Monitoring groundwater contamination and delineating source zones at industrial sites: uncertainty analyses using integral pumping tests

Field-scale characterisations of contaminant plumes in groundwater, as well as source zone delineations, are associated with uncertainties that can be considerable. A major source of uncertainty in environmental datasets is due to variability of sampling results, as a direct consequence of the heterogeneity of environmental matrices. We develop a methodology for quantifying uncertainties in field-scale mass flow and average concentration estimations, using integral pumping tests (IPTs), where the contaminant concentration is measured as a function of time in a pumping well. This procedure increases the sampling volume and reduces the effect of small-scale variability that may bias point-scale measurements. In particular, using IPTs, the interpolation uncertainty of conventional point-scale measurements is transformed to a quantifiable uncertainty related to the (unknown) plume position relative to the pumping well. We show that this plume position uncertainty generally influenced the predicted mass flows and average concentrations (of acenapthene, benzene and CHCs) to a greater extent than a boundary condition uncertainty related to the local water balance, considering 19 control planes at a highly heterogeneous industrial site in southwest Germany. Furthermore, large (order of magnitude) uncertainties only occurred if the conditions were strongly heterogeneous in the nearest vicinity of the well. We also develop a consistent methodology for an assessment of the combined effect of uncertainty in hydraulic conditions and uncertainty in reactive transport parameters for delimiting of both contaminant source zones and zones absent of source, based on (downgradient) IPTs.     

Polychlorinated biphenyls contamination in urban soil of Shanghai: level, compositional profiles and source identification

Surface soil samples taken from 55 sampling sites at the urban areas of Shanghai were collected and analyzed for the occurrence of 144 polychlorinated biphenyls (PCBs) by GC-μECD. The results showed that totally 74 PCB congeners were identified and the mean concentration of total PCBs was 3057 ng kg⁻¹ with a range of 232 to 11325 ng kg⁻¹. Compared with the related reports, the level of PCBs contamination in this study was approximately equal to the global background value in soils, but higher than Chinese background for rural and urban soils. According to the compositional profiles of PCBs homologues, a higher proportion of low chlorinated (from tri-CBs to hexa-CBs) was observed. The results indicated that PCB15 + 13, PCB18, PCB28, PCB104 + 47 and PCB153 were the most dominant congeners among the identified PCBs. Through homologues analysis, cluster analysis and principal component analysis (PCA), it was found that PCBs were stretched from mixed local sources, and appeared to be mostly originated by Aroclor 1260- and 1254-like mixtures as well as some samples influenced by Aroclor 1232 and 1242. The correlation analysis showed the relatively good correlation among the PCB homologues and soil total organic carbon (TOC), suggesting important influence of soil TOC on PCBs contamination in soil matrix in Shanghai region. The toxic equivalency (TEQ) concentrations of these six dioxin-like PCBs detected in urban soil samples range from 2.71 to 24.9 pg kg⁻¹-PCDDeq with a mean 8.18 pg kg⁻¹-PCDDeq.     

Herbicide contamination of surficial groundwater in Northern Italy

Data on herbicide pollution in groundwater are rather scarce; monitoring data are based on single investigation, focussing on limited area and on few compounds of interest. The large number of approved active ingredients (approximately 600 chemicals) makes difficult to obtain an accurate and actual information on herbicide application in different countries, even if herbicides are the second most important class of pesticides used in the European Union. The results of a two-year monitoring campaign undertaken in two areas intensively cultivated at Lombardy, Northern Italy, showed a diffuse groundwater contamination due to active ingredients and their metabolites. More than 50% of samples overcame M.A.C. and the most common herbicides were Atrazine, Terbuthylazine and Metolachlor, while DEA and DET metabolites were often characterized by greater concentrations than their relative active principles.     

