Degradation Products In Soil Research Articles

Promotion Mechanism of Atrazine Removal from Soil Microbial Fuel Cells by Semiconductor Minerals

In recent years, soil microbial fuel cells (Soil-MFCs) have attracted attention due to their simultaneous electricity production and contaminant removal functions, but soil electron transfer resistance limits their contaminant removal effectiveness. To overcome the above-mentioned drawbacks, in this study, a dual-chamber Soil-MFC was constructed using atrazine (ATR) as the target contaminant, and the electrochemical performance of Soil-MFC and ATR removal were enhanced by semiconductor mineral addition. Analysis of atrazine was performed in soil using HPLC and GC-MS, and analysis of metallic minerals using XPS. Anodic microorganisms were determined using high-throughput sequencing technology. The results showed that the addition of Fe3O4 increased the maximum output voltage of the device by 2.56 times, and the degradation efficiency of atrazine in the soil to 63.35%, while the addition of MnO2 increased the internal resistance of the device and affected the current output, and these changes were closely related to the ion dissolution rate of the semiconductor minerals. In addition, the addition of both minerals significantly increased the relative abundance of both Proteobacteria and Bacteroidota, and Fe3O4 simultaneously promoted the significant enrichment of Firmicutes, indicating that the semiconductor minerals significantly enhanced the enrichment of electroactive microorganisms near the anode. The structural equation modeling indicated that the semiconductor minerals achieved efficient degradation of ATR in the soil through a synergistic mechanism of metal ion leaching and microbial community structure changes. The detection of ATR and its degradation products in soil revealed that the degradation of ATR mainly included: (1) hydrolysis of atrazine by microorganisms to generate dehydroxylated atrazine (HYA); (2) reduced to diethyl atrazine (DEA) and diisopropyl atrazine (DIA) by extracellular electron reduction and re-dechlorination and hydrolysis to HYA. Semiconductor minerals make an important contribution to promoting microbial activity and extracellular electron reduction processes. The results of this study strengthen the power production and ATR removal efficiency of the Soil-MFC system and provide important theoretical support for the on-site removal of organic pollutants and the sustainable application of converting biomass energy into electricity.

Identification and Quantification of Dimethachlon Degradation Products in Soils and Their Effects on Soil Enzyme Activities.

In this study, high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS, Q-Exactive Orbitrap) and Compound Discoverer 3.3 were used to screen dimethachlon degradation products in soils. Four metabolites 4-(3,5-dichloroanilino)-4-oxobutanoic acid (DCBAA), 3,5-dichloroaniline (3,5-DCA), succinic acid, and muconic acid were confirmed by primary and secondary ion mass spectrometry comparisons between standards and samples. A quantitative analysis method of dimethachlon residues and four metabolites in soils was developed using HPLC-HRMS. Dimethachlon degradation in agricultural soil indoor unsterilized, sterilized, and field environments in three typical areas was measured. Dimethachlon degraded fast with a half-life of less than 1 day in three nonsterile soils. The maximum DCBAA and 3,5-DCA residues during degradation could reach 22.5-35.2% of the initial concentration of the parent dimethachlon. The metabolite DCBAA had a greater impact on soil enzyme activity than the parent dimethachlon.

Versatile derivatization for GC-MS and LC-MS: alkylation with trialkyloxonium tetrafluoroborates for inorganic anions, chemical warfare agent degradation products, organic acids, and proteomic analysis.

Analytical chemists resort to derivatization for improving the detection performance of certain categories of analytes. Within this context, alkylation reactions are regarded as an important asset for many methods based on GC-MS and LC-MS. Trialkyloxonium tetrafluoroborates (R[Formula: see text][BF4]-) are powerful alkylating agents with ionic liquid properties: they are nonvolatile salts soluble in water which are easier and safer to handle with respect to common alkylating agents like diazomethane. R[Formula: see text][BF4]- can perform the alkylation in both organic and aqueous media at pH conditions ranging from acidic to alkaline. Recent analytical applications of trialkyloxonium derivatizations include the high-precision determination of inorganic anions in complex matrices, the qualitative confirmation of chemical warfare agent degradation products in soils, the profiling of carboxylic acids in urine, and the detection of protein post-translational modifications induced by carbon dioxide. The common denominator for all methods presented can be found in the simplicity of the alkylation protocol which, in most of the cases, requires a single step addition of the reagent directly to the sample. Graphical Abstract Alkylation with trialkyloxonium salts for GC-MS and LC-MS analysis.

