The role of ferrous ions in the rapid degradation of oxamyl,methomyl and aldicarb in anaerobic soils

The carbamoyloxime pesticides methomyl, oxamyl and aldicarb, together with the oxidation products of aldicarb, are known to break down much more rapidly in certain anaerobic subsoils than in the aerobic topsoils from the same site. Ferrous ions have now been shown to be involved in this reaction. Oxamyl was degraded in aqueous solutions at 30°C containing 250 μg ml^?1 Fe²⁺ with a half-life of about 10 h, independent of pH in the range of 5.65–7.66; the observed products of this reaction were N,N-dimethyl-l-cyanoformamide and methanethiol. These same products, rather than the oximino hydrolysis product observed from degradation in aerobic soils, were rapidly and quantitatively formed from oxamyl in suspensions of anaerobic reduced subsoils (Fe²⁺ concentration 27–41 μg ml^?1 soil water), but oxamyl was rather stable in water-saturated Vredepeel subsoil (Fe²⁺ concentration 0.65 μg ml^?1) in which the redox potential was much higher. Methomyl behaved similarly. The rates of reaction in the suspensions of anaerobic subsoils were greater than expected from the concentrations of Fe²⁺ in the soil water, but most of the Fe²⁺ present in soil was bound to the soil particles by cation exchange and this bound Fe²⁺ may have participated. Breakdown of aldicarb was accelerated both in solutions of Fe²⁺ and in the suspensions of anaerobic reduced subsoils, though the rate enhancement was less than observed with methomyl and oxamyl; 2-methyl-2-methylthiopropionitrile and 2-methyl-2-methylthiopropionaldehyde were the observed products from aldicarb in anaerobic soil but only the former was produced in Fe²⁺ solutions; the corresponding nitriles and aldehydes were also yielded by aldicarb sulphoxide and aldicarb sulphone in the anaerobic, reduced subsoils.     

Controlled release of aldicarb from carboxymethyl cellulose microspheres: in vitro and field applications

Aldicarb is a carbamate pesticide that is widely used throughout the world in the protection of crops (eg cotton, nuts, potatoes, onion, tobacco, sugar beet and sugar cane). In Turkey, especially in the Çukurova region, it is used for the control of the cotton white fly (Bemisia tabaci) which attacks cotton plants cultivated in this region. Aldicarb contamination in surface and ground water is a serious problem in several countries, partly due to its high water solubility. It is also highly toxic to mammals. In order to overcome these problems, microspheres of aldicarb were prepared using carboxymethyl cellulose (CMC) as the biodegradable support material cross-linked with aluminium chloride. A strong hysteresis behaviour was observed upon drying and reswelling. Encapsulation efficiency was in the range 12–23% and aldicarb contents of 5.7–10.3 mg per 100 mg of microspheres was achieved. In vitro release was distinctly Fickian, and Higuchi constants were very close to 0.5. Release in pots revealed that only one sample had a release capability for more than four weeks. In the cotton plot much longer durations of release (more than seven weeks) were observed while a commercial granular formulation released its content immediately. It was thus possible to construct a controlled pesticide release system that prolonged the bioavailability to about eight weeks. © 1999 Society of Chemical Industry     

Effect of cropping cycles and repeated herbicide applications on the degradation of diclofop-methyl, bentazone, diuron, isoproturon and pendimethalin in soil

A greenhouse study was conducted to investigate the ability of four crops (wheat, corn, oilseed rape and soybean) to influence the degradation of bentazone, diclofop-methyl, diuron, isoproturon and pendimethalin in soil. The present study showed that microbial biomass-carbon was significantly higher in planted soils than in bulk soil, especially with wheat and corn, after several cropping cycles. The biomass in corn and soybean planted soils was adversely affected by bentazone but recovered after three cropping cycles. In wheat-planted soils, diclofop-methyl application resulted in persistent increase of the amount of microbial biomass. Bentazone did not show accelerated degradation even after five successive treatments, differing from diclofop-methyl, for which two applications were sufficient to enhance significantly its rate of degradation. Enhanced degradation of diclofop-methyl was even more pronounced in wheat-planted soil. The rates of mineralisation of diuron, isoproturon and pendimethalin were not affected after the first cropping cycle, but were significantly increased in planted soils after five cropping cycles. The results confirm that plants may promote pesticide degradation in soil by stimulating biodegradation processes. In the case of diclofop-methyl, stimulation of accelerated degradation was observed.     

