Chlorinated Solvent Source‐Zone Remediation via ZVI‐Clay Soil Mixing: 1‐Year Results

ZVI‐Clay is an emerging remediation approach that combines zero‐valent iron (ZVI)‐mediated degradation and in situ stabilization of chlorinated solvents. Through use of in situ soil mixing to deliver reagents, reagent‐contaminant contact issues associated with natural subsurface heterogeneity are overcome. This article describes implementation, treatment performance, and reaction kinetics during the first year after application of the ZVI‐Clay remediation approach at Marine Corps Base Camp Lejeune, North Carolina. Primary contaminants included trichloroethylene, 1,1,2,2‐tetrachloroethane, and related natural degradation products. For the field application, 22,900 m³ of soils were treated to an average depth of 7.6 m with 2% ZVI and 3% sodium bentonite (dry weight basis). Performance monitoring included analysis of soil and water samples. After 1 year, total concentrations of chlorinated volatile organic compounds (CVOCs) in soil samples were decreased by site‐wide average and median values of 97% and >99%, respectively. Total CVOC concentrations in groundwater were reduced by average and median values of 81% and >99%, respectively. In several of the soil and groundwater monitoring locations, reductions in total CVOC concentrations of greater than 99.9% were apparent. Further reduction in concentrations of chlorinated solvents is expected with time. Pre‐ and post‐mixing average hydraulic conductivity values were 1.7 × 10^?5 and 5.2 × 10^?8 m/s, respectively, indicating a reduction of about 2.5 orders of magnitude. By achieving simultaneous contaminant mass depletion and hydraulic conductivity reduction, contaminant flux reductions of several orders of magnitude are predicted.     

Presence of Semi‐Volatile Organic Contaminants in Shallow Groundwater of Selected Regions in China

A pioneering investigation of semi‐volatile organic compounds (SVOCs) in shallow groundwater in China was hereby reported. Representative groundwater samples were collected from three selected regions: Eastern Hai River Plain, Yangtze River Delta, and Yunnan‐Guizhou Plateau, and analyzed for 103 SVOCs linked to agricultural and industrial practices. Analytical results showed that 70 of the 103 SVOCs were present in the groundwater samples, a detection frequency of approximately 86%. Compounds detected most frequently included P,P′‐DDT (53.49%, MDL 0.0007 µg/L), 2,4‐dinitrotoluene (51.16%, MDL 0.02 µg/L), and phenol (51.16%, MDL 0.02 µg/L). Fifteen SVOCs, such as P,P′‐DDT, 2,4‐dinitrotoluene, heptachlor, and aldrin, were detected at concentrations exceeding the USA National Recommended Water Quality Criteria‐2009 (USNRWQC‐2009). Most of these 15 SVOCs belong to polycyclic aromatic hydrocarbons and organochlorine pesticides. The detection of SVOCs in the Yunnan‐Guizhou Plateau warrants special concern, since this region has limited human activities and been assumed as an environmentally pristine area. The data from this work are expected to contribute to the database of contemporary groundwater quality in China.     

Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

In situ chemical oxidation involves the introduction of a chemical oxidant into the subsurface for the purpose of transforming groundwater contaminants into harmless by‐products. Owing to oxidant persistence, groundwater samples collected at hazardous waste sites may contain both the contaminant(s) and the oxidant in a “binary mixture.” Binary mixtures composed of sodium persulfate (2.5 g/L; 10.5 mM) and volatile organic compounds (VOCs) (benzene, toluene, m‐xylene, perchloroethylene, trichloroethylene) were analyzed to assess the impact on the quality of the sample. A significant decline (49 to 100%) in VOC concentrations was measured in binary mixtures using gas chromatography (GC) purge and trap, and GC mass spectroscopy headspace methods. Preservation of the binary mixture samples was achieved through the addition of ascorbic acid (99 to 100% VOC average recovery). High concentrations of ascorbic acid (42 to 420 mM) did not interfere in the measurement of the VOCs and did not negatively impact the analytical instruments. High concentrations of ascorbic acid favored the reaction between persulfate and ascorbic acid while limiting the reaction between persulfate and VOCs. If an oxidant is detected and the binary sample is not appropriately preserved, the quality of the sample is likely to be compromised.     

