Mo Isotope Fractionation Research Articles

Effect of Manganese Oxide Mineralogy and Surface Mo Coverage on Mo Isotope Fractionation During the Adsorption Process

The large molybdenum (Mo) isotope fractionation from seawater is caused by the adsorption of Mo on manganese oxides. However, the effects of the manganese oxide mineralogy (crystal structure) and surface Mo coverage on Mo isotope fractionation have not been investigated. In this study, the isotope fractionation of Mo by adsorption on synthetic todorokite, birnessite, and δMnO2 was investigated under a wide range of surface Mo coverages. The Mo isotope fractionation changed from Δ98/95Mo = 2.18 ± 0.05‰ to 2.61 ± 0.06‰ for todorokite; from 1.25 ± 0.05‰ to 2.10 ± 0.05‰ for birnessite; and from 2.19 ± 0.07‰ to 2.73 ± 0.08‰ for δMnO2. The Mo isotope fractionations of the three manganese oxides were negatively correlated with surface coverage normalized to the specific surface area. The independence of the obtained correlation of the manganese oxide species indicates that the Mo isotope fractionation depends on the surface coverage but not on the mineralogy of the manganese oxides. The experimentally observed Mo isotope fractionation (<2.7‰) in manganese oxides generally underestimates the isotope fractionation in natural ferromanganese oxides (~3‰). According to the dependency of the Mo isotope fractionation on the surface coverage, the underestimation relative to previous experimental studies can be attributed to the lower Mo surface coverage of natural ferromanganese oxides.

Chemical speciation and rice uptake of soil molybdenum-Investigation with X-ray absorption spectroscopy and isotope fractionation

Molybdenum (Mo) contamination of farmland soils poses health risks due to Mo accumulation in crops like rice. However, the mechanisms regulating soil availability and plant uptake of Mo remain poorly understood. This study investigated Mo uptake by rice plants, focusing on Mo speciation and isotope fractionation in soil and rice plants. Soil Mo species were identified as sorbed Mo(VI) and Fe-Mo(VI) using X-ray absorption spectroscopy (XAS). Soil submergence during rice cultivation led to the reductive dissolution of Fe-associated Mo(VI) while increasing sorbed Mo(VI) and Ca-Mo(VI). Soil Mo release to soil solution was a dynamic process involving continuous dissolution/desorption and re-precipitation/sorption. Mo isotope analysis showed soil solution was consistently enriched in heavier isotopes during rice growth, attributed to re-sorption of released Mo and the uptake of Mo by rice plants. Mo was significantly associated with Fe in rice rhizosphere as sorbed Mo(VI) and Fe-Mo(VI), and around 60 % of Mo accumulated in rice roots was sequestrated by Fe plaque of the roots. The desorption of Mo from Fe hydroxides to soil solution and its subsequent diffusion to the root surface were the key rhizosphere processes regulating root Mo uptake. Once absorbed by roots, Mo was efficiently transported to shoots and then to grains, resulting in heavier isotope fractionation during the translocation within plants. Although Mo translocation to rice grains was relatively limited, human exposure via rice consumption remains a health concern. This study provides insights into the temporal dynamics of Mo speciation in submerged paddy soil and the uptake mechanisms of Mo by rice plants.

Molybdenum Isotope Fingerprinting of Microbial Sulfate Reduction in Seep Carbonate Rocks

AbstractUnderstanding the interaction between molybdenum (Mo) and organic matter during microbial sulfate reduction is critical for the use of Mo to reconstruct marine redox conditions throughout Earth's history. However, little is known about Mo isotope fractionation and how it relates to organic matter remineralization during microbial sulfate reduction. Here, we report Mo abundances and isotopic (δ98Mo) compositions for bulk‐rock, non‐lithogenic and sequentially extracted fractions, including carbonate (carb), pyrite, and organic matter (OM), of seep carbonate rocks. Our data indicate that the difference between δ98Mocarb and δ98MoOM (Δ98Mocarb‐OM) displays significant variability in the studied samples, ranging between 0.72 and 1.01‰. Remarkably, the obtained Δ98Mocarb‐OM values indicate correlative trends with stable carbon isotope ratios and bulk abundances of (a) total organic carbon, (b) Mo, and (c) pyrite in seep carbonates, which we interpret as reflecting sustained adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction. On this basis, we put forward the concept that Δ98Mocarb‐OM of authigenic carbonate rocks can be used as a measure of the intensity of sulfate reduction and for reconstructing past interactions between Mo and organic matter in marine sediments.

Diagenesis Decreasing the Mo Isotopic Composition in Estuarine Systems: Implications for Constraining Its Riverine Input to Ocean

AbstractUnderstanding the geochemical behavior of the Mo isotopes in estuarine systems is essential for determining the isotopic composition of riverine inputs to the ocean and for assessing the historical oxidation state of Earth’s ancient oceans. However, the extent and mechanisms of Mo isotope fractionation during estuarine processes are not yet fully understood. This study systematically investigated the seasonal and spatial variations in aqueous and particulate δ98Mo values within the Pearl River Estuary (PRE). Our research found that aqueous δ98Moaque. values in both summer and winter deviated significantly from the theoretical mixing line for the PRE. Based on the geochemical characteristics of the water column, particulate matter, and pore water in the PRE, we first propose that diagenesis release from sediments is the predominant factor resulting in lower than anticipated aqueous δ98Moaque. values. Given the prevalence of suboxic and anoxic sediments in estuarine and coastal areas, such diagenetic release may substantially decrease the global riverine influx of aqueous Mo isotopes to the ocean. Additionally, particulate δ98MoSPM values exhibit an increasing trend (from 0.02 to 1.62‰) with increasing salinity in both seasons, suggesting that the terrestrial input particulate δ98MoSPM value would be heavier than the mean value for UCC. We hypothesize that the adsorption and desorption processes involving Fe (hydro) oxides predominantly influence this trend. This study advances our understanding of the mechanisms of aqueous and particulate Mo isotopic fractionation in estuarine systems and would be helpful in constraining Mo isotopic compositions of rivers and oceans.

