Iron and manganese mobilisation due to dam height increase for a tropical reservoir in South East Asia.

The aim of this research was the analysis of the effect of a dam height raise on the water quality of a tropical reservoir used for drinking water purposes in South East Asia. Analyses of iron, manganese, pH and ammonia were performed over a 5-year period from daily water sampling at the reservoir. In addition, high-frequency monitoring data of nitrate, ammonium, pH and blue-green algae were obtained using a monitoring probe. The results showed that due to the raising of the reservoir water level, previously oxic sediments became submerged, triggering an increase in iron and manganese in particular due to the establishment of reducing conditions. Manganese concentrations with values up to 4 mg L-1 are now exceeding guideline values. The analysis strongly indicated that both iron and manganese have a seasonal component with higher iron and manganese concentrations during the wet season. Over a three-year period afterwards, concentrations did not go back to pre-raise levels. The change in water quality was accompanied by a change in pH from previous values of around 5 to pH values of around 6.5. Geochemical simulations confirmed the theory that the increasing concentrations of iron and manganese are due to the dissolution of MnO2 and ferric oxyhydroxides oxidising organic matter in the process. This study showed that changes in reservoir water levels with the establishment of reducing conditions can have long-term effects on the water quality of a reservoir.

Impact of a transformation from flood to drip irrigation on groundwater recharge and nitrogen leaching under variable climatic conditions.

The sustainability of agriculture in the Mediterranean climate is challenged by high irrigation water demands and nitrogen fertilizer losses to the environment, causing significant pressure on groundwater resources and groundwater-dependent ecosystems. Advanced irrigation technologies and improved fertilizer management have been promoted as key solutions to reduce the agricultural impact on aquatic systems. However, it remains unclear how different irrigation-fertilizer practices perform on the long-term under a highly variable climate, such as the Mediterranean one. Here, we conduct hydrological simulations over a fifty-year period to quantify the magnitude and dynamics of groundwater recharge and nitrogen leaching under five real-case irrigation-fertilizer practices observed in Valencia (eastern Spain). The Valencian Region is the largest citrus-producing region of Europe and current irrigation-fertilizer practices reflect the ongoing transformation of irrigation systems from flood to drip irrigation. Our simulations highlight three major implications of the irrigation transformation for groundwater resources. First, the transformation from flood to drip irrigation reduces the recharge fraction (19% vs. 16%) and especially the nitrogen leaching fraction (33% vs. 18%) on the long term. Second, the long-term performance of the two irrigation practices is subject to substantial inter-annual differences controlled by precipitation variability. The sensitivity of recharge and nitrogen leaching to annual meteorological conditions is stronger in drip irrigation, which eventually leads to a similar performance of flood and drip irrigation in wet years if fertilizer inputs are similar. Third, we identify a pronounced year-to-year nitrogen memory in the soil, whereby an enhanced (decreased) nitrogen leaching is observed after anomalously dry (wet) years, affecting the performance of irrigation-fertilizer practices. Overall, the study demonstrates the highly variable nature of the performance of irrigation-fertilizer practices, and the major findings can guide future efforts in designing sustainable water management strategies for agricultural areas with a Mediterranean climate.

Combined method of 3H/3He apparent age and on-site helium analysis to identify groundwater flow processes and transport of perchloroethylene (PCE) in an urban area.

Urban groundwater management requires a thorough and robust scientific understanding of flow and transport processes. 3H/3He apparent ages have been shown to efficiently help provide important groundwater-related information. However, this type of analysis is expensive as well as labor- and time-intensive, and hence limits the number of potential sampling locations. To overcome this limitation, we established an inter-relationship between 3H/3He apparent groundwater ages and 4He concentrations analyzed in the field with a newly developed portable gas equilibrium membrane inlet mass spectrometer (GE-MIMS) system, and demonstrated that the results of the simpler GE-MIMS system are an accurate and reliable alternative to sophisticated laboratory based analyses. The combined use of 3H/3He lab-based ages and predicted ages from the 3H/3He-4He age relationship opens new opportunities for site characterization, and reveals insights into the conceptual understanding of groundwater systems. For our study site, we combined groundwater ages with hydrochemical data, water isotopes (18O and 2H), and perchloroethylene (PCE) concentrations (1) to identify spatial inter-aquifer mixing between artificially infiltrated groundwater and water originating from regional flow paths and (2) to explain the spatial differences in PCE contamination within the observed groundwater system. Overall, low PCE concentrations and young ages occur when the fraction of artificially infiltrated water is high. The results obtained from the age distribution analysis are strongly supported by the information gained from the isotopic and hydrochemical data. Moreover, for some wells, fault-induced aquifer connectivity is identified as a preferential flow path for the transport of older groundwater, leading to elevated PCE concentrations.

