Distribution and relationship of uranium and radium along an allochthonously dominated wetland gradient.

Uranium mining may pose a large threat for freshwater ecosystems, caused by elevated concentrations of metals/radionuclides in drainage water. Important pollutants of such waters are uranium (U) and radium (Ra), because of their impact due to both radio- as well as chemo-toxicity. Despite the comprehensive knowledge about specific element speciation as well as fixation processes, less is known about the retention of U and Ra at a higher level of complexity (within allochthonous ecosystems as predominant for low order streams). Consequently, we investigated the distribution and retention potential of allochthonous ecosystems regarding U and Ra as well as changing U/Ra ratios. We found U predominantly transported over long distances, whereas Ra mainly precipitates immediately after reaching the surface, i.e. in the spring area. Although high U accumulation in organic rich sediments is found, still high transport rates are detected. Low overall fixation of U within the allochthonously dominated wetland results in an U transport over long distances. Consequently, large areas are affected by U mining activities and its post-mining impact, with U being more relevant compared to Ra.

Thunderbolt in biogeochemistry: galvanic effects of lightning as another source for metal remobilization.

Iron and manganese are relevant constituents of the earth's crust and both show increasing mobility when reduced by free electrons. This reduction is known to be controlled by microbial dissimilation processes. Alternative sources of free electrons in nature are cloud-to-ground lightning events with thermal and galvanic effects. Where thermal effects of lightning events are well described, less is known about the impact of galvanic lightning effects on metal mobilization. Here we show that a significant mobilization of manganese occurs due to galvanic effects of both positive and negative lightning, where iron seems to be unaffected with manganese being abundant in oxic forms in soils/sediments. A mean of 0.025 mmol manganese (negative lightning) or 0.08 mmol manganese (positive lightning) mobilization may occur. We suggest that lightning possibly influences biogeochemical cycles of redox sensitive elements in continental parts of the tropics/subtropics on a regional/local scale.

High mobilization of arsenic, metals and rare earth elements in seepage waters driven by respiration of old allochthonous organic carbon.

Metal and metalloid mobilization processes within seepage water are of major concern in a range of water reservoir systems. The mobilization process of arsenic and heavy metals within a dam and sediments of a drinking water reservoir was investigated. Principle component analysis (PCA) on time series data of seepage water showed a clear positive correlation of arsenic with iron and DOC (dissolved organic carbon), and a negative correlation with nitrate due to respiratory processes. A relationship of reductive metal and metalloid mobilization with respiration of old carbon was shown. The system is influenced by sediment layers as well as a recent DOC input from degraded ombrotrophic peatbogs in the catchment area. The isotopic composition ((12)C, (13)C and (14)C) of DOC is altered along the path from basin to seepage water, but no significant changes in structural parameters (LC-OCD-OND, FT-IR) could be seen. DIC (dissolved inorganic carbon) in seepage water partly originates from respiratory processes, and a higher relationship of it with sediment carbon than with the DOC inventory of infiltrating water was found. This study revealed the interaction of respiratory processes with metal and metalloid mobilization in sediment water flows. In contrast to the presumption that emerging DOC via respiratory processes mainly controls arsenic and metal mobilization it could be shown that the presence of aged carbon compounds is essential. The findings emphasize the importance of aged organic carbon for DOC, DIC, arsenic and metal turnover.

Changes in catchment conditions lead to enhanced remobilization of arsenic in a water reservoir.

Increasing arsenic concentrations in freshwater ecosystems is of global concern. Processes affecting arsenic fluxes in catchments are known. These processes are in turn controlled by the underlying geology and air pollution history. In contrast to the knowledge on catchment processes less is known about the hydrochemical processes controlling the fixation/remobilization of arsenic within lakes and artificial reservoirs. Consequently, we examined a reservoir system in the Ore Mts. (Germany) regarding its sink and source potentials affecting arsenic fluxes. This area was faced with heavy deposition inputs from coal burning based acid rain until the beginning of the 1990s. Hereafter concentrations of sulfate and nitrate in runoff waters decreased, whereas dissolved organic carbon (DOC) concentrations are still increasing. Along with this, arsenic concentrations in the water discharge from the catchments increase. Our results reveal that the sediments of the investigated reservoir system contain high inventories of arsenic in association with ferric and organic phases. A nitrate deficit dependent arsenic release is suggested. It is indicated that arsenic release from the reservoir sediments may be controlled by water nitrate concentration, which in turn is dependent on the nitrate concentration in the runoff water from the catchment.

Effects of gamma-sterilization on DOC, uranium and arsenic remobilization from organic and microbial rich stream sediments.

Organic-rich sediments are known to be effective accumulators for uranium and arsenic. Much is known about the capacity for metal or metalloid fixation by microbes and organic compounds as well as inorganic sediment particles. Experiments investigating the effect of microbes on the process of metal fixation in sediments require sterilized sediments as control treatment which is often realized by gamma-sterilization. Only few studies show that gamma-sterilization has an effect on the remobilization of metal and metalloids and on their physico-chemical properties. These studies deal with sediments with negligible organic content whereas almost nothing is known about organic-rich sediments including a probably high microbial activity. In view of this, we investigated the effect of gamma-sterilization of organic-rich sediments on uranium and arsenic fixation and release. After ten days within an exposure experiment we found a significant higher remobilization of uranium and arsenic in sterile compared to unsterile treatments. In line with these findings the content of dissolved organic carbon (DOC), manganese, and iron increased to even significantly higher concentration in the sterile compared to unsterile treatment. Gamma-sterilization seems to change the physico-chemical properties of organic-rich sediments. Microbial activity is effectively eliminated. From increased DOC concentrations in overlaying water it is concluded that microbes are eventually killed with leaching of cellular compounds in the overlaying water. This decreases the adsorption capacity of the sediment and leads to enhanced uranium and arsenic remobilization.

Invertebrates control metals and arsenic sequestration as ecosystem engineers.

Organic sediments are known to be a significant sink of inorganic elements in polluted freshwater ecosystems. Hence, we investigated the role of invertebrate shredders (the freshwater shrimp Gammarus pulex L.) in metal and arsenic enrichment into organic partitions of sediments in a wetland stream at former uranium mining site. Metal and metalloid content in leaf litter increased significantly during decomposition, while at the same time the carbon content decreased. During decomposition, G. pulex as a ecosystem engineer facilitated significantly the enrichment of magnesium (250%), manganese (560%), cobalt (310%), copper (200%), zinc (43%), arsenic (670%), cadmium (100%) and lead (1340%) into small particle sizes. The enrichments occur under very high concentrations of dissolved organic carbon. Small particles have high surface area that results in high biofilm development. Further, the highest amounts of elements were observed in biofilms. Therefore, invertebrate shredder like G. pulex can enhance retention of large amounts of metal and arsenic in wetlands.

Enrichment of uranium in particulate matter during litter decomposition affected by Gammarus pulex L.

Plant litter and organic matter of aquatic sediments provide a significant sink of soluble inorganic uranium species in contaminated ecosystems. The uranium content in detritus has been observed to increase significantly during decomposition. However, the influence of the decomposer community on uranium fixation remains unclear. In view of this, we investigated the influence of a shredder (the freshwater shrimp Gammarus pulex L) on uranium fixation and mobilization during the degradation of plant litter. Leaf litter from Alnus glutinosa (L.) Gaertn. with 1152 mg kg(-1) U of dry biomass (DM) and without uranium was used in a 14-day laboratory experiment. The uranium concentration in the particulate organic material (POM) at the end of experiment was 1427 mg kg(-1) DM. After 14 days of decay, the residues of the leaves show a uranium concentration of 644 mg kg(-1) DM. Uranium concentrations in the media initially increased reaching up to 63.9 microg L(-1) but finally decreased to an average value of 34.3 microg L(-1). Atthe same time, DOC levels increased from 2.43 mg L(-1) up to 11.4 mg L(-1) in the course of the experiment Hence, inorganic uranium fixation onto particulate organic matter was enhanced by the activity of G. pulex.