Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

The role of analytical science in natural resource decision making

There is a continuing debate about the proper role of analytical (positivist) science in natural resource decision making. Two diametrically opposed views are evident, arguing for and against a more extended role for scientific information. The debate takes on a different complexion if one recognizes that certain kinds of problem, referred to here as “wicked” or “trans-science” problems, may not be amenable to the analytical process. Indeed, the mistaken application of analytical methods to trans-science problems may not only be a waste of time and money but also serve to hinder policy development. Since many environmental issues are trans-science in nature, then it follows that alternatives to analytical science need to be developed. In this article, the issues involved in the debate are clarified by examining the impact of the use of analytical methods in a particular case, the spruce budworm controversy in New Brunswick. The article ends with some suggestions about a “holistic” approach to the problem.     

Imidacloprid residues in fruits,vegetables and water samples from Palestine

The aim of this work was to report on imidacloprid [IUPAC name 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] residues in some vegetables, fruits, and water samples collected from the West Bank, Palestine, in 1998 and 1999. Imidacloprid and its derivatives in the study samples were extracted by methanol/water and oxidized into 6-chloronicotinic acid and subsequently derivatized into 6-chloronicotinic acid trimethylsilyl ester before being determined by GC/MS. Imidacloprid residues were detected in more than half of the analyzed samples. The highest and lowest imidacloprid concentrations were found in eggplant (0.46 mg/kg) and green beans (0.08 mg/kg), respectively. An increase of 11–120% in imidacloprid concentration in the 1999 samples was observed when compared with those of 1998. This may suggest imidacloprid accumulation in the soil and/or increased use by local farmers. The imidacloprid residue concentrations in several crops were found to exceed the CODEX maximum residue limit.     

固相萃取-气相色谱/质谱法测定地下水中15种农药残留

通过优选色谱柱,进一步改进色谱分离条件,优化前处理方法,建立一种快速高效测定地下水中15种农药残留量的GC-MS方法。该法采用分段法选择离子(SIM)扫描,具有更高的灵敏度、较低的检出限和较高的回收率,检出限低于0.004 8μg/L,回收率为85.9%~107.4%。本方法的突出特点是前处理速度快、萃取溶剂用量少、环境污染小、色谱运行时间短,基本稳定在25 min内完成分析,适用于大批量样品检测。     

基于荧光素酶发光体系测试饮用水中农药的综合毒性

利用农药对荧光素酶催化的发光反应具有非常显著的抑制作用,对甲拌磷、乐果、毒死蜱、百草枯等4种农药分别进行单一毒性和等比混合法联合毒性测试,建立了一种快速检测饮用水中农药综合毒性的生物学方法。试验结果表明,单一农药乐果、甲拌磷、百草枯和毒死蜱的EC50值分别为7.56 mg/L、12.7 mg/L、19.0 mg/L和65.3 mg/L,毒性强弱顺序为乐果甲拌磷百草枯毒死蜱,相关系数≥0.995;将4种农药以等比方式配制成两两混合液后,当质量浓度为20.0 mg/L~100 mg/L时,除百草枯与毒死蜱表现为毒性协同外,其他两两混合农药的毒性以拮抗作用为主。     

Trends of organochlorine pesticides in drinking water supplies

The effectiveness of the treatment process for the removal of pesticides in the final water supplies in Delhi has been evaluated. Samples were collected during 2000–2005 from five water treatment plants (WTPs). Analysis was carried out to identify pesticides, which are more commonly encountered in treated drinking water. In most of the treatment plants, the concentrations of lindane, total endosulphan and total DDT were significantly less in the finished water. Monitoring of these less soluble pesticide in the finished water from WTPs was done quarterly to arrive at the quality trends and to plan for the mitigation action, in case the concentration of the parameter exceeded at any site or time.     

Adsorption distribution impact on preferential transport within horizontal flow constructed wetland (HFCW)

Predicting preferential water flow and solute transport in soils is in the interest of scientists and engineers in the fields of agricultural soil, forest hydrology, soil physics and wastewater treatment by constructed wetland. In artificial wetlands, any preferential pathway induces an insufficient residence time of pollutants in the soil, making an incomplete and unfinished biodegradation process, a wrong evaluation of the hydraulic residence time of the system which would hinder its management in a complete system with several entities of treatment and a non-homogeneous growth of the biofilm in the solid filter mass. This paper is a contribution in tracer experiment data analysis within a horizontal flow constructed wetland built in a storm water basin. A two-dimensional numerical model was used to simulate flow and reactive solute transport. The flow model was successfully calibrated in very dry soil conditions. The adsorption profiles used in the reactive transport modeling are those of five molecules: metolachlor, atrazine, deethylatrazine (DEA), deisopropylatrazine (DIA), and hydroxyatrazine (HA). We show that the adsorption distribution is an internal factor of soil which is responsible to the “preferential” pathway transport in a homogeneous gravel texture. The mean residence time of pollutants within the filter is strongly correlated with the average value of the adsorption coefficient. Moreover, we note a lack of significant impact of the heterogeneity of the medium on the statistical moments of breakthrough curve. It appears that a uni-modal breakthrough curve is not significant to the absence of preferential flow in the medium and at least a two-dimensional display can provide sufficient evidence on the presence or absence of preferential pathways. Finally, using a PLS regression, it is possible to perfectly discriminate the number of peaks of concentration and the asymmetry of the breakthrough curve.     

