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。     

骆马湖地区水体、沉积物中农药筛查和分布特征

采用气相色谱/质谱（GC/MS）非靶向筛查技术,分别于2019年11月5—7日（枯水期）、2020年4月24—26日（平水期）和2020年7月15—16日（丰水期）对骆马湖地区水体和沉积物中的农药残留进行了筛查并对其空间分布特征进行研究。结果表明,水中筛查出主要农药13种,除草剂占比62%,检出率＞95%的农药有丁草胺、环嗪酮、异丙甲草胺、多效唑、噻氟菌胺、稻瘟灵、毒死蜱、阿特拉津、避蚊胺和莠灭净,阿特拉津检出质量浓度最高（ND～10 599 ng/L,平均值为725.5 ng/L）,其次为多效唑（ND～2 089 ng/L,平均值为237.0 ng/L）和噻氟菌胺（ND～1 991 ng/L,平均值为237.2 ng/L）。与国内其他地区相比,骆马湖地区水中农药污染处于中等水平,其中阿特拉津、稻瘟灵和毒死蜱的生态风险值得重点关注。骆马湖及入湖河流水中农药总质量浓度呈现丰水期＞平水期＞枯水期的特点,与地表径流、农药的性质及其在水体中的释放等因素有关,丰水期入湖口和省界来水中农药对饮用水水源地的影响较大。沉积物中筛查出9种农药,总体含量不高,且仅扑灭净和避蚊胺检出率>95%,其余<20%。     

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.     

Quantification of pesticide residues on plastic mulching films in typical farmlands of the North China

• Pesticide residuals on mulching film of Shandong, Tianjin and Hebei. • Detected 29 pesticides in soil and 30 in mulching film. • Pesticides on plastic films: 86.4‒22213.2 ng/g and in soil: 9.3‒535.3 ng/g. • Pesticides on plastic films 20 times higher than in soil. Plastic debris as new pollutants attracts much attention in the recent years. The plastic mulching films is one of the most important plastic debirs source in the environment. The aim of this work was to investigate the current status of pesticide residues on the plastic mulching films. Based on the QuEChERS method, multi-residue methods for detection of pesticide residues with gas chromatography tandem mass spectrum (GC-MS) and high performance liquid chromatography tandem mass spectrum (HPLC-MS) were developed for the analysis of the pesticides residues in plastic film and soil samples from Tianjin, Hebei and Shandong. The total concentrations of pesticide residues were in the range of 86.4‒22213.2 ng/g in plastic film debris, which was about 20 times higher than that in soil (9.3‒535.3 ng/g). Residual level of pesticides varied greatly in different samples. The historical usage and recent application of pesticides were the main sources for pesticide residues on plastic films and soil. In short, plastic mulching films could act as a sink for pesticides in farmland and the ubiquitous pesticide residues on plastic films should draw more attention.     

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.     

不同年龄夜鹭卵中有机氯农药污染的生物指示

通过对太湖鼋头渚 2 0 0 0年采集的二龄、三龄和四龄夜鹭卵以及相应年龄组夜鹭的捕食物中有机氯残留的检测 ,发现捕食物中HCH和DDT的平均残留量随年龄增加而增加 .除γ HCH外 ,其它 15种有机氯农药在卵样中均有检出 ,残留水平最高的为p ,p′ DDE ,占有机氯农药残留总量的 85 %以上 .β HCH是六六六类中持留性最强的组分 ,其残留量仅次于p ,p′ DDE .研究发现 ,p ,p DDT和 β HCH检出率为 10 0 % ,而其它类型农药只有很低的检出率 ,这与我国有机氯农药使用的历史情况相吻合 .随着亲鸟年龄增加 ,卵中 β HCH残留量有所提高 ,p ,p′ DDE残留量似有先升后稍降的趋势 .统计结果表明 :各年龄组有机氯残留量差异不明显 ,因此在用夜鹭卵作有机氯污染的生物指示时可以不考虑年龄差异所带来的影响 .     

Mitigation of two pyrethroid insecticides in a Mississippi Delta constructed wetland

Constructed wetlands are a suggested best management practice to help mitigate agricultural runoff before entering receiving aquatic ecosystems. A constructed wetland system (180 m × 30 m), comprising a sediment retention basin and two treatment cells, was used to determine the fate and transport of simulated runoff containing the pyrethroid insecticides lambda-cyhalothrin and cyfluthrin, as well as suspended sediment. Wetland water, sediment, and plant samples were collected spatially and temporally over 55 d. Results showed 49 and 76% of the study's measured lambda-cyhalothrin and cyfluthrin masses were associated with vegetation, respectively. Based on conservative effects concentrations for invertebrates and regression analyses of maximum observed wetland aqueous concentrations, a wetland length of 215 m × 30 m width would be required to adequately mitigate 1% pesticide runoff from a 14 ha contributing area. Results of this experiment can be used to model future design specifications for constructed wetland mitigation of pyrethroid insecticides.     

Organchlorine content and shell thickness in brown booby (Sula leucogaster) eggs in the Gulf of California and the southern Pacific coast of Mexico

We determined egg concentrations of organochlorines and thickness of eggshells from brown boobies at eight colonies ranging from the northern Gulf of California to southern Mexico. The only common residue was that of DDE, which was found in almost all eggs. DDE content apparently reflected pre-1990 DDT use in nearby agricultural areas and, at one site, intensive mosquito control for high-end tourism development. There were no inter-colony differences in eggshell thickness, and variation in this variable likely reflected individual bird characteristics and/or individual feeding source. This variable was not a good proxy to DDE exposure of brown boobies, under current DDE levels in the brown booby trophic chain. In the northern Gulf of California, eggshell thickness has recovered to pre-DDT conditions. Our data indicate that the Gulf of California and southwestern coast of Mexico have a healthy near-shore marine environment, as far as organochlorines are concerned.     

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.     

Evidence for the Stepwise Behavioral Response Model (SBRM): the effects of Carbamate Pesticides on medaka (Oryzias latipes) in an online monitoring system

The Stepwise Behavioral Response Model (SBRM), which is a conceptual model, postulated that an organism displays a time-dependent sequence of compensatory Stepwise Behavioral Response (SBR) during exposure to pollutants above their respective thresholds of resistance. In order to prove the model, in this study, the behavioral responses (BRs) of medaka (Oryzias latipes) in the exposure of Arprocarb (A), Carbofuran (C) and Methomyl (M) were analyzed in an online monitoring system (OMS). The Self-Organizing Map (SOM) was utilized for patterning the obtained behavioral data in 0.1 TU (Toxic Unit), 1 TU, 2 TU, 5 TU, 10 TU and 20 TU treatments with control. Some differences among different Carbamate Pesticides (CPs) were observed in different concentrations and the profiles of behavior strength (BS) on SOM were variable depending upon levels of concentration. The time of the first significant decrease of BS (SD-BS) was in inverse ratio to the CP concentrations. Movement behavior showed by medaka mainly included No effect, Stimulation, Acclimation, Adjustment (Readjustment) and Toxic effect, which proved SBRM as a time-dependence model based on the time series BS data. Meanwhile, it was found that SBRM showed evident stress-dependence. Therefore, it was concluded that medaka SBR was both stress-dependent and time-dependent, which supported and developed SBRM, and data mining by SOM could be efficiently used to illustrate the behavioral processes and to monitor toxic chemicals in the environment.