Expres: An expert system for assessing the fate of pesticides in the subsurface

The expert system described here is designed to aid regulatory personnel in their assessment of the potential for pesticides to contaminate the soil and groundwater environment. The expert system, known as EXPRES (EXpert system for Pesticide Regulatory Evaluation Simulations), consists of existing numerical models which are used to simulate the transport and transformation of pesticides in the unsaturated zone, coupled with a knowledge-based system that guides the user through the choice of all the necessary information for characterizing the physical, meteorological, hydrogeological, pedological and agricultural settings of typical agricultural regions across Canada, as required by the pesticide model. The expert system is designed to be used as a management tool to aid in policy decisions. Thus, its purpose is to provide an assessment of the potential hazards and to identify if further study is warranted.     

An analytical model for the assessment of pesticide exposure levels in soils and groundwater

The movement and degradation of pesticide residues in soils and groundwater are complex processes affected by soil physical, (bio)chemical, and hydrogeological properties, climatic conditions, and agricultural practices. This work presents a physically-based analytical model suitable for long-term predictions of pesticide concentrations in groundwater. The primary interest is to investigate the impact of soil environment, related physical and (bio)chemical processes, especially, volatilization, crop uptake, and agricultural practices on long-term vulnerability of groundwater to contamination by pesticides. The soil is separated into root and intermediate vadose zones, each with uniform properties. Transport in each soil zone is modeled on the basis of complete mixing, by spatial averaging the related point multiphase-transport partial differential equation (i.e., linear-reservoir models). Transport in the aquifer, however, is modeled by a two-dimensional advection-dispersion transport equation, considering adsorption and first-order decay rate. Vaporization in the soil is accounted for by assuming liquid-vapor phase partitioning using Henry's law, and vapor flux (volatilization) from the soil surface is modeled by diffusion through an air boundary layer. Sorption of liquid-phase solutes by crops is described by a linear relationship which is valid for first-order (passive) crop uptake. The model is applied to five pesticides (atrazine, bromacil, chlordane, heptachlor, and lindane), and the potential for pesticide contamination of groundwater is investigated for sandy and clayey soils. Simulation results show that groundwater contamination can be substantially reduced for clayey soil environments, where bio(chemical) degradation and volatilization are most efficient as natural loss pathways for the pesticides. Also, uptake by cross can be a significant mechanism for attenuating exposure levels in ground-water especially in a sandy soil environment, and for relatively persisting pesticides. Further, simulations indicate that changing agricultural practices can have a profound effect on vulnerability of groundwater to mobile and relatively persisting pesticides.     

PESTICIDE OCCURRENCE IN GROUNDWATER IN TULARE COUNTY, CALIFORNIA

Geographic Information Systems (GIS) and statistical methodswere used to identify the major factors affecting pesticideleaching in groundwater from agricultural fields in TulareCounty, California. Residues of bromacil, diuron, and simazineincreased in groundwater during the 1980s. Bromacil, diuron,and simazine contamination were positively correlated to cropdiversity and water demand. Diuron and simazine were positively correlated to groundwater depth and negatively correlatedto soil water-holding capacity. DBCP concentration in groundwater was related to the crop coverage. The Goss model wasused to examine soil-pesticide interactions and a PesticideContamination Index (PCI) was developed. Areas having highleaching potentials were mainly associated with citrus andorchards and coarse-textured sandy soils along the SierraNevada foothills, while areas having low leaching potentialswere associated with field crops and clay soils of the southwest region. The PCI was largest for DBCP during the 1980s,suggesting that it was the most significant contaminant before1977 when it was widely used; however, wells were not testedfor this pesticide during that period. Twelve years after DBCPwas banned, it was still the most significant health riskcontaminant. Spatial maps showing the distribution of leachingpotentials and soil interactions for these pesticides canprovide useful information to regulatory and planning agenciesfor land use planning and pesticide management.     

