Summary of research results on bacterial degradation of trifluoroacetate (TFA), November, 1994-May, 1995
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Open-File Report↗
Geology topics
R.S. Oremland
Publications and source records attributed to R.S. Oremland.
Degradation of trifluoroacetate in oxic and anoxic sediments
THE deleterious effect of chlorofluorocarbons on stratospheric ozone has led to international cooperation to end their use. The search for acceptable alternatives has focused on hydrofluorocarbons (HFCs) or hydrochlorofluorocarbons (HCFCs) which are attractive because they have relatively short atmospheric residence times. HFCs and HCFCs are attacked by tropospheric hydroxyl radicals, leading to the formation of trifluoroacetate (TFA). Most of the atmospheric TFA is deposited at the Earth's surface, where it is thought to be highly resistant to bacterial attack. Therefore, use of HCFCs and HFCs may lead to accumulation of TFA in soils, where it could prove toxic or inhibitory to plants and soil microbial communities. Although little is known about the toxicity of TFA, monofluoroacetate, which occurs at low levels in some plants and which is susceptible to slow attack by aerobic soil microbes, is known to be acutely toxic. Here we report that TFA can be rapidly degraded microbially under anoxic and oxic conditions. These results imply that significant microbial sinks exist in nature for the elimination of TFA from the environment. We also show that oxic degradation of TFA leads to the formation of fluoroform, a potential ozone-depleting compound with a much longer atmospheric lifetime than the parent compounds.The deleterious effect of chlorofluorcarbons on stratospheric ozone has led to international cooperation to end their use. The search for acceptable alternatives has focused on hydroflnorocarbons (HFCs) or hydrochloroflnorcarbons (HCFs) which are attractive because they have relatively short atmospheric residence times. HFCs and HCFs are attacked by tropospheric hydroxyl radicals, leading to the formation of trifluoroacetate (TFA). Most of the atmospheric TFA is deposited at the Earth's surface, where it is thought to be highly resistant to bacterial attack. Therefore, use of HCFs and HCFs may lead to accummulation of TFA in soils, where it could prove toxic or inhibitory to plants and soil microbial communities. Although little is known about the toxicity of TFA, monofluoracetate, which occurs at low levels in some plants and which is susceptible to slow attack by aerobic soil microbes, is known to be acutely toxic. Here we report that TFA can be rapidly degraded microbially under anoxic and oxic conditions. These results imply that significant microbial sinks exist in nature for the elimination of TFA from the environment. We also show that oxic degradation of TFA leads to the formation of fluoroform, a potential ozone-depleting compound with a much longer atmospheric lifetime than the parent compounds.
Nature↗
Degradation of methyl bromide by methanotrophic bacteria in cell suspensions and soils
Cell suspensions of Methylococcus capsulatus mineralized methyl bromide (MeBr), as evidenced by its removal from the gas phase, the quantitative recovery of Br - in the spent medium, and the production of 14 CO 2 from [ 14 C]MeBr. Methyl fluoride (MeF) inhibited oxidation of methane as well as that of [ 14 C]MeBr. The rate of MeBr consumption by cells varied inversely with the supply of methane, which suggested a competitive relationship between these two substrates. However, MeBr did not support growth of the methanotroph. In soils exposed to high levels (10,000 ppm) of MeBr, methane oxidation was completely inhibited. At this concentration, MeBr removal rates were equivalent in killed and live controls, which indicated a chemical rather than biological removal reaction. At lower concentrations (1,000 ppm) of MeBr, methanotrophs were active and MeBr consumption rates were 10-fold higher in live controls than in killed controls. Soils exposed to trace levels (10 ppm) of MeBr demonstrated complete consumption within 5 h of incubation, while controls inhibited with MeF or incubated without O 2 had 50% lower removal rates. Aerobic soils oxidized [ 14 C]MeBr to 14 CO 2 , and MeF inhibited oxidation by 72%. Field experiments demonstrated slightly lower MeBr removal rates in chambers containing MeF than in chambers lacking MeF. Collectively, these results show that soil methanotrophic bacteria, as well as other microbes, can degrade MeBr present in the environment.
Applied and Environmental Microbiology↗
Selective inhibition of ammonium oxidation and nitrification-linked N2O formation by methyl fluoride and dimethyl ether
Methyl fluoride (CH 3 F) and dimethyl ether (DME) inhibited nitrification in washed-cell suspensions of Nitrosomonas europaea and in a variety of oxygenated soils and sediments. Headspace additions of CH 3 F (10% [vol/vol]) and DME (25% [vol/vol]) fully inhibited NO 2 - and N 2 O production from NH 4 + in incubations of N. europaea , while lower concentrations of these gases resulted in partial inhibition. Oxidation of hydroxylamine (NH 2 OH) by N. europaea and oxidation of NO 2 - by a Nitrobacter sp. were unaffected by CH 3 F or DME. In nitrifying soils, CH 3 F and DME inhibited N 2 O production. In field experiments with surface flux chambers and intact cores, CH 3 F reduced the release of N 2 O from soils to the atmosphere by 20- to 30-fold. Inhibition by CH 3 F also resulted in decreased NO 3 - + NO 2 - levels and increased NH 4 + levels in soils. CH 3 F did not affect patterns of dissimilatory nitrate reduction to ammonia in cell suspensions of a nitrate-respiring bacterium, nor did it affect N 2 O metabolism in denitrifying soils. CH 3 F and DME will be useful in discriminating N 2 O production via nitrification and denitrification when both processes occur and in decoupling these processes by blocking NO 2 - and NO 3 - production.