Arsenic removal with zero-valent iron filters in Burkina Faso: Field and laboratory insights.

Groundwater contaminated with geogenic arsenic (As) is frequently used as drinking water in Burkina Faso, despite adverse health effects. This study focused on testing low-cost filter systems based on zero-valent iron (ZVI), which have not yet been explored in West Africa for As removal. The active ZVI bed was constructed using small-sized iron nails, embedded between sand layers. Household filters were tested for nine months in a remote village relying on tube well water with As concentrations of 400-1350 µg/L. Daily filtered volumes were 40-60 L, with flow rates of ~10 L/h. In parallel, downscaled laboratory filter columns were run to find the best set-up for optimal As removal, with special attention given to the influence of input pH, flow rate and water/nail contact time. Arsenic removal efficiencies in the field were 60-80% in the first six months of operation. The laboratory experiments revealed that trapped air in the nail layer greatly lowered As removal due to preferential flow and decreased water/nail contact time. Measures taken to avoid trapped air led to a partial improvement in the field filters, but effluent As remained >50 µg/L. Similar structural modifications were however very successful in the laboratory columns, where As removal efficiencies were consistently >95% and effluent concentrations frequently <10 µg/L, despite inflow As >1000 µg/L. A constantly saturated nail bed and careful flow control is necessary for optimal As removal. Slow flow and longer pauses between filtrations are important for sufficient contact times and for transformation of brown amorphous Fe-hydroxides to dense magnetite with incorporated As(V). This preliminary study has shown that nail-based filters have the potential to achieve As removal >90% in a field context if conditions (filter bed saturation, flow rate, pauses between filtrations) are well controlled.

A global-scale dataset of direct natural groundwater recharge rates: A review of variables, processes and relationships.

Groundwater recharge indicates the existence of renewable groundwater resources and is therefore an important component in sustainability studies. However, recharge is also one of the least understood, largely because it varies in space and time and is difficult to measure directly. For most studies, only a relatively small number of measurements is available, which hampers a comprehensive understanding of processes driving recharge and the validation of hydrogeological model formulations for small- and large-scale applications. We present a new global recharge dataset encompassing >5000 locations. In order to gain insights into recharge processes, we provide a systematic analysis between the dataset and other global-scale datasets, such as climatic or soil-related parameters. Precipitation rates and seasonality in temperature and precipitation were identified as the most important variables in predicting recharge. The high dependency of recharge on climate indicates its sensitivity to climate change. We also show that vegetation and soil structure have an explanatory power for recharge. Since these conditions can be highly variable, recharge estimates based only on climatic parameters may be misleading. The freely available dataset offers diverse possibilities to study recharge processes from a variety of perspectives. By noting the existing gaps in understanding, we hope to encourage the community to initiate new research into recharge processes and subsequently make recharge data available to improve recharge predictions.

Pathline Density Distributions in a Null-Space Monte Carlo Approach to Assess Groundwater Pathways.

A null-space Monte-Carlo (NSMC) approach was applied to account for uncertainty in the calibration of the hydraulic conductivity (K) field for a three-dimensional groundwater flow model of a major water supply system in Switzerland. The approach generates different parameter realizations of the K field using the pilot point methodology. Subsequently, particle tracking (PT) was applied to each calibrated model, and the resulting particles are interpreted as the spatial pathline density distribution of multiple sources. The adopted approach offers advantages over classical PT which does not provide a means for treating uncertainty originating from the incomplete description of subsurface heterogeneity. Uncertainty in the K field is shown to strongly influence the spatial pathline distribution. Pathline spreading is particularly evident in locations where the information content of the head observations does not sufficiently constrain the estimated parameters. Despite the predictive uncertainty, the pumped drinking water at the study site is most likely dominated by artificially-infiltrated groundwater originating from the local infiltration canals. The model suggests that within the well field, the central pumping wells could be extracting regional groundwater, although the probability is relatively low. Nevertheless, a rigorous uncertainty assessment is still required since only a few realizations resulted in flow paths that support the field observations. Model results should therefore not be based on only one model realization; rather, an uncertainty analysis should be carried out to provide a sufficiently large suite of equally probable simulations that include all potential sources and pathways.

