Molybdenum isotope composition of the upper mantle and its origin:insight from mid-ocean ridge basalt

The molybdenum(Mo)isotope system is pivotal in reconstructing marine redox changes throughout Earth’s history and has emerged as a promising tracer for igneous and metamorphic processes.Understanding its composition and variation across major geochemical reservoirs is essential for its application in investigating high-temperature processes.However,there is debate regarding theδ^(98/95)Mo value of the Earth’s mantle,with estimates ranging from sub-chondritic to super-chondritic values.Recent analyses of global mid-ocean ridge basalt(MORB)glasses revealed significantδ^(98/95)Mo variations attributed to mantle heterogeneity,proposing a two-component mixing model to explain the observed variation.Complementary studies confirmed the sub-chondriticδ^(98/95)Mo of the depleted upper mantle,suggesting remixing of subduction-modified oceanic crust as a plausible mechanism.These findings underscore the role of Mo isotopes as effective tracers for understanding dynamic processes associated with mantle-crustal recycling.

Phosphorite generative processes around the Precambrian-Cambrian boundary in South China: An integrated study of Mo and phosphate O isotopic compositions

Large phosphorite deposits in Central Guizhou,China,were formed around the Precambrian/Cambrian boundary(PC/C),including the Ediacaran(Doushantuo stage)and early Cambrian(Gezhongwu stage).Among them,Gezhongwu phosphorite from Zhijin are enriched in rare earth elements(REE)plus yttrium(REY),reaching 3.503 million tons.Although phosphorites have attracted great attention,the specific sources P and REY remained unclear.To determine the P and REY sources and establish a phosphogenic model of PC/C phosphorite,we present an integrated dataset of Mo and phosphate O isotopes for the first time,along with carbonate C and O isotopes,geology,petrology,and geochemistry.In all samples,d18Op,Y/Ho,and Zr/Hf decreased from the Ediacaran to the early Cambrian,indicating increased terrigenous weathering fluxes while decreased upwelling water input.Furthermore,terrigenous weathering delivery significantly elevated marine REY concentrations in the Cambrian in Zhijin.The Ceanom and d98/95Mo suggest that seawater was oxidized in the later Ediacaran and became entirely oxic in the early Cambrian.The positive feedback between oxygen levels in atmosphere and primary productivity caused progressive oxygenation in ocean-atmosphere system and enable phosphorites to be formed by different mechanisms.Results show that the Lower Doushantuo consist of abiotic intraclasts and exhibited“seawaterlike”REY types,indicating abiological and mechanical reworking phosphogenesis.The Upper Doushantuo and Gezhongwu Formation contained mainly microbial debris and abiogenic intraclasts,and exhibit “hat-shaped”REY plots,suggesting microbially mediated phosphogenesis.Based on this data set,we developed a phosphogenic model illustrating formation of these two phosphorite deposits,wherein the Lower Doushantuo phosphorite formed through the reworking of pre-existing phosphatic sediments in anoxic and abiotic ocean,whereas the Upper Doushantuo and Gezhongwu phosphorite formed via microbial metabolisms in oxic and biotic conditions.Our study has implications on the PC/C phosphorite generative processes,as well as paleoenvironmental conditions.

Assessment of Different Digestion Procedures for Mo Isotope Measurements of Black and Grey Shales Using the Double Spike Technique

This study investigates the behavior of Mo and Mo isotopes (δ^(98)Mo) in shales following leaching with HCl and HNO_(3) with the aim of simplifying the shale dissolution procedure.Up to 6%of the Mo was lost and the Mo isotopes were unaffected when shales were leached using 9 M HCl after ashing.Bulk sample digestion or leaching by 4 M or more concentrated HCl after ashing were all found to be acceptable and reliable approaches to the analysis of Mo isotopes in shales.After black shale (CAGS-BS) was leached with 2 M HCl,1 M HCl,and 9 M HNO_(3),the Mo concentration ([Mo]) in the leachate was lower and δ^(98)Mo was heavier than that obtained from bulk digestion.A Mo isotope mass-balance model showed that the δ^(98)Mo in the residues was lighter than the δ^(98)Mo from the bulk digestion of CAGS-BS and of crustal igneous rocks.No more Mo was lost,nor did Mo isotope fractionation,if the double spike was added before rather than after ashing and followed by bulk digestion or leaching with 9 M HCl.For efficiency,leaching using 4 M or more concentrated HCl after ashing is preferred for Mo isotope measurements.

Mo marine geochemistry and reconstruction of ancient ocean redox states

Molybdenum(Mo) proxies, including bulk concentration and isotopic composition, have been increasingly used to reconstruct ancient ocean redox states. This study systematically reviews Mo cycles and their accompanying isotopic fractionations in modern ocean as well as their application in paleo-ocean redox reconstruction. Our review indicates that Mo enrichment in sediments mainly records the adsorption of Fe-Mn oxides/hydroxides and chemical bonding of H2 S. Thus, Mo enrichment in anoxic sediments generally reflects the presence of H2 S in the water column or pore waters. In addition to the effect of euxinia, sedimentary Mo enrichment is related to the size of the oceanic Mo reservoir. Given these primary mechanisms for oceanic Mo cycling, Mo abundance data and Mo/TOC ratios acquired from euxinic sediments in geological times show that fluctuations of the oceanic Mo reservoir are well correlated with oxygenation of the atmosphere and oceans and suggest that oxygenation occurred in phases. Mo proxies suggest that Mo isotopes in strongly euxinic sediments reflect the contemporaneous Mo isotopic composition of seawater, but other processes such as iron-manganese(Fe-Mn) adsorption and weak euxinia can result in different fractionations. Diagenesis may complicate Mo enrichment and its isotopic fractionation in sediments. With appropriate constraints on the Mo isotopic composition of seawater and various outputs, a Mo isotope mass-balance model can quantitatively reconstruct global redox conditions over geological history. In summary, Mo proxies can be effectively used to reconstruct oceanic redox conditions on various timescales due to their sensitivity to both local and global marine redox conditions. However, given the complexity of geochemical processes, particularly the effects of diagenesis, further work is required to apply Mo proxies to ancient oceans.