On the scope and management of pesticide pollution of Swedish groundwater resources: The Scanian example

Twenty-three south-Swedish public supply wells were studied to assess pesticide pollution of regional groundwater resources. Relations between pesticide occurrence, hydrogeology, and land use were analyzed using Kohonen’s Self-Organizing Maps approach. Pesticides are demonstrated to be substantially present in regional groundwater, with detections in 18 wells. Concentrations above the drinking water threshold are confirmed for nine wells. Observations indicate considerable urban influence, and lagged effects of past, less restricted use. Modern, oxic waters from shallow, unconfined, unconsolidated or fracture-type bedrock aquifers appear particularly vulnerable. Least affected waters appear primarily associated with deeper wells, anoxic conditions, and more confined sediment aquifers lacking urban influence. Comprehensive, standardized monitoring of pesticides in groundwater need to be implemented nationwide to enable sound assessments of pollution status and trends, and to develop sound groundwater management plans in accordance with the Water Framework Directive. Further, existing water protection areas and associated regulations need to be reassessed.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-014-0548-1) contains supplementary material, which is available to authorized users.     

Dynamic modeling of organophosphate pesticide load in surface water in the northern San Joaquin Valley watershed of California

The hydrology, sediment, and pesticide transport components of the Soil and Water Assessment Tool (SWAT) were evaluated on the northern San Joaquin Valley watershed of California. The Nash-Sutcliffe coefficients for monthly stream flow and sediment load ranged from 0.49 to 0.99 over the watershed during the study period of 1992-2005. The calibrated SWAT model was applied to simulate fate and transport processes of two organophosphate pesticides of diazinon and chlorpyrifos at watershed scale. The model generated satisfactory predictions of dissolved pesticide loads relative to the monitoring data. The model also showed great success in capturing spatial patterns of dissolved diazinon and chlorpyrifos loads according to the soil properties and landscape morphology over the large agricultural watershed. This study indicated that curve number was the major factor influencing the hydrology while pesticide fate and transport were mainly affected by surface runoff and pesticide application and in the study area.     

Estimation of emission fluxes from a horizontal flux budget method, exemplified with determination of pesticide volatilization

The paper describes an experimental set-up designed to measure the volatilization of different pesticides after application under full-scale field conditions. The pesticides were sprayed around the circumference of a circle and measurements of meteorology and air concentrations of pesticides were taken in the centre of the circle. The paper describes how the dimensions like the radius of the circle and height of the mast in the experimental set-up are found from theoretical considerations. A method to increase the confidence of the flux calculations is described. It utilizes that several substances were applied simultaneously and that a certain parameter in the fitted concentration profiles depends on turbulence only and thus have the same value for all substances. The design was used during two campaigns, conducted on the same location, one during fall on bare soil and one in spring on a barley crop.     

The use of a lacertid lizard as a model for reptile ecotoxicology studies: part 2--biomarkers of exposure and toxicity among pesticide exposed lizards

As part of a wider study examining the impacts of corn pesticides on lacertid lizards in north-western Portugal, we examined various physiological, biochemical, and histological biomarkers of exposure and effect among field populations of Podarcis bocagei. Biomarkers included body condition index, standard metabolic rate, locomotor performance, parasitization, glutathione oxidative pathways and related enzyme activity, lipid peroxidation and liver and testis histology. Few of the various biomarkers investigated provided statistically significant evidence of toxic effect. However, using a weight of evidence approach, we conclude that pesticides are affecting lizards living in the vicinity of pesticide exposed corn agriculture sites. Lizards from these locations present a profile of animals under metabolic stress with reduced condition indices, increased standard metabolic rate, lower incidence of hepatocyte vacuolation, altered iron metabolism, increased activation of GSH oxidation pathways, and even increased prevalence of hemoparasites.     

