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This note describes the development and testing of a novel, programmable reversing flow 1D (R1D) experimental column apparatus designed to investigate reaction, sorption, and transport of solutes in aquifers within dynamic reversing flow zones where waters with different chemistries mix. The motivation for constructing this apparatus was to understand the roles of mixing and reaction on arsenic discharging through a tidally fluctuating riverbank. The apparatus can simulate complex transient flux schedules similar to natural flow regimes The apparatus uses an Arduino microcontroller to control flux magnitude through two peristaltic pumps. Solenoid valves control flow direction from two separate reservoirs. In‐line probes continually measure effluent electrical conductance, pH, oxidation–reduction potential, and temperature. To understand how sensitive physical solute transport is to deviations from the real hydrograph of the tidally fluctuating river, two experiments were performed using: (1) a simpler constant magnitude, reversing flux direction schedule (RCF); and (2) a more environmentally relevant variable magnitude, reversing flux direction schedule (RVF). Wherein, flux magnitude was ramped up and down according to a sine wave. Modeled breakthrough curves of chloride yielded nearly identical dispersivities under both flow regimes. For the RVF experiment, Peclet numbers captured the transition between diffusion and dispersion dominated transport in the intertidal interval. Therefore, the apparatus accurately simulated conservative, environmentally relevant mixing under transient, variable flux flow regimes. Accurately generating variable flux reversing flow regimes is important to simulate the interaction between flow velocity and chemical reactions where Brownian diffusion of solutes to solid‐phase reaction sites is kinetically limited. Article impact statement: We developed a low‐cost programmable column experiment apparatus capable of automating reversing flows a range of flux magnitudes. [ABSTRACT FROM AUTHOR]

Hydraulic fracturing (HF) events consume high volumes of water over a short time. When groundwater is the source, the additional pumping by rig/frack supply wells (RFSWs) may impose costs on owners of other sector wells (OSWs) by lowering the hydraulic head. The Carrizo–Wilcox aquifer in south Texas is the main source of water for HF of the Eagle Ford Shale (EFS) Play. The objectives are to assess the impacts of groundwater pumping for HF supply on: (1) hydraulic heads in OSWs located nearby an RFSW and (2) volumetric fluxes between layers of the regional aquifer system compared to a baseline model without the effect of RFSW pumping. The study area spans the footprint of the EFS Play in Texas and extends from 2011 to 2020. The pumping schedules of 2500 RFSWs were estimated from reported pumped water volumes to supply 22,500 HF events. Median annual drawdowns in OSWs ranged from 0.2 to 6.6 m, whereas 95th percentile annual drawdowns exceeded 20 m. The magnitudes of drawdown increased from 2011 to 2020. Of the four layers that comprise the Carrizo–Wilcox aquifer, the upper Wilcox was the most intensively pumped for HF supply. During the peak HF year of 2014, the net flux to the upper Wilcox was 292 Mm3 compared to the baseline net flux for the same year of 278 Mm3—a relative gain of 14 Mm3. Pumping for HF supply has the potential to negatively impact nearby OSWs by capturing water from adjacent aquifer layers. [ABSTRACT FROM AUTHOR]

Abstract: The transition area between rivers and their adjacent riparian aquifers, which may comprise the hyporheic zone, hosts important biochemical reactions, which control water quality. The rates of these reactions and metabolic processes are temperature dependent. Yet the thermal dynamics of riparian aquifers, especially during flooding and dynamic groundwater flow conditions, has seldom been studied. Thus, we investigated heat transport in riparian aquifers during 3 flood events of different magnitudes at 2 sites along the same river. River and riparian aquifer temperature and water‐level data along the Lower Colorado River in Central Texas, USA, were monitored across 2‐dimensional vertical sections perpendicular to the bank. At the downstream site, preflood temperature penetration distance into the bank suggested that advective heat transport from lateral hyporheic exchange of river water into the riparian aquifer was occurring during relatively steady low‐flow river conditions. Although a small (20‐cm stage increase) dam‐controlled flood pulse had no observable influence on groundwater temperature, larger floods (40‐cm and >3‐m stage increases) caused lateral movement of distinct heat plumes away from the river during flood stage, which then retreated back towards the river after flood recession. These plumes result from advective heat transport caused by flood waters being forced into the riparian aquifer. These flood‐induced temperature responses were controlled by the size of the flood, river water temperature during the flood, and local factors at the study sites, such as topography and local ambient water table configuration. For the intermediate and large floods, the thermal disturbance in the riparian aquifer lasted days after flood waters receded. Large floods therefore have impacts on the temperature regime of riparian aquifers lasting long beyond the flood's timescale. These persistent thermal disturbances may have a significant impact on biochemical reaction rates, nutrient cycling, and ecological niches in the river corridor. [ABSTRACT FROM AUTHOR]