Management of the yellow beet cyst nematode with crop rotation,soil fumigation and granular nematicides

A trail field was managed for six years to test effects of short crop rotations, soil fumigation and granular nematicides on the population dynamics of the yellow beet cyst nematode (Heterodera trifolii f. sp.beta) and sugar-beet yields.In the two-year rotation, the cyst nematode population before planting varied from about the tolerance level (5 eggs per millilitre of soil) to 25 eggs per millitlitre of soil, leading to losses of sugar yield. Soil fumigation with metam-sodium effectively reduced the nematode density before planting, resulting in a 15 and 25% increase in sugar yield in the first two crops, respectively, but was insufficient to protect the third sugar-beet crop from yield-reducing nematode attack. This was attributed to the wet soil at the time of application and accelerated disappearence of the chemical in the soil through biological adaptation to repeated fumigation. Oxamyl or aldicarb granular nematicides applied as a side-dressing to the rows had insufficient effect to protect the sugar-beet from yield-reducing nematode attack. An overall treatment with aldicarb rotavated into the soil, alone and in addition to soil fumigation, increased sugar yield significantly. However in the two-year rotation, yield of the third sugar-beet crop treated with soil fumigation and granular nematicide was still lower than that of the untreated second crop in the three-year rotation.In the three-year rotation, thecyst nematode population before sugar-beet varied from hardly detectable to about the tolerance level. Here sugar-beet could be protected from yield-reducing nematode attack by soil fumigation or an overall treatment with granular nematicide. In the threeyear rotation with soil fumigation an increase ofRhizoctonia crown rot was observed in the second sugar-beet crop.Samenvatting Om de effecten na te gaan van korte rotaties, grondontsmetting en nematicide granulaten op het populatieverloop van de gele bietcystenematode (Heterodera trifolii f.sp.beta) en de opbrengsten van suikerbieten werd gedurende zes jaren een proef uitgevoerd op een natuurlijk besmet perceel van de proefboerderij Vredepeel.In de tweejarige rotatie variëerde de cystenematodepopulatie vóór het bietegewas boven de schadedrempel, wat resulteerde in verlaging van de suikeropbrengst. Grondontsmetting met metam-natrium veroorzaakte een effective vermindering van de dichtheid van de nematoden vóór de bieten en een verhoging van de suikeropbrengst van respectievelijk 15 en 25% bij de eerste twee gewassen, maar was onvoldeende om het derde bietegewas te beschermen tegen een opbrengst verminderende aantasting door nematoden. Dit was een gevolg van natte bodemomstandigheden bij het injecteren en het versneld verdwijenen van het middel door biologische adaptatie van de grond na herhaalde ontsmetting. Nematicide granulaten (oxamyl of aldicarb) naast de rij toegepast hadden onvoldoende effect om de bieten te beschermen tegen een opbrengstverminderende aantasting door nematoden. Een volvelds toepassing van in de grond gefreesde aldicarb alleen en toegevoegd na grondontsmetting verhoodge de suikeropbrengst beduidend. De opbrengst van het derde suikerbietegewas in de tweejarige rotatie was echter na toepassing van grondontsmetting en nematicide granulaten nog beduidend lager dan die van het onbehandelde tweede suikerbietegewas in de driejarige rotatie.In de driejarige rotatie variëerde de cystenematodepopulatie vóór het bietegewas van nauwelijks aantoonbaar tot nabij de tolerantiegrens. Hier kon het suikerbietegewas worden beschermd tegen een eventueel opbrengst verminderende nematodenaantasting door grondontsmetting of volveldstoepassing van nematicide granulaten.     

Rate, placement and timing of aldicarb applications to control Asian citrus psyllid, Diaphorina citri Kuwayama (Hemiptera: Psyllidae), in oranges

BACKGROUND: The Asian citrus psyllid (ACP), Diaphorina citri Kuwayama (Hemiptera: Psyllidae), is a cosmopolitan insect pest of citrus and vectors the bacterium Candidatus Liberibacter asiaticus, a suspected causal organism of citrus greening or ‘huanglongbing’ disease. Aldicarb 150 g kg^?1 GR (Temik^® 15 G) was evaluated at three rates, two placements and three timings for ACP control in orange trees. RESULTS: Application of aldicarb at 5.6, 2.8 and 1.4 kg AI ha^?1 in March 2006 reduced adults by 58–66%, 45–46% and 25–37% respectively compared with untreated controls in two separate trials. No difference was observed in placement (one versus two sides of the tree) or tree size (8 years old versus 12 years old). Application at 5.6 kg ha^?1 in January 2007 reduced adults by 86% and shoot infestation by 77% in spring, and was generally better than the November and especially February applications. Even more striking results were evident on adults caged on treated plants for 25 days in March. Spiders and ladybeetles were equally abundant in treated and untreated trees. CONCLUSION: Aldicarb application at 5.6 kg ha^?1 to the bed side of mature citrus trees 2–3 months before spring growth can suppress ACP through spring without a direct effect on principal psyllid natural enemies. Copyright © 2008 Society of Chemical Industry     

