Plant aided bioremediation in the vadose zone: model development and applications

Phytoremediation has the potential to enhance clean up of land contaminated by various pollutants. A mathematical model that includes a two-fluid phase flow model of water flow as well as a two-region soil model of contaminant reactions was developed and applied to various bioremediation scenarios in the unsaturated zone, especially to plant-aided bioremediation. To investigate model behavior and determine the main parameters and mechanisms that affect bioremediation in unplanted and planted soils, numerical simulations of theoretical scenarios were conducted before applying the model to field data. It is observed from the results that parameters affecting the contaminant concentration in the water phase, such as aqueous solubility, the octanol-water partition coefficient, and organic carbon content of the soil controlled the contaminant fate in the vadose zone. Simulation using the developed model also characterized the fate and transport of the contaminants both in planted and unplanted soils satisfactorily for field applications. Although phytoremediation has the potential for remediation of contaminated soils, results from both modeling and field studies suggested that plants may not always enhance the remediation efficiency when the soil already has a high microbial concentration, when the contaminant bioavailability is low, or when the overall reaction is mass transfer-limited. Therefore, other steps to increase contaminant bioavailability are needed in phytoremediation applications; natural purification mechanisms such as aging, volatilization, and natural bioremediation should be considered to maximize the plant effect and minimize the cost.     

Integrated methodology for assessing the HCH groundwater pollution at the multi-source contaminated mega-site Bitterfeld/Wolfen

A large-scale groundwater contamination characterises the Pleistocene groundwater system of the former industrial and abandoned mining region Bitterfeld/Wolfen, Eastern Germany. For more than a century, local chemical production and extensive lignite mining caused a complex contaminant release from local production areas and related dump sites. Today, organic pollutants (mainly organochlorines) are present in all compartments of the environment at high concentration levels. An integrated methodology for characterising the current situation of pollution as well as the future fate development of hazardous substances is highly required to decide on further management and remediation strategies. Data analyses have been performed on regional groundwater monitoring data from about 10 years, containing approximately 3,500 samples, and up to 180 individual organic parameters from almost 250 observation wells. Run-off measurements as well as water samples were taken biweekly from local creeks during a period of 18 months. A kriging interpolation procedure was applied on groundwater analytics to generate continuous distribution patterns of the nodal contaminant samples. High-resolution geological 3-D modelling serves as a database for a regional 3-D groundwater flow model. Simulation results support the future fate assessment of contaminants. A first conceptual model of the contamination has been developed to characterise the contamination in regional surface waters and groundwater. A reliable explanation of the variant hexachlorocyclohexane (HCH) occurrence within the two local aquifer systems has been derived from the regionalised distribution patterns. Simulation results from groundwater flow modelling provide a better understanding of the future pollutant migration paths and support the overall site characterisation. The presented case study indicates that an integrated assessment of large-scale groundwater contaminations often needs more data than only from local groundwater monitoring. The developed methodology is appropriate to assess POP-contaminated mega-sites including, e.g. HCH deposits. Although HCH isomers are relevant groundwater pollutants at this site, further organochlorine pollutants are present at considerably higher levels. The study demonstrates that an effective evaluation of the current situation of contamination as well as of the related future fate development requires detailed information of the entire observed system.     

Modeling of flow and contaminant transport in coupled stream-aquifer systems

This paper describes an integrated approach for modeling flow and contaminant transport in hydraulically connected stream-aquifer systems. The code, FTSTREAM, extended the capabilities of the ground-water model, FTWORK, to incorporate chemical fate and transport in streams. Flow in the stream network is modeled as an unsteady, spatially varying flow, while transport modeling is based on a one-dimensional advection-dispersion equation. In addition to sorption and decay during transport in ground water, the model incorporates volatilization, settling and decay during transport in surface water. The interaction between surface water and ground water is accommodated by a leakage term and is implemented in the model using an iterative Picard-type procedure to ensure mass conservation across the interface between the two systems. The modeling approach is used to simulate contaminant transport in the Mad River, Ohio, which is hydraulically connected to a buried valley aquifer of sand and gravel outwash. The river is a receiving stream in the upstream part of the modeled area. Downstream, heavy pumping from a municipal well field causes the river to become a loosing stream. Induced infiltration from the river is responsible for a considerable portion of the well yield. The flow and transport model, developed for this study, simulates coupling between flow in the aquifer and the river. Hypothetical sources of contamination are introduced at selected locations in the upstream portion of the aquifer. The model is then used to simulate the expected transport in both the aquifer and the stream. A series of simulations elucidates the role of the river in facilitating the transport of the hypothetical contaminants in ground water and surface water. Effect of sorption, retardation and volatilization on contaminant transport is also examined for the case of the volatile organic compounds.     

