Alkyl halide formation from degradation of carboxylic acids in the presence of Fe(III) and halides under light irradiation.

Advanced oxidation processes (AOPs) have been widely used in water and wastewater treatment and have shown excellent performance in remediating contaminated water. However, their oxidation byproducts, including halogenated organics, have recently attracted increasing attention. Alkyl halides are among the most important environmental pollutants in nature. Here, we report a Fenton-like reaction in which alkyl halides can form during the photodegradation of aliphatic carboxylic acids in the presence of Fe(III) and halides. Chloromethane, chloroethane, and 1-chloropropane were produced from the degradation of acetic acid, propionic acid and n-butyric acid, respectively. CH3Cl, CH2Cl2 and CHCl3 were all identified as the products of acetic acid with the yields of approximately 5.1%, 0.2% and 0.005%, respectively. It was demonstrated that hydroxyl radicals, halogen radicals and alkyl radicals were involved in the formation of alkyl halides. A possible mechanism of chloromethane formation was proposed based on the results. In real samples of saline water, the addition of carboxylic acid and Fe(III) significantly promoted the generation of CH3Cl under xenon lamp irradiation. The results indicated that the coexistence of Fe(III), halides and carboxylic acids enhanced the photochemical release of alkyl halides. The reactions described in this paper may contribute to knowledge on the mechanism of halogenated byproduct formation during AOPs.

Assessment of gas chromatography methodology approach for the trace evaluation of carcinogenic impurity, methyl chloride, in trimetazidine dihydrochloride.

OBJECTIVE: A simple and robust head space/gas chromatography with flame ionisation sensor (HS/GC/FIS) approach for the trace evaluation of carcinogenic impurity, methyl chloride, in trimetazidine dihydrochloride (TRD) drug ingredient and its formulation is described. METHOD: This HS/GC/FIS approach was based on separation and analysis of CH3Cl content on DB-624 [75.0m - length, 0.53mm - internal diameter, 3.0µm - film thickness] column using nitrogen as carrier gas flowing through the column at 3mL/min stream rate. Detection of eluted CH3Cl was accomplished with flame ionization sensor at a set temperature of 260̊C. RESULTS: The optimised HS/GC/FIS methodological approach was thoroughly validated, demonstrating that it was linear with range of 5.0ppm to 1508.4ppm, sensitive with detection limit of 1.65ppm and quantification limit of 5.01ppm, reproducible with RSD values of 2.10-2.35%, accurate with recoveries of 81.9-99.0%, robust with percent variation of 7.5-12.22% with respect to changes in oven temperature, injector temperature, detector temperature and practical for regular TRD quality control. CONCLUSION: The findings revealed that with this optimised HS/GC/FIS methodological approach, the trace amounts of carcinogenic impurity (methyl chloride) in TRD drug ingredient and formulation could be successfully measured.

Design and fabrication of new anticancer sensor for monitoring of daunorubicin using 1-methyl-3-octylimidazolinium chloride and tin oxide/nitrogen-doped graphene quantum dot nanocomposite electrochemical sensor.

In this study, a novel tin oxide/nitrogen-doped graphene quantum dot nanocomposite (SnO2-NDGQD) and 1-methyl-3-octylimidazolinium chloride (1M3OICl) ionic liquid amplified carbon paste electrode (CPE) was fabricated as an efficient and fast-response sensor to determine daunorubicin, an anticancer drug. The electrochemical characteristics of daunorubicin at the surface of the 1M3OICl/SnO2-NDGQD/CPE was explored via various voltammetric methods. The high-resolution transmission electron microscope (HR-TEM) images were recorded to examine the morphological structure of the as-synthesized nanocomposites. The 1M3OICl/SnO2-NDGQD/CPE offered a wide linear concentration of 0.001-280.0 µM with a low detection limit of 0.40 nM at the optimized experimental conditions using square wave voltammetric (SWV) method. In a nutshell, the developed electrode illustrated outstanding selectivity in the presence of interfering agents and long-term stability. The1M3OICl/SnO2-NDGQD/CPE was used as new and powerful analytical tool for determination of daunorubicin in real samples with recovery range 98.75%-104.8%.

Evaluation of volatile organic compound (VOC) emissions from memory foam mattresses and potential implications for consumer health risk.