B-type esterases in the snail Xeropicta derbentina: an enzymological analysis to evaluate their use as biomarkers of pesticide exposure

The study was prompted to characterize the B-type esterase activities in the terrestrial snail Xeropicta derbentina and to evaluate its sensitivity to organophosphorus and carbamate pesticides. Specific cholinesterase and carboxylesterase activities were mainly obtained with acetylthiocholine (K_m = 77.2 mM; V_max = 38.2 mU/mg protein) and 1-naphthyl acetate (K_m = 222 mM, V_max = 1095 mU/mg protein) substrates, respectively. Acetylcholinesterase activity was concentration-dependently inhibited by chlorpyrifos-oxon, dichlorvos, carbaryl and carbofuran (IC50 = 1.35 × 10⁻⁵-3.80 × 10⁻⁸ M). The organophosphate-inhibited acetylcholinesterase activity was reactivated in the presence of pyridine-2-aldoxime methochloride. Carboxylesterase activity was inhibited by organophosphorus insecticides (IC50 = 1.20 × 10⁻⁵-2.98 × 10⁻⁸ M) but not by carbamates. B-esterase-specific differences in the inhibition by organophosphates and carbamates are discussed with respect to the buffering capacity of the carboxylesterase to reduce pesticide toxicity. These results suggest that B-type esterases in X. derbentina are suitable biomarkers of pesticide exposure and that this snail could be used as sentinel species in field monitoring of Mediterranean climate regions.     

Comprehensive estimate of the theoretical maximum daily intake of pesticide residues for chronic dietary risk assessment in Argentina

A chronic dietary risk assessment for pesticide residues was conducted for four age groups of the Argentinian population following the procedure recommended by the WHO. The National Theoretical Maximum Daily Intake (NTMDI) for 308 pesticides was calculated for the first time, using the Maximum Residue Limits (MRLs) from several Argentinean regulations and food consumption data from a comprehensive National Nutrition and Health Survey. The risk was estimated by comparing the TMDI with the Acceptable Daily Intakes (ADI) identified by various sources. Furthermore, for each of the compounds with a TMDI >65% of the ADI, a probabilistic analysis was conducted to quantify the probability of exceeding the ADI. In this study 27, 22, 10, and 6 active ingredients (a.i.) were estimated to exceed the 100% of the ADI for the different population groups: 6–23 month-old children, 2–5 year-old children, pregnant women, and 10–49 year-old women, respectively. Some of these ADI-exceeding compounds (carbofuran, diazinon, dichlorvos, dimethoate, oxydemeton-methyl and methyl bromide) were found in all four of these groups. Milk, apples, potatoes, and tomatoes were the foods that contributed most to the intake of these pesticides. The study is of primary importance for the improvement of risk assessment, regulations, and monitoring activities.     

Monitoring H2S air pollution caused by the industrial exploitation of geothermal energy: The pitfall of using lichens as bioindicators

This study showed that NH₃ emitted from geothermal power plants affects the surrounding epiphytic lichen vegetation and diversity, confounding the interpretation of lichen diversity counts in terms of air pollution by H₂S. The presence of nitrophytic lichen species around geothermal installations, determined by NH₃, caused relatively high diversity values that were not related with the levels of air pollution by H₂S. It is recommended that in the presence of NH₃ emission, nitrophytic species are excluded from the calculation of lichen diversity values.     

Ring test of a method for assessing the phototransformation of chemicals in water

Seven types of apparatus have been used to measure the quantum yields for direct phototransformation in water of 4 chemicals (pentachlorophenol; 2,4-dichlorophenol; 3,4-dichloroaniline; 4-nitrophenol) under polychromatic (12 laboratories) and monochromatic (3 laboratories) light, according to a common test protocol. The results with both types of light were in good agreement. The reproducibility and accuracy of quantum yields obtained with the ECETOC/University of Clermont-Ferrand apparatus with polychromatic light (6 laboratories) were similar to or better than those obtained with monochromatic light. A disadvantage of the method with polychromatic light is that the calculation is more complicated, but this can be overcome by the use of a desk-top computer. On the other hand experiments with polychromatic light permit the determination of quantum yields of substances of low photoreactivity.     

