Persistence,degradation and leaching of coumaphos in soil

Abstract

Dissipation, degradation and leaching of fresh ¹⁴C coumaphos, alkylated ¹⁴C coumaphos and aged residues of ¹⁴C coumaphos from vats were studied in alkaline sandy loam soil in soil columns in the field under subtropical conditions in Delhi for a year. Dissipation, degradation and bound residue formation was more in case of alkali treated coumaphos than fresh coumaphos. After 365 days total residues of fresh coumaphos accounted for 33.25% while that of alkali treated coumaphos was 19.12%. Bound residue formation was almost double in case of alkali treated coumaphos (18.95%) than fresh coumaphos (9.53%) after 150 days followed by release of bound residue in both the cases. The proportion of metabolites 4 ‐ methylumbelliferone, chlorferon and potasan collectively was 86.05% in fresh coumaphos extractable residues while the same was 91.74% in alkali treated coumaphos after 365 days. Aged residues from vats containing copper sulphate and buffer were found to be more persistent in soil as total residues remained were 95.58% in comparison with 83.09% total residues of aged residues from vats containing only buffer after 150 days of treatment. Copper sulphate seems to inhibit the degradatiion of coumaphos in soil by microorganisms. Chlorferon was the major metabolite in generally all the samples. Coumaphos did not leach below 10 cm in all the cases.     

Efficacy of new mass-trapping devices against Bactrocera oleae (Diptera tephritidae) for minimizing pesticide input in agroecosystems

Decreasing pesticide use in olive groves is central to controlling pathogens and pests such as Bactrocera oleae. This has led to the development of mass trapping devices which not only minimize pesticide use but, with improved efficacy of attractants, also decrease costs associated with pest control and ensures that the quality of olive oil is safe for human consumption. This study was undertaken to test a new device which utilizes reduced quantities of both insecticide (lambda-cyalothrin) as well as the female olive fly pheromone (1,7-dioxaspiro-(5.5)-undecane). The new device was tested against an older device manufactured by the same company. The use of plastic polymers as substrate for encapsulating the pheromone allowed for a slower pheromone release, prolonging the efficacy and duration and thus reducing costs. The density of adult populations was monitored using yellow chromotropic traps that were checked every ten days and the degree of olive infestation, as determined by preimago stages, was assessed by analyzing 100 drupes per plot. Infestation analyses were performed every ten days. The control plot had the lowest density of adults and the highest drupe infestation rate. The new devices were more effective than the older devices in both attracting adults and controlling infestation of drupes. Moreover, the new devices containing reduced amounts of pheromone and insecticide were cheaper and exhibited longer functional efficacy. In addition to the slower release of attractants, the plastic polymers used in these newer devices were also more resistant to mechanical and weather degradations. Results demonstrate that mass trapping can indeed be an effective means of controlling B. oleae via eco-sustainable olive farming.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

江汉平原农村食品中农药残留研究

研究了湖北省潜江市农村６类食品中农药的残留情况，采样测定结果表明，在被检食品中有机氯农药污染普遍存在，但残留量均低于最大残留限量（ＭＲＬ），以植物油残留量为最大；有机磷农药残留只在蔬菜中检出，检出率以根菜类为最大，叶菜类次之，果菜类和花菜类最小；菊酯类农药残留较少；杀菌剂多菌灵残留未检出。     

不同环境介质中异丙隆残留的前处理方法研究

利用高效液相色谱法(HPLC)测定水、土壤和植物中除草剂异丙隆的残留量.采用LC-18固相萃取小柱分离、净化和富集水中异丙隆残留;利用丙酮/水(体积比为3:1)振荡提取土壤中的异丙隆残留,并通过硅胶柱层析净化、分离;以乙酸乙酯为提取剂,采用超声波提取植物样品中的异丙隆残留,并用Florisil固相萃取小柱净化、分离.利用HPLC-UVD(Ultraviolet Detector,紫外检测器)定性、定量测定水、土壤和植物样品中异丙隆残留量.结果表明,异丙隆HPLC的线性检测范围为0.1～16 mg/L,决定系数\%R2\%=0.999 9,最低检测浓度为0.012 mg/L.水的加标回收率为90.7%～91.1%,相对标准偏差为3.0%～12.0%;土壤的加标回收率为88.4%～97.4%,相对标准偏差为6.9%～9.8%;植物的加标回收率为94.4%～99.9%,相对标准偏差为4.6%～9.0%.研究为异丙隆残留的检测提供了一种有效方法.     

