The Trinity peridotite (northern CA) contains numerous lithologic sequences consisting of dunite to harzburgite to spinel lherzolite to plagioclase lherzolite. Previous workers have documented geochemical gradients in these sequences consistent with melt-rock reaction processes occurring around dunites, interpreted to reflect conduits for melt ascent. We have undertaken a study of Li isotope compositions of clinopyroxene and some olivine within these sequences using ion probe techniques to test the hypothesis that the geochemical gradients are related to diffusive fluxing of alkali elements into or away from the melt conduit.Results show large variations in 7 Li/ 6 Li occurring in a consistent pattern across three transects from dunite to plagioclase lherzolite within the Trinity peridotite. Specifically, measurements of average ␦ 7 Li for single thin sections along the traverse reveal a low in ␦ 7 Li in the harzburgite adjacent to the dunite returning to higher values farther from the dunite with a typical offset of ϳ10 per mil in the low ␦ 7 Li trough. This pattern is consistent with a process whereby Li isotopes are fractionated during diffusion through a melt either from the dunite conduit to the surrounding peridotite, or from the surrounding peridotite into the dunite conduit. The patterns in 7 Li/ 6 Li occur over a length scale similar to the decrease in REE concentration in these same samples. Explaining both the trace element and Li isotopic gradients requires a combined process of alkali diffusion and melt extraction.We develop a numerical model and examine several scenarios of the combined diffusion-extraction process. Using experimentally constrained values for the change in Li diffusion coefficient with isotope mass, large changes in ␦ 7 Li as a function of distance can be created in year to decade timescales. The addition of the melt extraction term allows larger Li concentration gradients to be developed and thus produces larger isotopic fractionations than diffusion only models. The extraction aspect of the model can also account for the observed decrease in rare earth element concentrations across the transects.
The attenuation of groundwater contamination via chemical reaction is traditionally evaluated by monitoring contaminant concentration through time. However, this method can be confounded by common transport processes (e.g., dilution, sorption). Isotopic techniques bypass the limits of concentration methods, and so may provide improved accuracy in determining the extent of reaction. We apply measurements of 238U/235U to a U bioremediation field experiment at the Rifle Integrated Field Research Challenge Site in Rifle, Colorado. An array of monitoring and injection wells was installed on a 100 m2 plot where U(VI) contamination was present in the groundwater. Acetate-amended groundwater was injected along an up-gradient gallery to encourage the growth of dissimilatory metal reducing bacteria (e.g., Geobacter species). During amendment, U concentration dropped by an order of magnitude in the experiment plot. We measured 238U/235U in samples from one monitoring well by MC-ICP-MS using a double isotope tracer method. A significant approximately 1.00 per thousand decrease in 238U/235U occurred in the groundwater as U(VI) concentration decreased. The relationship between 238U/235U and concentration corresponds approximately to a Rayleigh distillation curve with an effective fractionation factor (alpha) of 1.00046. We attribute the observed U isotope fractionation to a nuclear field shift effect during enzymatic reduction of U(VI)(aq) to U(IV)(s).
We present a concerted international effort to cross‐calibrate five synthetic Th isotope reference materials (UCSC Th “A”, OU Th “U”, WUN, IRMM‐35 and IRMM‐36), and six rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR‐2, USGS W‐2, USGS BHVO‐2, LV18) using multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS). We then compare our new values with a compilation of literature mass spectrometric data for these reference materials and derive recommended “consensus”230Th/232Th values for each. We also present isotope dilution U and Th concentration data for four rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR‐2, USGS W‐2).
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