Speciation and Kinetics of Trihalomethane Formation in Drinking Water in Mexico

Water chlorination continues to be one of the most common water disinfection processes, especially in developing countries. When natural organic matter (NOM) is present, the process produces disinfection by-products (DBPs), some of them being trihalomethanes (THMs). This study determined the presence, speciation, and kinetics of THMs formation in the water supply for the northern area of the city of Toluca, Mexico. The results show that the concentrations of THMs are below the maximum allowable limits of 200 μg/L in accordance with NOM-127-SSA1-1994. Regarding THMs speciation, the presence of chloroform was more frequently observed in domestic water; furthermore, in one sample in which bromoform was present, it dominated over the chlorine species. Regarding the kinetics of THMs formation, a maximum concentration of THMs (THMs_Max) of 13.02 μg/L was obtained, and the time required to reach 50% THMs_Max ( t ₅₀) was 39.45 min.     

Preserving Ground Water Samples With Hydrochloric Acid Does Not Result in the Formation of Chloroform

Water samples collected for the determination of volatile organic compounds (VOCs) are often preserved with hydrochloric acid (HCl) to inhibit the biotransformation of the analytes of interest until the chemical analyses can he performed. However, it is theoretically possible that residual free chlorine in the HCl can react with dissolved organic carbon (DOC) to form chloroform via the haloform reaction. Analyses of 1501 ground water samples preserved with HCl from the U.S. Geological Survey's National Water-Quality Assessment Program indicate that chloroform was the most commonly detected VOC among 60 VOCs monitored. The DOC concentrations were not significantly larger in samples with detectable chloroform than in those with no delectable chloroform, nor was there any correlation between the concentrations of chloroform and DOC. Furthermore, chloroform was detected more frequently in shallow ground water in urban areas (28.5% of the wells sampled) than in agricultural areas (1.6% of the wells sampled), which indicates that its detection was more related to urban land-use activities than to sample acidification. These data provide strong evidence that acidification with HCl does not lead to the production of significant amounts of chloroform in ground water samples. To verify these results, an acidification study was designed to measure the concentrations of all trihalomethanes (THMs) that can form as a result of HCl preservation in ground water samples and to determine if ascorbic acid (C₆H₈O₆) could inhibit this reaction if it did occur. This study showed that no THMs were formed as a result of HCl acidification, and that ascorbic acid had no discernible effect on the concentrations of THMs measured.     

Development of an Enzyme Immunoassay for the Analysis of the Atrazine Metabolite Hydroxyatrazine Entwicklung eines Enzymimmunoassays zur Analyse des Atrazin-Metaboliten Hydroxyatrazin

A highly sensitive and specific enzyme immunoassay (EIA) is described for the detection of the atrazine metabolite hydroxyatrazine. Polyclonal antibodies were raised in rabbits by immunization with a hapten-bovine serum albumin (BSA) conjugate containing 8 hapten residues per molecule of BSA. An EIA with a horseradish peroxidase (HRP) hapten tracer was optimized in microtitre plates. A concentration of 50% B/B₀ was found at 0.10 μg/L for hydroxyatrazine. A limit of determination for hydroxyatrazine was reached at approximately 0.01 μg/L, i.e. well below the maximum concentration permitted by the EU guidelines for drinking water and the drinking water ordinance of the FRG. The assay did not require concentration or clean-up steps for drinking water or ground water samples. Validation experiments confirmed a good accuracy and precision. Hydroxyatrazine is reported to be the main atrazine metabolite found in soil samples. As organic solvents are usually employed for soil extraction, the influence of methanol as representative organic solvent on the assay was examined. Up to a concentration of 5% (v/v) methanol, the organic solvent did not affect the assay.     