广东某市疫情期间污水中精神药物的分布特征和滥用评价

采用污水流行病学的方法，研究了2020年新冠疫情期间及前后广东省某市生活污水中两种典型精神药物甲基苯丙胺和氯胺酮的赋存特征及其变化情况，并运用手机信令数据分析人口总数、结构特征及其变动规律，进而将两者结合分析了疫情期间及前后两种药物的消费量变化特征.结果表明，疫情期间该市实际人口相对于疫情前下降了约45%，两种药物总消费量相对于疫情前下降了约75%.总消费量的显著下降很大程度是由疫情期间实际人口下降造成的.实际上，疫情期间该市甲基苯丙胺和氯胺酮的人均消费水平相对于疫情前下降不到50%.考虑到疫情期间严格的管控措施，这一下降幅度说明这两种精神类药物滥用极其顽固；而疫情后两种药物的消费量及在环境中的浓度又基本恢复到疫情前的水平，进一步证明了精神类药物滥用的顽固性.     

Validation of QuEChERS-based method for determination of flusilazole residues in grape by high-performance liquid chromatography with photodiode array detector

A high-performance liquid chromatography with photodiode array detector analytical method was developed to determine the residue levels of flusilazole in grape and investigate the dissipation pattern and safety. The results showed that the mean recoveries were in the range of 86%–90%. Limits of detection and quantification were 0.008 and 0.02 mg/kg, respectively. The residue levels of flusilazole were best described by first-order rate kinetics and with half-lives ranging from 4.2 days (recommended dose) to 4.6 days (double the recommended dose). In conclusion, flusilazole at the recommended or even at double the recommended doses does not pose any apparent hazards to consumers.     

Experimental investigation of the efficiency of triple rinsing of agricultural containers regarding their characterization as non-hazardous wastes

The efficiency of water rinsing for removing fenthion from non-combustible used pesticide containers was investigated. Four hundred empty containers from four olive oil producing areas in Greece were studied. Following triple rinsing cleaning procedures, the amount of fenthion retained in the container ranged from 0.01% to 0.1% w/w of its initial concentration. Extraction was accomplished with acetone, and the extracts were analyzed with a capillary gas chromatographic system coupled with flame ionization detector. The results obtained showed that triple rinsing is an effective procedure for removing fenthion from used pesticide containers, since the remaining pesticide concentration was below the legislated threshold value. Consequently, the containers can be handled as non-hazardous solid wastes.     

贵州梵净山九龙池沉积物14C年代学研究及全新世碳累积速率变化

放射性碳同位素加速器质谱（ASM¹⁴C）测年法是湖泊沉积物定年的主要方法,并且是全新世年代学研究的热点。随着对全新世古气候与环境变化研究的深入,选取不同介质定年可能对年代模型的准确性造成误差,进而影响到气候指标的解译。本文选取贵州东北部梵净山九龙池沉积物中树枝、树叶、树皮、种子等植物残体和全样有机质作为测年介质,利用ASM¹⁴C进行定年。结果表明,相比全样有机质,使用植物残体定年可以在一定程度上避免碳库效应的影响。但相比于原位沉积且生长年限较短的叶片,树枝的定年结果偏老,不是一种理想的定年介质。另外,根据定年结果及总有机碳含量重建了全新世九龙池的碳累积速率,发现碳累积速率可以指示该地区亚洲夏季风强度的变化历史。