Adsorption of lambda-cyhalothrin and cypermethrin on two typical Chinese soils as affected by copper

Background, aim, and scope  Pesticides and heavy metals pollution in soil environment has become a serious problem in many countries including China. Repeated applications of bordeaux mixture (a blend of copper sulfate and calcium hydroxide) and pyrethroid (Pys) insecticides have led to elevated copper (Cu) and Pys concentrations in vineyard surface soils. However, few studies focused on the interaction of Pys and heavy metals in the soil environment. Our previous studies had indicated the combined effect of cypermethrin (CPM) and Cu on soil catalase activity. Also, we had suggested that the addition of Cu could catalyze photo-degradation of CPM and lambda-cyhalothrin (λ-CHT) in aqueous solution and restrain their degradation in soil. To better understand the potential influence of Cu on the fate of Pys in the soil environment, the aim of the present work was to examine the effect of Cu on the adsorption of λ-CHT and CPM on two typical Chinese soils with different soil characteristics, which was one of the key processes controlling the fate of Pys, and to provide more information about the potential ecological risk of chemicals on the soil ecosystem. Fourier transform infrared and point charges analysis using the MOPAC program of the Gaussian system were also used to reveal the probable adsorption mechanism of λ-CHT and CPM on soils. Materials and methods  Two vineyard soils with different properties were chosen as experimental samples. They were sampled from 0 to 10 cm, dried, and sieved to 2 mm. Each soil was spiked with copper sulfate solution to obtain the following total soil Cu concentrations: 100, 200, 400, 800, and 1,600 mg·kg⁻¹. The treated soils were incubated for 2 weeks and then dried at 20°C. For each soil sample and at each soil Cu concentration, the adsorption of λ-CHT and CPM was measured using a batch equilibrium method. The concentration of λ-CHT was determined by HPLC, and the amount of λ-CHT and CPM adsorbed by the soil sample at equilibrium was determined by the difference between the initial and equilibrium concentrations in solution corrected by the blank adsorption measurement. Results  Without the addition of Cu, the adsorption of λ-CHT and CPM on Black soil is greater than that on Red soil, while the adsorption of λ-CHT on both soils is significantly stronger than that of CPM. As the soil Cu concentration increased from 19 (or 18; background) to 1,600 mg·kg⁻¹, the adsorption coefficient (K _d) of λ-CHT decreased from 12.2 to 5.9 L·kg⁻¹ for Red soil, and from 26.1 to 16.8 L·kg⁻¹ for Black soil, whereas the CPM adsorption coefficient in both soils decreased nearly by 100% (K _d decreased from 9.4 to 0.2 L·kg⁻¹ for Red soil and from 16.2 to 0.5 L·kg⁻¹ for Black soil). Discussion  Pys adsorption is a surface phenomenon which depends on the surface area and the organic matter content. Thus, the Black soil, having higher organic matter and greater surface area than that of the Red soil, show greater adsorption affinity to λ-CHT and CPM. In our study, the different adsorption affinity of the two Pys was obtained, which was probably attributed to differences with respect to their physical–chemical properties. Further comparison upon the two Pys was conducted. The point charges of halogen atoms in the λ-CHT and CPM were calculated, the differences of which probably lead to the fact that λ-CHT has a stronger binding capacity to soils than CPM. Also, FTIR spectra show that competitive adsorption occurs between CPM and Cu for the same adsorption sites, which is responsible for the obtained suppression of CPM adsorption affected by Cu. Conclusions  Lambda-cyhalothrin shows a significantly stronger adsorption than cypermethrin on both soils. This phenomenon may be due to several reasons: (1) λ-CHT has lower solubility and a higher octanol–water partition coefficient value than CPM; (2) λ-CHT consists of specific isomers, whereas CPM is mixtures of eight different isomers; (3) the chlorine and fluorine atoms in the λ-CHT have a negative point charge, whereas the chlorine atoms in the CPM have a positive point charge. As the soil Cu concentrations increased from 19 (or 18) mg·kg⁻¹ to 1,600 mg·kg⁻¹, the adsorption coefficient of λ-CHT and CPM decreased on both soils. This is mainly due to a competition between Cu and Pys for occupying the adsorption sites on soils. The information from this study have important implications for vineyard and orchard soils, which often contain elevated levels of Cu and Pys. These results are also useful in assessing the environmental fate and health effect of λ-CHT and CPM. Recommendations and perspectives  It is important for environmental scientists and engineers to get a better understanding of soil–metal–organic contaminant interactions. However, pesticide adsorption involves complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behavior of pesticide. Therefore, considerable research should be carried out to understand the mechanism of interaction between Pys and heavy metal on soils clearly.     