Identification of Multiple Sources of Groundwater Contamination by Dual Isotopes

Chlorinated solvents are one of the most commonly detected groundwater contaminants in industrial areas. Identification of polluters and allocation of contaminant sources are important concerns in the evaluation of complex subsurface contamination with multiple sources. In recent years, compound‐specific isotope analyses (CSIA) have been employed to discriminate among different contaminant sources and to better understand the fate of contaminants in field‐site studies. In this study, the usefulness of dual isotopes (carbon and chlorine) was shown in assessments of groundwater contamination at an industrial complex in Wonju, Korea, where groundwater contamination with chlorinated solvents such as trichloroethene (TCE) and carbon tetrachloride (CT) was observed. In November 2009, the detected TCE concentrations at the study site ranged between nondetected and 10,066 µg/L, and the CT concentrations ranged between nondetected and 985 µg/L. In the upgradient area, TCE and CT metabolites were detected, whereas only TCE metabolites were detected in the downgradient area. The study revealed the presence of separate small but concentrated TCE pockets in the downgradient area, suggesting the possibility of multiple contaminant sources that created multiple comingling plumes. Furthermore, the variation of the isotopic (δ¹³C and δ³⁷Cl) TCE values between the upgradient and downgradient areas lends support to the idea of multiple contamination sources even in the presence of detectable biodegradation. This case study found it useful to apply a spatial distribution of contaminants coupled with their dual isotopic values for evaluation of the contaminated sites and identification of the presence of multiple sources in the study area.     

Dissolved Organic Carbon in Groundwater Overlain by Irrigated Sugarcane

Elevated dissolved organic carbon (DOC) has been detected in groundwater beneath irrigated sugarcane on the Burdekin coastal plain of tropical northeast Australia. The maximum value of 82 mg/L is to our knowledge the highest DOC reported for groundwater beneath irrigated cropping systems. More than half of the groundwater sampled in January 2004 (n = 46) exhibited DOC concentrations greater than 30 mg/L. DOC was progressively lower in October 2004 and January 2005, with a total decrease greater than 90% indicating varying load(s) to the aquifer. It was hypothesized that the elevated DOC found in this groundwater system is sourced at or near the soil surface and supplied to the aquifer via vertical recharge following above average rainfall. Possible sources of DOC include organic‐rich sugar mill by‐products applied as fertilizer and/or sugarcane sap released during harvest. CFC‐12 vertical flow rates supported the hypothesis that elevated DOC (>40 mg/L) in the groundwater results from recharge events in which annual precipitation exceeds 1500 mm/year (average = 960 mm/year). Occurrence of elevated DOC concentrations, absence of electron acceptors (O₂ and NO₃^–) and both Fe²⁺ and Mn²⁺ greater than 1 mg/L in shallow groundwater suggest that the DOC compounds are chemically labile. The consequence of high concentrations of labile DOC may be positive (e.g., denitrification) or negative (e.g., enhanced metal mobility and biofouling), and highlights the need to account for a wider range of water quality parameters when considering the impacts of land use on the ecology of receiving waters and/or suitability of groundwater for irrigated agriculture.     

Rapid Analysis of 1,4‐Dioxane in Groundwater by Frozen Micro‐Extraction with Gas Chromatography/Mass Spectrometry

An innovative micro‐extraction of aqueous samples coupled with gas chromatography/mass spectrometry in selected ion‐monitoring mode (GC/MS‐SIM) was developed to selectively analyze for 1,4‐dioxane with low part‐per‐billion detection sensitivity. Recoveries of 1,4‐dioxane ranged from 93% to 117% for both spiked laboratory reagent water and natural groundwater matrices, the later having elevated organic carbon content (8.34 ± 0.31 mg/L as total organic carbon). We observed that freezing the aqueous sample along with the extraction solvent enhanced the extraction efficiency, minimized physical interferences, and improved sensitivity resulting in a limit of detection for 1,4‐dioxane to approximately 1.6 μg/L. This method substantially reduces the labor, time, reagents and cost, and uses instruments that are commonly found in analytical laboratories. This method requires a relatively small sample volume (200 μL), and can be considered a green analytical method as it minimizes the use of toxic solvents and the associated laboratory wastes.     

