A high-resolution monitoring station for the in situ assessment of nitrate-related redox processes at an agricultural site.

Biogeochemical redox processes control the chemical behavior of many major and trace elements, making their comprehension crucial for predicting and protecting environmental health. Nitrogen (N) is especially susceptible to changes in soil redox conditions and affects the cycles of other redox-sensitive species. Elevated N concentrations, in nitrate form, in agricultural soils and associated freshwater ecosystems constitute a problem in many parts of the world. Although a wide variety of measures have been adopted, their assessment through concentration measurements in groundwater and surface water of the different monitoring networks has shortcomings. Nitrate, as a non-point pollutant, is subject to several processes (e.g., transformation and retardation) before it is detected, making it impossible to evaluate measurements' effectiveness reliably. Thus, we designed and constructed a monitoring station featuring commercially available products and self-manufactured components at an agricultural site for the in situ assessment of nitrate-related processes by high-resolution monitoring of hydraulic (soil water content, matric potential, groundwater head) and hydrogeochemical variables (oxidation-reduction potential and groundwater and pore water chemistry) within the vadose zone and the shallow aquifer. The monitoring station has proven to be a reliable tool. Changes over depth and time of measured variables have been identified, allowing the detection of the transient behavior of the redox reactive zone and the interpretation of ongoing denitrification processes and other redox nitrate-triggered phenomena, such as uranium roll-front and selenium accumulation at the redox interface. Measuring both geochemical and soil water variables allows for the calculation of in situ solute inputs into the groundwater and their reaction rates.

Fate of five pharmaceuticals under different infiltration conditions for managed aquifer recharge.

Infiltration of treated wastewater (TWW) to recharge depleted aquifers, often referred to as managed aquifer recharge, is a solution to replenish groundwater resources in regions facing water scarcity. We present a mass balance approach to infer the amounts of five pharmaceuticals (carbamazepine, diclofenac, fenoprofen, gemfibrozil, and naproxen) degraded in column experiments based on concentrations of pharmaceuticals in the aqueous and solid (sorbed) phases. Column experiments were conducted under three different conditions: continuous infiltration, wetting and drying cycles, and wetting and drying cycles with elevated concentrations of antibiotics (which may reduce microbially aided degradation of other compounds). A mass balance comparing pharmaceutical mass in the water phase over the 16-month duration of the experiments to mass sorbed to the soil was used to infer the mass of pharmaceuticals degraded. Results show sorption as the main attenuation mechanism for carbamazepine. About half of the mass of diclofenac was degraded with wetting and drying cycles, but no significant degradation was found for continuous infiltration, while 32% of infiltrated mass sorbed. Fenoprofen was degraded in the shallow and aerobic part of the soil, but degradation appeared to cease beyond 27 cm depth. Gemfibrozil attenuated through a combination of degradation and sorption, with slight increases in attenuation with depth from both mechanisms. Naproxen degraded progressively with depth, resulting in attenuation of >90% of the mass. In the column with elevated concentrations of antibiotics, the antibiotics attenuated to about 50% or less of inflow concentrations by 27 cm depth and within this zone, less degradation of the other compounds was observed.

Uranium in groundwater - A synopsis based on a large hydrogeochemical data set.