Environmental Fate of RNA Interference Pesticides: Adsorption and Degradation of Double-Stranded RNA Molecules in Agricultural Soils.

Double-stranded RNA (dsRNA) pesticides are a new generation of crop protectants that interfere with protein expression in targeted pest insects by a cellular mechanism called RNA interference (RNAi). The ecological risk assessment of these emerging pesticides necessitates an understanding of the fate of dsRNA molecules in receiving environments, among which agricultural soils are most important. We herein present an experimental approach using phosphorus-32 (32P)-radiolabeled dsRNA that allows studying key fate processes of dsRNA in soils with unprecedented sensitivity. This approach resolves previous analytical challenges in quantifying unlabeled dsRNA and its degradation products in soils. We demonstrate that 32P-dsRNA and its degradation products are quantifiable at concentrations as low as a few nanograms of dsRNA per gram of soil by both Cerenkov counting (to quantify total 32P-activity) and by polyacrylamide gel electrophoresis followed by phosphorimaging (to detect intact 32P-dsRNA and its 32P-containing degradation products). We show that dsRNA molecules added to soil suspensions undergo adsorption to soil particle surfaces, degradation in solution, and potential uptake by soil microorganisms. The results of this work on dsRNA adsorption and degradation advance a process-based understanding of the fate of dsRNA in soils and will inform ecological risk assessments of emerging dsRNA pesticides.

Root uptake and translocation of 14C-heptachlor and its degradation products in soil by zucchini and tomato seedlings.

To investigate root uptake and translocation of heptachlor and its degradates (cis-heptachlor epoxide and 1-hydroxychlordene) in soil, zucchini and tomato seedlings were transplanted to soil approximately four months after treatment with 14C-heptachlor. The results indicated that a relation between the root concentration factor and the log P ow did not follow Briggs' theory, probably due to the contribution of plant metabolism. It also appeared that a compound with a lower log P ow tends to show higher mobility from root to shoot.

Degradation products of polycondensed aromatic moieties (black carbon or pyrogenic carbon) in soil: Methodological improvements and comparison to contemporary black carbon concentrations

AbstractIt was found that benzenepolycarboxylic acids (BPCA) do naturally occur in soils. They can be assumed as black carbon degradation products. We propose an improved method to analyse black carbon degradation products in soil. Method optimization comprised extraction duration, sample clean‐up, and chromatographic separation conditions. The method is also suitable for subsequent isotope ratio mass spectrometry of individual BPCA. Accuracy was checked with quartz sand and soil samples spiked with known amounts of BPCA. In soil samples with varying properties we compared contents of black carbon and black carbon degradation products, i.e., total and free BPCA contents, respectively. Results show that our proposed method can extract black carbon degradation products from soil after 48 h of extraction with 500 mM NaOH compared to 72 h of the original method. Polyvalent cations should be removed by Dowex 50 W X 8, 200–400 mesh, while original cation removal with Merck cation exchange resin was not successful. Free BPCA can be separated and quantified directly by ion exchange chromatography followed by ultraviolet spectroscopy or isotope ratio mass spectrometry, while the original method involved another two days for derivatization and isolation of derivatized BPCA. Recovery of spiked BPCA to a range of different soil samples was 81 ± 19%. Free BPCA concentrations of a Cambisol, Chernozem, Ferralsol, and Anthrosol varied between 0 and 0.24 g kg−1 contributing 0–38% of total black carbon concentration. Free BPCA correlated with total black carbon, total organic carbon, and negatively with pH. However, further studies with a larger set of samples are necessary to systematically investigate conditions for black carbon degradation and, thus free BPCA formation in soils.

Biocide Runoff from Building Facades: Degradation Kinetics in Soil.

