Effects of butachlor on microbial populations and enzyme activities in paddy soil

This paper reports the influences of the herbicide butachlor (n-butoxymethlchloro -2', 6'-diethylacetnilide) on microbial populations, respiration, nitrogen fixation and nitrification, and on the activities of dehydrogenase and hydrogen peroxidase in paddy soil. The results showed that the number of actinomycetes declined significantly after the application of butachlor at different concentrations ranging from 5.5 microg g(-1) to 22.0 microg g(-1) dried soil, while that of bacteria and fungi increased. Fungi were easily affected by butachlor compared to the bacteria. The growth of fungi was retarded by butachlor at higher concentrations. Butachlor however, stimulated the growth of anaerobic hydrolytic fermentative bacteria, sulfate-reducing bacteria (SRB) and denitrifying bacteria. The increased concentration of butachlor applied resulted in the higher number of SRB. Butachlor inhibited the growth of hydrogen-producing acetogenic bacteria. The effect of butachlor varied on methane-producing bacteria (MPB) at different concentrations. Butachlor at the concentration of 1.0 microg g(-1) dried soil or less than this concentration accelerated the growth of MPB, while at 22.0 microg g(-1) dried soil showed an inhibition. Butachlor enhanced the activity of dehydrogenase at increasing concentrations. The soil dehydrogenase showed the highest activity on the 16th day after application of 22.0 microg g(-1) dried soil of butachlor. The hydrogen peroxidase could be stimulated by butachlor. The soil respiration was depressed during the period from several days to more than 20 days, depending on concentrations of butachlor applied. Both the nitrogen fixation and nitrification were stimulated in the beginning but reduced greatly afterwards in paddy soil.     

Aldicarb and carbofuran transport in a Hapludalf influenced by differential antecedent soil water content and irrigation delay

Pesticide use in agroecosystems can adversely impact groundwater quality via chemical leaching through soils. Few studies have investigated the effects of antecedent soil water content (SWC) and timing of initial irrigation (TII) after chemical application on pesticide transport and degradation. The objectives of this study were to investigate the effects of antecedent soil water content (wet vs dry) and timing of initial irrigation (0h Delay vs 24h Delay) on aldicarb [(EZ)-2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime] and carbofuran [2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate] transport and degradation parameters at a field site with Menfro silt loam (fine-silty, mixed, superactive, mesic Typic Hapludalf) soils. Aldicarb and carbofuran were applied to plots near field capacity (wet) or near permanent wilting point (dry). Half of the dry and wet plots received irrigation water immediately after chemical application and the remaining plots were irrigated after a 24h Delay. The transport and degradation parameters were estimated using the method of moments. Statistical significance determined for SWC included averages across TII levels, and significance determined for TII included averages across SWC levels. For the dry treatment, aldicarb was detected 0.10 m deeper (P<0.01) on two of the four sampling dates and carbofuran was detected at least 0.10 m deeper (P<0.05) on all of the sampling dates compared to the wet treatment. Pore water velocity was found to be higher (P<0.10) in the dry vs wet treatments on three of four dates for aldicarb and two of four dates for carbofuran. Retardation coefficients for both pesticides showed similar evidence of reduced values for the dry vs wet treatments. These results indicate deeper pesticide movement in the initially dry treatment. For aldicarb and carbofuran, estimated values of the degradation rate were approximately 40-49% lower in the initially dry plots compared to the initially wet plots, respectively. When the initial irrigation was delayed for 24h, irrespective of antecedent moisture conditions, a 30% reduction in aldicarb degradation occurred. This study illustrates the deeper transport of pesticides and their increased persistence when applied to initially dry soils.     

Persistence of the herbicide butachlor in soil after repeated applications and its effects on soil microbial functional diversity

Effects of repeated applications of the herbicide butachlor (N-(butoxymethyl)-2-chloro -N-2′,6′-dimethyl acetanilide) in soil on its persistence and soil microbial functional diversity were investigated under laboratory conditions. The degradation half-lives of butachlor at the recommended dosage in soil were calculated to be 12.5, 4.5, and 3.2 days for the first, second, and third applications, respectively. Throughout this study, no significant inhibition of the Shannon-Wiener index H′ was observed. However, the Simpson index 1/D and McIntosh index U were significantly reduced (P ≤ 0.05) during the initial 3 days after the first application of butachlor, and thereafter gradually recovered to a similar level to that of the control soil. A similar variation but faster recovery in 1/D and U was observed after the second and third Butachlor applications. Therefore, repeated applications of butachlor led to more rapid degradation of the herbicide, and more rapid recovery of soil microorganisms. It is concluded that repeated butachlor applications in soil had a temporary or short-term inhibitory effect on soil microbial communities.     

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.     