Nitrate Leaching by Atmospheric N Deposition to Upper Groundwater in the Sandy Regions of The Netherlands in 1990

Anthropogenic increase in atmospheric nitrogen (N) deposition in nature areas results in nitrate leaching to groundwater, threatening its quality. Member states of the European Union are obliged to reduce groundwater nitrate concentrations and to monitor this reduction. The relationship between N deposition and groundwater nitrate concentrations is quantified using a field survey and geographical information. Nitrate concentrations of the uppermost metre of groundwater in nature areas in the sandy regions in 1990 were related to geographical data by means of regression analysis. In this way nitrate concentrations could be explained by potential ammonia deposition, soil type, vegetation and land use. We found that about 35% of 54 kg ha(-1) a(-1) atmospheric N deposition was leached to the upper groundwater as nitrate, resulting in a mean NO3 concentration of about 30 mg L(-1). The critical N load for exceeding the EC limit value (50 mg L(-1)) in the sandy regions of The Netherlands composed of natural vegetation will be about 80 kg ha(-1) a(-1). Leaching is less than expected for nature areas but comparable with leaching of N surpluses in pastures in The Netherlands. A reduction in nitrate leaching by 25% or more can currently be detected via a new field survey.     

A Time-Dependent System for Evaluating Groundwater Contamination Hazard Rating of Municipal Solid Waste Dumps

In developing countries, several old municipal solid waste dumps (unlined landfills) exist adjacent to large cities, releasing contaminants to the underlying aquifer, thus posing the hazard of groundwater contamination. These uncontrolled waste dumps need to be prioritized in terms of the groundwater contamination hazard posed by them, so that necessary control and remedial measures can be undertaken in a phased manner. This paper presents a time-dependent system for evaluating groundwater contamination hazard rating of municipal solid waste dumps. The system is based on source–pathway–receptor relationships and evaluates the relative value of hazard posed by a site over its entire leaching life, on a scale of 0–1,000. The system parameters have been selected based on literature and expert opinions. The Delphi technique is used to derive the relative importance weights of the system parameters. The proposed system is compared with six selected existing hazard rating systems. The comparison, made by way of score range analysis, shows that the proposed system exhibits a much wider range of hazard scores for various scenarios of site conditions, and hence the proposed system is more sensitive to varied site conditions. The application of different systems to six municipal solid waste dumps located in four cities of India shows that, whereas the existing systems individually produce clustered scores and return the same rank to more than one site, the proposed system produces significantly varying scores and return different ranks to different sites. This demonstrates that the proposed system improves decision making and makes a better basis for prioritization of municipal solid waste dumps for adopting control and remedial measures.     

Pesticide occurrence in groundwater and the physical characteristics in association with these detections in Ireland

This study explores the associations of pesticide occurrence in groundwater to geological characteristics of the monitoring points (MPs) contributing area. Pesticide analyses were undertaken during a 2-year groundwater monitoring campaign which generated 845 samples. MCPA and mecoprop were the most frequently detected pesticides in groundwater. Each MP (n?=?158) had a specifically delineated zone of contribution (ZOC) and the dominant physical characteristics present from nine national datasets were recorded for each ZOC. Associations between detections in groundwater and the dominant physical characteristic in each MPs ZOC tested were then statistically analyzed using Fisher’s exact test, logistic regression, and multiple logistic regression. The original physical characteristic datasets used that were associated with detections in groundwater were the type of MP, aquifer type, and Quaternary deposit type. Logistic regression revealed that springs, regionally important aquifer types, aquifers with a karstic flow regime, and alkaline Quaternary deposits in existence above karst aquifers in a MP’s ZOC were more likely to have a pesticide detection in groundwater. Multiple regression from this exploratory work showed some mutual dependency between soil association, aquifer type, and the Geological Survey of Ireland groundwater vulnerability map. The combination of national monitoring data and physical attribute datasets can be used to explore key areas where groundwater is more vulnerable to pesticide contamination.     

Numerical modelling of the environmental impact of landfill leachate leakage on groundwater quality – a field application

Waste disposal facilities are mainly responsible for the gradual quality degradation of subsurface freshwater reservoirs. The main objective of this work is to identify the groundwater contamination risk due to potential leachate leakage and seepage beneath the municipal landfill of the City of Patras in Greece. A groundwater and leachate mass transport model of the underlying aquifer was developed for this purpose. The derived simulation results indicate that, depending on the permeability of the soil at the location of leakage, the contamination risk for the groundwater can be high. In order to quantify the magnitude and the extent of the leakage, a risk assessment model for the leachate contaminant plume was developed. The risk assessment analysis shows that the municipal drinking wells are under high risk of contamination.     

Classification of alluvial soils according to their potential environmental risk: a case study for Belgian catchments

Alluvial soils may represent important sinks of contaminants as a result of the deposition of contaminated sediments along the river by overbank flooding or after dredging. Because of the erosion of alluvial deposits or the release of contaminants from sediments, alluvial soils can also be a source of contamination. In this paper, a risk assessment for contaminated (alluvial) soils is presented. The approach, mainly based on physico-chemical soil characteristics, single extractions and leaching tests, is illustrated by means of a case study from four Belgian catchments. The extractions and leaching tests that were used have been validated by European testing programs and can provide valuable information for classifying the potential environmental risks of soils. Irrespective of the location, pH, organic carbon content and 'mobilisable' metal concentrations were the most important factors explaining 'mobile' metal concentrations in the alluvial soils. Additionally, the data of the physico-chemical soil characterization, extractions and leaching tests were combined with local and regional factors to classify the alluvial soils in different categories according to their actual and potential risk for the environment.     

Assessment of phenol infiltration resilience in soil media by HYDRUS-1D transport model for a waste discharge site

The movement of contaminants through soil imparts a variety of geo-environmental problem inclusive of lithospheric pollution. Near-surface aquifers are often vulnerable to contamination from surface source if overlying soil possesses poor resilience or contaminant attenuation capacity. The prediction of contaminant transport through soil is urged to protect groundwater from sources of pollutants. Using field simulation through column experiments and mathematical modeling like HYDRUS-1D, assessment of soil resilience and movement of contaminants through the subsurface to reach aquifers can be predicted. An outfall site of effluents of a coke oven plant comprising of alarming concentration of phenol (4–12.2 mg/L) have been considered for studying groundwater condition and quality, in situ soil characterization, and effluent characterization. Hydrogeological feature suggests the presence of near-surface aquifers at the effluent discharge site. Analysis of groundwater of nearby locality reveals the phenol concentration (0.11–0.75 mg/L) exceeded the prescribed limit of WHO specification (0.002 mg/L). The in situ soil, used in column experiment, possess higher saturated hydraulic conductivity (K _S ?=?5.25?×?10^?4 cm/s). The soil containing 47 % silt, 11 % clay, and 1.54 % organic carbon content was found to be a poor absorber of phenol (24 mg/kg). The linear phenol adsorption isotherm model showed the best fit (R ²?=?0.977, RMSE?=?1.057) to the test results. Column experiments revealed that the phenol removal percent and the length of the mass transfer zone increased with increasing bed heights. The overall phenol adsorption efficiency was found to be 42–49 %. Breakthrough curves (BTCs) predicted by HYDRUS-1D model appears to be close fitting with the BTCs derived from the column experiments. The phenol BTC predicted by the HYDRUS-1D model for 1.2 m depth subsurface soil, i.e., up to the depth of groundwater in the study area, showed that the exhaustion point was reached within 12 days of elapsed time. This clearly demonstrated poor attenuation capacity of the soil to retard migration of phenol to the groundwater from the surface outfall site. Suitable liner, based on these data, may be designed to inhibit subsurface transport of phenol and thereby to protect precious groundwater from contamination.     

Groundwater contamination and its effect on health in Turkey

The sources of groundwater pollution in Turkey are identified, and pathways of contaminants to groundwater are first described. Then, the effects of groundwater quality on health in Turkey are evaluated. In general, sources of groundwater contamination fall into two main categories: natural and anthropogenic sources. Important sources of natural groundwater pollution in Turkey include geological formations, seawater intrusion, and geothermal fluid(s). The major sources of anthropogenic groundwater contamination are agricultural activities, mining waste, industrial waste, on-site septic tank systems, and pollution from imperfect well constructions. The analysis results revealed that natural contamination due to salt and gypsum are mostly found in Central and Mediterranean regions and arsenic in Aegean region. Geothermal fluids which contain fluoride poses a danger for skeleton, dental, and bone problems, especially in the areas of Denizli, Isparta, and Ayd?n. Discharges from surface water bodies contaminate groundwater by infiltration. Evidence of such contamination is found in Upper K?z?l?rmak basin, Gediz basin, and Büyük Melen river basin and some drinking water reservoirs in ?stanbul. Additionally, seawater intrusion causes groundwater quality problems in coastal regions, especially in the Aegean coast. Industrial wastes are also polluting surface and groundwater in industrialized regions of Turkey. Deterioration of water quality as a result of fertilizers and pesticides is another major problem especially in the regions of Mediterranean, Aegean, Central Anatolia, and Marmara. Abandoned mercury mines in the western regions of Turkey, especially in ?anakkale, ?zmir, Mu?la, Kütahya, and Bal?kesir, cause serious groundwater quality problems.     

Using multi-criteria decision analysis to assess the vulnerability of drinking water utilities

Outbreaks of microbiological waterborne disease have increased governmental concern regarding the importance of drinking water safety. Considering the multi-barrier approach to safe drinking water may improve management decisions to reduce contamination risks. However, the application of this approach must consider numerous and diverse kinds of information simultaneously. This makes it difficult for authorities to apply the approach to decision making. For this reason, multi-criteria decision analysis can be helpful in applying the multi-barrier approach to vulnerability assessment. The goal of this study is to propose an approach based on a multi-criteria analysis method in order to rank drinking water systems (DWUs) based on their vulnerability to microbiological contamination. This approach is illustrated with an application carried out on 28 DWUs supplied by groundwater in the Province of Québec, Canada. The multi-criteria analysis method chosen is measuring attractiveness by a categorical based evaluation technique methodology allowing the assessment of a microbiological vulnerability indicator (MVI) for each DWU. Results are presented on a scale ranking DWUs from less vulnerable to most vulnerable to contamination. MVI results are tested using a sensitivity analysis on barrier weights and they are also compared with historical data on contamination at the utilities. The investigation demonstrates that MVI provides a good representation of the vulnerability of DWUs to microbiological contamination.     

Use of cluster and principal component analyses to profile areas in California where ground water has been contaminated by pesticides

An empirical approach to profiling areas of ground water contamination by pesticides was devised that did not rely upon determining the level of vulnerability between land areas and that did not assume any particular pathway for ground water contamination. Climatic and soil data were obtained for 1-square mile sections of land in California where pesticide residues had been found in well water samples and the detection was attributed to legal agricultural applications. These sections were designated as known contaminated (KC) sections. Climate and soil data were also obtained for sections which lacked either well sampling data or a positive pesticide detection. These sections were designated as candidate sections. Statistical procedures were used to cluster groups of KC sections first with respect to climate characteristics and then with respect to soil characteristics. Principal components analysis (PCA) was used to construct a statistical profile of soil variables for each cluster of KC sections. A method based on the PCA was developed to compare the similarity of soil profiles derived for each KC section cluster to individual candidate sections. Since the profiling scheme was based only on data from KC sections, candidate sections that did not match any KC cluster profile could only be considered dissimilar to contaminated sections, receiving a status of not-classified. This profiling method is flexible and it can be revised to incorporate updated well sampling information.     