Sulfate contamination in groundwater from a carbonate-hosted mine

Sulfide oxidation in a carbonate environment produces groundwater contamination with high sulfate making the water unsuitable for drinking supplies. The zinc-lead mines near Shullsburg, Wisconsin are located in the Galena-Platteville Formation, a carbonate aquifer that was dewatered during mining. Sulfate levels have reached as high as 40 nmol/l in some local wells and eleven wells were abandoned.Geochemical modeling of chemical reactions and isotope effects using the USGS computer program PHREEQE showed the importance of dolomite, calcite, CO₂, and siderite or iron hydroxide in controlling the water chemistry. The decrease in sulfate levels with time indicated that dilution by incoming recharge water was an ongoing process. The results of carbon isotope reaction modeling are consistent with dilution of contaminated water. The evidence for localization of contamination and dilution means that area farmers have seen the worst of the contamination. The mechanism of contamination was further examined by microbiological sampling and sulfur isotope determinations, which indicated that bacteria of the Thiobacillus species that thrive under neutral pH conditions may have catalyzed sulfide oxidation.Research into the chemical evolution of contamination in this environment not only explains how sulfide oxidation causes contamination despite buffering by carbonate rocks, but also suggests how oxidation is initiated in the case of acid mine drainage.     

Assessment of pesticide contamination in Akkar groundwater,northern Lebanon

According to its high production and value, Akkar is considered as the second agricultural region in Lebanon. Groundwater constitutes the principal source of water in Akkar including drinking water of local inhabitants in Akkar. As such, the contamination of groundwater by organic pollutants can impact directly the population health. In this study, we evaluated the contamination status of groundwater in this region. Three classes of pesticides including 19 organochlorine (OC) pesticides, 8 organophosphorus (OP) pesticides, and 6 organonitrogen (ON) pesticides were monitored in 15 groundwater samples collected from different villages on the Akkar plain. Samples were extracted by using solid phase extraction (SPE) and analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The results showed high contamination of Akkar groundwater by OCs with levels that can reach 58.9 μg/L. They were detected in the majority of the sample and represent 95–100% of ∑pesticides. Our results showed the recent use of these molecules with an average level of 0.3 and 0.39 μg/L for ∑HCHs and DDTs, respectively. Their concentrations were higher than those observed in the same region in 2014 and other regions elsewhere. OPs were also detected at high levels and among them, methylparathion was the predominant OP detected (44.6 μg/L). For ONs, lower levels were measured in all samples with a mean value of 5.6 μg/L. As a conclusion of this work, groundwater on the plain of Akkar was remarkably contaminated by the studied pesticides; indefinitely, more efforts should be taken to manage the pesticide use in this region, assess, and reduce their effects on human health. In the future, the application of organic farming can be a great solution to the groundwater contamination problem.     

Toxicity identification evaluation of leachates from municipal solid waste landfills: a multispecies approach

The toxicity of leachates from two municipal solid waste (MSW) landfills in Southern Italy was characterized using a toxicity identification evaluation procedure. The chemical and physical fractionation techniques were: pH adjustment, pH adjustment/filtration, pH adjustment/C(18) solid phase extraction, graduated pH and EDTA chelation. All the samples exhibited acute toxicity towards the bacterium Vibrio fischeri, the freshwater rotifer Brachionus calyciflorus and the freshwater crustaceans Thamnocephalus platyurus and Daphnia magna. Statistical techniques were used to determine the discriminatory power and the toxicity detection capacity of the different assays and to choose a minimal battery of tests for the toxicity identification of leachates. Toxicity was closely associated with pH, generally increasing at higher pH levels and decliming at lower ones. Furthermore, results showed that toxicants could be characterized as cations, basic chemicals, suspended solids and apolar compounds.     

Joint propagation of variability and imprecision in assessing the risk of groundwater contamination

Estimating risks of groundwater contamination often require schemes for representing and propagating uncertainties relative to model input parameters. The most popular method is the Monte Carlo method whereby cumulative probability distributions are randomly sampled in an iterative fashion. The shortcoming of the approach, however, arises when probability distributions are arbitrarily selected in situations where available information is incomplete or imprecise. In such situations, alternative modes of information representation can be used, for example the nested intervals known as “possibility distributions”. In practical situations of groundwater risk assessment, it is common that certain model parameters may be represented by single probability distributions (representing variability) because there are data to justify these distributions, while others are more faithfully represented by possibility distributions (representing imprecision) due to the partial nature of available information. This paper applies two recent methods, designed for the joint-propagation of variability and imprecision, to a groundwater contamination risk assessment. Results of the joint-propagation methods are compared to those obtained using both interval analysis and the Monte Carlo method with a hypothesis of stochastic independence between model parameters. The two joint-propagation methods provide results in the form of families of cumulative distributions of the probability of exceeding a certain value of groundwater concentration. These families are delimited by an upper cumulative distribution and a lower distribution respectively called Plausibility and Belief after evidence theory. Slight differences between the results of the two joint-propagation methods are explained by the different assumptions regarding parameter dependencies. Results highlight the point that non-conservative results may be obtained if single cumulative probability distributions are arbitrarily selected for model parameters in the face of imprecise information and the Monte Carlo method is used under the assumption of stochastic independence. The proposed joint-propagation methods provide upper and lower bounds for the probability of exceeding a tolerance threshold. As this may seem impractical in a risk-management context, it is proposed to introduce “a-posteriori subjectivity” (as opposed to the “a-priori subjectivity” introduced by the arbitrary selection of single probability distributions) by defining a single indicator of evidence as a weighted average of Plausibility and Belief, with weights to be defined according to the specific context.     

