A study of the disappearance of pesticides during composting using a gas chromatography-tandem mass spectrometry technique

A simple method for multi-residue analysis of pesticides by low-pressure gas chromatography-tandem mass spectrometry (LP-GC-MS-MS) has been validated in compost samples. The pesticide residues were extracted from the lyophilised samples with organic solvent by stirring. No sample clean-up was required prior to the analysis. The method was applied to determine the fate of two organochlorine pesticides (lindane and endosulfan) and two organophosphates (malathion and chlorpyrifos-methyl) during the composting process in the reactor of a pilot plant. Malathion, chlorpyrifos-methyl and lindane residues almost fully disappeared after 8 days of maturation in the reactor, while endosulfan residues were only partially degraded. Alongside this, a study of natural disappearance of the pesticides was carried out in the laboratory and a characteristic time profile was traced for each pesticide class.     

Factors controlling degradation of pesticides in soil

Rates of pesticide degradation in soil exhibit a high degree of variability, the sources of which are usually unclear. Combining data from incubations performed using a range of soil properties and environmental conditions has resulted in greater understanding of factors controlling such degradation. The herbicides clomazone, flumetsulam, atrazine, and cloransulam-methyl, as well as the former insecticide naphthalene offer examples of degradation kinetics controlled by coupling competing processes which may in turn be regulated separately by environmental conditions and soil properties. The processes of degradation and volatilization appear to compete for clomazone in solution; sorbed clomazone is degraded only after the solution phase is depleted. Similarly, volatilization of naphthalene is enhanced when degradation has been inhibited by high nutrient levels. Degradation of the herbicide flumetsulam has been shown to be regulated by sorption, even though the compound has a relatively low affinity for the soil. The fate pathway for cloransulam-methyl shifts from mineralization to formation of metabolities, bound residues and physically occluded material as temperature increases. Atrazine degradation in soil may be controlled in part by the presence of inorganic nitrogen, as the herbicide appears to be used as a nitrogen source by micro-organisms. New insight gained from measurement of multiple fate processes is demonstrated by these examples.     

Distribution and breakdown of DDT in orchard soil

Amounts of DDT and its breakdown products were determined in soil in an apple orchard in Herefordshire. Samples were taken for a number of years (1972–79) after use of the insecticide in the orchard had ceased in 1969. The results were compared with those obtained in an investigation of the same orchard in 1968. From 1968 to 1979, soil residues of pp′-DDT, p′--DDT and pp′--TDE decreased gradually whereas those of pp′--DDE increased, and there were linear relationships between log (concentration) and time. The calculated time for 50% decrease in concentration (Dt₅₀) was 11.7 years for pp′--DDT, 3.3 years for pp′--TDE and 7.1 years for op′--DDT; the time for doubling the concentration for pp′--DDE was 9.1 years. Regression analysis on the two major components (pp′--DDT+pp′--DDE) indicated that the total amount (2.7 mg kg^?1) was not decreasing with time. It was concluded that during a post-spray era, the breakdown of pp′--DDT to pp′--DDE was a significant feature of the persistence of DDT, and that, in contrast to the findings of other workers who sampled when DDT was being used, there were no losses by volatilisation. There was an exponential decrease in the amount of DDT residues with increasing soil depth and approximately 90% was found in the top 10 cm of the undisturbed soil profile.     

Effects of glyphosate on soil microbial communities and its mineralization in a Mississippi soil

Transgenic glyphosate-resistant (GR) soybean [Glycine max (L.) Merr.] has enabled highly effective and economical weed control. The concomitant increased application of glyphosate could lead to shifts in the soil microbial community. The objective of these experiments was to evaluate the effects of glyphosate on soil microbial community structure, function and activity. Field assessments on soil microbial communities were conducted on a silt loam soil near Stoneville, MS, USA. Surface soil was collected at time of planting, before initial glyphosate application and 14 days after two post-emergence glyphosate applications. Microbial community fatty acid methyl esters (FAMEs) were analyzed from these soil samples and soybean rhizospheres. Principal component analysis of the total FAME profile revealed no differentiation between field treatments, although the relative abundance of several individual fatty acids differed significantly. There was no significant herbicide effect in bulk soil or rhizosphere soils. Collectively, these findings indicate that glyphosate caused no meaningful whole microbial community shifts in this time period, even when applied at greater than label rates. Laboratory experiments, including up to threefold label rates of glyphosate, resulted in up to a 19% reduction in soil hydrolytic activity and small, brief (<7 days) changes in the soil microbial community. After incubation for 42 days, 32-37% of the applied glyphosate was mineralized when applied at threefold field rates, with about 9% forming bound residues. These results indicate that glyphosate has only small and transient effects on the soil microbial community, even when applied at greater than field rates.     

