Yuxu Zhang

Molybdenum isotopic records across the Precambrian-Cambrian boundary

Molybdenum (Mo) isotopic data from early Cambrian formations in southern China demonstrate the importance of non-euxinic sediments as a promising archive for coeval seawater Mo records. For the first time, in analogue to noneuxinic, nonskeletal carbonates, we report that the pristine phosphorites also can preserve the ambient fluid, which make the pristine phosphorites a new potential fingerprinting tool to record the coeval paleoseawater. Pristine phosphorite and dolomite samples of two early Cambrian formations in southern China suggest that early Cambrian seawater may have had δ 97/95 Mo values of at least 1.4‰, similar to modern oceans. Low δ 97/95 Mo (as low as −0.5‰) values were obtained from reworked phosphorite, but evidence suggests that these are reflecting Mo related to Fe oxyhydroxide minerals rather than the coeval seawater. In contrast, late Precambrian dolomite just below the transition to the Cambrian would indicate a δ 97/95 Mo of coeval seawater slightly heavier than that of the Mesoproterozoic (0.9‰–1‰ versus 0.8‰), suggesting that oceanic circulation patterns may have been thoroughly reorganized by that time, and may have triggered biological diversification from the Ediacaran to the early Cambrian.

Isotopic delta values of molybdenum standard reference and prepared solutions measured by MC-ICP-MS: Proposition for delta zero and secondary references

We report the isotopic composition of five molybdenum (Mo) standard reference solutions and four fractions from one of these solutions eluted through anion resin column relative to a sixth reference solution. The reference solutions were National Institute of Standards and Technology (NIST) SRM 3134 (lot#891307), Johnson Matthey Specpure (JMC)-Mo Sie (lot #602332B), JMC-Mo Wen (lot#13989C), Merck (lot#170334), Sigma-Aldrich (lot#207306) and Prolabo. Measurements were conducted using Isoprobe multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) at the Centre de Recherches Petrographiques et Geochimiques (France) and Nu Plasma MC-ICP-MS at either the Ecole Normale Superieure de Lyon (France) or the Laboratory of Isotope Geology in the Ministry of Land and Resources (China). The sample-standard bracketing method was employed to correct the mass bias for Mo isotopes during instrumental measurement. Except for the Merck Mo solution, all the Mo solutions were identical in isotopic composition within error. Although the JMC Mo solution has been used as the internal reference material by various groups, uncertainty may still occur with different lot numbers and availability might be limited. Here, we propose the NIST 3134 Mo solution as a new candidate for delta zero reference material, used for reporting Mo isotopic composition of natural samples. Isotopic compositions for four eluted fractions of the Sigma-Aldrich Mo solution were 2.18‰, 0.98‰, −1.10‰ and −1.95‰ for δ97/95Mo relative to the NIST Mo standard. These values span the range of reported isotopic compositions for natural terrestrial and experimental samples (approximately −0.5‰ to 1.6‰ for δ97/95Mo). We propose these eluted fractions to be used as a secondary reference for Mo isotope measurements. Mo solutions are available at CRPG upon request.

Characteristics of Cd isotopic compositions and their genetic significance in the lead-zinc deposits of SW China

Up to now, the evaporation and condensation, as well as the biological absorption and inorganic absorptions, have been proved to be major factors in Cd isotope fractionation. And Cd isotopes have been widely applied in studies on the universal evolution and marine environment and so on. However, only a few researches have been conducted in applying Cd isotopes to trace the source of metallogenic material and the evolution of the ore-forming fluid in a complex mineralization environment, especially in a hydrothermal ore-formation system. We measured the Cd isotopic compositions of sphalerite, galena, and ores from five lead-zinc deposits in SW China, and found that the δ114/110Cd values varied from −1.53‰ to 0.34‰, with a total range of 1.87‰, which is greater than most of measured geological samples. Meanwhile, through contrasting the Cd content with Cd isotopic compositions of different deposits, it may be concluded that different genetic lead-zinc deposits have different Cd content and isotopic compositions, which could be a tool for the studies on the origin of ore deposits. Also, the biomineralization and crystal fractionation may also result in Cd isotope fractionation. In a word, although the research of Cd isotopes is presently at the preliminary stage (especially in hydrothermal ore-formation system), this study demonstrated that Cd isotopes can give a clue in tracing the evolution of ore-forming fluid and metallogenic environment.

Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits

Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ114/110Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ114/110Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits.

Precise Mo isotope ratio measurements of low-Mo (ng g−1) geological samples using MC-ICP-MS

Although molybdenum (Mo) isotopic compositions of carbonatites, phosphorites and siliceous rocks can be used as proxies to reconstruct conditions of marine chemistry throughout geological time, only a few studies have, so far, analysed these low-Mo (ng g−1) geological samples because of analytical limitations. In this study, a low blank, high yield two-column Mo purification procedure was developed for various low-Mo geological samples. The sample-standard bracketing (SSB) and double-spike (DS) methods for mass fractionation correction were used to compare the accuracy of Mo isotope ratio measurements. Six Mo reference materials, NIST SRM 3134 Mo, JMC Mo, SC+1 and SC−1 (eluted fractions of Sigma-Aldrich Mo), CRM GSR-6 limestone and USGS BCR-2 basalt, were used as quality controls. The results showed that the Mo delta values of reference materials and geological samples corrected by the SSB and DS methods were, within error, consistent with each other and the DS method was the method of choice for samples with <0.5 μg g−1 Mo. The average instrument long-term (over 1 year) external reproducibility of NIST SRM 3134 Mo was better than ±0.03‰ amu−1 (2SD, n = 288) and the analytical precision of low-Mo (101 to 103 ng g−1) geological samples was better than ±0.04‰ amu−1. This method can facilitate Mo isotope ratio measurements in geological samples with a low Mo content, offering a possibility to study a wider range of Mo reservoirs in geological processes.