Most of the knowledge on the occurrence of Uranium (U) in groundwater comes from in-situ manipulation experiments in the field, computational modelling studies or from laboratory analyses where individual processes of U mobilization were studied in isolation. Because of Uranium's vital redox chemistry it interacts, often simultaneously, with many other element cycles (e.g., sulfur, carbon, iron, and manganese) making it difficult to predict U concentrations in natural environments. For the present study a large data set was analyzed to predict the occurrence of U in groundwater from basic hydrochemistry. The data set consists of more than 8000 chemical groundwater analyses (including Uranium concentrations) from more than 2000 sampling locations. A strong relation between U concentrations and electric conductivity as well as alkalinity was observed, suggesting that weathering of geogenic source material and desorption from mineral surfaces is the principle mechanism of U release. Except for aquifers with strongly reducing conditions this process leads to a slow but continuous accumulation of U in groundwater in most cases. Importantly, the occurrence of U is modulated by the prevailing redox conditions in an aquifer. Uranium concentrations were moderate under oxic conditions and highest under manganese and nitrate-reducing conditions (heterotrophic as wells as autotrophic nitrate reduction). Only in iron- and sulfate-reducing groundwater the probability of U concentrations above 1 µg l-1 was virtually zero, as these ground waters act as U sinks. The combination of mineral weathering (especially carbonates) with mobilization of U under manganese and nitrate reducing conditions results in the highest risk of detecting U. In contrast, a low risk is associated with low pH (<7) and low mineralization of groundwater, which is the case in granitic catchments, for example. Our results further provide evidence, that agricultural practices such as liming, use of fertilizers and irrigation influence the occurrence of U in groundwater in multiple ways. Accurate management of aquifers underlying farmland will therefore become more and more important in the future. In summary, we find that the vulnerability of an aquifer to elevated U concentrations cannot be explained by a single factor. This complicates efforts to target elevated U concentrations in groundwaters that are abstracted for drinking water production.

Ex situ groundwater treatment triggering the mobilization of geogenic uranium from aquifer sediments.

Uranium (U) concentrations in groundwater extracted for drinking water usage from a Quaternary fluvial aquifer partly exceed the German drinking water guideline of 10µgL-1. Responsible sources and mobilization processes were unknown and gave rise to this study. Land use of the watershed is mainly agricultural leading to groundwater nitrate concentrations >50mgL-1 and a need for water treatment prior to utilization as drinking water. This is successfully accomplished by addition of nutrients triggering bacterial nitrate reduction, followed by the addition of NaOH for water softening and CO2 for pH adjustment, with subsequent reinfiltration into the aquifer. Three boreholes were drilled to obtain a total of 127 solid samples from Quaternary and underlying Tertiary sediments. Geochemistry and mineralogy were assessed using elemental analysis (CS, ICP-MS), X-ray diffraction and scanning electron microscopy to complement hydrochemical data and unravel U occurrence in the subsurface. Solid phase U fractionation was characterized by a sequential extraction procedure, U remobilization potential by a 137days column experiment. Shallow Quaternary sediments yielded low U contents <1µgg-1, higher values were found in depths of more than 20m below ground surface. Here, strata of elevated Corg and Cinorg contain up to 14µgg-1 U, mainly bound in organic and carbonate fractions. Groundwater U concentrations >10µgL-1 almost exclusively appear in this same depth range, and only in wells influenced by water treatment runoff. Results suggest that the applied water treatment approach triggers U remobilization from geogenic sources in the aquifer. The most probable mechanism is dissolution of U bearing calcite induced by CO2 application; redox reactions and pH-driven desorption appear to play a minor role in mobilization. We conclude that groundwater treatment should carefully account for unwanted hydrogeochemical side effects triggering the mobilization of geogenic trace elements such as uranium.

Model-based quality management of groundwater resources - catchment area Liedern, Germany.

Strategies of groundwater protection in agricultural dominated areas are mainly based on a general reduction of the input of nutrients like nitrate. However, preventive measures in different parts of the catchment may provide very different effects on raw water quality. Exemplified on the case study 'Liedern' (BEW GmbH Bocholt, Germany) it is shown that hydrogeochemical processes along the flow path and in the well strongly affect the results of agricultural measures in terms of modality and efficiency. Thus, a reduction of fertilization in the vicinity of the well gallery leads to a decrease of nitrate concentration in the raw water. Whereas agricultural measures in the eastern part of the catchment do not influence nitrate, but cause a reduction of the iron concentration and rate of incrustation in the wells after 18 years. In this study we present a management tool that enables assessment of future trends in raw water quality. The tool is based on a reactive transport model which considers land use dynamics as an instrument to influence groundwater/raw water quality. A thermodynamic equilibrium approach is applied for modelling hydrogeochemical processes between aqueous, solid and gaseous phases. Kinetically controlled reactions like the microbial degradation of organic carbon are expressed by multiplicative Michaelis-Menten equations.