A method for monitoring ground water quality near waste storage facilities

A practical optimization approach developed in this paper derives effective monitoring configurations for detecting contaminants in ground water. The approach integrates numerical simulation of contaminant transport and mathematical programming. Well sites identified by the methodology can be monitored to establish the occurrence of a contaminant release before a plume migrates to a regulatory compliance boundary. Monitoring sites are established along several horizons located between the downgradient margin of a contaminant source and a compliance boundary. A horizon can form an effective line of defense against contaminant migration to the compliance boundary if it is spanned (covered) by a sufficient number of sites to yield a well spacing that is equal to or less than a maximum value established by numerical modeling. The objective function of the integer programming model formulation expresses the goals of: (1) covering a maximum number of siting horizons, and (2) allocating wells to the single most effective horizon. The latter is determined from well spacing requirements and the width of the zone of potential contaminant migration traversed by the horizon. The methodology employs a highly tractable linear programming model formulation, and the user is not required to predefine a set of potential well sites. These attributes can facilitate its implementation in practice.     

Implications and concerns of deep-seated disposal of hydrocarbon exploration produced water using three-dimensional contaminant transport model in Bhit Area, Dadu District of Southern Pakistan

A three-dimensional contaminant transport model has been developed to simulate and monitor the migration of disposal of hydrocarbon exploration produced water in Injection well at 2,100 m depth in the Upper Cretaceous Pab sandstone, Bhit area in Dadu district of Southern Pakistan. The regional stratigraphic and structural geological framework of the area, landform characteristics, meteorological parameters, and hydrogeological milieu have been used in the model to generate the initial simulation of steady-state flow condition in the underlying aquifer’s layers. The geometry of the shallow and deep-seated characteristics of the geological formations was obtained from the drilling data, electrical resistivity sounding surveys, and geophysical well-logging information. The modeling process comprised of steady-state simulation and transient simulation of the prolific groundwater system of contamination transport after 1, 10, 30 years of injection. The contaminant transport was evaluated from the bottom of the injection well, and its short- and long-term effects were determined on aquifer system lying in varying hydrogeological and geological conditions.     

Bioremediation With Oxygen-Releasing Solids: A Mathematical Model

The use of oxygen releasing solids in passive wells has become of considerable interest in the bioremediation of groundwater contaminated with hydrocarbons and other biodegradable contaminants. Labor, operating, and maintenance costs of this technology are quite competitive with more conventional techniques in many instances. Because of the small rates of mass transport by transverse dispersion, however, a pin-stripe pattern of alternating contaminant and oxygen distribution is expected downgradient of a line of wells which is unacceptable if it extends beyond the point of compliance downgradient. A mathematical model is presented which permits determination of the maximum well spacing in an array of wells which will yield effective remediation within a specified distance of a plume of contaminated groundwater passing through the array. Transverse dispersion of both oxygen and the contaminant is assumed, and biodegradation is modeled by means of Monod kinetics. Longitudinal numerical dispersion is minimized by the use of a asymmetrical upwind algorithm for modeling advection. Modeling results are presented showing the dependence of model behavior on input parameters.     

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.     

Estimating contaminant attenuation half-lives in alluvial groundwater systems

One aspect of describing contamination in an alluvial aquifer is estimating changes in concentrations over time. A variety of statistical methods are available for assessing trends in contaminant concentrations. We present a method that extends trend analysis to include estimating the coefficients for the exponential decay equation and calculating contaminant attenuation half-lives. The conceptual model for this approach assumes that the rate of decline is proportional to the contaminant concentration in an aquifer. Consequently, the amount of time to remove a unit quantity of the contaminant inventory from an aquifer lengthens as the concentration decreases. Support for this conceptual model is demonstrated empirically with log-transformed time series of contaminant data. Equations are provided for calculating system attenuation half-lives for non-radioactive contaminants. For radioactive contaminants, the system attenuation half-life is partitioned into the intrinsic radioactive decay and the concentration reduction caused by aquifer processes. Examples are presented that provide the details of this approach. In addition to gaining an understanding of aquifer characteristics and changes in constituent concentrations, this method can be used to assess compliance with regulatory standards and to estimate the time to compliance when natural attenuation is being considered as a remediation strategy. A special application of this method is also provided that estimates the half-life of the residence time for groundwater in the aquifer by estimating the half life for a conservative contaminant that is no longer being released into the aquifer. Finally, the ratio of the half-life for groundwater residence time to the attenuation half-life for a contaminant is discussed as a system-scale retardation factor which can be used in analytical and numerical modeling.     