Applied and Environmental Microbiology↗
In situ bacterial selenate reduction in the agricultural drainage systems of western Nevada
Dissimilatory in situ selenate reduction to elemental selenium in sediments from irrigated agricultural drainage regions of western Nevada was measured at ambient Se oxyanion concentrations. Selenate reduction was rapid, with turnover rate constants ranging from 0.04 to 1.8 h -1 at total Se concentrations in pore water of 13 to 455 nM. Estimates of removal rates of selenium oxyanions were 14, 38, and 155 μ mol m -2 day -1 for South Lead Lake, Massie Slough, and Hunter Drain, respectively.
Nevada↗
Dissimilatory selenate reduction potentials in a diversity of sediment types
We measured potential rates of bacterial dissimilatory reduction of 75 SeO 4 2− to 75 Se 0 in a diversity of sediment types, with salinities ranging from freshwater (salinity = 1 g/liter) to hypersaline (salinity = 320 g/liter and with pH values ranging from 7.1 to 9.8. Significant biological selenate reduction occurred in all samples with salinities from 1 to 250 g/liter but not in samples with a salinity of 320 g/liter. Potential selenate reduction rates (25 nmol of SeO 4 2− per ml of sediment added with isotope) ranged from 0.07 to 22 μmol of SeO 4 2− reduced liter −1 h −1 . Activity followed Michaelis-Menten kinetics in relation to SeO 4 2− concentration ( K m of selenate = 7.9 to 720 μM). There was no linear correlation between potential rates of SeO 4 2− reduction and salinity, pH, concentrations of total Se, porosity, or organic carbon in the sediments. However, potential selenate reduction was correlated with apparent K m for selenate and with potential rates of denitrification ( r = 0.92 and 0.81, respectively). NO 3 − , NO 2 − , MoO 4 2− , and WO 4 2− inhibited selenate reduction activity to different extents in sediments from both Hunter Drain and Massie Slough, Nev. Sulfate partially inhibited activity in sediment from freshwater (salinity = 1 g/liter) Massie Slough samples but not from the saline (salinity = 60 g/liter) Hunter Drain samples. We conclude that dissimilatory selenate reduction in sediments is widespread in nature. In addition, in situ selenate reduction is a first-order reaction, because the ambient concentrations of selenium oxyanions in the sediments were orders of magnitude less than their K m s.
California, Nevada↗
Acetylene as a substrate in the development of primordial bacterial communities
The fermentation of atmospheric acetylene by anaerobic bacteria is proposed as the basis of a primordial heterotrophic food chain. The accumulation of fermentation products (acetaldehyde, ethanol, acetate and hydrogen) would create niches for sulfate-respiring bacteria as well as methanogens. Formation of acetylene-free environments in soils and sediments would also alter the function of nitrogenase from detoxification to nitrogen-fixation. The possibility of an acetylene-based anaerobic food chain in Jovian-type atmospheres is discussed. ?? 1988 Kluwer Academic Publishers.
Origins of Life and Evolution of the Biosphere↗
Bacterial ethane formation from reduced, ethylated sulfur compounds in anoxic sediments
Trace levels of ethane were produced biologically in anoxic sediment slurries from five chemically different aquatic environments. Gases from these locations displayed biogenic characteristics, having 12 C-enriched values of δ 13 CH 4 (−62 to −86%.), δ 13 C 2 H 6 (−35 to −55%.) and high ratios (720 to 140,000) of CH 4 [C 2 H 6 + C 3 H 8 ] "> CH4[C2H6+ C3H8] . Endogenous production of ethane by slurries was inhibited by autoclaving or by addition of the inhibitor of methanogenic bacteria, 2-bromoethanesulfonic acid (BES). Ethane formation was stimulated markedly by ethanethiol (ESH), and, to a lesser extent, by diethylsulfide (DES). Formation of methane and ethane in ESH- or DES-amended slurries was blocked by BES. Experiments showed that ethionine (or an analogous compound) could be a precursor of ESH. Ethylamine or ethanol additions to slurries caused only a minor stimulation of ethane formation. Similarly, propanethiol additions resulted in only a minor enhancement of propane formation. Cell suspensions of a methyltrophic methanogen produced traces of ethane when incubated in the presence of DES, although the organism did not grow on this compound. These results indicate that methanogenic bacteria produce ethane from the traces of ethylated sulfur compounds present in recent sediments. Preliminary estimates of stable carbon isotope fractionation associated with sediment methane formation from dimethylsulfide was about 40%., while ethane formation from DES and ESH was only 4. 6 and 6.5%., respectively.
