Scott J Markich — Page 2

PubMed2002

Uranium speciation and bioavailability in aquatic systems: an overview.

The speciation of uranium (U) in relation to its bioavailability is reviewed for surface waters (fresh- and seawater) and their sediments. A summary of available analytical and modeling techniques for determining U speciation is also presented. U(VI) is the major form of U in oxic surface waters, while U(IV) is the major form in anoxic waters. The bioavailability of U (i.e., its ability to bind to or traverse the cell surface of an organism) is dependent on its speciation, or physicochemical form. U occurs in surface waters in a variety of physicochemical forms, including the free metal ion (U4+ or UO2(2+)) and complexes with inorganic ligands (e.g., uranyl carbonate or uranyl phosphate), and humic substances (HS) (e.g., uranyl fulvate) in dissolved, colloidal, and/or particulate forms. Although the relationship between U speciation and bioavailability is complex, there is reasonable evidence to indicate that UO2(2+) and UO2OH+ are the major forms of U(VI) available to organisms, rather than U in strong complexes (e.g., uranyl fulvate) or adsorbed to colloidal and/or particulate matter. U(VI) complexes with inorganic ligands (e.g., carbonate or phosphate) and HS apparently reduce the bioavailability of U by reducing the activity of UO2(2+) and UO2OH+. The majority of studies have used the results from thermodynamic speciation modeling to support these conclusions. Time-resolved laser-induced fluorescence spectroscopy is the only analytical technique able to directly determine specific U species, but is limited in use to freshwaters of low pH and ionic strength. Nearly all of the available information relating the speciation of U to its bioavailability has been derived using simple, chemically defined experimental freshwaters, rather than natural waters. No data are available for estuarine or seawater. Furthermore, there are no available data on the relationship between U speciation and bioavailability in sediments. An understanding of this relationship has been hindered due to the lack of direct quantitative U speciation techniques for particulate phases. More robust analytical techniques for determining the speciation of U in natural surface waters are needed before the relationship between U speciation and bioavailability can be clarified.

Animals↗

PubMed2002

Freshwater bivalve shells as archival indicators of metal pollution from a copper-uranium mine in tropical northern Australia.

Freshwater bivalves (Velesunio angasi) were sampled in 1996 from the Finniss River in tropical northern Australia at 10 sites a priori exposed and nonexposed to acid rock drainage (ARD), containing elevated metal concentrations, from the rehabilitated Rum Jungle copper-uranium mine. Secondary ion mass spectrometry (SIMS) was used to measure Cu, Mn, Zn, U, Ni, Co, Pb, and Fe/Ca ratios across the annual shell laminations of the longest-lived bivalves found at each site, with the aim of evaluating the ability of the shells to archive measured annual metal inputs and their temporal patterns. At sites not contaminated by ARD, relatively constant and similar (baseline) SIMS signals were found for all metals in the shell laminations of V. angasi, dating as far back as 1965. At sites contaminated by ARD, relatively constant, but variably elevated, SIMS signals were evident for Cu, Mn, Zn, Ni, and Co in the shell, which extended back to the end of rehabilitation (1986) only. Since rehabilitation, the temporal patterns of Cu, Zn, and Mn observed in the shells at the most contaminated sites reflected those of the measured annual dissolved loads in the surface waters. The average concentrations of Cu, Mn, Zn, Ni, and Co in the shells decreased (3-13-fold) with increasing distance downstream of the mine site, until concentrations characteristic of the noncontaminated sites were reached. This geographic pattern of decline in pollution signal in the shell with increasing distance downstream of the pollution input is consistent with the pattern established for water and sediment chemistry. Overall, the SIMS results support the proposition that the shells of V. angasi can be used as archival indicators of metal pollution in surface waters of the Finniss River over their lifetime.

Animals↗