Early diagenesis of anthropogenic uranium in lakes receiving deep groundwater from the Kiruna mine, northern Sweden.

The uranium (U) concentrations and isotopic composition of waters and sediment cores were used to investigate the transport and accumulation of U in a water system (tailings pond, two lakes, and the Kalix River) receiving mine waters from the Kiruna mine. Concentrations of dissolved U decrease two orders of magnitude between the inflow of mine waters and in the Kalix River, while the concentration of the element bound to particulate matter increases, most likely due to sorption on iron­manganese hydroxides and organic matter. The vertical distribution of U in the water column differs between two polluted lakes with a potential indication of dissolved U supply from sediment's pore waters at anoxic conditions. Since the beginning of exposure in the 1950s, U concentrations in lake sediments have increased >20-fold, reaching concentrations above 50 µg g-1. The distribution of anthropogenic U between the lakes does not follow the distribution of other mine water contaminants, with a higher relative proportion of U accumulating in the sediments of the second lake. Concentrations of redox-sensitive elements in the sediment core as well as Fe isotopic composition were used to re-construct past redox-conditions potentially controlling early diagenesis of U in surface sediments. Two analytical techniques (ICP-SFMS and MC-ICP-MS) were used for the determination of U isotopic composition, providing an extra dimension in the understanding of processes in the system. The (234 U)/(238 U) activity ratio (AR) is rather uniform in the tailings pond but varies considerably in water and lake sediments providing a potential tracer for U transport from the Kiruna mine through the water system, and U immobilization in sediments. The U mass balance in the Rakkurijoki system as well as the amount of anthropogenic U accumulated in lake sediments were evaluated, indicating the immobilization in the two lakes of 170 kg and 285 kg U, respectively.

External carbon addition for enhancing denitrification modifies bacterial community composition and affects CH4 and N2O production in sub-arctic mining pond sediments.

Explosives used in mining operations release reactive nitrogen (N) that discharge into surrounding waters. Existing pond systems at mine sites could be used for N removal through denitrification and we investigated capacity in tailings and clarification pond sediments at an iron-ore mine site. Despite differences in microbial community structure in the two ponds, the potential denitrification rates were similar, although carbon limited. Therefore, a microcosm experiment in which we amended sediment from the clarification pond with acetate, cellulose or green algae as possible carbon sources was conducted during 10 weeks under denitrifying conditions. Algae and acetate treatments showed efficient nitrate removal and increased potential denitrification rates, whereas cellulose was not different from the control. Denitrifiers were overall more abundant than bacteria performing dissimilatory nitrate reduction to ammonium (DNRA) or anaerobic ammonium oxidation, although DNRA bacteria increased in the algae treatment and this coincided with accumulation of ammonium. The algae addition also caused higher emissions of methane (CH4) and nitrous oxide (N2O). The bacterial community in this treatment had a large proportion of Bacteroidia, sulfate reducing taxa and bacteria known as fermenters. Functional gene abundances indicated an imbalance between organisms that produce N2O in relation to those that can reduce it, with the algae treatment showing the lowest relative capacity for N2O reduction. These findings show that pond sediments have the potential to contribute to mitigating nitrate levels in water from mining industry, but it is important to consider the type of carbon supply as it affects the community composition, which in turn can lead to unwanted processes and increased greenhouse gas emissions.

Sedimentary records of δ(13)C, δ(15)N and organic matter accumulation in lakes receiving nutrient-rich mine waters.

Organic C and total N concentrations, C/N ratios, δ(15)N and δ(13)C values in (210)Pb-dated sediment cores were used to reconstruct historical changes in organic matter (OM) accumulation in three Swedish lakes receiving nutrient-rich mine waters. Ammonium-nitrate-based explosives and sodium cyanide (NaCN) used in gold extraction were the major N sources, while lesser amounts of P originated from apatite and flotation chemicals. The software IsoSource was used to model the relative contribution of soil, terrestrial and littoral vegetation, and phytoplankton detritus in the lake sediments. In one lake the IsoSource modelling failed, suggesting the presence of additional, unknown OM sources. In two of the lakes sedimentary detritus of littoral vegetation and phytoplankton had increased by 15-20% and 20-35%, respectively, since ~1950, when N- and P-rich mine waters began to reach the lakes. Today, phytoplankton is the dominating OM component in these lake sediments, which appears to be a eutrophication effect related to mining operations. Changes in the N isotopic composition of biota, lake water, and sediments related to the use of ammonium-nitrate-based explosives and NaCN were evident in the two studied systems. However, N isotope signals in the receiving waters (δ(15)N~+9‰ to +19‰) were clearly shifted from the primary signal in explosives (δ(15)N-NO3=+3.4±0.3‰; δ(15)N-NH4=-8.0±0.3‰) and NaCN (δ(15)N=+1.1±0.5‰), and direct tracing of the primary N isotope signals in mining chemicals was not possible in the receiving waters. Systems where mine waters with a well known discharge history are a major point source of N with well-defined isotopic composition should, however, be suitable for further studies of processes controlling N isotope signatures and their transformation in aquatic systems receiving mine waters.