Geochimica et Cosmochimica Acta↗
Microbial and biogeochernical processes Soda Lake, Nevada
Meromictic, alkaline lakes represent modern-day analogues of lacustrine source rock depositional environments. In order to further our understanding of how these lakes function in terms of limnological and biogeochemical processes, we have conducted an interdisciplinary study of Big Soda Lake. Annual mixolimnion productivity (ca. 500 g m -2 ) is dominated by a winter diatom bloom (60% of annual) caused by upward transport of ammonia to the epilimnion. The remainder of productivity is attributable to chemoautotrophs (30%) and photosynthetic bacteria (10%) present at the oxic -anoxic interface from May to November. Studies of bacterial heterotrophy and particulate fluxes in the water column indicate that about 90% of annual productivity is remineralized in the mixolimnion, primarily by fermentative bacteria. However, high rates of sulphate reduction (9-29 mmol m -2 yr -1 ) occur in the monimolimnion waters, which could remineralize most (if not all) of the primary productivity. This discrepancy has not as yet been fully explained. Low rates of methanogenesis also occur in the monimolimnion waters and sediments. Most of the methane is consumed by anaerobic methane oxidation occurring in the monimolimnion water column. Other bacterial processes occurring in the lake are also discussed. Preliminary studies have been made on the organic geochemistry of the monimolimnion sediments. Carbon-14-dating indicates a lower depositional rate prior to meromixis and a downcore enrichment in 13 C of organic carbon and chlorophyll derivatives. Hydrous pyrolysis experiments indicate that the sediment organic matter is almost entirely derived from the water column with little or no contribution from terrestrial sources. The significance of the organics released by hydrous pyrolysis is discussed.
Book chapter↗
Chemistry and microbiology of a sewage spill in South San Francisco Bay
During three weeks of September 1979, the breakdown of a waste treatment plant resulted in the discharge of a large volume (1.5×10 7 m 3 ) of primary-treated sewage into a tributary of South San Francisco Bay, California. Chemical and microbial changes occurred within the tributary as decomposition and nitrification depleted dissolved oxygen. Associated with anoxia were relatively high concentrations of particulate organic carbon, dissolved CO 2 , CH 4 , C 2 H 4 , NH + 4 , and fecal bacteria, and low phytoplankton biomass and photosynthetic oxygen production. South San Francisco Bay experienced only small changes in water quality, presumably because of its large volume and the assimilation of wastes that occurred within the tributary. Water quality improved rapidly in the tributary once normal tertiary treatment resumed.
California↗
Autotrophic processes in meromictic Big Soda Lake, Nevada.
Daily rates of oxygenic photosynthesis (OP) by phytoplankton, anoxygenic photosynthesis (AP) by purple sulfur bacteria, and chemoautotrophic productivity (CP = dark CO2 assimilation) were measured once each season. Total daily productivity and the relative importance of each autotrophic process varied with seasonal changes in vertical mixing, light availability, and the biomass of phototrophs. Daily productivity was highest (2830 mg C.m-2) and was dominated by OP in winter when the mixolimnion was isothermal, the biomass of phytoplankton was high, and the biomass of purple sulfur bacteria was low. During the summer-fall period of thermal stratification, phytoplankton biomass decreased, a plate of purple sulfur bacteria formed below the oxycline, and daily rates of dark CO2 assimilation (CP = 390-680 mg C.m-2) exceeded phototrophic productivity (OP + AP = 200-370 mg C.m-2). Total annual productivity was approx 500 g C.m-2, of which 60% was produced by phytoplankton (mostly in winter), 30% by chemoautotrophs (nitrifying and sulfur-oxidizing bacteria), and only 10% by photosynthetic bacteria. -Authors
Limnology and Oceanography↗
Low-temperature formation of hydrocarbon gases in San Francisco Bay sediment (California, U.S.A.)
To understand the processes responsible for the presence of low-molecular-weight hydrocarbons (C1-C4) in anoxic environments, we studied sediments collected from an anaerobic estuarine mudflat. In these sediments methane (C1) was several orders of magnitude more abundant than all other C2-C4 hydrocarbons; the C1 (C2 + C3) ratio was ??? 13,000. Mean ethane/ethene and propane/propene ratios were 0.4 and 0.7, respectively. Production of C1-C4 hydrocarbons was monitored during prolonged incubation (7 months) of sediments at 27?? and 4??C. Samples stored at 27??C generated significant quantities of C1-C4 hydrocarbon gases. Incubation at 4??C inhibited production of these gases. Several bactericides were tested with respect to their ability to inhibit formation of gaseous hydrocarbons. Sodium azide, chloroform, and 2-bromoethanesulfonic acid effectively inhibited methane formation, but not ethene formation in dilute continuously-shaken sediment slurries. Zephiran chloride only caused partial inhibition of methanogenesis (46%) and ethene generation (34%) in these slurries. In experiments with more concentrated unshaken sediment slurries, however, zephiran chloride and sodium azide did not block formation of methane, ethane, or propane. Only storage at -10??C prevented production of these gases. These results indicate that C1-C4 hydrocarbons can be formed by low-temperature reactions, possibly mediated by microorganisms. ?? 1982.
Chemical Geology↗