Adsorption, transport and degradation of fipronil termiticide in three Hawaii soils

BACKGROUND: The behavior of the termiticide fipronil in soils was studied to assess its potential to contaminate ground and surface water. This study characterizes (1) adsorption of fipronil in three different soils, (2) transport of fipronil through leaching and runoff under simulated rainfall in these soils and (3) degradation of fipronil to fipronil sulfide and fipronil sulfone in these soils. RESULTS: The adsorption experiments showed a Freundlich isotherm for fipronil with K_oc equal to 1184 L kg^?1. In the leaching experiments, the concentration of fipronil and its metabolites in leachate and runoff decreased asymptotically with time. The concentration of fipronil in the leachate from the three soils correlated inversely with soil organic carbon content. The degradation experiment showed that the half‐life of fipronil in the soils ranged from 28 to 34 days when soil moisture content was 75% of field capacities, and that 10.7–23.5% of the degraded fipronil was transformed into the two metabolites (fipronil sulfide and fipronil sulfone). CONCLUSION: Fipronil showed large losses through leaching but small losses via runoff owing to low volumes of runoff water generated and/or negligible particle‐facilitated transport of fipronil. The half‐life values of fipronil in all three soils were similar. Copyright © 2011 Society of Chemical Industry     

Effects of fosthiazate and aldicarb on populations of plant-growth-promoting bacteria, root-lesion nematodes and bacteria-feeding nematodes in the root zone of potatoes

A 2-year study investigated the relationship between the nematicides aldicarb and fosthiazate and populations of plant growth-promoting (PGP) and plant-growth-inhibiting (PGI) bacteria, and root-lesion nematodes and bacteria-feeding nematodes in the root-zone soils of potatoes. Fewer ( P  < 0.05) bacterial genera and species were recovered from aldicarb-treated soils than from the fosthiazate and untreated soils but bacterial population densities were greatest in the aldicarb-treated soils. In potato plantlet bioassays using root-zone bacteria from the three soil sources, bacteria from the aldicarb-treated soils reduced ( P  < 0.01) the mean wet and dry weight of shoots and roots compared with those from the fosthiazate and untreated soils. In the field, fosthiazate (but not aldicarb) significantly increased tuber yields and reduced nematode population densities of Pratylenchus penetrans in roots and soil. Population densities of bacteria-feeding nematodes (primarily Diplogaster lheritieri ) were not affected by either nematicide. Aldicarb appeared to suppress the populations of plant-growth-promoting bacteria that contribute to enhanced growth in potatoes. This is attributed to the long-term use of aldicarb at the trial site, which may have encouraged the selection, or adaptation, of soil microorganisms that degrade carbamate pesticides but do not enhance potato growth.     

苦皮滕素Ⅴ在土壤中的消解动态及降解产物

为指导苦皮藤素制剂的科学合理使用,采用高效液相色谱-电喷雾多级串联质谱技术(HPLC-ESI-MS/MS)研究了苦皮藤素V在4种土壤中的消解动态及其降解产物。结果表明:苦皮藤素V在江西红土和陕西黄土中消解缓慢,90 d的消解率仅为68.0%和65.0%;在黑龙江黑土和天津碱土中消解相对较快,90 d时消解率分别为84.9%和95.1%。苦皮藤素V在4种土壤中的主要降解产物为一系列在其C-1、C-2和C-8位发生酯键水解而形成的3-羟基、4-羟基及5-羟基的二氢沉香呋喃多元酯。     

异噁唑草酮在土壤表面光解及在土壤中的降解和淋溶特性

为合理评估除草剂异唑草酮的环境风险,在实验室模拟条件下,研究了异唑草酮在土壤 (红壤土)表面光解以及在不同质地土壤 (潮土、水稻土和红壤土) 中的降解和淋溶特性。结果表明:异唑草酮在土壤表面的光解遵循一级反应动力学方程c_t = 4.23e–0.008t (r = 0.937),半衰期为82.5 h;其在潮土、水稻土和红壤土中的降解均符合一级动力学方程,好氧条件下,异唑草酮在3种土壤中的降解半衰期分别为10.5、43.3和139 h,厌氧条件下的降解半衰期分别为19.4、18.4和158 h;其在潮土、水稻土和红壤土中的淋溶系数 (R_f) 分别为0.417 0、0.083 3和0.083 3。研究表明:异唑草酮在土壤表面光解速率较慢,而在土壤中好氧及厌氧条件下降解速率均较快,残留期短;其在土壤中淋溶性较弱,不易对周围环境及地下水造成污染风险。     

