Contaminants In Groundwater Systems Research Articles

Microplastics in groundwater: An overview of source, distribution, mobility constraints and potential health impacts during the anthropocene

Microplastics (MPs) have already been detected in various environmental matrices like soil, sediment, and surface water, and recently in groundwater also. The occurrence of MPs in groundwater depends up on the transportation through recharge and may controlled by source and local hydrogeology, and partly on the process of surface water-groundwater interaction (SW-GW). Based on the available studies, we intended to establish a hypothetical overview on the source and process-dependent occurrence of MPs in groundwater across terrestrial and coastal aquifers. Groundwater recharge from agricultural stagnant water, losing streams near dumping sites and agricultural fields, effluents from wastewater treatment plants, septic system failure etc. are the potential sources of MPs in groundwater. The factors like sea level rise and tidal pumping are among the major factors which may control the migration of MPs in coastal aquifer along with the physical and chemical properties of the aquifer media. These MPs have another ecological concern as they can adsorb persistent organic pollutants as well as heavy metals and transfer them to animal tissues through food chain. Studies are being conducted mainly focusing the MP contamination in surface water, marine environment and soil, and very limited studies are available to address the source of MPs in groundwater. However, no such study has been done on the existence, profusion, or environmental factors that contribute to MP pollution in the groundwater in relation to the present climate change scenario. Understanding the extent of MP contamination in groundwater systems is necessary for developing effective management strategies and minimizing their impact on the environment and human health. This study focusses on the source along with the controlling factors of the migration of MPs towards groundwater including the effect of climate change.

Release efficiencies of potassium permanganate controlled-release biodegradable polymer (CRBP) pellets embedded in polyvinyl acetate (CRBP-PVAc) and polyethylene oxide (CRBP- PEO) for groundwater treatment

In-situ chemical oxidation (ISCO) is a commonly used method for the remediation of environmental contaminants in groundwater systems. However, traditional ISCO methods are associated with several limitations, including safety and handling concerns, rebound of groundwater contaminants, and difficulty in reaching all areas of contamination. To overcome these limitations, novel Controlled-Release Biodegradable Polymer (CRBP) pellets containing the oxidant KMnO₄ were designed and tested. The CRBP pellets were encapsulated in Polyvinyl Acetate (CRBP-PVAc) and Polyethylene Oxide (CRBP-PEO) at different weight percentages, baking temperatures, and time. Their release efficiency was tested in water, soil, and water and soil mixture media. Results showed that CRBP-PVAc pellets with 60 % KMnO₄ and baked at 120 °C for 2 min had the highest release percentage and rate across different conditions tested. Natural organic matter was also found to be an important factor to consider for in-field applications due to its potential reducing effect with MnO4−. Overall, the use of CRBP pellets offers an innovative and sustainable solution to remediate contaminated groundwater systems, with the potential to overcome traditional ISCO limitations. These findings suggest that CRBP pellets could provide sustained and controlled release of the oxidant, reducing the need for multiple injections and minimizing safety and handling concerns. This study represents an important step towards developing a new and effective approach for ISCO remediation.

Role of Al substitution in the reduction of ferrihydrite by Shewanella oneidensis MR-1.

Substitution of aluminum under natural environmental conditions has been proven to inhibit the transformation of weakly crystalline iron (oxyhydr)-oxides towards well crystalline iron oxides, thereby enhancing their long-term stability. However, exploration on the role of aluminum substitution in bacteria-mediated iron oxides transformation is relatively lacking, especially in the anaerobic underground condition where iron (oxyhydr)-oxides are easy to reduced. In this study, we selected four different levels of substitution aluminum prevalent in iron oxides under natural conditions, which are 0mol%, 10mol%, 20mol%, and 30mol% (mol Al/mol (Al + Fe)) respectively. With the presence of Shewanella oneidensis MR-1, we conducted a 15-day anaerobic microcosm experiment in simulated groundwater conditions. The experiment data suggested that aluminum substitution result in a decrease in bio-reduction rate constants of ferrihydrite from 0.24 in 0mol% Al to 0.17 in 30mol% Al. Besides, when containing substituted aluminum, secondary minerals produced by biological reduction of ferrihydrite changed from magnetite to akaganeite. These results were attributed to the surface coverage of Al during the reduction process, which affects the contact between S. oneidensis MR-1 and the unexposed Fe(III), thus inhibiting the further reduction of ferrihydrite. Since iron (oxyhydr)-oxides exhibit a strong affinity on multiple kinds of pollutants, results in this study may contribute to predicting the migration and preservation of contaminants in groundwater systems.