突发环境污染事件应对措施探讨

随着经济的高速发展,环境安全隐患逐渐显现,中国进入环境污染事故高发期,做好环境污染事件的防范工作刻不容缓。针对突发环境污染事件应对中存在的主要问题,提出了构建预防应急体系、建立有效的环境问责制、合理处置安全事故、建立全民参与机制和建立环境污染责任险制度等应对突发环境污染事件措施。     

The weight method: a new screening method for estimating pesticide deposition from knapsack sprayers in developing countries

Investigations of occupational and environmental risk caused by the use of agrochemicals have received considerable interest over the last decades. And yet, in developing countries, the lack of staff and analytical equipment as well the costs of chemical analyses make it difficult, if not impossible, to monitor pesticide contamination and residues in humans, air, water, and soils. A new and simple method is presented here for estimation of pesticide deposition in humans and soil after application. The estimate is derived on the basis of water mass balance measured in a given number of high absorbent papers under low evaporative conditions and unsaturated atmosphere. The method is presented as a suitable, rapid, low cost screening tool, complementary to toxicological tests, to assess occupational and environmental exposure caused by knapsack sprayers, where there is a lack of analytical instruments. This new method, called the “weight method”, was tested to obtain drift deposition on the neighbouring field and the clothes of the applicator after spraying water with a knapsack sprayer in one of the largest areas of potato production in Colombia. The results were confirmed by experimental data using a tracer and the same set up used for the weight method. The weight method was able to explain 86% of the airborne drift and deposition variance.     

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min^?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76–128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m^?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

Pesticide residues in rivers of a Brazilian Rain Forest Reserve: assessing potential concern for effects on aquatic life and human health

Pesticide residues in water, sediment, and fish samples from rivers of a Brazilian Rain Forest Reserve were measured in November 1998, March 1999, and January 2000. Concentrations of the individual pesticides were compared to ecotoxicological benchmarks based on acute toxicity tests, and to regulatory guidelines to determine the potential concern for effects on aquatic life and human health. Pesticides and metabolites were detected at all 7 sites surveyed. Residues of a total of 27 pesticides or metabolites were found in water and/or sediment samples and fish have accumulated some of the most persistent of these residues. Measured concentrations in water and sediment indicated concern for preservation of aquatic fauna. Several pesticides in water were above levels for drinking water recommended by Brazilian and/or European Union authorities, indicating also a concern for human health.     

Improving the knowledge of pesticide and nitrate transfer processes using age-dating tools (CFC, SF6, H) in a volcanic island (Martinique, French West Indies)

Numerous successful examples of CFC and SF₆ groundwater dating applications were recently published. However the proposed CFC/SF₆ method needs various hydrodynamic parameters that are not always available. In order to predict groundwater-quality trends in areas where the hydrogeological context is poorly known, a dating method using tritium, CFC and SF₆ was successfully implemented in Martinique. Hydrogeological understanding is limited in this volcanic island where groundwater contamination by pesticides and nitrate has been recently proven in various areas. A negative correlation was observed between nitrate concentrations and groundwater ages while pesticide contamination showed a more complex schema. Consequently the presence of old groundwater clearly explained the absence or low pesticide and nitrate concentrations in some areas. However a possible degradation of the water quality is to be feared in the future. In view of the relatively long transfer times and the complexity of the remobilization processes of solutes, the expected effects of any modifications in the use of fertilizers, or of changes in pesticide-use legislation, would take a long time to become apparent.     

Fate of metolachlor under subirrigation in a sandy soil: A lysimeter study

Abstract

A three‐year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2‐chloro‐N‐(2‐ethyl‐6‐methlphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography.

Results obtained in this three year study, (1993–1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures

In the routine São Paulo state (Brazil) surface water quality-monitoring program, which includes the Salmonella microsome mutagenicity assay as one of its parameters, a river where water is taken and treated for drinking water purposes has repeatedly shown mutagenic activity. A textile dyeing facility employing azo-type dyes was the only identifiable source of mutagenic compounds. We extracted the river and drinking water samples with XAD4 at neutral and acidic pH and with blue rayon, which selectively adsorbs polycyclic compounds. We tested the industrial effluent, raw, and treated water and sediment samples with YG1041 and YG1042 and compared the results with the TA98 and TA100 strains. The elevated mutagenicity detected with YG-strains suggested that nitroaromatics and/or aromatic amines were causing the mutagenicity detected in the samples analyzed. Positive responses for the blue rayon extracts indicated that mutagenic polycyclic compounds were present in the water samples analyzed. The mutagen or mixture of mutagens present in the effluent and water samples cause mainly frameshift mutations and are positive with and without metabolic activation. The Salmonella assay combined with different extraction procedures proved to be very useful in the identification of the origin of the pollution and in the identification of the classes of chemical compounds causing the mutagenic activity in the river analyzed.     