A review of threats to groundwater quality in the anthropocene.

Awareness concerning sustainable groundwater consumption under the context of land use and climate change is gaining traction, raising the bar for adequate understanding of the complexities of natural and anthropogenic processes and how they affect groundwater quality. The heterogeneous characteristics of aquifers have hampered comprehensive source, transport and contaminant identification. As questions remain about the behavior and prediction of well-known groundwater contaminants, new concerns around emerging contaminants are on the increase. This review highlights some of the key contaminants that originate from anthropogenic activities, organized based on land use categories namely agricultural, urban and industrial. It further highlights the extensive overlap, in terms of both provenance as well as contaminant type, between the different land use sectors. A selection of case studies from literature that describe the continued concern of established contaminants, as well as new and emerging compounds, are presented to illustrate the many qualitative threats to global groundwater resources. In some cases, the risk of groundwater contamination lacks adequate gravity, while in others the underlying physical and societal processes are not fully understood and activities may commence without adequately considering potential impacts. In the agricultural context, the historic and current application of fertilizers and plant protectants, use of veterinary pharmaceuticals and hormones, strives to safeguard the growing food demands. In the context of a sprawling urban environment, waste, human pharmaceuticals, and urban pesticide outputs are increasing, with adequate runoff and sanitation infrastructure often lagging. Finally, industrial activities are associated with accidental leaks and spills, while the large-scale storage of industrial byproducts has led to legacy contaminants such as those stemming from raw mineral extraction. With this review paper, we aim to underscore the need for transdisciplinary research, along with transboundary communication, using sound science and adaptive policy and management practice in order to procure sustainable groundwater quality.

Characterization of a managed aquifer recharge system using multiple tracers.

Knowledge about the residence times of artificially infiltrated water into an aquifer and the resulting flow paths is essential to developing groundwater-management schemes. To obtain this knowledge, a variety of tracers can be used to study residence times and gain information about subsurface processes. Although a variety of tracers exists, their interpretation can differ considerably due to subsurface heterogeneity, underlying assumptions, and sampling and analysis limitations. The current study systematically assesses information gained from seven different tracers during a pumping experiment at a site where drinking water is extracted from an aquifer close to contaminated areas and where groundwater is artificially recharged by infiltrating surface water. We demonstrate that the groundwater residence times estimated using dye and heat tracers are comparable when the thermal retardation for the heat tracer is considered. Furthermore, major ions, acesulfame, and stable isotopes (δ2H and δ18O) show that mixing of infiltrated water and groundwater coming from the regional flow path occurred and a vertical stratification of the flow system exist. Based on the concentration patterns of dissolved gases (He, Ar, Kr, N2, and O2) and chlorinated solvents (e.g., tetrachloroethene), three temporal phases are observed in the ratio between infiltrated water and regional groundwater during the pumping experiment. Variability in this ratio is significantly related to changes in the pumping and infiltration rates. During constant pumping rates, more infiltrated water was extracted, which led to a higher dilution of the regional groundwater. An infiltration interruption caused however, the ratio to change and more regional groundwater is extracted, which led to an increase in all concentrations. The obtained results are discussed for each tracer considered and its strengths and limitations are illustrated. Overall, it is demonstrated that aquifer heterogeneity and various subsurface processes necessitate application of multiple tracers to quantify uncertainty when identifying flow processes.

Estimating the spatial distribution of artificial groundwater recharge using multiple tracers.

