Biodegradation of insecticide carbofuran by Paracoccus sp. YM3

A bacterium (Paracoccus sp. YM3) capable of degrading carbofuran was isolated from carbofuran-contaminated sludge. The strain was shown to metabolize carbofuran (50 mg L^?1) to carbofuran-7-phenol in minimal salt medium within 6 days in which the pesticide was the only source of carbon. Carbofuran and its main metabolite were analyzed by high performance liquid chromatography (HPLC). The addition of an other carbon source led to accelerated biodegradation. The relevant degrading-enzyme was intracellular and inducible. A tobacco hypersensitivity experiment showed that YM3 could eliminate carbofuran in soils effectively and safely. This is the first report of a Paracoccus sp. that could degrade carbofuran. The present study may provide a basis for biotreatment of wastewaters and bioremediation of carbofuran-contaminated soils.     

Biodegradation of carbofuran in soils within Nzoia River Basin,Kenya

Carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) has been used within the Nzoia River Basin (NRB), especially in Bunyala Rice Irrigation Schemes, in Kenya for the control of pests. In this study, the capacity of native bacteria to degrade carbofuran in soils from NRB was investigated. A gram positive, rod-shaped bacteria capable of degrading carbofuran was isolated through liquid cultures with carbofuran as the only carbon and nitrogen source. The isolate degraded 98% of 100-μg mL^?1 carbofuran within 10 days with the formation of carbofuran phenol as the only detectable metabolite. The degradation of carbofuran was followed by measuring its residues in liquid cultures using high performance liquid chromatography (HPLC). Physical and morphological characteristics as well as molecular characterization confirmed the bacterial isolate to be a member of Bacillus species. The results indicate that this strain of Bacillus sp. could be considered as Bacillus cereus or Bacillus thuringiensis with a bootstrap value of 100% similar to the 16S rRNA gene sequences. The biodegradation capability of the native strains in this study indicates that they have great potential for application in bioremediation of carbofuran-contaminated soil sites.     

Effects of conditioning,cross‐conditioning,and microbial growth on development of enhanced biodegradation of insecticides in soil

Abstract

Pretreatment of a Drummer‐Catlin soil mixture with granular formulations of carbofuran or trimethacarb enhanced biodegradation of subsequent treatments with the technical formulations. Degradation of carbofuran was enhanced by pretreatments with trimethacarb, and degradation of trimethacarb was enhanced by pretreatments with carbofuran. Bendiocarb degradation was enhanced by pretreatments of soil with carbofuran or trimethacarb. In bioassays with southern corn rootworm larvae, biological activity of carbofuran, trimethacarb, and bendiocarb was rapidly lost in soils pretreated with granular formulations. Pretreatment of soil with granular terbufos did not enhance the biodegradation of subsequent applications of technical terbufos. Several microbial biomass assays showed an increase in specific carbofuran‐degrading bacteria in soils that were pretreated with carbofuran. Bacteria were isolated that could grow on carbofuran and apparently degrade it when present with another carbon source.     

Carbofuran residues in organic soils in Southwestern Ontario, 1977

Organic soils from 22 farms with a history of carbofuran use for soil insect control were sampled in November, 1977. Analysis for carbofuran was by electron capture gas chromatography of the heptaflurobutyric derivative. Nineteen of the 22 soils contained detectable (sensitivity 0.02 ppm) carbofuran residues. However only 8 of the soils contained greater than 0.5 ppm total carbofuran. The highest total carbofuran residue was 1.5 ppm, of which 0.31 ppm was 3-ketocarbofuran. In other soil samples 3-ketocarbofuran comprised 7-50% of the total carbofuran residue. No 3-hydroxycarbofuran was detected. The order of persistence of granular application of 3 insecticides as seed-furrow treatments was ethion greater than fonofos greater than carbofuran.     