Influencing factors and a proposed evaluation methodology for predicting groundwater contamination potential from stormwater infiltration activities.

To offset the detrimental effects of urbanization on groundwater recharge, stormwater managers are focusing on infiltrating much of the runoff from a site that was generated because of development. For this to be effective, tools are required to predict the potential for contamination resulting from this infiltration for many site conditions, because infiltration should be stressed in areas where the least potential for causing groundwater contamination exists. Factors that influence contamination potential include the pollutant concentration in the runoff directed to the infiltration device and the ability of the underlying soil to remove the pollutant. The groundwater contamination potential of some pollutants, even those with high concentrations and moderate-to-high mobilities, can be reduced with proper pretreatment before infiltration. This paper presents a methodology that can be used to evaluate infiltration as an management option and introduces two different levels of models that could be used to evaluate contamination potential.     

Evaluation of groundwater contamination in a coastal area of south-eastern Sicily

This investigation was under taken to evaluate the groundwater resources contamination due to intensive agricultural practices (particularly greenhouses). The study-area is located in the coastal area of the Ragusa province (South-East Sicily), where numerous existing greenhouses may cause the contamination of groundwater systems (unconfined and confined aquifers) beneath the cropped land. The pollution risk is mainly related with the seepage process of macro-elements nitrogen (N), phosphorus (P), potassium (K), held in the irrigation water and the massive use of fertilizers and pesticides, that may pass through the unsaturated zone of the soil profile. Moreover, the area is characterized by the presence of several wells (about 15 wells/km2) for agricultural use that cause the aquifer overexploitation and the consequent risk of seawater intrusion. The agriculture practices adopted in the study area (irrigation volumes, fertilizer concentrations, use of pesticides…) were monitored since February 2009; moreover, the pollution risk of the aquifers was evaluated through the analysis of groundwater water samples collected (monthly) in the monitoring wells; in particular, nitrogen compounds, soluble phosphorous (PO?2?), potassium, as well as the main pesticides commonly used in the study area, were measured.The results show that electrical conductivity and chloride concentration values can cause reduction of production and leaf damage problems, respectively, for most of the monitored farm systems. The high nitrogen compounds concentrations observed in the monitored wells can cause health and environmental problems. Moreover high pesticide contamination of groundwater was found in two of the five monitored wells.     

Heavy metal contamination and exposure risk assessment via drinking groundwater in Vehari,Pakistan

Environmental Science and Pollution Research - The presence of toxic substances in aquifers, particularly potentially toxic heavy metals, is an important environmental and social concern worldwide....     

Quantification of groundwater contamination in an urban area using integral pumping tests

In this paper, the integral groundwater investigation method is used for the quantification of PCE and TCE mass flow rates at an industrialized urban area in Linz, Austria. In this approach, pumping wells positioned along control planes perpendicular to the groundwater flow direction are operated for a time period on the order of days and sampled for contaminants. The concentration time series of the contaminants measured during operation of the pumping wells are then used to determine contaminant mass flow rates, mean concentrations and the plume shapes and positions at the control planes. The three control planes used in Linz were positioned downstream of a number of potential source zones, which are distributed over the field site. By use of the integral investigation method, it was possible to identify active contaminant sources, quantify the individual source strength in terms of mass flow rates at the control planes and estimate the contaminant plume position relative to the control planes. The source zones emitting the highest PCE and TCE mass flow rates could be determined, representing the areas where additional investigation and remediation activities will be needed. Additionally, large parts of the area investigated could be excluded from further investigation and remediation activities.     