Stable isotopes of water, organic micropollutants and hydrochemistry data are powerful tools for identifying different water types in areas where knowledge of the spatial distribution of different groundwater is critical for water resource management. An important question is how the assessments change if only one or a subset of these tracers is used. In this study, we estimate spatial artificial infiltration along an infiltration system with stage-discharge relationships and classify different water types based on the mentioned hydrochemistry data for a drinking water production area in Switzerland. Managed aquifer recharge via surface water that feeds into the aquifer creates a hydraulic barrier between contaminated groundwater and drinking water wells. We systematically compare the information from the aforementioned tracers and illustrate differences in distribution and mixing ratios. Despite uncertainties in the mixing ratios, we found that the overall spatial distribution of artificial infiltration is very similar for all the tracers. The highest infiltration occurred in the eastern part of the infiltration system, whereas infiltration in the western part was the lowest. More balanced infiltration within the infiltration system could cause the elevated groundwater mound to be distributed more evenly, preventing the natural inflow of contaminated groundwater. Dedicated to Professor Peter Fritz on the occasion of his 80th birthday.

Groundwater arsenic contamination in Burkina Faso, West Africa: Predicting and verifying regions at risk.

Arsenic contamination in groundwater from crystalline basement rocks in West Africa has only been documented in isolated areas and presents a serious health threat in a region already facing multiple challenges related to water quality and scarcity. We present a comprehensive dataset of arsenic concentrations from drinking water wells in rural Burkina Faso (n=1498), of which 14.6% are above 10µg/L. Included in this dataset are 269 new samples from regions where no published water quality data existed. We used multivariate logistic regression with arsenic measurements as calibration data and maps of geology and mineral deposits as independent predictor variables to create arsenic prediction models at concentration thresholds of 5, 10 and 50µg/L. These hazard maps delineate areas vulnerable to groundwater arsenic contamination in Burkina Faso. Bedrock composed of schists and volcanic rocks of the Birimian formation, potentially harbouring arsenic-containing sulphide minerals, has the highest probability of yielding groundwater arsenic concentrations >10µg/L. Combined with population density estimates, the arsenic prediction models indicate that ~560,000 people are potentially exposed to arsenic-contaminated groundwater in Burkina Faso. The same arsenic-bearing geological formations that are positive predictors for elevated arsenic concentrations in Burkina Faso also exist in neighbouring countries such as Mali, Ghana and Ivory Coast. This study's results are thus of transboundary relevance and can act as a trigger for targeted water quality surveys and mitigation efforts.

Does river restoration affect diurnal and seasonal changes to surface water quality? A study along the Thur River, Switzerland.

Changes in river water quality were investigated along the lower reach of the Thur River, Switzerland, following river restoration and a summer storm event. River restoration and hydrological storm events can each cause dramatic changes to water quality by affecting various bio-geochemical processes in the river, but have to date not been well documented, especially in combination. Evaluating the success of river restoration is often restricted in large catchments due to a lack of high frequency water quality data, which are needed for process understanding. These challenges were addressed in this study by measuring water quality parameters including dissolved oxygen (DO), temperature, pH, electrical conductivity (EC), nitrate and dissolved organic carbon (DOC) with a high temporal frequency (15 min-1h) over selected time scales. In addition, the stable isotopes of water (δD and δ(18)O-H2O) as well as those of nitrate (δ(15)N-NO3(-) and δ(18)O-NO3(-)) were measured to follow changes in water quality in response to the hydrological changes in the river. To compare the spatial distribution of pre- and post-restoration water quality, the sampling stations were chosen upstream and downstream of the restored section. The diurnal and seasonal changes were monitored by conducting 24-hour campaigns in three seasons (winter, summer and autumn) in 2012 and 2013. The amplitude of the diurnal changes of the various observed parameters showed significant seasonal and spatial variability. Biological processes--mainly photosynthesis and respiration--were found to be the major drivers of these diurnal cycles. During low flow in autumn, a reduction of nitrate (attributed to assimilation by autotrophs) in the pre-dawn period and a production of DOC during the daytime (attributed to photosynthesis) were observed downstream of the restored site. Further, a summer storm event was found to override the influence of these biological processes that control the diurnal changes. High frequency daily monitoring of key water quality parameters over different seasons is shown to be essential in evaluating river restoration success.

Implications of hydrologic connectivity between hillslopes and riparian zones on streamflow composition.

