Barrier-controlled monitored natural attenuation

Three existing technologies (source containment, source reduction, and monitored natural attenuation) are integrated in barrier-controlled monitored natural attenuation (BCMNA)--a new approach for managing plumes of contaminated groundwater and remediating contaminated sites. The basic BCMNA concept uses a low-permeability, nonreactive barrier to release contaminants into an aquifer at a rate that optimizes natural attenuation. A simplified, one-dimensional model of the process is developed, and a hypothetical example of BCMNA is presented for a site contaminated with benzene. The analytical solution is used to demonstrate how contaminant concentrations can be controlled at a downgradient point of environmental compliance by manipulating design variables. BCMNA provides a greater degree of process control and risk reduction than monitored natural attenuation alone. BCMNA also holds promise for reducing remediation costs because (1) barriers can be constructed relatively inexpensively and (2) a cost-effective amount of source reduction can be applied inside the contained area with the BCMNA system remaining in place to safely complete the remediation process after source reduction is terminated. Further numerical modeling and a demonstration project are recommended to address important details and prove the concept.     

Saturated zone denitrification: potential for natural attenuation of nitrate contamination in shallow groundwater under dairy operations

We present results from field studies at two central California dairies that demonstrate the prevalence of saturated-zone denitrification in shallow groundwater with 3H/ 3He apparent ages of < 35 years. Concentrated animal feeding operations are suspected to be major contributors of nitrate to groundwater, but saturated zone denitrification could mitigate their impact to groundwater quality. Denitrification is identified and quantified using N and O stable isotope compositions of nitrate coupled with measurements of excess N2 and residual NO3(-) concentrations. Nitrate in dairy groundwater from this study has delta15N values (4.3-61 per thousand), and delta18O values (-4.5-24.5 per thousand) that plot with delta18O/delta15N slopes of 0.47-0.66, consistent with denitrification. Noble gas mass spectrometry is used to quantify recharge temperature and excess air content. Dissolved N2 is found at concentrations well above those expected for equilibrium with air or incorporation of excess air, consistent with reduction of nitrate to N2. Fractionation factors for nitrogen and oxygen isotopes in nitrate appear to be highly variable at a dairy site where denitrification is found in a laterally extensive anoxic zone 5 m below the water table, and at a second dairy site where denitrification occurs near the water table and is strongly influenced by localized lagoon seepage.     

Statistical modeling of global geogenic arsenic contamination in groundwater

Contamination of groundwaters with geogenic arsenic poses a major health risk to millions of people. Although the main geochemical mechanisms of arsenic mobilization are well understood, the worldwide scale of affected regions is still unknown. In this study we used a large database of measured arsenic concentration in groundwaters (around 20,000 data points) from around the world as well as digital maps of physical characteristics such as soil, geology, climate, and elevation to model probability maps of global arsenic contamination. A novel rule-based statistical procedure was used to combine the physical data and expert knowledge to delineate two process regions for arsenic mobilization: "reducing" and "high-pH/ oxidizing". Arsenic concentrations were modeled in each region using regression analysis and adaptive neuro-fuzzy inferencing followed by Latin hypercube sampling for uncertainty propagation to produce probability maps. The derived global arsenic models could benefit from more accurate geologic information and aquifer chemical/physical information. Using some proxy surface information, however, the models explained 77% of arsenic variation in reducing regions and 68% of arsenic variation in high-pH/oxidizing regions. The probability maps based on the above models correspond well with the known contaminated regions around the world and delineate new untested areas that have a high probability of arsenic contamination. Notable among these regions are South East and North West of China in Asia, Central Australia, New Zealand, Northern Afghanistan, and Northern Mali and Zambia in Africa.     