微生物农药在烟草生产上的应用现状分析与建议

本文就微生物农药在烟草生产上的研究与应用概况进行了综述,并阐述了目前存在的问题：（1）行业推荐产品较少,大部分研究产品处于室内试验和中试阶段;（2）行业从业人员以及烟农对微生物农药认识不足;（3）微生物农药产品稳定性和成本价格存在差距。建议加大微生物菌剂的开发力度和大田试验验证及商品化程度的完善,并加强行业人员对微生物农药重视意识的培训。     

农药污染土壤的植物修复研究

植物可以吸收、转移元素和化合物,可以积累、代谢和稳定污染物,具修复被污染土壤等作用值得关注。本文综述了植物修复被农药污染土壤的机理和研究现状,列举了修复各种有机污染物的典型植物,及对此方法存在的问题和发展前景作了相应的讨论。     

Field test of a mathematical model for non-equilibrium transport of pesticides in soil

A model for the transport of pesticides in non-structured arable soil has been tested under field conditions. Three classes of sorption site are distinguished in the model. Sorption at class 1 sites is assumed to be at equilibrium whereas sorption at class 2 and class 3 sites is calculated using rate equations. Class 2 sites equilibrate on a time scale of days and class 3 sites equilibrate on a time scale of hundreds of days. In the model, the liquid phase is assumed to be homogeneous and completely mobile. The model was validated in two field experiments on a loamy sand soil using the herbicides cyanazine and metribuzin and using bromide ion as a tracer of liquid flow in soil. Ignoring sorption at class 3 sites resulted in large discrepancies between calculated and measured concentration profiles. Calculated concentration profiles were sensitive to the desorption rate constant for class 3 sites.     

Movement of pesticides to surface waters from a heavy clay soil

A field experiment at Cockle Park, Northumberland on a clay loam soil (Dunkeswick series) cropped with winter wheat investigated the effects of drainage and season of application on pesticide movement. Isoproturon, mecoprop, fonofos and trifluralin were applied in two consecutive seasons at normal agricultural rates to three hydrologically isolated plots each of 0.25 ha. Two of the plots were mole-drained and the third was an undrained control. Surfacelayer flow and drainflow from each plot were monitored at 10-min intervals. Samples of flow were analysed for pesticides to evaluate transport of applied chemicals from the site. Despite widely differing properties (K_oc 20–8000 ml g^?1, t_1/2 10–60 days), all four pesticides were found in surface-layer flow and mole drainflow from the site. Maximum concentrations of pesticides in flow ranged from 0.1 to 121 μg litre^?1 (aqueous phase) and < 0.2 to 48 μg litre^?1 (particulate phase). Over two contrasting seasons, total losses of pesticides in flow followed total amounts of flow and were approximately four and five times larger, respectively, in 1990/91 than in 1989/90. The maximum loss occurred from the undrained plot and was 2.8 g isoproturon (0.45% of that applied). Total losses of autumn-applied pesticides from an undrained plot were up to four times greater than losses from a mole-drained plot. Mole drainage decreased movement of pesticides from this slowly permeable soil by reducing the amount of surfacelayer flow. Maximum concentrations of mecoprop and isoproturon in drainflow were 10–20 times larger following spring application than after application in autumn. Bypass flow down soil cracks was an important process by which pesticide was lost from the site, with transport to the drainage system via mole channels (55 cm depth) after less than 0.5 and 6.7 mm net drainage in the two winters.     

