A field trial for in-situ bioremediation of 1,2-DCA

Historic spillages of chlorinated hydrocarbons at a vinyl chloride plant in the Rotterdam Botlek area in The Netherlands have lead to contamination of the underlying aquifer. The principal contaminant is 1,2-dichloroethane (1,2-DCA). The contamination is temporarily contained by a pump-and-treat system. A field trial was carried out to investigate the feasibility of treating the dissolved phase of 1,2-DCA via reductive dechlorination by injection of an aqueous solution of methanol, ammonium chloride and sodium chloride into the confined aquifer using an array of eight boreholes. Biodegradation of 1,2-DCA was localised. This was attributed to limited mixing of the carbon substrate within the test zone. In addition, clogging of recharge wells complicated groundwater circulation.     

1,2-二氯乙烷和1,2-二氯丙烷在某污染场地包气带的吸附-解吸特性

1,2-二氯乙烷(1,2-DCA)和1,2-二氯丙烷(1,2-DCP)是某污染场地地下水中检出最高的挥发性有机污染物。文中采用批试验方法,研究污染场地包气带中三种不同深度土壤样品对1,2-DCA和1,2-DCP的吸附-解吸特性。结果表明:土壤中有机质决定其吸附行为,三种土壤对1,2-DCA和1,2-DCP的吸附符合Henry线性等温方程,分配系数在20.49～22.43L.kg-1,1,2-DCA和1,2-DCP在三种土壤中分别具有相似的吸附能力;同一土壤中两种目标污染物的吸附能力为Kd(1,2-DCA)>Kd(1,2-DCP),但差别不大。1,2-DCA和1,2-DCP在三种土壤中的解吸可用Freundlich等温方程拟合,解吸的难易程度与土壤中黏粒含量相关,黏粒含量越高,目标污染物的解吸越困难,第三层(地下4.9～5.1m)土壤的防污能力较强;两种污染物在三种土壤中的解吸都存在明显的滞后效应,1,2-DCP的滞后指数比1,2-DCA的大。     

Effect of geochemical conditions on fate of organic compounds in groundwater

In situ microcosms were successfully used to study the degradation of a range of organic compounds in two pristine aquifers, one aerobic (Vejen) and one anaerobic (Villa Farm). Degradation and sorption behavior in the laboratory column microcosms packed with Villa Farm sediment was very similar to that in the in situ microcosms. However, when the columns were packed with quartz and equilibrated with aerated Villa Farm groundwater, behavior mirrored that at Vejen, indicating that oxygen rather than sediment or groundwater composition was the critical parameter. The aromatic and polyaromatic compounds (benzene, toluene,o-xylene, naphthalene) degraded under aerobic conditions only. The organochlorine compounds (trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, 1,4-dichlorobenzene and 1,2-dichlorobenzene) showed little or no sign of degradation either aerobically or anaerobically. Interpretation of the data was complicated by strong sorption to the Villa Farm sediment but tetrachloromethane, nitrobenzene, ando-nitrophenol appeared to degrade under anaerobic conditions only. Phenol degraded rapidly under both sets of conditions.     

Experimental investigations on the formation of excess air in quasi-saturated porous media

The formation of an excess of dissolved gas (“excess air”) in quasi-saturated media was studied by analyzing and interpreting dissolved noble gas concentrations in laboratory column experiments. Using quartz sand filled columns of 1 m length, two different experimental designs were realized. In the first, groundwater recharge was simulated by a unidirectional vertical water flow through the columns. In the second, groundwater level fluctuations in an aquifer zone without active infiltration were reproduced by cyclic water level fluctuations in the columns. The reproducible generation of excess air under these defined, near natural conditions was successful. Partial or complete dissolution of air bubbles entrapped in the quartz sand could be identified as the mechanism responsible for the generation of excess air. Depending on the experimental design, supersaturation of the dissolved atmospheric noble gases ranging between 1.4% ΔNe and 16.2% ΔNe was found. The measured noble gas patterns were interpreted using inverse modeling and conceptual gas exchange models and were compared to results of numerical simulations of gas bubble dissolution in water filled soil columns. The gas composition in most of the samples resembles either unfractionated pure atmospheric excess air or is fractionated in accordance with closed-system equilibration between entrapped air and surrounding water. In addition to the amount of entrapped air, the hydrostatic pressure exerted on the entrapped air bubbles is the dominating parameter responsible for the total amount of dissolved air. The composition of the excess air component is controlled by the water flow regime, the bubble size distribution, the initially dissolved gas concentrations and the initially entrapped gas composition.     

