Implementing Atmospheric Fate in Regulatory Risk Assessment of Pesticides: (How) Can It Be Done?

Atmospheric fate of pesticides and their possible effects in ecosystems beyond the immediate surrounding of the application site are not actively considered in currently used regulatory risk assessment schemes. Concern with respect to atmospheric transport and subsequent deposition of pesticides in non-target areas is however growing. In this article the results of discussions on the possibilities of implementing atmospheric fate in regulatory risk assessment are presented. It is concluded that implementing atmospheric fate in regulatory risk assessment schemes is possible and that, from a scientific point of view, these schemes should distinguish between pesticides on the basis of both their possibility/probability to reach non-target areas and on their toxicity. This implies that application of the precautionary principle or use of intrinsic pesticide properties alone is not considered justifiable. It is recommended that the risk assessment scheme should follow a tiered approach. The first tier should be entered only if the existing regulatory risk assessment procedure, including a local PEC:PNEC calculation, has been passed and involves a test for the pesticide's total atmospheric emission potential, i.e. its potential for becoming airborne during and after application. The second tier, which is only entered if the total emission potential is higher than a certain trigger value, should consist of a PEC:PNEC calculation for regional off-site areas (10-50 km) (tier 2A). If the pesticide's atmospheric transport potential is expected to exceed a certain value, the PEC:PNEC ratio should also be calculated for more remote areas (>1000 km) (tier 2B).     

Environmental Risk Assessment for Pesticides in the Atmosphere; The Results of an International Workshop

The Health Council of the Netherlands organised an international workshop on the fate of pesticides in the atmosphere and possible approaches for their regulatory environmental risk assessment. Approximately forty experts discussed what is currently known about the atmospheric fate of pesticides and major gaps in our understanding were identified. They favoured a tiered approach for assessing the environmental risks of atmospheric dispersion of these chemicals. In the first tier a pesticide's potential for emission during application, as well as its volatilisation potential should be assessed. Estimates of the former should be based on the application method and the formulation, estimates of the latter on a compound's solubility in water, saturated vapour pressure and octanol/water partition coefficient. Where a pesticide's potential for becoming airborne exceeds critical values, it should be subjected to a more rigorous second tier evaluation which considers its toxicity to organisms in non-target areas. This evaluation can be achieved by calculating and comparing a predicted environmental concentration (PEC) and a predicted no-effect concentration (PNEC). By applying an extra uncertainty factor the PNEC can be provisionally derived from standard toxicity data that is already required for the registration of pesticides. Depending on the distance between the source and the reception area, the PEC can be estimated for remote areas using simple dispersion, trajectory type models and for nearby areas using common dispersion models and standard scenarios of pesticide use. A pesticide's atmospheric transport potential is based on factors such as its reaction rate with OH radicals. It should be used to discriminate between those compounds for which only the risks to nearby ecosystems have to be assessed, and those for which the risks to remote ecosystems also have to be determined. The participants were of the opinion that this approach is, in principle, scientifically feasible, although the remaining uncertainties are substantial. Further field and laboratory research is necessary to gain more reliable estimates of the physico-chemical properties of pesticides, to validate and improve environmental fate models and to validate the applicability of standard toxicity data. This will increase both the accuracy of and our confidence in the outcome of the risk assessment.     

Quantification of imidacloprid uptake in maize crops

The systemic imidacloprid is one of the most used insecticides in the world for field and horticultural crops. This neurotoxicant is often used as seed-dressing, especially for maize, sunflower, and rape. Using a LC/MS/MS technique (LOQ = 1 microg/kg and LOD = 0.1 microg/kg), the presence of imidacloprid has been measured in maize from field samples at the time of pollen shed, from less than 0.1 microg/kg up to 33.6 microg/kg. Numerous random samples were collected throughout France from 2000 to 2003. The average levels of imidacloprid measured are 4.1 microg/kg in stems and leaves, 6.6 microg/kg in male flowers (panicles), and 2.1 microg/kg in pollen. These values are similar to those found previously in sunflower and rape. These results permit evaluation of the risk to honeybees by using the PEC/PNEC ratios (probable exposition concentrations/predicted no effect concentration). PEC/PNEC risk ratios were determined and ranged between 500 and 600 for honeybees foraging on maize treated with imidacloprid by seed dressing. Such a high risk factor can be related to one of the main causes of honeybee colony losses.     

