Stochastic evaluation of mass discharge from pointlike concentration measurements

The contaminant mass discharge crossing a control plane is an important metric in the assessment of natural attenuation at contaminated sites. For risk-assessment purposes, the mass discharge must be estimated together with a level of uncertainty. We present a conditional Monte Carlo approach that allows estimating the statistical distribution of mass discharge. The approach is based on conditioning multiple realizations of the hydraulic conductivity field on all data available. We jointly determine a first-order decay coefficient in each realization, leading to conditional statistical distributions of all estimated parameters and the total mass discharge. The resulting statistical distribution of contaminant mass discharges can be used in the assessment of risks at the contaminated site. The method is applied to data of hypothetical test cases, which gives the opportunity to compare estimation results to the true field. As concentration data, we account for pointlike measurements obtained in multi-level sampling wells. The obtained empirical distribution of mass discharge crossing the multi-level sampling fence could be well fitted by a log-normal distribution.     

Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.     

A field comparison of BTEX mass flow rates based on integral pumping tests and point scale measurements

Measuring contaminant flow rates at control cross sections is the most accurate method to evaluate natural attenuation processes in the saturated subsurface. In most instances, point scale measurement is the method of choice due to practical reasons and cost factors. However, at many field sites, the monitoring network is too sparse for a reliable estimation of contaminant and groundwater flow rates. Therefore, integral pumping tests have been developed as an alternative. In this study, we compare mass flow rates obtained by integral pumping test results and point scale data. We compare results of both methods with regard to uncertainties due to estimation errors and mass flow estimations based on two different point scale networks. The differences between benzene and groundwater flow rate estimates resulting from point scale samples and integral pumping tests were 6.44% and 6.97%, respectively, demonstrating the applicability of both methods at the site. Point scale-based data, especially with use of cost efficient Direct-Push technique, can be applied to show the contaminant distribution at a site and may be followed by a denser point scale network or an integral method. Nevertheless, a combination of both methods decreases uncertainties.     

Changes in contaminant mass discharge from DNAPL source mass depletion: evaluation at two field sites

Changes in contaminant fluxes resulting from aggressive remediation of dense nonaqueous phase liquid (DNAPL) source zone were investigated at two sites, one at Hill Air Force Base (AFB), Utah, and the other at Ft. Lewis Military Reservation, Washington. Passive Flux Meters (PFM) and a variation of the Integral Pumping Test (IPT) were used to measure fluxes in ten wells installed along a transect down-gradient of the trichloroethylene (TCE) source zone, and perpendicular to the mean groundwater flow direction. At both sites, groundwater and contaminant fluxes were measured before and after the source-zone treatment. The measured contaminant fluxes (J; ML(-2)T(-1)) were integrated across the well transect to estimate contaminant mass discharge (M(D); MT(-1)) from the source zone. Estimated M(D) before source treatment, based on both PFM and IPT methods, were approximately 76 g/day for TCE at the Hill AFB site; and approximately 640 g/day for TCE, and approximately 206 g/day for cis-dichloroethylene (DCE) at the Ft. Lewis site. TCE flux measurements made 1 year after source treatment at the Hill AFB site decreased to approximately 5 g/day. On the other hand, increased fluxes of DCE, a degradation byproduct of TCE, in tests subsequent to remediation at the Hill AFB site suggest enhanced microbial degradation after surfactant flooding. At the Ft. Lewis site, TCE mass discharge rates subsequent to remediation decreased to approximately 3 g/day for TCE and approximately 3 g/day for DCE approximately 1.8 years after remediation. At both field sites, PFM and IPT approaches provided comparable results for contaminant mass discharge rates, and show significant reductions (>90%) in TCE mass discharge as a result of DNAPL mass depletion from the source zone.     

