Environmental relevance monitoring and assessment of ochreous precipitates, hydrochemistry and water sources from abandoned coal mine drainage.

This study investigated the mineralogical and chemical characteristics of ochreous precipitates and mine water samples from abandoned Upper Carboniferous hard coal mines in an extensive former mining area in western Germany. Mine water characteristics have been monitored and assessed using a multi-methodological approach. Thirteen mine water discharge locations were sampled for hydrochemical analysis, with a total of 46 water samples seasonally collected in the whole study area for stable isotopic analyses. Mineralogical composition of 13 ochreous precipitates was identified by a combination of powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FE-SEM/EDS). Results showed that abandoned mine drainage was characterized by circumneutral pH, Eh values ranging from 163 to 269 mV, relatively low concentrations of Fe and Mn, and was dominated by HCO3- > SO42- > Cl- > NO3- and Na+ > Ca2+ > Mg2+ > K+. Goethite and ferrihydrite were the dominant precipitated Fe minerals, with traces of quartz, dolomite, and clay minerals. Some metal and metalloid elements (Mn, Al, Si, and Ti) were found in the ochreous sediments. The role of bacteria in the formation of secondary minerals was assessed with the detection of Leptothrix ochracea. The δ18O and δ2H values of mine water plotted on and close to the GMWL and LMWLs indicated local derivation from meteoric water and represented the annual mean precipitation isotopic composition. Results might help to develop strategies for the management of water resources, contaminated mine water, and public health.

Modified microbiology through enhanced denitrification by addition of various organic substances-temperature effect.

Worldwide, the environmental nitrate (NO3-) problem is increasingly coming into focus. These increases in NO3- concentration result mainly from agricultural inputs and are further exacerbated by decreasing and finite geogenic NO3- degradation capacity in aquifers. Thus, treatment methods are becoming more and more important. In this study, the effects of enhanced denitrification with addition of organic carbon (C) on thereby autochthonous occurring microbiology and compared at room temperature as well as 10 °C were investigated. Incubation of bacteria and fungi was carried out using natural sediments without degradation capacity and groundwater with high NO3- concentrations. Addition of the four applied substrates (acetate, glucose, ascorbic acid, and ethanol) results in major differences in microbial community. Cooling to 10 °C changes the microbiology again. Relative abundances of bacteria are strongly influenced by temperature, which is probably the explanation for different denitrification rates. Fungi are much more sensitive to the milieu change with organic C. Different fungi taxa preferentially occur at one of the two temperature approaches. Major modifications of the microbial community are mainly observed whose denitrification rates strongly depend on the temperature effect. Therefore, we assume a temperature optimum of enhanced denitrification specific to each substrate, which is influenced by the microbiology.

Denitrification in the vadose zone: Modelling with percolating water prognosis and denitrification potential.

Transport and transformation processes of nitrogen in the soil are an essential part of understanding the relationship between agricultural input and nitrate (NO3-) concentrations in groundwater. The presented study describes these transformation processes around NO3- degradation at a water catchment in the Lower Rhine Embayment, Germany. Despite intensive agriculture, extracted groundwater at a depth of 21 to 22 m shows unexpectedly very low NO3- levels, below 3 mg/L NO3- for all wells. The local water supplier therefore carried out investigations in this area and generated soil data from 22 representative areas (142 soil samples from 82 drilling meters from the surface to a max. depth of 5.5 m) and groundwater analyses from 17 groundwater monitoring wells (from 3 to 5 m below ground surface). Soil types are predominantly luvisol and gleysol. The substrate in the topsoil is mainly clayey silt; underneath there are mostly medium-grained sands with partial silt intercalations which appear as a separate layer. Based on this dataset, the percolating water residence times and the NO3- leaching potential were calculated in this study. Together with the nitrogen surplus and with the help of reactive transport modelling, the denitrification potential in the vadose zone was simulated. The comparison of simulation results with laboratory-measured data shows a high correlation. Substantial NO3- reduction in the vadose zone was observed: dependent on soil type, reduction capacity and water residence time, up to 25% of the NO3- was reduced here. The applied modelling is considered an improvement in NO3- degradation potential assessment because it considers many relevant variables such as precipitation, soil parameters (grain size, field capacity, available water capacity, coarse fragments) and nitrogen input. Therefore, a transfer to other sites with comparable hydro(geo)logical conditions is possible, also due to relatively easily determinable input data. This assessment of nitrogen degradation in the vadose zone will be a useful tool for NO3- levels forecast in groundwater.