常规施药机具喷施微生物农药研究

针对微生物农药含有大量菌丝、菌核生物的特点,通过试验与测定,研究常规施药机具作业时产生的工作压力、流体速度、流道结构等参数变化对微生物农药活性的影响。试验表明:随着工作压力、液体流速的增加,活菌吸附定殖数逐渐增多;气体流速在35 m/s时,活菌的吸附定殖效果最好;水稻病害防治效果较明显。     

The microbial biodegradation of paraquat in soil

The microbial degradation of [¹⁴C]paraquat using cultures from two agricultural soils was investigated. The experiments were carried out in the absence of light, under aerobic conditions. Degradation was rapid, with 50% mineralisation to [¹⁴C]carbon dioxide occurring within three weeks. HPLC, capillary electrophoresis and mass spectroscopy confirmed that the majority (>85%) of the remaining radiochemical in solution was [¹⁴C]oxalic acid, and that no paraquat remained.     

Study of diuron in soil solution by means of a novel simple technique using glass microfibre filters

Retention by a glass fibre filter of the liquid phase of a clay loam soil treated with ¹⁴C-diuron provides a novel method for analysis of the herbicide in soil solution. At 26.3% (w/w) soil moisture content, less than 10% of the applied diuron was found in solution, and this percentage decreased slightly with diuron dose. The herbicide was rapidly adsorbed on soil during the first day, but adsorption continued and the concentration of diuron in solution could be further reduced by 36–50% during the following 6 days. Drying the soil after treatment, with possible crystallization of herbicide applied at high doses, tended to fix the solution concentrations. Ethanol (3% v/v) in soil water favoured herbicide dissolution. Increasing soil moisture to 36.3% (w/w) slightly decreased the concentration of the herbicide in solution, but increased the percentage held in solution. Frost and a drying-rewetting cycle had little or no subsequent effect on diuron concentration in soil solution.     

蒙古沙冬青根围土壤微生物分布及与土壤因子相关性研究

为了探明蒙古沙冬青(Ammopiptanthus monglicus)根围土壤微生物分布和土壤因子生态作用,2012年6月选取内蒙古磴口、阿拉善左旗和乌拉特后旗3个样地,按0-10、10-20、20-30、30-40、40-50cm5个土层采集根围土壤样品,系统研究了土壤微生物数量和生态分布。结果表明:五大类土壤微生物数量及分布与蒙古沙冬青及样地生态条件有关,不同样地不同土层微生物数量差异显著,垂直动态分布明显。3样地均是细菌>芽孢菌>放线菌>固氮菌>真菌。0-20cm土层显著高于其它土层,最大值均在10-20cm,并随土层加深,数量有减少趋势。同一土层,磴口的土壤细菌、芽孢菌、固氮菌、放线菌显著高于乌拉特后旗和阿拉善左旗;乌拉特后旗的真菌显著高于磴口和阿拉善左旗。相关性分析表明:土壤细菌、真菌和放线菌均与土壤有机C、碱解N和碱性磷酸酶极显著正相关。     

Factors influencing entry of pesticides into soil water

Leaching of pesticides and hence the risk of contamination of ground-water depends on the physicochemical properties of the pesticide, the properties of the soil and the weather. Lipophilicity is the most important physicochemical property influencing the movement of un-ionised pesticides through soil. Water solubility is usually only an important factor in leaching for a few moderately polar solids with high melting points. Organic matter content is the most important property of the soil for un-ionised pesticides whilst the mobility of weak acids depends on soil pH. Permanent anions and weak acids can be very weakly adsorbed and hence might easily reach groundwater. Applications in autumn are more likely to reach groundwater than those in spring because soil temperatures are low and rainfall exceeds evaporation in winter, enabling mobile pesticides to penetrate to subsoils where degradation rates can be very slow. Concentrations of pesticide in water entering subsoils cannot be reliably simulated to an accuracy of better than an order of magnitude because the complex patterns of water flow and the slow diffusion processes of the pesticide are insufficiently understood. The consequences of applying a mobile pesticide to soil where drainage is impeded or where the water table is near the surface need to be anticipated before it is registered for treatment of the soil.     

Modelling the behaviour of organic chemicals in soil and ground water

The development, testing and application of computer models for the behaviour of organic chemicals, especially pesticides, in soil and ground water has been reviewed. Detailed data are needed on the structure and properties of the soil and ground-water systems, and on the flow of water through these systems. Adsorption and transformation of organic chemicals can be studied in the laboratory and the results introduced into the models. The mathematical techniques most frequently used for the solution of the differential equations are briefly discussed. Some models for the behaviour of pesticides in the root zone have been tested against results of field trials and some interesting deviations between computations and measurements emerged. Techniques for the simulation of the behaviour of organic chemicals in the ground-water zone are also available. However input data for the models are often lacking, as are also results of field studies for testing the models.     