Using sequential conditioning to explore uncertainties in geostatistical characterization and in groundwater transport predictions

Rapid transmission of contaminants in groundwater can occur in alluvial gravel aquifers that are permeated by highly conductive small-scale open framework gravels (OFGs). This open framework gravel structure and the associated distribution of hydraulic properties is complex, and so assessments of contamination risks in these aquifers are highly uncertain. Geostatistical models, based on lithological data, can be used to quantitatively characterize this structure. These models can then be used to support analyses of the risks of contamination in groundwater systems. However, these geostatistical models are themselves accompanied by significant uncertainty. This is seldom considered when assessing risks to groundwater systems. Geostatistical model uncertainty can be reduced by assimilating information from hydraulic system response data, but this process can be computationally challenging. We developed a sequential conditioning method designed to address these challenges. This method is demonstrated on a transition probability based geostatistical simulation model (TP), which has been shown to be superior for representing the connectivity of high permeability pathways, such as OFGs. The results demonstrate that the common modelling practice of adopting a single geostatistical model may result in realistic predictions being overlooked, and significantly underestimate the uncertainties of groundwater transport predictions. This has important repercussions for uncertainty quantification in general. It also has repercussions if using ensemble-based methods for history matching, since it also relies on geostatistical models to generate prior parameter distributions. This work highlights the need to explore the uncertainty of geostatistical models in the context of the predictions being made.

Review of Current Issues and Management Strategies of Microplastics in Groundwater Environments

Microplastic contamination has become widespread in natural ecosystems around the globe as a result of the tremendous rise in plastic production over the last 70 years. However, microplastic pollution in marine and riverine habitats has received more attention than that of terrestrial environments or even groundwater. This manuscript reviews the current issues, potential occurrences, and sources of the emerging problem of microplastic contamination in groundwater systems. The most prevalent types of plastic detected in groundwater are polyethylene and polyethylene terephthalate, and fibers and fragments represent the most commonly found shapes. The vertical transportation of microplastics in agricultural soils can affect groundwater aquifer systems, which is detrimental to those who use groundwater for drinking as well as to microorganisms present in the aquifers. Moreover, this review sheds light on the interlinkage between sustainable development goals and groundwater microplastic contamination issues as part of the strategies for the management of microplastic contamination in groundwater. Overall, this review reveals a lack of interest and a gap in knowledge regarding groundwater microplastic pollution and highlights future perspectives for research in this area.

Competitive inhibition of catalytic nitrate reduction over Cu–Pd-hematite by groundwater oxyanions

The presence of various oxyanions in the groundwater could be the main challenge for the successive application of Cu–Pd-hematite bimetallic catalyst to aqueous NO3− reduction due to the inhibition of its catalytic reactivity and alteration of product selectivity. The batch experiments showed that the reduction kinetics of NO3− was strongly suppressed by ClO4−, PO43−, BrO3− and SO32− at low concentrations (>5 mg/L) and HCO3−, CO32−, SO42− and Cl− at high concentrations (20–500 mg/L). The presence of anions significantly changing the end-product selectivities influenced high N2 selectivity. The selectivity toward N2 increased from 55% to 60%, 60%, and 70% as the concentrations of PO43−, SO32−, and SO42− increased, respectively. It decreased from 55% to 35% in the presence of HCO3− and CO32− in their concentration range of 0–500 mg/L. The production of NO2− was generally not detected, while the formation of NH4+ was observed as the second by-product. It was found that the presence of oxyanions in the NO3− reduction influenced the reactivity and selectivity of bimetallic catalysts by i) competing for active sites (PO43−, SO32−, and BrO3− cases) due to their similar structure, ii) blockage of the promoter and/or noble metal (HCO3−, CO32−, SO42−, Cl− and ClO4− cases), and iii) interaction with the support surface (PO43− case). The results can provide a new insight for the successful application of catalytic NO3− reduction technology with high N2 selectivity to the contaminated groundwater system.