Quality Assessment of Southeast Nile Delta Groundwater for Irrigation

The Nile Delta aquifer has deteriorated in the quality of the groundwater due to domestic, agricultural and industrial activities. In order to examine this, a dataset of thirty-one shallow groundwater samples and four surface water samples were collected in May 2014. The objective of our study is to investigate the hydrochemical characteristics of the groundwater at El-Khanka region in El-Qalubia governorate, southern Nile Delta to discuss the possibility of groundwater use for agricultural purpose. Groundwater types were defined, and the suitability for use in irrigation was evaluated. The factor analysis was conducted to investigate the relationship between the thirteen variables for exploring the loading of them in the model. Then, the principal component analysis was performed to identify the linear combination of variables that account for the greatest amount of common variance. Results showed that groundwater samples are mainly alkaline with an average pH value of 8.60. The total dissolved solids (TDS) range from 350 to 1456 mg/L. The highest concentrations of the anions and cations are sulfate (\(\rm{SO}_4^{2-}\)) and sodium (Na⁺) respectively. The residual sodium carbonate (RSC) is less than 1.25 meq/L. Also, all groundwater samples are located in good and permissible salinity with TDS < 1500 mg/L. In addition, all samples are located in the low sodium hazard zone where sodium adsorption ratio (SAR) is less than 10. Therefore, it is concluded that, the groundwater is suitable for irrigation use in El-Qalubia Governorate. Four factors with Eigenvalues above 1.0 which correlated to each other contributed to the model with 81% of the total variance and governed the spatial variability of the aquifer.     

Factors Controlling the Regional Distribution of Vanadium in Groundwater

Although the ingestion of vanadium (V) in drinking water may have possible adverse health effects, there have been relatively few studies of V in groundwater. Given the importance of groundwater as a source of drinking water in many areas of the world, this study examines the potential sources and geochemical processes that control the distribution of V in groundwater on a regional scale. Potential sources of V to groundwater include dissolution of V rich rocks, and waste streams from industrial processes. Geochemical processes such as adsorption/desorption, precipitation/dissolution, and chemical transformations control V concentrations in groundwater. Based on thermodynamic data and laboratory studies, V concentrations are expected to be highest in samples collected from oxic and alkaline groundwater. However, the extent to which thermodynamic data and laboratory results apply to the actual distribution of V in groundwater is not well understood. More than 8400 groundwater samples collected in California were used in this study. Of these samples, high (≥50 µg/L) and moderate (25 to 49 µg/L) V concentrations were most frequently detected in regions where both source rock and favorable geochemical conditions occurred. The distribution of V concentrations in groundwater samples suggests that significant sources of V are mafic and andesitic rock. Anthropogenic activities do not appear to be a significant contributor of V to groundwater in this study. High V concentrations in groundwater samples analyzed in this study were almost always associated with oxic and alkaline groundwater conditions, which is consistent with predictions based on thermodynamic data.     

Use of an Artificial Sweetener to Identify Sources of Groundwater Nitrate Contamination

The artificial sweetener acesulfame (ACE) is a potentially useful tracer of waste water contamination in groundwater. In this study, ACE concentrations were measured in waste water and impacted groundwater at 12 septic system sites in Ontario, Canada. All samples of septic tank effluent (n = 37) had ACE >6 µg/L, all samples of groundwater from the proximal plume zones (n = 93) had ACE >1 µg/L and, almost all samples from the distal plume zones had ACE >2 µg/L. Mean mass ratios of total inorganic nitrogen/ACE at the 12 sites ranged from 680 to 3500 for the tank and proximal plume samples. At five sites, decreasing ratio values in the distal zones indicated nitrogen attenuation. These ratios were applied to three aquifers in Canada that are nitrate‐stressed and an urban stream where septic systems are present nearby to estimate the amount of waste water nitrate contamination. At the three aquifer locations that are agricultural, low ACE values (<0.02‐0.15 µg/L) indicated that waste water contributed <15% of the nitrate in most samples. In groundwater discharging to the urban stream, much higher ACE values (0.2‐11 µg/L) indicated that waste water was the likely source of >50% of the nitrate in most samples. This study confirms that ACE is a powerful tracer and demonstrates its use as a diagnostic tool for establishing whether waste water is a significant contributor to groundwater contamination or not.     