Developments in application technology

Pesticides are applied in diverse situations, but in each, careful consideration has to be given to applying the optimum dosage accurately with minimal exposure of the active substance to the operator. Emphasis is given to ways in which application equipment, suitable for both small-scale and large farms has been adapted to meet health and safety requirements. New developments in nozzle design provide users with greater flexibility in optimising pesticide delivery, while minimising spray volumes. Changes in equipment design that influence dose transfer are discussed.     

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) for monitoring chlorinated trace organic contaminants in Hong Kong coastal waters

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) was carried out at five sites, representing a gradient of contaminant concentrations, in Hong Kong coastal waters. Mussels, originally collected from a “clean” location, were deployed along with SPMDs at each site for 30 days. Analyses for chlorinated pesticides and polychlorinated biphenyls (PCBs) indicated that SPMDs have potential as monitoring tools, and to some extent can overcome the problems associated with mussels, such as natural variability, differing age, sex, and physical condition. However, in most cases, SPMDs failed to rank the sites in the same order as mussels in terms of contaminant concentrations. Nonetheless, in localities where mussels cannot survive – as shown at Kwun Tong in the present experiment – SPMDs may be valuable in providing an indication of potentially bio-available lipophilic pollutants.     

钦州湾沉积物有机氯农药赋存特征与生态风险

利用GC-ECD测定了钦州湾沉积物中17种有机氯农药的含量,并对其组分分布和来源进行了分析。结果表明,样品中有机氯农药的总量为1.50～129ng/g,滴滴涕(DDTs)浓度为0.59～126ng/g,六六六(HCHs)的浓度为nd～2.65ng/g。有机氯农药的分布特征为茅尾海>钦州外湾,茅尾海东岸>西岸。组分分布特征分析显示,DDTs主要来自于历史积累,林丹在某些采样区域内有近期输入。与国内外不同地区沉积物中有机氯农药残留相比,钦州湾沉积物中有机氯农药污染处于低到中等水平。以沉积物生态风险评估值为基准的分析表明,研究区内DDT含量存在较大的生态风险。     

Molten hydroxide for detoxification of chlorine-containing waste: Unraveling chlorine retention efficiency and chlorine salt enrichment

Hazardous waste dechlorination reduces the potential of creating dioxins during the incineration process. To investigate the salt effect on waste dechlorination, molten hydroxides with a low melting temperature were utilized for the pre-dechlorination and decomposition of chlorine-containing organic wastes(COWs) including trichlorobenzene(TCB),perchloroethylene, hexachlorobenzene and chlordane. The results showed that a eutectic mixture of caustic sodium and potassium hydroxides(41 wt.% NaOH and 59 wt.% KOH) led to a low melting point below 300°C and a relatively high chlorine retention efficiency(CRE) with TCB as a representative COWs. The amounts of hydroxides, reaction time, and temperature all had notable influence on CRE. When the mass ratio of hydroxides to TCB reached 30:1,approximately 98.1% of the TCB was destroyed within 2.5 hr at 300°C with CRE of 71.6%.According to the residue analysis, the shapes of reaction residues were irregular with particles becoming swollen and porous. The benzene ring and C–Cl bonds disappeared, while carboxyl groups formed in the residues. The stripped chlorine was retained and condensed to form chloride salts, and the relative abundance of the chloride ions associated with the mass of TCB in residues increased from 0 to 75.0% within the 2.5 hr reaction time. The observed concentration of dioxins in residues was 5.6 ngTEQ/kg. A reaction pathway and possible additional reactions that occur in this dechlorination system were proposed. Oxidizing agents may attack TCB and facilitate hydrogenation/dechlorination reactions, making this process a promising and environmentally friendly approach for chlorine-containing organic waste treatment.     