A method for the analysis of organophosphorus pesticide residues in Mexican axolotl

A method based on matrix solid-phase dispersion (MSPD) was developed for quantitative extraction of three organophosphorus pesticides (OPPs) from the Mexican axolotl, Ambystoma mexicanum. The determination was carried out using high- performance liquid chromatography (HPLC) with diode array spectrophotometric UV detection (DAD). The MSPD extraction with octadecylsilyl (C18) sorbent combined with a silica gel clean-up and acetonitrile elution was optimised for chlorpyrifos, fenthion and methyl parathion. The method was validated, yielding recovery values higher than 90%. The precision, expressed as the relative standard deviation (RSD), was less than or equal to 6% in muscle samples at spiking levels of 10 and 5 ppm. Linearity was studied from 15 to 60 ppm for chlorpyrifos and fenthion, and from 7.5 to 30 ppm for methyl parathion. The limits of detection (LODs) were found to be less than or equal to 0.5 ppm_.This method was applied to the analysis of samples from a chlorpyrifos-exposed axolotl, demonstrating its use as an analytical tool for toxicological studies.     

Pesticides in the groundwater of a spring draining a sandy aquifer: temporal variability of concentrations and fluxes

A 250 ha agricultural catchment has been characterized with respect to its hydrogeology and groundwater contamination by pesticides from October 1999 to August 2004. Five years after the ending of atrazine (At) application, used since the sixties, At and deethylatrazine (DEA) are still systematically quantified at the outlet of the watershed with concentrations from 0.07 to 0.43 microg l(-1) for At, and between 0.14 and 1.16 microg l(-1) for DEA. Isoproturon and chlortoluron are detected in only one (0.3 microg l(-1)) and two (0.7 and 2.0 microg l(-1)) of the 124 semi-monthly samples, respectively. DEA concentrations can be very different between two samples with a 15-day time step. The annual mean exported fluxes of cumulated At and DEA are stable, which indicates a long time transfer in the unsaturated or saturated zone with a progressive leaching of the stock of At and DEA probably accumulated in the soil and the vadose zone. These fluxes, between 0.90% and 2.82% of the annual mean dose of At applied before 1999, similar to those calculated in several studies at the bottom of the root zone, could be explained by low adsorption and degradation properties of At and DEA in the unsaturated and saturated zone.     

Modelling the fate of hydrophobic organic contaminants in a boreal forest catchment: A cross disciplinary approach to assessing diffuse pollution to surface waters

The fate of hydrophobic organic compounds (HOCs) in soils and waters in a northern boreal catchment was explored through the development of a chemical fate model in a well-characterised catchment system dominated by two land types: forest and mire. Input was based solely on atmospheric deposition, dominated by accumulation in the winter snowpack. Release from soils was governed by the HOC concentration in soil, the soil organic carbon fraction and soil-water DOC content. The modelled export of selected HOCs in surface waters ranged between 11 and 250 ng day⁻¹ during the snow covered period, compared to 200 and 9600 ng/d during snow-melt; highlighting the importance of the snow pack as a source of these chemicals. The predicted levels of HOCs in surface water were in reasonable agreement to a limited set of measured values, although the model tended to over predict concentrations of HOCs for the forested sub-catchment, by over an order of magnitude in the case of hexachlorobenzene and PCB 180. This possibly reflects both the heterogeneity of the forest soils and the complicated and changing hydrology experienced between the different seasons.     

Environmental conditions enhance toxicant effects in larvae of the ground beetle Pterostichus oblongopunctatus (Coleoptera: Carabidae)

The wide geographical distribution of ground beetles Pterostichus oblongopunctatus makes them very likely to be exposed to several environmental stressors at the same time. These could include both climatic stress and exposure to chemicals. Our previous studies demonstrated that the combined effect of nickel (Ni) and chlorpyrifos (CHP) was temperature (T)-dependent in adult P. oblongopunctatus. Frequently the different developmental stages of an organism are differently sensitive to single stressors, and for a number of reasons, such as differences in exposure routes, their interactions may also take different forms. Because of this, we studied the effects of the same factors on the beetle larvae. The results showed that all factors, as well as their interactions, influenced larvae survival. The synergistic effect of Ni and CPF was temperature-dependent and the effect of Ni × T interaction on the proportion of emerged imagines indicated stronger toxicity of Ni at 25 °C than at 10 °C.