Absorption of current use pesticides by snapping turtle (Chelydra serpentina) eggs in treated soil

Reptiles often breed within agricultural and urban environments that receive frequent pesticide use. Consequently, their eggs and thus developing embryos may be exposed to pesticides. Our objectives were to determine (i) if turtle eggs are capable of absorbing pesticides from treated soil, and (ii) if pesticide absorption rates can be predicted by their chemical and physical properties. Snapping turtle (Chelydra serpentina) eggs were incubated in soil that was treated with 10 pesticides (atrazine, simazine, metolachlor, azinphos-methyl, dimethoate, chlorpyrifos, carbaryl, endosulfan (I and II), captan, and chlorothalonil). There were two treatments, consisting of pesticides applied at application rate equivalents of 1.92 or 19.2 kg a.i/ha. Eggs were removed after one and eight days of exposure and analyzed for pesticides using gas chromatography coupled with a mass selective detector (GC-MSD) or high performance liquid chromatography (HPLC). Absorption of pesticides in eggs from soil increased with both magnitude and duration of exposure. Of the 10 pesticides, atrazine and metolachlor generally had the greatest absorption, while azinphos-methyl had the lowest. Chlorothalonil was below detection limits at both exposure rates. Our preliminary model suggests that pesticides having the highest absorption into eggs tended to have both low sorption to organic carbon or lipids, and high water solubility. For pesticides with high water solubility, high vapor pressure may also increase absorption. As our model is preliminary, confirmatory studies are needed to elucidate pesticide absorption in turtle eggs and the potential risk they may pose to embryonic development.     

Farmworker children's residential non-dietary exposure estimates from micro-level activity time series

Farmworkers' children may have increased pesticide exposure through dermal absorption and non-dietary ingestion, routes that are difficult to measure and model. The Cumulative Aggregate Simulation of Exposure (CASE) model, integrates the complexity of human behavior and variability of exposure processes by combining micro-level activity time series (MLATS) and mechanistic exposure equations. CASE was used to estimate residential non-dietary organophosphate pesticide exposure (i.e., inhalation, dermal, and non-dietary ingestion) to California farmworker children and evaluate the micro-activity approach. MLATS collected from children and distributions developed from pesticide measurements in farmworkers' residences served as inputs. While estimated diazinon exposure was greater for inhalation, chlorpyrifos exposure was greater for the other routes. Greater variability existed between children (σ_B² = 0.22–0.39) than within each child's simulations (σ_W² = 0.01–0.02) for dermal and non-dietary ingestion. Dermal exposure simulations were not significantly different than measured values from dosimeters worn by the children. Non-dietary ingestion exposure estimates were comparable to duplicate diet measurements, indicating this route may contribute substantially to aggregate exposure. The results suggest the importance of the micro-activity approach for estimating non-dietary exposure. Other methods may underestimate exposure via these routes. Model simulations can be used to identify at-risk children and target intervention strategies.     

Persistence of organochlorine chemical residues in fish from the Tombigbee River (Alabama, USA): Continuing risk to wildlife from a former DDT manufacturing facility

Organochlorine pesticide and total polychlorinated biphenyl (PCB) concentrations were measured in largemouth bass from the Tombigbee River near a former DDT manufacturing facility at McIntosh, Alabama. Evaluation of mean p,p′- and o,p′-DDT isomer concentrations and o,p′- versus p,p′-isomer proportions in McIntosh bass indicated that DDT is moving off site from the facility and into the Tombigbee River. Concentrations of p,p′-DDT isomers in McIntosh bass remained unchanged from 1974 to 2004 and were four times greater than contemporary concentrations from a national program. Total DDT in McIntosh bass exceeded dietary effect concentrations developed for bald eagle and osprey. Hexachlorobenzene, PCBs, and toxaphene concentrations in bass from McIntosh also exceeded thresholds to protect fish and piscivorous wildlife. Whereas concentrations of DDT and most other organochlorine chemicals in fish have generally declined in the U.S. since their ban, concentrations of DDT in fish from McIntosh remain elevated and represent a threat to wildlife.