Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R²) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.     

不同政策对农户农药施用行为的影响

农户不规范的施药行为是引发农产品质量安全风险最直接的原因,为规范农户的施药行为,政府颁布并实施了多种政策,但大多收效甚微。农户不规范的施药行为主要表现在过量使用高毒农药、施用过程中不按规定操作以及农药残留物的处理问题上,如何针对农户不同的施药行为制定相应的政策,以达到有效规范农户施药行为的效果,这是本文研究的主要目的。文章基于全国986个农户的调查数据,运用有序logistic模型,分别回归了不同政策对农户过量施用农药的行为、不遵守施药间隔期的行为以及在施药过程中不阅读标签说明的行为的影响程度,结果表明:强令禁止高毒农药、对违反农产品安全生产进行处罚以及对收购的农产品进行检测等命令控制政策对农户是否过量施用农药的行为具有较强的规范效应,但对农户在施药过程中是否阅读标签说明的规范效果不佳;农药施用技术培训、农产品安全生产宣传教育等宣传培训的政策能有效规范农户在施药前阅读标签说明,但对农户是否过量施用农药的影响不大;以市场为基础的激励政策对农户过量施用农药、阅读标签说明以及遵守间隔期均有显著的规范效果。由此提出,政府在实施命令控制政策的同时,应加强农产品安全知识的宣传力度,定期为农户提供农药施用技术培训;由于以市场为基础的激励政策能有效弥补命令控制政策的监管漏洞,从而更有效的规范农户的施药行为,因此要建立激励惩罚机制,对使用生物农药、施用有机肥等具有正外部性的投入行为进行补贴,对使用高污染、高毒农药的行为进行征税,充分发挥市场为基础的监管政策的有效性。     

Processes affecting the movement of organochlorine pesticides (OCPs) between soil and air in an industrial site in Turkey

Soil and atmospheric concentrations, dry deposition and soil-air gas exchange of organochlorine pesticides (OCPs) were investigated at an industrial site in Aliaga, Izmir, Turkey. Current-use pesticides, endosulfan and chlorpyrifos, had the highest atmospheric levels in summer and winter. Summertime total (gas + particle) OCP concentrations in air were higher, probably due to increased volatilization at higher temperatures and seasonal local/regional applications of current-use pesticides. Particle deposition fluxes were generally higher in summer than in winter. Overall average dry particle deposition velocity for all the OCPs was 4.9 ± 4.1 cm s⁻¹ (average ± SD). ΣDDXs (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) were the most abundant OCPs in Aliaga soils (n = 48), probably due to their heavy historical use and persistence. Calculated fugacity ratios and average net gas fluxes across the soil-air interface indicated volatilization for α-CHL, γ-CHL, heptachlorepoxide, cis-nonachlor, trans-nonachlor, and p,p′-DDT in summer, and for α-CHL, γ-CHL, trans-nonachlor, endosulfan sulfate, and p,p′-DDT in winter. For the remaining OCPs, soil acted as a sink during both seasons. Comparison of the determined fluxes showed that dry particle, gas-phase, and wet deposition are significant OCP input mechanisms to the soil in the study area.     

Endosulfan in China 1—gridded usage inventories

Background, aim, and scope  Endosulfan, an organochlorine pesticide (OCP), is genotoxic in mammalian cells and generally considered to be toxic and classified by the World Health Organization and the US Environmental Protection Agency as priority pollutants and a nominator for inclusion in a future iteration of the persistent organic pollutants treaty. Endosulfan is a currently used pesticide and still being used worldwide. The general trend of total global endosulfan use has increased continuously since the first year when this pesticide was applied. It is critical to create national endosulfan usage/emission inventories for China to carry out source–receptor relation analysis, risk assessment, and other research related to endosulfan in this country. Chinese inventories have been published for some OCPs, such as technical HCH and lindane, DDT, and chlordane; for endosulfan, however, there has not been any usage inventory available on any scales (national or provincial), although endosulfan has been widely used since 1994 in this country. This is the first part of the work. The goal of this paper is to quantify the historical production and usage of endosulfan in China and to compile gridded historical usage inventories of endosulfan for this country. Based on these usage inventories, emission and residue inventories will be created, which is the goal of the second part of the work. Materials and methods  Due to the lack of national production and usage information of endosulfan in China, a method to estimate the use of endosulfan was developed. First, information of crops on which endosulfan is applied and average endosulfan use and annual application frequencies of endosulfan on these crops were collected. Secondly, usage of endosulfan on each crop was estimated using the national cropland area for each province from Chinese government reports. Finally, with the help of GIS (geographic information system), the usage data of this insecticide was allocated to a grid system, with a 1/4° longitude by 1/6° latitude resolution, with a size for each grid cell of approximately 25 km by 25 km. Results and discussion  The use of endosulfan in agriculture in China started on cotton in 1994, and on wheat, tea, tobacco, apples, and other fruits in 1998. Endosulfan usage on cotton, wheat, tea, tobacco, and apples in China has been estimated to be approximately 25,700 t between 1994 and 2004. The province with the highest usage of endosulfan is Henan Province, with a total usage reaching 4,000 t, followed by the uses in Xinjiang Autonomous Region (3,200 t), Shandong Province (3,000 t), Hebei Province (2,100 t), and Anhui Province (1,900 t). Gridded usage inventories of endosulfan at a 1/4° longitude by 1/6° latitude resolution have been created, which indicate that the intensive endosulfan use was in the south of Hebei Province, west of Shandong Province, east of Henan Province, north of Anhui Province, east of Jiangsu Province, and some areas in Yunnan Province and Xinjiang Autonomous Region. General agreement has been found between the usage data from our estimation and the small amount of usage data published in China. Conclusions  This is the first national gridded endosulfan usage inventory produced for China. The annual applications of endosulfan from 1994 to 2004 in China were estimated based on the total areas of major crops, on which endosulfan was applied, and spatial distribution of the application was generated at provincial and prefecture levels. With the help of GIS, endosulfan usage based on prefecture was transferred to a 1/4° longitude by 1/6° latitude gridding system. The satisfaction of the inventories was supported by the consistence between the estimation of the annual usage and the reported annual production of endosulfan. Recommendations and perspectives  This gridded endosulfan usage inventory created in this study will be improved upon availability of new information of endosulfan. The usage inventories can be used to create gridded emission and residue inventories for this insecticide. It is believed that this work will pave the way for further endosulfan studies in China and beyond.     