Applicability of selected stable isotopes to study the hydrodynamics and contaminant transport within mining areas in Romania and Finland

Abstract Mining operations disturb the natural hydrological cycle at a local scale by creating new pathways for water flow and conveying large amounts of water, both for use in ore beneficiation and through the dewatering of mining workings. Sulfide minerals exposed to water and oxygen are oxidized through chemical and microbial-enhanced reactions, significantly altering the quality of water (acid mine drainage). Stable isotopes may reveal important information concerning water origin and transfer, as well as chemical processes and solute fluxes within the aqueous environment. Several case studies illustrate the use of stable isotope techniques for clarifying aspects related to water circulation in mining areas within Romania and Finland. Hydrogen and oxygen stable isotopes coupled with total dissolved solids have been used to characterize mine water and for assessing water sources, flow paths and mixing processes at some Romanian mining sites. At Talvivaara mine in Finland, water isotopes and chemical composition were used to determine the extent of waste water contamination in groundwater systems after a leakage at gypsum ponds.

Bi2O3/rGO/MonO3n-1 all-solid-state ternary Z-scheme for visible-light driven photocatalytic degradation of bisphenol A and acetaminophen in groundwater

Abstract A series of Bi2O3/rGO/MonO3n-1 all-solid-state ternary Z-scheme were successfully synthesized by a mixed hydrothermal and wet-chemical route. The new materials are highly efficient under visible-light irradiation for the degradation of rhodamine B, bisphenol A, and acetaminophen and it was shown that the best performing composite was able to degrade up to 77 % of acetaminophen in groundwater samples. The synthesized materials were characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray Powder Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Nitrogen Adsorption-Desorption Isotherm and UV–vis Diffuse Reflectance spectroscopy. It was found that the presence of rGO plays an important role in the material since it helps in delaying the recombination time of photogenerated electron/hole (e−/h+) pairs, greatly improving the photocatalytic activity of Bi2O3. The excellent photocatalytic activity under visible-light irradiation of Bi2O3/rGO/MonO3n-1 makes it a promising material for the degradation of emerging contaminants in groundwater systems.

CrVI and Trace Element Contaminated Groundwater Systems Connected with Ophiolitic Rocks.

The level and distribution of chromium (as total chromium and CrVI) and other trace elements were investigated from surface and groundwater samples collected over three periods (n = 155) from Mersin (Turkey) in terms of their origins and potential health risk. The maximum total chromium is 41µg/L and some of the samples have CrVI contents above 5µg/L, which is the maximum permissible level of CrVI under Italian regulations. The dominant water facies are Ca-HCO3 and Mg-HCO3 types based on the Piper diagram. The Ca-HCO3 type waters originate mainly from interaction with carbonate rocks, and the Mg-HCO3 type waters originate from serpentinite dissolution. Chromium contents are higher in Mg-HCO3 water types and the highest concentrations are found in samples from ophiolitic rocks and industrial areas. The As, Fe, Pb, Al, and Ni contents of some samples are above the EU limits in industrial areas.