Atmospheric Transport and Air-Surface Exchange of Pesticides

Atmospheric transport and exchange of pesticides with soil, vegetation, water and atmospheric particles are discussed, with an emphasis on applying physicochemical properties of the compound to describe environmental partitioning. The octanol-air partition coefficient is promoted as a unifying property for describing volatilization of pesticides from soil and sorption to aerosols. Present-day sources of organochlorine (OC) pesticides to the atmosphere are continued usage in certain countries and volatilization from contaminated soils where they were used in the past. Models are available to predict volatilization from soil; however, their implementation is hampered by lack of soil residue data on a regional scale. The need to differentiate "new" and "old" sources is increasing, as countries negotiate international controls on persistent organic pollutants (POPs). A new technique, based on the analysis of individual pesticide enantiomers, is proposed to follow emission of chiral OC pesticides from soil and water. Air monitoring programs in the Arctic show the ubiquitous presence of OC pesticides, PCBs and other POPs, and recently a few "modern" pesticides have been identified in fog and surface seawater. Atmospheric loadings of POPs to oceans and large lakes take place mainly by air-water gas exchange. In the case of OC pesticides and PCBs, aquatic systems are often near air-water equilibrium or even oversaturated. Measurement of water/air fugacity ratios suggests revolatilization of PCBs and several OC pesticides in the Great Lakes and, for α-hexachloroacyclohexane (α-HCH), in the Arctic Ocean. Outgassing of α-HCH in large lakes and arctic waters has been confirmed by enantiomeric tracer studies. The potential for pesticides to be atmospherically transported depends on their ability to be mobilized into air and the removal processes that take place enroute: wet and dry deposition of gases and particles and chemical reactions in the atmosphere. Measurement of reaction rate constants for pesticides in the gas and particle phase at a range of environmental temperatures is a critical research need. The transport distance of a chemical is related to its overall environmental persistence, determined by the partitioning among different compartments (water, sediment, soil, air), degradation rates in each compartment and mode of emission (into water, soil, air). Several pesticides found in the arctic environment have predicted lifetimes in the gas phase of only a few days in temperate climates, pointing out the need for monitoring and evaluation of persistence in cold regions.     

Effects of Copper on the Sorption of Phthalate Esters to Yellow River Sediment

Recent developments in satellite remote sensing technologies resulted in the ability to observe major pollution events such as dust and smoke around the world on a daily basis. Satellite imagery can sometimes detect long-range transport episodes. In this paper, a high CO episode at remote GAW station, Mt. Waliguan, detected by MOPITT CO dataset during the end of April 2002, is described. CO concentrations above 600 hPa almost doubled on 27 April and CMDL surface sample measurements also observed this significant CO enhancement. Using NCEP data, satellite fire products data and backward trajectory model we suggest that this high CO episode of 27 April is not a local pollution event, but that it is due to long-range transport from active biomass burning and biofuel burning areas located in the border areas of Pakistan and India. The trajectory cluster analysis shows that the origins of 5-day backward trajectories, for air masses reaching Mt. Waliguan station, at all altitudes, mainly overlap with the fire spot locations detected by TRMM data and biofuel burning in India.     