Water flow path interactions with soil hydraulic properties in till soil at Gårdsjön, Sweden

In 1989, in a hydrological research programme within a deacidification project in the Gårdsjön area in southwest Sweden, flow paths and residence times of soil water and groundwater in microcatchments were examined to support the interpretation of the hydrochemical changes. Saturated hydraulic conductivity and soil water retention were analysed on more than 100 cylinder samples. The catchments have shallow sandy-silty till soil with a mean depth in the main catchment of 43 cm. Porosity of the mineral soil in the main catchment was high and ranged from 38 to 85%. The samples from the B-horizon had generally higher porosity. Porosity and the content of organic matter were correlated. The soil water retention was relatively high at all tensions, likely owing to the high content of organic matter. Dissolved organic substances were most probably transported from the shallow soil on the steep sides of the catchment down to the valley where it precipitated. The high porosities could be a consequence of long-term weathering, provided that the organic substances present have increased the leaching of the weathering products. Measured values of saturated hydraulic conductivity were close to log-normally distributed with a mean for all samples of 3 × 10⁻⁵ m s⁻¹. There was a significant increase in conductivity toward the ground surface with the mean conductivity of the samples in the uppermost 10 cm of the mineral soil of 4 × 10⁻⁵ m s⁻¹, which was about 13 times higher than the conductivity of 3 × 10⁻⁶ m s⁻¹ at 1 m depth. From the relationship between runoff at the catchment outlet and groundwater levels, the conductivity was estimated to be 15–200 times higher in the upper soil layer than in the deeper ones. In one profile, 44–64% of the yearly lateral flow was estimated to occur above 30 cm depth. The conductivity was correlated with the content of drainable water, which indicated the importance of the largest pores for the saturated hydraulic conductivity.     

Presence of Antibiotics in Shallow Groundwater in the Northern and Southwestern Regions of China

Antibiotics are widely used, and there is a serious concern about its adverse impacts on the environment and human health. To our knowledge, prior to this work, there was no evidence of the potential presence of antibiotics in groundwater in China, despite populous speculations. This study reported the detection of 35 target antibiotics of 6 groups (chloramphenicois, lincosamides, marcrolides, quinolones, sulfonamides, and tetracyclines), in shallow groundwater samples collected in northern and southwestern China. Thirty‐four of thirty‐five target antibiotics were detected in the groundwater samples; 73 of 74 monitoring wells contained at least one antibiotic; and at least two antibiotics were detected in 72 of the 74 wells. Ofloxacin (1199.7 ng/L), lincomycin (860.7 ng/L), and norfloxacin (441.9 ng/L) as well as antibiotics with the highest detection frequency such as sulfapyridine (70%), norfloxacin (69%), and lincomycin (64%) were detected at elevated concentrations. The highest detection frequency and concentration of lincosamides were observed in those groundwater samples, but no clear distribution patterns were observed for the six antibiotic groups. Moreover, shallow groundwater in southwestern China seemed to contain most antibiotics, likely due to the high antibiotics discharge and frequent exchange of groundwater with surface matrices. The findings from this work suggest that groundwater in China has been widely contaminated by antibiotics, and presumably other pharmaceutical compounds that have not been investigated to date.     