Indicator-based data assimilation with multiple-point statistics for updating an ensemble of models with non-Gaussian parameter distributions

Ground-water flow and the transport of contaminants in groundwater systems are strongly controlled by geologic heterogeneities. Because, the data available to model these subsurface heterogeneities are generally sparse, the observed groundwater flow, piezometric head at well locations, or the concentration profile of solutes provide valuable additional information about these complex subsurface systems. Regardless, there is likely to be considerable uncertainty associated with the predictions of the subsurface heterogeneities. This has motivated the development of several ensemble-based schemes for assimilating flow response data into predictions of subsurface heterogeneities. Most ensemble-based data assimilation methods including ensemble Kalman filter (EnKF) or indicator-based data assimilation (InDA), used for assimilation of dynamic data into geologic models, utilize statistics in the form of covariances calculated using the ensemble of models to perform model updates. These covariance based updates do not preserve the complex spatial characteristics of geologic structures that are better represented using multiple-point statistics. Additionally, in EnKF, the mismatch between the observed and the simulated values are assumed to be linearly related to the parameter updates, and the distribution of the state variable is assumed to be multi-Gaussian. The spatial distribution of the primary variables like facies can be non-Gaussian because of the spatial continuity exhibited by channel facies (sands) and non-channel facies (clay), that have distinctly different properties. Also, the relationship between the mismatch and the parameter updates can be strongly non-linear. In indicator-based data assimilation (InDA) method the indicator transforms of parameter and mismatch variables are used, which affords the treatment of these variables as bi-variate non-Gaussian. Furthermore, in the indicator transformed space, restrictive linear assumption can also be lifted as the indicator transform is invariant under non-linear transformations. However, the updates are still governed by the bivariate interactions between the state variables. A multiple-point extension of InDA is proposed in this paper which utilizes existing multiple-point simulation algorithms like single normal equation simulation (SNESIM) in combination with InDA, to preserve the spatial characteristics of the geologic model while at the same time honor the observed flow or transport response. The proposed method is applied to a synthetic groundwater system with complex channel distributions. The channel features of the final updated ensemble of models is shown to converge towards the reference model and the ensemble flow responses are also shown to match the reference flow response.

Resilience of groundwater systems in the presence of Bisphenol A under uncertainty

Assessing the health risks associated with emerging contaminants in groundwater systems is a complex issue that has been receiving increased attention in indirect potable reuse applications. Among several emerging contaminants, our study focuses on developing a numerical model that aims to compute the transport characteristics of Bisphenol A (BPA) in a 3D spatially heterogeneous aquifer under uncertainty. Traditional approaches that characterize the health risk of BPA to humans rely on the monotonic dose-response (MDR) relationship with a regulatory dose limit. Recent public health studies indicate that BPA can cause endocrine-related health effects in specific low dose ranges, which requires the consideration of the non-monotonic dose-response (NMDR) model. This work investigates the impact of different BPA DR models (i.e., monotonic vs. non-monotonic) on the resilience of the aquifer against BPA contamination in the presence of hydrogeological heterogeneity. For the resilience estimation, a systematic stochastic methodology linking risk characterization to aquifer resilience is established. Our results show the importance of the interplay between the DR models and aquifer heterogeneity on controlling the uncertainty of the resilience loss RL (d) at a specified environmentally sensitive target. In the increased level of aquifer heterogeneity, the uncertainty bounds are higher for RL estimated through the NMDR model as opposed to the MDR model. Moreover, RL is controlled by η (–), the ratio of the volumetric flow rate at the source zone to the average flow rate at the background aquifer. In a risk management perspective, the consideration of the NMDR model needs to be emphasized due to its impact on the uncertainty of RL. A critical case is when the land use of a contamination site indicates a large number of the vulnerable population to endocrine-related health effects. In this case, η as an indicator of aquifer resilience can reduce the uncertainty of RL.