固体碳源生物膜处理地下水硝酸盐污染的脱氮性能研究

采用聚己内酯(PCL)为固体碳源和生物膜载体,研究填充率和水力停留时间(HRT)对生物膜反应器脱氮的影响。结果表明:(1)40%(体积分数)的填充率较合适,4h为最佳HRT。此时反应器硝酸盐氮去除率为88%,出水硝酸盐氮质量浓度平均值为8.80mg/L。(2)丛毛单胞菌属(Comamonas)、热单胞菌属(Thermomonas)、固氮螺菌属(Azospira)和长绳菌属(Longilinea)为反应器的主要菌属,且填充率40%的反应器以上菌属相对丰度总和最高(70%)。     

玉米秆碳源去除地下水硝酸盐

研究比较了经氢氧化钠、氨水预处理的玉米秆和玉米芯作为生物反硝化碳源时,不同氮负荷条件下的脱氮性能。结果表明,经3%氢氧化钠溶液预处理的玉米秆,在不同氮负荷下均具有较高的硝酸盐去除率,最高达到了97.17%。在原位净化模拟实验中,用该方法预处理的玉米秆作为可渗透反应墙(PRB)的填充介质,硝酸盐和总氮的去除率分别达到了89.68%和84.97%,且出水中没有亚硝酸盐氮和氨氮的积累。结果表明,经3%氢氧化钠溶液预处理的玉米秆,可以作为地下水原位净化修复的固相碳源。     

基于自然语言处理和机器学习的疑似土壤污染企业识别

针对污染场地识别的精准性不高、科学性不足、全面性不够和数据共享难度大等问题,以南方某地级市为研究区,借助大数据平台,基于自然语言处理和机器学习,通过引入摘要中热词权重构建改进型朴素贝叶斯模型,并对兴趣点(POI)数据进行中类行业预测和污染企业识别。结果表明,与随机森林算法和XGBoost算法相比,朴素贝叶斯算法的性能最佳;企业名称+经营范围构建有语义词汇库后,朴素贝叶斯算法的准确率、召回率和综合评价指标(F₁)值得到大幅提升,分别提高了0.23、0.23和0.23;采用权重1.27和平滑参数α为1.10后,建立了改进型朴素贝叶斯模型,实现了行业类别预测,相应的准确率、召回率和F₁值分别为0.63、0.62和0.63;识别出研究区中26个疑似土壤污染行业有关1774家企业。改进型朴素贝叶斯模型能够有效地预测疑似土壤污染企业,具有较好的准确率与召回率,能够为场地污染识别与风险管控实践提供理论依据和设计参数。     

Successive identification of biodegradation rates for multiple sequentially reactive contaminants in groundwater.

At the field scale, the biodegradation rate is usually estimated from analytical solutions to single species transport with first-order reactions, using measured data as input. Because many contaminants, e.g., chlorinated solvents, are degraded in a sequential pattern, with degradation products further reacting to produce new species, it is of great interest to quantify the transformation rate of every reaction. The conventional inverse solutions for identifying the transformation rates are limited to single species problems. In the present study, we propose a successive optimization approach to identify the biodegradation rate for each species by using a previously developed analytical solution to multi-species first-order reactive transport using data obtained at the field scale. By specifying a link between analytical solutions to sequentially reactive transport problems and optimization methods and assuming constant transport parameters (velocity, dispersivities, and retardation factors), the first-order transformation rates are optimized successively from parent species to its daughter species.     

Hydrochemical characteristics and identification of groundwater pollution sources in tropical savanna