运用红边参数估算叶片叶绿素含量

Soil samples collected from several sites along an altitudinal transect on the eastern slope of the Tibetan Plateau were analyzed for hexachlorobenzenes(HCHs) and dichlorodiphenyltrichloroethanes(DDTs).The results showed that HCHs and DDTs were found in the soil samples from the remote high altitude areas away from source regions,which confirmed the long-range atmospheric transport phenomenon of these organochlorine pesticides(OCPs) insecticides.The OCP concentrations in the soils had a significant negative correlation with altitude;they showed a trend to increase with decreasing altitude,but the increase was not continuous,being interrupted at some moderate-altitude sites on the transect.The distances from the source region,landforms,soil properties,and physical-chemical properties of OCPs were more important than total organic carbon content to the distribution of OCPs in soils disturbed by human activities.An analysis of the compositions of HCH isomers and DDTs revealed predominantly low ratios of α-HCH to γ-HCH,ranging from 0.06 to 4.79,which suggested current lindane inputs.On the other hand,low p,p-DDT/p,p-DDE and o,p-DDT/p,p-DDT ratios were observed,indicating mainly aged historical DDT residues in the study area.     

Environmental risk assessment of a metal-contaminated area in the Tropics. Tier I: screening phase

Purpose  

The present study presents data on the screening phase (tier 1) of a site-specific ecological risk assessment in a former smelter area heavily contaminated with metals (Santo Amaro, Bahia, Brazil). Joining information from three lines of evidence (LoE), chemical, ecotoxicological, and ecological, integrated risk values were calculated to rank sites within the area and identify those that may need further investigation in tier 2.     

Input of pesticides by atmospheric deposition

Sampling and analytical methods were developed to examine the input of various pesticides on noncultivated areas of the FAM (Research Network on Agroecosystems) Research Station Scheyern. Off-target drift from pesticide application on nearby cultivated land, as well as input due to long-range atmospheric transport, were measured. The wet deposition was determined by a cooled wet-only sampler. Bulk samplers and specially designed samplers with glass-fiber surface were used for total deposition measurements. Analysis of pesticides was carried out using liquid/liquid or solid-phase extraction and high performance liquid chromatography-UV (HPLC-UV) or gas chromatography-nitrogen/phosphorus-sensitive detector/MS (GC-NPD/MS) detection. Obtained results demonstrated that for several compounds, total deposition, i.e. the sum of wet and dry deposition, was marginally higher than wet deposition alone. In contrast, total deposition data of pesticides having been applied near the sampling site exceeded wet deposition values by orders of magnitude. In addition to direct drift, determined as droplets depositing near pesticide application areas, an indirect drift represented by particle-associated or gaseous transport was observed, both of which contributed considerably to total deposition. Therefore, to determine the input of pesticides to nontarget areas in the close vicinity of pesticide application, direct and indirect drift, and background deposition must be considered.     

Long-term trends of pesticides in Norwegian agricultural streams and potential future challenges in northern climate

Effective plant protection practices and use of chemical pesticides are a prerequisite for maintaining yields of sufficient quality and quantity in conventional agriculture today. Despite regulatory efforts to ensure safe use, reports have indicated that residual amounts of pesticides and their metabolites occur in surface and ground water and may have non-target effects on aquatic organisms. The objective of the present study was to identify environmental challenges of pesticide use in the northern climate by evaluating long-term pesticide monitoring data compiled by the Norwegian Agricultural Environmental Monitoring Programme. Pesticide use data and pesticide concentrations measured in stream water from six small agricultural catchments in Norway were analysed. Observed trends in pesticide detection frequencies, measured concentrations and cumulative risk from the six monitoring sites were compared. The results demonstrated the need for continued focus on the herbicides metribuzin and aclonifen, and potential concerns regarding use of the fungicide prothioconazole and the insecticide imidacloprid. The six monitoring sites represented the diversity of intensively cropped areas in Norway and differed with respect to estimated cumulative risk. Vegetable and potato cropping areas showed not only the highest level of total environmental risk, but also a statistically significant decreasing trend over the monitoring period. Cereal cropping areas exhibited no statistically significant time-dependent trends in the studied parameters but did show an increase in fungicide use that requires continued attention. The need for risk assessment of mixture toxicity effects and improved monitoring strategy is also discussed. In conclusion, the present results imply that the current global focus on multiple stressors and mixture toxicity of pesticides in stream water is equally relevant in cold climatic conditions.     