The goal of this study was to test hollow-fiber ultrafiltration as a method for concentrating in situ bacteria and viruses in groundwater samples. Water samples from nine wells tapping a shallow sandy aquifer in a densely populated village in Bangladesh were reduced in volume approximately 400-fold using ultrafiltration. Culture-based assays for total coliforms and Escherichia coli, as well as molecular-based assays for E. coli, Bacteroides, and adenovirus, were used as microbial markers before and after ultrafiltration to evaluate performance. Ultrafiltration increased the concentration of the microbial markers in 99% of cases. However, concentration factors (CF = post-filtration concentration/pre-filtration concentration) for each marker calculated from geometric means ranged from 52 to 1018 compared to the expected value of 400. The efficiency was difficult to quantify because concentrations of some of the markers, especially E. coli and total coliforms, in the well water (WW) collected before ultrafiltration varied by several orders of magnitude during the period of sampling. The potential influence of colloidal iron oxide precipitates in the groundwater was tested by adding EDTA to the pre-filtration water in half of the samples to prevent the formation of precipitates. The use of EDTA had no significant effect on the measurement of culturable or molecular markers across the 0.5 to 10 mg/L range of dissolved Fe concentrations observed in the groundwater, indicating that colloidal iron did not hinder or enhance recovery or detection of the microbial markers. Ultrafiltration appears to be effective for concentrating microorganisms in environmental water samples, but additional research is needed to quantify losses during filtration. [ABSTRACT FROM AUTHOR]

Nearly half of the world's urban population depends on aquifers for drinking water. These are increasingly vulnerable to pollution and overexploitation. Besides anthropogenic sources, pollutants such as arsenic (As) are also geogenic and their concentrations have, in some cases, been increased by groundwater pumping. Almost 40 % of Mexico's population relies on groundwater for drinking water purposes; much the aquifers in semi-arid and arid central and northern Mexico is contaminated by As. These are agricultural regions where irrigation water is primarily provided from intenstive pumping of the aquifers leading to long-standing declines in the water table. The focus of this study is the main aquifer within the Comarca Lagunera region in Northern Mexico. Although the scientific evidence demonstrates that health effects are associated with long-term exposure to elevated As concentrations, this knowledge has not yielded effective groundwater development and public health policy. A multidisciplinary approach - including the evaluation of geochemistry, human health risk and development and public health policy - was used to provide a current account of these links. The dissolved As concentrations measured exceeded the corresponding World Health Organization guideline for drinking water in 90 % of the sampled wells; for the population drinking this water, the estimated probability of presenting non-carcinogenic health effects was >90 %, and the lifetime risk of developing cancer ranged from 0.5 to 61 cases in 10,000 children and 0.2 to 33 cases in 10,000 adults. The results suggest that insufficient policy responses are due to a complex and dysfunctional groundwater governance framework that compromises the economic, social and environmental sustainability of this region. These findings may valuable to other regions with similar settings that need to design and enact better informed, science-based policies that recognize the value of a more sustainable use of groundwater resources and a healthier population., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Elevated dissolved arsenic (As) concentrations in the shallow aquifers of Bangladesh are primarily caused by microbially-mediated reduction of As-bearing iron (Fe) (oxy)hydroxides in organic matter (OM) rich, reducing environments. Along the Meghna River in Bangladesh, interactions between the river and groundwater within the hyporheic zone cause fluctuating redox conditions responsible for the formation of a Fe-rich natural reactive barrier (NRB) capable of sequestering As. To understand the NRB's impact on As mobility, the geochemistry of riverbank sediment (<3 m depth) and the underlying aquifer sediment (up to 37 m depth) was analyzed. A 24-hr sediment-water extraction experiment was performed to simulate interactions of these