Intrinsic biodegradation of toluene coupled to the microbial reduction of ferric iron: laboratory column experiments

Intrinsic biodegradation of toluene coupled with the microbial reduction of ferric iron (Fe(III)) as the terminal electron acceptor was studied by using laboratory column experiments under continuous flow conditions. Columns were packed with contaminated aquifer sediment and N₂-purged groundwater taken from the western part of the Gardermoen aquifer. The columns were operated anaerobically at 8 °C (in-situ temperature). Chloride was initially used to characterize flow properties of the columns. Intrinsic biodegradation of toluene, including abiotic loss and biological loss, was estimated by comparing breakthrough curves of toluene for live columns and sterilized control columns based on mass balance in steady-state conditions. The column experiments were run at two different flow velocities. The estimated average intrinsic rate was -0.73 and -0.53 mM day^-1 for pore-water velocities of 1.75 and 2.68 cm h^-1, respectively, corresponding to -0.27 and -0.22 mM day^-1 in biological loss rate. The results indicate that intrinsic biodegradation of toluene could be used as an efficient remediation approach for contaminated groundwater at the Gardermoen fire-fighting training site.     

Electrokinetic retention, migration and remediation of nitrates in silty loam soil under hydraulic gradients

Contamination of groundwater by nitrates leaching from intensive agricultural and livestock operations have become a major concern for surrounding communities that use groundwater as their water supply. High levels of nitrate in drinking water poses a significant risk to human health, i.e., methaemoglobinaemia (“blue baby” syndrome).

The traditional pump-and-treat method is ineffective in medium to fine-textured agricultural soils due to the low hydraulic conductivity. This paper presents the results of a laboratory experiment investigating the feasibility of using electrokinetic treatment in retaining, accumulating, moving and remediating nitrates in a silty loam soil under hydraulic gradients.

A hydraulic gradient of 1.25 was applied to the horizontal soil columns to simulate a groundwater movement system. The study was performed in two stages. During the first stage of the experiment, the anode located at the inflow end of the columns was able to retard the movement of nitrates even under a hydraulic gradient of 1.25. After 15 days of flow, the effluent nitrate concentration in the control column rose to 90 mg l⁻¹ while no nitrates were detected in the effluent from columns subjected to the electrokinetic treatment.

After 15 days, the polarity of the electrodes was switched and this second stage lasted another 20 days. The cathode near the inflow end promoted the conversion of nitrates entering the column to other forms. The anode near the outflow end promoted the migration and accumulation of negatively charged nitrate ions towards the outflow end. By the 12th day, the nitrate concentrations in the electrokinetically treated columns were brought down to <5 mg NO₃-N l⁻¹. Electrokinetic treatment retarded nitrate movement against a hydraulic gradient of 1.25 and effectively restored a medium-textured soil contaminated with NO₃-N.

The NO₂-N level remained below 1 mg l⁻¹ throughout the experiment. The hydraulic conductivity varied between 1.0E–7 and 3.6E–7 m s⁻¹. The current requirement varied between 3 and 6 mA.     