Groundwater pollution of the watershed is mainly influenced by the multifaceted interactions of natural and anthropogenic processes. In this study, classic chemical and multivariate statistical methods were utilized to assess the groundwater quality and ascertain the potential contamination sources affecting the groundwater quality of Galma sub-watershed in a tropical savanna. For this purpose, the data set of 18 groundwater quality variables covering 57 different sampling boreholes (BH) was used. The groundwater samples essentially contained the cations in the following order of dominance: Ca²⁺ ?>?Na⁺ ?>?Mg²⁺ ?>?K⁺. However, the anions had HCO₃^–?>?Cl^–?>?SO₄^–2?>?NO₃^– respectively. The hydrochemical facies classified the groundwater types of the sub-watershed into mixed Ca–Mg–Cl type of water, which means no cations and anions exceeds 50%. The second dominant water type was Ca–Cl. The Mg–HCO₃ water type was found in BH 9, and Na–Cl water type in BH 29 of the studied area. The weathering of the basement rocks was responsible for the concentrations of these ions in the groundwater chemistry of the sub-watershed. Hierarchical cluster analysis (HCA) grouped the groundwater samples (boreholes) into five clusters that are statistically significant regarding the similarities of groundwater quality characteristics. The principal component analysis (PCA) extracted two major principal components explained around 65% of the variance and suggested the natural and anthropogenic processes especially the agricultural pollutants including synthetic fertilizers, and leaching of agricultural waste as the main factors affecting the groundwater quality. The integrated method proved to be efficient and robust for groundwater quality evaluation, as it guaranteed the precise assessment of groundwater chemistry in the sub-watershed of the tropical savanna. The findings of this investigation could be useful to the policy makers for developing effective groundwater management plans for the groundwater resources and protection of the sub-watershed.

     

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。     

Bioassay-directed identification of toxic organic compounds in creosote-contaminated groundwater

Despite the fact that creosote mainly consists of polycyclic aromatic hydrocarbons (PAHs), more polar compounds like phenolics, benzenes and N-, S-, O-heterocyclics dominate the groundwater downstream from creosote-contaminated sites. In this study, bioassay-directed fractionation, combined with fullscan GC-MS, identified organic toxicants in creosote-contaminated groundwater. An organic extract of creosote-contaminated groundwater was fractionated on a polar silica column using high performance liquid chromatography (HPLC), and the toxicity of the fractions was measured by the Microtox-bioassay. PAHs, which comprise up to 85% of pure creosote, accounted for only about 13% of total toxicity in the creosote-contaminated groundwater, while methylated benzenes, phenolics and N-heterocyclics accounted for ca. 80% of the measured toxicity. The fraction containing alkylated quinolines was the most toxic single fraction, accounting for 26% of the total measured toxicity. The results imply that focus on PAHs may underestimate risks associated with creosote-contaminated groundwater, and that environmental risk assessment should focus to a higher degree on substituted PAHs and phenolics because they are more toxic than the unsubstituted ones. Additionally, benzenes and N-heterocyclics (e.g., alkylated quinolines) should be assessed.     

Cooperative identification for critical periods and critical source areas of nonpoint source pollution in a typical watershed in China

Environmental Science and Pollution Research - Critical periods (CPs) and critical source areas (CSAs) refer to the high-risk periods and areas of nonpoint source (NPS) pollution in a watershed,...     

Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface water and groundwater

This study aimed to provide the first and comprehensive data on the occurrence of 17 target pharmaceuticals and personal care products (PPCPs) in urban water environment in Singapore. Meanwhile, this study also verified the suitability of these PPCPs as specific markers of raw wastewater contamination in receiving water bodies in highly urbanized areas where both surface water and groundwater are not impacted by the discharge of treated wastewater effluents. Analytical results of wastewater showed that among 17 target PPCPs examined, only 5 PPCPs were detected in 100 % of raw wastewater samples, including acetaminophen (ACT), carbamazepine (CBZ), caffeine (CF), diethyltoluamide (DEET), and salicylic acid (SA). Similarly, these PPCPs were found in most surface water and groundwater. Interestingly, the three PPCPs (ACT, CBZ, and SA) were only detected in surface water and groundwater in the sampling sites close to relatively older sewer systems, while they were absent in background samples that were collected from the catchment with no known wastewater sources. This suggests that ACT, CBZ, and SA can be used as specific molecular markers of raw wastewater in surface water and groundwater. This study also confirmed that CF and DEET were not really associated with wastewater sources, thus cannot serve well as specific molecular markers of wastewater contamination in receiving water bodies. To the best knowledge of the authors, the use of ACT and SA as specific molecular markers of raw wastewater contamination in urban surface waters and groundwater was first reported. Further studies on the use of ACT, CBZ, and SA along with other chemical/microbial markers are recommended to identify and differentiate contamination sources of surface waters/groundwater.