Transfer and transformation mechanisms of Fe bound-organic carbon in the aquitard of a lake-wetland system during reclamation

Organic carbon (OC) can help control greenhouse gas emissions by participating in biogeochemical reactions and preventing the migration of contaminants in groundwater systems. The association of OC with Fe (Iron) oxide minerals plays a significant role in stabilizing OC and regulating the biogeochemical cycles of OC on the earth’s surface. Reclaiming farmland from lakes changes an original lake into a wetland, but the destiny of Fe bound-OC in the underlying aquitard during this process has been poorly understood. The mechanisms of migration and transformation of Fe bound-OC were investigated in subsurface aquitard sediments of three typical boreholes in the Chen Lake wetland, central China. The Fe bound-OC content in the natural sedimentary conditions (borehole A), transition area (borehole B), and intensive reclamation area (borehole C) were 0.17–3.87, 0.28–3.98 and 0.13–7.08 mg g−1, respectively. The reclamation changed the redox, water, and infiltration conditions of the surface environment, resulting in a transformation of Fe oxides phases, and then cause the change of content and structure of Fe bound-OC. The fresh organic matter provided by undecomposed crops causes oxygen- and nitrogen-rich compounds to combine with Fe oxides extensively through adsorption, resulting in higher δ13C values of Fe bound-OC than non-Fe bound-OC. Fe bound-OC has strong resistance to biodegradation. The Fe bound-OC: total OC ratios generated by adsorption and coprecipitation on the surface layer (0 to −3.5 m) of borehole C was 10.37% and 18.86%, 6.92% and 12.46% higher than those of boreholes A and B, respectively. Coprecipitation has a stronger OC-binding ability and enriches more carboxylates and aromatics, while adsorption gradually assumed a dominant position in OC-Fe interaction in deep aquitard. The reduction dissolution of Fe oxide causes Fe bound-OC to transfer into pore water, leading to an increase of Fe ion and dissolved OC in deep strata.

Assessment of arsenic exposure by drinking well water and associated carcinogenic risk in peri-urban areas of Vehari, Pakistan.

Arsenic (As) is a highly toxic and carcinogenic element. It has received considerable consideration worldwide in recent years due to its highest toxicity to human, and currently, high concentrations observed in the groundwater. Some recent media and research reports also highlighted possible As contamination of groundwater systems in Pakistan. However, there is a scarcity of data about As contents in groundwater in different areas/regions of the country. Consequently, the current study estimated the As concentration in the groundwater used for drinking purpose in 15 peri-urban sites of district Vehari, Pakistan. In total, 127 groundwater samples were collected and examined for As contents in addition to physicochemical characteristics such as temperature, electrical conductivity, pH, total soluble salts, chloride, carbonates, bicarbonates, sodium, potassium, lithium, calcium and barium. Results indicated that the groundwater samples were not fully fit for drinking purposes with several parameters, especially the alarming levels of As (mean As: 46.9µg/L). It was found that 83% groundwater samples of peri-urban sites in district Vehari have As concentration greater than WHO lower permissible limit (10µg/L). The risk assessment parameters (mean hazard quotient: 3.9 and mean cancer risk: 0.0018) also showed possible carcinogenic and non-carcinogenic risks associated with ingestion of As-contaminated groundwater at peri-urban sites. Based on the findings, it is anticipated that special monitoring and management of groundwater is necessary in the studied area in order to curtail the health risks associated with the use of As-contaminated drinking water. Moreover, appropriate remediation and removal of As from groundwater is also imperative for the study area before being used for drinking purpose to avoid As exposure and related risks to the local community.

Controlling factors and driving mechanisms of nitrate contamination in groundwater system of Bandung Basin, Indonesia, deduced by combined use of stable isotope ratios, CFC age dating, and socioeconomic parameters

