Prediction of pesticide volatilization with PELMO 3.31

In the current EU risk assessment for pesticide registration, the European Community requires prediction of the concentration of each pesticide in air. A number of mathematical models are used to assess the fate of pesticides in groundwater, surface water and soil. PELMO 3.20 calculates the volatilization fluxes from bare soil and was improved in the new version PELMO 3.31 to include the effect of temperature and sorption in dry soil. The objective of this study was to evaluate the new version of PELMO 3.31 in predicting the pesticide volatilization under field conditions. Procymidone, malathion, and ethoprophos were the test compounds in two different seasons (autumn and winter). Comparing simulation results obtained with PELMO 3.31, after calibration, with the previous version PELMO 3.20 shows that the estimated volatilization results seems improved for malathion, similar or slightly overestimating in the warmer season for ethoprophos, and similar or slightly underestimating in the colder season for procymidone. The new release of PELMO allows a more accurate estimation of pesticides volatilization from soil as function of meteorological factors, especially for medium or low volatility pesticides. Some difficulties remain, such as the determination of the active air layer and the sorption increment with the soil drying.     

The properties of emulsifiers that enhance the replication of viruses in cell cultures

Some of a variety of commercial emulsifiers were capable of enhancing the sensitivity of mammalian cells in culture to infection with several viruses. Those viruses which were enhanced in their replication were single-stranded RNA viruses whereas the double-stranded viruses tested were non-responders. In addition, some cells lines, as compared to others, responded in a more sensitive manner to the active emulsifiers.     

Estimating pesticide runoff in small streams

Surface runoff is one of the most important pathways for pesticides to enter surface waters. Mathematical models are employed to characterize its spatio-temporal variability within landscapes, but they must be simple owing to the limited availability and low resolution of data at this scale. This study aimed to validate a simplified spatially-explicit model that is developed for the regional scale to calculate the runoff potential (RP). The RP is a generic indicator of the magnitude of pesticide inputs into streams via runoff. The underlying runoff model considers key environmental factors affecting runoff (precipitation, topography, land use, and soil characteristics), but predicts losses of a generic substance instead of any one pesticide. We predicted and evaluated RP for 20 small streams. RP input data were extracted from governmental databases. Pesticide measurements from a triennial study were used for validation. Measured pesticide concentrations were standardized by the applied mass per catchment and the water solubility of the relevant compounds. The maximum standardized concentration per site and year (runoff loss, R_Loss) provided a generalized measure of observed pesticide inputs into the streams. Average RP explained 75% (p < 0.001) of the variance in R_Loss. Our results imply that the generic indicator can give an adequate estimate of runoff inputs into small streams, wherever data of similar resolution are available. Therefore, we suggest RP for a first quick and cost-effective location of potential runoff hot spots at the landscape level.     

Changes in pesticide adsorption with time at high soil to solution ratios

Adsorption of six pesticides (2,4-D, dicamba, fluroxypyr, fluazifop-P, metsulfuron-methyl and flupyrsulfuron-methyl) in nine contrasting soils was measured using two techniques: (i) a classical batch method and (ii) a centrifugation method that allowed the measurement of adsorption at a realistic soil to solution ratio after one and seven days. Although the batch method gived significantly higher values of Kd than the centrifugation method for the more strongly sorbed molecules in the more sorptive soils, it tended to give lower adsorption coefficients compared to the centrifugation method when adsorption was lower. Discrepancies between the two methods were probably mainly due to the vigorous shaking applied in the batch technique that artificially enhances the availability of adsorption sites. This implies that shortly after application, more pesticide may be present in the soil solution and thus be available for degradation, plant uptake or leaching than will be predicted from adsorption coefficient determined using the batch method. Adsorption significantly increased between one and seven days and the extractability of total residues decreased with time. The increase in adsorption was not directly related to the level of adsorption although it was more important in soils containing more organic carbon (p=0.022). These results confirm the importance of time-dependent processes and the necessity to include them in risk assessment procedures. The centrifugation technique is a useful method to measure adsorption of pesticides at realistic soil moisture contents and seems to be an adequate technique to characterise the fraction of pesticide that is available for leaching at a given time after application.     

