Basin scale sources of siltation in a contaminated hydropower reservoir.

Siltation and the loss of hydropower reservoir capacity is a global challenge with a predicted 26 % loss of storage at the global scale by 2050. Like in many other Latin American contexts, soil erosion constitutes one of the most significant water pollution problems in Chile with serious siltation consequences downstream. Identifying the sources and drivers affecting hydropower siltation and water pollution is a critical need to inform adaptation and mitigation strategies especially in the context of changing climate regimes e.g. rainfall patterns. We investigated, at basin scale, the main sources of sediments delivered to one of the largest hydropower reservoirs in South America using a spatio-temporal geochemical fingerprinting approach. Mining activities contributed equivalent to 9 % of total recent sediment deposited in the hydropower lake with notable concentrations of sediment-associated pollutants e.g. Cu and Mo in bed sediment between the mine tributary and the reservoir sediment column. Agricultural sources represented ca. 60 % of sediment input wherein livestock production and agriculture promoted the input of phosphorus to the lake. Evaluation of the lake sediment column against the tributary network showed that the tributary associated with both dominant anthropogenic activities (mining and agriculture) contributed substantially more sediment, but sources varied through time: mining activities have reduced in proportional contribution since dam construction and proportional inputs from agriculture have increased in recent years, mainly promoted by recent conversion of steep lands from native vegetation to agriculture. Siltation of major hydropower basins presents a global challenge exemplified by the Rapel basin. The specific challenges faced here highlight the urgent need for co-design of evidence-led, context-specific solutions that address the interplay of drivers both within and without the basin and its communities, enhancing the social acceptability of sediment management strategies to support the sustainability of clean, hydropower energy production.

Distribution and storage of uranium, and its decay products, in floodplain sediments.

Industrialised rivers contain legacy contaminants stored in their sediments and floodplain soils which may inhibit attainment of environmental quality criteria. The River Fal catchment, SW England, is impacted by inputs from uranium mining and clay production and serves as an exemplar for understanding the consequences of medium-term process dynamics in contaminated basins. Radionuclides were determined, by gamma spectroscopy, in six cores from the river floodplain with the aim of quantifying the activities of 238U, and its decay products, and the bomb fallout radionuclides137Cs and 241Am. Activity concentrations of 238U implied inputs from mining, accentuated by flood events and historic industrial accidents, whereas 210Pb activities included a significant input of unsupported 210Pb linked to processed mine spoil. The radionuclide inventories did not decrease systematically downstream revealing evidence of attenuation of particulate radionuclides within the river floodplain sediment column. Storage of legacy contaminants in fluvial systems, at levels in excess of contemporary environmental quality guidelines, emphasises the challenges posed by changing climatic conditions. This scenario raises significant consequences for the management of uranium-contaminated, fertile riverine floodplains within Europe.

Legacy radionuclides in cryoconite and proglacial sediment on Orwell Glacier, Signy Island, Antarctica.

Cryoconite is a specific type of material found on the surface of glaciers and icesheets. Samples of cryoconite were collected from the Orwell Glacier and its moraines, together with suspended sediment from the proglacial stream on Signy Island, part of the South Orkney Islands, Antarctica. The activity concentrations of certain fallout radionuclides were determined in the cryoconite, moraine and suspended sediment, in addition to particle size composition and %C and %N. For cryoconite samples (n = 5), mean activity concentrations (±1SD) of 137Cs, 210Pbun and 241Am were 13.2 ± 20.9, 66.1 ± 94.0 and 0.32 ± 0.64 Bq kg-1, respectively. Equivalent values for the moraine samples (n = 7) were 2.56 ± 2.75, 14.78 ± 12.44 and <1.0 Bq kg-1, respectively. For the composite suspended sediment sample, collected over 3 weeks in the ablation season, the values (± counting uncertainty) for 137Cs, 210Pbun and 241Am were 2.64 ± 0.88, 49.2 ± 11.9 and <1.0 Bq kg-1, respectively. Thus, fallout radionuclide activity concentrations were elevated in cryoconite relative to moraine and suspended sediment. In the case of 40K, the highest value was for the suspended sediment (1423 ± 166 Bq kg-1). The fallout radionuclides in cryoconite were 1-2 orders of magnitude greater than values in soils collected from other locations in Antarctica. This work further demonstrates that cryoconite likely scavenges fallout radionuclides (dissolved and particulate) in glacial meltwater. In the case of 40K, the greater value in suspended sediment implies a subglacial source. These results are amongst the relatively few that demonstrate the presence of fallout radionuclides in cryoconites at remote locations in the Southern Hemisphere. This work adds to the growing contention that elevated activities of fallout radionuclides, and other contaminants, in cryoconites are a global phenomenon and may be a risk to downstream terrestrial and aquatic ecosystems.