Number of populations, industry, and economic activities in Indonesia are growing rapidly and these impacts on natural environments raise awareness about water quality issue over the country. Bandung Basin, one of the most growing rapidity urban areas in Indonesia, was assessed for NO3− contamination in groundwater systems, and its controlling factors and driving mechanisms were investigated with the aim to demonstrate novelty on the use of combination of parameters of stable isotope ratios in nitrate (δ15N and δ18O in NO3−), groundwater age (using CFC-12 age tracer), and socioeconomic parameters (land-use, population, and economic database). Groundwater NO3− concentrations at present time did not exceed HWO limit for all the analyzed samples (3.00 mg/L in average with maximum value of 20.69 mg/L, n = 102). Dual stable isotopic analysis together with CFC-12 groundwater age determination suggest that anthropogenic activities are the major causes for increasing NO3− concentrations in groundwater. Those activities under respective land-use are industrial and domestic wastes for urban areas and chemical fertilizers for paddy and plantations areas. In general shallow unconfined aquifer is more vulnerable to NO3− contamination compared with deep confined aquifer because denitrification partly occurs in deep anoxic aquifer and this led attenuation of NO3− pollution in groundwater flowing. However, it seems likely at groundwater depression cones in urban areas that more concentrated waters are transported from shallow aquifer into deep aquifer system through downward vertical fluxes due to excessive pumping. Principal component analysis (PCA) on NO3− concentrations with socioeconomic parameters indicated that industrial and population growths are the main factors related to groundwater NO3− contamination. This result corresponds to CFC-age dating which shows younger (more recently recharged) groundwaters as being more contaminated than older ones do. Our study implies that NO3− contamination in this area may become more severe in future with a lack of necessary controls and treatment for human-induced nitrogen sources. Proposed approach is useful to understand how the NO3− contaminant behaves in large basin aquifer system under urban environments and might be applicable in other developing regions too because increasing populations may be associated with increasing nitrogen loadings.

Elevated Indoor Volatile Organic Compound Exposure in the Niger Delta Region of Nigeria.

The implications of environmental contamination on human health in the Niger Delta region of Nigeria remain a topic of growing international public health interest. To better understand ongoing air pollution and initiate remediation efforts, the United Nations Environmental Programme (UNEP) report recommended the monitoring of volatile organic compounds (VOCs) across different media (water, soil, and air) in Ogoniland, an at-risk population in the Niger Delta region of Nigeria. In this pilot study, we measured indoor VOC concentrations in the indoor air of 20 households in Ogale, an Ogoniland community whose groundwater system is contaminated with benzene at levels 900 times the World Health Organization guidelines and evaluated self-reported health conditions and predicted cancer risks and hazards from inhalation exposure to VOCs. We detected higher concentrations of benzene (mean = 25.7 μg/m3, SD = 23.2 μg/m3) and naphthalene (mean = 7.6 μg/m3, SD = 13.8 μg/m3) than has been reported in other regions. Although study participants reported health symptoms consistent with VOC exposure, we were underpowered to detect a significant association between select indoor VOCs and these self-reported health symptoms using univariate logistic regression models. These findings suggest that that the health symptoms reported by participants may be poor proxies for the underlying disease processes associated with adverse health outcomes due to VOC exposure in this community and that the burden of adverse health effects due to VOC exposure may stem from the contaminated groundwater system. We estimated a non-cancer hazard quotient of 3 from exposure to naphthalene and lifetime excess cancer risks from exposure to naphthalene, benzene, p-dichlorobenzene, carbon tetrachloride, and ethylbenzene of 3 × 10−4, 2 × 10−4, 6 × 10−5, 6 × 10−6, and 1 × 10−5, respectively. These results exceed common risk benchmarks in the United States, suggesting a need for further studies to characterize VOC exposures, sources, and associated health risks in the Niger Delta.

Source and fate of nitrate in contaminated groundwater systems: Assessing spatial and temporal variations by hydrogeochemistry and multiple stable isotope tools