Sorption of hydrophobic pesticides on a Mediterranean soil affected by wastewater, dissolved organic matter and salts

Irrigation with treated wastewaters as an alternative in countries with severe water shortage may influence the sorption of pesticides and their environmental effects, as wastewater contains higher concentrations of suspended and dissolved organic matter and inorganic compounds than freshwater. We have examined the sorption behaviour of three highly hydrophobic pesticides (the herbicide pendimethalin and the insecticides α-cypermethrin and deltamethrin) on a Mediterranean agricultural soil using the batch equilibration method. We considered wastewater, extracts from urban sewage sludge with different dissolved organic carbon contents, and inorganic salt solutions, using Milli Q water as a control. All pesticides were strongly retained by soil although some sorption occurred on the walls of the laboratory containers, especially when wastewater and inorganic salt solutions were used. The calculation of distribution constants by measuring pesticide concentrations in soil and solution indicated that pendimethalin sorption was not affected whereas α-cypermethrin and deltamethrin retention were significantly enhanced (ca. 5 and 2 times, respectively) when wastewater or salt solutions were employed. We therefore conclude that the increased sorption of the two pesticides caused by wastewater cannot be only the result of its dissolved organic carbon content, but also of the simultaneous presence of inorganic salts in the solution.     

浅谈农药生态毒性试验的设计思路及评价方法

从试验周期、剂量和控制水平三方面探讨了农药生态毒性试验的设计思路以及试验结果与安全性评价的衔接．按照试验持续的时间，农药生态毒性试验可分为急性和慢性二种类型．由于实际当中农药的急性和慢性毒害往往同时存在，相应地，急性和慢性毒性试验亦需要同时进行．农药生态毒性试验在选择剂量时可以考虑，也可以不考虑田间污染水平．两种设计的评价方法也不相同．室内试验、半田间试验和田间试验构成农药生态毒性试验的三个阶段．     

漓江沉积柱芯有机氯农药垂向分布特征与来源

用GC/ECD内标法定量法首次测定了广西桂林漓江沉积柱中19种有机氯农药(OCPs)的含量,结果表明:漓江沉积柱芯中OCPs浓度范围为4.75～489.4ng/g(均值43.26ng/g),在国内处于中等污染水平。OCPs、HCHs表现出下游污染程度高于上游,但DDTs则相反,这是由于上游的取样点蚂蟥洲附近有大量餐饮业造成的。沉积柱垂直分布表明,漓江近期受到人为污染影响。总体上漓江沉积物中HCHs污染大于DDTs,符合当地的农药使用历史。同分异构体比值表明研究区DDT主要是历史使用农药残留并得到了较好的降解,且以厌氧生物降解为主,当地在使用三氯杀螨醇可能性不大;沉积物中工业六六六尚未降解完全,同时周围可能有林丹输入。     

Review: Windows of exposure to pesticides for increased risk of childhood leukemia

Leukemia is the leading cause of cancer resulting in mortality of children, and there is some evidence suggesting the increased incidence rate increasing during the recent decades. Limited human evidence indicates an increased risk of developing leukemia in childhood as a result of pesticide exposure, with possible significance of exposure occurring during the developmental periods including preconception, pregnancy, and childhood. This review examines the results of relevant literature on the timing of pesticide exposure and leukemia diagnosed in childhood. Results suggest that the risk from pesticide exposure seems to be greater during pregnancy. Other findings indicate that maternal occupational exposure may be more of a greater concern than the paternal occupational exposure; and that the residential indoor use of pesticides tends to result in higher risk estimates than the residential outdoor use. Only limited data are available on particular pesticides, genetic factors, critical windows of exposure during development, and their association with different histological types of leukemia.     

长江口—杭州湾有机污染历史初步研究──BHC与DDT的地层学记录

近年来长江口──杭州湾表层沉积物中BHC与DDT的含量与以前表层沉积物有关资料的对比,以及经较高精度定年柱状样中BHC与DDT的会向分布特征均显示,有机氯农药广泛使用作为一个污染事件,自开始到逐渐消退均在沉积记录中得到了较好的反映,研究结果表明,污染物的分子地层学记录对恢复有机污染史具有重要意义.尽管近年来表层沉积物中有机氯农药含量己经降至很低,但是由于细颗粒沉积物再悬浮以及海洋浮游生物对有机氯农药的高度富集,其对海洋环境的影响仍然不可忽视.