Behaviour of forchlorfenuron residues in grape,soil and water

Persistence of forchlorfenuron residues in grape berries at harvest following its dip application as single or split doses to grape berry clusters and periodic dissipation of forchlorfenuron residues in grape berries following foliar spray application were studied. Periodic dissipation of forchlorfenuron residues following its fortification in soil and water were also studied. Splitting the dip application concentration of forchlorfenuron to grape berries reduced its residues in the berries at harvest, which persisted for more than 65 days from all treatments. In case of foliar application, however, the residues of forchlorfenuron in/on the grape berries persisted for 15-20 days only from three treatment concentrations of 2, 3 and 4 ml/l and dissipated with half-lives of 3.4-4.5 days. The residues of forchlorfenuron dissipated faster in soils maintained at field capacity moisture condition than in air dry soils. There was wide variation in its residue persistence in soil (DT50 = 15.1-121.3 days) depending on soil type and moisture condition. Forchlorfenuron residues persisted for more than 30 days in water and its dissipation was fastest at a water salinity level of 3.85 mmho/ cm although the rate of dissipation was not significantly affected by the change in salinity level from <0.04 to 5.90 mmho/cm.     

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.     

Characterization and growth response of bacteria in soil following application of carbofuran.

Enhanced biodegradation of carbofuran (2, 3-dihydro-2, 2 dimethyl-7-benzofuranyl methyl carbamate) is an economically significant, but poorly understood, microbial phenomenon in soil. A series of experiments was conducted to examine short term changes in soil bacterial populations stimulated by carbofuran application at field rates. In the field experiment, commercially formulated carbofuran and butylate (S-ethyl diisobutyl carbamothioate) were applied at 5.6 kg ai ha-1 and 8.4 kg ai ha-1, respectively, on a soil (Putnam silt loam) exhibiting enhanced degradation of carbofuran. In laboratory studies, technical grade carbofuran (20 mg kg-1 soil) was applied to samples of the field soil. Bacterial populations were estimated using non-selective (tryptic soy agar) and selective media containing carbofuran or butylate. Largest population increases in pesticide-treated soil were observed between 7 and 15 days after treatment (DAT) compared to populations in non-treated soil. Significant increases (P less than 0.05) in total bacterial populations and presumed carbofuran-degraders due to carbofuran application were associated with increased populations of Pseudomonas spp. and Flavobacterium spp. Application of carbofuran appeared to provide a competitive advantage to these species over actinomycetes persisting beyond 20 DAT. Growth responses of bacteria to carbofuran in the Putnam soil were compared to those in a native prairie soil (Mexico silt loam), which exhibited a much slower rate of carbofuran degradation. Bacterial population response to carbofuran was measurable, but small and short-lived. Perpetuation of the enhanced degradation phenomenon may lie in a persistent pesticide-induced competitive advantage given to a very small segment of the microbial population. This advantage may not be detectable after 20 days using conventional plating techniques.     

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.     

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.     

Butachlor degradation in tropical soils: effect of application rate, biotic-abiotic interactions and soil conditions

The degradative characteristics of butachlor (N-Butoxymethyl-2-chloro-2',6'-diethyla- cetanilide) were studied under controlled laboratory conditions in clay loam alluvial (AL) soil (Typic udifluvent) and coastal saline (CS) soil (Typic endoaquept) from rice cultivated fields. The application rates included field rate (FR), 2-times FR (2FR) and 10-times FR (10FR). The incubation study was carried out at 30 degrees C with and without decomposed cow manure (DCM) at 60% of maximum water holding capacity (WHC) and waterlogged soil condition. The half-life values depended on the soil types and initial concentrations of butachlor. Butachlor degraded faster in AL soil and in soil amended with DCM under waterlogged condition. Microbial degradation is the major avenue of butachlor degradation from soils.     

Effects of malathion and chlorpyrifos on acetylcholinesterase and antioxidant defense system in Oxya chinensis (Thunberg) (Orthoptera: Acrididae)

The study was undertaken to evaluate the effects of malathion and chlorpyrifos on acetylcholinesterase (AChE), esterase (EST) activity and antioxidant system after topical application with different concentration to Oxya chinensis. The results showed that malathion and chlorpyrifos inhibited EST, AChE activity and increased malondialdehyde (MDA) contents. A change in superoxide dismutase (SOD), catalase (CAT), glutathione S-transferase (GST), glutathione peroxidase (GPx), and glutathione reductase (GR) activity combined with reduced glutathione (GSH) and total glutathione (tGSH) contents was found in O. chinensis after malathion and chlorpyrifos treatments. Malathion and chlorpyrifos increased SOD and CAT activity compared with the control. With the concentrations increasing, SOD and CAT activity showed the similar tendency, namely, SOD and CAT activity increased at the lower concentrations and decreased at the higher concentrations. The results showed that malathion and chlorpyrifos decreased significantly GR activity. GST and GPx activity at the studied concentrations of chlorpyrifos was lower than that of the control. However, no significance was observed. GPx and GST activity in malathion treated grasshoppers showed a biphasic response with an initial increase followed by a decline in its activity. Malathion and chlorpyrifos decreased GSH contents and the ratio of GSH/GSSG. The present findings indicated that the toxicity of malathion and chlorpyrifos might be associated with oxidative stress.     