Chemical emissions from two new memory foam mattresses were evaluated in a simulated consumer use environment over the course of 32 days. Passive 12- and 24-h samples (n = 62) were collected for various VOCs. Airborne concentrations of chemicals associated with the mattresses (2-propanol, acetone, chloromethane, toluene, and ΣVOC) peaked during the first day after installation and progressively decayed over the course of the following 31 days. Emission rates were derived using a two-phase, double exponential source decay model paired with a one-compartment generalized indoor air quality model; short- and long-term emission half-lives for individual chemicals were on the order of hours (approximately 4 or 12 h) and days (approximately 24 days), respectively. Model-estimated average ΣVOC concentrations for the 32-day period of the study were approximately 20 and 33 µg/m3 for Mattress 1 and 2, respectively, while the modeled one-year average concentrations were 2.7 and 4.2 µg/m3, respectively. First-year trends for both mattresses were qualitatively similar, with the sum of 2-propanol, acetone, chloromethane, and toluene contributing to approximately 81% and 95% of the first-year ΣVOC concentration of Mattress 1 and 2, respectively. The airborne concentrations of individual chemicals and ΣVOC measured and modeled in this study were well below available health-based benchmarks for individual chemicals and within available indoor air quality recommendations for ΣVOC, suggesting that it is unlikely that the use of the models of mattresses evaluated in this study would pose a health risk to consumers.

13 C-chloromethane incubations provide evidence for novel bacterial chloromethane degraders in a living tree fern.

Chloromethane (CH3 Cl) is the most abundant halogenated volatile organic compound in the atmosphere and contributes to stratospheric ozone depletion. CH3 Cl has mainly natural sources such as emissions from vegetation. In particular, ferns have been recognized as strong emitters. Mitigation of CH3 Cl to the atmosphere by methylotrophic bacteria, a global sink for this compound, is likely underestimated and remains poorly characterized. We identified and characterized CH3 Cl-degrading bacteria associated with intact and living tree fern plants of the species Cyathea australis by stable isotope probing (SIP) with 13 C-labelled CH3 Cl combined with metagenomics. Metagenome-assembled genomes (MAGs) related to Methylobacterium and Friedmanniella were identified as being involved in the degradation of CH3 Cl in the phyllosphere, i.e., the aerial parts of the tree fern, while a MAG related to Sorangium was linked to CH3 Cl degradation in the fern rhizosphere. The only known metabolic pathway for CH3 Cl degradation, via a methyltransferase system including the gene cmuA, was not detected in metagenomes or MAGs identified by SIP. Hence, a yet uncharacterized methylotrophic cmuA-independent pathway may drive CH3 Cl degradation in the investigated tree ferns.

Methyl Chloride and Methyl Bromide Production and Consumption in Coastal Antarctic Tundra Soils Subject to Sea Animal Activities.

Methyl chloride (CH3Cl) and methyl bromide (CH3Br) are the predominant carriers of natural chlorine and bromine from the troposphere to the stratosphere, which can catalyze the destruction of stratospheric ozone. Here, penguin colony soils (PCS) and the adjacent tundra soils (i.e., penguin-lacking colony soils, PLS), seal colony soils (SCS), tundra marsh soils (TMS), and normal upland tundra soils (UTS) in coastal Antarctica were collected and incubated for the first time to confirm that these soils were CH3Cl and CH3Br sources or sinks. Overall, tundra soil acted as a net sink for CH3Cl and CH3Br with potential flux ranges from -18.1 to -2.8 pmol g-1 d-1 and -1.32 to -0.24 pmol g-1 d-1, respectively. The deposition of penguin guano or seal excrement into tundra soils facilitated the simultaneous production of CH3Cl and CH3Br and resulted in a smaller sink in PCS, SCS, and PLS. Laboratory-based thermal treatments and anaerobic incubation experiments suggested that the consumption of CH3Cl and CH3Br was predominantly mediated by microbes while the production was abiotic and O2 independent. Temperature gradient incubations revealed that increasing soil temperature promoted the consumption of CH3Cl and CH3Br in UTS, suggesting that the regional sink may increase with Antarctic warming, depending on changes in soil moisture and abiotic production rates.

Sources and sinks of chloromethane in a salt marsh ecosystem: constraints from concentration and stable isotope measurements of laboratory incubation experiments.

