Anthropogenic contaminants as tracers in an urbanizing karst aquifer

Karst aquifers are uniquely vulnerable to contamination. In the Barton Springs segment of the karstic Edwards aquifer (Texas, U.S.A.), urban contaminants such as pesticides and volatile organic compounds frequently are detected in spring base flow. To determine whether contaminant concentrations change in response to storms, and if they therefore might act as tracers of focused recharge, samples were collected from Barton Springs at closely spaced intervals following three storms. Two herbicides (atrazine and simazine), two insecticides (carbaryl and diazinon), and a solvent (tetrachloroethene) described breakthrough curves over a 1-week period following one or more storms. The breakthrough curves were decomposed into two to five log-normal subcurves, which were interpreted as representing pulses of contaminants moving through the aquifer. Each subcurve could be used in the same way as an artificial tracer to determine travel time to and recovery at the spring. The contaminants have several advantages over artificial tracers: they represent the actual compounds of interest, they are injected essentially simultaneously at several points, and they are injected under those conditions when transport is of the most interest, i.e., following storms. The response of storm discharge, specific conductance, and contaminant loading at the spring depended on initial aquifer flow conditions, which varied from very low (spring discharge of 0.48 m3/s) to high (spring discharge of 2.7 m3/s): concentrations and recovery were the highest when initial aquifer flow conditions were low. This behavior provides information about aquifer structure and the influence of aquifer flow condition on transport properties.     

A multi-directional tracer test in the fractured Chalk aquifer of E. Yorkshire, UK

A multi-borehole radial tracer test has been conducted in the confined Chalk aquifer of E. Yorkshire, UK. Three different tracer dyes were injected into three injection boreholes and a central borehole, 25 m from the injection boreholes, was pumped at 330 m(3)/d for 8 days. The breakthrough curves show that initial breakthrough and peak times were fairly similar for all dyes but that recoveries varied markedly from 9 to 57%. The breakthrough curves show a steep rise to a peak and long tail, typical of dual porosity aquifers. The breakthrough curves were simulated using a 1D dual porosity model. Model input parameters were constrained to acceptable ranges determined from estimations of matrix porosity and diffusion coefficient, fracture spacing, initial breakthrough times and bulk transmissivity of the aquifer. The model gave equivalent hydraulic apertures for fractures in the range 363-384 microm, dispersivities of 1 to 5 m and matrix block sizes of 6 to 9 cm. Modelling suggests that matrix block size is the primary controlling parameter for solute transport in the aquifer, particularly for recovery. The observed breakthrough curves suggest results from single injection-borehole tracer tests in the Chalk may give initial breakthrough and peak times reasonably representative of the aquifer but that recovery is highly variable and sensitive to injection and abstraction borehole location. Consideration of aquifer heterogeneity suggests that high recoveries may be indicative of a high flow pathway adjacent, but not necessarily connected, to the injection and abstraction boreholes whereas low recoveries may indicate more distributed flow through many fractures of similar aperture.     

Prediction of contaminant transport in fractured carbonate aquifer types: a case study of the Permian Magnesian Limestone Group (NE England,UK)

Viruses and bacteria which are characterized by finite lives in the subsurface are rapidly transported via fractures and cavities in fractured and karst aquifers. Here, we demonstrate how the coupling of a robust outcrop characterization and hydrogeophysical borehole testing is essential for prediction of contaminant velocities and hence wellhead protection areas. To show this, we use the dolostones of the Permian Magnesian Limestone aquifer in NE England, where we incorporated such information in a groundwater flow and particle tracking model. Within this aquifer, flow in relatively narrow (mechanical aperture of ~?10^?1–1 mm) fractures is coupled with that in pipe cavities (~?0.20-m diameter) following normal faults. Karstic cavities and narrow fractures are hydraulically very different. Thus, the solutional features are represented within the model by a pipe network (which accounts for turbulence) embedded within an equivalent porous medium representing Darcian flowing fractures. Incorporation of fault conduits in a groundwater model shows that they strongly influence particle tracking results. Despite this, away from faulted areas, the effective flow porosity of the equivalent porous medium remains a crucial parameter. Here, we recommend as most appropriate a relatively low value of effective porosity (of 2.8?×?10^?4) based on borehole hydrogeophysical testing. This contrasts with earlier studies using particle tracking analyses on analogous carbonate aquifers, which used much higher values of effective porosity, typically ~?10² times higher than our value, resulting in highly non-conservative estimates of aquifer vulnerability. Low values of effective flow porosities yield modelled flow velocities ranging from ~?100 up to ~?500 m/day in un-faulted areas. However, the high fracturing density and presence of karstic cavities yield modelled flow velocities up to ~?9000 m/day in fault zones. The combination of such flow velocities along particle traces results in 400-day particle traces up to 8-km length, implying the need for large well protection areas and high aquifer vulnerability to slowly degrading contaminants.