Unsaturated zone arsenic distribution and implications for groundwater contamination

Arsenic compounds have been applied at the land surface as pesticides in agricultural areas globally. The purpose of this study was to evaluate the fate of anthropogenic arsenic applications related to agriculture, using arsenic applications on cotton in the southern High Plains (SHP), Texas, as a case study and examining possible linkages with contamination of the underlying Ogallala aquifer in this region, where 36% of wells exceed the new EPA 10 microg/L standard. Unsaturated zone soil samples were collected from boreholes beneath natural ecosystems (grassland/ shrubland) to provide a control (no arsenic application) (5 profiles) and cotton cropland (20 profiles) for analyses of water-extractable arsenic, vanadium, phosphate, chloride, and nitrate. Natural ecosystem profiles have high arsenic concentrations at depth (maximum of 7.2-69.6 microg As/ kg dry soil at 5.9-21.4 m depth) that are attributed to a geologic source. Most profiles beneath cotton cropland have high arsenic concentrations within the upper meter (profile means 1.7 to 31.6 microg/kg) that correlate with phosphate (r = 0.70, p < 0.01) and are attributed to anthropogenic arsenic application associated with phosphate fertilizer application. High arsenic concentrations at >1 m depth (profile means < or =36.3 microg/kg) found in cropland profiles are attributed to a geologic source because of similarity with profiles beneath natural ecosystems, lack of correlation with phosphate, and pore-water ages that predate anthropogenic arsenic application in many profiles. GIS analyses showed poor correlations between groundwater arsenic and percent cultivated land (r = -0.15, p < 0.01), groundwater nitrate (r = 0.30, p < 0.01), and water table depth (r= -0.31, p < 0.01), further supporting the idea that anthropogenic-derived arsenic in the shallow subsurface is not linked to groundwater arsenic contamination in this region.     

Peer reviewed: evaluating natural attenuation for groundwater cleanup

The National Research Council has issued the first comprehensive assessment of when natural attenuation works.     

"Phytoscreening": the use of trees for discovering subsurface contamination by VOCs

We tested the possibility of using tree cores to detect unknown subsurface contamination by chlorinated volatile organic compounds (Cl-VOCs) and petroleum hydrocarbons, a method we term "phytoscreening". The scope and limitations of the method include the following: (i) a number of widespread Cl-VOC contaminants are readily found in tree cores, although those with very high vapor pressures or low boiling points may be absent; (ii) volatile petroleum hydrocarbons were notwell-expressed in tree cores; (iii) trees should be sampled during active evapotranspiration and from directions that are well exposed to sunlight; (iv) there is not necessarily a direct correlation between concentrations measured in tree cores and those in the subsurface; (v) detection of a contaminant in a tree core indicates that the subsurface is contaminated with the pollutant; (vi) many possible causes of false negatives may be predicted and avoided. We sampled trees at 13 random locations in the Tel Aviv metropolitan area and identified Cl-VOCs in tree coresfromthree locations. Subsequently, subsurface contamination at all three sites was confirmed. Phytoscreening is a simple, fast, noninvasive, and inexpensive screening method for detecting subsurface contamination, and is particularly useful in urban settings where conventional methods are difficult and expensive to employ.     

Chromium(VI) bioremoval by Pseudomonas bacteria: role of microbial exudates for natural attenuation and biotreatment of Cr(VI) contamination

Laboratory batch and column experiments were conducted to investigate the role of microbial exudates, e.g., exopolymeric substance (EPS) and alginic acid, on microbial Cr(VI) reduction by two different Pseudomonas strains (P. putida P18 and P. aeuroginosa P16) as a method for treating subsurface environment contaminated with Cr(VI). Our results indicate that microbial exudates significantly enhanced microbial Cr(VI) reduction rates by forming less toxic and highly soluble organo-Cr(III) complexes despite the fact Cr(III) has a very low solubility under the experimental conditions studied (e.g., pH 7). The formation of soluble organo-Cr(III) complexes led to the protection of the cells and chromate reductases from inactivation. In systems with no organic ligands, soluble organo-Cr(III) end products were formed between Cr(III) and the EPS directly released by bacteria due to cell lysis. Our results also provide evidence that cell lysis played an important role in microbial Cr(VI) reduction by Pseudomonas bacteria due to the release of constitutive reductases that intracellularly and/or extracellularly catalyzed the reduction of Cr(VI) to Cr(III). The overall results highlight the need for incorporation of the release and formation of organo-Cr(III) complexes into reactive transport models to more accurately design and monitor in situ microbial remediation techniques for the treatment of subsurface systems contaminated with Cr(VI).     