Enhanced degradation of carbofuran in Pacific Northwest soils

Persistence of 14C-carbonyl carbofuran was measured in Pacific Northwest soils that had received 1-14 applications of the insecticide for root weevil control on perennial crops. Insecticide decay curves were obtained in nonautoclaved soil and several autoclaved soil samples from previously-treated fields and in nonautoclaved soils from paired control sites not previously treated with carbofuran. The insecticide usually degraded faster in soil from previously-treated fields than in soil from corresponding control fields. Among 26 previously-treated fields, the pseudo half-life (time for 50% loss) of carbofuran was less than one wk in 11 soils, 1-3 wks in 8 soils and greater than 4 wks in the remaining soils. Among the nontreated control fields the pseudo half-life was greater than 2 wks in all cases and greater than 15 wks in 5 of the soils. The carbofuran decay curve always possessed an initial lag phase where soil mixing enhanced insecticide decline. Carbofuran degraded very slowly in autoclaved soil samples. The half-life of carbofuran exceeded 16 wk in all autoclaved soils tested and in most instances 85-90% of the original dosage remained when the tests were terminated 112 days after treatment. These results provided evidence that many of the soils which received applications of carbofuran over the past several years have developed a capacity to degrade carbofuran very rapidly.     

A laboratory study of the persistence of carbofuran and its 3‐hydroxy‐ and 3 keto‐metabolites in sterile and natural mineral and organic soils

Abstract

In a laboratory study, the persistence of carbofuran and its 3‐hydroxy‐ and 3‐keto‐metabolites was examined separately over 16 wk in sterile and natural organic (muck) and mineral (loam) soils. Carbofuran was relatively persistent in sterile soils; at 8 wk 77% remained in the sterile muck and about 50% remained in the sterile loam. In the natural muck 25% of initial carbofuran remained at 8 wk whereas in the natural loam carbofuran had completely disappeared by that time. The 3‐ketocarbofuran was very short‐lived even in the sterile muck where only 50% remained at 1 wk. The 3‐hydroxycarbofuran degraded appreciably on zero day in the natural soils (with conversion to 3‐ketocarbofuran) and about 90% had disappeared in 1 wk. A more detailed study of the persistence of 3‐hydroxycarbofuran in the natural soils showed complete disappearance in 2 days in loam and in 3 days in muck. The 3‐ketocarbofuran produced from the 3‐hydroxy‐carbofuran reached a maximum concentration in 1 day and then disappeared within 4 days in loam and about 1 wk in muck.     

Hepatic monooxygenase (CYP1A and CYP3A) and UDPGT enzymatic activities as biomarkers for long-term carbofuran exposure in tench (Tinca tinca L)

The effect of a long-term exposure of tenchs to different concentrations (10 and 100 micro g/L) of the pesticide carbofuran has been evaluated. Microsomal hepatic cytochrome P450 subfamily 1A (CYP1A) and 3A (CYP3A) activities, as well as the phase II enzyme uridine diphospho-glucuronosyltransferase (UDPGT) activity were evaluated as adequate biomarkers of fish exposure to environmentally relevant concentrations of the pesticide carbofuran in freshwater ecosystems. A clear time-dependent inhibition of both CYP1A and UDPGT activities was observed in fish exposed to the highest dose of carbofuran with respect to controls, whereas in the case of CYP3A activity, values of exposed animals did not show a clear pattern of alteration during the experiment. The results of the present study demonstrated that hepatic CYP1A and UDPGT activities from tench could be considered as sensitive biomarkers for carbamate pesticides in polluted water, thus allowing future and ecologically relevant biomonitoring studies with this species.     

Limitations on the role of incorporated organic matter in reducing pesticide leaching.

The use of organic amendments has been suggested as a method of controlling pesticide leaching through soils. The enarenados soils of the intensive horticulture of the Almeria province of southern Spain contain buried organic matter horizons above a soil layer amended with clay. This region is ideal for understanding the potential for and limitations of organic amendments in preventing pesticide pollution. This study measured the sorption and degradation potential of carbofuran in this soil system and the hydrological behaviour of the soil horizons. The sorption of carbofuran was controlled by the organic carbon content, the degradation was strongly pH-dependent and the acidic organic layer protected the sorbed carbofuran against degradation. Hydrologically, the soil system is dominated by ponding above an amended clay layer and by the presence of macropores that can transport water through this clay. A simple model is proposed on this basis and shows that although high levels of dissolved organic carbon can be released by buried organic horizons, the major control on re-release of sorbed pesticide is the potential for sorption hysteresis in this organic layer. A comparison of sorption and degradation data for carbamate insecticides used in the region with groundwater observations for these compounds shows that no amount of incorporated organic would protect against pollution from highly water-soluble compounds.     