sediments with oxic river water. The sediment and the sediment-water extracts were analyzed for inorganic and organic chemical parameters. Results revealed no differences between the elemental composition of riverbank and aquifer sediments, which contained 40 ± 12 g/kg of Fe and 7 ± 2 mg/kg of As, respectively. Yet the amounts of inorganic and organic constituents extracted were substantially different between riverbank and aquifer sediments. The water extracted 6.4 ± 16.1 mg/kg of Fe and 0.03 ± 0.02 mg/kg of As from riverbank sediments, compared to 154.0 ± 98.1 mg/kg of Fe and 0.55 ± 0.40 mg/kg of As from aquifer sediments. The riverbank and aquifer sands contained similar amounts of sedimentary organic matter (SOM) (17,705.2 ± 5157.6 mg/kg). However, the water-extractable fraction of SOM varied substantially, i.e., 67.4 ± 72.3 mg/kg in riverbank sands, and 1330.3 ± 226.6 mg/kg in aquifer sands. Detailed characterization showed that the riverbank SOM was protein-like, fresh, low molecular weight, and labile, whereas SOM in aquifer sands was humic-like, older, high molecular weight, and recalcitrant. During the dry season, oxic conditions in the riverbank may promote aerobic metabolisms, limiting As mobility within the NRB., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Shallow (<30 m) reducing groundwater commonly contains abundant dissolved arsenic (As) in Bangladesh. We hypothesize that dissolved As in iron (Fe)-rich groundwater discharging to rivers is trapped onto Fe(III)-oxyhydroxides which precipitate in shallow riverbank sediments under the influence of tidal fluctuations. Therefore, the goal of this study is to compare the calculated mass of sediment-bound As that would be sequestered from dissolved groundwater As that discharges through riverbanks of the Meghna River to the observed mass of As trapped within riverbank sediments. To calculate groundwater discharge, a Boussinesq aquifer analytical groundwater flow model was developed and constrained by cyclical seasonal fluctuations in hydraulic heads and river stages observed at three sites along a 13 km reach in central Bangladesh. At all sites, groundwater discharges to the river year-round but most of it passes through an intertidal zone created by ocean tides propagating upstream from the Bay of Bengal in the dry season. The annualized groundwater discharge per unit width at the three sites ranges from 173 to 891 m 2 /yr (average 540 m 2 /yr). Assuming that riverbanks have been stable since the Brahmaputra River avulsed far away from this area 200 years ago and dissolved As is completely trapped within riverbank sediments, the mass of accumulated sediment As can be calculated by multiplying groundwater discharge by ambient aquifer As concentrations measured in 1969 wells. Across all sites, the range of calculated sediment As concentrations in the riverbank is 78-849 mg/kg, which is higher than the observed concentrations (17-599 mg/kg). This discovery supports the hypothesis that the dissolved As in groundwater discharge to the river is sufficient to account for the observed buried deposits of As along riverbanks., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

This study identifies causes of rising arsenic (As) concentrations over 17 years in an inter-montane aquifer system located just north of the Trans-Mexican-Volcanic-Belt in the Mesa central physiographic region that is extensively developed by long-screened production wells. Arsenic concentrations increased by more than 10 µg/L in 14% (3/22) of re-sampled wells. Similarly, in a larger scale analysis wherein As concentrations measured in 137 wells in 2016 were compared to interpolated, baseline concentrations from 246 wells in 1999, As concentrations rose more than 10 µg/L in 30% of wells. Between 1999 and 2016, the percentage of all wells sampled in each basin-wide sampling campaign exceeding the World Health Organization's 10 µg/L drinking water limit increased from 38 to 64%. Principal Components Analysis (PCA), step-wise multiple regression, and Random Forest modeling (RF) revealed that high As concentrations are closely associated with high pH and temperature, and high concentrations of fluoride (F), molybdenum (Mo), lithium (Li), sodium (Na) and silica (Si), but low calcium (Ca) and nitrate (NO 3 ) concentrations. Pumping-induced mixing with hot, geothermally impacted groundwater generates alkaline water through hydrolysis of silicate minerals. The rising pH converts oxyanion sorption sites from positive to negative releasing As (and Mo) to pore waters. The negative correlation between nitrate and As concentrations can be explained by conservative mixing of shallow, young groundwater with geothermally influenced groundwater. Therefore water carrying an anthropogenic contaminant dilutes water carrying geogenic contaminants. This process is enabled by long well screens. Over-exploitation of aquifers in geothermal regions for agriculture can drive As concentrations in water from production wells to toxic levels even as the total dissolved solids remain low., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier Ltd.)