Evaluation of plant products from the Legnicko–Głogowski region for their contamination with arsenic

Contents of arsenic were determined in plant products originating from the region of two copperworks, G?ogów and Legnica. Analyses were carried out by means of atomic absorption spectrometry, using an MHS-10 unit for hydride generation (acetylene/argon), after wet mineralisation of samples.     

Limited temporal variability of arsenic concentrations in 20 wells monitored for 3 years in Araihazar, Bangladesh

Millions of people in Bangladesh have probably switched their water consumption to wells that meet the local standard for As in drinking water of 50 microg/L as a result of blanket field testing throughout the country. It is therefore important to know if As concentrations in those wells could change over time. To address this issue, we report here precise groundwater As analyses for time-series samples collected from a suite of 20 tube wells containing < or =50 microg/L As and ranging from 8 to 142 m in depth. For 17 out of 20 wells, the standard deviation of groundwater As concentrations was <10 microg/L over the 3-year monitoring period (n = 24-44 per well). Six of the 17 wells are community wells, each of which serves the needs of several hundred people in particularly affected villages. Of the three wells showing larger fluctuations in chemical composition including As, two are very shallow (8 and 10 m). Variations in As concentrations for one of these wells (50 +/- 32 microg/L, n = 36), as well as another shallow well showing smaller variations (48 +/- 5 microg/L, n = 36), appear to be coupled to seasonal precipitation and recharge linked to the monsoon. The other shallow well showing larger variations in composition indicates a worrisome and steady increase in As concentrations from 50 to 70 microg/L (n = 36) over 3 years. The time series of As (30 +/- 11 microg/L, n = 24) and other constituents in one deep community well (59 m) show large fluctuations that suggest entrainment of shallow groundwater through a broken PVC pipe. Even though the majority of wells that were initially safe remained so for 3 years, our results indicate that tube wells should be tested periodically.     

Identifying the sources of subsurface contamination at the Hanford Site in Washington using high-precision uranium isotopic measurements

In the mid-1990s, a groundwater plume of uranium (U) was detected in monitoring wells in the B-BX-BY Waste Management Area at the Hanford Site in Washington. This area has been used since the late 1940s to store high-level radioactive waste and other products of U fuel-rod processing. Using multiple-collector ICP source magnetic sector mass spectrometry, high-precision uranium isotopic analyses were conducted of samples of vadose zone contamination and of groundwater. The isotope ratios 236U/238U, 234U/238U, and 238U/235U are used to distinguish contaminant sources. On the basis of the isotopic data, the source of the groundwater contamination appears to be related to a 1951 overflow event at tank BX-102 that spilled high-level U waste into the vadose zone. The U isotopic variation of the groundwater plume is a result of mixing between contaminant U from this spill and natural background U. Vadose zone U contamination at tank B-110 likely predates the recorded tank leak and can be ruled out as a significant source of groundwater contamination, based on the U isotopic composition. The locus of vadose zone contamination is displaced from the initial locus of groundwater contamination, indicating that lateral migration in the vadose zone was at least 8 times greater than vertical migration. The time evolution of the groundwater plume suggests an average U migration rate of approximately 0.7-0.8 m/day showing slight retardation relative to a groundwater flow of approximately 1 m/day.     

Arsenic contamination of Bangladesh paddy field soils: implications for rice contribution to arsenic consumption

Arsenic contaminated groundwater is used extensively in Bangladesh to irrigate the staple food of the region, paddy rice (Oryza sativa L.). To determine if this irrigation has led to a buildup of arsenic levels in paddy fields, and the consequences for arsenic exposure through rice ingestion, a survey of arsenic levels in paddy soils and rice grain was undertaken. Survey of paddy soils throughout Bangladesh showed that arsenic levels were elevated in zones where arsenic in groundwater used for irrigation was high, and where these tube-wells have been in operation for the longest period of time. Regression of soil arsenic levels with tube-well age was significant. Arsenic levels reached 46 microg g(-1) dry weight in the most affected zone, compared to levels below l0 microg g(-1) in areas with low levels of arsenic in the groundwater. Arsenic levels in rice grain from an area of Bangladesh with low levels of arsenic in groundwaters and in paddy soils showed that levels were typical of other regions of the world. Modeling determined, even these typical grain arsenic levels contributed considerably to arsenic ingestion when drinking water contained the elevated quantity of 0.1 mg L(-1). Arsenic levels in rice can be further elevated in rice growing on arsenic contaminated soils, potentially greatly increasing arsenic exposure of the Bangladesh population. Rice grain grown in the regions where arsenic is building up in the soil had high arsenic concentrations, with three rice grain samples having levels above 1.7 microg g(-1).     