Effect of temperature,organic amendment rate and moisture content on the degradation of 1,3‐dichloropropene in soil

1,3‐Dichloropropene (1,3‐D), which consists of two isomers, (Z)‐ and (E)‐1,3‐D, is considered to be a viable alternative to methyl bromide, but atmospheric emission of 1,3‐D is often associated with deterioration of air quality. To minimize environmental impacts of 1,3‐D, emission control strategies are in need of investigation. One approach to reduce 1,3‐D emissions is to accelerate its degradation by incorporating organic amendments into the soil surface. In this study, we investigated the ability of four organic amendments to enhance the rate of degradation of (Z)‐ and (E)‐1,3‐D in a sandy loam soil. Degradation of (Z)‐ and (E)‐1,3‐D was well described by first‐order kinetics, and rates of degradation for the two isomers were similar. Composted steer manure (SM) was the most reactive of the organic amendments tested. The half‐life of both the (Z)‐ and (E)‐isomers in unamended soil at 20 °C was 6.3 days; those in 5% SM‐amended soil were 1.8 and 1.9 days, respectively. At 40 °C, the half‐life of both isomers in 5% SM‐amended soil was 0.5 day. Activation energy values for amended soil at 2, 5 and 10% SM were 56.5, 53.4 and 64.5 kJ mol^?1, respectively. At 20 °C, the contribution of degradation from biological mechanisms was largest in soil amended with SM, but chemical mechanisms still accounted for more than 58% of the (Z)‐ and (E)‐1,3‐D degradation. The effect of temperature and amendment rate upon degradation should be considered when describing the fate and transport of 1,3‐D isomers in soil. Use of organic soil amendments appears to be a promising method to enhance fumigant degradation and reduce volatile emissions. Published in 2001 for SCI by John Wiley & Sons, Ltd     

Retention and degradation of metribuzin in sandy loam and clay soils of Lebanon

The retention and degradation of metribuzin herbicide were studied under two environmental conditions. Field studies were carried out on two soils, a sandy loam soil (soil A) and a clay soil (soil B). Metribuzin was applied with a jet sprayer at 1060 g a.i. ha^?1 and 1960 g a.i. ha^?1 on soils A and B respectively. Reconstituted soil columns were used to study the herbicide movement and metabolism in the two soils. Analyses of metribuzin and its metabolites were carried out using standardized methods. The results indicated a very weak capacity of adsorption of metribuzin in the two soils, and the weak adsorbed fraction is easily desorbed. Degradation and mobility of metribuzin in the field and laboratory soil columns were very intense and rapid. Soil A favoured reductive deamination whereas soil B favoured oxidative desulphuration and the respective metabolites deaminometribuzin and diketometribuzin yield the same product deaminodiketometribuzin. Both leaching by rainfall and degradation were important in the disappearance of metribuzin from the soils.     

Effect of recent cropping history and herbicide use on the degradation rates of isoproturon in soils

Five soil samples were taken from each of five fields with different crop management histories. Three of the fields were in an arable rotation, the fourth field was temporary grassland, and the final field was under permanent grass. Of the three arable fields, two had been cropped with winter wheat in three of the preceding 6 years, and the third had last been cropped with winter wheat once only, 6 years previously. With one exception, the winter wheat had been sprayed with the herbicide isoproturon. The rate of isoproturon degradation in laboratory incubations was strongly related to the previous management practices. In the five soils from the field that had been treated most regularly with isoproturon in recent years, <2.5% of the initial dose remained after 14 days, indicating considerable enhancement of degradation. In the soils from the field with two applications of the herbicide in the past 6 years, residues after 27 days varied from 5% to 37% of the amount applied. In soils from the other three sites, residue levels were less variable, and were inversely related to microbial biomass. In studies with selected soils from the field that had received three applications of isoproturon in the previous 6 years, kinetics of degradation were not first‐order but were indicative of microbial adaptation, and the average time to 50% loss of the herbicide (DT₅₀) was 7.5 days. In selected soils from the field that had received just one application of isoproturon, degradation followed first‐order kinetics, indicative of cometabolism. Pre‐incubation of isoproturon in soil from the five fields led to significant enhancement of degradation only in the samples from the two fields that had a recent history of isoproturon application.     