Biocides are common additives in building materials. In-can and film preservatives in polymer-resin render and paint, as well as wood preservatives are used to protect facade materials from microbial spoilage. Biocides leach from the facade material with driving rain, leading to highly polluted runoff water (up to several mg L-1 biocides) being infiltrated into the soil surrounding houses. In the present study the degradation rates in soil of 11 biocides used for the protection of building materials were determined in laboratory microcosms. The results show that some biocides are degraded rapidly in soil (e.g., isothiazolinones: T1/2 < 10 days) while others displayed higher persistence (e.g., terbutryn, triazoles: T1/2 ≫ 120 days). In addition, mass balances of terbutryn and octylisothiazolinone were determined, including nine (terbutryn) and seven (octylisothiazolinone) degradation products, respectively. The terbutryn mass balance could be closed over the entire study period of 120 days and showed that relative persistent metabolites were formed, while the mass balances for octylisothiazolinone could not be closed. Octylisothiazolinone degradation products did not accumulate over time suggesting that the missing fraction was mineralized. Microtox-tests revealed that degradation products were less toxic toward the bacterium Aliivibrio fischeri than their parent compounds. Rain is mobilizing these biocides from the facades and transports them to the surrounding soils; thus, rainfall events control how often new input to the soil occurs. Time intervals between rainfall events in Northern Europe are shorter than degradation half-lives even for many rapidly degraded biocides. Consequently, residues of some biocides are likely to be continuously present due to repeated input and most biocides can be considered as "pseudo-persistent"-contaminants in this context. This was verified by (sub)urban soil screening, where concentrations of up to 0.1 μg g-1 were detected for parent compounds as well as terbutryn degradation products in soils below biocide treated facades.

Phytoremediation of azoxystrobin and its degradation products in soil by P. major L. under cold and salinity stress

Azoxystrobin is a broad-spectrum, systemic and soil-applied fungicide used for crop protection against the four major classes of pathogenic fungi. The use of azoxystrobin use has induced water pollution and ecotoxicological effects upon aquatic organisms, long half-life in soils, as well as heath issues. Such issues may be solved by phytoremediation. Here, we tested the uptake and translocation of azoxystrobin and its degradation products by Plantago major, under cold stress and salt stress. The result demonstrated that azoxystrobin significantly accumulated in P. major roots under salinity conditions more than that in the P. major roots under cold conditions and natural condition within two days of experimental period. In P. major roots and leaves, the chromatograms of HPLC for azoxystrobin and metabolites under natural condition (control) and stressed samples (cold stress and salt stress) show different patterns of metabolism pathways reflecting changes in the degradation products. Azoxystrobin carboxylic acid (AZ-acid) formed by methyl ester hydrolysis was an important route in the roots and the leaves. AZ-pyOH and AZ-benzoic were detected in P. major roots under cold and salt stress, while did not detected in P. major roots under natural condition. In the leaves, AZ-pyOH and AZ-benzoic were detected in all treatments between 4 and 12days of exposure. Shoots of the stressed plants had greater H2O2 and proline contents than was observed in the control plants. The level of 100mM NaCl treatment induced significantly higher peroxidase (POD) activity than the non-treated control group. Leaf Chlorophyll contents in the plants at 80 and 100mM NaCl were significantly reduced than was observed in the control plants. I concluded that P. major had a high potential to contribute to remediation of saline-soil contaminated with azoxystrobin.

Degradation study of mesotrione and other triketone herbicides on soils and sediments

Triketone compounds are considered to be less stable in the ecosystems in comparison with other herbicides. However, their degradation processes in environment are under investigation as both parents and degradation products can exhibit toxicity on non-target organisms. The objective of this research was to investigate the degradation of triketone herbicides: mesotrione, sulcotrione, and tembotrione, as well as their degradation products in soils and sediments. The degradation studies were conducted in soil and sediment samples with different physicochemical properties. All experiments were conducted under standard experimental conditions; therefore, it was possible to assess the influence of pH, organic carbon (OC) content of soils and sediments, and the sunlight on the stability of triketones and their degradation products. The conditions of extraction and chromatographic determination were optimized for the determination of triketones and their degradation products in laboratory-spiked sediment and soil samples. The triketone degradation products exhibited higher stability in soil and sediment samples in comparison with parent herbicides. Soil microorganisms accelerated the degradation of all investigated compounds. In alkaline soil and sediments, all analytes exhibited higher stability in comparison with the acidic sorbents. The influence of OC content in sorbents was not evident. Photodegradation was the main path of triketones decomposition in soils and sediments. Since the stability of triketone herbicides may be significant, depending on the environmental conditions, the monitoring of the concentration of these compounds and in particular their degradation products should be conducted under the field conditions.