Influence of cabin conditions on placement and response of contaminant detection sensors in a commercial aircraft

Potential causalities due to airborne disease transmission and risk of chem-bio terrorism in commercial airliner cabins can be reduced by fast responses. Fast responses are only possible by using sensors at appropriate locations in the cabins. Cost, size and weight factors restrict the number of sensors that could be installed inside a cabin. Since release locations and seating patterns of passengers can impact airborne contaminant transports, this study first addressed this impact by using a validated computational fluid dynamics (CFD) program in a four-row mockup of twin-aisle airliner cabin. It was observed that occupancy patterns and release locations have little influence on longitudinal contaminant transports though localized variations of contaminant concentrations may exist. The results show that response time of the sensors is considerably reduced with the increase in number of sensors. If only a single sensor is available across a cabin cross-section then it should be placed at the middle of the ceiling. A cabin model of a fully occupied twin-aisle airliner with 210 seats was also build to study the diverse contaminant distribution trends along cabin length. The results reveal that seating arrangements can make cross-sectional airflow pattern considerably asymmetrical. Similar airflow patterns make the longitudinal contaminant transport in the business and economy classes alike. The presence of galleys greatly affected the longitudinal transport of contaminants in a particular cabin section. The effects due to galleys were less significant if a multipoint sampling system was used. The multipoint sampling system can also reduce the number of sensors required in a cabin.     

Comparison of field-observed and model-predicted plume trends at fuel-contaminated sites: implications for natural attenuation rates

Subsequent to modeling of natural attenuation processes to predict contaminant trends and plume dynamics, monitoring data were used to evaluate the effectiveness of natural attenuation at reducing contaminant concentrations in groundwater at seven fuel-contaminated sites. Predicted and observed contaminant trends at seven sites were compared in order to empirically assess the accuracy of some fundamental model input parameters and assumptions. Most of the models developed for the study sites tended to overestimate plume migration distance, source persistence, and/or the time required for the benzene, toluene, ethyl benzene, and xylenes (BTEX) plumes to attenuate. Discrepancies between observed and predicted contaminant trends and plume behavior suggested that the influence of natural attenuation process may not have been accurately simulated. The conservatism of model simulations may be attributed to underestimation of natural source weathering rates, overestimation of the mass of contaminant present in the source area, and/or use of overly conservative first-order solute decay rates.     

Associations between distance lags,groundwater velocities,and detection efficiencies in groundwater monitoring networks

Effects of distance lags between landfills and monitoring wells on contaminant detection capability were quantified in several groundwater velocity settings. Detection efficiency calculations were made with and without imposing a time limit on contaminant travel. In general, longer distance lags yieldedhigher detection efficiencies. However, detection efficienciesdecreased as monitoring wells approached a buffer zone boundaryimposing a maximum permissible contaminant transport distance.Imposing a time limit on contaminant travel substantially reduced detection efficiency in low velocity settings, especiallyat longer distance lags. Time limits were less significant in high velocity settings where contaminants more quickly reachedmonitoring wells. Detection efficiencies also decreased as velocity increased, but decreases were minor once the velocityreached a threshold value.     

Performance Evaluation of Multiple Groundwater Flow and Nitrate Mass Transport Numerical Models

Environmental Modeling & Assessment - Benchmarking of different numerical models simulating groundwater flow and contaminant mass transport is the aim of the present study, in order to...     