Laboratory and pilot studies on reclamation of a salt-affected alluvial soil

Soil column experiments showed that a surficial sodic soil is efficiently reclaimed using freshwater, after the addition of saturated gypsum solution. Gypsum application in the field was beneficial in terms of maintaining high soil permeability, increased water infiltration and neutral pH after a rainfall event. In the present paper, two different reclamation techniques for the plough layer of a sandy loam sodic soil were tested in laboratory columns, 25 cm long and 10 cm in diameter; the first using freshwater alone and the second using a saturated gypsum solution. The dynamics of salt removal were studied by continuous analysis of the water drained from the bottom of the columns. When freshwater was used, sodium presented the lower removal rate and adversely affected soil permeability. When gypsum solution was used, calcium was present in the flushing solution and the effect of sodium dominance on clay dispersion and soil clogging was limited. The results presented in this study are of practical importance with respect to the reclamation of sodic soils found in the coastal area of the east Nestos Delta, Greece, where freshwater is limited, due to seawater intrusion, and saline groundwater is used for irrigation.     

Pesticide transport and transformation modeling in soil column and groundwater contamination prediction

Pesticide transport and transformation were modeled in soil column from the soil surface to groundwater zone. A one dimensional dynamic mathematical and computer model is formulated to simulate two types of pesticides namely 2,4-dichlorophenoxy acetic acid and 1,2-dibromo 3-chloro propane in soil column. This model predicts the behavior and persistence of these pesticides in soil column and groundwater. The model is based on mass balance equation, including convective transport, dispersive transport and chemical adsorption in the phases such as solid, liquid and gas. The mathematical solution is obtained by finite difference implicit method. The model was verified with experimental measurements and also with analytical solution. The simulation results are in good agreement with measured values. The major findings of this research are the development of the model which can calculate and predict the concentration of pesticides in soil profiles, as well as groundwater after 4, 12, 31 days of pesticide application under steady state and unsteady water flow condition. With the results of this study, the distribution of various types of pesticides in soil column to groundwater table can be predicted.     

土壤类型及组分对热活化过硫酸盐氧化降解土壤中挥发性氯代烃的影响

为了探究高级氧化技术对土壤中有机氯代烃的氧化降解作用,为ISCO（in situ chemical oxidation）技术体系提供重要的理论依据和数据支撑,考察了热活化过硫酸盐（persulfate,PS）氧化降解不同类型土壤（砂类土壤、黏土类土壤）中挥发性氯代烃污染物（三氯乙烯（TCE）、三氯乙烷（TCA）、顺式-1,2-二氯乙烯（cis-1,2-DCE）、1,2-二氯乙烷（1,2-DCA））的效能;同时,通过硫酸盐与土壤相互作用过程研究,探究了不同土壤介质中有机质和无机组分在过硫酸盐消耗中所占比例。结果表明：在50℃时,热活化过硫酸盐可有效降解土壤中1,2-DCA、cis-1,2-DCE、TCA和TCE,砂类土壤介质中4种氯代烃降解效果依次为25%、89%、5%和61%,黏土类土壤介质中4种氯代烃降解效果依次为35%、86%、8%和63%;4种氯代烃的降解效果从高到低顺序依次为cis-1,2-DCE、TCE、1,2-DCA、TCA,砂类土壤中的氯代烃总体降解效果优于黏土类土壤中氯代烃的降解效果。另外,土壤中过硫酸盐氧化降解氯代烃反应研究发现,砂类和黏土类土壤介质组分中有机质消耗率分别为81.3%和72.6%,铁元素消耗率分别为80.5%和38.6%,表明土壤介质组分与过硫酸盐发生了氧化还原反应,从而导致过硫酸盐自身的大量消耗。由此可知,土壤介质中的有机质、铁元素等矿物质均参与过硫酸盐的消耗过程,且土壤有机质、铁元素与氯代烃之间在消耗过硫酸盐反应上存在竞争关系,土壤组分过多地消耗了过硫酸盐,导致了氯代烃的氧化降解效率较低。因此,针对实际有机氯代烃污染场地,采用过硫酸盐氧化技术进行修复时,过硫酸盐的实际投加量要远高于化学计量值,需充分考虑到土壤组分对过硫酸盐自身的消耗作用。     