Enhanced degradation of carbofuran in pacific northwest soils

Abstract

Persistence of ¹⁴C‐carbonyl carbofuran was measured in Pacific Northwest soils that had received 1–14 applications of the insecticide for root weevil control on perennial crops. Insecticide decay curves were obtained in nonautoclaved soil and several autoclaved soil samples from previously‐treated fields and in nonautoclaved soils from paired control sites not previously treated with carbofuran. The insecticide usually degraded faster in soil from previously‐treated fields than in soil from corresponding control fields. Among 26 previously‐treated fields, the pseudo half‐life (time for 50% loss) of carbofuran was < one wk in 11 soils, 1–3 wks in 8 soils and > 4 wks in the remaining soils. Among the nontreated control fields the pseudo half‐life was > than 2 wks in all cases and > than 15 wks in 5 of the soils. The carbofuran decay curve always possessed an initial lag phase where soil mixing enhanced insecticide decline. Carbofuran degraded very slowly in autoclaved soil samples. The half‐life of carbofuran exceeded 16 wk in all autoclaved soils tested and in most instances 85–90% of the original dosage remained when the tests were terminated 112 days after treatment. These results provided evidence that many of the soils which received applications of carbofuran over the past several years have developed a capacity to degrade carbofuran very rapidly.     

Comparison of batch, stirred flow chamber, and column experiments to study adsorption, desorption and transport of carbofuran within two acidic soils

Different methods (batch, column and stirred flow chamber experiments) used for adsorption and desorption of carbofuran studies were compared. All tested methods showed that the carbofuran adsorption was higher in the soil with the higher organic matter content, whereas the opposite behaviour was observed for the percentage of carbofuran desorbed. However, different methods have revealed some discrepancies in carbofuran adsorption/desorption kinetics. Although batch method showed interesting data on equilibrium experiments, such as a low heterogeneity for the carbofuran adsorption sites independent of soil organic matter content, it had some disadvantages for carbofuran adsorption/desorption kinetic studies. The disadvantages were related with the excessive limitations of this method on kinetics, i.e., no difference could be detected between different soils. However, with column and stirred flow chamber methods the carbofuran adsorption/desorption kinetics of different soils could be compared. Moreover, the absolute values of carbofuran adsorption/desorption and its rate were higher in the stirred flow chamber than in the batch and column experiments. Using stirred flow chamber experiments the carbofuran desorption was significantly faster than its adsorption, whereas carbofuran using column experiments they were similar. These discrepancies should be considered when the results obtained only with one method is discussed.     

Bioavailability and biodegradation of prosulfocarb in soil

Active microbial degraders of the herbicide prosulfocarb (PSC) were isolated to evaluate their performance in soil with a view to their use for bioremediation. The isolated cultures (a microbial consortium and a Pseudomonas sp. strain) were active when tested in mineral medium with PSC as the only carbon source, but had an adverse effect on the soil indigenous microflora. Biodegradation in the inoculated soils was thus lower than in the uninoculated soil when only the indigenous microflora was present. Further tests showed that the strong affinity of PSC for soil organic matter affected its bioavailability and hence its biodegradation by the inocula. Bioremediation of PSC contaminated soils could thus be undertaken by biostimulation of indigenous microflora.     

A comparative study on the dissipation and microbial metabolism of organophosphate and carbamate insecticides in orchaqualf and fluvaquent soils of West Bengal