Modeling the flow and leachate transport in the vadose and saturated zones of a municipal landfill

The purpose of the present study was to evaluate the groundwater contamination due to the construction and operation of the municipal landfill of Amari, Rethymno, Crete. The groundwater flow and leachate transport in the vadose and saturated zones were studied and simulated, using three different models: the one-dimensional groundwater flow and contaminant transport model for the vadose zone Pesticide Root Zone Model (PRZM-3), the Geographical Information System (GIS) Argus ONE and the three-dimensional groundwater flow and contaminant transport model Princeton Transport Code (PTC). The simulation time was 30 and 20 years, and the results obtained, according to the models and the existing hydrogeological conditions, were very encouraging and reassuring about the groundwater quality of the broad region.     

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.     

An Alternative Process Model of Preferential Contaminant Travel Times in the Unsaturated Zone: Application to Rainier Mesa and Shoshone Mountain, Nevada

Simulating contaminant transport in unsaturated zones with sparse hydraulic property information is a difficult, yet common, problem. When contaminant transport may occur via preferential flow, simple modeling approaches can provide predictions of interest, such as the first arrival of contaminant, with minimal site characterization. The conceptual model for unsaturated zone flow at Rainier Mesa and Shoshone Mountain, Nevada National Security Site, establishes the possibility of preferential flow through lithologies between potential radionuclide sources and the saturated zone. After identifying preferential flow as a possible contaminant transport process, we apply a simple model to estimate first arrival times for conservatively transported radionuclides to reach the saturated zone. Simulated preferential flow travel times at Rainier Mesa are tens to hundreds of years for non-ponded water sources and 1 to 2 months for continuously ponded water sources; first arrival times are approximately twice as long at Shoshone Mountain. These first arrival time results should then be viewed as a worst-case scenario but not necessarily as a timescale for a groundwater-contamination hazard, because concentrations may be very low. The alternative approach demonstrated here for estimating travel times can be useful in situations where predictions are needed by managers for the fastest arrival of contaminants, yet budgetary or time constraints preclude more rigorous analysis, and when additional model estimates are needed for comparison (i.e., model abstraction).     

Estimating aquatic toxicity as determined through laboratory tests of great lakes sediments containing complex mixtures of environmental contaminants

We developed and evaluated a total toxic units modeling approach for predicting mean toxicity as measured in laboratory tests for Great Lakes sediments containing complex mixtures of environmental contaminants (e.g., polychlorinated biphenyls, polycyclic aromatic hydrocarbons, pesticides, chlorinated dioxins, and metals). The approach incorporates equilibrium partitioning and organic carbon control of bioavailability for organic contaminants and acid volatile sulfide (AVS) control for metals, and includes toxic equivalency for planar organic chemicals. A toxic unit is defined as the ratio of the estimated pore-water concentration of a contaminant to the chronic toxicity of that contaminant, as estimated by U.S. Environmental Protection Agency Ambient Water Quality Criteria (AWQC). The toxic unit models we developed assume complete additivity of contaminant effects, are completely mechanistic in form, and were evaluated without any a posteriori modification of either the models or the data from which the models were developed and against which they were tested. A linear relationship between total toxic units, which included toxicity attributable to both iron and un-ionized ammonia, accounted for about 88% of observed variability in mean toxicity; a quadratic relationship accounted for almost 94%. Exclusion of either bioavailability components (i.e., equilibrium partitioning control of organic contaminants and AVS control of metals) or iron from the model substantially decreased its ability to predict mean toxicity. A model based solely on un-ionized ammonia accounted for about 47% of the variability in mean toxicity. We found the toxic unit approach to be a viable method for assessing and ranking the relative potential toxicity of contaminated sediments.The U.S. Government right to retain a non-exclusive royalty free licence in and to any copyright is acknowledged.     

Aluminium in UK rivers: a need for integrated research related to kinetic factors, colloidal transport, carbon and habitat