兰州地区PCBs的长距离传输潜力及其总持久性模拟研究

运用TaPL3（version3.00）模型计算了7种PCBs同系物在兰州地区通过大气和水体的特征迁移距离（CTD）及其总持久性（Po）v,讨论了其长距离传输潜力（LRTP）和Pov之间的关系,并以PCB28为例,应用灵敏度分析方法对模型的不确定性进行了研究。结果显示,兰州地区PCB28、PCB52、PCB77、PCB101、PCB138、PCB153和PCB180通过大气的CTDair在250～2500km之间,Pov在500～33000d之间,PCB138、PCB153和PCB180对源区影响较大;通过水体的CTDwater在6500～61000km之间,Pov在850～36000d之间,PCB28、PCB52、PCB77和PCB101对源区影响较大。7种PCBs的同系物LRTP和Pov之间没有直接的联系,就排放到大气中的PCBs而言,对Pov和CTD影响最大的参数都是理化参数;就排放到水体中的PCBs而言,Pov比CTD更依赖于PCBs的理化性质,而CTD比Pov更依赖于环境条件。同国外的研究相比,兰州地区PCB28通过大气的CTDair偏低,通过水体的CTDwater偏高,PCB28通过大气和水体的Pov都偏高。     

Heavy metal concentrations in some non-vascular plants in an Amazonian rainforest

The presence of acid rain in the remote Amazon rainforest of southwestern Venezuela suggests the possibility of long-range transport of industrial pollutants to that region. Heavy metal concentrations were analyzed in samples of bryophytes and epiphyllous organisms growing on leaves and on bark in this forest. Concentrations of Cd, Pb, Ni, and Cr were higher in leaves with epiphylls than in leaves without epiphylls. All heavy metal concentrations in bryophytes from the Amazon basin site were lower than in bryophytes from temperature zones. The results indicate that long-range transport of air pollutants from industrial centers to the remote Amazon basin is occurring at only extremely low rates. Heavy metal concentrations in bryophytes and epiphylls at this site may still be considered close to present day background levels.     

生态毒理学工具在评价石油化工厂区土地耕作适宜性中的运用

The demand for simple and rapid bioassays in ecotoxicological evaluations is of paramount importance in order to speed up environmental monitoring programs. In this study we performed bioassays with lettuce seeds and two species of terrestrial isopods （Armadillidium vulgare and Porcellio dilatatus） for the ecotoxicological assessment of a landfarming soil from a petrochemical complex area. The solubilized content of test soil demonstrated a concentration-response type toxic effect on seed germination rate, and a delay on germination, but showed toxic effect on seedlings wet weight only at the highest concentration. Toxic effects were also observed in mortality rate and avoidance behavior of the two woodlice species. These results demonstrated the sensitiveness of the organisms studied, and highlighted the possibility to use these bioassays in environmental monitoring programs in areas contaminated with fossil fuels.     

基于景观结构的沱江流域土地利用生态风险时空变化

本文以沱江流域为研究对象,基于2005—2020年的遥感数据,从景观结构的角度,利用GIS和GeoDa软件,同时结合土地利用类型转移矩阵,构建景观土地生态风险评价模型,分析了研究区土地生态风险的时空变化特征。结果表明：①耕地为研究区的景观本底值,受自然和人为因素的影响,15年间,耕地和林地面积减少,建设用地、水域、草地、未利用地面积增加,新增建设用地面积最多,91.95% 来源于耕地,是建设用地的主要来源。②2005—2020年的生态风险指数,经计算,全局莫兰指数(Moran’s I))值均为正数,在99% 的置信度标准下,通过了显著性检验,说明生态风险区在空间上具有显著的正相关关系且呈现空间聚集状态,“高-高”聚集是土地生态风险的主要聚集模式。③15年间,在空间分布上,低风险等级整体上有向中下游转移的趋势,研究区以高风险区和较高风险区为主,分别呈片状和条带状较集中地分布于流域上游的山区和中下游的丘陵地区,分别占到研究区总面积的49.20% 和48.98%;从面积变化的趋势来看,低风险区、较低风险区、中等风险区面积逐年分别增加了1 122.91、3 581.10、21 698.83 hm²,较高风险区面积先增加后减少,总体增加了582 436.94 hm²,高风险区面积先减少后增加,总体减少了608 839.78 hm²,沱江流域土地利用生态风险整体上趋于减弱;总体来看,除较高风险区向高风险区少量转化外,其余均以较高等级风险区向较低风险区转移占比较多,风险区的转化均表现为相邻等级之间的互相转化,说明研究区生态风险变化相对稳定,没有急剧变化的区域。     

