Kay Knöller

Sulfur transformations in pilot-scale constructed wetland treating high sulfate-containing contaminated groundwater: A stable isotope assessment

Current understanding of the dynamics of sulfur compounds inside constructed wetlands is still insufficient to allow a full description of processes involved in sulfur cycling. Experiments in a pilot-scale horizontal subsurface flow constructed wetland treating high sulfate-containing contaminated groundwater were carried out. Application of stable isotope approach combined with hydro-chemical investigations was performed to evaluate the sulfur transformations. In general, under inflow concentration of about 283 mg/L sulfate sulfur, sulfate removal was found to be about 21% with a specific removal rate of 1.75 g/m(2)·d. The presence of sulfide and elemental sulfur in pore water about 17.3 mg/L and 8.5 mg/L, respectively, indicated simultaneously bacterial sulfate reduction and re-oxidation. 70% of the removed sulfate was calculated to be immobilized inside the wetland bed. The significant enrichment of (34)S and (18)O in dissolved sulfate (δ(34)S up to 16‰, compared to average of 5.9‰ in the inflow, and δ(18)O up to 13‰, compared to average of 6.9‰ in the inflow) was observed clearly correlated to the decrease of sulfate loads along the flow path through experimental wetland bed. This enrichment also demonstrated the occurrence of bacterial sulfate reduction as well as demonstrated by the presence of sulfide in the pore water. Moreover, the integral approach shows that bacterial sulfate reduction is not the sole process controlling the isotopic composition of dissolved sulfate in the pore water. The calculated apparent enrichment factor (ɛ = -22‰) for sulfur isotopes from the δ(34)S vs. sulfate mass loss was significantly smaller than required to produce the observed difference in δ(34)S between sulfate and sulfide. It indicated some potential processes superimposing bacterial sulfate reduction, such as direct re-oxidation of sulfide to sulfate by oxygen released from plant roots and/or bacterial disproportionation of elemental sulfur. Furthermore, 41% of residual sulfate was calculated to be from sulfide re-oxidation, which demonstrated that the application of stable isotope approach combined with the common hydro-chemical investigations is not only necessary for a general qualitative evaluation of sulfur transformations in constructed wetlands, but also leads to a quantitative description of intermediate processes.

The Bode hydrological observatory: a platform for integrated, interdisciplinary hydro-ecological research within the TERENO Harz/Central German Lowland Observatory

This article provides an overview about the Bode River catchment that was selected as the hydrological observatory and main region for hydro-ecological research within the TERrestrial ENvironmental Observatories Harz/Central German Lowland Observatory. It first provides information about the general characteristics of the catchment including climate, geology, soils, land use, water quality and aquatic ecology, followed by the description of the interdisciplinary research framework and the monitoring concept with the main components of the multi-scale and multi-temporal monitoring infrastructure. It also shows examples of interdisciplinary research projects aiming to advance the understanding of complex hydrological processes under natural and anthropogenic forcings and their interactions in a catchment context. The overview is complemented with research work conducted at a number of intensive research sites, each focusing on a particular functional zone or specific components and processes of the hydro-ecological system.

Stable sulfur and oxygen isotope fractionation of anoxic sulfide oxidation by two different enzymatic pathways.

The microbial oxidation of sulfide is a key reaction of the microbial sulfur cycle, recycling sulfur in its most reduced valence state back to more oxidized forms usable as electron acceptors. Under anoxic conditions, nitrate is a preferential electron acceptor for this process. Two enzymatic pathways have been proposed for sulfide oxidation under nitrate reducing conditions, the sulfide:quinone oxidoreductase (SQR) pathway and the Sox (sulfur oxidation) system. In experiments with the model strains Thiobacillus denitrificans and Sulfurimonas denitrificans, both pathways resulted in a similar small sulfur and oxygen isotope fractionation of -2.4 to -3.6‰ for (34)S and -2.4 to -3.4‰ for (18)O. A similar pattern was detected during the oxidation of sulfide in a column percolated with sulfidic, nitrate amended groundwater. In experiments with (18)O-labeled water, a strong oxygen isotope fractionation was observed for T. denitrificans and S. denitrificans, indicating a preferential incorporation of (18)O-depleted oxygen released as water by nitrate reduction to nitrogen. The study indicates that nitrate-dependent sulfide oxidation might be monitored in the environment by analysis of (18)O-depleted sulfate.

Anomalous fluoride concentration in groundwater - is it natural or pollution? A stable isotope approach.