天津市北塘水库水质咸化原因和防治对策

为确定天津市北塘水库作为南水北调供水调节和事故备用水库的水质安全性,于2005年7-12月,监测分析水体、底泥和库周土壤中全盐量和Cl-浓度的变化,研究水源补给、底泥释放、降雨蒸发和地下水水位变动等因素对水库水质的影响.结果表明在目前蓄潮白新河水的条件下,北塘水库水中的Cl-浓度变化幅度为302-409 mg/L,超过饮用水水源地的水质标准(GB3838-2002).库区0-100 cm底泥全盐量平均值为0.253%,Cl-含量为0.048%,分别是库周土壤的1/8和1/18.3.因此,蓄水造成水库底泥盐分的大量释放.经计算,Cl-的平均释放强度为1.3g/(m2·d).南水北调通水后,若水库保持在5.60m以上的运行水位,底泥释放虽造成Cl-浓度上升,但水质能达到供水水源地的标准.水库周边地下水的矿化度为59.63g/L,Cl-浓度为26.17 g/L,远高于水库水体的含盐量,但只要在5.60m以上水位运行,水库就不会受到高矿化度地下水的补给影响.因此,在合理调度的基础上,北塘水库作为天津市南水北调供水调节和事故备用水库是安全的.     

Application of the Response Surface Method for Optimization of Headspace Liquid Phase Microextraction of Trihalomethanes in Drinking Water

An optimized analysis method based on headspace liquid phase microextraction (HS‐LPME) and gas chromatography coupled with mass spectrometry was proposed for the determination of trihalomethanes (THMs) in drinking water. The response surface method (RSM) was used to optimize the extraction of THMs for analysis by HS‐LPME. The temperature, extraction time and NaCl concentration were found to be important extraction parameters. The coefficient of determination (R²) for the model was 94.97%. A high probability value (P < 0.0001) for the regression indicated that the model had a high level of significance. The optimum conditions were seen to be: temperature 42.0°C, NaCl concentration 0.30 g/mL, and extraction time 28 min. The response variable was the summation of the THMs chromatography peak areas and the reproducibility of this was investigated in five replicate experiments under the optimized conditions. The relative standard deviations (RSD%) of the THMs ranged from 8.0–11.6%. The limits of detection (LODs), based on a signal‐to‐noise ratio (S/N) of three ranged from 0.42–0.78 μg/L, and were lower than the maximum limits for THMs in drinking water established by the WHO.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part I: Drug Residues and other Polar Contaminants in Berlin Surface and Groundwater

Several polar contaminants were found in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. Residues of pharmaceuticals and N-(phenylsulfonyl)-sarcosine originating from various sewage treatment plants effluents were found at concentrations up to the μg/L-level in the surface water, whereas the concentrations of polar pesticides such as dichlorprop and mecoprop were always below 0.1 μg/L. The pharmaceuticals most frequently detected in the surface water samples include clofibric acid, diclofenac, ibuprofen, propiphenazone, and two other drug metabolites. Additional investigations of groundwater wells of a drinking water plant have shown that polar contaminants such as drug residues or N-(phenylsulfonyl)-sarcosine easily leach through the subsoil into the groundwater aquifers when contaminated surface water is used for groundwater recharge in drinking water production.     

Surveying Upstate NY Well Water for Pesticide Contamination: Cayuga and Orange Counties

Private wells in Cayuga and Orange counties in New York were sampled to determine the occurrence of pesticide contamination of groundwater in areas where significant pesticide use coincides with shallow or otherwise vulnerable groundwater. Well selection was based on local groundwater knowledge, risk modeling, aerial photo assessments, and pesticide application database mapping. Single timepoint samples from 40 wells in each county were subjected to 93‐compound chromatographic scans. All samples were nondetects (reporting limits ≤1 μg/L), thus no wells from either county exceeded any of 15 state groundwater standards or guidance values. More sensitive enzyme‐linked immunosorbent assays (ELISA) found two wells with quantifiable atrazine in each county (0.1–0.3 μg/L), one well with quantifiable diazinon (0.1 μg/L) in Orange County, and one well with quantifiable alachlor (0.2 μg/L) in Cayuga County. Trace detections (<0.1 μg/L) in Cayuga County included atrazine (five wells), metolachlor (six wells), and alachlor (one well), including three wells with multiple detections. All 12 Cayuga County wells with ELISA detections had either corn/grain or corn/forage rotations as primary surrounding land uses (although 20 other wells with the same land uses had no detections) and all quantified detections and most trace detections occurred in wells up to 9‐m deep. Orange County trace (<0.1 μg/L) ELISA detections (atrazine three wells, diazinon one well, and metolachlor five wells) and quantified detections were only generally associated with agricultural land uses. Finding acceptable drinking water quality in areas of vulnerable groundwater suggests that water quality in less vulnerable areas will also be good.     