     

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.     

The use of multilevel sampling techniques for determining shallow aquifer nitrate profiles

Nitrate is a worldwide pollutant in aquifers. Shallow aquifer nitrate concentrations generally display vertical stratification, with a maximum concentration immediately below the water level. The concentration then gradually decreases with depth. Different techniques can be used to highlight this stratification. The paper aims at comparing the advantages and limitations of three open hole multilevel sampling techniques (packer system, dialysis membrane samplers and bailer), chosen on the base of a literary review, to highlight a nitrate vertical stratification under the assumption of (sub)horizontal flow in the aquifer. The sampling systems were employed at three different times of the year in a shallow aquifer piezometer in northern Italy. The optimal purge time, equilibration time and water volume losses during the time in the piezometer were evaluated. Multilevel techniques highlighted a similar vertical nitrate stratification, present throughout the year. Indeed, nitrate concentrations generally decreased with depth downwards, but with significantly different levels in the sampling campaigns. Moreover, the sampling techniques produced different degrees of accuracy. More specifically, the dialysis membrane samplers provided the most accurate hydrochemical profile of the shallow aquifer and they appear to be necessary when the objective is to detect the discontinuities in the nitrate profile. Bailer and packer system showed the same nitrate profile with little differences of concentration. However, the bailer resulted much more easier to use.

     

A method for determining volatile organic solvents in chalk pore waters (Southern and Eastern England) and its relevance to the evaluation of groundwater contamination

Conventional methods of sampling groundwater in Chalk aquifers sample the mobile water in the fissures only and not the non-mobile water held in the microporous matrix. However, the microporous matrix can play an important role in modifying groundwater quality by attenuating contaminant migration through diffusion exchange and, in the long term, by acting as a reservoir for contaminant retention.A method for extracting and analysing chalk pore waters for chlorinated solvents has been developed. Chalk pore water-depth profiles at the site of a spillage of tetrachloroethene demonstrated that the immiscible phase of the solvent had migrated to depths of 50 m, producing solvent concentrations in the matrix pore waters of up to 40,000 μg L⁻¹.In addition, the pore water-depth profile indicated that the immiscible phase had ponded upon a less permeable horizon within the Chalk aquifer at shallow depths.     

Reevaluating Epidemiological Monitoring

For a two-year period, the chemistry of daily precipitation samples for a site in southern Indiana was analyzed for effect of seasons and synoptic storm types. The storms were classified as frontal, cyclonic, convective and other. Statistically significant (5 percent level) higher concentrations of sulfate, ammonium and hydrogen ion and lower sodium occurred in the warm seasons (April-September) than in the cold (October-March); nitrate, chloride and calcium concentrations were similar in both seasons. In general, convective and frontal storms contained the highest concentrations of ions, and cyclonic and other the lowest. Frontal storms showed significant higher sulfate, nitrate, ammonium and hydrogen ion and lower sodium in warm seasons than in cold, while cyclonic storms yielded significant (1 percent level) higher nitrate in the cold seasons. These results are generally consistent with the well-known behavior of the meteorological weather system categories.     

Modelling the geochemical fate and transport of wastewater-derived phosphorus in contrasting groundwater systems