Determination of fluorotelomer alcohols and their degradation products in biosolids-amended soils and plants using ultra-high performance liquid chromatography tandem mass spectrometry

Degradation of fluorotelomer alcohols (FTOHs) was recognized as an additional source of perfluorocarboxylic acids (PFCAs). Quantification of FTOHs and their degradation products can help shed light on the sources and fates of PFCAs in the environment. In this study, an analytical method was developed for the determination of 6:2 and 8:2 FTOHs, and their degradation products of poly- and perfluorinated acids, including fluorotelomer saturated and unsaturated carboxylic acids (FTCAs and FTUCAs), secondary polyfluorinated alcohols and PFCAs in biosolids-amended soils and plants using ultra-high performance liquid chromatography tandem mass spectrometry (UPLC–MS/MS). The extract efficiencies of different methods including ethyl acetate and methanol (MeOH) for FTOHs and acetonitrile, MeOH, methyl tert-butyl ether (MTBE), NaOH-MeOH and NaOH-MTBE for poly- and perfluorinated acids were tested. The results showed that 6:2 and 8:2 FTOHs and their degradation products could be simultaneously and satisfactorily extracted by MeOH, cleaned up by Envi-Carb graphitized carbon and solid phase extraction, respectively, and determined by UPLC–MS/MS separately. NaOH in the extractant caused the conversion of 6:2 FTCA and 8:2 FTCA into the corresponding FTUCAs. The selected methods have matrix recoveries ranged from 52% to 102%, and detection limits of 0.01–0.46ng/g dry weight for FTOHs and their degradation products in soil and plant. The optimized method was applied successfully to quantify FTOHs and their degradation products in two biosolids-amended soils and plants. The total concentrations of FTOHs in the soils were 44.1±5.8 and 82.6±7.1ng/g, and in plants tissues 3.58±0.25 and 8.33±0.66ng/g. The total concentrations of poly- and perfluorinated acids in the soils were 168.0±13.2 and 349.6±11.2ng/g, and in plants tissues 78.0±6.4 and 75.5±5.3ng/g.

Effects of diphenylarsinic acid on bacterial and archaeal community structures in an anaerobic paddy soil

DPAA is often found as one of the major degradation products in soil and groundwater contaminated with diphenylcyanoarsine or diphenylchloroarsine. These compounds were produced mainly during the World Wars as chemical warfare agents. This study investigated the effect of DPAA contamination on soil bacterial and archaeal community structures under anaerobic conditions in a model experiment using 16S rRNA targeted PCR–DGGE fingerprinting of DNA extracted from the contaminated soil. DPAA decreased in anaerobically incubated soil cultures due to microbiological activity. Addition of rice straw partially enhanced the extent of DPAA degradation. Inorganic arsenic acid, PAA, and an unknown arsenical species were detected as degradation products using LC–ICPMS. PCR–DGGE fingerprinting for bacterial community analysis revealed that anaerobic bacterial and archaeal species, including Clostridium and Methanosarcina, became abundant in the incubated soil within a week. In the soil cultures incubated with DPAA, while a few bacterial bands found on the DGGE gels disappeared or became weaker, most of the bands showed no significant changes. Addition of DPAA had no significant effect on archaeal communities. These findings suggest that, even though DPAA may have a direct effect on some abundant bacterial species, overall bacterial and archaeal community structures under the anaerobic soil conditions tended to be stable regardless of DPAA contamination.

Analysis of cypermethrin residues and its main degradation products in soil and formulation samples by gas chromatography-electron impact-mass spectrometry in the selective ion monitoring mode

A fast, simple and inexpensive sample preparation method based on the matrix solid-phase extraction (SPE) technique is proposed for the isolation of cypermethrin and its metabolite residues from soils. Both the extraction and clean-up procedures were carried out in two steps and target compounds were determined by gas chromatography coupled with electron-impact mass spectrometry (GC-EI/MS). The characteristic ions and fragmentation mechanism of cypermethrin were evaluated by electron impact ionization mass spectrometry (EI/MS). After the optimization of different parameters, such as the extraction solvent, the pesticide was extracted from the matrix with methanol/acetone in a Soxhlet extractor, cleaned up on a Florisil column by elution with a mixture of 30% ethyl acetate in n-hexane and analyzed by gas chromatography-electron impact ionization mass spectrometry (GC-EI/MS) in the selected ion-monitoring mode (SIM) with permethrin as internal standard. Recovery was in the range 77–118% with relative standard deviations (RSD) between 2.5% and 10.2%. The limit of detection (LOD) was 6.5 µg/kg for cypermethrin. The developed method was linear in the injection range 6–30 ng, with correlation coefficients greater than 0.9957.