The microbial formation of the 23-keto derivative from avermectin B2a in soil

The nematicide avermectin B_2a, as the [5-³H]-labelled compound, formulated on attapulgite clay and mixed into pots of moist soil, had a half-life of between 2.5 and 3 days in sandy loam soil under greenhouse conditions. A major metabolite, the 23-keto derivative, was identified and shown to be much more persistent than the parent compound. This metabolite is responsible for the prolonged nematicidal activity of avermectin B_2a applied to soil.     

Modelling the effects of alcohol ethoxylates on diffusion of pesticides in the cuticular wax of Chenopodium album leaves

Cuticular waxes represent the first and, in most cases, the limiting barrier for foliar uptake of pesticides from solution. Sorption of pesticides in reconstituted cuticular wax (wax/water partition coefficients) of Chenopodium album L. and in isolated cuticular membranes (cuticle/water partition coefficients) of Prunus laurocerasus L. was determined. Diffusion coefficients of pesticides in reconstituted cuticular wax of C. album leaves were size-dependent, increasing with increasing molar volume. In the presence of alcohol ethoxylates, diffusion coefficients were enhanced by up to two orders of magnitude, and size selectivity was significantly decreased. The accelerating effect and the decrease in size selectivity were attributed to plasticisation of the cuticular wax by the alcohol ethoxylates increasing the fluidity in the wax. A free volume model adopted from polymer science was successfully applied to predict diffusion coefficients of pesticides on the basis of the transport properties of the wax (size selectivity and crystallinity), the molar volume of the diffusing compound and the accelerator concentration in the wax.     

Photolytic versus microbial degradation of clomazone in a flooded California rice field soil

BACKGROUND: Clomazone is a popular herbicide used on California rice fields and exhibits rapid anaerobic microbial degradation (t_1/2 = 7.9 days). To test the potential of direct and indirect photolytic degradation as a cofactor in the overall degradation rate, sacrificial time‐series microcosms were amended with water, non‐sterilized soil + water and sterilized soil + water. Clomazone was added to each microcosm, which was then exposed to natural and artificial sunlight over 35 days. Water and acetonitrile extracts were analyzed for clomazone and metabolites via LC/MS/MS. RESULTS: The calculated pseudo‐first‐order degradation rate constants (k) were k_water = 0–0.005 ± 0.003 day^?1, k_sterile = 0–0.005 ± 0.003 day^?1 and k_non?sterile = 0.010 ± 0.002–0.044 ± 0.007 day^?1, depending on light type. The formation of ring‐open clomazone, a microbial metabolite, correlated with clomazone degradation. Trace amounts of 5‐hydroxyclomazone (m/z = 256 → 125), aromatic hydroxyclomazone (m/z = 256 → 141) and an unknown product (m/z = 268 → 125) were observed. CONCLUSIONS: The photolytic degradation rate depends on both light type and the quality of the chromophores that induce indirect photolysis. Microbial degradation was found to be sensitive to temperature fluctuations. Overall, microbes are shown to be more detrimental to the environmental fate of clomazone than photolysis. Copyright © 2012 Society of Chemical Industry     

The effect of the annual use of pesticides on soil microorganisms,pesticide residues in the soil and barley yields

A study has been made of the influence of pesticides used annually on soil microorganisms and crop yields. The persistence of these pesticides in the soil was also investigated. The herbicides MCPA, glyphosate, maleic hydrazide and tri-allate, and the insecticide parathion, were applied on experimental plots on which barley was grown during the years 1973-1981. The fungicide 2-methoxyethylmercury chloride was used every year for dressing the seeds grown in pesticide-treated plots. The pesticide treatments did not affect significantly the numbers of several groups of soil microorganisms. A slight increase was, however, observed in the nitrification activity in the soil. The barley yields were on average higher on pesticide-treated plots than on controls because of successful weed control. Pesticide residues in the soil were generally very low; for example, for parathion they were below 0.02 mg kg^?1 within 11 days, and for MCPA 0.06 mg kg^?1 within 7 days. However, the glyphosate residue was 1.6 mg kg^?1 in the autumn 2 days after the treatment, and the residue settled to a level of 0.2 mg kg^?1 during the following summer. No clear dependence was observed between the residue level and the time between treatment and sampling.