光合细菌改善Cd、Pb及呋喃丹污染土壤的微生物群落DNA序列多样性的研究

应用DNA随机扩增多态性(RAPD)分子标记技术研究了光合细菌(PSB)对Cd、Pb及呋喃丹污染土壤的微生物群落DNA序列多样性的影响.结果表明,Cd、Pb及呋喃丹单一污染或3者复合污染土壤的微生物群落DNA序列的丰富度相对对照土样(S0)都有不同程度的增加,受Cd、Pb或呋哺丹污染,可能会引起土壤微生物群落DNA序列...     

Butachlor Degradation in Tropical Soils: Effect of Application Rate,Biotic-Abiotic Interactions and Soil Conditions

The degradative characteristics of butachlor (N-Butoxymethyl-2-chloro-2′,6′-diethyla- cetanilide) were studied under controlled laboratory conditions in clay loam alluvial (AL) soil (Typic udifluvent) and coastal saline (CS) soil (Typic endoaquept) from rice cultivated fields. The application rates included field rate (FR), 2-times FR (2FR) and 10-times FR (10FR). The incubation study was carried out at 30°C with and without decomposed cow manure (DCM) at 60% of maximum water holding capacity (WHC) and waterlogged soil condition. The half-life values depended on the soil types and initial concentrations of butachlor. Butachlor degraded faster in AL soil and in soil amended with DCM under waterlogged condition. Microbial degradation is the major avenue of butachlor degradation from soils.     

锐颈特与马拉硫磷交替使用对麦穗鱼脑乙酰胆碱酯酶活性恢复的 …

研究了５％锐颈特县浮剂与９５％马拉硫磷文替使用对麦穗鱼（Ｐｓｅｕｄｏｒａｓｂｏｒａ ｐａｒｏａ）乙酰胆碱酯酶（ＡＣｈＥ,ＥＣ３．１．１．７）活性的影响。结果表明,０．２ｍｇ／Ｌ,锐颈物与２ｍｇ／Ｌ马拉硫磷交替使用均影响被抑制的ＡＣｈＥ活性恢复。文中还探讨了研究农药影响对于合理评价农药环境毒性的意义。     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.     

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.     

Effect of systemic herbicides on N2-fixing and phosphate solubilizing microorganisms in relation to availability of nitrogen and phosphorus in paddy soils of West Bengal

A field experiment has been conducted with four systemic herbicides viz., butachlor [N-(butoxymethyl)-2-chloro-2',6'-diethyl-acetanilide], fluchloralin [N-(2-chloroethyl)-(2,6-dinitro-N-propyl-4-trifluoromethyl) aniline], oxadiazon [5-terbutyl-3-(2,4-dichloro-5-isopro poxyphenyl)-1,3,4-oxadiazol-2-one] and oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenyl)-4-(trifluoromethyl) benzene] at their recommended field rates (2.0, 1.5, 0.4 and 0.12kga.i.ha(-1), respectively) to investigate their effects on growth and activities of aerobic non-symbiotic N(2)-fixing bacteria and phosphate solubilizing microorganisms in relation to availability of nitrogen and phosphorus in the rhizosphere soils as well as yield of the rice crop (Oryza sativa L cv. IR-36). Application of herbicides, in general, highly stimulated the population and activities of the target microorganisms, which resulted in a greater amount of atmospheric nitrogen fixation and phosphate solubilization in the rhizosphere soils of the test crop. The greater microbial activities subsequently augmented the mineralization and availability of nitrogen and phosphorus in the soil solution, which in turn increased the yield of the crop. Among the herbicides, oxyfluorfen was most stimulative followed by fluchloralin and oxadiazon in augmenting the microbial activities in soil. Butachlor also accentuated the mineralization and availability of nitrogen due to higher incitement of non-symbiotic N(2)-fixing bacteria in paddy soil. The grain and straw yields of the crop were also significantly increased due to the application of oxyfluorfen (20.2% and 21%) followed by fluchloralin (13.1% and 15.4%) and butachlor (9.1% and 10.2%), respectively.     

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)     

Kinetics of mass and DNA decomposition in tomato leaves

This laboratory study investigated the kinetics of leaf and DNA content decomposition in two varieties of tomato (Palmiro and Admiro) after incubation in soil for 35 days. Results revealed that the decrease of dry matter in leaves in both varieties did not follow a single exponential function and was better described by a double exponential model. Composite half-decrease times were 3.4 and 2.4 days for Palmiro and Admiro respectively. The same pattern was observed for DNA mass loss, although this was closer to a single exponential model with composite half-decrease times of 1.5 and 1.4 days. Genomic analysis showed that DNA in dried leaves at room temperature (not inoculated in the soil), remains intact or presents a weak degradation, and DNA extracted from leaves inoculated in non-sterile soil showed degradation after two days. These results indicate that before release an important quantity of DNA may be degraded inside plant tissues during decomposition in soil.     

Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.