Adsorption and degradation of thiazopyr in compost‐amended and non‐amended soils

Adsorption and degradation of thiazopyr on two unamended soils and a soil amended annually during 8 years with compost were studied under laboratory conditions and compared with the results obtained on soils amended with fresh sewage sludge compost. The adsorption isotherms fitted the Freundlich equation well and a marked sorption increase was found in amended soils. Degradation data followed first‐order kinetics and thiazopyr had a half‐life of about 75 days at 25 °C and 60% water‐holding capacity of soil. The addition of fresh compost markedly decreased the rate of thiazopyr degradation, whereas the compost mineralised in the field after annual additions had only a small influence. Incubation studies with sterile soils showed a very significant decrease of the degradation rate, indicating that degradation by micro‐organisms was the main pathway of thiazopyr degradation in the soils studied. © 2001 Society of Chemical Industry     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

烯酰吗啉顺反异构体在土壤中的降解动态研究

实验室条件下,研究了烯酰吗啉在土壤中的降解动态特性。结果表明,烯酰吗啉在供试吉林黑土、河南褐土和江西红土中的降解半衰期分别为69、69和462 d,在土壤中的降解性能为中等至难降解。其Z式异构体在吉林黑土、河南褐土和江西红土中的降解半衰期分别为89、126和533 d,E式异构体的降解半衰期分别为53、29和408 d,在3种土壤中Z式异构体的降解速率均低于E式异构体。河南褐土中E/Z的比值在降解过程中发生了明显变化。实验室条件下,烯酰吗啉在土壤中的降解速率明显低于其在田间土壤中的降解速率。     

Applying non-steady-state compartmental analysis to investigate the simultaneous degradation of soluble and sorbed glyphosate (N-(phosphonomethyl)glycine) in four soils

The decomposition behaviour of glyphosate in four Victorian soils was investigated at two temperatures using non-steady-state compartmental analysis. At 25°C, glyphosate degradation was shown numerically to be derived from two different sources where the rate of release from each source behaved in accordance with first-order kinetics. Over the first 40 day period for each of the soils, glyphosate was derived simultaneously from the labile and non-labile phase, whilst after the first 40 days, glyphosate was derived solely from the non-labile phase. At this temperature, the amount of glyphosate partitioned into the labile phase ranged from 24·1 to 34·5%, whilst the amount partitioned into the sorbed, non-labile phase ranged from 67·2 to 74·9%. The half-lives for glyphosate within each phase was calculated and ranged from six to nine days for the labile phase to 222–835 days for the non-labile phase. Glyphosate appeared to be more strongly held in the acidic Rutherglen soil than in the alkaline soils studied, and this was thought to be related to the substantially lower pH and higher Fe content of the acidic soil. At 10°C, glyphosate was shown numerically to be derived from two different sources for two of the soils. However, for the two remaining soils, glyphosate appeared to be derived either from a single phase or from two phases at either the same rate or at differential rates where the rate of release from one phase was sufficiently fast to mask the rate of release from the other. At this temperature, more glyphosate was partitioned into the non-labile phase of the Walpeup and Rutherglen soils than at 25°C. However, the rate of release of glyphosate from this phase increased for the Walpeup soil relative to that at 25°C, but decreased substantially for the Rutherglen soil. This suggests that different mechanisms for the binding of glyphosate into the non-labile phase may exist between soils. © 1998 SCI.     

Occurrence and mobility of the insecticide permethrin in rivers in the Southern Humber catchment,UK

The synthetic pyrethroid insecticides cis‐ and trans‐permethrin are widely used, particularly in sheep‐dips and for mothproofing within the textile industry. This study aims to establish the concentrations and mobility of permethrin within rivers in the Humber catchment, which contain some of the highest densities of wool‐scouring activity in the world. Our approach was to utilise three different surveys: (a) weekly and storm‐responsive sampling of ‘whole waters’ in the rivers Aire, Ouse, Don, Trent and Calder; (b) intensive sampling of ‘whole waters’ and suspended sediments in the rivers Aire (0.5 h) and Calder (1 h); (c) a bed‐sediment survey of the River Calder. Sediments were extracted by supercritical fluid extraction and all samples were analysed by gas chromatography with mass spectrometry. Results demonstrated the presence of permethrin in ‘whole waters’ and sediments, particularly in the rivers Aire and Calder, and at concentrations in the bed‐sediment likely to cause ecotoxicological effects to benthic macro‐invertebrates. Mass‐balance calculations indicated some loss of permethrin from the water column during transport, with the greatest losses at low river‐discharge. Isomer ratios (trans:cis) give retention times of permethrin in different components of the system as ‘whole water’ < suspended sediments < bed‐sediments, with estimates of 4–26 days for suspended sediments and a maximum of 103–125 days for surface bed‐sediments. © 2000 Society of Chemical Industry