Over the past decades, groundwater quality has deteriorated worldwide by nitrate pollution due to the intensive use of fertilizers in agriculture, release of untreated urban sewage and industrial wastewater, and atmospheric deposition. Likewise, groundwater is increasingly polluted by sulfate due to the release of domestic, municipal and industrial wastewaters, as well as through geothermal processes, seawater intrusion, atmospheric deposition, mineral dissolution, and acid rain. The urbanized and industrialized Monterrey valley has a long record of elevated nitrate and sulfate concentrations in groundwater with multiple potential pollution sources. This study aimed to track different sources and transformation processes of nitrate and sulfate pollution in Monterrey using a suite of chemical and isotopic tracers (δ 2 H-H 2 O, δ 18 O-H 2 O, δ 15 N-NO 3 , δ 18 O-NO 3 δ 34 S-SO 4 , δ 18 O-SO 4 ) combined with a probability isotope mixing model. Soil nitrogen and sewage were found to be the most important nitrate sources, while atmospheric deposition, marine evaporites and sewage were the most prominent sulfate sources. However, the concentrations of nitrate and sulfate were controlled by denitrification and sulfate reduction processes in the transition and discharge zones. The approach followed in this study is useful for establishing effective pollution management strategies in contaminated aquifers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The impacts of long-term pumping on groundwater chemistry remain unclear in the Manas River Basin, Northwest China. In this study, major ions within five surface water and 105 groundwater samples were analyzed to identify hydrogeochemical processes affecting groundwater composition and evolution along the regional-scale groundwater flow paths using the multivariate techniques of hierarchical cluster analysis (HCA) and principal components analysis (PCA) and traditional graphical methods for analyzing groundwater geochemistry. HCA classified the groundwater samples into four clusters (C1 to C4). PCA reduced the dimensionality of geochemical data into three PCs, which explained 86% of the total variance. The results of HCA and PCA were used to identify three zones: "recharge," "transition," and "discharge." In the recharge zone the groundwater type is Ca-HCO 3 -SO 4 and is primarily impacted by the dissolution of calcite and silicate weathering. In the transition zone the groundwater type is Ca-HCO 3 -SO 4 -Cl and is impacted by rock dissolution and reverse ion exchange. In the discharge zone the groundwater type is Na-Cl and is impacted by evaporation and reverse ion exchange. In addition, anthropogenic activities impact the groundwater chemistry in the study area. The groundwater type generally changes from Ca-HCO 3 -SO 4 in the recharge area to Na-Cl in the discharge area along the regional-scale groundwater flow paths. This study provides a process-based knowledge for understanding the interaction of groundwater flow patterns and geochemical evolution within the Manas River Basin., (© 2018, National Ground Water Association.)

Fluoride (F), naturally found in aquifers around the world at toxic concentrations, causes disease in millions of people. The long-term stability, however, of those concentrations within intensively pumped aquifers is poorly characterized. We assessed long-term stability in the spatial distribution of F concentrations in an intensively pumped aquifer within the semi-arid, inter-montane Independence Basin in central Mexico between 1999 and 2016. Although stable in 16 re-sampled wells, F concentrations increased in some localities across the basin by as much as 4mg/L. Changes in recharge pathways to the deep aquifer were identified by analyzing changes in δ 2 H, δ 18 O and Cl/Br mass ratios. In 1999, δ 2 H and δ 18 O values suggested the aquifer was recharged in the mountains. In 2016, however, substantial increases in δ 18 O values in the center of the basin suggest recharge water is derived from rainfall that had experienced increased evaporation. In 1999, the mass ratio Cl/Br in groundwater was slightly enriched over local rainfall, and followed a single mixing line on a plot of Cl. vs. Cl/Br. In 2016, however, three distinct groupings of wells were evident, all following different mixing lines. These changes suggest input from new sources including urban sewage, evaporate dissolution, connate sea water and geothermal waters. Step-wise multiple regression was used to quantify the impact of physical and chemical parameters on F concentrations. In 1999, Li (6.8±1.7) and Na (0.01±0.004) drove F concentrations (R 2 =0.54). In 2016, Na (0.013±0.0018), HCO 3 (0.004±0.001), Ca (-0.0018±0.00045), and Mg (-0.055±0.023) drove F concentrations (0.78). Irrigation pumping and urban expansion within semi-arid, groundwater-dependent, inter-montane basins drive mixing of disparate groundwater chemistries and introduces new sources of recharge to aquifers inducing changes in aquifer chemistry including increasing concentrations of geogenic toxic elements., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Microbial communities are the driving force behind the degradation of contaminants like aromatic hydrocarbons in groundwater ecosystems. However, little is known about the response of native microbial communities to contamination in pristine environments as well as their potential to recover from a contamination event. Here, we used an indoor aquifer mesocosm filled with sandy quaternary calciferous sediment that was continuously fed with pristine groundwater to study the response, resistance and resilience of microbial communities to toluene contamination over a period of almost two years, comprising 132days of toluene exposure followed by nearly 600days of recovery. We observed an unexpectedly high intrinsic potential for toluene degradation, starting within