基于土地利用的三峡库区生态屏障带生态风险评价

[目的]揭示三峡库区生态屏障带生态风险,为库区生态风险评估及土地利用优化提供理论依据。[方法]基于遥感影像数据,运用RS与GIS技术,计算土地利用相对合理性指数,同时构建生态风险评价模型,划分高程/坡度带定量评价三峡库区生态屏障带的生态风险情况,划分生态风险等级,并对生态风险进行空间自相关分析。[结果]较低生态风险区占比例最大,为36.77%,高生态风险区及较高生态风险区主要分布在沿长江两岸建设用地及耕地较为集中的区域,土地利用相对合理性指数随高程增高逐渐变大,随坡度增大逐渐减小,研究区生态风险空间自相关分析呈现出十分显著的局部自相关性。[结论]研究区内生态风险总体呈现较低值,沿江高值区需对土地利用进行重点优化。     

基于ALOS和PPS的退耕还林工程监测——以沽源县九连城镇为例

以ALOS数据作为卫星遥感数据信息源,利用计算机进行监督分类和人机交互式解译,可提取工程区实际退耕还林面积,但对所有图斑进行实地植被状况调查的费用是非常昂贵和费时的。采用不等概抽样方法(PPS),将给定的遥感解译图斑面积/各工程实施图斑面积作为辅助因子,根据30块工程实际面积和GPS实地量测退耕还林面积,估计工程保存造林总面积,将两者提取面积做了对比分析。分析结果表明,该方法分析精度达到86.2%,对及时掌握工程实施进度及质量,也具有极其重要的意义。     

The use of comprehensive two-dimensional gas chromatography and structure–activity modeling for screening and preliminary risk assessment of organic contaminants in soil, sediment, and surface water

Purpose

This article aims to investigate the use and benefits of using comprehensive two-dimensional gas chromatography (GC?×?GC) and structure?Cactivity relationship modeling for screening and prioritization of organic contaminants in complex matrices. The benefit of applying comprehensive screening techniques to samples with high organic contaminant content is primarily that compounds with diverse physicochemical properties can be analyzed simultaneously. Here, a heavily contaminated industrial area was surveyed for organic pollutants by analyzing soil, sediment, and surface water samples. The hazard of the pollutants were ranked using SARs.

Material and methods

The water samples were liquid?Cliquid extracted using dichloromethane and directly analyzed by GC?× GC?Ctime-of-flight mass spectrometry (GC?×?GC?CTofMS). Soil and sediment samples were extracted with dichloromethane in an ultrasonic bath and subjected to gel permeation chromatography to eliminate lipids and humic matter. The low molecular weight fraction was then analyzed with GC?×?GC?CTofMS.

Results and discussion

More than 10,000 components were found in each sample, of which ca. 300 individual compounds were unambiguously identified using the National Institute of Standards and Technology mass spectra library and authentic reference standards. Alkanes, polycyclic aromatic hydrocarbons, and phthalates were generally the most abundant and were found in all matrices. In contrast, chlorinated compounds such as chlorophenols, biphenyls, and chlorinated pesticides were only detected in samples from a few hotspot regions. The toxicities of the most frequently detected compounds and of the compounds detected at the highest concentrations in samples from hotspot regions were estimated by ecological structure?Cactivity relationships. The ratio of the measured concentration to the predicted toxicity level was then calculated for each compound and used for an initial risk assessment in order to prioritize compounds for further transport and fate modeling, complementary measurements, and more advanced risk assessments.

