Modeling Parent and Metabolite Fate and Transport in Subsurface Drained Fields With Directly Connected Macropores1

Abstract: Few studies exist that evaluate or apply pesticide transport models based on measured parent and metabolite concentrations in fields with subsurface drainage. Furthermore, recent research suggests pesticide transport through exceedingly efficient direct connections, which occur when macropores are hydrologically connected to subsurface drains, but this connectivity has been simulated at only one field site in Allen County, Indiana. This research evaluates the Root Zone Water Quality Model (RZWQM) in simulating the transport of a parent compound and its metabolite at two subsurface drained field sites. Previous research used one of the field sites to test the original modification of the RZWQM to simulate directly connected macropores for bromide and the parent compound, but not for the metabolite. This research will evaluate RZWQM for parent/metabolite transformation and transport at this first field site, along with evaluating the model at an additional field site to evaluate whether the parameters for direct connectivity are transferable and whether model performance is consistent for the two field sites with unique soil, hydrologic, and environmental conditions. Isoxaflutole, the active ingredient in BALANCE^® herbicide, was applied to both fields. Isoxaflutole rapidly degrades into a metabolite (RPA 202248). This research used calibrated RZWQM models for each field based on observed subsurface drain flow and/or edge of field conservative tracer concentrations in subsurface flow. The calibrated models for both field sites required a portion (approximately 2% but this fraction may require calibration) of the available water and chemical in macropore flow to be routed directly into the subsurface drains to simulate peak concentrations in edge of field subsurface drain flow shortly after chemical applications. Confirming the results from the first field site, the existing modification for directly connected macropores continually failed to predict pesticide concentrations on the recession limbs of drainage hydrographs, suggesting that the current strategy only partially accounts for direct connectivity. Thirty‐year distributions of annual mass (drainage) loss of parent and metabolite in terms of percent of isoxaflutole applied suggested annual simulated percent losses of parent and metabolite (3.04 and 1.31%) no greater in drainage than losses in runoff on nondrained fields as reported in the literature.     

DDT in fish from the Bulgarian region of the Black Sea

In spite of a worldwide reduction in the utilization of organochlorine pesticides (OCPs), they are still a problem for the aquatic environment and human health. The Black Sea is still being polluted with persistent chemicals, including OCPs. Aquatic organisms (sprat, scad, bluefish, shad, belted bonito, goby, and black mussel) with different feeding behaviours were sampled on a seasonal basis from the Bulgarian region of the Black Sea, and the concentrations of 13 OCP residues were determined. Although many of the OCPs were not detected in the samples, in all samples 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) was present mainly in the form of its metabolites 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDE). Only about 12% of the total DDT was present as the parent compound pp-DDT, which suggests that it was not being used recently in the region. The total DDT concentrations were generally below 150 μg kg^-1 fresh weight, but higher levels—up to 354 μg kg^-1 fresh weight—were also measured for fish species with a high fat content. Between-species differences were observed, even when the concentrations were presented on a fat-level basis. DDT concentrations did not show any significant changes over the 2-yr sampling period. Fish sampled in the northern areas of the Bulgarian Black Sea coast seemed to contain higher DDT levels than those from the southern areas, suggesting a major (historical) influence of the Danube River. For permanent monitoring purposes, the utility of Black Sea gobies and scad should be considered.     

沱江沉积物中有机氯农药分布特征及其与藻类有机质的关系和生态风险评估

使用气相色谱-质谱联用仪分析了长江支流沱江流域48个表层沉积物中有机氯农药（organochlorine pesticides,OCPs）的残留水平,探讨了其分布和组成特征及其与总有机碳（total organic carbon,TOC）、藻类有机质之间的关系,以及评估其生态风险.结果表明沱江流域表层沉积物中OCPs的总含量为3.17~127 ng·g^-1,其中六六六（hexachlorocyclohexane,HCHs）类农药的含量为2.83~86.0 ng·g^-1,滴滴涕（dichlorodiphenyltrichloroethane,DDTs）类农药的含量为0.340~40.9 ng·g^-1.OCPs空间分布特点为：上游 < 中游 < 下游 < 支流.HCHs和DDTs的组成成分分析表明,沱江流域存在林丹输入的现象,主要来自于历史残留,这与绝大多数流域的DDTs的输入状况相似.OCPs含量与TOC、藻类有机质含量之间存在着极显著的正相关性关系,表明藻类有机质在TOC对沉积物中的OCPs分配中起更为重要的作用.生态风险评估表明,沱江流域表层沉积物的有机氯农药存在较大的生态风险,可能对河流的底栖生物及生态环境造成明显的影响.     