Development and Validation of an Analytical Method to Determine Fipronil and its Degradation Products in Soil Samples

The aim of this study was to develop a methodology for identifying and quantifying Fipronil and its degradation products in soil by gas chromatography-electron capture detector previously extracted using a focused ultrasound probe. This methodology was obtaining a range of recovery between 85% and 120%, decreasing approximately solvent used time and cost, respect to other methodologies such as bath ultrasonic, solid-phase extraction, liquid-liquid extraction and soxhlet. The method was validated in fortified matrix, presented linearity in the range of 25-400 μg kg(-1), and limit of detection for Fipronil and their products desulfinyl, sulfide and sulfone was 14.7, 9.8, 8.9 and 10.7 μg kg(-1), respectively. This process was applied to samples of agricultural soils, where two degradation products desulfinyl and sulfone were found.

Bioremediation of β-cypermethrin and 3-phenoxybenzaldehyde contaminated soils using Streptomyces aureus HP-S-01

Using laboratory and field experiments, the ability of Streptomyces aureus HP-S-01 to eliminate β-cypermethrin (β-CP) and its metabolite 3-phenoxybenzaldehyde (3-PBA) in soils was investigated. In the laboratory, 80.5% and 73.1% of the initial dose of β-CP and 3-PBA (50mgkg(-1)) was removed in sterilized soils within 10days, respectively, while in the same period, disappearance rate of β-CP and 3-PBA in non-sterilized soils was higher and reached 87.8% and 79.3%, respectively. Furthermore, the disappearance process followed the first-order kinetics and the half-life (T (1/2)) for β-CP and 3-PBA reduced by 20.3-52.9 and 133.7-186.8days, respectively, as compared to the controls. The addition of sucrose to the soils enhanced the ability of strain HP-S-01 to eliminate β-CP and 3-PBA. Similar results were observed in the field experiments. The introduced strain HP-S-01 quickly adapted to the environment and rapidly removed β-CP and 3-PBA without any lag phases in the field experiments. Compared with the controls, 47.9% and 67.0% of applied dose of β-CP and 3-PBA was removed from the soils without extra carbon sources and 52.5% and 73.3% of β-CP and 3-PBA was eliminated in soils supplemented with sucrose within 10days, respectively. Analysis of β-CP degradation products in soil indicated that the tested strain transform β-CP to 3-PBA and α-hydroxy-3-phenoxy-benzeneacetonitrile. However, both intermediates were transient and they disappeared after 10days. Therefore, the selected actinomyces strain HP-S-01 is suitable for the efficient and rapid bioremediation of β-CP contaminated soils.

Soil microbial degradation of neonicotinoid insecticides imidacloprid, acetamiprid, thiacloprid and imidaclothiz and its effect on the persistence of bioefficacy against horsebean aphid Aphis craccivora Koch after soil application

The neonicotinoids imidacloprid, imidaclothiz, acetamiprid and thiacloprid consist of similar structural substituents but differ considerably with respect to soil use. Therefore, the effects of soil microbial activity on the degradation and bioefficacy persistence of the four neonicotinoids were evaluated. In unsterilised soils, 94.0% of acetamiprid and 98.8% of thiacloprid were degraded within 15 days, while only 22.5% of imidacloprid and 25.1% of imidaclothiz were degraded over a longer period of 25 days. In contrast, in sterilised soils, the degradation rates of acetamiprid and thiacloprid were respectively only 21.4% and 27.6%, whereas the degradation rates of imidaclothiz and imidacloprid were respectively 9.0% and almost 0% within 25 days. The degradation products of imidacloprid and imidaclothiz were identified as olefin, nitroso or guanidine metabolites, the degradation product of thiacloprid was identified as an amide metabolite and no degradation product of acetamiprid was detected. A bioefficacy assay revealed that the bioefficacy and persistence of imidacloprid, imidaclothiz, acetamiprid and thiacloprid against horsebean aphid A. craccivora were related to their degradation rate and the bioefficacy of their degradation products in soil. Soil microbial activity played a key role in the bioefficacy persistence of neonicotinoid insecticides and therefore significantly affected their technical profile after soil application.