蜂窝陶瓷载体生物膜技术处理农药废水

以蜂窝陶瓷为载体进行生物挂膜,处理经化学预处理后的某农药厂有机磷和除虫菊酯类混合废水。对处理结果、蜂窝陶瓷载体及其生物挂膜法的特点进行了深入讨论。当废水的COD为1 600～1 700 mg/L,TP(总磷)为70～80mg/L,DMAC(二甲基乙酰胺)为0.8～1.2 mg/L,甲醇为8～12 mg/L,pH为6.8～7.2,水温为27～30℃,流量为0.1 m3/h,水力停留时间为15 h,进水容积负荷约为2.5 kg COD/(m3.d)时,发现15 d就完成生物挂膜,连续运行20 d COD去除率为73%～75%,TP去除率为53%～55%,DMAC去除率为54%～57%,甲醇去除率为91%～93%。与同样条件下的普通活性污泥处理相比,COD去除率提高85%,TP去除率提高83%,DMAC去除率提高119%,甲醇去除率提高27%,排出的剩余活性污泥量减少89%。测得的活性生物膜量为1.8 kg/m2,生物膜的厚度为1.5～2 mm,用偏光显微镜摄取了载体表面生物膜的图像。     

Assessment of hazards associated with pesticide container disposal and of rinsing procedures as a means of enabling disposal of pesticide containers in sanitary landfills

To study problems associated with pesticide container disposal, a small vegetable production area in southwestern Ontario, the Thedford Marsh, was selected as the site for a model study. A container collection system was organized during the 1981 growing season, with collections being made from the ca. 50 growers on the marsh twice each month. In addition to the regular collection program a cleanup service for empty pesticide containers stored on farms or discarded on public lands also was initiated. More than 3600 containers were collected and disposed of at an authorized landfill site. Ca. 2/3 were herbicide containers, ca. 1/4 were insecticide containers, and 3% were fungicide containers. Unrinsed containers contained as much as 5 1/2% of the original contents with an average of 1%. Containers rinsed by the triple rinse method or using rinsing devices (E-Z Rinse, JET Rinse) generally contained less than 0.1% of the original content. Some formulations presented rinsing problems due to settling and caking. The results indicated that, while unacceptable quantities of pesticide residues remain in unrinsed containers, most rinsed pesticide containers will be acceptable for disposal at municipal sanitary landfill sites.     

臭氧深度氧化法处理2,4-二氯苯氧乙酸农药废水

对臭氧深度氧化法降解农药2,4-二氯苯氧乙酸(2,4-D)废水进行了研究。实验结果表明,紫外光催化臭氧化降解2,4-D成效显著,臭氧/紫外(UV)深度氧化法是最好的臭氧化处理方法。2,4-D200mg/L的水样,反应30min,2,4-D降解完全,75min时矿化率达75%以上。碱性反应氛围有利于臭氧化反应进行。自由基抑制剂(叔丁醇)的加入,显著降低臭氧化反应去除2,4-D的效果,自由基参与的反应历程对于2,4-D的降解十分重要。双氧水的引入对2,4-D降解无明显促进作用,这是因为双氧水分解消耗OH-,没有缓冲的反应体系pH降低,限制了双氧水的分解和.OH自由基链反应。总之,单独臭氧化对2,4-D降解有一定的反应效率,在有利于.OH产生的体系中,2,4-D降解效率进一步提高。     

Bound pesticide residues in soils: a review

This article is a review of the current state of knowledge regarding the formation and biological/environmental significance of bound pesticide residues in soils. We begin by defining various terms used in our discussions and identifying the types/classes of pesticides which may be added to soil and interact with it. We then consider various soil properties and aspects of land management which will influence the nature and degree of the soil-pesticide association and discuss the possible physical and chemical binding mechanisms. We then move on to consider the role of microorganisms and other forms of soil biota in bound residue formation and the bioavailability of soil-borne pesticide residues. The review ends with a consideration of the significance of bound pesticide residues.     

Abnormal glucose regulation in pyrethroid pesticide factory workers

The purpose of this study was to investigate associations between pyrethroids occupational exposures, and risk of abnormal glucose regulation. Data from total of 3080 subjects in two pesticide factories were used. This was a population-based case-controlled study in China. In total, 18.3% of subjects with impaired glucose regulation (IGR) and 6.5% of subjects with diabetes, and the prevalence of abnormal glucose regulation was 24.8%, 86 subjects had known type 2 diabetes and 114 had newly diagnosed diabetes. The prevalence of subjects with abnormal glucose regulation increased from 21.3% in the controls to 29.3% in the exposures (χ² = 33.182, P < 0.001). Multivariate logistic regression was used to control potential confounders and calculate odd ratios as the estimate of effect. An indication of increased risk for abnormal glucose regulation was noted for exposure to pyrethroids (OR = 1.482, 95%CI = 1.238-1.774). Abnormal glucose regulation is common in subjects exposed to pyrethroids. The present investigation indicates the adverse health effects of pyrethroids are underestimated.     

Organophosphate pesticide exposure and child health in China

Currently, organophosphate pesticides (OPs) are widely used for agriculture in China and around the world. A few epidemiological studies have examined the association between exposure to OPs and children’s health, but these studies reported inconsistent results. In view of the limitations of testing techniques and the intrinsic incompleteness of scientific evidence from current studies, we have considered some issues which may be interpreted and handled with caution.     