Chloromethane (CH3Cl) is the most abundant long-lived chlorinated organic compound in the atmosphere and contributes significantly to natural stratospheric ozone depletion. Salt marsh ecosystems including halophyte plants are a known source of atmospheric CH3Cl but estimates of their total global source strength are highly uncertain and knowledge of the major production and consumption processes in the atmosphere-halophyte-soil system is yet incomplete. In this study we investigated the halophyte plant, Salicornia europaea, and soil samples from a coastal salt marsh site in Sardinia/Italy for their potential to emit and consume CH3Cl and using flux measurements, stable isotope techniques and Arrhenius plots differentiated between biotic and abiotic processes. Our laboratory approach clearly shows that at least 6 different production and consumption processes are active in controlling atmospheric CH3Cl fluxes of a salt marsh ecosystem. CH3Cl release by dried plant and soil material was substantially higher than that from the fresh material at temperatures ranging from 20 to 70 °C. Results of Arrhenius plots helped to distinguish between biotic and abiotic formation processes in plants and soils. Biotic CH3Cl consumption rates were highest at 30 °C for plants and 50 °C for soils, and microbial uptake was higher in soils with higher organic matter content. Stable isotope techniques helped to distinguish between formation and degradation processes and also provided a deeper insight into potential methyl moiety donor compounds, such as S-adenosyl-l-methionine, S-methylmethionine and pectin, that might be involved in the abiotic and biotic CH3Cl production processes. Our results clearly indicate that cycling of CH3Cl in salt marsh ecosystems is a result of several biotic and abiotic processes occurring simultaneously in the atmosphere-plant-soil system. Important precursor compounds for biotic and abiotic CH3Cl formation might be methionine derivatives and pectin. All formation and degradation processes are temperature dependent and thus environmental changes might affect the strength of each source and sink within salt marsh ecosystems and thus considerably alter total fluxes of CH3Cl from salt marsh ecosystems to the atmosphere.

A bioinspired strategy for designing well-ordered nanotubular structures by templateless electropolymerization of thieno[3,4-b]thiophene-based monomers.

Here, a bioinspired strategy is used to prepare well-ordered nanotubular structures, as observed in animals and plants, such as gecko toe pads or corals. The nanotubes are obtained by templateless electropolymerization of thieno[3,4-b]thiophene-based monomers with various aromatic groups in an organic solvent (dichloromethane). The most interesting and robust structures were obtained with carbazole and pyrene substituents to the base monomer structure, since these groups participate significantly in the polymerization and also have strong π-stacking interactions. The addition of water to electropolymerization solvent significantly impacted the formation of nanotubes, as it caused the release of a significant amount of H2 and O2 bubbles, depending on the electropolymerization method. Identifying templateless approaches to vary nanotubular structures is very interesting, as these materials are sought-after for applications in water harvesting systems. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology (part 3)'.

Photochemical Generation of Methyl Chloride from Humic Aicd: Impacts of Precursor Concentration, Solution pH, Solution Salinity and Ferric Ion.

Methyl chloride (CH3Cl) is presently understood to arise from biotic and abiotic processes in marine systems. However, the production of CH3Cl via photochemical processes has not been well studied. Here, we reported the production of CH3Cl from humic acid (HA) in sunlit saline water and the effects of the concentration of HA, chloride ions, ferric ions and pH were investigated. HA in aqueous chloride solutions or natural seawater were irradiated under an artificial light, and the amounts of CH3Cl were determined using a purge-and-trap and gas chromatography-mass spectrometry. CH3Cl was generated upon irradiation and its amount increased with increasing irradiation time and the light intensity. The formation of CH3Cl increased with an increase of HA concentration ranging from 2 mg L-1 to 20 mg L-1 and chloride ion concentration ranging from 0.02 mol L-1 to 0.5 mol L-1. The photochemical production of CH3Cl was pH-dependent, with the highest amount of CH3Cl generating near neutral conditions. Additionally, the generation of CH3Cl was inhibited by ferric ions. Finally, natural coastal seawater was irradiated under artificial light and the concentration of CH3Cl rose significantly. Our results suggest that the photochemical process of HA may be a source of CH3Cl in the marine environment.

Chlorine Isotope Fractionation of the Major Chloromethane Degradation Processes in the Environment.