An experiment has been conducted under laboratory conditions to investigate the effect of phorate (an organophosphate insecticide) and carbofuran (a carbamate insecticide) at their recommended field rates (1.5 and 1.0 kga.i.ha-1, respectively) on the growth and multiplication of microorganisms as well as rate of dissipation and persistence of the insecticidal residues including their metabolites in laterite (typic orchaqualf) and alluvial (typic fluvaquent) soils of West Bengal. Application of phorate and carbofuran in general, induced growth and development of bacteria, actinomycetes, fungi, N2-fixing bacteria and phosphate solubilizing microorganisms in both the soils and the stimulation was more pronounced with phorate as compared to carbofuran. Application of phorate recorded highest stimulation of fungi in laterite and actinomycetes in alluvial soil. Carbofuran on the other hand, augmented fungi and N2-fixing bacteria in laterite and actinomycetes in alluvial soil. Bacterial population was inhibited due to the application of carbofuran in alluvial soil. Phorate sulfoxide and phorate sulfone, the two metabolites of phorate and 3-hydroxycarbofuran and 3-ketocarbofuran, the two metabolites of carbofuran isolated were less persistent in both the soils. Phorate persisted in laterite and alluvial soils up to 45 and 60 days, respectively depicting the half-life (T1/2) 9.7 and 11.5 days, respectively while the T1/2 of carbofuran for the said soils were 16.9 and 8.8 days, respectively. No metabolite of carbofuran was detected in soils after 30 days of incubation while phorate sulfone persisted in alluvial soil even after 60 days of application of the insecticide.     

Residues of carbosulfan and its metabolites carbofuran and 3-hydroxy carbofuran in rice field ecosystem in China

The fate of carbosulfan (seed treatment dry powder) was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of carbosulfan, carbofuran, and 3-hydroxyl carbofuran in brown rice, rice straw, paddy water, and soil. The target compounds were extracted using acetonitrile or dichloromethane, cleaned up on acidic alumina or florisil solid phase extraction (SPE) cartridge, and analyzed by gas chromatography. The average recoveries of carbosulfan, carbofuran and 3-hydroxy carbofuran in brown rice, rice straw, paddy water, and soil ranged from 72.71% to 105.07%, with relative standard deviations of 2.00–8.80%. The limits of quantitation (LOQs) of carbosulfan, carbofuran and 3-hydroxy carbofuran in the samples (brown rice, rice straw, paddy water and soil) were 0.011, 0.0091, 0.014, 0.010 mg kg^?1, 0.016, 0.019, 0.025, 0.013 mg kg^?1, and 0.031, 0.039, 0.035, 0.036 mg kg^?1, respectively. The trials results showed that the half-lives of carbosulfan, carbofuran and 3-hydroxy carbofuran in rice straw were 4.0, 2.6 days, 3.9, 6.0 days, and 5.8, 7.0 days in Zhejiang and Hunan, respectively. Carbosulfan, carbofuran and 3-hydroxy carbofuran were detected in soils. Carbosulfan and 3-hydroxy carbofuran were almost undetectable in paddy water. Carbofuran was detected in paddy water. The final residues of carbosulfan, carbofuran and 3-hydroxy carbofuran in brown rice were lower than 0.05 mg kg^?1, which were lower than 0.5 mg kg^?1 (MRL of carbosulfan) or 0.1 mg kg^?1 (MRL of carbofuran). Therefore, a dosage of 420 g active ingredient per 100 kg seed was recommended, which could be considered as safe to human beings and animals. These would contribute to provide the scientific basis of using this insecticide.     

A comparison of the persistence in a clay loam of single and repeated annual applications of seven granular insecticides used for corn rootworm control