Intensive farming usually imply a degradation of groundwater resources worldwide. In particular, nitrate concentrations exceeding the 50 mg L−1 limit established for drinking water pose the human health at risk. Therefore, assessing the impact of farming on groundwater, in terms of space and time, is of fundamental importance for policy decision makers and land managers. This study was aimed at assessing the nitrate source and fate in groundwater by combining hydrogeochemical and isotopic tools. The study area is located in the coastal plain of Arborea (Italy), a nitrate vulnerable zone (NVZ) due to intensive farming and animal husbandry (28,000 bovine livestock units). This area represents Mediterranean environments where groundwater resources are of relevant importance.In order to assess the present level of groundwater contamination and evaluate temporal variations, 6 hydrogeochemical surveys were carried out bimonthly at 13 sampling sites located in an area of 6 km2. Additional samples were collected in specific surveys (82 water samples in total). The physical-chemical parameters, nitrogen species concentrations, major and minor components were determined, together with the boron, hydrogen, oxygen, nitrogen, and sulfur isotopic delta values.Results showed that groundwater samples were of meteoric origin, as indicated by the δ2H and δ18OH2O values. The groundwater showed near-neutral pH (6.8–7.9) and different values of redox potential (0.2 ÷ 0.5 V), dissolved oxygen (2 ÷ 6 mg L−1), electrical conductivity (0.8 ÷ 2.1 mS cm−1) and chemical composition (sodium-chloride ÷ calcium-bicarbonate). Nitrate was not homogeneously distributed in groundwater, being observed a large range of concentrations, from <1 up to 162 mg L−1. The above differences reflected the variability of groundwater circulation at small scale, which in turn controlled the interaction of water with different sediments (sands and/or clays). The shallow wells (about 5 m depth), screened in groundwater interacting mainly with sands, showed marked variations under the monitoring period, with nitrate peaks reflecting high leaching of nitrate in correspondence of fertilization and irrigation periods. The deeper wells (15–37 m depth) showed high to moderate nitrate when screened in sandy aquifer, whereas they had very low nitrate and relatively high ammonium (up to 1.8 mg L−1) when clay layers were intercepted.Trends of δ15N and δ18ONO3 values in the nitrate of shallow groundwater were related to the nitrate concentration observed over the monitored period. This dual isotope systematic showed a likely source of nitrate in groundwater from either manure or sewage. The δ11B signature coupled to δ15N values clearly identified the manure as the predominant source of nitrate in the shallow and deep groundwater at Arborea. Relative enrichments in heavy nitrogen coupled to high concentrations of nitrate in groundwater were mainly attributed to volatilization processes occurring during the storage of animal wastes prior to application on the soil. Mixing of groundwater with seawater was not recognized, whereas mixing between shallow and deep groundwater may have occurred locally.Natural attenuation of nitrate contamination was observed in the deep groundwater interacting with lagoon clays rich in organic matter. Heterotrophic denitrification processes were highlighted by relatively high δ15N, δ18ONO3, δ34S and δ18OSO4 values in association with low SO42−/Cl− and high HCO3−/SO42− molar ratios observed in the groundwater with low concentration of nitrate.Results of this study showed that site-specific investigations are required for designing the best practices aimed at preserving groundwater resources under Mediterranean conditions. The spreading of animal waste on soils affects groundwater systems and likely extends over long time, strongly depending on the time lag of nutrient transport from source areas to receptor wells. Therefore, adequate monitoring of groundwater quality is required in areas of intensive farming.

Preliminary Study on Dimensionless Expression of Bacterial Chemotaxis in Simulated Contaminated System

The use of chemotactic bacteria in bioremediation may improve the efficiency and decrease the cost of restoration of contaminated groundwater system. However, most previous studies focused at the laboratory scale and could hardly apply to the field scale. In this study, a dimensionless equation was formulated to solve this problem. First, the main influential factors were extracted from previous researches and then one set of dimensionless numbers was obtained based on Buckingham theory. After collecting parameter values and supplementing missing data, Chemotaxis number (Ch), the ratio of accumulated bacterial concentration to its initial value, was correlated with a combination of dimensionless numbers. For a Chemotaxis number greater than one, the bioremediation strategy is expected to be effective, and chemotactic bacteria are expected to accumulate around nonqueous phase liquid (NAPL) contaminant sources efficiently.

