Global variability and controls on the accumulation of fallout radionuclides in cryoconite.

The accumulation of fallout radionuclides (FRNs) from nuclear weapons testing and nuclear accidents has been evaluated for over half a century in natural environments; however, until recently their distribution and abundance within glaciers have been poorly understood. Following a series of individual studies of FRNs, specifically 137Cs, 241Am and 210Pb, deposited on the surface of glaciers, we now understand that cryoconite, a material commonly found in the supraglacial environment, is a highly efficient accumulator of FRNs, both artificial and natural. However, the variability of FRN activity concentrations in cryoconite across the global cryosphere has never been assessed. This study thus aims to both synthesize current knowledge on FRNs in cryoconite and assess the controls on variability of activity concentrations. We present a global database of new and previously published data based on gamma spectrometry of cryoconite and proglacial sediments, and assess the extent to which a suite of environmental and physical factors can explain spatial variability in FRN activity concentrations in cryoconite. We show that FRNs are not only found in cryoconite on glaciers within close proximity to specific sources of radioactivity, but across the global cryosphere, and at activity concentrations up to three orders of magnitude higher than those found in soils and sediments in the surrounding environment. We also show that the organic content of cryoconite exerts a strong control on accumulation of FRNs, and that activity concentrations in cryoconite are some of the highest ever described in environmental matrices outside of nuclear exclusion zones, occasionally in excess of 10,000 Bq kg-1. These findings highlight a need for significant improvements in the understanding of the fate of legacy contaminants within glaciated catchments. Future interdisciplinary research is required on the mechanisms governing their accumulation, storage, and mobility, and their potential to create time-dependent impacts on downstream water quality and ecosystem sustainability.

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter.

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.

Land Ocean Interaction: processes, functioning and environmental management: a UK perspective.

The hydrochemical and physical functioning of UK river basins, estuaries and coastal waters through to the open sea are outlined in relation to British environmental research over the last ten or more years. An overview of a considerable body of published work is presented in the context of current findings and future research challenges. This is linked to this special issue of Science of the Total Environment 'Land Ocean Interaction: processes, functioning and environmental management: a UK perspective' for which this contribution provides a conclusion.

Land-ocean interaction: processes, functioning and environmental management from a UK perspective: an introduction.

This paper provides a foreword to a special edition of Science of the Total Environment concerned with land-ocean interaction from a UK perspective as linked to processes, functioning and environmental management. The volume structure is presented together with an outline of the nature of the individual papers. The areas covered are: (1) freshwater chemistry, (2) riverine sedimentology, (3) tidal river, estuarine and coastal chemistry, (4) estuarine and coastal sediments and (5) shelf-sea-ocean linkages. The foreword provides as an introductory link to the broader perspectives of contemporary UK research in this area, which comes in a conclusions paper at the end of the volume.

Fractionation and reactivity of platinum group elements during estuarine mixing.

The fractionation of platinum group elements (PGE) rhodium(III), palladium(II), and platinum(IV), has been studied after their addition in aqueous form to unfiltered river water samples (Tugela river, South Africa) and to mixtures of river water and seawater. The particulate fraction of PGE averaged about 70 (Rh), 50 (Pd), and 25% (Pt) of total metal and was dependent on both particle concentration and salinity. The aqueous (<0.45 microm) pool of PGE was dominated by entities of less than 0.1 microm in diameter, and for Pd and Rh hydrophobic complexes of metal, operationally defined by their retention on a C-18 column, were significant. Distribution coefficients, based on the w/w concentration of metal on particles relative to the corresponding concentration in the aqueous pool, either increased (Rh and Pd) or declined (Pt) with increasing salinity. These observations are interpreted in terms of a number of general and metal-specific mechanisms. Thus, the behavior of Pd appears to be controlled by its association with relatively small (<0.1 microm) dissolved organic ligands, a significant fraction of which is hydrophobic and is subject to salting out upon estuarine mixing. Rhodium may also be partly subject to this mechanism of removal, but kinetic considerations and results of X-ray analysis of filter-retentates suggest that adsorption of cationic hydroxychlorides and the destabilization and precipitation of hydroxy-complexes induced by the rise in pH across the estuarine gradient are more important. Unlike Pd, the binding of Pt by organic ligands is kinetically hindered. Thus, in contrast to Pd, particle-water reactivity of Pt is controlled by electrostatic interactions between the particle surface and inorganic aqueous species. The results of this study improve our understanding of and ability to predict the transport and fate of PGE in estuaries where these metals are mobilized or discharged.

Visualisation of natural aquatic colloids and particles -- a comparison of conventional high vacuum and environmental scanning electron microscopy.

The applicability of environmental scanning electron microscopy (ESEM; imaging of hydrated samples) and conventional high vacuum scanning electron microscopy (SEM; imaging of dried samples at high vacuum) for the observation of natural aquatic colloids and particles was explored and compared. Specific attention was given to the advantages and limitations of these two techniques when used to assess the sizes and morphologies of complex and heterogeneous environmental systems. The observation of specimens using SEM involved drying and coating, whereas ESEM permitted their examination in hydrated form without prior sample preparation or conductive coating. The two techniques provided significantly different micrographs of the same sample. SEM provided sharper images, lower resolution limits (10 nm or lower), but more densely packed particles, suggesting aggregation, and different morphological features than ESEM, suggesting artefacts due to drying. ESEM produced less easily visualised materials, more complex interpretation, slightly higher resolution limits (30-50 nm), but these limitations were more than compensated for by the fact that ESEM samples retained, at least to some extent, their morphological integrity. The results in this paper show that SEM and ESEM should be regarded as complementary techniques for the study of aquatic colloids and particles and that ESEM should be more widely applied to aquatic environmental systems than hitherto.