the first two weeks after the first exposure. The contamination led to a shift from oxic to anoxic, primarily nitrate-reducing conditions as well as marked cell growth inside the contaminant plume. Depth-resolved community fingerprinting revealed a low resistance of the native microbial community to the perturbation induced by the exposure to toluene. Distinct populations that were dominated by a small number of operational taxonomic units (OTUs) rapidly emerged inside the plume and at the plume fringes, partially replacing the original community. During the recovery period physico-chemical conditions were restored to the pristine state within about 35days, whereas the recovery of the biological parameters was much slower and the community composition inside the former plume area had not recovered to the original state by the end of the experiment. These results demonstrate the low resilience of sediment-associated groundwater microbial communities to organic pollution and underline that recovery of groundwater ecosystems cannot be assessed solely by physico-chemical parameters., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Groundwater is routinely analyzed for fecal indicators but direct comparisons of fecal indicators to the presence of bacterial and viral pathogens are rare. This study was conducted in rural Bangladesh where the human population density is high, sanitation is poor, and groundwater pumped from shallow tubewells is often contaminated with fecal bacteria. Five indicator microorganisms (E. coli, total coliform, F+RNA coliphage, Bacteroides and human-associated Bacteroides) and various environmental parameters were compared to the direct detection of waterborne pathogens by quantitative PCR in groundwater pumped from 50 tubewells. Rotavirus was detected in groundwater filtrate from the largest proportion of tubewells (40%), followed by Shigella (10%), Vibrio (10%), and pathogenic E. coli (8%). Spearman rank correlations and sensitivity-specificity calculations indicate that some, but not all, combinations of indicators and environmental parameters can predict the presence of pathogens. Culture-dependent fecal indicator bacteria measured on a single date did not predict total bacterial pathogens, but annually averaged monthly measurements of culturable E. coli did improve prediction for total bacterial pathogens. A qPCR-based E. coli assay was the best indicator for the bacterial pathogens. F+RNA coliphage were neither correlated nor sufficiently sensitive towards rotavirus, but were predictive of bacterial pathogens. Since groundwater cannot be excluded as a significant source of diarrheal disease in Bangladesh and neighboring countries with similar characteristics, the need to develop more effective methods for screening tubewells with respect to microbial contamination is necessary., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A majority of households in Bangladesh rely on pond water for hygiene. Exposure to pond water fecal contamination could therefore still contribute to diarrheal disease despite the installation of numerous tubewells for drinking. The objectives of this study are to determine the predominant sources (human or livestock) of fecal pollution in ponds and examine the association between local population, latrine density, latrine quality and concentrations of fecal bacteria and pathogens in pond water. Forty-three ponds were analyzed for E. coli using culture-based methods and E. coli, Bacteroidales and adenovirus using quantitative PCR. Population and sanitation spatial data were collected and measured against pond fecal contamination. Humans were the dominant source of fecal contamination in 79% of the ponds according to Bacteroidales measurements. Ponds directly receiving latrine effluent had the highest concentrations of fecal indicator bacteria (up to 10⁶ Most Probable Number (MPN) of culturable E. coli per 100 mL). Concentrations of fecal indicator bacteria correlated with population surveyed within a distance of 30-70 m (p<0.05) and total latrines surveyed within 50-70 m (p<0.05). Unsanitary latrines (visible effluent or open pits) within the pond drainage basin were also significantly correlated to fecal indicator concentrations (p<0.05). Water in the vast majority of the surveyed ponds contained unsafe levels of fecal contamination attributable primarily to unsanitary latrines, and to lesser extent, to sanitary latrines and cattle. Since the majority of fecal pollution is derived from human waste, continued use of pond water could help explain the persistence of diarrheal disease in rural South Asia., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Eight saturated column experiments were conducted to examine the effects of solution chemistry and grain size on the transport of colloids through crushed silica sand. Two sizes of colloids, 0.025-microm bacteriophage (MS-2) and 1.5-microm carboxylated microspheres, were used as surrogates for the transport of pathogenic viruses and bacteria, respectively. Increasing the Ca(2+) concentration from 1 to 4.8 mM (along with background monovalent ions) resulted in complete attenuation (>6-log decrease in C/C(0)) of MS-2, but caused only a 1-log reduction (C/C(0)=0.1) in the concentration of the microspheres. Decreasing grain size from medium sand (d(50)=0.70 mm) to fine sand (d(50)=0.34 mm) resulted in substantial decreases in effluent concentrations of both the MS-2 (5-log decrease) and microspheres (>2.5-log decrease). Comparison of observed colloid retention to that predicted by a recently published correlation equation for colloid filtration revealed that the model can considerably underpredict (by 4 orders of magnitude or more) colloid retention by angular sand over distances as short as 20 cm. This indicates that state-of-the-art colloid filtration models are still limited in applicability to natural systems.