Chloromethane (CH3Cl) is an important source of chlorine in the stratosphere, but detailed knowledge of the magnitude of its sources and sinks is missing. Here, we measured the stable chlorine isotope fractionation (εCl) associated with the major abiotic and biotic CH3Cl sinks in the environment, namely, CH3Cl degradation by hydroxyl (·OH) and chlorine (·Cl) radicals in the troposphere and by reference bacteria Methylorubrum extorquens CM4 and Leisingera methylohalidivorans MB2 from terrestrial and marine environments, respectively. No chlorine isotope fractionation was detected for reaction of CH3Cl with ·OH and ·Cl radicals, whereas a large chlorine isotope fractionation (εCl) of -10.9 ± 0.7‰ (n = 3) and -9.4 ± 0.9 (n = 3) was found for CH3Cl degradation by M. extorquens CM4 and L. methylohalidivorans MB2, respectively. The large difference in chlorine isotope fractionation observed between tropospheric and bacterial degradation of CH3Cl provides an effective isotopic tool to characterize and distinguish between major abiotic and biotic processes contributing to the CH3Cl sink in the environment. Our findings demonstrate the potential of emerging triple-element isotopic approaches including chlorine to carbon and hydrogen analysis for the assessment of global cycling of organochlorines.

Simple and Efficient Truncation of Virtual Spaces in Embedded Wave Functions via Concentric Localization.

We present a strategy to generate "concentrically local orbitals" for the purpose of decreasing the computational cost of wave function-in-density functional theory (WF-in-DFT) embedding. The concentric localization is performed for the virtual orbitals by first projecting the virtual space onto atomic orbitals centered on the embedded atoms. Using a one-particle operator, these projected orbitals are then taken as a starting point to iteratively span the virtual space, recursively creating virtual orbital "shells" with consecutively decreasing correlation energy recovery at each iteration. This process can be repeated to convergence, allowing for tunable accuracy. Assessment of the proposed scheme is performed by application to the potential energy diagram of the Menshutkin reaction of chloromethane and ammonia inside a segment of a carbon nanotube and the torsional potential of a simplified version of the retinal chromophore.

Modelling of the methyl halide biodegradation in bacteria and its effect on environmental systems.

Methyl halide group of pesticides are being used widely in past decades as fumigant but due to their hazardous effect, these pesticides are not sold directly. They are volatile and gaseous in nature and may easily come in the contact of trophosphere and stratosphere. In troposphere, they are harmful to the living beings; nevertheless, in stratosphere they react with ozone and degrade the ozone layers. In this study, we have investigated the in-silico pathways of methyl halide and its toxic effect on living systems like pest, humans and environment. Till date, limited studies provide the understanding of degradation of methyl halide and its effect on the environment. This leads to availability of scanty information for overall bio-magnifications of methyl halides at molecular and cellular level. The model developed in the present study explains how a volatile toxic compound not only affects living systems on earth but also on environmental layers. Hub nodes were also evaluated by investigating the developed model topologically. Methyl transferase system is identified as promising enzyme in response to degradation of methyl halides.

Isotopic Characterization (2H, 13C, 37Cl, 81Br) of Abiotic Degradation of Methyl Bromide and Methyl Chloride in Water and Implications for Future Studies.

Methyl bromide (CH3Br) and methyl chloride (CH3Cl) significantly contribute to stratospheric ozone depletion. The atmospheric budgets of both compounds are unbalanced with known degradation processes outweighing known emissions. Stable isotope analysis may be capable to identify and quantify emissions and to achieve a balanced budget. Degradation processes do, however, cause isotope fractionation in methyl halides after emission and hence knowledge about these processes is a crucial prerequisite for any isotopic mass balance approach. In the current study, triple-element isotope analysis (2H, 13C, 37Cl/81Br) was applied to investigate the two main abiotic degradation processes of methyl halides (CH3X) in fresh and seawater: hydrolysis and halide exchange. For CH3Br, nucleophilic attack by both H2O and Cl- caused significant primary carbon and bromine isotope effects accompanied by a secondary inverse hydrogen isotope effect. For CH3Cl only nucleophilic substitution by H2O was observed at significant rates causing large primary carbon and chlorine isotope effects and a secondary inverse hydrogen isotope effect. Observed dual-element isotope ratios differed slightly from literature values for microbial degradation in water and hugely from radical reactions in the troposphere. This bodes well for successfully distinguishing and quantifying degradation processes in atmospheric methyl halides using triple-element isotope analysis.

Methylotrophs and Methylotroph Populations for Chloromethane Degradation.

Chloromethane is a halogenated volatile organic compound, produced in large quantities by terrestrial vegetation. After its release to the troposphere and transport to the stratosphere, its photolysis contributes to the degradation of stratospheric ozone. A better knowledge of chloromethane sources (production) and sinks (degradation) is a prerequisite to estimate its atmospheric budget in the context of global warming. The degradation of chloromethane by methylotrophic communities in terrestrial environments is a major underestimated chloromethane sink. Methylotrophs isolated from soils, marine environments and more recently from the phyllosphere have been grown under laboratory conditions using chloromethane as the sole carbon source. In addition to anaerobes that degrade chloromethane, the majority of cultivated strains were isolated in aerobiosis for their ability to use chloromethane as sole carbon and energy source. Among those, the Proteobacterium Methylobacterium (recently reclassified as Methylorubrum) harbours the only characterisized 'chloromethane utilization' (cmu) pathway, so far. This pathway is not representative of chloromethane-utilizing populations in the environment as cmu genes are rare in metagenomes. Recently, combined 'omics' biological approaches with chloromethane carbon and hydrogen stable isotope fractionation measurements in microcosms, indicated that microorganisms in soils and the phyllosphere (plant aerial parts) represent major sinks of chloromethane in contrast to more recently recognized microbe-inhabited environments, such as clouds. Cultivated chloromethane-degraders lacking the cmu genes display a singular isotope fractionation signature of chloromethane. Moreover, 13CH3Cl labelling of active methylotrophic communities by stable isotope probing in soils identify taxa that differ from the taxa known for chloromethane degradation. These observations suggest that new biomarkers for detecting active microbial chloromethane-utilizers in the environment are needed to assess the contribution of microorganisms to the global chloromethane cycle.

Physiological responses of Chlorella pyrenoidosa to 1-hexyl-3-methyl chloride ionic liquids with different cations.

Ionic liquids (ILs) are massively used in multiple fields of industry, and consequently, they have entered the environment and become potential threats to the respective ecosystems. In this paper, the toxicity of two different cationic types of ILs (1-hexyl-3-methyl pyridine chloride ([C6Py]Cl) and 1-hexyl-3-methyl imidazole chloride ([C6MIM]Cl)) to Chlorella pyrenoidosa (C. pyrenoidosa) was investigated. Growth inhibition increased with increasing ILs concentrations. C. pyrenoidosa showed a certain recovery at low ILs concentrations, the growth inhibition decreased from 6.13% to 1.57% of the control from 24 h to 96 h, respectively, in 0.5 mg/L [C6MIM]Cl treatment. However, growth inhibition was negatively related with exposure time at high concentrations, and the strongest toxic effects were observed after 48 h. The IC50 values (half inhibitory concentration) were 8.47, 6.65, 6.91 and 7.11 mg/L of [C6MIM]Cl, respectively, in 24, 48, 72, and 96 h, and were 9.05, 6.83, 7.79 and 8.14 mg/L of [C6Py]Cl, respectively. Chlorophyll content declined with higher concentrations of the ILs. The values of chlorophyll fluorescence parameters: the maximum effective quantum yield of photosystem II (PSII) (Fv/Fm), maximum quantum yield in PSII (Fv/F0), and photosynthetic efficiency in PSII (Y(II)), decreased, whereas the minimal fluorescence (F0) increased following the ILs treatment, indicating damage to the photosystem II. [C6MIM]Cl and [C6Py]Cl caused deformation of algae cells, plasmolysis, and damage of the cell membrane and cell wall, and affected organelle structure. Reactive oxygen species (ROS) concentrations increased with higher ILs concentrations from, and superoxide dismutase and catalase activity first increased and then decreased, indicating that the antioxidant defense system was activated to counteract ROS. ROS was the main stress in C. pyrenoidosa induced by ILs, and compared with [C6Py]Cl, [C6MIM]Cl were more toxic to C. pyrenoidosa.

Evaluation of developmental toxicity of Methyl Chloride (Chloromethane) in rats, mice, and rabbits.

Methyl Chloride (MeCl; Chloromethane) is a high production volume chemical (>1000 t/a) and is used as an industrial solvent. Based on cardiac lesions reported in developmental toxicity studies in mice, but not in rats, manufacturers decided to classify MeCl as a developmental toxicant, cat. 2. Recently, the European Chemical Agency required a developmental toxicity study in a non-rodent species. No developmental toxicity was observed in rabbits in the recently completed, GLP, OECD 414 guideline study. In view of the absence of cardiac effects in rats and rabbits, the purpose of this review is to consider whether the cardiac effects reported in mice should be considered real effects and, if so, their potential for relevance to humans. This paper provides substantive new evidence with data from a third species and shows that an evaluation of the integrated scientific evidence indicates the reported developmental cardiac effects in mice, if not an artifact, are unlikely to be relevant to humans. As such the classification of MeCl for developmental toxicity was reconsidered.

Methanol consumption drives the bacterial chloromethane sink in a forest soil.

