Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as ε(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically light soils at depth (ε(205)Tl ≈ -4), and the Tl emissions, which produce Tl-enriched topsoils with ε(205)Tl as high as ±0. The latter interpretation is supported by analyses of the CKD, which is also characterized by ε(205)Tl ≈ ± 0, and the same ε(205)Tl value was found for a pyrite from the deposit that produced the cocombusted pyrite roasting waste. Additional measurements for samples from a locality in China, with outcrops of Tl sulfide mineralization and associated high natural Tl backgrounds, reveal significant isotope fractionation between soils (ε(205)Tl ≈ +0.4) and locally grown green cabbage (ε(205)Tl between -2.5 and -5.4). This demonstrates that biological isotope fractionation cannot explain the isotopically heavy Tl in the Lengerich topsoils and the latter are therefore clearly due to anthropogenic Tl emissions from cement processing. Our results thus establish that isotopic data can reinforce receptor modeling for the toxic trace metal Tl.
Please cite this article as: Prytulak, J., Brett, A., Webb, M., Plank, T., Rehkämper, M., Savage, P.S., Woodhead, J., Thallium elemental behavior and stable isotope fractionation during magmatic processes, Chemical Geology (2016), doi: 10.1016/j.chemgeo. 2016.11.007 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT AbstractStable thallium (Tl) isotopes are an extremely sensitive tracer for the addition of small amounts of sediments or materials altered at low temperatures to the source(s) of mantle-derived melts. The ability of Tl to trace such materials is due to the large concentration contrast between the mantle (Tl < 2ng/g) and possible exotic inputs (Tl ~100ng/g to >g/g), which also often display fractionated Tl isotope compositions.However, the magnitude of Tl isotope fractionation induced by igneous processes alone has not been systematically assessed. Here, two suites of co-genetic magmas, spanning a large range of differentiation, from Hekla, Iceland, and Anatahan, in the Mariana arc, are used to assess the behavior of thallium and its stable isotope variations during magmatic processes. Thallium behaves as a near-perfectly incompatible lithophile element throughout magmatic evolution, mirroring elements such as Rb, Cs, and K. Lavas from Hekla have restricted Cs/Tl ratios and stable Tl isotope compositions, which overlap with mantle estimates. Lavas from subductionrelated Anatahan volcano also have a restricted range in Tl isotope composition, which overlaps with Hekla and MORB, demonstrating that fractional crystallisation and partial melting does not fractionate stable Tl isotopes. Subduction environments display variable Cs/Tl, indicating that the subduction process commonly fractionates these two elements. The immunity of thallium stable isotopes to fractionation by magmatic processes coupled with its extreme sensitivity for tracing pelagic sediments, FeMn crusts and low temperature altered oceanic crust highlight its value in elucidating the nature of mantle sources of both oceanic basalts and arc lavas.Critically, meaningful interpretation of thallium isotope compositions need not be restricted to primitive lavas.
Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Magnetite is a particularly favourable site for heterogeneous bubble nucleation in magma and yet 11 only very rarely is evidence for this preserved, owing to the myriad of processes that act to
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractWe report the solubility of water in Apollo 15 basaltic 'Yellow Glass' and an iron-free basaltic analog composition at 1 atm and 1350 °C. We equilibrated melts in a 1-atm furnace with flowing H 2 /CO 2 gas mixtures that spanned ~8 orders of magnitude in fO 2 (from three orders of magnitude more reducing than the iron-wüstite buffer, IW−3.0, to IW+4.8) and ~4 orders of magnitude in pH 2 /pH 2 O (from 0.003 to 24). Based on Fourier transform infrared spectroscopy (FTIR), our quenched experimental glasses contain 69-425 ppm total water (by weight). Our results demonstrate that under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH 2 O in the furnace atmosphere and is independent of fO 2 and pH 2 /pH 2 O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H 2 in our iron-free experiments is <~4 ppm, even at oxygen fugacities as low as IW−2.3 and pH 2 /pH 2 O as high as 11; (5) Secondary ion mass spectrometry (SIMS) analyses of water in iron-rich glasses equilibrated under variable fO 2 conditions may be strongly influenced by matrix effects, even when the concentration of water in the glasses is low; and (6) Our results can be used to constrain the entrapment pressure of lunar melt inclusions and the partial pressures of water and molecular hydrogen in the carrier gas of the lunar pyroclastic glass beads. We find that the most water-rich melt inclusion of Hauri et al.(2011) would be in equilibrium with a vapor with pH 2 O ~3 bar and pH 2 ~8 bar. We constrain the partial pressures of water and molecular hydrogen in the carrier gas of the lunar pyroclastic glass beads to be 0.0005 bar and 0.0011 bar respectively. We calculate that batch degassing of lunar magmas containing initial volatile contents of 1200 ppm H 2 O (dissolved primarily as hydroxyl) and 4-64 ppm C would produce enough vapor to reach the critical vapor volume fraction thought to be required for magma 2 fragmentation (~65-75 vol. %) at a total pressure of ~5 bar (corresponding to a depth beneath the lunar surface of ~120 m). At a fragmentation pressure of ~5 bar, the calculated vapor composition is dominated by H 2 , supporting the hypothesis that H 2 , rather than CO, was the primary propellant of the lunar fire fountain eruptions. The results of our batch degassing model suggest that initial melt compositions with >~200 ppm C would be required for the vapor composition to be dominated by CO rather than H 2 at 65-75 % vesicularity.
Thallium stable isotope ratio and mass fraction measurements were performed on sixteen geological reference materials spanning three orders of magnitude in thallium mass fraction, including both whole rock and partially separated mineral powders. For stable isotope ratio measurements, a minimum of three independent digestions of each reference material was obtained. High‐precision trace element measurements (including Tl) were also performed for the majority of these RMs. The range of Tl mass fractions represented is 10 ng g−1 to 16 μg g−1, and Tl stable isotope ratios (reported for historical reasons as ε205Tl relative to NIST SRM 997) span the range −4 to +2. With the exception – attributed to between‐bottle heterogeneity – of G‐2, the majority of data are in good agreement with published or certified values, where available. The precision of mean of independent measurement results between independent dissolutions suggests that, for the majority of materials analysed, a minimum digested mass of 100 mg is recommended to mitigate the impact of small‐scale powder heterogeneity. Of the sixteen materials analysed, we therefore recommend for use as Tl reference materials the USGS materials BCR‐2, COQ‐1, GSP‐2 and STM‐1; CRPG materials AL‐I, AN‐G, FK‐N, ISH‐G, MDO‐G, Mica‐Fe, Mica‐Mg and UB‐N; NIST SRM 607 and OREAS14P.
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