Interaction between nitrogen and phosphorus cycles in mining-affected aquatic systems-experiences from field and laboratory measurements.

The main objectives of this study were to (a) study the interaction between N and P cycles in mining-affected aquatic systems and (b) to quantify release rates of sedimentary soluble reactive phosphorus (SRP) that may be related to this interaction. Sediment cores and water from Lake Bruträsket (Boliden, northern Sweden) were collected and a time series of water sampling and flow measurements was conducted in the Brubäcken stream connected to the lake. Factors affecting SRP release were studied in a sediment incubation experiment and water column experiments. Field and laboratory measurements indicated that pH and dissolved oxygen are two important factors for SRP release. At the end of the low-oxygen incubation, an SRP concentration of 56 µg L(-1) resulted in a sedimentary flux of 1.1 mg SRP m(-2) day(-1). This is ~10 times higher than the flux of 0.12 mg SRP m(-2) day(-1) obtained from depth integration of vertical SRP profiles measured in the lake, and ~100 times higher than the external flux of 0.014 mg SRP m(-2) d(-1) into the lake (based on catchment area). Field measurements indicated that oxidation of organic matter and mining-related chemicals (ammonium and thiosulphates) may result in increased internal SRP flux from the sediment. Increased P loading in the lake as a result of low-oxygen conditions could change water column total nitrogen/total phosphorus ratios from 27 to 17, consequently changing the lake from being P-limited to be co-limited by N and P. The obtained findings point to possible interaction between the cycles of nitrogen (oxygen consumption) and P (flux from sediment) that may be important for nutrient regulation in mine water recipients.

Modelling nitrogen transformations in waters receiving mine effluents.

This paper presents a biogeochemical model developed for a clarification pond receiving ammonium nitrogen rich discharge water from the Boliden concentration plant located in northern Sweden. Present knowledge about nitrogen (N) transformations in lakes is compiled in a dynamic model that calculates concentrations of the six N species (state variables) ammonium-N (N(am)), nitrate-N (N(ox)), dissolved organic N in water (N(org)), N in phytoplankton (N(pp)), in macrophytes (N(mp)) and in sediment (N(sed)). It also simulates the rate of 16 N transformation processes occurring in the water column and sediment as well as water-sediment and water-atmosphere interactions. The model was programmed in the software Powersim using 2008 data, whilst validation was performed using data from 2006 to 2007. The sensitivity analysis showed that the state variables are most sensitive to changes in the coefficients related to the temperature dependence of the transformation processes. A six-year simulation of N(am) showed stable behaviour over time. The calibrated model rendered coefficients of determination (R(2)) of 0.93, 0.79 and 0.86 for N(am), N(ox) and N(org), respectively. Performance measures quantitatively expressing the deviation between modelled and measured data resulted in values close to zero, indicating a stable model structure. The simulated denitrification rate was on average five times higher than the ammonia volatilisation rate and about three times higher than the permanent burial of N(sed) and, hence, the most important process for the permanent removal of N. The model can be used to simulate possible measures to reduce the nitrogen load and, after some modification and recalibration, it can be applied at other mine sites affected by N rich effluents.

Simultaneous measurements of As, Mo, Sb, V and W using a ferrihydrite diffusive gradients in thin films (DGT) device.