Anoxic nitrogen cycling in a hydrocarbon and ammonium contaminated aquifer

Nitrogen fate and transport through contaminated groundwater systems, where N is both ubiquitous and commonly limits pollutant attenuation, must be re-evaluated given evidence for new potential microbial N pathways. We addressed this by measuring the isotopic composition of dissolved inorganic N (DIN = NH4+, NO2−, and NO3−) and N functional gene abundances (amoA, nirK, nirS, hszA) from 20 to 38 wells across an NH4+, hydrocarbon, and SO42− contaminated aquifer. In-situ N attenuation was confirmed on three sampling dates (0, +6, +12 months) by the decreased [DIN] (4300 - 40 μM) and increased δ15N-DIN (5‰–33‰) over the flow path. However, the assumption of negligible N attenuation within the plume was complicated by the presence of alternative electron acceptors (SO42−, Fe3+), both oxidizing and reducing functional genes, and N oxides within this anoxic zone. Active plume N cycling was corroborated using an NO2− dual isotope based model, which found the fastest (∼10 day) NO2− turnover within the N and electron donor rich central plume. Findings suggest that N cycling is not always O2 limited within chemically complex contaminated aquifers, though this cycling may recycle the N species rather than attenuate N.

Interaction of dissolution, sorption and biodegradation on transport of BTEX in a saturated groundwater system: Numerical modeling and spatial moment analysis

Interaction of various physical, chemical and biological transport processes plays an important role in deciding the fate and migration of contaminants in groundwater systems. In this study, a numerical investigation on the interaction of various transport processes of BTEX in a saturated groundwater system is carried out. In addition, the multi-component dissolution from a residual BTEX source under unsteady flow conditions is incorporated in the modeling framework. The model considers Benzene, Toluene, Ethyl Benzene and Xylene dissolving from the residual BTEX source zone to undergo sorption and aerobic biodegradation within the groundwater aquifer. Spatial concentration profiles of dissolved BTEX components under the interaction of various sorption and biodegradation conditions have been studied. Subsequently, a spatial moment analysis is carried out to analyze the effect of interaction of various transport processes on the total dissolved mass and the mobility of dissolved BTEX components. Results from the present numerical study suggest that the interaction of dissolution, sorption and biodegradation significantly influence the spatial distribution of dissolved BTEX components within the saturated groundwater system. Mobility of dissolved BTEX components is also found to be affected by the interaction of these transport processes.

Contaminant concentration versus flow velocity: drivers of biodegradation and microbial growth in groundwater model systems

Aromatic hydrocarbons belong to the most abundant contaminants in groundwater systems. They can serve as carbon and energy source for a multitude of indigenous microorganisms. Predictions of contaminant biodegradation and microbial growth in contaminated aquifers are often vague because the parameters of microbial activity in the mathematical models used for predictions are typically derived from batch experiments, which don’t represent conditions in the field. In order to improve our understanding of key drivers of natural attenuation and the accuracy of predictive models, we conducted comparative experiments in batch and sediment flow-through systems with varying concentrations of contaminant in the inflow and flow velocities applying the aerobic Pseudomonas putida strain F1 and the denitrifying Aromatoleum aromaticum strain EbN1. We followed toluene degradation and bacterial growth by measuring toluene and oxygen concentrations and by direct cell counts. In the sediment columns, the total amount of toluene degraded by P. putida F1 increased with increasing source concentration and flow velocity, while toluene removal efficiency gradually decreased. Results point at mass transfer limitation being an important process controlling toluene biodegradation that cannot be assessed with batch experiments. We also observed a decrease in the maximum specific growth rate with increasing source concentration and flow velocity. At low toluene concentrations, the efficiencies in carbon assimilation within the flow-through systems exceeded those in the batch systems. In all column experiments the number of attached cells plateaued after an initial growth phase indicating a specific “carrying capacity” depending on contaminant concentration and flow velocity. Moreover, in all cases, cells attached to the sediment dominated over those in suspension, and toluene degradation was performed practically by attached cells only. The observed effects of varying contaminant inflow concentration and flow velocity on biodegradation could be captured by a reactive-transport model. By monitoring both attached and suspended cells we could quantify the release of new-grown cells from the sediments to the mobile aqueous phase. Studying flow velocity and contaminant concentrations as key drivers of contaminant transformation in sediment flow-through microcosms improves our system understanding and eventually the prediction of microbial biodegradation at contaminated sites.