Removal technology for pesticide contaminants in potable water

Abstract

Granular activated carbon adsorption is one of the reliable and effective means of removing organochlorine pesticides from water. Continuous stirred tank and fix bed reactor systems were used for the screening of indigenous granular activated carbons in the removal of organochlorine pesticides from water at low microgram levels in simulated samples. The carbon dose reguired to treat raw water at initial concentrations of 5–10 ug/1 of Y‐HCH, p,p'‐DDT and p,p'‐DDE to <2 ug/1 potable level was computed. Data leads to the development of a tap attachable water treatment unit for pesticides removal for applications on domestic scale.     

Assessing washing methods for reduction of pesticide residues in Capia pepper with LC-MS/MS

Abstract

The effects of washing treatments on removal rates of some pesticides residues (acetamiprid, chlorpyrifos and formetanate hydrochloride) on pepper were investigated. Method verification was conducted through spiking pepper samples at 0.1, 1.0 and 10.0 × MRL. QuEChERS method produced average recovery of 104.91% with relative standard deviation (RSD) of 13.41%. LOQ values of acetamiprid, chlorpyrifos and formetanate hydrochloride were estimated as 2, 10 and 5?µg/kg, respectively. Capia peppers grown in open fields were sprayed three times with pesticides. Peppers were harvested after 1st, 2nd and 3rd day of the treatments. Then the peppers were subjected to tap water, acetic acid and citric acid washing and ultrasonic cleaning treatments (for 2 and 5?min). Based on three different harvest times and two different washing durations, processing factors (PFs) and reduction rates were calculated for each washing treatment. The residues gradually decreased during washing treatments with increasing process duration. Similarly, a gradual reduction was noted with the progress of harvest times. This in turn corresponded to an increase in PF. Ultrasonic cleaning and citric acid (9%) washing were more effective than the others. Non-systemic pesticides (chlorpyrifos) were more readily removed than the systemic ones (acetamiprid). Similarly, highly soluble pesticides exhibited higher reduction.     

In situ assays with tropical cladocerans to evaluate edge-of-field pesticide runoff toxicity

Tropical regions’ economy is usually based on agriculture, which involves an intensive use, and even frequent overuse, of pesticides. Nevertheless, not much research has been done on the impact of pesticides on tropical aquatic ecosystems, which are often contaminated by runoff-related pesticide inputs due to unpredictable and torrential rainfalls. This study aimed to: (i) adapt and evaluate a short-term sublethal in situ assay using post-exposure feeding as an endpoint, to the tropical cladoceran species Diaphanosoma brachyurum (collected at the Pedra do Cavalo dam in the Paraguaçu River basin, Bahia, Brazil), and, (ii) assess the role of the standard species Daphnia magna as an adequate laboratory surrogate. Lethal and sublethal (post-exposure feeding) responses were assessed for the two species. To evaluate these responses under environmentally realistic exposure conditions, a runoff event was simulated in an agricultural area previously contaminated with different deltamethrin concentrations. The resultant runoff water was used to set up microcosms with different dilutions, simulating the entrance of runoff water in an adjacent lentic system. An in situ assay with D. brachyurum was performed inside the microcosms, allowing to discriminate the effects due to deltamethrin from those due to other potential stressors associated with the experimental design (e.g. organism handling, load of suspended particles, microcosm design). Water samples were collected from microcosms to conduct a laboratory assay with D. magna. The in situ methodologies revealed to be suitable to conduct assays with D. brachyurum under tropical conditions, since all exposed organisms were successfully retrieved from the chambers. Furthermore, none of the potential stressors associated with the experimental design influenced the daphnids’ performance. The tropical cladoceran species, exposed under more realistic conditions, revealed to be more sensitive than the laboratory standard species: lethal effects were only observed for D. brachyurum and sublethal effects were noticed at a lower deltamethrin concentration for this species than for D. magna.     

华北某农药厂周边的滴滴涕污染状况初步研究

对华北某从事滴滴涕加工的农药厂周边的土壤和植物样品进行了取样分析,利用气相色谱/电子捕获检测器(GC/ECD)法测定了样品中的滴滴涕含量.结果表明,在生产区域下风向900 m内采集的土壤样品中的滴滴涕超过《土壤环境质量标准》规定的三级标准(1.0 mg/kg);植物样品中的滴滴涕均大于0.2 mg/kg,超出《粮食、蔬菜等食品中六六六、滴滴涕残留量标准》的相关限值.     