The ferrihydrite-backed DGT (diffusive gradients in thin films), recently developed for arsenic and phosphate measurements was, for the first time, characterized with respect to molybdate, antimonate, vanadate and tungstate determination. Arsenate was included in the characterization to allow comparison with literature data and thus provide quality control of the measurements. In addition to laboratory experiments, field measurements were carried out in a natural stream in northern Sweden affected by mine drainage. It was shown that ferrihydrite-DGT is suitable for simultaneous determination of labile arsenic, molybdate, antimonate, vanadate and tungstate over a wide pH range. Diffusion coefficients were estimated using two different methods; diffusion cell and direct uptake to DGT devices in synthetic solutions. Estimations of the coefficients using the direct uptake method were performed between pH 4 and 8. The results from the two methods agreed well irrespective of pH, except for molybdate and antimonate that showed decreased values at pH 8. Adsorption of the analytes to ferrihydrite gel-discs was rapid at all pH values. However, there was a tendency toward lower adsorption affinity for antimonate compared to the other anions. 100% recovery of accumulated analytes was achieved through complete dissolution of the ferrihydrite adsorbent using 1.4 molL(-1) HNO(3) with 0.1 molL(-1) HF. From field sampling it was concluded that the opportunities for accurate antimonate and molybdate determination decrease at pH≥8.7. DGT-labile concentrations were generally lower than dissolved concentrations. Relatively lower DGT concentrations, compared to dissolved (<0.45 µm), were observed under a period when ferric oxide precipitations were detected on the DGT protective filter.

Size and density distribution of sulfide-producing microniches in lake sediments.

The technique of diffusive gradients in thin films (DGT) with measurements by computer-imaging densitometry (CID) was used to study the in situ, two-dimensional distribution of sulfide-producing microniches in sediments from a eutrophic lake (Esthwaite Water, UK). The DGT-CID technique precipitates and immobilizes the net pore-water flux of dissolved sulfide as black Ag2S by reaction with a AgI binding gel. The mass of accumulated sulfide is then determined from a scanned grayscale image of this gel. DGT probes deployed in laboratory mesocosms of homogeneously mixed sediment, then analyzed at high spatial resolution (approximately 0.1 mm), showed that apparent niche areas (operationally defined by DGT-CID) were <1 mm2 for 30% of the niches. In eight DGT probes deployed in undisturbed sediment cores, the proportion of microniche-related sulfide flux was > or =1-8% of the total horizontal net pore-water flux of sulfide. This study suggests that microniches that introduce local redox gradients are common in sediments. As fluxes within these microenvironments can considerably exceed background values, consideration of the dynamics of the biogeochemical processes occurring at these sites is likely to be key to improving our understanding of early diagenesis. Measurement procedures and three-dimensional reaction-transport models should be designed with the aim of furthering understanding of the complexities associated with locally supplied particles of reactive organic matter.

Potential biogeochemical and ecological development of a flooded tailings impoundment at the Kristineberg Zn-Cu mine, northern Sweden.

The potential short-term (10(2) years) biogeochemical and ecological effects of diverting stream water (pH 4.9-6.7) into a limed, flooded tailings impoundment (pH 8-12) were studied by combining geochemical and biological data. In the long-term perspective, the successional development of lakes was used as a natural analogue. Based on the vertical distribution of temperature and total dissolved solids (TDS < 0.22 microm), the impoundment can be characterised as a continuous/discontinuous cold polymictic lake, with holomictic summer circulation. A re-inoculation study indicated that the growth of autotrophic, aerobic bacteria (presumably Acidithiobacillus ferrooxidans) presently is inhibited by the high pH in the impoundment. In a short-term perspective, termination of liming and diversion of stream water into the impoundment will result in a complex interplay between physical, biogeochemical and ecological effects. A reduced vertical mixing of the approximately 2-m-deep water column, dissolution of calcite and gypsum (compounds of a sludge formed in the impoundment) and an enhanced microbiological activity are major expected effects. The dissolution of calcite may act as a pH buffer and result in metal remobilisation from the sludge. Excluding autochthonous organic matter produced in the impoundment, streamwater input of suspended matter and formation of settling flocculants are expected to result in a sediment accumulation rate of approximately 1.5 mg cm(-2) year(-1) (1.6-3.3 cm/10(2) years). Settling allochthonous organic C (0.15-0.30 mg C cm(-2) year(-1)) may serve as an oxygen barrier and as a reservoir of organic compounds capable of driving redox reactions. In a long-term perspective, a hydroseral development into a wetland/peatland can be expected, with a bog lake, poor fen or flat bog as final stage. This development presupposes a decreasing pH when liming is terminated and stream water is diverted into the impoundment. It also assumes that the impoundment will be similar to an acidified lake, and that the succession is driven by Sphagnum colonizing the impoundment. If the hydrological conditions/water level is affected (e.g., by climatic changes or a dam failure), a terrestrialization culminating in coniferous forest on peat soil may occur.