氮类污染物在土壤中迁移转化规律试验研究

在分析氮物质迁移过程的基础上,借助于土柱物理模型试验装置,试验研究了氮类污染物在土壤中迁移转化规律,得到了NH₄+-N、NO₃--N在土柱内的时空变化过程。在分析实测资料后,建立了考虑氮的迁移和转化的数学模型。根据实测资料和数学模型的数值解,运用最优化技术率定模型参数,参数验证结果与独立的实测值吻合良好。     

Experimental Studies on Behaviour of Stone Columns in Layered Soils

Stone columns are found to be effective and economical ground improvement technique in soft grounds. Understanding its behaviour when they are installed in stratified soils, in particular when the upper layer consists of weak soil, will be of great practical significance. This paper presents results from a series of laboratory plate load tests carried out in unit cell tanks to investigate the behaviour of stone columns in layered soils, consisting of weak soft clay overlying a relatively stronger silty soil, for various thicknesses of the top layer. Tests were carried out with two types of loading (1) the entire area in the unit cell tank loaded, to estimate the stiffness of improved ground and (2) only the stone column loaded, to estimate the limiting axial capacity. Laboratory tests were carried out on a column of 90 mm diameter surrounded by layered soil, for an area ratio of 15%. It is found that the depth of top weak layer thickness has a significant influence on the stiffness, load bearing capacity and bulging behavior of stone columns.     

土层结构对非饱和毛细水盐运移的影响

层状土层之间孔隙结构和水力学性质的不连续性对土体水盐运移有显著影响。基于现场调查,设计了两种不同粒径土层二元结构组合(黄土-砂质粉土和黄土-粉质黏土)的室内土柱试验,通过模型试验讨论了不同地下水补给条件下土层结构对毛细水分布和盐分累积的影响。试验结果表明:在毛细水补给条件下,黄土-砂质粉土构成的上细下粗型土层结构有利于毛细水盐运移,经过60 d蒸发后,其表层SO_4~(2-)含量是上粗下细型土柱的两倍。在无毛细水补给条件下,砂质粉土层中水盐向上迁移总量和迁移速率大于粉质黏土层,最终上细下粗型土柱中上覆土层各层位离子含量均大于上粗下细型土柱。研究结果为层状土区盐渍土病害的防治提供了试验参考。     

Geoenvironmental site investigation using different techniques in a municipal solid waste disposal site in Brazil

Different geoenvironmental site investigation techniques to assess contamination from a municipal solid waste disposal site in Brazil are presented here. Superficial geophysical investigation (geoelectrical survey), resistivity piezocone penetration tests (RCPTU), soil samples collected with direct-push samplers and water samples collected from monitoring wells were applied in this study. The application of the geoelectrical method was indispensable to identify the presence and flow direction of contamination plumes (leachate) as well as to indicate the most suitable locations for RCPTU tests and soil and water sampling. Chemical analyses of groundwater samples contributed to a better understanding of the flow of the contaminated plume. The piezocone presented some limitations for tropical soils, since the groundwater level is sometimes deeper than the layer which is impenetrable to the cone, and the soil genesis and unsaturated conditions affect soil behavior. The combined interpretation of geoelectrical measurements and soil and water samplings underpinned the interpretation of RCPTU tests. The interpretation of all the test results indicates that the contamination plume has already overreached the landfill’s west-northwest borders. Geoenvironmental laboratory test results suggest that contamination from the solid waste disposal site has been developing gradually, indicating the need for continuous monitoring of the groundwater.     