Analytical model of solute transport by unsteady unsaturated gravitational infiltration

Penetration of reactive solute into a soil during a cycle of water infiltration and redistribution is investigated by deriving analytical closed form solutions for fluid flux, moisture content and contaminant concentration. The solution is developed for gravitational flow and advective transport and is applied to two scenarios of solute applications encountered in the applications: a finite pulse of solute dissolved in irrigation water and an instantaneous pulse broadcasted onto the soil surface. Through comparison to simulations of Richards' flow, capillary suction is shown to have contrasting effects on the upper and lower boundaries of the fluid pulse, speeding penetration of the wetting front and reducing the rate of drying. This leads to agreement between the analytical and numerical solutions for typical field and experimental conditions. The analytical solution is further incorporated into a stochastic column model of flow and transport to compute mean solute concentration in a heterogeneous field. An unusual phenomenon of plume contraction is observed at long times of solute propagation during the drying stage. The mean concentration profiles match those of the Monte-Carlo simulations for capillary length scales typical of sandy soils.     

Development of the hybrid cells in series model to simulate ammonia nutrient pollutant transport along the Umgeni River

Discharge of organic waste results in high nutrient pollution of the water bodies which is a major menace to the environment. A high quantity of nutrients such as ammonia causes a reduction in the dissolved oxygen level and induces algal growth in the water bodies. Water quality models have been the tools to evaluate the rate at which streams can disperse the pollutants they receive. Many water quality models are flawed either because of their inadequacy to completely simulate the advection component of the pollutant transport, or because of the limited application of the models, due to inaccurate estimation of model parameters. The hybrid cell in series (HCIS) developed by Ghosh et al. (2004) has been able to overcome such difficulties associated with the mixing cell-based models. Thus, the current study focuses on developing an analytical solution for the pollutant transport of the ammonia concentration through the plug flow, the first and second well-mixed cells of the HCIS model. The HCIS model coupled with the first order kinetic equation for ammonia nutrient was developed to simulate the ammonia pollutant concentration in the water column. The ammonia concentration at various points along the river system was assessed by considering the effects of the transformation of ammonia to nitrite, the uptake of ammonia by the algae, the respiration rate of the algae and the input of benthic source to the ammonia concentration in the water column. The proposed model was tested using synthetic data, and the HCIS-NH₃ model simulations for spatial and temporal variation of ammonia pollutant transport were analysed. The simulated results of the HCIS-NH₃ model agreed with the Fickian-based advection-dispersion equation (ADE) for simulating ammonia concentration solved using an explicit finite difference scheme. The HCIS-NH₃ model also showed a good agreement with the observed data from the Umgeni River, except during rainy periods.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Volatilization of contaminants from suspended sediment in a water column during dredging