Fate of the organophosphorus pesticide profenofos in cotton fiber

Pesticides carried by cotton fiber are potential risk for production workers and consumers. Dissipation behaviour of a commonly used cotton pesticide profenofos in cotton fiber during growing period and scouring treatment was investigated. The results showed that profenofos in the fiber from the pre-opened and post-opened bolls both decreased to undetectable amounts 21?days after pesticide application. However, a minority of profenofos was converted to a strongly irritant compound, 4-bromo-2-chlorophenol and retained a non-negligible amount in cotton fiber even after 28?days. Profenofos and its degradation product could be completely removed during the conventional cotton scouring process. The degradation half-time of profenofos in scouring bath was only 3.0?min, and the degradation product was also 4-bromo-2-chlorophenol. Cotton products made of profenofos-carrying fiber are safe; however, the scouring waste should be detoxicated before discharge due to the accumulation of 4-bromo-2-chlorophenol in the scouring bath. These results could be useful for evaluating the risk of cotton fiber from the profenofos applied fields.     

Assessment and review of organochlorine pesticide pollution in Kyrgyzstan

The current study describes the preliminary assessment and securing activities of the largest and most hazardous POPs-contaminated sites in Kyrgyzstan. In 2010, cattle died and population were found with high pesticide levels in blood, human milk, and placenta. In the first phase of the study, a historic assessment of the pesticide dumping at the landfill/dump sites have been conducted. In the second phase, soil analysis for organochlorine pesticides in the areas of the pesticide disposal sites, the former pesticides storehouses, agro-air strips, and the cotton-growing fields were conducted. By this assessment, a first overview of the types and sources of pollution and of the scale of the problem is compiled including information gaps. From major pesticides used, DDT, DDE, and HCH were measured in the highest concentrations. With the limited analytical capacity present, a reasonable risk assessment could be performed. This paper also reports on practical risk reduction measures that have been carried out recently at the two major pesticide disposal sites with support of a Dutch environmental engineering company, an international NGO (Green Cross Switzerland) and local authorities from the Suzak region within an UN project. Local population living near the sites of the former pesticide storehouses and agro-airstrips are advised not to cultivate vegetables and melons or to raise cattle on these areas. Instead, it is recommended to grow technical crops or plant trees. Further recommendations on monitoring and assessment is given including the suggestion to consider the findings in the National Implementation Plan of Kyrgyzstan.     

Green pre-concentration techniques during pesticide analysis in food samples

The ever-increasing demand for determining pesticides at low concentration levels in different food matrices requires a preliminary step of pre-concentration which is considered a crucial stage. Recently, the parameter of “greenness” during sample pre-concentration of pesticides in food matrices is as important as selectivity in order to avoid using harmful organic solvents during sample preparation. Developing new green pre-concentration techniques is one of the key subjects. Thus, to reduce the impact on the environment during trace analysis of pesticides in food matrices, new developments in pre-concentration have gone in three separate directions: the search for more environmentally friendly solvents, miniaturization and development of solvent-free pre-concentration techniques. Eco-friendly solvents such as supercritical fluids, ionic liquids and natural deep eutectic solvents have been developed for use as extraction solvents during pre-concentration of pesticides in food matrices. Also, miniaturized pre-concentration techniques such as QuEChERS, dispersive liquid–liquid micro-extraction and hollow-fiber liquid-phase micro-extraction have been used during trace analysis of pesticides in food samples as well as solvent-free techniques such as solid-phase micro-extraction and stir bar sorptive extraction. All these developments which are aimed at ensuring that pesticide pre-concentration in different food matrices is green are critically reviewed in this paper.     

Monitoring of pesticide residues in a cotton crop soil

Abstract

This paper reports on the residues of methyl parathion (O,O‐dimethyl O‐4‐nitrophenyl phosphorothioate), trifluralin (α, α, α‐trifluoro‐2, 6‐dinitro‐N, N‐dipropyl‐p‐toluidine), endosulfan [(1, 4, 5, 6, 7, 7‐hexachloro‐8, 9, 10‐trinorborn‐5‐en‐2, 3‐ylenebismethylene) sulfite] and dimethoate (O, O‐dimethyl S‐methylcarbamoylmethyl phosphorodithioate) in a cotton crop soil. Soil samples (0–15 cm) were collected at different periods from the cotton crop farm and subjected to Soxhlet extraction. The extracted material was analysed after clean‐up by a HP5890 II gas Chromatograph equipped with a ⁶³Ni electron‐capture detector (ECD‐⁶³Ni) and fitted with a 25m x 0,2mm i.d. fused silica capillary column [Ultra‐2 (5% phenylmethyl polysiloxane)]. The recoveries of the pesticide residues from the spiked control soil were determined after Soxhlet extraction and C₁₈ cartridges clean‐up by using radiotracer techniques with the corresponding ¹⁴C‐pesticides. The results show that in the cotton crop soil the pesticide residues under study were present in the range of 0.1 to 0.4 mg ? kg^‐1. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite.