Evaluation of natural and anthropogenic influences on the Guadalquivir River (Spain) by dissolved heavy metals and nutrients

To evaluate both the natural and anthropogenic influences on surface waters of Guadalquivir River (SW-Spain), concentrations of dissolved trace metals (Mn, Co, Ni, Cu, Cd, Zn, and Pb), inorganic nutrients (N-NH(4)(+), N-NO(3)(-), N-NO(2)(-), and P-PO(4)(3-)) and other variables as conductivity, pH, dissolved oxygen (DO) and suspended solids (SS) were measured during a three-years period (2001-2003). Samples were taken at 26 stations twice a year, during rain and dry periods. The analysis of variance (ANOVA) suggested that temporal variations within the period of study were statistically negligible. Spatial distributions identified three different zones, mainly influenced by sewage (Eastern Zone), agriculture runoffs (Central Zone), and estuarine processes (Western Zone), respectively. Principal Component and Cluster Analysis allowed to identify the variables controlling the water quality of each zone as: N-NH(4)(+), N-NO(2)(-), Mn, and Co, (Eastern Zone), SS, and P-PO(4)(3-) (Central Zone), and Cd, pH and conductivity (Western Zone). Other variables such as Ni, Cu, Zn or N-NO(3)(-), influenced two different zones, while Pb presented a singular behavior.     

Herbicide leaching on a recharge area of the Guarany aquifer in Brazil

The region of Ribeir?o Preto City, located in Southeast of Brazil, S?o Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 microg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 microg/L, which is above the allowable 0.1 microg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, "Chemical Movement in Layered Soil," as simulation model. No leaching into the depth of the water table at 40 m was found.     

Herbicide Leaching on a Recharge Area of the Guarany Aquifer in Brazil

Abstract

The region of Ribeirão Preto City, located in Southeast of Brazil, São Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 μg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 μg/L, which is above the allowable 0.1 μg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, “Chemical Movement in Layered Soil,” as simulation model. No leaching into the depth of the water table at 40 m was found.     

Spatial and temporal distribution of the leaching of surface applied tracers from an irrigated monolith of a loamy vineyard soil

Fresh water scarcity is an increasing problem worldwide. Strategies to alleviate water scarcity include the use of low-quality water for irrigation. The risk of groundwater contamination by pollutants in this water is affected by soil heterogeneity and preferential flow. These risk factors can be assessed by measuring the spatio-temporal redistribution of uniformly applied water and solutes. We placed a soil monolith (height 29 cm) from an Australian vineyard on a 100-cell multi-compartment sampler (MCS). At this vineyard, treated wastewater is used in response to the severe shortage of water in the summer. We studied the leaching risk associated with heterogeneous or preferential flow by irrigating the soil column with 24 applications to simulate one year. We applied simulated rainfall as well as wastewater (which contained chloride) during summer while relying on rainfall only in winter. We compared the chloride leaching with the leaching of bromide, which was applied during one of the applications as a pulse. During the entire simulated year, leaching of solutes from the monolith was measured. The results indicate that the assumption of uniform flow would underestimate the risk for the fresh groundwater reserves: 25 % of the solutes are transported though 6 % of the soil’s cross-section. The spatial distribution of drainage and solute leaching varied little during the experiment. Consequently, the mass flux density pattern of the bromide pulse was comparable to that of the repeatedly applied chloride. However, the MCS data suggested lateral ‘escape’ from chloride to non-mobile areas, which means in the long run, considerable quantities of these solutes can build up in areas that do not receive irrigation water.     

Evaluation of soil temperature effect on herbicide leaching potential into groundwater in the Brazilian Cerrado

The effect of annual variations in the daily average soil temperatures, at different depths, on the calculation of pesticide leaching potential indices is presented. This index can be applied to assess the risk of groundwater contamination by a pesticide. It considers the effects of water table depth, daily recharge net rate, pesticide sorption coefficient, and degradation rate of the pesticide in the soil. The leaching potential index is frequently used as a screening indicator in pesticide groundwater contamination studies, and the temperature effect involved in its calculation is usually not considered. It is well known that soil temperature affects pesticide degradation rates, air-water partition coefficient, and water-soil partition coefficient. These three parameters are components of the attenuation and retardation factors, as well as the leaching potential index, and contribute to determine pesticide behavior in the environment. The Arrhenius, van't Hoff, and Clausius-Clapeyron equations were used in this work to estimate the soil temperature effect on pesticide degradation rate, air-water partition coefficient, and water-soil partition coefficient, respectively. The relationship between leaching potential index and soil temperature at different depths is presented and aids in the understanding of how potential pesticide groundwater contamination varies on different climatic conditions. Numerical results will be presented for 31 herbicides known to be used in corn and soybean crops grown on the municipality of S?o Gabriel do Oeste, Mato Grosso do Sul State, Brazil.     

One-at-a-time sensitivity analysis of pollutant loadings to subsurface properties for the assessment of soil and groundwater pollution potential

Chemical leak was numerically simulated for four chemical substances: benzene (light non-aqueous phase liquid (NAPL)), tetrachloroethylene (dense NAPL), phenol (soluble in water), and pentachlorophenol (white crystalline solid) in a hypothetical subsurface leak situation using a multiphase compositional transport model. One metric ton of chemical substances was assumed to leak at a point 3.51 m above the water table in a homogeneous unconfined aquifer which had the depth to water table of 7.135 m, the hydraulic gradient of 0.00097, the recharge rate of 0.7 mm/day, and the permeability of 2.92?×?10^?10 m². For comparison, surface spill scenarios, which had a long pathway from source to the water table, were simulated. Using the model results, point-source pollutant loadings to soil and groundwater were calculated by multiplying mass, impact area, and duration above and below the water table respectively. Their sensitivity to subsurface properties (depth to water table, recharge rate, porosity, organic carbon content, decay rate, hydraulic gradient, capillary pressure, relative permeability, permeability) was analyzed, with changing each parameter within acceptable ranges. The study result showed that the pollutant loading to groundwater was more sensitive to the subsurface properties than the pollutant loading to soil. Decay rate, groundwater depth, hydraulic gradient and porosity were influential to pollutant loadings. The impact of influential parameters on pollutant loadings was nonlinear. The dominant subsurface properties of pollution loadings (e.g., decay rate, groundwater depth, hydraulic gradient, and porosity for groundwater) also affect the vulnerability, and the subsurface pollutant loadings defined in this study are dependent on chemical properties as well, which indicates that the influential hydrogeological and physicochemical parameters to pollutant loadings can be used for pollution potential assessment. The contribution of this work is the suggestion that the sensitivity of pollutant loadings can be used for pollution potential assessment. Soil and groundwater pollution potential of chemicals are discussed altogether for leak scenarios. A physics-based model is used to understand the impact of subsurface properties on the fate and transport of chemicals above and below the water table, and consequently their impact on the pollutant loading to soil and groundwater.

     

The application of a simplified method to map the aerobic acetate mineralization rates at the groundwater table of the Netherlands

A simplified method is used to assess the microbial activity of subsoils and soils across a broad geographic scale. Acetate was selected because it is a major intermediate in catabolic biochemical pathways. In order to get minimal disturbance, only a small amount of tritium labelled acetate and water is added to the subsoil material. After an incubation time, the subsoil material is separated from the water by centrifugation and the formed tritium labelled water is separated from the remaining acetate by evaporation. The data of 128 locations in the Netherlands were plotted in a soil map and were also compared with the depth, dry weight, electric conductivity, pH and nitrate concentration. The peat areas consisted of limed meadows with a high groundwater level whereas the sand areas often showed deeper groundwater levels and a lower pH. The subsoils at the groundwater table of the peat areas, which are in contact with soil air, showed a higher mineralization rate compared with the surface soils in our study. In contrast, the mineralization rate of the subsoil at the groundwater table of sandy soils showed on average a factor 30 lower rate. Nevertheless, the self purification capacity of the subsoil can be vital under weather conditions where the surface soil becomes less active.     

Effect of dissolved oxygen concentration on nitrite accumulation in nitrifying sequencing batch reactor.

A mathematical model based on Activated Sludge Model No. 3 (International Water Association, London) and laboratory-scale experiments were used to investigate ammonia conversion by nitrification in a sequencing batch reactor (SBR). The purpose of the study was to assess the effect of dissolved oxygen concentration on nitrite accumulation in the SBR. As the dissolved oxygen concentration in the SBR depends on the balance between oxygen consumption and oxygen transfer rates, ammonium conversion was measured for different air flowrate values to obtain different dissolved oxygen concentration profiles during the cycle. The ammonia concentration in the feeding medium was 500 mg ammonium as nitrogen (N-NH4(+))/L, and the maximum nitrite concentration achieved during a cycle was approximately 50 mg nitrite as nitrogen (N-NO2)/L. The air flow supplied to the reactor was identified as a suitable parameter to control nitrite accumulation in the SBR. This identification was carried out based on experimental results and simulation with a calibrated model. At a low value of the volumetric mass-transfer coefficient (kLa), the maximum nitrite concentration achieved during a cycle depends strongly on k(L)a, whereas, at a high value of k(L)a, the maximum nitrite concentration was practically independent of kL(a).     

Fluoride in weathered rock aquifers of southern India: Managed Aquifer Recharge for mitigation

Climatic condition, geology, and geochemical processes in an area play a major role on groundwater quality. Impact of these on the fluoride content of groundwater was studied in three regions—part of Nalgonda district in Telangana, Pambar River basin, and Vaniyar River basin in Tamil Nadu, southern India, which experience semi-arid climate and are predominantly made of Precambrian rocks. High concentration of fluoride in groundwater above 4 mg/l was recorded. Human exposure dose for fluoride through groundwater was higher in Nalgonda than the other areas. With evaporation and rainfall being one of the major contributors for high fluoride apart from the weathering of fluoride rich minerals from rocks, the effect of increase in groundwater level on fluoride concentration was studied. This study reveals that groundwater in shallow environment of all three regions shows dilution effect due to rainfall recharge. Suitable managed aquifer recharge (MAR) methods can be adopted to dilute the fluoride rich groundwater in such regions which is explained with two case studies. However, in deep groundwater, increase in fluoride concentration with increase in groundwater level due to leaching of fluoride rich salts from the unsaturated zone was observed. Occurrence of fluoride above 1.5 mg/l was more in areas with deeper groundwater environment. Hence, practicing MAR in these regions will increase the fluoride content in groundwater and so physical or chemical treatment has to be adopted. This study brought out the fact that MAR cannot be practiced in all regions for dilution of ions in groundwater and that it is essential to analyze the fluctuation in groundwater level and the fluoride content before suggesting it as a suitable solution. Also, this study emphasizes that long-term monitoring of these factors is an important criterion for choosing the recharge areas.     

An analytical solution for vertical transport of volatile chemicals in the vadose zone

An analytical solution is presented for one-dimensional vertical transport of volatile chemicals through the vadose zone to groundwater. The solution accounts for the important transport mechanisms of the steady advection of water and gas, diffusion and dispersion in water and gas, as well as adsorption, and first-order degradation. By assuming a linear, equilibrium partitioning between water, gas and the adsorbed chemical phases, the dependent variable in the mathematical model becomes the total resident concentration. The general solution was derived for cases having a constant initial total concentration over a discrete depth interval and a zero initial total concentration elsewhere. A zero concentration gradient is assumed at the groundwater table. Examples are given to demonstrate the application of the new solution for calculating the case of a non-uniform initial source concentration, and estimating the transport of chemicals to the groundwater and the atmosphere. The solution was also used to verify a numerical code called VLEACH. We discovered an error in VLEACH, and found that the new solution agreed very well with the numerical results by corrected VLEACH. A simplified solution to predict the migration of volatile organic chemical due to the gas density effect has shown that a high source concentration may lead to significant downward advective gas-phase transport in a soil with a high air-permeability.     

Macro-porosity and leaching of atrazine in tilled and orchard loamy soils

Atrazine is the most commonly detected herbicide in the groundwater. Leaching of atrazine largely depends on soil management practices. The aim of this study was to examine leaching of atrazine in tilled and orchard silty loam soils. The experimental objects included: conventionally tilled field (CT) with main tillage operations including pre-plow (10 cm) + harrowing, mouldboard ploughing (20 cm), and a 35 year-old apple orchard (OR) with a permanent sward. To determine leaching of atrazine soil columns of undisturbed structure were taken with steel cylinders of 21.5 cm diameter and 20 cm high from the depth of 0–20 cm. All columns were equilibrated at water content corresponding to field capacity (0.21 kg kg⁻¹). Atrazine suspended in distilled water was dripped uniformly onto the surface of each column. Then water was infiltrated and breakthrough times of leachates were recorded. Atrazine concentration in the leachates was determined by means of HPLC Waters. Macro-porosity and percolation rate were higher in OR than CT soil. Cumulative recovery % of the atrazine applied was 1.267% for OR and approximately one third more from the CT soil but the rate of leaching (per unit of time) was greater from the OR soil. The lower leaching under OR than CT can be due to a greater SOM and the presence of earthworm burrows with organic burrow linings that could adsorb atrazine and contribute to preferential flow allowing solutes to bypass parts whereas the greater rate of leaching due to a greater infiltration rate.The results indicate potential of management practices for minimizing atrazine leaching.     

Leaching of glyphosate and AMPA under two soil management practices in Burgundy vineyards (Vosne-Romanée, 21-France)

Some drinking water reservoirs under the vineyards of Burgundy are contaminated with herbicides. Thus the effectiveness of alternative soil management practices, such as grass cover, for reducing the leaching of glyphosate and its metabolite, AMPA, through soils was studied. The leaching of both molecules was studied in structured soil columns under outdoor conditions for 1 year. The soil was managed under two vineyard soil practices: a chemically treated bare calcosol, and a vegetated calcosol. After 680 mm of rainfall, the vegetated calcosol leachates contained lower amounts of glyphosate and AMPA (0.02% and 0.03%, respectively) than the bare calcosol leachates (0.06% and 0.15%, respectively). No glyphosate and only low amounts of AMPA (<0.01%) were extracted from the soil. Glyphosate, and to a greater extent, AMPA, leach through the soils; thus, both molecules may be potential contaminants of groundwater. However, the alternative soil management practice of grass cover could reduce groundwater contamination by the pesticide.     

Use pattern of pesticides and their predicted mobility into shallow groundwater and surface water bodies of paddy lands in Mahaweli river basin in Sri Lanka

Pesticides applied on agricultural lands reach groundwater by leaching, and move to offsite water bodies by direct runoff, erosion and spray drift. Therefore, an assessment of the mobility of pesticides in water resources is important to safeguard such resources. Mobility of pesticides on agricultural lands of Mahaweli river basin in Sri Lanka has not been reported to date. In this context, the mobility potential of 32 pesticides on surface water and groundwater was assessed by widely used pesticide risk indicators, such as Attenuation Factor (AF) index and the Pesticide Impact Rating Index (PIRI) with some modifications. Four surface water bodies having greater than 20% land use of the catchment under agriculture, and shallow groundwater table at 3.0 m depth were selected for the risk assessment. According to AF, carbofuran, quinclorac and thiamethoxam are three most leachable pesticides having AF values 1.44 × 10^?2, 1.87 × 10^?3 and 5.70 × 10^?4, respectively. Using PIRI, offsite movement of pesticides by direct runoff was found to be greater than with the erosion of soil particles for the study area. Carbofuran and quinclorac are most mobile pesticides by direct runoff with runoff fractions of 0.01 and 0.08, respectively, at the studied area. Thiamethoxam and novaluron are the most mobile pesticides by erosion with erosion factions of 1.02 × 10^?4 and 1.05 × 10^?4, respectively. Expected pesticide residue levels in both surface and groundwater were predicted to remain below the USEPA health advisory levels, except for carbofuran, indicating that pesticide pollution is unlikely to exceed the available health guidelines in the Mahaweli river basin in Sri Lanka.     

Linking a one-dimensional pesticide fate model to a three-dimensional groundwater model to simulate pollution risks of shallow and deep groundwater underlying fractured till

The one-dimensional pesticide fate model MACRO was loose-linked to the three-dimensional discrete fracture/matrix diffusion model FRAC3DVS to describe transport of the pesticide mecoprop in a fractured moraine till and local sand aquifer (5-5.5 m depth) overlying a regional limestone aquifer (16 m depth) at Havdrup, Denmark. Alternative approaches to describe the upper boundary in the groundwater model were examined. Field-scale simulations were run to compare a uniform upper boundary condition with a spatially variable upper boundary derived from Monte-Carlo simulations with MACRO. Plot-scale simulations were run to investigate the influence of the temporal resolution of the upper boundary conditions for fluxes in the groundwater model and the effects of different assumptions concerning the macropore/fracture connectivity between the two models. The influence of within-field variability of leaching on simulated mecoprop concentrations in the local aquifer was relatively small. A fully transient simulation with FRAC3DVS gave 20 times larger leaching to the regional aquifer compared to the case with steady-state water flow, assuming full connectivity with respect to macropores/fractures across the boundary between the two models. For fully transient simulations 'disconnecting' the macropores/fractures at the interface between the two models reduced leaching by a factor 24. A fully connected, transient simulation with FRAC3DVS, with spatially uniform upper boundary fluxes derived from a MACRO simulation with 'effective' parameters is therefore recommended for assessing leaching risks to the regional aquifer, at this, and similar sites.     

Microbial Contamination of Groundwater at Small Community Water Supplies in Finland

The raw water quality and associations between the factors considered as threats to water safety were studied in 20 groundwater supplies in central Finland in 2002-2004. Faecal contaminations indicated by the appearance of Escherichia coli or intestinal enterococci were present in five small community water supplies, all these managed by local water cooperatives. Elevated concentrations of nutrients in raw water were linked with the presence of faecal bacteria. The presence of on-site technical hazards to water safety, such as inadequate well construction and maintenance enabling surface water to enter into the well and the insufficient depth of protective soil layers above the groundwater table, showed the vulnerability of the quality of groundwater used for drinking purposes. To minimize the risk of waterborne illnesses, the vulnerable water supplies need to be identified and appropriate prevention measures such as disinfection should be applied.     

Temporal and spatial patterns of micropollutants in urban receiving waters

Based on a monitoring program over the course of a year, we characterize the temporal and spatial distribution of selected micropollutants in an urban watershed within the city of Leipzig, Germany. Micropollutants revealed a ubiquitous presence in untreated and treated wastewater, surface water and groundwater. The loads of 4-nonylphenol in the effluents of the municipal wastewater treatment plant followed a seasonal trend, whereas the loads of all other micropollutants were highly variable and not correlated to seasons. In the surface water, load seasonality of caffeine, galaxolide and tonalide resulted from a rapid removal with increased water temperature. The loads of 4-nonylphenol and of caffeine in the colder months increased when rainfall occurred. In the groundwater, complex spatial and temporal patterns were apparent and were related to varying input, retardation and removal processes. As a consequence, an assessment of micropollutants in urban waters should consider different micropollutants' temporal and spatial variability.     

Temporal changes in kerosene content and composition in field soil as a result of leaching

A field experiment was designed to determine the combined effect of leaching and natural attenuation on the redistribution dynamics of kerosene--a volatile petroleum hydrocarbon mixture (VPHM)--and of its selected individual components in the soil subsurface. Variables included the composition of contaminant spilled, the soil water content before contamination and the leaching pattern. Temporal changes in the residual kerosene concentration and composition in the soil subsurface of the experimental field during 39 days and leaching by 500 mm of irrigation water were determined to a depth of 100 cm. The main processes controlling contaminant attenuation were volatilization and redistribution with depth. Soil hydration status was found to affect the attenuation, redistribution and composition of VPHM in the porous media. An initial relative increase of n-alkanes in the subsurface compared with the total VPHM in the first leaching period was a result of the volatilization of low vapor pressure compounds. The redistribution of individual components in the soil profile during leaching was in accordance with their physico-chemical properties.     

Critical loads and their exceedances at intensive forest monitoring sites in Europe

Intensive forest monitoring by means of harmonised methods has been conducted in Europe for more than a decade. Risks of atmospheric nitrogen and sulphur deposition are assessed by means of calculations of critical loads and their exceedances. In the present study throughfall and bulk deposition of nitrate (N-NO(3)), ammonium (N-NH(4)) and sulphate (S-SO(4)) show marked spatial patterns and temporal trends. In the period of observation (1999-2004), sulphate deposition on intensive monitoring plots decreased by about one quarter. This is in line with the reduction of S deposition by 70% since 1981 in Europe as a result of successful air pollution control politics under the Convention on Long-range Transboundary Air Pollution (CLRTAP). However, sulphate and especially nitrate and ammonium deposition were found to still exceed critical loads at many forest sites, indicating a continued need for further implementation of air pollution abatement strategies.     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

Redistribution of contaminants by a fluctuating water table in a micro-porous, double-porosity aquifer: field observations and model simulations

Large seasonal fluctuations of the water table are characteristic of aquifers with a low specific yield, including those fractured, double-porosity aquifers that have significant matrix porosity containing virtually immobile porewater, such as the Chalk of northern Europe. Where these aquifers are contaminated, a strong relationship between water table elevation and contaminant concentration in groundwater is commonly observed, of significance to the assessment, monitoring, and remediation of contaminated groundwater. To examine the processes governing contaminant redistribution by a fluctuating water table within the 'seasonally unsaturated zone', or SUZ, profiles of porewater solute concentrations have been established at a contaminated site in southern England. These profiles document the contaminant distribution in porewater of the Chalk matrix over the SUZ at a greater level of detail than recorded previously. A novel double-porosity solute transport code has been developed to simulate the evolution of the SUZ matrix porewater contaminant profiles, given a fluctuating water table, when the groundwater is initially contaminated and the SUZ is initially free of contamination. The model is simply characterised by: the matrix-fracture porosity ratio, the matrix block geometry, and a characteristic diffusion time. De-saturation and re-saturation of fractures is handled by a new approximation method. Contaminant accumulates in the upper levels of the SUZ, where it is less accessible to mobile groundwater, and acts as a persistent secondary source of contamination once the original source of contamination has been removed or has become depleted. The 'SUZ process' first attenuates the progress of contaminants in groundwater, and subsequently controls the slow release of contamination back to the mobile groundwater, thus prolonging the duration of groundwater contamination by many years. The SUZ process should operate in any fractured, micro-porous lithology e.g. fractured clays and mudstones, making this approach widely applicable.