Sources, distribution, and risk assessment of organochlorine pesticides in Nairobi City, Kenya

The distribution and sources of organochlorine pesticides (OCPs) in air and surface waters were monitored in Nairobi City using triolein-filled semipermeable membrane devices (SPMDs). The SPMDs were extracted by dialysis using n-hexane, followed by cleanup by adsorption chromatography on silica gel cartridges. Sample analysis was done by GC-ECD and confirmed by GC–MS. Separation of means was achieved by analysis of variance, followed by pair-wise comparison using the t-test (p≤ 0.05). The total OCPs ranged between 0.018 – 1.277 ng/m³ in the air and <LOD – 1391.000 ng/m³ in surface waters. Based on the results, the means of Industrial Area, Dandora and Kibera were not significantly different (p≤ 0.05), but were higher (p≤ 0.05) than those of City square and Ngong’ Forest. The results revealed non-significant (p≤ 0.05) contribution of long-range transport to OCP pollution in Nairobi City. This indicated possible presence of point sources of environmental OCPs in the city. The water-air fugacity ratios indicated that volatilization and deposition played an important role in the spatial distribution of OCPs in Nairobi City. This indicated that contaminated surface waters could be major sources of human exposure to OCPs, through volatilization. The incremental lifetime cancer risks (ILCR) determined from inhalation of atmospheric OCPs were 2.3745  ×  10^?13 – 1.6845  ×  10^?11 (adult) and 5.5404  ×  10^?13 – 3.9306  ×  10^?11 (child) in the order: Dandora > Kibera > Industrial Area > City Square > Ngong’ Forest. However, these were lower than the USEPA acceptable risks, 10^?6 – 10^?4. This study concluded that atmospheric OCPs did not pose significant cancer risks to the residents.     

鄂东鸭儿湖地区大气中有机氯农药特征及土-气交换

采用聚氨酯泡沫-被动采样法（PUF-PAS）采集鸭儿湖地区大气样,研究典型污染源地区大气中有机氯农药（OCPs）组成、来源及土-气交换现状。鸭儿湖地区大气中OCPs主要组成为艾氏剂（Aldrin）、滴滴涕（DDTs）、六六六（HCHs）、六氯苯（HCB）、甲氧滴滴涕（Methoxychlor）和a-硫丹（α-Endosulfan）,约占OCPs总量的84%。较高浓度Aldrin（平均浓度为161.25 pg/m³）广泛存在应引起高度重视。HCHs（平均浓度为89.64 pg/m³）和DDTs（平均浓度为92.29 pg/m³）普遍存在且含量高,污染程度比较明显。HCHs异构体中β-HCH高于α-HCH,远远高于γ-HCH和δ-HCH,说明HCHs经过长期降解已逐渐稳定下来;来源分析推测存在工业HCHs的使用或者受大气长距离传输影响。DDTs在各点位分布明显不同于HCHs,且各点位DDTs的六种组成均存在很大差别,可能由于点位地理位置以及农药使用情况导致;来源分析推测大气中DDTs主要来自历史残留。鸭儿湖地区OCPs土气交换研究表明,HCHs主要表现为从大气向土壤中沉降;DDTs在大多数点位源于土壤中历史残留的挥发,部分点位受到大气长距离传输影响。     

Concentration and Distribution of Persistent Organic Pollutants (POPs) in Harbour Dredging Sediments: A Pilot Study Using a Statistical Approach for a More Efficient Characterisation and Management