A 1D reactive transport model (RTM) is used to obtain a mechanistic understanding of the fate of phosphorus (P) in the saturated zone of two contrasting aquifer systems. We use the field data from two oxic, electron donor-poor, wastewater-impacted, sandy Canadian aquifers, (Cambridge and Muskoka sites) as an example of a calcareous and non-calcareous groundwater system, respectively, to validate our reaction network. After approximately 10 years of wastewater infiltration, P is effectively attenuated within the first 10 m down-gradient of the source mainly through fast sorption onto calcite and Fe oxides. Slow, kinetic sorption contributes further to P removal, while precipitation of phosphate minerals (strengite, hydroxyapatite) is quantitatively unimportant in the saturated zone. Nitrogen (N) dynamics are also considered, but nitrate behaves essentially as a conservative tracer in both systems. The model-predicted advancement of the P plume upon continued wastewater discharge at the calcareous site is in line with field observations. Model results suggest that, upon removal of the wastewater source, the P plume at both sites will persist for at least 20 years, owing to desorption of P from aquifer solids and the slow rate of P mineral precipitation. Sensitivity analyses for the non-calcareous scenario (Muskoka) illustrate the importance of the sorption capacity of the aquifer solids for P in modulating groundwater N:P ratios in oxic groundwater. The model simulations predict the breakthrough of groundwater with high P concentrations and low N:P ratios after 17 years at 20 m from the source for an aquifer with low sorption capacity (<0.02% w/w Fe(OH)(3)). In this type of system, denitrification plays a minor role in lowering the N:P ratios because it is limited by the availability of labile dissolved organic matter.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.     

Laboratory analog and numerical study of groundwater flow and solute transport in a karst aquifer with conduit and matrix domains

New mathematical and laboratory methods have been developed for simulating groundwater flow and solute transport in karst aquifers having conduits imbedded in a porous medium, such as limestone. The Stokes equations are used to model the flow in the conduits and the Darcy equation is used for the flow in the matrix. The Beavers–Joseph interface boundary conditions are adopted to describe the flow exchange at the interface boundary between the two domains. A laboratory analog is used to simulate the conduit and matrix domains of a karst aquifer. The conduit domain is located at the bottom of the transparent plexiglas laboratory analog and glass beads occupy the remaining space to represent the matrix domain. Water flows into and out of the two domains separately and each has its own supply and outflow reservoirs. Water and solute are exchanged through an interface between the two domains. Pressure transducers located within the matrix and conduit domains of the analog provide data that is processed and stored in digital format. Dye tracing experiments are recorded using time-lapse imaging. The data and images produced are analyzed by a spatial analysis program. The experiments provide not only hydraulic head distribution but also capture solute front images and mass exchange measurements between the conduit and matrix domains. In the experiment, we measure and record pressures, and quantify flow rates and solute transport. The results present a plausible argument that laboratory analogs can characterize groundwater water flow, solute transport, and mass exchange between the conduit and matrix domains in a karst aquifer. The analog validates the predictions of a numerical model and demonstrates the need of laboratory analogs to provide verification of proposed theories and the calibration of mathematical models.     

Filtration and transport of Bacillus subtilis spores and the F-RNA phage MS2 in a coarse alluvial gravel aquifer: implications in the estimation of setback distances

Filtration of Bacillus subtilis spores and the F-RNA phage MS2 (MS2) on a field scale in a coarse alluvial gravel aquifer was evaluated from the authors' previously published data. An advection-dispersion model that is coupled with first-order attachment kinetics was used in this study to interpret microbial concentration vs. time breakthrough curves (BTC) at sampling wells. Based on attachment rates (katt) that were determined by applying the model to the breakthrough data, filter factors (f) were calculated and compared with f values estimated from the slopes of log (cmax/co) vs. distance plots. These two independent approaches resulted in nearly identical filter factors, suggesting that both approaches are useful in determining reductions in microbial concentrations over transport distance. Applying the graphic approach to analyse spatial data, we have also estimated the f values for different aquifers using information provided by some other published field studies. The results show that values of f, in units of log (cmax/co) m(-1), are consistently in the order of 10(-2) for clean coarse gravel aquifers, 10(-3) for contaminated coarse gravel aquifers, and generally 10(-1) for sandy fine gravel aquifers and river and coastal sand aquifers. For each aquifer category, the f values for bacteriophages and bacteria are in the same order-of-magnitude. The f values estimated in this study indicate that for every one-log reduction in microbial concentration in groundwater, it requires a few tens of meters of travel in clean coarse gravel aquifers, but a few hundreds of meters in contaminated coarse gravel aquifers. In contrast, a one-log reduction generally only requires a few meters of travel in sandy fine gravel aquifers and sand aquifers. Considering the highest concentration in human effluent is in the order of 10(4) pfu/l for enteroviruses and 10(6) cfu/100 ml for faecal coliform bacteria, a 7-log reduction in microbial concentration would comply with the drinking water standards for the downgradient wells under natural gradient conditions. Based on the results of this study, a 7-log reduction would require 125-280 m travel in clean coarse gravel aquifers, 1.7-3.9 km travel in contaminated coarse gravel aquifers, 33-61 m travel in clean sandy fine gravel aquifers, 33-129 m travel in contaminated sandy fine gravel aquifers, and 37-44 m travel in contaminated river and coastal sand aquifers. These recommended setback distances are for a worst-case scenario, assuming direct discharge of raw effluent into the saturated zone of an aquifer. Filtration theory was applied to calculate collision efficiency (alpha) from model-derived attachment rates (katt), and the results are compared with those reported in the literature. The calculated alpha values vary by two orders-of-magnitude, depending on whether collision efficiency is estimated from the effective particle size (d10) or the mean particle size (d50). Collision efficiency values for MS-2 are similar to those previously reported in the literature (e.g. ) [DeBorde, D.C., Woessner, W.W., Kiley, QT., Ball, P., 1999. Rapid transport of viruses in a floodplain aquifer. Water Res. 33 (10), 2229-2238]. However, the collision efficiency values calculated for Bacillus subtilis spores were unrealistic, suggesting that filtration theory is not appropriate for theoretically estimating filtration capacity for poorly sorted coarse gravel aquifer media. This is not surprising, as filtration theory was developed for uniform sand filters and does not consider particle size distribution. Thus, we do not recommend the use of filtration theory to estimate the filter factor or setback distances. Either of the methods applied in this work (BTC or concentration vs. distance analyses), which takes into account aquifer heterogeneities and site-specific conditions, appear to be most useful in determining filter factors and setback distances.     