CCT-ICP-MS测定饮用天然矿泉水中微量砷

采用碰撞池技术（CCT）和电感耦合等离子体质谱法（ICP-Ms）对饮用天然矿泉水中微量元素砷进行测定。通过在线加入内标校正基体效应和接口效应,应用仪器碰撞池技术消除元素质量数干扰,测定元素校正曲线相关系数在0．9995以上,元素检出限0．033μg·L^-1,RSD％〈10（n=12）,加标回收率在95．5％．108．0％之间,该方法灵敏度高,干扰少,结果较为满意。     

陕西省新鲜果蔬中砷污染状况调查及其暴露评估

目的了解陕西省新鲜水果和蔬菜中砷的污染状况及评价其对人体的潜在危害。方法 2012—2015年共采集1 270份新鲜蔬菜和363份新鲜水果并测定砷含量,分别从年份、类别和地区三方面进行统计分析,以食品添加剂专家委员会(JECFA)制定的砷暂定每周可耐受摄入量(PTWI)为标准对居民经食用果蔬所致砷的暴露量进行评估,并应用美国环保局推荐的健康风险评价模型对其引起的健康风险进行评价。结果近4年来果蔬中的砷平均含量范围为0.013~0.036 mg/kg;8类蔬菜的砷含量相近,6类水果中瓜果类的砷含量较高,平均值为0.052mg/kg;陕西省宝鸡、延安和商洛地区果蔬砷含量较高。整体而言,陕西居民经食用果蔬所致砷平均暴露量低于JECFA制定砷的PTWI及其所引起的平均个人年风险值亦小于国际放射防护委员会(ICRP)推荐的标准5.0×10~(-5)a~(-1),但偏高暴露引起的健康风险不容忽视。结论陕西省部分果蔬样品存在砷污染情况,居民通过食用果蔬所致砷的暴露量在安全范围内,其所引起的健康风险有待进一步研究。     

Level of natural hepatotoxin (Indospicine) contamination in Australian camel meat

Camel meat production for human consumption and pet food manufacture accounts for a relatively small part of overall red meat production in Australia. Reliable statistical data for the Australian production and consumption of camel meat are not available; however, it is estimated that 300,000 feral camels roam within the desert of central Australia, with an annual usage of more than 3000 camels for human consumption, 2000 for pet food manufacture and a smaller number for live export. Despite a small Australian camel meat production level, the usage of camel meat for pet food has been restricted in recent years due to reports of serious liver disease and death in dogs consuming camel meat. This camel meat was found to contain residues of indospicine, a non-proteinogenic amino acid found in certain Indigofera spp., and associated with mild to severe liver disease in diverse animals after dietary exposure to this hepatotoxin. The extent of indospicine-contaminated Australian camel meat was previously unknown, and this study ascertains the prevalence of such residue in Australian camel meat. In this study, indospicine levels in ex situ (95 samples collected from an abattoir in Queensland) and in situ (197 samples collected from camels after field culling in central Australia) camel meat samples were quantitated using a validated ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The quantitation results showed 46.7% of the in situ- and 20.0% of the ex situ-collected camel meat samples were contaminated by indospicine (more than the limit of detection (LOD) of 0.05 mg kg^–1 fresh weight). The overall indospicine concentration was higher (p < 0.05) in the in situ-collected samples. Indospicine levels detected in the present study are considered to be low; however, a degree of caution must still be exercised, since the tolerable daily intake for indospicine is currently not available for risk estimation.     