Halogenated volatile organic compounds (VOCs) emitted by terrestrial ecosystems, such as chloromethane (CH3Cl), have pronounced effects on troposphere and stratosphere chemistry and climate. The magnitude of the global CH3Cl sink is uncertain since it involves a largely uncharacterized microbial sink. CH3Cl represents a growth substrate for some specialized methylotrophs, while methanol (CH3OH), formed in much larger amounts in terrestrial environments, may be more widely used by such microorganisms. Direct measurements of CH3Cl degradation rates in two field campaigns and in microcosms allowed the identification of top soil horizons (i.e., organic plus mineral A horizon) as the major biotic sink in a deciduous forest. Metabolically active members of Alphaproteobacteria and Actinobacteria were identified by taxonomic and functional gene biomarkers following stable isotope labeling (SIP) of microcosms with CH3Cl and CH3OH, added alone or together as the [13C]-isotopologue. Well-studied reference CH3Cl degraders, such as Methylobacterium extorquens CM4, were not involved in the sink activity of the studied soil. Nonetheless, only sequences of the cmuA chloromethane dehalogenase gene highly similar to those of known strains were detected, suggesting the relevance of horizontal gene transfer for CH3Cl degradation in forest soil. Further, CH3Cl consumption rate increased in the presence of CH3OH. Members of Alphaproteobacteria and Actinobacteria were also 13C-labeled upon [13C]-CH3OH amendment. These findings suggest that key bacterial CH3Cl degraders in forest soil benefit from CH3OH as an alternative substrate. For soil CH3Cl-utilizing methylotrophs, utilization of several one-carbon compounds may represent a competitive advantage over heterotrophs that cannot utilize one-carbon compounds.

Empirical data in support of a skin notation for methyl chloride.

This article presents the first empirical experimental data on the skin absorption of methyl chloride gas using an in vitro technique and human skin. Methyl chloride is a commonly used industrial agent that is known to be an inhalational hazard but is also reported to be absorbed through human skin in amounts that contribute substantially to systemic intoxication. As a result, is has been assigned a skin notation by the ACGIH. Other than predictive models, there is a general paucity of experimental data on the skin absorption of methyl chloride and therefore a distinct lack of empirical evidence in the open literature to support the assignment of a skin notation for this chemical. This study found that methyl chloride permeates through human epidermis when exposed at high atmospheric concentrations within relatively short timeframes. Therefore, providing important initial empirical evidence in support of the assignment of a skin notation.

Chloromethane Degradation in Soils: A Combined Microbial and Two-Dimensional Stable Isotope Approach.

Chloromethane (CHCl, methyl chloride) is the most abundant volatile halocarbon in the atmosphere and involved in stratospheric ozone depletion. The global CHCl budget, and especially the CHCl sink from microbial degradation in soil, still involves large uncertainties. These may potentially be resolved by a combination of stable isotope analysis and bacterial diversity studies. We determined the stable isotope fractionation of CHCl hydrogen and carbon and investigated bacterial diversity during CHCl degradation in three soils with different properties (forest, grassland, and agricultural soils) and at different temperatures and headspace mixing ratios of CHCl. The extent of chloromethane degradation decreased in the order forest > grassland > agricultural soil. Rates ranged from 0.7 to 2.5 µg g dry wt. d for forest soil, from 0.1 to 0.9 µg g dry wt. d for grassland soil, and from 0.1 to 0.4 µg g dry wt. d for agricultural soil and increased with increasing temperature and CHCl supplementation. The measured mean stable hydrogen enrichment factor of CHCl of -50 ± 13‰ was unaffected by temperature, mixing ratio, or soil type. In contrast, the stable carbon enrichment factor depended on CHCl degradation rates and ranged from -38 to -11‰. Bacterial community composition correlated with soil properties was independent from CHCl degradation or isotope enrichment. Nevertheless, increased abundance after CHCl incubation was observed in 21 bacterial operational taxonomical units (OTUs at the 97% 16S RNA sequence identity level). This suggests that some of these bacterial taxa, although not previously associated with CHCl degradation, may play a role in the microbial CHCl sink in soil.

Plant-Pesticide Interactions and the Global Chloromethane Budget.

Ecological, signaling, metabolic, and chemical processes in plant-microorganism systems and in plant-derived material may link the use of chlorinated pesticides in the environment with plant chloromethane emission. This neglected factor should be taken into account to assess global planetary budgets of chloromethane and impacts on atmospheric ozone depletion.