岩溶水系统中微生物迁移机制

对桂林罗锦响水岩岩溶水系统雨前、雨中和雨后水中及悬浮物上携带的细菌数量变化规律分析表明,在雨期,岩溶地下河水质变化对地表水质响应迅速,表现为在一定时期内地下水与地表水中的细菌总数可达到同一个数量级;地下水中TSS与细菌总数的变化具有一致性,即细菌总数随TSS的升降而升降,说明细菌大多是附着在悬浮颗粒物运移的;同时,岩溶区地下河局部存在的溶潭等蓄水构造对污染物具有明显的纳污与稀释效应,是岩溶地下河系统产生自净作用的主要场所。TSS与地下水流速呈正相关,而附着在悬浮颗粒物上的细菌占地下水中细菌总数的比例与流速呈负相关。地下河洞口的堆积物对微生物具有明显的截留作用,其对微生物的吸附和缓慢释放,是导致地下河在很长一段时间内都会受到微生物污染的主要原因。     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 microg/L to 191 microg/L with a mean concentration of 33 microg/L. Groundwater is mainly Ca-HCO(3) type with high concentrations of dissolved As, Fe, and Mn, but low level of SO(4). The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 microg/L. Deeper aquifer (>100 m depth) has a mean arsenic concentration of 18 microg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Occurrence and behavior of wastewater indicators in the Santa Ana River and the underlying aquifers.

The occurrence and behavior of wastewater indicator compounds in the Santa Ana River (SAR) water and the underlying aquifer recharged by the SAR has been studied. The SAR contains a high proportion of tertiary treated wastewater effluents, up to 100% during summer and fall. The following water quality parameters were quantified: four specific wastewater indicator compounds, ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), a naphthalene dicarboxylate (NDC) isomer, alkylphenol polyethoxy carboxylates (APECs), and selected haloacetic acids (HAAs), nitrate, dissolved oxygen (DO), DOC, total carbohydrate, and phenolic substances. Statistical analysis indicated that normal distribution was adequate to describe the probability distribution of the constituents in most cases. In the river, the concentrations of wastewater indicator compounds decreased as the fraction of storm runoff increased. EDTA and NDC were detected in a monitoring well near the river and in two production wells 1.8 and 2.7 km down gradient with little apparent attenuation. By contrast, NTA, APECs, bromochloro- and dibromoacetic acids appeared to be attenuated significantly during infiltration of river water and groundwater transport.     