Dissolved aluminium concentrations ([Al]) in the <0.45 μm filtered fraction are described for 54 UK river sites covering rural, acidic/acid sensitive, agricultural and urban typologies, and wide pH range (4 to 11). High [Al] occurred under acidic conditions and for acid runoff neutralised by bicarbonate rich groundwater. Thermodynamic analysis indicates Al hydroxide/hydroxy-silicate oversaturation at circumneutral pH across the rivers, but undersaturation at lower/higher pH. The oversaturation reflects in part the presence of Al bearing colloids as indicated by (1) [Al] being correlated with components associated with both lithogenic (Fe, Ti and lanthanides) colloids and organic carbon, (2) baseflow studies using cross-flow ultrafiltration and (3) comparison of our data with Acid Waters Monitoring Network (AWMN) information on labile and non-labile Al. Tree harvesting and emission reductions of SO(x) in acidic and acid sensitive catchments in mid-Wales led to acidification reversal, lower [Al] and changing [H(+)] - [Al] relationships. The [Al] decline was confined to acidic conditions while [Al] increased during the later part of the monitoring period with a peak around 2002 for moorland and forested systems. Colloidal production across the flow range was indicated late in the record by comparison of our data with information collected by the AWMN for a site in mid-Wales. This production seems interlinked with organic carbon and with dissolved CO(2) changes. In order for further understanding of Al hydrogeochemistry in river systems there is a need to integrate research that moves from equilibrium to kinetic and colloidal consideration including the critical issues of organic and inorganic controls within the context of bioavailability and aquatic stress. The colloidal Al may well be of low environmental concern to fish and other factors such as habitat may well be critical.     

Modelling the Competitive Sorption Process of Multiple Solutes During their Transport in Porous Media

A general mathematical model to solve the advection–dispersion transport equation for multiple solutes was developed, where the dual porosity mobile–immobile mass transfer, the two-site non-equilibrium model and first-order transformation reactions were included. The two-site model was expressed with an equilibrium sorption term and a kinetic term. One of three kinetic models could be used: the non-linear, the bilinear and the pore diffusion model. The traditional Freundlich or Langmuir isotherms were employed to simulate no-interaction between the solutes, but with the extended Freundlich or extended Langmuir isotherms, a competitive sorption could be simulated. The transport equation was solved with the Moving Concentration Slope method. The mathematical model was tested and further simplified by using real data from soil column experiments, with 1,2-cis-dichloroethene and trichloroethene as model contaminants and silica gel and real soil samples as porous medium.     

Magnesium hydroxide bulk and colloid-associated 152Eu in an alkaline environment: colloid characterisation and sorption properties in the presence and absence of carbonate

The distribution of 152Eu between magnesium hydroxide bulk, colloids and solution has been assessed under alkaline conditions, such as those in nuclear fuel storage ponds. The colloidal phase has been characterised by two complementary methods: coupled ultrafiltration-ICP-AES and scanning electron microscopy. The quantity and the size distribution of the colloidal phase is strongly ionic strength-dependent. A decrease of the quantity of colloids, in particular the larger size ranges, has been observed with increasing ionic strength. Small colloids (1 kDa-10 kDa fraction) are predominant at all ionic strengths. The morphology of colloids, observed by field-emission gun scanning electron microscopy, appears to change from hexagonal prismatic (characteristic to the mineral) to spherical (energetically more favourable) as size decreases. The distribution of 152Eu between the solid and liquid/colloidal phases has been investigated at carbonate concentrations ranging from 0 to 10(-2) M by coupled ultrafiltration and gamma-spectrometry. Mg(OH)2 bulk appears to be a very strong sorbent for 152Eu, since complete sorption onto the bulk happens for carbonate concentrations as high as 10(-3) M. Scavenging of 152Eu by Mg(OH)2 colloids is negligible in the presence of Mg(OH)2 bulk. The distribution of 152Eu between liquid and colloidal phases has been investigated in the absence of bulk at various carbonate concentrations. A significant uptake of 152Eu by the colloids in solution has been observed, which decreases with increasing carbonate concentration. 152Eu appears to be mainly associated to the smallest colloids (1 kDa-10 kDa fraction). There is a strong correlation between the sorption properties and the surface area of the colloids.     

