A critical examination of the possible application of zinc stable isotope ratios in bivalve mollusks and suspended particulate matter to trace zinc pollution in a tropical estuary.

The application of zinc (Zn) isotopes in bivalve tissues to identify zinc sources in estuaries was critically assessed. We determined the zinc isotope composition of mollusks (Crassostrea brasiliana and Perna perna) and suspended particulate matter (SPM) in a tropical estuary (Sepetiba Bay, Brazil) historically impacted by metallurgical activities. The zinc isotope systematics of the SPM was in line with mixing of zinc derived from fluvial material and from metallurgical activities. In contrast, source mixing alone cannot account for the isotope ratios observed in the bivalves, which are significantly lighter in the contaminated metallurgical zone (δ66ZnJMC = +0.49 ± 0.06‰, 2σ, n = 3) compared to sampling locations outside (δ66ZnJMC = +0.83 ± 0.10‰, 2σ, n = 22). This observation suggests that additional factors such as speciation, bioavailability and bioaccumulation pathways (via solution or particulate matter) influence the zinc isotope composition of bivalves.

Effects of different water storage procedures on the dissolved Fe concentration and isotopic composition of chemically contrasted waters from the Amazon River Basin.

RATIONALE: Although recent studies have investigated the Fe isotopic composition of dissolved, colloidal and particulate phases from continental and oceanic natural waters, few efforts have been made to evaluate whether water sample storage and the separation of different pore-size fractions through filtration can cause any change to the Fe isotopic compositions. The present study investigates the possible biases introduced by different water storage conditions on the dissolved Fe concentration and isotopic composition of chemically different waters. METHODS: Water samples were collected from an organic-rich river and from mineral particulate-rich rivers. Filtered and unfiltered water samples were stored either at room temperature or frozen at -18°C in order to assess possible biases due to (i) different water storage temperature, and (ii) storage of bulk (unfiltered) vs filtered water. Iron isotope measurements were performed by Multicollector Inductively Coupled Plasma Mass Spectrometry with a Thermo Electron Neptune instrument, after Fe purification using anion-exchange resins. RESULTS: Our data reveal that bulk water storage at room temperature without filtration produces minor changes in the dissolved Fe isotopic composition of mineral particulate-rich waters, but significant isotopic composition changes in organic-rich waters. In both cases, however, the impact of the different procedures on the Fe concentrations was strong. On the other hand, the bulk water stored frozen without filtration produced more limited changes in the dissolved Fe concentrations, and also on isotopic compositions, relative to the samples filtered in the field. The largest effect was again observed for the organic-rich waters. CONCLUSIONS: These findings suggest that a time lag between water collection and filtration may cause isotopic exchanges between the dissolved and particulate Fe fractions. When it is not possible to filter the samples in the field immediately after collection, the less detrimental approach is to freeze the bulk water sample until filtration, to reduce isotopic artifacts.

Rapid neodymium release to marine waters from lithogenic sediments in the Amazon estuary.

Rare earth element (REE) concentrations and neodymium isotopic composition (ɛNd) are tracers for ocean circulation and biogeochemistry. Although models suggest that REE release from lithogenic sediment in river discharge may dominate all other REE inputs to the oceans, the occurrence, mechanisms and magnitude of such a source are still debated. Here we present the first simultaneous observations of dissolved (<0.45 µm), colloidal and particulate REE and ɛNd in the Amazon estuary. A sharp drop in dissolved REE in the low-salinity zone is driven by coagulation of colloidal matter. At mid-salinities, total dissolved REE levels slightly increase, while ɛNd values are shifted from the dissolved Nd river endmember (-8.9) to values typical of river suspended matter (-10.6). Combining a Nd isotope mass balance with apparent radium isotope ages of estuarine waters suggests a rapid (3 weeks) and globally significant Nd release by dissolution of lithogenic suspended sediments.

The influence of the Amazonian floodplain ecosystems on the trace element dynamics of the Amazon River mainstem (Brazil).

The purpose of this paper is to forecast the role of riverine wetlands in the transfer of trace elements. One of the largest riverine wetlands in the world is the floodplain (várzea) of the Amazon River and its tributaries (Junk and Piedade, 1997). The central Amazon wetlands are constituted by a complex network of lakes and floodplains, named várzeas, that extend over more than 300,000 km2 (Junk, W.J., The Amazon floodplain--a sink or source for organic carbon? In Transport of Carbon and Minerals in Major World Rivers, edited by E.T. Degens, S. Kempe, R. Herrera, SCOPE/UNEP; 267-283, 1985.) and are among the most productive ecosystems in the world due to the regular enrichment in nutrients by river waters In order to understand if the adjacent floodplain of Amazon River have a significant influence on the trace element concentrations and fluxes of the mainstem, the concentrations of selected elements (i.e., Al, Mn, Fe, Co, Cu, Mo, Rb, Sr, Ba, and U) have been measured in the Amazon River water (Manacapuru Station, Amazonas State, Brazil) and in lake waters and plants (leaves) from a várzea(Ilha de Marchantaria, Amazonas State, Brazil) during different periods of the hydrological cycle. Four plant species (two perennial species: Pseudobombax munguba and Salix humboldtiana, and two annual herbaceous plants: Echinochloa polystachya and Eichhornia crassipes) were selected to represent the ecological functioning of the site. Time series obtained for dissolved Mn and Cu (<0.20 microm) in Amazon River water could not be explained by tributary mixing or instream processes only. Therefore, the contribution of the waters transiting the floodplains should be considered. These results suggest that the chemical composition of the waters draining these floodplains is controlled by reactions occurring at sediment-water and plant-water interfaces. Trace elements concentrations in the plants (leaves) vary strongly with hydrological seasonality. Based on the concentration data and the biological productivity of floodplain ecosystems, a first order approximation of trace element storage (permanent or temporary) in the vegetation of these floodplains was made. It was found that floodplain-mainstem elemental fluxes make a significant contribution to the dissolved flux of the Amazon River. This study is part of the Brazilian_French joint research program Hybam (Hydrology and Geochemistry of the Amazonian Basin).