Forecasting nitrate evolution in an alluvial aquifer under distinct environmental and climate change scenarios (Lower Rhine Embayment, Germany).

When investigating future nitrate (NO3-) concentrations in groundwater, climate change has a major role as it determines the future water budget and, in turn, the conditions in the aquifer which will finally have a decisive effect on NO3- concentrations. In this study, the different effects on water balance and NO3- concentration under three projected climate scenarios - RCP 2.6, RCP 4.5, and RCP 8.5 - are analysed in a water protection area in the Lower Rhine Embayment in Germany. Recharge values were calculated from downscaled precipitation and temperature data for the 21st century in a water budget that considers land use in the evapotranspiration term. Nitrate concentration evolution is estimated using recharge and expected fertilization rates with a lumped-parameter model. In order to be able to map the NO3- concentration, the investigation area is divided into 1000 × 1000 m cells. Each cell is assigned a specific NO3- input and a NO3- degradation capacity. Results show significant variations in NO3- development projected with the different climate scenarios due to different temperatures and consequently actual ET, and precipitation. Nevertheless, nitrate concentrations clearly increase in all projections. The total NO3- mass increases most strongly with RCP 8.5 until 2099 (by 89% compared to 2020) and least with RCP 4.5 (by 50%). Further projections show a 20% reduction in agricultural NO3- input can reduce NO3- concentrations, but insufficiently to comply with drinking water guidelines in all regions and aquifers. The model indicates that NO3- input loads should be defined according to future recharge variations governed by climate change. Consequently, a time-varying fertilization rate specific for each region, with their own turnover time and degradation rate, must be estimated to meet pollution environmental goals.

Geogenic arsenic and uranium in Germany: Large-scale distribution control in sediments and groundwater.

Arsenic (As) and uranium (U) are naturally occurring trace elements with potentially adverse effects on human health. This work revisits nine case studies on As/U accumulation and remobilization mechanisms in aquifers with different geological and stratigraphical backgrounds to develop a systematic overview of Germany's geogenic inventory of these trace elements. It uses geochemical proxies for a total of 270 solid samples to explain their spatio-temporal distribution: while Pleistocene geological development can explain their extensive absence in sediments and related groundwater in northern Germany, their abundance and distribution in the central and southern parts are widely controlled by sediment provenance geochemistry. Only highly felsic origin (Moldanubian Variscides) enables creation of elevated U in the systems while lower degrees of provenance felsicity (Rhenohercynian Variscides) appear to be sufficient for As presence. Postdepositional (hydro)geological and anthropogenically triggered intra-basinal processes of trace element accumulation, redistribution and eventually remobilization to groundwater contribute to the present-day situation. Therefore, the ultimate control of these incompatible trace elements is magmatic, even in old sedimentary systems, and still clearly traceable in nowadays large-scale geogenic As and U distribution in Germany and probably elsewhere.

Drinking Water Uranium and Potential Health Effects in the German Federal State of Bavaria.

Mainly due to its nephrotoxic and osteotoxic potential, uranium (U) increasingly finds itself in the spotlight of environmental and health-related research. Germany decided on a binding U guideline value in drinking water of 10 µg/L, valid since 2011. It is yet widely unknown if and how public health was affected by elevated U concentrations before that. In this ecological study we summarized available drinking water U data for the German federal state of Bavaria (703 analyses in total for 553 different municipalities) at county level (for 76 out of 96 Bavarian counties, representing about 83% of Bavaria's and about 13% of Germany's total population) in terms of mean and maximum U concentration. Bavaria is known to regionally exhibit mainly geogenically elevated groundwater U with a maximum value of 40 µg/L in the database used here. Public health data were obtained from federal statistical authorities at county resolution. These included incidence rates of diagnosed diseases suspected to be potentially associated with chronic U uptake, e.g., diseases of the skeleton, the liver or the thyroid as well as tumor and genito-urinary diseases. The datasets were analyzed for interrelations and mutual spatial occurrence using statistical approaches and GIS as well as odds ratios and relative risks calculations. Weak but significant positive associations between maximum U concentrations and aggregated ICD-10 diagnose groups for growths/tumors as well as liver diseases were observed, elevated incidence rates of thyroid diseases seem to occur where mean drinking water U concentrations exceed 2 µg/L. Here, we discuss obtained results and their implications for potential impacts of hydrochemistry on public health in southeast Germany.