In May 1983, granular formulations of carbofuran, chlorpyrifos, disulfoton, fonofos, isofenphos, phorate, and terbufos were applied in incorporated bands to duplicate 2 m2 field plots of clay loam. Insecticide concentrations were determined in the bands at 0,1,2,3,4,6,8,10,12,16, and 20 wk. Following spring cultivation, the insecticides were applied to the same plots in 1984 and 1985. In addition, carbofuran was applied to previously untreated plots in 1984 and all 7 materials were applied to previously untreated plots in 1985. Sampling and analysis were carried out as in 1983. Persistence was assessed on the basis of the disappearance rates measured for the 1st 8 wk and of a calculated Effectiveness Potential (the ratio of the average residue in the upper 5 cm of the band at 8, 10 and 12 wk and the published LC95 for western corn rootworm in clay loam soil). Soils treated with carbofuran and isofenphos in 1984 and all soils treated in 1985 were tested for anti-insecticide activity. Soil cores from some carbofuran, chlorpyrifos and terbufos treated plots were sectioned vertically to establish the distribution of the insecticides during 1985. In addition, granular and pure chemical forms of isofenphos and carbofuran were applied at 10 ppm to anti-isofenphos and anti-carbofuran active and control soils (from field plots) maintained at 10 and 20% moisture in the laboratory to assess the effect of formulation and moisture on persistence in active soils. Insecticide concentrations were determined at 0,1,3,7, 10,14,21,28, and 35 days. The persistence of chlorpyrifos, terbufos and phorate was relatively constant over the 3 years and between plots receiving single and multiple treatments. Disulfoton and fonofos behavior was more variable and that of carbofuran and isofenphos was extremely variable. Anti-insecticide activity against carbofuran and isofenphos was detectable 2 wk after an initial application and was still present the following spring. Anti-insecticide activity against fonofos, terbufos sulfoxide, phorate sulfone and disulfoton sulfone was also generated in this soil. Anti-insecticide activity against chlorpyrifos, disulfoton, terbufos and phorate was not present. Carbofuran, chlorpyrifos and terbufos (+ metabolites) present in the upper 5 cm of soil averaged 93, 94 and 94%, respectively, of the total core contents over 12 wk. Significant moisture dependent differences were observed between the behavior of granular carbofuran and granular isofenphos in anti-insecticide active soils.(ABSTRACT TRUNCATED AT 400 WORDS)     

金属纳米材料在厌氧条件下对脱氮副球菌反硝化作用的影响

以脱氮副球菌YF1为实验菌株,研究纳米Fe0和纳米Fe/Ni 2种金属纳米材料对菌体生长及其反硝化作用的影响。实验结果表明:添加纳米材料到反应体系中会降低实验菌株的生长量和生物反硝化作用,纳米Fe/Ni对实验菌株的毒性比纳米Fe0大。在含硝态氮初始浓度为100 mg/L的反硝化培养基中接种脱氮副球菌,于30℃培养20 h,脱氮率为89.47%,而菌+1 000 mg/L纳米Fe/Ni的体系脱氮率仅为64.33%;菌+1 000 mg/L纳米Fe0体系的脱氮率为76.36%。不同体系的反硝化过程均可采用零级动力学模型进行拟合(相关系数R2>0.92)。这2种金属纳米材料对实验菌株的生长量及其反硝化作用的影响程度,与体系的pH和温度有较大关系。     

Influence and persistence of phorate and carbofuran insecticides on microorganisms in rice field

An experiment was conducted in microplots (4 m x 4 m) with two insecticides, phorate and carbofuran at rates of 1.5 and 1.0 kga.i.ha(-1) respectively, to investigate its effect on the population and distribution of bacteria, actinomycetes and fungi as well as the persistence of the insecticidal residues in rhizosphere soils of rice (Oryza sativa L., variety IR-50). Application of the insecticides stimulated the population of bacteria, actinomycetes and fungi in the rhizosphere soils, and the stimulation was more pronounced with phorate as compared to carbofuran. Both the insecticides did not have marked effect on the numbers of Streptomyces and Nocardia in the rhizosphere soils. However, the growth of Bacillus, Escherichia, Flavobacterium, Micromonospora, Penicillium, Aspergillus and Trichoderma with phorate and that of Bacillus, Corynebacterium, Flavobacterium, Aspergillus and Phytophthora with carbofuran were increased. On the other hand, the numbers of Staphylococcus, Micrococcus, Fusarium, Humicola and Rhizopus under phorate and Pseudomonas, Staphylococcus, Micrococcus, Klebsiella, Fusarium, Humicola and Rhizopus under carbofuran were inhibited. Both the insecticides persisted in the rhizosphere soil for a short period of time and the rate of dissipation of carbofuran was higher than that of phorate in the soil depicting the half-life (T1/2) 9.1 and 10.4 days, respectively.     