Selenium attenuation via reductive precipitation in unsaturated waste rock as a control on groundwater impacts in the Idaho phosphate patch

Phosphate mining in southeastern Idaho has historically resulted in the release of dissolved metals and inorganics to groundwater and surface water, primarily due to leachate from waste rock in backfilled pits and overburden storage piles. Selenium (Se) is of particular concern due to its high concentration in leachate and its limited attenuation downgradient of source zones under oxic conditions. Assessments of potential groundwater/surface water impacts from waste rock typically involve laboratory characterization using saturated and unsaturated flow columns packed with waste rock. In this study, we compare the results of saturated and unsaturated column tests with groundwater quality data from the Mountain Fuel, Champ, South and Central Rasmussen Ridge Area (SCRRA), Smoky Canyon, Ballard, Henry, and Enoch Valley Mines, to understand the release and attenuation of Se in different geochemical environments. Column studies and field results demonstrate that the ratio of aqueous Se to aqueous sulfate (Se:SO₄ ratio) is a useful metric for understanding Se release and attenuation, where the extent of sulfate reduction is much less than Se reduction. Comparison of dissolved Se and sulfate results suggests that the net leachability of Se from unsaturated waste rock is variable. Overall, Se concentrations in groundwater directly beneath waste rock dumps is not as high as would be predicted from unsaturated columns. Lower Se:SO₄ ratios are observed immediately beneath waste rock dumps and backfilled pits relative to areas receiving shallow waste rock runoff. It is hypothesized that Se released in the oxic upper portions of the waste rock is subsequently attenuated via reductive precipitation at depth in unsaturated, low-oxygen portions of the waste rock. This highlights an important mechanism by which Se may be naturally attenuated within waste rock piles prior to discharge to groundwater and surface water. These results have important implications for mining practices in the region. A better understanding of Se dynamics can help drive waste rock management during active mining and capping/water management options during post-mining reclamation.     

Finite element modelling of laterally loaded lime–cement columns using a damage plasticity model

The behaviour of laterally loaded lime–cement columns in a shear box was studied. Laboratory tests are presented together with numerical analyses where the columns are simulated by a concrete damage plasticity model that considers stiffness degradation. Seven model tests were investigated where the columns were installed in a single column pattern and in rows with different column overlap in order to investigate the influence of the degree of overlapping of the columns in the rows. The results of the numerical evaluations showed good agreement with the experimental shear stress–displacement relation and a good accuracy with respect to the fractures developed.     

Prediction of Land Subsidence Under Cyclic Pumping Based on Laboratory and Numerical Simulations

In this study subsidence due to groundwater withdrawal was investigated. Kerman Province in Iran is struggling with land subsidence problem due to extensive groundwater withdrawal mainly for farming. The rate and type of groundwater withdrawal has very important impact on settlement rate. In this research, effective parameters on land subsidence caused by groundwater withdrawal were determined by laboratory tests. Sampling had done up to depth of 300 m mainly with remolded specimens from Shams-abad, Nouq plain in Kerman province. Similar to the field preconsolidation pressure was applied on specimens in the laboratory. Rate of applied stress on prepared specimens was similar to effect of oscillation of groundwater level. In order to model the actual soil behavior in the laboratory, one-dimensional consolidation device (odometer) was adopted for testing. In these tests, the effect of loading caused by seasonal oscillation of groundwater table is considered by means of cyclic loading in the testing which has great effect on rate of settlements. The results of tests show that when the water table level periodically increases and decreases the amount of settlement decrease, comparing with the case when the groundwater table drop to a constant level. In order to predict the further effects of groundwater level oscillation and actual field condition on land subsidence, a finite element model based on Biots’ three-dimensional consolidation theory was developed. After calibration of finite element model with laboratory tests, this model was used for prediction the effect of groundwater level oscillation on actual field conditions.     

Vertical bearing capacity behaviour of single T-shaped soil–cement column in soft ground: laboratory modelling,field test,and calculation

The T-shaped soil–cement column is a variable-diameter column, which has an enlarged column cap at the shallow depth, resulting in the column shape being analogous to the letter “T”. In this study, 1-g laboratory and full-scale field loading tests were employed to investigate the vertical bearing capacity behaviour of a single T-shaped column in soft ground. Pressure cells were set in a T-shaped column in the field to measure the vertical column stress above and below the column cap during the loading test. After the loading test, several columns were excavated to investigate their failure modes. The results indicated that, since the section area of the column cap was remarkably higher than that of the deep-depth column, the stress concentration occurred in the deep-depth column just under the cap, leading to column failure. Based on this failure mode, a simplified method was proposed to estimate the ultimate bearing capacity of a single T-shaped column; the comparison of estimated and measured results indicated the applicability of the proposed method.     