Hydrological responses in mountainous headwater catchments are often highly non-linear with a distinct threshold-related behavior, which is associated to steep hillslopes, shallow soils and strong climatic variability. A holistic understanding of the dominant physical processes that control streamflow generation and non-linearity is required in order to assess potential negative effects of agricultural land use and water management in those areas. Therefore, streamflow generation in a small pre-Alpine headwater catchment (Upper Rietholzbach (URHB), ~1km(2)) was analyzed over a 2-year period by means of rainfall-response analysis and water quality data under explicit consideration of the joint behaviors of climate forcing and shallow groundwater dynamics. The runoff coefficients indicate that only a small fraction of the total catchment area (1-26%) generates streamflow during rainfall events. Hereby, the valley bottom areas (riparian zones) were the most important event-water source whereas only the lower parts of the hillslopes became hydrologically connected to the river network with higher antecedent moisture conditions. However, a distinct threshold-like behavior could not be observed, suggesting a more continuous shift from a riparian-zone to a more hillslope-dominated streamflow hydrograph. Regular manure application on the hillslopes in combinations with lateral hillslope groundwater flux and long groundwater residence times in the riparian zones resulted in a higher mineralization (e.g., total phosphorous) and significant denitrification in the valley bottom area. Despite the important role of the riparian zones for event-flow generation in the URHB, their nutrient buffer capacity is expected to be small due to the low permeability of the local subsurface material. The findings of this integrated analysis are summarized in a conceptual framework describing the hydrological functioning of hillslopes and riparian zones in the URHB.

NOM degradation during river infiltration: effects of the climate variables temperature and discharge.

Most peri-alpine shallow aquifers fed by rivers are oxic and the drinking water derived by riverbank filtration is generally of excellent quality. However, observations during past heat waves suggest that water quality may be affected by climate change due to effects on redox processes such as aerobic respiration, denitrification, reductive dissolution of manganese(III/IV)- and iron(III)(hydr)oxides that occur during river infiltration. To assess the dependence of these redox processes on the climate-related variables temperature and discharge, we performed periodic and targeted (summer and winter) field sampling campaigns at the Thur River, Switzerland, and laboratory column experiments simulating the field conditions. Typical summer and winter field conditions could be successfully simulated by the column experiments. Dissolved organic matter (DOM) was found not to be a major electron donor for aerobic respiration in summer and the DOM consumption did not reveal a significant correlation with temperature and discharge. It is hypothesized that under summer conditions, organic matter associated with the aquifer material (particulate organic matter, POM) is responsible for most of the consumption of dissolved oxygen (DO), which was the most important electron acceptor in both the field and the column system. For typical summer conditions at temperatures >20 °C, complete depletion of DO was observed in the column system and in a piezometer located only a few metres from the river. Both in the field system and the column experiments, nitrate acted as a redox buffer preventing the release of manganese(II) and iron(II). For periodic field observations over five years, DO consumption showed a pronounced temperature dependence (correlation coefficient r = 0.74) and therefore a seasonal pattern, which seemed to be mostly explained by the temperature dependence of the calculated POM consumption (r = 0.7). The river discharge was found to be highly and positively correlated with DO consumption (r = 0.85), suggesting an enhanced POM input during flood events. This high correlation could only be observed for the low-temperature range (T < 15 °C). For temperatures >15 °C, DO consumption was already high (almost complete) and the impact of discharge could not be resolved. Based on our results, we estimate the risk for similar river-infiltration systems to release manganese(II) and iron(II) to be low during future average summer conditions. However, long-lasting heat waves might lead to a consumption of the nitrate buffer, inducing a mobilization of manganese and iron.

New methods to estimate 2D water level distributions of dynamic rivers.

River restoration measures are becoming increasingly popular and are leading to dynamic river bed morphologies that in turn result in complex water level distributions in a river. Disconnected river branches, nonlinear longitudinal water level profiles and morphologically induced lateral water level gradients can evolve rapidly. The modeling of such river-groundwater systems is of high practical relevance in order to assess the impact of restoration measures on the exchange flux between a river and groundwater or on the residence times between a river and a pumping well. However, the model input includes a proper definition of the river boundary condition, which requires a detailed spatial and temporal river water level distribution. In this study, we present two new methods to estimate river water level distributions that are based directly on measured data. Comparing generated time series of water levels with those obtained by a hydraulic model as a reference, the new methods proved to offer an accurate and faster alternative with a simpler implementation.

A socio-ecological adaptive approach to contaminated mega-site management: from 'control and correct' to 'coping with change'.