Fluoride anomalies (up to 11 mg/l) have been detected in groundwater of the central region of Rio Grande do Sul State, Southern Brazil, in an area where fluorosis is endemic. Two hypotheses are investigated concerning the fluoride origin: lithochemical affiliation from regional rock or contamination by fertilisers application. These hypotheses are discussed based on the stable isotope data of water, nitrate, and sulphate, which indicates that the local precipitation is the main groundwater recharge source. The isotopic composition of groundwater sulphate is similar to that of fertiliser sulphate. However, a conclusive assignment of groundwater sulphate to fertiliser origin is not indicated because further possible sulphate sources fall into the same isotopic range. In contrast, the isotopic composition of dissolved nitrate suggests that there is no direct relationship to the use of NPK fertilisers. Hence, an origin of the high fluoride content in groundwater related to long-term rock–water interactions seems likely.

Regional nitrogen dynamics in the TERENO Bode River catchment, Germany, as constrained by stable isotope patterns

Interactions between hydrological characteristics and microbial activities affect the isotopic composition of dissolved nitrate in surface water. Nitrogen and oxygen isotopic signatures of riverine nitrate in 133 sampling locations distributed over the Bode River catchment in the Harz Mountains, Germany, were used to identify nitrate sources and transformation processes. An annual monitoring programme consisting of seasonal sampling campaigns in spring, summer and autumn was conducted. δ15N and δ18O of nitrate and corresponding concentrations were measured as well as δ2H and δ18O of water to determine the deuterium excess. In addition, precipitation on 25 sampling stations was sampled and considered as a potential input factor. The Bode River catchment is strongly influenced by agricultural land use which is about 70 % of the overall size of the catchment. Different nitrogen sources such as ammonia (NH4) fertilizer, soil nitrogen, organic fertilizer or nitrate in precipitation show partly clear nitrate isotopic differences. Processes such as microbial denitrification result in fractionation and lead to an increase in δ15N of nitrate. We observed an evident regional and partly temporal variation of nitrate isotope signatures which are clearly different between main landscape types. Spring water sections within the high mountains contain nitrate in low concentrations with low δ15NNO3 values of −3 ‰ and high δ18ONO3 values up to 13 ‰. High mountain stream water sub-catchments dominated by nearly undisturbed forest and grassland contribute nitrate with δ15NNO3 and δ18ONO3 values of −1 and −3.5 ‰, respectively. In the further flow path, which is affected by an increasing agricultural land use and urban sewage, we recognized an increase in δ15NNO3 and δ18ONO3 up to 22 and 18 ‰, respectively, with high variations during the year. A correlation seems to exist between the percentage of agricultural land use area and the corresponding δ15NNO3 values for sub-catchments. A shift towards heavier isotope values in stream water samples taken in July 2012 is significant (p-value = 6 · 10−6) compared to samples from March and October 2012. We also see a season-depending impact of microbial denitrification. Denitrification, especially evident in the lowlands, predominantly takes place in the riverbeds. In addition, mixing processes of different nitrate sources and temperature-depending biological processes such as nitrification have to be taken into consideration. Constant-tempered groundwater does not play a noticeable role in the processes of the stream water system. As constrained from oxygen isotope signatures, precipitation associated with low nitrate concentrations does not have an obvious impact on stream water nitrate in the high mountain region.

Characterization of the relationship between microbial degradation processes at a hydrocarbon contaminated site using isotopic methods.

Decisions to employ monitored natural attenuation (MNA) as a remediation strategy at contaminated field sites require a comprehensive characterization of the site-specific biodegradation processes. In the present study, compound-specific carbon and hydrogen isotope analysis (CSIA) was used to investigate intrinsic biodegradation of benzene and ethylbenzene in an aquifer with high levels of aromatic and aliphatic hydrocarbon contamination. Hydrochemical data and isotope fractionation analysis of sulfate and methane was used complementarily to elucidate microbial degradation processes over the course of a three year period, consisting of six sampling campaigns, in the industrial area of Weißandt-Gölzau (Saxony-Anhalt, Germany). Enrichment of (13)C and (2)H isotopes in the residual benzene and ethylbenzene pool downgradient from the pollution sources provided evidence of biodegradation of BTEX compounds at this site, targeting both compounds as the key contaminants of concern. The enrichment of heavy sulfur isotopes accompanied by decreasing sulfate concentrations and the accumulation of isotopically light methane suggested that sulfate-reducing and methanogenic processes are the major contributors to overall biodegradation in this aquifer. Along the contaminant plume, the oxidation of methane with δ(13)C(CH4) values of up to +17.5‰ was detected. This demonstrates that methane formed in the contaminant source can be transported along groundwater flow paths and be oxidized in areas with higher redox potentials, thereby competing directly with the pollutants for electron acceptors. Hydrochemical and isotope data was summarized in a conceptual model to assess whether MNA can be used as viable remediation strategy in Weißandt-Gölzau. The presented results demonstrate the benefits of combining different isotopic methods and hydrochemical approaches to evaluate the fate of organic pollutants in contaminated aquifers.