基于支持向量机的地下水质量综合评价

提出基于支持向量机（SVM）机器学习算法的地下水质量评价模型。首先给出了训练样本生成和数据规范化处理的具体方法,然后采用支持向量机的多分类算法构建模型,并使用k折交叉核实方法对参数进行验证优化。最后通过实证分析,并与单因子指数法、模糊综合评价法和BP神经网络法的评价结果对比分析可知,该方法简便易行,评价结果客观且准确度较高,具有很强的实用性。     

Contaminant transport in groundwater in the presence of colloids and bacteria: Model development and verification

Colloids and bacteria (microorganisms) naturally exist in groundwater aquifers and can significantly impact contaminant migration rates. A conceptual model is first developed to account for the different physiochemical and biological processes, reaction kinetics, and different transport mechanisms of the combined system (contaminant–colloids–bacteria). All three constituents are assumed to be reactive with the reactions taking place between each constituent and the porous medium and also among the different constituents. A general linear kinetic reaction model is assumed for all reactive processes considered. The mathematical model is represented by fourteen coupled partial differential equations describing mass balance and reaction processes. Two of these equations describe colloid movement and reactions with the porous medium, four equations describe bacterial movement and reactions with colloids and the porous medium, and the remaining eight equations describe contaminant movement and its reactions with bacteria, colloids, and the porous medium. The mass balance equations are numerically solved for two-dimensional groundwater systems using a third-order, total variance-diminishing scheme (TVD) for the advection terms. Due to the complex coupling of the equations, they are solved iteratively each time step until a convergence criterion is met. The model is tested against experimental data and the results are favorable.     

Estimating contaminant mass discharge: a field comparison of the multilevel point measurement and the integral pumping investigation approaches and their uncertainties

In this field study, two approaches to assess contaminant mass discharge were compared: the sampling of multilevel wells (MLS) and the integral groundwater investigation (or integral pumping test, IPT) that makes use of the concentration-time series obtained from pumping wells. The MLS approached used concentrations, hydraulic conductivity and gradient rather than direct chemical flux measurements, while the IPT made use of a simplified analytical inversion. The two approaches were applied at a control plane located approximately 40m downgradient of a gasoline source at Canadian Forces Base Borden, Ontario, Canada. The methods yielded similar estimates of the mass discharging across the control plane. The sources of uncertainties in the mass discharge in each approach were evaluated, including the uncertainties inherent in the underlying assumptions and procedures. The maximum uncertainty of the MLS method was about 67%, and about 28% for the IPT method in this specific field situation. For the MLS method, the largest relative uncertainty (62%) was attributed to the limited sampling density (0.63 points/m(2)), through a novel comparison with a denser sampling grid nearby. A five-fold increase of the sampling grid density would have been required to reduce the overall relative uncertainty for the MLS method to about the same level as that for the IPT method. Uncertainty in the complete coverage of the control plane provided the largest relative uncertainty (37%) in the IPT method. While MLS or IPT methods to assess contaminant mass discharge are attractive assessment tools, the large relative uncertainty in either method found for this reasonable well monitored and simple aquifer suggests that results in more complex plumes in more heterogeneous aquifers should be viewed with caution.     

Predicting natural attenuation of xylene in groundwater using a numerical model.

The aquifer beneath an abandoned refinery in the Lower Rhine area, Germany, was contaminated with a number of different mineral oil products. Groundwater sampling in the area around the former xylene plant revealed that a xylene plume had developed in the underlying groundwater, and moreover, that there is strong evidence for in situ microbial xylene degradation with oxygen, nitrate, sulfate and ferric iron as electron acceptors. In order to prevent further xylene spreading, three pumping wells extracting contaminated water were installed downgradient of the spill zone. The numerical reactive transport code Transport Biochemisty Chemistry (TBC) was applied to this situation to quantify the relation of microbial degradation to xylene removal by the pumping wells. It could be shown that the unamended in situ degradation was an appreciable xylene removal process that contributed to about one-third to the total xylene removal (degradation plus extraction). A further objective of the model application was to predict xylene spreading under regional flow conditions, i.e. without operation of the three pumping wells, to consider the possible effects of natural xylene attenuation. To accomplish this, the model calibrated for the situation with operating wells was transferred to the hydraulic situation of regional flow while retaining the parameters of the biochemical model. It turned out that the xylene plume that is expected to develop downgradient of the source area will be limited to an extension of not more than 1000 m. An interesting feature of the simulations results was that xylene degradation under iron-reducing conditions, which was of minor importance for the situation with operating pumping wells, becomes the dominant degradation mechanism under regional flow conditions. Moreover, iron reduction will be the key process in controlling plume evolution. The model application illustrates that multi-species reactive transport models are needed to adequately transfer reactive processes from one hydraulic situation to another, while single species models are not suited for this predictive task.     

