HR: 1340h
AN: H43C-0390    [Abstracts]
TI: Rhenium and Molybdenum in Rivers and Estuaries.
AU: * Walker, B D
EM: lekker@ucsc.edu
AF: WHOI, MS 25, Woods Hole, MA 02543 United States
AU: * Walker, B D
EM: lekker@ucsc.edu
AF: UCSC, EMS Rm D342, Santa Cruz, CA 95064 United States
AU: Peucker-Ehrenbrink, B
EM: behrenbrink@whoi.edu
AF: WHOI, MS 25, Woods Hole, MA 02543 United States
AB: Due to their redox-sensitive nature, the geochemical cycles of Re and Mo are linked to the global organic carbon cycle. Reducing sediments constitute a globally important sink and weathering of organic-rich sediments is responsible for a large portion of the Re and - to a lesser extent - Mo flux to the oceans (Colodner et al., 1993; Jaffe et al., 2002). Riverine concentrations of Re and Mo are a function of the river basin lithology, but are also likely to be affected by anthropogenic contributions (Colodner et al., 1995). Current estimates of global natural riverine Re flux are restricted to single analyses of four major rivers, which characterize only 23%\ of the global freshwater flux (Colodner et al., 1993). Annual variability of Re and Mo concentrations in rivers has not been studied. A single study of Re concentrations along the salinity gradient of the Amazon shelf is suggestive of conservative mixing, but scatter in the data do not allow to exclude the possibility of Re addition in the low-salinity end of the profile (Colodner et al., 1993). Careful evaluation of samples from the Hudson River estuary using a variety of extraction techniques indicates that spike-sample equilibration was not fully achieved using commonly used methods. We have therefore developed a simple, clean and efficient method of extracting Re from filtered water samples. Our method utilizes syringe filtration, prolonged heating to achieve spike-sample equilibration, batch equilibration with TEVA resin, and extraction of Re and Mo using syringe filtration. Rhenium concentrations in the Hudson, Housatonic and Connecticut rivers are 38 pM, 6.6 pM and 14 pM, respectively, much higher than the estimated global average of 2.1 pM (Colodner et al., 1993). Molybdenum concentrations are 4.6 nM, 5.5 nM, 7.8 nM, respectively. These rivers drain basins of Precambrian basement as well as predominantly Paleozoic sediments and have been substantially urbanized. Data for a salinity profile along the Hudson River estuary are suggestive of conservative mixing of Mo. However, data for Re indicate non-conservative mixing with a significant Re source between 5 and 12 psu. This feature could reflect an anthropogenic point source near Croton Point. Alternatively, it could be caused by a process that transfers Re, but not Mo, from the particulate into the operationally defined dissolved phase. Preliminary data for a Mississippi delta salinity profile suggest projected Re and Mo concentrations of about 90 pM and 26 nM for the freshwater end member, respectively. Our results indicate that the surficial Re cycle is more complex then previously thought. It requires further evaluation before a global estimate of natural riverine Re flux can be accurately constrained. A revision of the marine residence time of Re may be required.
DE: 4235 Estuarine processes
DE: 1806 Chemistry of fresh water
DE: 1030 Geochemical cycles (0330)
DE: 1065 Trace elements (3670)
DE: 1094 Instruments and techniques
SC: Hydrology [H]
MN: 2004 AGU Fall Meeting