Local physical habitat quality cloud the effect of predicted pesticide runoff from agricultural land in Danish streams

The combination of intensive agricultural activities and the close connectivity between land and stream emphasise the potential risk of pesticide exposure in Danish streams. Benthic macroinvertebrates are applied in the assessment of stream ecological status, and some sensitive species have been shown to respond strongly to brief pulses of pesticide contamination. In this study we investigate the impact of agriculturally derived pesticides on stream macroinvertebrate communities in Denmark. As a measure of toxic pressure we apply the Runoff Potential. We investigated a total of 212 streams. These were grouped into distinct classes according to the magnitude of pesticide contamination in the period from 2003-2006. A total of 24 different macroinvertebrate indices were applied to detect effects of pesticide runoff (e.g. the SPEAR-index and the number of EPT taxa). We found high predicted pesticide runoff in 39% of the streams, but we found no significant effect of predicted pesticide exposure on stream macroinvertebrate indices. We, additionally, examined the influence of a series of environmental parameters ranging from site scale to catchment scale on the macroinvertebrate community. Relative proportions of gravel, sand and silt in bed sediments explained most of the variation in macroinvertebrate indices as well as the upstream riparian habitat quality. We suggest that the Runoff Potential model overestimate pesticide runoff contamination in Danish streams due the presence of buffer strips enforced by Danish legislation. When pesticide runoff contamination is low to moderate, poor physical properties (indirectly related to agricultural activity) are the main impediment for the ecological quality of Danish streams.     

Fate of carbosulfan and monocrotophos in sandy loam soils of Pakistan under field conditions at different watertable depths

Information regarding pesticide mobility is critical for the evaluation of pesticide management practices. For this purpose, lysimetric studies were conducted to develop assessment schemes to protect groundwater from unacceptable effects caused by pesticide use. By using these studies, specific monitoring actions and prevention measures for the protection of waters can be studied, and the results thus obtained can provide the local authorities and the decision makers with an identification tool for demarcating risk areas. Pesticide residues were found at the bottom of lysimeters in the following pattern i.e., 1.52 > 2.1 > 2.74 m which could represent an "index of risk" for groundwater pollution. Regressions built for carbofuran and monocrotophos against watertable depths showed a decreasing trend of pesticide in higher watertable treatments. These findings support the existence of a significant role for chromatographic flow in sandy texture soil. Moreover, the higher values of pesticide residue at the bottom of lysimeters reflect that chromatographic flow as well as preferential flow pattern prevails during higher precipitation events. The precipitation received during the study was higher than the 10 year average and can be considered relatively as a worst case scenario. Finally, the authors have recommended a standardized pesticide monitoring scheme for groundwater in accordance with the already validated generic schemes in developed countries.     

基于双指标多等级的土壤重金属生态风险评价

采用土壤中重金属的全量和有效态双重指标,建立基于多等级综合评估的土壤中重金属生态风险评价模型,将联合概率曲线法引入土壤评价模型,分析重金属暴露浓度与毒性数据的概率分布,考察重金属对土壤生物的毒害程度,从而确定土壤中重金属对于生态系统的风险。建立从简单到复杂的多等级综合评价方法,表征重金属的污染等级、浓度效应、多种重金属污染物的协同效应、不同重金属的毒性效应和土壤对不同重金属污染物的敏感性。选择典型地区采集有代表性的土壤样品,测定不同重金属的总量和有效态,验证评价模型的实用性和评价分级的合理性。旨在解决土壤重金属风险评价的方法学问题,为土壤环境质量管理提供支持。     

Leachable 226Ra in Philippine phosphogypsum and its implication in groundwater contamination in Isabel, Leyte, Philippines

Phosphogypsum (PG), the major waste material in phosphate fertilizer processing, has been known to contain enhanced levels of naturally-occurring radionuclides especially (226)Ra.The lack of radioactivity data regarding Philippine phosphogypsum and its environmental behavior in the Philippine setting has brought concern on possible contamination of groundwater beneath the phosphogypsum ponds in Isabel, Leyte, Philippines. The radioactivity of Philippine phosphogypsum was determined and the leaching of (226)Ra from phosphogypsum and through local soil was quantified. Level of (226)Ra in groundwater samples in Isabel, Leyte, Philippines was also quantified to address the primary concern. It was found that the (226)Ra activity in Philippine phosphogypsum is distributed in a wide range from 91.5 to 935 Bq/kg. As much as 5% of (226)Ra can be leached from Philippine PG with deionized water. In vitro soil leach experiments suggest that the soil in the phosphate fertilizer plant area would be able to deter the intrusion of (226)Ra into the water table. Compared to reported values of natural groundwater levels of (226)Ra, the concentration of this radionuclide in Isabel, Leyte groundwater suggest that there is no (226)Ra intrusion brought about by the presence of phosphogypsum ponds in the area.     