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.

Groundwater uranium origin and fate control in a river valley aquifer.

Groundwater in a Quaternary gravel aquifer partly exhibits uranium (U) concentrations exceeding the new German drinking water limitation (22% of the samples >10 µg L(-1)). This study assesses relevant U reservoirs and hydrogeochemical processes responsible for U transfer between them. A large data set of solid materials (sediments and soils, 164 samples total) and groundwater (114 samples total) characteristics was created in terms of geo- and hydrochemistry, mineralogy, U microdistribution, and mobilization potential. Results show that U primarily derived from lignitic inclusions in Tertiary sediments is transported to and accumulated (complexation to organic substance and UO2 precipitation) in lowland moor peats of the river valley grown on the aquifer gravels. The alkaline character of the system predefines a hydrogeochemical framework fostering U mobility. Elevated concentrations (up to 96 µg L(-1) U) occur downstream of the moor areas and under Mn/NO3-reducing groundwater conditions. Oxic and stronger reduced settings are rather little affected. Supporting previous laboratory studies, this suggests enhanced U mobility in the presence of nitrate also in the field scale. While no anthropogenic U input was detected in the study area, agricultural usage of the moor areas triggers geogenic U release via nitrate fertilization, surface peat degradation, and erosion.

Crossing redox boundaries--aquifer redox history and effects on iron mineralogy and arsenic availability.

Cretaceous shallow marine sediments from northwestern Germany exhibit a distinct colour and geochemical boundary in a depth of several decametres, witnessing a terrestrial oxidative paleo redox process which resulted in cement loss and oxidation of Fe(II) phases. Sediment samples were obtained from boreholes drilled in near-coastal and further basinward paleo environments, including both reduced and oxidized redox facies, to characterize As and Fe occurrence in unaltered layers and redistributional consequences of the redox event. Geochemical and mineralogical composition and As fractionation were assessed. Arsenic resides in pyrite in the reduced section with a bulk rock maximum concentration of 39 µg g(-1), calculated Aspyrite is ~0.2 wt.%. Siderite concretions in the fine sands do not function as As sinks, neither does glauconite whose general As/Fe leaching behaviour was characterized. In the zone of redox transition, reduced and oxidized phases coexist and elevated As concentrations (up to 73 µg g(-1)) with high proportions of reactive As were detected. Arsenic behaviour changes from relatively homogeneous Fe sulphide-control in the unaltered sediments to very heterogeneous Fe hydroxide-control above the paleo redox boundary. The studied characteristics determine recent As availability in the subsurface and must be considered during groundwater extraction from this highly important aquifer.

Enrichment processes of arsenic in oxidic sedimentary rocks - from geochemical and genetic characterization to potential mobility.

Sedimentary marine iron ores of Jurassic age and Tertiary marine sandy sediments containing iron hydroxides concretions have been sampled from boreholes and outcrops in two study areas in Germany to examine iron and arsenic accumulation processes. Samples were analyzed for bulk rock geochemistry (INAA/ICP-OES), quantitative mineralogy (XRD with Rietveld analysis), element distribution (electron microprobe) and arsenic fractionation (sequential extraction). Bulk Jurassic ores contain an average arsenic content of 123 µg g(-1) hosted in mainly goethite ooids which slowly formed in times of condensed sedimentation. Enrichment occurred syndepositionally and is therefore characterized as primary. Iron concretions in Tertiary sediments mainly consist of goethite and yield arsenic up to 1860 µg g(-1). The accumulation process is secondary as it took place in the course of oxidation of the originally reduced marine sediments under terrestrial conditions, leading to element redistribution and local enrichment in the near-surface part. The scale of enrichment was assessed calculating Enrichment Factors, indicating that arsenic accumulation was favoured over other potential contaminants. In spite of higher bulk arsenic contents in the oxidic rocks, the mainly pyrite-hosted As pool within the reduced deeper part of the Tertiary sediments is shown to have a higher potential for remobilization and creation of elevated arsenic concentrations in groundwater.