The Italian guidelines concerning the dumping of dredgingmaterials implies chemical, physical and microbiologicalcharacterisation of dumping sediments collected through aspecific sampling strategy.POP's such as PCB's and organochlorine pesticides, areconsidered as priority pollutants in all the InternationalConventions for the protection of the marine environment, inconsequence of their persistence, toxicity and bioaccumulation capacity.In the present article the concentrations and distribution ofPCB's and organochlorine pesticides in dredging sediments ofPiombino harbour (northern Thyrrenian sea) were investigates.The results showed high POP's concentrations in all the studiedareas. The maximum values were: 3.94 mg kg^-1 dry weight for PCB's(IUPAC Nos. 28; 52; 101, 118; 137; 153; 180; 209); 2.04 mg kg^-1 d.w.for HCH's (-, -, - and -hexachlorocyclohexane isomers); 0.28 mg kg^-1 d.w. for DD's (DDT + DDE + DDD).Subsequently, the data related to each pollutant were treatedwith statistical tests, in order to verify how well the samplingstrategy is able to represent the distribution of contaminantsin the dredging area. Finally, management strategies werederived for the studied dredging sediments.     

固相微萃取-毛细管气相色谱法快速同步分析水中有机氯及有机磷农药

固相微萃取是一种快速、简便,集萃取浓缩进样于一体的样品前处理技术,具有分析时间短、灵敏度高、无需有机溶剂的优点.用固相微萃取富集水中8种有机氯及7种有机磷农药,毛细管气相色谱ECD检测器分离分析,整个分析过程只需26min,检出限可达0.002～1μg/L,已用于地表水中有机氯及有机磷农药含量的测定.     

Determination of organophosphorus pesticides and related compounds in water samples by membrane extraction and gas chromatography

A membrane extraction-gas chromatography method was developed fordetermination of organophosphorus pesticides and related compounds including methamidophos, DDVP, dimethoate, methyl parathion, parathion, thiophosphoric acid trimethyl ester, and thiophosphoramidic acid dimethyl ester in water samples. In thismethod, surface-modified acetic cellulose membranes were used to extract the target analytes in water samples, the extracted analytes were back-extracted into a small amount of methanol, andgas chromatography with pulsed flame photometric detector (GC-PFPD) was used to determine the concentrations of targetanalytes in the extracts. The recoveries obtained for thetarget analytes spiked into the water samples ranged from 66to 94%. The method detection limit for each target analyte was 0.05 g L^-1. The method developed in this study had shown the advantages of being cheap, simple, fast, and reliable. It had been used successfully to determine the concentrations of target analytes in river water samples.     

微波萃取-气相色谱/质谱法测定土壤中的有机氯农药

通过微波萃取提取土壤中的有机氯农药,萃取溶液经浓硫酸脱色、佛罗里硅土柱净化,最后用气相色谱/质谱法分析.以石英砂为基体进行加标回收测定,有机氯农药的回收率在75.5%～103%之间,检出限为0.01μg/kg.     

Distribution of Chlorinated Organic Pollutants in Harbor Sediments of Livorno (Italy): A Multivariate Approach to Evaluate Dredging Sediments

Dredging is a very important procedure for harbor management. InItaly the guidelines for the offshore dumping of dredged materials are issued by the Ministry of Environment. Theydescribed a few steps of dredging activities, such as thesampling strategy, but do not deal with limits or guide-valuesfor the chemical, physical and biological composition of theresulting sediments. The quality of dredged materials is mainlydependent on the presence of inorganic and organic pollutants.In particular, polychlorinated biphenyls (PCBs) and organo-chlorinated pesticides are seen as a high priority inmarine environment by international organizations because oftheir persistence, toxicity and bioaccumulation capacity.In this article the presence of some PCBs and organo-chlorinatedpesticides in sediment samples collected from the harbor ofLivorno (Northern Tyrrhenian Sea) was investigated. Theconcentration of HCHs, Aldrin, Chlordanes, DDEs, DDTs, and PCBsin 12 representative sites ranged between <1 g kg^–1and 95, 19, 32, 35, 107, and 111 g kg^–1, respectively.The application of univariate and multivariate statisticaltechniques, such as linear regression analysis and principalcomponent analysis, to the experimental data showed a differentdistribution of PCBs in the two sediment layers. On thecontrary, the vertical distribution of the other investigatedpollutants was more homogeneous and affected by randomvariability. The multivariate approach was an important tool to establish more rational criteria for the management of dredged materials.