Heavy metal concentrations in groundwaters and soils of Thane Region of Maharashtra, India

Thane district is one of the most industrialized districts in Maharashtra. The heavy industrialization and the increasing urbanization are responsible for the rapidly increasing stress on the water and soil environment of the area. Therefore, an attempt has been made through comprehensive study on the groundwater contamination and soil contamination due to heavy metals in Thane region of Maharashtra. The area undertaken for the study was Thane and its suburbans Kalwa, Divajunction, Dombivali, Kalyan, and Ulhasnagar. Industrialization and urbanization lead to generation of large volumes of wastewater from domestic, commercial, industrial, and other sources, which discharged in to natural water bodies like river and creek in this region. Groundwater samples and soil samples were collected from residential, commercial, agriculture, and industrial areas. Groundwater samples were analyzed for various water quality parameters. The analytical data shows very high concentration of total dissolved solids, total hardness, total alkalinity, chemical oxygen demand, chloride etc. Groundwater and soil samples were analyzed for ten heavy metals by inductively coupled plasma (ICPE-9000) atomic emission spectroscopy. The analytical data reveal that, very high concentration level of arsenic, cadmium, mercury, and nickel throughout the industrial area. The random dumping of hazardous waste in the industrial area could be the main cause of the groundwater and soil contamination spreading by rainwater and wind. In the residential areas the local dumping is expected to be the main source for heavy metals. A comparison of the results of groundwater with WHO guidelines show that most of the groundwater sampling station are heavily contaminated with organic matter and heavy metals. Groundwater samples are heavily contaminated by arsenic, cadmium, mercury, and nickel. Similarly, the results of heavy metals in soil compared with Swedish soil guideline values for polluted soil show that soil samples collected from residential, commercial and industrial areas are heavily contaminated by arsenic, cadmium, mercury, and nickel.     

Movement of petroleum hydrocarbons in sandy coastal soils

In a field trial, oiled beach sand was buried in a coastal dune system in south Wales. A monitoring programme was designed to assess the rate of leaching of inorganic ions and hydrocarbons from the deposit. Active breakdown of the weathered oil occurred within the oiled beach sand, but hydrocarbons from the original material, or arising as a result of degradation, did not follow the same leaching pattern as inorganic ions; they remained within the original deposit. The results suggest that weathered oil coming ashore from spills at sea can be mixed with sand and buried to degrade in coastal soils, without risk of groundwater contamination by hydrocarbons.     

CLFUG: A GIS‐scaleable model of pesticide fate in the soil–groundwater system based on clearance and fugacity paradigms

A model of pesticide transport through the soil profile based on clearance and fugacity paradigms is presented, and an example of its application in a GIS environment is shown. A validation of the model at the field plot scale is presented using data obtained at a crop in a semiarid irrigated agricultural basin which was treated with Lindane. The adequacy at the regional scale is tested by inspection of the model predictions and the measured concentrations of the pesticide obtained from a regional phreatimetric net. The clearance concept is used to obtain estimates of the volumes of some environmental phases. These are further used to solve the equations of thermodynamic equilibrium at equal fugacity and obtain concentration estimates. The model closely reproduces the observed percolation trends, and is consistent with the regional pattern of Lindane distribution in groundwater. An application of the model as unitary module for the simulation of non‐point pesticide sources in a raster GIS frame is shown. Its performance (run time, data needed, etc.) is comparable to that of other existing algorithms, and presents some advantages to planners and evaluators of environmental quality in that it incorporates an explicit 2‐D approach and allows the identification of polluted areas downslope with respect to those directly treated with the pesticides. Further, it can be implemented in a variety of GIS and spatial data processors.