Composition of deposited sediment and its temporal variation in a disturbed tropical catchment in the Kelantan river basin, Peninsular Malaysia.

Pristine tropical river systems are coming under increasing pressure from the development of economic resources such as forestry and mining for valuable elements. The Lebir catchment, north eastern Malaysia, is now under development as a result of unregulated tree felling and mining for essential and rare metals. Two sediment cores, one in the upstream reaches and the other from the downstream reaches, were taken from flood prone area of the Lebir River, Malaysia, and analysed for their elemental composition by XRF, specifically Al, Si, Fe, Ca, K, Mg, Mn, V, Cu, Ni, Pb, Cr, Zn, As, Th and U. Activities of fallout radionuclides, 137Cs and 210Pb were also determined to from a geochronological context. The elemental concentrations in the soils were assessed in terms of their enrichment factor and Si, Ca, K, Mg, Mn, V, Cu, Ni and Zn were found not to be enriched, whereas As, Th and U had elevated enrichment factors. The Th and U were particularly enriched in the downstream core indicating inputs from a tributary that drains a catchment with known deposits of Th and possibly U. The results suggest that the growth in economic development is fostering the transport of contaminants by the major rivers which, in turn, is contaminating the riverine floodplains. This points to the need for a more integrated and holistic approach to river basin management to maintain the environmental quality of these fragile aquatic systems.

Extreme levels of fallout radionuclides and other contaminants in glacial sediment (cryoconite) and implications for downstream aquatic ecosystems.

Glaciers in most parts of the world are retreating, releasing water and sediments to downstream rivers. Studies have found elevated levels of fallout radionuclides (FRNs) and other contaminants in glacial sediments, especially cryoconite, in European glaciers and Greenland. However, there are no equivalent studies for glaciers in North America. We report concentrations of FRNs (i.e. 137Cs, 210Pbun and 241Am) and other contaminants (i.e. metal(loids), phosphorus) in cryoconite and proglacial sediments from a glacier in British Columbia, Canada, and compare values to suspended sediments from the downstream river. The mean concentrations of 137Cs, 210Pbun and 241Am in cryoconite were 2,123 ± 74, 7,535 ± 224 and 11.5 ± 3.0 Bq kg-1, respectively, which are an order of magnitude greater than those for most soils and surficial materials. FRNs were much lower in suspended sediments and decreased with distance away from the glacier. Geochemical elements were enriched in cryoconite relative to local clastic materials and upper continental crust. Concentrations of FRNs in cryoconite were correlated with organic matter, which suggests this is important in controlling the scavenging of hydrophobic contaminants in glacial meltwater. Low concentrations of FRNs and contaminants in suspended sediments suggest that glacial meltwater and the delivery of cryoconite have limited impact on downstream aquatic ecosystems.

Are low doses of tritium genotoxic to Mytilus edulis?

The genotoxic effects of tritium (3H) in the adult life stage of Mytilus edulis have been evaluated by the induction of micronuclei (MN) and DNA single strand breaks/alkali labile sites (Comet assay) in the haemocytes of exposed individuals. Assays were optimised and validated using ethylmethane sulfonate (EMS) as a reference genotoxic agent over different exposure periods. M. edulis were exposed, for 96 h, to a range of concentrations of 3H equivalent to a dose range of 12-485 microGy h(-1). Results revealed a dose-dependent increase for both the MN and Comet assays, and for both EMS and 3H. Since less than 500 microGy h(-1) 3H is capable of inducing genetic damage, generic doses recommended by the IAEA for the protection of aquatic biota may be overestimated for some organisms.

Impact of low doses of tritium on the marine mussel, Mytilus edulis: genotoxic effects and tissue-specific bioconcentration.