铬渣的热解无害化处理

采用热解工艺无害化处理铬渣,探讨了稻秆在铬渣无害化处理中的作用.研究了热解温度、稻秆与铬渣质量比、铬渣粒径及保温时间对铬渣热解无害化处理的影响,并分析了热解前后热解产物中铬元素形态的变化.结果表明,热解工艺能有效地将铬渣中Cr(Ⅵ)还原,稻秆热解过程中产生的气相挥发分对Cr(Ⅵ)的还原起核心作用.较为适宜的热解条件:热解温度为400 ℃,稻秆与铬渣质量比为0.10,铬渣粒径<2 000 μm,保温时间为10 min.在该热解条件处理下,热解产物中的Cr(Ⅵ)质量浓度为121 mg/kg,低于热解前铬渣中的Cr(Ⅵ)(3 400 mg/kg).热解后,可交换态及碳酸盐结合态铬含量降低,大部分铬转化成了稳定的有机结合态和残渣态,极大地降低了铬渣的危害.第一作者:张大磊,男,1982生,博士研究生,研究方向为固体废弃物热处理.     

污水污泥裂解及其性能的研究

以碘吸附值为裂解残渣吸附性能的指标,通过单因素实验和正交实验,确定了制备裂解残渣的最佳工艺条件,并对残渣的表面元素组成、孔结构组成、晶相组成和吸附性能等性质进行了表征。结果显示：以浓度均为5 mol/L的ZnCl₂和H₂SO₄作活化剂、复配比2∶1、活化温度600℃、活化时间1 h、固液比1∶2.5,制得的裂解残渣酸洗后碘值平均值可达892.8 mg/g;用制备的裂解残渣对苯酚废水进行处理,室温下振荡5 min,苯酚去除率即可达到87.9%,且符合Langmuir吸附等温线方程和Freundlich吸附等温线方程。     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Environmental Exposure of Aquatic and Terrestrial Biota to Triclosan and Triclocarban1

Abstract: The synthetic biocides triclosan (5‐chloro‐2‐(2,4‐dichlorophenoxy)phenol) and triclocarban (3,4,4′‐trichlorocarbanilide) are routinely added to a wide array of antimicrobial personal care products and consumer articles. Both compounds can persist in the environment and exhibit toxicity toward a number of biological receptors. Recent reports of toxicological effects in wildlife, human cell cultures, and laboratory animals have heightened the interest in the occurrence of these biocide and related toxic effects. The present study aimed to summarize published environmental concentrations of biocides and contrast them with toxicity threshold values of susceptible organisms. Environmental occurrences and toxicity threshold values span more than six orders of magnitude in concentration. The highest biocide levels, measured in the mid parts‐per‐million range, were determined to occur in aquatic sediments and in municipal biosolids destined for land application. Crustacea and algae were identified as the most sensitive species, susceptible to adverse effects from biocide exposures in the parts‐per‐trillion range. An overlap of environmental concentrations and toxicity threshold values was noted for these more sensitive organisms, suggesting potential adverse ecological effects in aquatic environments. Affirmative evidence for this is lacking, however, since studies examining environmental occurrences of biocides vis‐à‐vis the health and diversity of aquatic species have not yet been conducted.     

河流沉积物中有机污染物的分析研究进展

总结了近年来河流沉积物中有机污染物的研究进展 ,集中评述了国内有关沉积物中多环芳烃、有机氯农药和多氯联苯的分析研究现状 ,包括样品采集、样品前处理和样品分析 ,并对今后河流、湖泊及水库沉积物中污染物的分析工作作了展望     

惠州农业土壤、灌溉水和农产品中有机氯农药的残留

用气相色谱法(GC-ECD)对惠州市51个农业土壤样品、12个灌溉水样品和21个农产品样品中的HCHs和DDTs残留量进行了测定.HCHs平均含量分别为土壤1.66μg/kg、灌溉水5.86ng/L、农产品24.74μg/kg;DDTs平均含量分别为土壤4.98μg/kg、灌溉水2.06ng/L、农产品41.72μg/kg,土壤中有机氯农药通过多种方式进入到水体及农产品中.从HCHs和DDTs异构体组成可以看出,环境中绝大多数农药残留是由于历史上使用造成的,个别地区可能还有新的污染输入.同其它地区相比,惠州农业土壤和灌溉水中的有机氯农药残留水平较低,但农产品尤其是蔬菜中DDTs富集程度较高.