Remedial dredging of contaminated bed sediments in rivers and lakes results in the suspension of sediment solids in the water column, which can potentially be a source for evaporation of hydrophobic organic compounds (HOCs) associated with the sediment solids. Laboratory experiments were conducted in an oscillating grid chamber to simulate the suspension of contaminated sediments and flux to air from the surface of the water column. A contaminated field sediment from Indiana Harbor Canal (IHC) and a laboratory-inoculated University Lake (UL) sediment, Baton Rouge, LA, were used in the experiments, where water and solids concentration and particle size distribution were measured in addition to contaminant fluxes to air. A transient model that takes into account contaminant desorption from sediment to water and evaporation from the water column was used to simulate water and sediment concentrations and air fluxes from the solids suspension. In experiments with both sediments, the total suspended solids (TSS) concentration and the average particle diameter of the suspended solids decreased with time. As expected, the evaporative losses were higher for compounds with higher vapor pressure and lower hydrophobicity. For the laboratory-inoculated sediment (UL), the water concentrations and air fluxes were high initially and decreased steadily implying that contaminant release to the water column from the suspended solids was rapid, followed by evaporative decay. For the field sediments (IHC), the fluxes and water concentrations increased initially and subsequently decreased steadily. This implied that the initial desorption to water was slow and that perhaps the presence of oil and grease and aging influenced the contaminant release. Comparison of the model and experimental data suggested that a realistic determination of the TSS concentration that can be input into the model was the most critical parameter for predicting air emission rates.     

综合调水对苏州河周边水系水质影响的数值模拟

进行长期有效的水资源综合调度是实现2010年苏州河河水变清的综合整治目标的一项重要措施。为进一步论证该项措施对周边水系的水质影响,为综合调水提供科学的决策依据,利用MIKE11模型系统建立了上海市苏州河水系的水动力、水质模型,进行苏州河综合调水对黄浦江以及蕴藻浜水质的影响作用的数值模拟。分析表明,苏州河综合调水对松浦大桥取水口水质基本没有影响,并可以在一定程度上改善黄浦江干流中下游河段的水质;东引北排初期会增加蕴藻浜干流的污染负荷,持续调水6d后蕴藻浜干流河段的水质将得到改善。     

Laboratory studies to characterize the efficacy of sand capping a coal tar-contaminated sediment

Placement of a microbial active sand cap on a coal tar-contaminated river sediment has been suggested as a cost effective remediation strategy. This approach assumes that the flux of contaminants from the sediment is sufficiently balanced by oxygen and nutrient fluxes into the sand layer such that microbial activity will reduce contaminant concentrations within the new benthic zone and reduce the contaminant flux to the water column. The dynamics of such a system were evaluated using batch and column studies with microbial communities from tar-contaminated sediment under different aeration and nutrient inputs. In a 30-d batch degradation study on aqueous extracts of coal tar sediment, oxygen and nutrient concentrations were found to be key parameters controlling the degradation rates of polycyclic aromatic hydrocarbons (PAHs). For the five PAHs monitored (naphthalene, fluorene, phenanthrene, anthracene, and pyrene), degradation rates were inversely proportional to molecular size. For the column studies, where three columns were packed with a 20-cm sand layer on the top of a 5 cm of sediment layer, flow was established to sand layers with (1) aerated water, (2) N(2) sparged water, or (3) HgCl(2)-sterilized N(2) sparged water. After steady-state conditions, PAH concentrations in effluents were the lowest in the aerated column, except for pyrene, whose concentration was invariant with all effluents. These laboratory scale studies support that if sufficient aeration can be achieved in the field through either active and passive means, the resulting microbially active sand layer can improve the water quality of the benthic zone and reduce the flux of many, but not all, PAHs to the water column.     

Column studies to investigate the fate of veterinary antibiotics in clay soils following slurry application to agricultural land

The environment may be exposed to veterinary medicines administered to livestock due to the application of organic fertilisers to land. For other groups of substances that are applied to agricultural land (e.g. pesticides), preferential flow in underdrained clay soils has been identified as an extremely important pathway by which pollution of surface waters can occur. Three soil column leaching experiments have therefore been carried out using a clay soil to investigate the fate of a range of antibiotics from the sulphonamide, tetracycline and macrolide groups. These column studies complemented a range of other experiments at the field and semi-field scales, as well as modelling studies which are being reported in separate papers. Each column study had a different objective. The first examined the effect of pig slurry on the mobility of antibiotics in clay loam soil. The second experiment investigated changes in soil water pH due to the application of slurry. The final experiment quantified the extent to which soil tillage prior to slurry application can reduce the leaching of antibiotic residues found in slurry. It was found that slurry had no impact on the leaching of oxytetracycline although soil water pH was affected significantly by slurry application. It was also shown that pre-tillage can substantially reduce the leaching of antibiotic residues through macroporous clay soils.     