Biodegradation kinetics of the benzimidazole fungicide thiophanate-methyl by bacteria isolated from loamy sand soil

Degradation of the fungicide thiophanate-methyl (TM) by Enterobacter sp. TDS-1 and Bacillus sp. TDS-2 isolated from sandy soil previously treated with TM was studied in mineral salt medium (MSM) and soil. Both strains were able to grow in MSM supplemented with TM (50 mg l(-1)) as the sole carbon source. Over a 16 days incubation period, 60 and 77% of the initial dose of TM were degraded by strains TDS-1 and TDS-2, respectively, and disappearance of TM was described by first-order kinetics. Medium supplementation with glucose markedly stimulated bacterial growth; while the final rate of TM degradation was reduced by 21 and 27% for strains TDS-1 and TDS-2, respectively as compared to medium with TM only. Moreover, this additional carbon source changed the TM degradation kinetics, which proceeded according to a zero-order model. This effect was linked to substrate competition and/or a strong decrease of medium pH. Isolates degraded TM (100 mg kg(-1)) in soil with rate constants of 0.186 and 0.210 day(-1), following first-order rate kinetics, and the time in which the initial TM concentration was reduced by 50% (DT50) in soils inoculated with strains TDS-1 and TDS-2 were 6.3 and 5.1 days, respectively. Analysis of TM degradation products in soil showed that the tested strains may have the potential to transform carbendazim (MBC) to 2-aminobenzimidazole (2-AB), and may be useful for a bioremediation of MBC-polluted soils.

Analysis of benzoxazinone derivatives in plant tissues and their degradation products in agricultural soils

Plant allelopathy may be considered an additional means of weed control in modern agriculture, but its means of action are not well understood and knowledge of specific allelochemicals involved in allelopathy is required. Benzoxazinoids are a chemical family with the most active allelopathic compounds in some crops (e.g., wheat, rye or maize). The analysis of these analytes has been based mainly on gas chromatography coupled to mass spectrometry (MS) and liquid chromatography (LC) coupled to ultraviolet detection. To improve the sensitivity and selectivity, new methodologies (e.g., LC coupled to MS and tandem MS) are being developed. Less information is available on the analytical strategies to determine their degradation products in soil samples. This article presents an overview of recent advanced analysis of benzoxazinone derivatives in plant tissues and their degradation products in agricultural soils.

Colloidal Cutin-Like Substances Cross-Linked to Siderophore Decomposition Products Mobilizing Plutonium from Contaminated Soils

Relatively recently, inorganic colloids have been invoked to reconcile the apparent contradictions between expectations based on classical dissolved-phase Pu transport and field observations of "enhanced" Pu mobility (Kersting et al. Nature 1999, 397, 56-59). A new paradigm for Pu transport is mobilization and transport via biologically produced ligands. This study for the first time reports a new finding of Pu being transported, at sub-pM concentrations, by a cutin-like natural substance containing siderophore-like moieties and virtually all mobile Pu. Most likely, Pu is complexed by chelating groups derived from siderophores that are covalently bound to a backbone of cutin-derived soil degradation products, thus revealing the history of initial exposure to Pu. Features such as amphiphilicity and small size make this macromolecule an ideal collector for actinides and other metals and a vector for their dispersal. Cross-linking to the hydrophobic domains (e.g., by polysaccharides) gives this macromolecule high mobility and a means of enhancing Pu transport. This finding provides a new mechanism for Pu transport through environmental systems that would not have been predicted by Pu transport models.

Fast and direct screening of solid materials for their potential liberation of hydrophobic organic compounds using hot cell membrane inlet mass spectrometry

We demonstrate that solid materials can be screened directly and without any pretreatment for their potential liberation of chemicals into the surroundings using a hot (150-250 degrees C) sample cell membrane inlet mass spectrometer with electron ionization. Three very different types of solids were tested: polymers (in this context regarded as a solid), tea leaves and pesticide-contaminated soil. From the polymers phthalates and other additives were liberated; from the tea leaves flavor additives and caffeine were liberated; and from the contaminated soil degradation products of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) were liberated. In all cases we detected characteristic compounds directly from the untreated sample with an analytical turnover of 8-10 samples per hour. Improved selectivity of compounds penetrating the membrane was achieved either by operating the hot cell at different temperatures or by using variations in the time trend of individual ions following insertion of a piece of the solid material into the hot cell.

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1 μg l −1 for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02 μg g −1, respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001−0.005 μg g −1.