Conclusions

The advantage of using of GC?×?GC?CTofMS for preliminary screenings of contaminated areas was evaluated at a polluted area in northern Sweden. The area was found to carry organic pollutants such as polyaromatic hydrocarbons, aliphatic hydrocarbons, polychlorinated biphenyls, phthalic compounds, and many chlorinated pesticides. Preliminary risk assessments indicate which compounds to use for subsequent remediation experiments based on their availability on the site or toxicity.     

农药残留风险评估在蔬菜水果和食用菌监测中的应用研究

为了解我国西北地区蔬菜水果和食用菌的质量安全情况及暴露风险,本试验从2018至2020年在我国甘肃省平凉市进行样品抽取,共测定2 435份蔬菜水果和食用菌样品中46种农药残留的含量.通过农药残留风险评估方法分析了 9类别蔬菜水果和食用菌中农药残留的分布和相关性,并对蔬菜和水果中农药残留情况进行了风险排序,以及暴露风险、...     

海南岛农业台风灾害风险评估与可持续发展对策

海南岛是中国台风频发地区之一,开展海南岛农业台风灾害风险评估研究,可为海南岛优化农业种植布局和加强农业防灾减灾提供技术支撑。该研究基于自然灾害系统理论和方法,结合海南岛气象、自然地理与社会经济等要素,综合考虑致灾因子危险性、孕灾环境暴露性、承灾体脆弱性,研究构建了海南岛农业台风灾害风险评估方法与指标体系,并基于2001-2020年历年海南岛台风发生数据进行了海南岛农业台风灾害风险评估,在此基础上提出了农业台风灾害防灾减灾与可持续发展对策。结果表明,海南岛农业台风灾害风险指数处于0.40～0.80之间,平均0.61,整体上呈现出北部及沿海地区的灾害风险高于中部山区的趋势;致灾因子危险性、孕灾环境暴露性在全岛北部和沿海地区指数较高,承灾体脆弱性在琼海、陵水和三亚等市县指数较高。同时提出了3种农业台风防灾减灾与可持续发展对策,包括调整农业种植布局、提升风险监测预警能力和加强农业政策保险投入等。海南岛各市县农业台风灾害风险的差异以及相应的对策,可支撑相关部门为不同灾害风险程度区域建立防灾方法提供指导依据。     

Organochlorine pesticides (OCPs) in soils near and around Lake Son-Kul in the western Tian Shan Mountains,Central Asia

Purpose

Summer pasture development and tourism near and around Lake Son-Kul in the western Tian Shan Mountains has resulted in a local source of organochlorine pesticides (OCPs) that lack monitoring and evaluation.

Materials and methods

Twenty-eight soil samples were collected from the Lake Son-Kul Basin (SKB) and Naryn River Valley (NRV) to measure OCP concentrations and evaluate their composition, transport processes, and ecological risks.

Results and discussion

Except for the high OCP concentration measured at one location, site 7 (145.32 ng/g dw), total OCP concentrations in the SKB ranged from 2.36 to 24.13 ng/g dw, slightly higher than concentrations in the NRV (1.69–7.45 ng/g dw) and similar to values in polar regions. Among the OCPs, HCHs and methoxychlor were the predominant compounds that accumulated in soils, followed by DDTs and Aldrins, whereas Chlors and Endos displayed lowest concentrations, indicating that animal husbandry is the main agricultural activity in the study area. Most of the less volatile pesticides, including β-HCH, p,p-DDT, and Chlors, represent past use from local sources, for instance the pesticides warehouse at site 7. More volatile compounds such as α-HCH, γ-HCH, and p’p-DDE represent exogenous atmospheric transport to the study area, as demonstrated by their isomeric ratios. Ecological risk assessment showed that the surface environment of the study area remains in good condition.

Conclusions

Findings from this study provided a snapshot of the current status of OCP contamination in soils of the Lake Son-Kul region. Although historical OCP contamination has impacted the lake’s ecology, catchment soils display low levels of OCP contamination.