Simulation of tracer experiments using a numerical model for point sources in a sheared atmosphere

In order to predict the distribution of material emanating from a point-source with adequate spatial resolution, the model was based on discrete solutions for serially-released puffs. The “across-wind” distribution of each puff was resolved into its zeroth, first and second moments in a moving frame of reference. Numerical solution for these moments accounted for spatially- and temporally-variant velocity and diffusivity profiles. It was found that the interaction of wind-shear and vertical diffusion spread material over a much larger area than is suggested by the popular Gaussian distribution, especially when a change in wind direction induces shear in a second dimension. Data collected in a series of detailed field experiments showed that the model provided significantly better predictions than an equivalent Gaussian Puff Model.     

某矿区土壤和地下水重金属污染调查与评价

为了解湘南某矿区土壤和地下水重金属污染状况,对该矿区东河流域附近重金属污染源进行了调查,同时,对地下水和土壤样品进行了采样分析,结果表明：（1）该矿区东河流域附近的主要污染源有18个,其中有色金属选厂、尾矿库、采矿场和冶炼厂是排放重金属较多的污染源;（2）20个采样点中土壤重金属Pb、Cd、Zn、As和Hg大部分超过国家土壤环境质量标准（GB15618-1995）,综合污染指数P综〉1,该矿区主要的重金属污染元素为Cd、As和Hg,且土壤中Cd、Zn和As的含量两两之间存在着极显著的正线性相关关系;（3）重金属元素在土壤中的纵向迁移不明显,该矿区附近20个采样点的地下水并未受到污染,综合污染指数P综〈1。20个采样点地下水Pb、Cd、Zn、As、Hg浓度均能达到地下水质量标准（GB／T14848．9）中的Ⅲ类标准。     

Field demonstration and evaluation of the Passive Flux Meter on a CAH groundwater plume

This study comprises the first application of the Passive Flux Meter (PFM) for the measurement of chlorinated aliphatic hydrocarbon (CAH) mass fluxes and Darcy water fluxes in groundwater at a European field site. The PFM was originally developed and applied to measurements near source zones. The focus of the PFM is extended from near source to plume zones. For this purpose, 48 PFMs of 1.4 m length were constructed and installed in eight different monitoring wells in the source and plume zone of a CAH-contaminated field site located in France. The PFMs were retrieved, sampled, and analyzed after 3 to 11 weeks of exposure time, depending on the expected contaminant flux. PFM evaluation criteria include analytical, technical, and practical aspects as well as conditions and applicability. PFM flux data were compared with so-called traditional soil and groundwater concentration data obtained using active sampling methods. The PFMs deliver reasonable results for source as well as plume zones. The limiting factor in the PFM applicability is the exposure time together with the groundwater flux. Measured groundwater velocities at the field site range from 2 to 41 cm/day. Measured contaminant flux data raise up to 13 g/m²/day for perchloroethylene in the plume zone. Calculated PFM flux averaged concentration data and traditional concentration data were of similar magnitude for most wells. However, both datasets need to be compared with reservation because of the different sampling nature and time. Two important issues are the PFM tracer loss during installation/extraction and the deviation of the groundwater flow field when passing the monitoring well and PFM. The demonstration of the PFM at a CAH-contaminated field site in Europe confirmed the efficiency of the flux measurement technique for source as well as plume zones. The PFM can be applied without concerns in monitoring wells with European standards. The acquired flux data are of great value for the purpose of site characterization and mass discharge modeling, and can be used in combination with traditional soil and groundwater sampling methods.     

An atmospheric stability index based on radon progeny measurements for the evaluation of primary urban pollution

An atmospheric stability index for the evaluation of urban primary pollution, based on the elaboration of natural radioactivity data yielded by a stability monitor, has been developed. The instrument determines the atmospheric concentration of the short-lived decay products of radon, whose emanation rate can be assumed to be constant in the time and space scale of observation. The index gives information about the dilution properties of the lower boundary layer and allows to highlight the relevant role of the dilution factor in determining primary pollution events.The atmospheric stability indices have been calculated during a 1-yr study carried out in the urban area of Rome (October 1999–September 2000). On the basis of the index, every day of the period has been classified in terms of intensity of a potential primary pollution event. The comparison between this classification and the real concentration value of primary pollutants, measured in the background urban station of Rome, yielded very good results. This shows that the index constitutes a powerful and valuable tool for describing primary pollution events in urban areas and confirms that the role played by the mixing properties of the lower boundary layer is essential in determining primary pollution in urban areas.     

Multivariate statistical evaluation of trace elements in groundwater in a coastal area in Shenzhen, China

Multivariate statistical techniques are efficient ways to display complex relationships among many objects. An attempt was made to study the data of trace elements in groundwater using multivariate statistical techniques such as principal component analysis (PCA), Q-mode factor analysis and cluster analysis. The original matrix consisted of 17 trace elements estimated from 55 groundwater samples colleted in 27 wells located in a coastal area in Shenzhen, China. PCA results show that trace elements of V, Cr, As, Mo, W, and U with greatest positive loadings typically occur as soluble oxyanions in oxidizing waters, while Mn and Co with greatest negative loadings are generally more soluble within oxygen depleted groundwater. Cluster analyses demonstrate that most groundwater samples collected from the same well in the study area during summer and winter still fall into the same group. This study also demonstrates the usefulness of multivariate statistical analysis in hydrochemical studies.     

Electrolytic transformation of ordinance related compounds (ORCs) in groundwater: laboratory mass balance studies

Electrolytic reactive barriers (e(-) barriers) consist of closely spaced permeable electrodes installed across a groundwater contaminant plume in a permeable reactive barrier format. Application of sufficient potential to the electrodes results in sequential oxidation and reduction of the target contaminant. The objective of this study was to quantify the mass distribution of compounds produced during sequential electrolytic oxidation and reduction of ordinance related compounds (ORCs) in a laboratory analog to an e(-) barrier. In this study, a series of column tests were conducted using RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) and TNT (2,4,6-trinitrotoluene) as representative ORCs. The experimental setup consisted of a plexiglass column packed with quartz-feldspar sand to simulate aquifer conditions. A single set of porous electrodes consisting of expanded titanium-mixed metal oxide mesh was placed at the midpoint of the sand column as a one-dimensional analog to an e(-) barrier. Constant current of 20mA (variable voltage) was applied to the electrode set. Initial studies involved quantification of reaction products using unlabeled RDX and TNT. Approximately 70% of the influent concentration was transformed, in one pass, through sequential oxidation-reduction for both contaminants. Following the unlabeled studies, (14)C labeled RDX and TNT were introduced to determine the mass balance. An activity balance of up to 96% was achieved for both (14)C-RDX and (14)C-TNT. For both contaminants, approximately 21% of the influent activity was mineralized to (14)CO(2). The proportion of the initial activity in the dissolved fraction was different for the two test contaminants. Approximately 30% of the initial (14)C-RDX was recovered as unreacted in the dissolved phase. The balance of the (14)C-RDX was recovered as non-volatile, non-nitroso transformation products. None of the (14)C-RDX was sorbed to the column sand packing. For (14)C-TNT approximately 51% of the initial activity was recovered in the dissolved phase, the majority was unreacted TNT. The balance of the (14)C-TNT was either sorbed to the sand packing (approximately 24%) or dissolved/mineralized as unidentified ring cleavage products ( approximately 4%).     