Despite growing scientific, public and regulatory concern over the discharge of radioactive substances, no serious attempts have been made to develop a rationale to evaluate the impact of environmentally relevant radionuclides in the aquatic environment. In this study, we have evaluated the genotoxic effects and tissue-specific concentration of tritium (added as tritiated water, HTO) in the adult life stage of the edible mussel, Mytilus edulis. The genotoxic effects were quantified in terms of the induction of: (a) micronuclei (MN), and (b) DNA single-strand breaks/alkali-labile sites using alkaline single-cell gel electrophoresis (Comet assay) in the haemocytes of exposed animals. The assays were optimised and validated using a range of concentrations (18-56 mgl(-1)) of ethylmethane sulfonate (EMS), a direct-acting reference genotoxic agent, over different exposure periods. Mussels were exposed to a series of concentrations of HTO equivalent to a dose range from 12 to 485 muGyh(-1) for 96 h, and different tissues and organs were then extracted and analysed. The study revealed a dose-dependent increase in the response for both the MN test and the Comet assay and for both EMS and HTO. In addition, HTO delivering dose rates below 500 muGyh(-1) was shown to be capable of inducing genetic damage in the haemocytes of these bivalves. The study also showed that inorganic tritium accumulated differentially in mussel tissues in a dose-dependent manner, with the gut accumulating the highest amount of radioactivity, followed by the gill, mantle, muscle, foot and byssus thread. The faeces and pseudo-faeces accumulated least radioactivity over the exposure period. Differential accumulation of radionuclides has significant implications for biomonitoring programmes, for this and other aquatic organisms. The study also suggests that the generic dose limits recommended by the International Atomic Energy Agency for the protection of aquatic biota might not be applicable to all aquatic organisms.

Extra- and intra-cellular accumulation of platinum group elements by the marine microalga, Chlorella stigmatophora.

To better understand the marine biogeochemistry of the platinum group elements (PGE), Rh(III), Pd(II) and Pt(IV) were added in combination and at ppb concentrations to cultures of the marine microalga, Chlorella stigmatophora, maintained in sea water at 15 °C and under 60 µmol m(-2) s(-1) PAR. The accumulation of PGE was established in short-term (24-h) exposures, and under varying conditions of algal biomass and PGE concentration, and in a longer-term exposure (156-h) by ICP-MS analysis of sea water and nitric acid digests and EDTA washes of the alga. In short-term exposures, and under all conditions, the extent of accumulation by C. stigmatophora was in the order: Rh > Pd >> Pt; and Pd was internalised (or resistant to EDTA extraction) to a considerably greater extent than Rh and Pt. Accumulation isotherms were quasi-linear up to added PGE concentrations of 30 µg L(-1) and all metals displayed a significant reduction in accumulation on a weight-normalised basis with increasing density (biomass) of C. stigmatophora, an effect attributed to the production of exudates able to stabilise metals in sea water through complexation. In the longer-term exposure, kinetic constraints on the reactivities of Rh and, in particular, Pt, resulted in final degrees of accumulation and internalisation by C. stigmatophora that were greatest for Rh and similar between Pd and Pt. Among the PGE, therefore, Rh is predicted to participate in biological removal and transport processes in the marine environment to the greatest extent while decoupling in the biogeochemistries of Pd and Pt is predicted in shorter-term or more transient processes.

Tissue-specific assimilation, depuration and toxicity of nickel in Mytilus edulis.

The tissue-specific accumulation and time-dependent depuration of radioactive (63)Ni by the byssus, gut, foot, gills, kidney, adductor muscle and faeces of Mytilus edulis has been investigated using a pulse-chase technique. The rate and extent of depuration of (63)Ni varied between tissues and, after 168 h, the concentration factors and assimilation efficiencies ranged from 1 to 35 L kg(-1) and 5%-13%, respectively. Mussels were also exposed to a range of environmentally-realistic concentrations of dissolved Ni, prior to the analysis of biological endpoints. The clearance rate was concentration-dependent and at the highest concentration decreased by 30%. Neutral red retention (NRR) assays indicated a cytotoxic response and DNA strand breaks were observed in the haemocytes. The association of DNA damage with that of physiological and cytotoxic effects suggests that Ni exerts a significant impact on Mytilus edulis at cellular and genetic levels.

Tissue-specific incorporation and genotoxicity of different forms of tritium in the marine mussel, Mytilus edulis.