Assessment of the Flow Dynamic of a Mining Lake by Stable Isotope Investigations

For water samples from mining lake ML 111 of the Lusatian Lignite District and surrounding aquifers δ34S(SO4-b), δ15N(NH4+), δD, and δ18O (H2O) values have been determined to asess the flow dynamic of the in- and outflow scenario. The high mineralization and acidification (pH > 2.6) of the lake water results from an intensive interaction with the surrounding dump sites and the inflow of extremely sulfate rich dump water (up to 4,100mg/1 SO4-). δ34S values range from -7‰ to + 7°CDT in the inflow aquifers. The lake water is considered to be a mixture of different water bodies. The evaporation signature in the outflow aquifer suggests that the groundwater consists of 60% lake water. The nitrogen transfer is explained by 15N signature of ammonium. Sulfate reduction, perceptible in outflow and dump aquifer, cannot be proved within the mining lake by 34S and hydrochemistry.

Evaluation of the Sulfate Dynamics in Groundwater by Means of Environmental Isotopes

Abstract Elevated sulfate concentrations and their heterogeneous distribution in the drinking water catchment area Torgau-Mockritz (Germany) were investigated by means of multiple isotope signatures such as δ34S, δ18O-H2O, δD, tritium, and 85Kr. δ34S values of the groundwater sulfate vary between -19…+ 37‰ CDT. No simple correlation exists between sulfate concentrations and δ34S. Superimposition of different sulfur sources and mobilization processes combined with a complicated groundwater movement create a complex distribution pattern. The oxidation of reduced sedimentary sulfur has to be regarded as a main source of dissolved sulfate at least regionally. Tritium and 14C data revealed that old groundwater can be excluded as source for high sulfate contents. Correlated temporal variations in the concentrations of tritium and sulfate are observed in deeper sampling positions. Highly variable δ18O and δD, as detected in parts of the catchment area, indicate local influences of surface water infiltration into the aquifer. The spatial distribution of isotope signatures enables the identification of zones with descending younger water or hindered groundwater movement and hence provides useful hints for flow modeling.

No nitrification in lakes below pH 3.

Lakes affected by acid mine drainage (AMD) or acid rain often contain elevated concentrations of ammonium, which threatens water quality. It is commonly assumed that this is due to the inhibition of microbial nitrification in acidic water, but nitrification was never directly measured in mine pit lakes. For the first time, we measured nitrification by (15)NH4Cl isotope tracer addition in acidic as well as neutral mine pit lakes in Spain and Germany. Nitrification activity was only detected in neutral lakes. In acidic lakes no conversion of (15)NH4(+) to (15)NO3(-) was observed. This was true both for the water column as well as for biofilms on the surface of macrophytes or dead wood and the oxic surface layer of the sediment. Stable isotope analysis of nitrate showed (18)O values typical for nitrification only in neutral lakes. In a comparison of NH4(+) concentrations in 297 surface waters with different pH, ammonium concentrations higher 10 mg NH4-N L(-1) were only observed in lakes below pH 3. On the basis of the results from stable isotope investigations and the examination of a metadata set we conclude that the lower limit for nitrification in lakes is around pH 3.

Evaluation of groundwater dynamics and quality in the Najd aquifers located in the Sultanate of Oman

The Najd, Oman, is located in one of the most arid environments in the world. The groundwater in this region is occurring in four different aquifers A to D of the Hadhramaut Group consisting mainly of different types of limestone and dolomite. The quality of the groundwater is dominated by the major ions sodium, calcium, magnesium, sulphate, and chloride, but the hydrochemical character is varying among the four aquifers. Mineralization within the separate aquifers increases along the groundwater flow direction from south to north-northeast up to high saline sodium-chloride water in aquifer D in the northeast area of the Najd. Environmental isotope analyses of hydrogen and oxygen were conducted to monitor the groundwater dynamics and to evaluate the recharge conditions of groundwater into the Najd aquifers. Results suggest an earlier recharge into these aquifers as well as ongoing recharge takes place in the region down to present day. Mixing of modern and submodern waters was detected by water isotopes in aquifer D in the mountain chain (Jabal) area and along the northern side of the mountain range. In addition, δ2H and δ18O variations suggest that aquifers A, B, and C are assumed to be connected by faults and fractures, and interaction between the aquifers may occur. Low tritium concentrations support the mixing assumption in the recharge area. The knowledge about the groundwater development is an important factor for the sustainable use of water resources in the Dhofar region.