Comparison of different groundwater vulnerability evaluation models of typical karst areas in north China: a case of Hebi City

Environmental Science and Pollution Research - Groundwater pollution is a serious problem in north China. However, the study on the vulnerability of karst groundwater is mainly in south China, and...     

Loss of crop yields in India due to surface ozone: an estimation based on a network of observations

Surface ozone is mainly produced by photochemical reactions involving various anthropogenic pollutants, whose emissions are increasing rapidly in India due to fast-growing anthropogenic activities. This study estimates the losses of wheat and rice crop yields using surface ozone observations from a group of 17 sites, for the first time, covering different parts of India. We used the mean ozone for 7 h during the day (M7) and accumulated ozone over a threshold of 40 ppbv (AOT40) metrics for the calculation of crop losses for the northern, eastern, western and southern regions of India. Our estimates show the highest annual loss of wheat (about 9 million ton) in the northern India, one of the most polluted regions in India, and that of rice (about 2.6 million ton) in the eastern region. The total all India annual loss of 4.0–14.2 million ton (4.2–15.0%) for wheat and 0.3–6.7 million ton (0.3–6.3%) for rice are estimated. The results show lower crop loss for rice than that of wheat mainly due to lower surface ozone levels during the cropping season after the Indian summer monsoon. These estimates based on a network of observation sites show lower losses than earlier estimates based on limited observations and much lower losses compared to global model estimates. However, these losses are slightly higher compared to a regional model estimate. Further, the results show large differences in the loss rates of both the two crops using the M7 and AOT40 metrics. This study also confirms that AOT40 cannot be fit with a linear relation over the Indian region and suggests for the need of new metrics that are based on factors suitable for this region.     

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.     

Direct measurements of the tile drain and groundwater flow route contributions to surface water contamination: From field-scale concentration patterns in groundwater to catchment-scale surface water quality

Enhanced knowledge of water and solute pathways in catchments would improve the understanding of dynamics in water quality and would support the selection of appropriate water pollution mitigation options. For this study, we physically separated tile drain effluent and groundwater discharge from an agricultural field before it entered a 43.5-m ditch transect. Through continuous discharge measurements and weekly water quality sampling, we directly quantified the flow route contributions to surface water discharge and solute loading. Our multi-scale experimental approach allowed us to relate these measurements to field-scale NO₃ concentration patterns in shallow groundwater and to continuous NO₃ records at the catchment outlet. Our results show that the tile drains contributed 90-92% of the annual NO₃ and heavy metal loads. Considering their crucial role in water and solute transport, enhanced monitoring and modeling of tile drainage are important for adequate water quality management.     

基于时序蒙特卡罗方法的某铬盐场污染地下水泄漏风险

突发性污染地下水泄漏对周围水环境的影响具有重要研究意义。借鉴时序蒙特卡罗(SMC)方法来模拟污染源运行状态,并结合相应的河流水质模型,对污染地下水泄漏后造成的河流水质超标风险概率进行研究;利用健康风险评价模型,对污染物泄漏时水环境造成的人体健康风险进行评价。以某铬盐场为例验证该方法的稳定性和实用性。结果表明,该场地受污染的地下水对人体健康产生的危害程度为中级,其超标风险概率随模拟时间的增加而趋于稳定。     

市政污泥流变特性及圆管流数值模拟研究

通过对市政污泥粘度测量实验,得到污泥剪切速率与剪切应力关系数据,并且观察到剪切稀化现象;运用分段拟合方法求解出初始屈服应力和临界剪切速率,从而得到全范围污泥流变曲线。在此基础上,建立污泥管流模型并完成计算,计算结果与参考文献中经验公式和实验结果接近。且可知管径、流速以及流动指数对管道流动的影响显著。人口流速不变的条件下,减小流动管径33％,驱动压力增大了152．1％;管径不变条件下,提高人口流速10倍,驱动压力增大了11倍;保持管径和入口流速条件不变,增大流动指数10倍,驱动压力减少了20．2％。