Degradation of carbofuran in water by solar photocatalysis in presence of photosensitizers

The effect of the presence of photosensitizers, methylene blue (MB) and rose Bengal (RB), on the degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) in water in a solar photocatalytic system was investigated. It was found that as compared to MB, RB generally showed a stronger effect on the decomposition of carbofuran under comparable conditions. Among the conditions studied, adding 2 x 10(-6) M of RB, that corresponding to 2% of the initial concentration of carbofuran solution in the system, rendered the most effective degradation of carbofuran. As a result, a carbofuran removal percentage of 69.9%, a mineralization efficiency of 28.0%, and a microtoxicity reduction of 65.0% could be achieved. The degradation and mineralization of carbofuran was found to follow the pseudo-first order reaction kinetics. The decomposition mechanism of carbofuran was further investigated through identification of the intermediates to elaborate the influence of dye photosensitizer on the solar photocatalysis of carbofuran in water. On the basis of the intermediates identified, including carbofuran phenol, 3-hydroxy carbofuran phenol, and substituted alcohols (3-phenoxy 1-propanol, 2-ethyl 1-hexanol, 2-butoxyl ethanol), it appears that hydrolysis and hydroxylation were the two key mechanisms for decomposing carbofuran during the process of solar photocatalysis with the aid of dye photosensitizer.     

Hepatic monooxygenase (CYP1A and CYP3A) and UDPGT enzymatic activities as biomarkers for long-term carbofuran exposure in tench (Tinca tinca L)

The effect of a long-term exposure of tenchs to different concentrations (10 and 100 μ g/L) of the pesticide carbofuran has been evaluated. Microsomal hepatic cytochrome P450 subfamily 1A (CYP1A) and 3A (CYP3A) activities, as well as the phase II enzyme uridine diphospho-glucuronosyltransferase (UDPGT) activity were evaluated as adequate biomarkers of fish exposure to environmentally relevant concentrations of the pesticide carbofuran in freshwater ecosystems. A clear time-dependent inhibition of both CYP1A and UDPGT activities was observed in fish exposed to the highest dose of carbofuran with respect to controls, whereas in the case of CYP3A activity, values of exposed animals did not show a clear pattern of alteration during the experiment. The results of the present study demonstrated that hepatic CYP1A and UDPGT activities from tench could be considered as sensitive biomarkers for carbamate pesticides in polluted water, thus allowing future and ecologically relevant biomonitoring studies with this species.     

New bacterial strain of the genus Ochrobactrum with glyphosate-degrading activity

Thirty bacterial strains with various abilities to utilize glyphosate as the sole phosphorus source were isolated from farm soils using the glyphosate enrichment cultivation technique. Among them, a strain showing a remarkable glyphosate-degrading activity was identified by biochemical features and 16S rRNA sequence analysis as Ochrobactrum sp. (GDOS). Herbicide (3 mM) degradation was induced by phosphate starvation, and was completed within 60 h. Aminomethylphosphonic acid was detected in the exhausted medium, suggesting glyphosate oxidoreductase as the enzyme responsible for herbicide breakdown. As it grew even in the presence of glyphosate concentrations as high as 200 mM, Ochrobactrum sp. could be used for bioremediation purposes and treatment of heavily contaminated soils.     

Degradation of Carbofuran in Water by Solar Photocatalysis in Presence of Photosensitizers

The effect of the presence of photosensitizers, methylene blue (MB) and rose Bengal (RB), on the degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) in water in a solar photocatalytic system was investigated. It was found that as compared to MB, RB generally showed a stronger effect on the decomposition of carbofuran under comparable conditions. Among the conditions studied, adding 2 × 10^?6 M of RB, that corresponding to 2% of the initial concentration of carbofuran solution in the system, rendered the most effective degradation of carbofuran. As a result, a carbofuran removal percentage of 69.9%, a mineralization efficiency of 28.0%, and a microtoxicity reduction of 65.0% could be achieved. The degradation and mineralization of carbofuran was found to follow the pseudo-first order reaction kinetics. The decomposition mechanism of carbofuran was further investigated through identification of the intermediates to elaborate the influence of dye photosensitizer on the solar photocatalysis of carbofuran in water. On the basis of the intermediates identified, including carbofuran phenol, 3-hydroxy carbofuran phenol, and substituted alcohols (3-phenoxy 1-propanol, 2-ethyl 1-hexanol, 2-butoxyl ethanol), it appears that hydrolysis and hydroxylation were the two key mechanisms for decomposing carbofuran during the process of solar photocatalysis with the aid of dye photosensitizer.