Mega-sites have a notable impact on surrounding ecological systems. At such sites there are substantial risks associated with complex socio-ecological interactions that are hard to characterize, let alone model and predict. While the urge to control and clean-up mega-sites (control and correct) is understandable, rather than setting a goal of cleaning up such sites, we suggest a more realistic response strategy is to address these massive and persistent sources of contamination by acknowledging their position as new features of the socio-ecological landscapes within which they are located. As it seems nearly impossible to clean up such sites, we argue for consideration of a 'coping with change' rather than a 'control and correct' approach. This strategy recognizes that the current management option for a mega-site, in light of its physical complexities and due to changing societal preferences, geochemical transformations, hydrogeology knowledge and remedial technology options may not remain optimal in future, and therefore needs to be continuously adapted, as community, ecology, technology and understanding change over time. This approach creates an opportunity to consider the relationship between a mega-site and its human and ecological environments in a different and more dynamic way. Our proposed approach relies on iterative adaptive management to incorporate mega-site management into the overall socio-ecological systems of the site's context. This approach effectively embeds mega-site management planning in a triple bottom line and environmental sustainability structure, rather than simply using single measures of success, such as contaminant-based guidelines. Recognizing that there is probably no best solution for managing a mega-site, we present a starting point for engaging constructively with this seemingly intractable issue. Therefore, we aim to initiate discussion about a new approach to mega-site management, in which the complexity of the problems posed by mega-sites is reflected upon in its entirety. These complexities are associated with uncertainties and unknowns that have to be addressed, as they have an impact on the strategies being developed and applied. We contend that the best that can be hoped for in mega-site management is an acceptable solution for the current state of affairs, with good flexibility to modify strategies as new site conditions, remediation possibilities, community preferences and management objectives develop over time.

Diversity and expression of different forms of RubisCO genes in polluted groundwater under different redox conditions.

Groundwater polluted with methyl-tert-butyl ether (MTBE) and ammonium was investigated for chemolithoautotrophic CO(2) fixation capabilities based on detailed analyses of ribulose-1,5-bisphosphate carboxylase/oxygenase (RubisCO) large subunit genes. Samples retrieved from a groundwater conditioning unit, characterized by different redox conditions, were examined for the presence of form IA, form IC (cbbL) and form II (cbbM) RubisCO genes and transcripts obtained from DNA- and RNA-extracts. Form IA RubisCO sequences, which revealed a complex and distinct variety in different sampling stations, were expressed in the original groundwater and in samples amended with oxygen, but not in the aquifer groundwater enriched with nitrate. Form IC RubisCO genes were exclusively detected in groundwater supplied with oxygen and sequences were affiliated with cbbL genes in nitrifying bacteria. cbbM genes were not expressed in the oxygen-amended groundwater, probably due to the low CO(2) /O(2) substrate specificity of this enzyme. Most form II RubisCO transcripts were affiliated with RubisCO genes of denitrifiers, which are important residents in the groundwater supplied with nitrate. The distinct distribution pattern and diversity of RubisCO genes and transcripts obtained in this study suggest that the induction of different RubisCO enzymes is highly regulated and closely linked to the actual environmental conditions.

Towards optimal sampling schedules for integral pumping tests.

Conventional point sampling may miss plumes in groundwater due to an insufficient density of sampling locations. The integral pumping test (IPT) method overcomes this problem by increasing the sampled volume. One or more wells are pumped for a long duration (several days) and samples are taken during pumping. The obtained concentration-time series are used for the estimation of average aquifer concentrations C(av) and mass flow rates M(CP). Although the IPT method is a well accepted approach for the characterization of contaminated sites, no substantiated guideline for the design of IPT sampling schedules (optimal number of samples and optimal sampling times) is available. This study provides a first step towards optimal IPT sampling schedules by a detailed investigation of 30 high-frequency concentration-time series. Different sampling schedules were tested by modifying the original concentration-time series. The results reveal that the relative error in the C(av) estimation increases with a reduced number of samples and higher variability of the investigated concentration-time series. Maximum errors of up to 22% were observed for sampling schedules with the lowest number of samples of three. The sampling scheme that relies on constant time intervals ∆t between different samples yielded the lowest errors.