Atmospheric deposition and storm induced runoff of heavy metals from different impermeable urban surfaces

Contaminants deposited on impermeable surfaces migrate to stormwater following rainfall events, but accurately quantifying their spatial and temporal yields useful for mitigation purposes is challenging. To overcome limitations in current sampling methods, a system was developed for rapid quantification of contaminant build-up and wash-off dynamics from different impervious surfaces. Thin boards constructed of concrete and two types of asphalt were deployed at different locations of a large carpark to capture spatially distributed contaminants from dry atmospheric deposition over specified periods of time. Following experimental exposure time, the boards were then placed under a rainfall simulator in the laboratory to generate contaminant runoff under controlled conditions. Single parameter effects including surface roughness and material composition, number of antecedent dry days, rain intensity, and water quality on contaminant build-up and wash-off yields could be investigated. The method was applied to quantify spatial differences in deposition rates of contaminants (TSS, zinc, copper and lead) at two locations varying in their distance to vehicle traffic. Results showed that boards exposed at an unused part of the carpark >50 m from vehicular traffic captured similar amounts of contaminants compared with boards that were exposed directly adjacent to the access route, indicating substantial atmospheric contaminant transport. Furthermore, differences in contaminant accumulation as a function of surface composition were observed. Runoff from asphalt boards yielded higher zinc loads compared with concrete surfaces, whereas runoff from concrete surfaces resulted in higher TSS concentrations attributed to its smoother surfaces. The application of this method enables relationships between individual contaminant behaviour and specific catchment characteristics to be investigated and provides a technique to derive site-specific build-up and wash-off functions required for modelling contaminant loads from impermeable surfaces.     

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.     

Size distribution and composition of phosphorus in the East Tiao River, China: the significant role of colloids

The environmental risk of aquatic phosphorus (P) critically depends on its mobility and bioavailability, both of which are greatly affected by the size distribution and composition of P. The size distribution (particulate, colloidal and truly dissolved phase) of P, composed of molybdate reactive P (MRP) and molybdate unreactive P (MUP), was determined at twenty-three typical sections of the East Tiao River, China in the plum rain season. Results indicated particulate P was dominant followed by the truly dissolved P, while colloidal P was quantitatively the lowest in the whole river. From upstream to downstream, particulate P sharply increased, along with a slight decrease of truly dissolved P. However, colloidal P remained at a relatively stable level in the whole river, ranging from below detection limit to 0.025 mg L(-1), 0 to 13.4% of total P (TP). Furthermore, colloidal MRP exhibited a rising trend downriver as compared to upriver, with the notable transfer of MRP from the truly dissolved phase to particulate and colloidal phases. Particle concentration effect for colloids, observed in the study of MRP distribution, further corroborated the role of colloids in MRP solid/liquid partitioning. These observations, in this large-scale field investigation, fitted the "colloidal pumping" hypothesis. It may be concluded that colloids act as the intermediate and buffer in the dynamically balanced transfer of P from truly dissolved phase to large particulate phase, having a significant role in size distribution of P.     

RISK ASSESSMENT METHODOLOGY FOR KARST AQUIFERS: (2) SOLUTE-TRANSPORT MODELING

Ground-water flow and solute-transport simulation modeling are major components of most exposure and risk assessments of contaminated aquifers. Model simulations provide information on the spatial and temporal distributions of contaminants in subsurface media but are difficult to apply to karst aquifers in which conduit flow is important. Ground-water flow and solute transport in karst conduits typically display rapid-flow velocities, turbulent-flow regimes, concentrated pollutant-mass discharge, and exhibit open-channel or closed-conduit flow. Conventional ground-water models, dependent on the applicability of Darcy`s law, are inappropriate when applied to karst aquifers because of the (1) nonapplicability of Darcian-flow parameters, (2) typically nonlaminar flow regime, and (3) inability to locate the karst conduits through which most flow and contaminant transport occurs. Surface-water flow and solute-transport models conditioned on a set of parameters determined empirically from quantitative ground-water tracing studies may be effectively used to render fate-and-transport values of contaminants in karst conduits. Hydraulic-flow and geometric parameters developed in a companion paper were used in the surface-water model, TOXI5, to simulate hypothetical slug and continuous-source releases of ethylbenzene in a karst conduit. TOXI5 simulation results showed considerable improvement for predicted ethylbenzene-transport rates and concentrations over qualitative tracing and analytical ground-water model results. Ethylbenzene concentrations predicted by TOXI5 simulations were evaluated in exposure and risk assessment models.