Assessment of nitrate pollution in the Grand Morin aquifers (France): combined use of geostatistics and physically based modeling

The objective of this work is to combine several approaches to better understand nitrate fate in the Grand Morin aquifers (2700 km(2)), part of the Seine basin. cawaqs results from the coupling of the hydrogeological model newsam with the hydrodynamic and biogeochemical model of river ProSe. cawaqs is coupled with the agronomic model Stics in order to simulate nitrate migration in basins. First, kriging provides a satisfactory representation of aquifer nitrate contamination from local observations, to set initial conditions for the physically based model. Then associated confidence intervals, derived from data using geostatistics, are used to validate cawaqs results. Results and evaluation obtained from the combination of these approaches are given (period 1977-1988). Then cawaqs is used to simulate nitrate fate for a 20-year period (1977-1996). The mean nitrate concentrations increase in aquifers is 0.09 mgN L(-1)yr(-1), resulting from an average infiltration flux of 3500 kgN.km(-2)yr(-1).     

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation

This paper concludes that back diffusion from one or a few thin clayey beds in a sand aquifer can cause contaminant persistence above MCLs in a sand aquifer long after the source zone initially causing the plume is isolated or removed. This conclusion is based on an intensive case study of a TCE contaminated site in Florida, with the processes evaluated using numerical modeling. At this site, the TCE DNAPL zone formed decades ago, and was hydraulically isolated by means of an innovative system performing groundwater extraction, treatment and re-injection. Treated water is re-injected in a row of injection wells situated a short distance downgradient of the extraction wells, creating a clean-water displacement front to efficiently flush the downgradient plume. This scheme avoids the creation of stagnation zones typical of most groundwater pump-and-treat systems, thereby minimizing the time for aquifer flushing and therefore downgradient cleanup. The system began operation in August 2002 and although the performance monitoring shows substantial declines in concentrations, detectable levels of TCE and degradation products persist downgradient of the re-injection wells, long after the TCE should have disappeared based on calculations assuming a nearly homogenous sand aquifer. Three hypotheses were assessed for this plume persistence: 1) incomplete source-zone capture, 2) DNAPL occurrence downgradient of the re-injection wells, and 3) back diffusion from one or more thin clay beds in the aquifer. After careful consideration, the first two hypotheses were eliminated, leaving back diffusion as the only plausible hypothesis, supported by detailed measurements of VOC concentrations within and near the clay beds and also by numerical model simulations that closely represent the field site hydrogeologic conditions. The model was also used to simulate a more generalized, hypothetical situation where more thin clayey beds occur in a sand aquifer with an underlying aquitard. While there is no doubt that DNAPL source mass reduction can eventually improve downgradient groundwater quality, the magnitude and time scale over which the improvement occurs is the major uncertainty given current characterization approaches. This study shows that even one thin clay bed, less than 0.2 m thick, can cause plume persistence due to back diffusion for several years or even decades after the flux from the source is completely isolated. Thin clay beds, which have a large storage capacity for dissolved and sorbed contaminant mass, are common in many types of sandy aquifers. However, without careful inspection of continuous cores and sampling, such thin clay beds, and their potential for causing long-term back-diffusion effects, can easily go unnoticed during site characterization.     

Characteristics of highway stormwater runoff.

Highway stormwater runoff was monitored at three highway sites in Los Angeles, California, during the 2000 to 2003 wet seasons. Event mean concentrations (EMCs), partial event mean concentrations (PEMCs), and mass first flush (MFF) factors were calculated for more than 20 water quality parameters for samples from 20 storm events from each site. The early runoff had higher concentrations, as indicated by the PEMCs at 30 and 60 minutes into the storm, which were 1.9 to 7.4 times higher than the EMCs. A strong first flush was observed for chemical oxygen demand (COD) and other organic pollutants, with 40% of the pollutant mass being discharged in the first 20% of the runoff. A weak first flush was observed for ionic pollutants, such as nitrate and nitrite. Pearson correlation analyses of the EMCs, PEMCs, and MFFs showed strong correlations among dissolved organic carbon, COD, total Kjeldahl nitrogen, oil and grease, and ammonia-nitrogen. Contrary to generally held beliefs, poor correlation between total suspended solids and most other conventional pollutants was observed. In addition, poor correlation between most monitored pollutants and storm characteristics, except for antecedent dry days, was observed.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 µg/L to 191 µg/L with a mean concentration of 33 µg/L. Groundwater is mainly Ca–HCO₃ type with high concentrations of dissolved As, Fe, and Mn, but low level of SO₄. The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 µg/L. Deeper aquifer (> 100 m depth) has a mean arsenic concentration of 18 µg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.