MTBE Transport Screening Analysis in Vadose Zone Risk and Liability Apportionment Assessment

The problem of allocating liability cleanup costs is an arduous task when more than one potentially responsible party has contributed to the groundwater plume. This problem is most likely to be encountered when dealing with methyl-tert -butyl-ether (MTBE) contamination, as MTBE is seen to travel large distances in underlying aquifers. There has been a significant effort in the recent past to develop liability allocation methodologies that incorporate fate and transport behavior and toxicological characteristics of the contaminants. The application of such methods often requires estimation of contaminant input from the vadose zone into the underlying aquifer. A screening level analysis is presented here to develop preliminary insights on relative mass contributions arising from different source types. The analysis illustrates how different vadose zone conceptualizations lead to vastly different contaminant loadings. Parametric studies indicate that the contaminant flux into the aquifer is very sensitive to changes in water infiltration rates. Hence, a reliable estimate of this parameter is critical for equitable allocation of remedial costs. Conceptual model formulation, should focus on identifying whether the fuel present in the aquifer can flow as a separate phase. It is also important to obtain reliable estimates for fluid saturations at the site.     

Ozonation of pentachlorophenol in unsaturated soils

A heterogeneous model was developed to describe interactions between ozone and hydrophobic organic compounds, exemplified by pentachlorophenol, in highly gas-saturated vadose zones where water moisture was limited to a thin film on soil particle surfaces. The soil was assumed to be free of soil organic matter. The model included a set of transient equations considering diffusion with simultaneous chemical reaction and hydrophobic partitioning. From dimensionless analysis, it was found that the film concentrations of ozone and the hydrophobic organic component were dependent on the Damk?hler numbers. Effects of Damk?hler numbers on the film profiles of components were examined. With the interfacial flux of ozone calculated from film profiles, dimensionless governing equations of ozone transport and contaminant removal across an experimental column were established. These equations were dependent on the Stanton number. One-dimensional column experiments were conducted to test the model. The optimal time for flow rate adjustment during the process was approximated. Finally, effects of ozone velocity and ozone gas concentration on the Stanton number were evaluated.     

MTBE Transport Screening Analysis in Vadose Zone Risk and Liability Apportionment Assessment

The problem of allocating liability cleanup costs is an arduous task when more than one potentially responsible party has contributed to the groundwater plume. This problem is most likely to be encountered when dealing with methyl- tert -butyl-ether (MTBE) contamination, as MTBE is seen to travel large distances in underlying aquifers. There has been a signi®cant effort in the recent past to develop liability allocation methodologies that incorporate fate and transport behavior and toxicological characteristics of the contaminants. The application of such methods often requires estimation of contaminant input from the vadose zone into the underlying aquifer. A screening level analysis is presented here to develop preliminary insights on relative mass contributions arising from different source types. The analysis illustrates how different vadose zone conceptualizations lead to vastly different contaminant loadings. Parametric studies indicate that the contaminant flux into the aquifer is very sensitive to changes in water infiltration rates. Hence, a reliable estimate of this parameter is critical for equitable allocation of remedial costs. Conceptual model formulation, should focus on identifying whether the fuel present in the aquifer can flow as a separate phase. It is also important to obtain reliable estimates for fluid saturations at the site.     

Simulation of carrier-facilitated transport of phenanthrene in a layered soil profile

The appropriate prediction of the fate of the contaminant is an essential step when evaluating the risk of severe groundwater pollutions-in particular in the context of natural attenuation. We numerically study the reactive transport of phenanthrene at the field scale in a multilayer soil profile based on experimental data. The effect of carrier facilitation by dissolved organic carbon is emphasized and incorporated in the model. Previously published simulations are restricted to the saturated zone and/or to homogeneous soil columns at the laboratory scale. A numerical flow and transport model is extended and applied to understand and quantify the relevant processes in the case of a strongly sorbing hydrophobic organic compound that is subject to carrier facilitation in the unsaturated zone. The contaminant migration is investigated on long- and short-term time scales and compared to predictions without carrier facilitation. The simulations demonstrate the importance of carrier facilitation and suggest strongly to take this aspect into account. By carrier facilitation breakthrough times at the groundwater level decreased from 500 to approximately 8 years and concentration peaks increased by two orders of magnitude in the long-term simulation assuming a temporary spill in an initially unpolluted soil with a non-sorbing carrier.     