Metal Retention Experiments for the Design of Soil‐Mix Technology Permeable Reactive Barriers

Soil‐mix technology is effective for the construction of permeable reactive barriers (PRBs) for in situ groundwater treatment. The objective of this study was to perform initial experiments for the design of soil‐mix technology PRBs according to (i) sorption isotherm, (ii) reaction kinetics and (iii) mass balance of the contaminants. The four tested reactive systems were: (i) a granular zeolite (clinoptilolite–GZ), (ii) a granular organoclay (GO), (iii) a 1:1‐mixture GZ and model sandy clayey soil and (iv) a 1:1:1‐mixture of GZ, GO and model soil. The laboratory experiments consisted of batch tests (volume 900 mL and sorbent mass 18 g) with a multimetal solution of Pb, Cu, Zn, Cd and Ni. For the adsorption experiment, the initial concentrations ranged from 0.01 to 0.5 mM (2.5 to 30 mg/L). The maximum metal retention was measured in a batch test (300 mg/L for each metal, volume 900 mL, sorbent mass 90–4.5 g). The reactive material efficiency order was found to be GZ > GZ‐soil mix > GZ‐soil‐GO mix > GO. Langmuir isotherms modelled the adsorption, even in presence of a mixed cations solution. Adsorption was energetically favourable and spontaneous in all cases. Metals were removed according to the second order reaction kinetics; GZ and the 1:1‐mix were very similar. The maximum retention capacity was 0.1–0.2 mmol/g for Pb in the presence of clinoptilolite; for Cu, Zn, Cd and Ni, it was below 0.05 mmol/g for the four reactive systems. Mixing granular zeolite, organoclay and model soil increased the chemisorption. Providing that GZ is reactive enough for the specific conditions, GZ can be mixed to obtain the required sorption. Granular clinoptilolite addition to soil is recommended for PRBs for metal contaminated groundwater.     

Investigation of Arsenotrophic Microbiome in Arsenic‐Affected Bangladesh Groundwater

Arsenotrophic bacteria contribute to the nutrient cycling in arsenic (As) affected groundwater. This study employed a culture‐independent and ‐dependent investigation of arsenotrophic microbiomes in As affected groundwater samples collected from Madhabpur, Sonatengra, and Union Porishod in Singair Upazila, Manikganj, Bangladesh. Total As contents, detected by Atomic Absorption Spectrophotometry (AAS) of the samples, were 47 µg/L (Madhabpur, SNGW‐1), 53 µg/L (Sonatengra, SNGW‐2), and 12 µg/L (Union porishod, SNGW‐3), whereas the control well (SNGW‐4; depths >150 m) showed As content of 6 µg/L. Denaturing Gradient Gel Electrophoresis (DGGE) analysis of the amplified 16S rRNA gene from As‐affected groundwater samples revealed the dominance of aerobic bacteria Pseudomonas within heterogeneous bacterial populations. DGGE of heterotrophic enrichments supplemented with arsenite [As (III)] for 4 weeks showed the dominance of Chryseobacterium, Flavobacterium, and Aquabacterium, whereas the dominant genera in that of autotrophic enrichments were Aeromonas, Acinetobacter, and Pseudomonas. Cultured bacteria retrieved from both autotrophic and heterotrophic enrichments were distinguished into nine genotypes belonging to Chryseobacterium, Acinetobacter, Escherichia, Pseudomonas, Stenotrophomonas, Janibacter, Staphylococcus, and Bacillus. They exhibited varying range of As(III) tolerance from 4 to 27 mM. As(III) transformation potential was confirmed within the isolates with oxidation rate as high as 0.143 mM/h for Pseudomonas sp. Sn 28. The arsenotrophic microbiome specifies their potential role in groundwater As‐cycling and their genetic information provide the scientific basis for As‐bioremediation.