Impact of ethanol on the natural attenuation of MTBE in a normally sulfate-reducing aquifer

Side-by-side experiments were conducted in an aquifer contaminated with methyl-tert-butyl ether (MTBE) at a former fuel station to evaluate the effect of ethanol release on the fate of pre-existing MTBE contamination. On one side, for approximately 9 months we injected groundwater amended with 1-3 mg/L benzene, toluene, and o-xylene (BToX). On the other side, we injected the same, adding approximately 500 mg/L ethanol. The fates of BToX in both sides ("lanes") were addressed in a prior publication. No MTBE transformation was observed in the "No Ethanol Lane." In the "With Ethanol Lane", MTBE was transformed to tert-butyl alcohol (TBA) underthe methanogenic and/or acetogenic conditions induced by the in situ biodegradation of the ethanol downgradient of the injection wells. The lag time before onset of this transformation was less than 2 months and the pseudo-first-order reaction rate estimated after 7-8 months was 0.046 d(-1). Our results imply that rapid subsurface transformation of MTBE to TBA may be expected in situations where strongly anaerobic conditions are sustained and fluxes of requisite nutrients and electron donors allow development of an active acetogenic/methanogenic zone beyond the reach of inhibitory effects such as those caused by high concentrations of ethanol.     

Using tree core samples to monitor natural attenuation and plume distribution after a PCE spill

The potential of using tree core samples to detect and monitor natural attenuation of perchloroethene (PCE) in groundwater was investigated at a PCE-contaminated site. In the area of the known plume with PCE concentrations between 0.004 and > 40 mg/L, cores were collected from tree trunks at a height of about 1 m above ground surface. Tree sampling of the site was completed in under six hours. Chlorinated ethenes were analyzed by headspace GC/MS. PCE (0.001 to 7 mg/ kg) and natural attenuation products, TCE (< 0.001 to 0.4 mg/ kg) and c-DCE (< 0.001 to 0.46 mg/kg), were detected in tree cores. 1,1-dichloroethene and vinyl chloride were not detected, corresponding to very low concentrations in the groundwater. The contaminant plume was mapped from the concentrations measured in trees, which delineated a probable hot spot area that had been undetected in decades of traditional groundwater monitoring. Natural attenuation products in tree cores increased with distance from the known source area. Concentrations of PCE and reductive dechlorination products in tree cores were correlated with the corresponding groundwater concentrations. Within a range of limitations, tree-core sampling provides a rapid, reliable and inexpensive method to investigate the extent of shallow contamination by chlorinated ethenes in soil and groundwater.     

Fungal and bacterial metabolites associated with natural contamination of locally processed rice (Oryza sativa L.) in Nigeria

This study reports the fungal and bacterial metabolites associated with natural contamination of 38 composite samples of locally processed rice from five agro-ecological zones of Nigeria (AEZs). The samples were evaluated for the presence of microbial metabolites by LC-MS/MS. Among the identified metabolites, 63 fungal and 5 bacterial metabolites were measured at varying concentrations and occurrence levels. Fusarium toxins had the highest incidence of 79%, but occurred in low amounts with fumonisin B₁ (FB₁) having the highest percentage incidence of 39.5% and a mean of 18.5 µg/kg. Among the Aspergillus toxins, aflatoxins (AFs) occurred in 36.9% of the rice samples, with aflatoxin B₁ (AFB₁) having the highest occurrence level of 18.4% and a mean value of 5 µg/kg. About 12 metabolites had incidence levels > 50%, including beauvericin (BEA) and tryptophol, which had occurrence levels of 100%. Among the emerging toxins under evaluation by international organisations such as the European Food Safety Authority (EFSA) and the Food and Agriculture Organisation of the United Nations (FAO), citrinin, sterigmatocystin (STER) and beauvericin were detected with maximum values of 207, 125 and 131 μg/kg, respectively. This paper also reports the first documented evidence of the contamination of Nigerian rice by bacterial and Alternaria metabolites, nivalenol, kojic acid, STER, moniliformin, fusaric acid, fumonisin B₃, citrinin, 3-nitropropionic acid, andrastin A, cytochalasins, emodin and physicon.