Pharmaceuticals on a sewage impacted section of a Mediterranean River (Llobregat River,NE Spain) and their relationship with hydrological conditions

Introduction  

Mediterranean rivers are characterized by a high flow variability, which is strongly influenced by the seasonal rainfall. When water scarcity periods occur, water flow, and dilution capacity of the river is reduced, increasing the potential environmental risk of pollutants. On the other hand, floods contribute to remobilization of pollutants from sediments. Contamination levels in Mediterranean rivers are frequently higher than in other European river basins, including pollution by pharmaceutical residues. Little attention has been paid to the transport behavior of emerging contaminants in surface waters once they are discharged from WWTP into a river. In this context, this work aimed to relate presence and fate of emerging contaminants with hydrological conditions of a typical Mediterranean River (Llobregat, NE Spain).     

复合介质渗透反应格栅去除地下水中的氨氮

针对受低浓度氨氮污染的地下水,实验筛选组合了不同的反应介质,利用串联的多介质填充柱模拟渗透反应格栅,通过物理吸附及生物硝化-反硝化作用来实现氮的去除。结果表明,在进水氨氮浓度为10 mg/L、流速为0.5 m/d的条件下,模拟柱对氨氮的去除率达到98%以上,且不会出现亚硝酸盐及硝酸盐浓度的升高。水体经过释氧柱后溶解氧由2mg/L升高至10 mg/L以上,表明释氧材料可提供硝化细菌所需的好氧环境。好氧柱中填充易于生物挂膜的生物陶粒及对氨氮有较强吸附能力的沸石,二者联用通过生物硝化-物理吸附协同作用实现对氨氮的去除,其中生物作用实现的氨氮去除量占总去除量的50%左右。后续厌氧反应柱填充海绵铁除氧并利用松树皮颗粒作为碳源,创造反硝化菌生长条件,硝酸盐氮浓度可由10 mg/L降低至5 mg/L以下,实现对好氧反应阶段所产生的硝酸盐的去除,避免了地下水的二次污染。     

Quantifying the importance of diffuse minewater pollution in a historically heavily coal mined catchment

There has been considerable progress in developing treatment systems for point sources of minewater pollution in recent years; however, there remains a knowledge gap in the characterisation and remediation of diffuse minewater sources. Data are presented from the River Gaunless catchment, a historically heavily coal mined catchment in the northeast of England. Instream iron (Fe) loadings were monitored alongside loadings arising from point minewater discharges over a 12-month period to assess the dynamic importance of diffuse sources of minewater pollution. In low flow, diffuse sources account for around 50% of instream loading, a proportion which increases to 98% in high flow conditions. The low flow sources appear to be dominated by direct discharge of contaminated groundwater to surface waters in lower reaches of the catchment. In high flow, resuspended Fe-rich sediments, which are both naturally occurring and derived from historic mining, become the dominant diffuse source of Fe in the water column.     

湘江株洲段丰水期镉污染负荷总量测算及分配

以2010年8月湘江干流株洲段代表性断面水质与底泥监测资料以及其他资料为基础,采用WASP7模型模拟该江段丰水期镉浓度,并进行镉污染负荷测算与分配。研究结果表明,WASP7模型较好地重现了镉浓度的变化规律,8月份该河段上游镉入流量2 446.33 kg,下游出流量3 076.44 kg,区间增量630.12 kg,其中点源负荷量241.67 kg,占38.4%,面源负荷量304.49 kg,占48.3%,内源负荷量为83.96 kg,占13.3%。