediation of PCBs is the use of microorganisms to degrade PCBs from contaminated sites, relying on multiple microorganisms' co-metabolism. Anaerobic microorganisms dechlorinate PCBs first, and other microorganisms that are capable of doing BH pathway can break down the dechlorinated PCBs to usable intermediates like acyl-CoA or carbon dioxide. If no BH pathway-capable microorganisms are present, dechlorinated PCBs can be mineralized with help of fungi and plants. However, there are multiple limiting factors for this co-metabolism.

<i>In situ</i> bioremediation

Bioremediation is the process of decontaminating polluted sites through the usage of either endogenous or external microorganism. In situ is a term utilized within a variety of fields meaning "on site" and refers to the location of an event. Within the context of bioremediation, in situ indicates that the location of the bioremediation has occurred at the site of contamination without the translocation of the polluted materials. Bioremediation is used to neutralize pollutants including Hydrocarbons, chlorinated compounds, nitrates, toxic metals and other pollutants through a variety of chemical mechanisms. Microorganism used in the process of bioremediation can either be implanted or cultivated within the site through the application of fertilizers and other nutrients. Common polluted sites targeted by bioremediation are groundwater/aquifers and polluted soils. Aquatic ecosystems affected by oil spills have also shown improvement through the application of bioremediation. The most notable cases being the Deepwater Horizon oil spill in 2010 and the Exxon Valdez oil spill in 1989. Two variations of bioremediation exist defined by the location where the process occurs. Ex situ bioremediation occurs at a location separate from the contaminated site and involves the translocation of the contaminated material. In situ occurs within the site of contamination In situ bioremediation can further be categorized by the metabolism occurring, aerobic and anaerobic, and by the level of human involvement.

Reductive dehaholagenses (EC 1.97.1.8) are a group of enzymes utilized in organohalide respiring bacteria. These enzymes are mostly attached to the periplasmic side of the cytoplasmic membrane and play a central role in energy-conserving respiratory process for organohalide respiring bacteria by reducing organohalides. During such reductive dehalogenation reaction, organohalides are used as terminal electron acceptors. They catalyze the following general reactions:

<span class="mw-page-title-main">Chlorine cycle</span>

The chlorine cycle (Cl) is the biogeochemical cycling of chlorine through the atmosphere, hydrosphere, biosphere, and lithosphere. Chlorine is most commonly found as inorganic chloride ions, or a number of chlorinated organic forms. Over 5,000 biologically-produced chlorinated organics have been identified.

References

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  22. 1 2 Ju, Xiumin (2005). "Reductive Dehalogenation of Gas-phase Trichloroethylene using Heterogeneous Catalytic and Electrochemical Methods". University of Arizona Campus Repository.
  23. ↑ Chemical degradation methods for wastes and pollutants: environmental and industrial applications. Tarr, Matthew A. New York: M. Dekker. 2003. ISBN   978-0-203-91255-3. OCLC   54061528.{{cite book}}: CS1 maint: others (link)
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