Effects of land use on the spatial distribution of trace metals and volatile organic compounds in urban groundwater, Seoul, Korea

To investigate the urban groundwater contamination by eight trace metals and 69 volatile organic compounds (VOCs) in relation to land use in Seoul, a total of 57 groundwater samples collected from wells were examined using a non-parametric statistical analysis. Land use was classified into five categories: less-developed, residential, agricultural, traffic, and industrial. A comparison of analyzed data with US EPA and Korean standards for drinking water showed that some metals and VOCs exceeded the standards in a few localities, such as Fe (N=5), Mn (N=6), Cu (N=1), TCE (N=6), PCE (N=8), 1,2-DCA (N=1), and 1,2-dichloropropane (N=1). Among the 69 investigated VOCs, 19 compounds such as some gasoline-related compounds (e.g., toluene) and chlorinated compounds (e.g., chloroform, PCE, TCE) were detected in groundwater. Non-parametric statistical analysis showed that the concentrations of most trace metals (Fe, Mn, As, Cr, Pb, Cd) and some VOCs (especially, TCE, PCE, chloroform; toluene, carbon tetrachloride, bromodichloromethane, CFC113) are significantly higher in the industrial, residential, and traffic areas (P<0.05), indicating that anthropogenic contamination of urban groundwater by those chemicals is growing. Those chemicals can be used as effective indicators of anthropogenic contamination of groundwater in urban areas and therefore a special attention is warranted for a safe water supply in those areas. The results of this study suggest that urban groundwater quality in urban areas is closely related with land use.     

Precise method for continuous measurement of fluorescent microspheres during flow

A sensitive and reliable continuous detection method for fluorescent microspheres using a laboratory spectrofluorometer and a micro-flow-through-cell with a volume of 100?µL was developed and first applied for column testing using three different sizes of fluorescent microspheres (0.2, 1 and 3?µm) and solute fluorescent tracers. Calibrations prior to column transport experiments with different ionic strengths of the background solution show a linear relationship between fluorescence intensity and number of microspheres, with a detection limit of ~10³/mL (for 1?µm microspheres). Thus short-pulse experiments with low microsphere input numbers and a high temporal resolution of the tracer breakthrough curve can be used to quantify the microsphere transport behavior, independent of background fluorescence, in a detailed and precise manner. The proposed method gives precise results for a wide range of tracer experiments in soil columns for different background solutions and soil substrates; furthermore the concentrations of colloidal and solute fluorescent tracers can be evaluated in a short period. A new software tool (Cocos) enables processing of the fluorescence spectra so that fluorescence intensity and particle concentration over time can be obtained easily.     

Influence of topsoil of pyroclastic origin on microbial contamination of groundwater in fractured carbonate aquifers

The aim of the research was to analyse the influence of a topsoil of pyroclastic origin on microbial contamination of groundwater in a carbonate aquifer and verify the reliability of thermotolerant coliforms and fecal enterococci as bacterial indicators. The research was carried out through hydrogeological and microbiological monitoring at an experimental field site in Italy during two hydrologic years and through column tests in a laboratory. The taxonomic classification of fecal indicators detected in spring water samples was performed using API20 galleries. Fecal enterococci were also identified by means of 16S rRNA gene sequencing. The topsoil of pyroclastic origin significantly retains both thermotolerant coliforms and fecal enterococci. Results of column tests carried out in soil blocks collected randomly within the test site suggest that Escherichia coli was more retained than Enterococcus faecalis, even though this difference is statistically significant in only two out of six soil samples. Thus, a non-uniform difference in retention is expected at field scale. This suggestion is in agreement with the results of the microbiological monitoring. In fact, fecal enterococci were a more reliable indicator than thermotolerant coliforms for detecting contamination at both seasonal springs of the aquifer system, while no significant differences were observed at the perennial spring.