Marine mussels (Mytilus edulis) were exposed to seawater spiked with tritiated water (HTO) at a dose rate of 122 and 79 µGy h(-1) for 7 and 14 days, respectively, and tritiated glycine (T-Gly) at a dose rate of 4.9 µGy h(-1) over 7 days. This was followed by depuration in clean seawater for 21 days. Tissues (foot, gills, digestive gland, mantle, adductor muscle and byssus) and DNA extracts from tissues were analysed for their tritium activity concentrations. All tissues demonstrated bio-accumulation of tritium from HTO and T-Gly. Tritium from T-Gly showed increased incorporation into DNA compared to HTO. About 90% of the initial activity from HTO was depurated within one day, whereas T-Gly was depurated relatively slowly, indicating that tritium may be bound with different affinities in tissues. Both forms of tritium caused a significant induction of micronuclei in the haemocytes of mussels. Our findings identify significant differential impacts on Mytilus edulis of the two chemical forms of tritium and emphasise the need for a separate classification and control of releases of tritiated compounds, to adequately protect the marine ecosystem.

Distribution of tritium in estuarine waters: the role of organic matter.

Tritium is an important environmental radionuclide whose reactivity with ligands and solids in aquatic systems is assumed to be limited. We studied the fractionation and sorption of tritium (added as tritiated water) in river water and seawater, and found that its distribution appears to be influenced by its affinity for organic matter. Tritium rapidly equilibrates with dissolved organic ligands that are retained by a reverse-phase C18 column, and with suspended sediment particles. Significantly, a measurable fraction of sorbed tritium associates with proteinaceous material that is potentially available to sediment-feeding organisms. These characteristics have not been reported previously and cannot be accounted for solely by isotopic exchange with hydrogen. Nevertheless, they are in qualitative agreement with available measurements of tritium in estuarine and coastal waters where its principal discharge is as tritiated water. Further research into the estuarine biogeochemical behaviour of tritium is required and radiological distribution coefficients and concentration factors that are assumed for this radionuclide may require reconsideration.

Behaviour of palladium(II), platinum(IV), and rhodium(III) in artificial and natural waters: influence of reactor surface and geochemistry on metal recovery.

The recovery of dissolved platinum group elements (PGE: Pd(II), Pt(IV) and Rh(III)) added to Milli-Q water, artificial freshwater and seawater and filtered natural waters has been studied, as a function of pH and PGE concentration, in containers of varying synthetic composition. The least adsorptive and/or precipitative loss was obtained for borosilicate glass under most of the conditions employed, whereas the greatest loss was obtained for low-density polyethylene. Of the polymeric materials tested, the adsorptive and/or precipitative loss of PGE was lowest for fluorinated ethylene propylene (Teflon). The loss of Pd(II) in freshwater was significant due to its affinity for surface adsorption and its relatively low solubility. The presence of natural dissolved organic matter increases the recovery of Pd(II) but enhances the loss of Pt(IV). The loss of Rh(III) in seawater was significant and was mainly due to precipitation, whereas Pd(II) recovery was enhanced, compared to freshwater, because of its complexation with chloride. The results have important implications regarding protocols employed for sample preservation and controlled laboratory experiments used in the study of the speciation and biogeochemical behaviour of PGE.

Adsorption kinetics of platinum group elements in river water.

The uptake of platinum group elements (PGE) by different preparations of estuarine sediment suspended in filtered river water has been examined. For a given PGE, adsorption time courses to untreated sediment and to sediment whose hydrous metal oxides or organic matter had been removed by appropriate chemical treatments were similar. Adsorption of Rh(lll) and Pt(IV) proceeded via a first-order reversible reaction. For Rh, forward rate constants were 1 order of magnitude greater than reverse rate constants, but for Pt, forward and reverse constants were comparable. Respective system response times, required to attain 63% of the new equilibrium, ranged from about 10 to 30 h and 2 to 20 h. In contrast, rapid, initial uptake of Pd(ll) was succeeded, in most instances, by a protracted period of desorption, requiring a more complex mechanistic interpretation. In all cases, adsorption was reduced following a period of PGE equilibration with filtered river water, suggesting that complexation with natural organic ligands exerts a significant control on the adsorption process by, for example, stabilizing PGE in solution. Exchangeability of adsorbed PGE, evaluated by ammonium acetate extraction, decreased in the order Pd > Pt > Rh, in qualitative agreement with the proposed or modeled adsorption mechanisms. Experimental results, together with independent assessments of PGE mobility from secondary sources (e.g. road dust), indicate that Pd has the greatest potential for long-range transport and bioaccumulation in the aquatic environment.