Molybdenum isotopic fractionation in the Panzhihua mafic layered intrusion in the Emeishan large igneous province, southwest China

Abstract The large Mo isotopic fractionations between different geological reservoirs make this isotopic system a potentially useful tool for constraining the origins of magmatism. However, the effect of magmatic differentiation on Mo isotopes is still controversial. In this study, we obtained Mo isotope data for the Panzhihua gabbroic intrusion (i.e., including mineral separates of clinopyroxene, plagioclase, magnetite, and ilmenite). The whole-rock samples and mineral separates exhibit large Mo isotopic fractionations with δ98/95Mo values as follows: magnetite (–0.73‰ to –0.32‰) < clinopyroxene (–0.32‰ to –0.10‰) < ilmenite (0.06‰ to 0.36‰) < plagioclase (0.33‰ to 0.83‰). Iron-Ti oxides have Mo contents that are one order of magnitude higher than those of clinopyroxene and plagioclase. Mass balance calculations based on Mo isotopes and contents are consistent with an accumulated origin for the Panzhihua intrusion. Rayleigh fractionation modeling shows that the removal of magnetite and ilmenite results in significant Mo isotopic fractionation in the residual magma. Due to the low Mo contents of clinopyroxene and plagioclase, Mo isotopes are not significantly fractionated by the removal of these minerals. Therefore, our study highlights that fractionation of Fe-Ti oxides can cause considerable Mo isotopic fractionation; consequently, caution is needed when using Mo isotopes to infer magma origins.

Seawater‐Fluid Composition Records From Molybdenum Isotopes of Sequentially Extracted Phases of Seep Carbonate Rocks

AbstractAuthigenic molybdenum (Moauth) in marine sediments holds great potential to archive the Mo isotopic composition of seawater and biogeochemical processes. However, the factors that control authigenic Mo isotope (δ98Moauth) distribution patterns remain poorly constrained. Here, we report Mo abundances and δ98Mo compositions for bulk‐rock (bulk) and sequentially extracted fractions—including total authigenic (auth; i.e., non‐lithogenic fraction), carbonate (carb), iron and manganese oxyhydroxides, pyrite (py), and organic fractions (OM)—of authigenic carbonates recovered from various hydrocarbon seep sites in the Gulf of Mexico and the South China Sea. Extracted pyrite fractions exhibit Mo contents varying from 0.1 to 23.4 μg/g and generally dominate the Mo budget of seep carbonate rocks. Our data indicate large ranges of δ98Mobulk and δ98Moauth values relative to NIST 3134 (0.25‰), varying from 1.02 to 1.98‰ (n = 4) and from 0.15 to 3.07‰ (n = 34), respectively. The difference in δ98Mo values between carbonate and pyrite fractions of seep carbonate rocks formed under sulfidic conditions increases with higher Moauth contents, suggesting a control of dissolved hydrogen sulfide concentrations on Mo isotope fractionation during carbonate precipitation. Compared with δ98Moauth and δ98Mopy, δ98Mocarb of seep carbonate rocks formed under sulfidic conditions shows a relatively narrow range with an average of 1.98 ± 0.31‰ (1 SD; n = 10), providing constraints on the δ98Mo composition of seawater in the course of Earth history. Overall, our findings show that the δ98Mo composition of sequentially extracted phases of carbonate‐rich sedimentary rocks can provide insights into seawater‐sediment interactions and biogeochemical pathways of Mo during early diagenesis.

Molybdenum isotope heterogeneity of metal sulfides from magmatic hydrothermal systems

The sensitivity of molybdenum (Mo) stable isotopes to redox changes enables innovative geochemical means of tracing the evolution of medium- to high-temperature magmatic hydrothermal processes. However, the Mo isotope geochemical behaviors and fractionation mechanisms in magmatic-hydrothermal systems are still unclear. This study performed high-precision Mo isotope research on well-characterized hydrothermal metal sulfides (pyrite, chalcopyrite, molybdenite and pyrrhotite) from different metallogenic stages and the ore-forming porphyries and surrounding rocks from the giant Pulang porphyry copper deposit in Yunnan, Southwest China, to better understand Mo isotope behaviors in magmatic hydrothermal systems. The results show that compared to the high-temperature magmatic system with homogeneous Mo concentrations (1.44 ppm to 11.3 ppm) and δ98Mo values (−0.41‰ ± 0.05 to −0.08‰ ± 0.03), medium- to high-temperature hydrothermal stage molybdenite displays slightly lighter δ98Mo values (−0.90‰ ± 0.04 to 0.08‰ ± 0.04), and pyrite, chalcopyrite and pyrrhotite, which have low Mo concentrations (0.13 ppm to 28.5 ppm), feature significant δ98Mo variations from −0.34 ± 0.04‰ to 3.01 ± 0.03‰. The absence of fractionated but low δ98Mo values in the magmatic system, combined with the lack of any correlation between the δ98Mo and geochemical index values (e.g., Co/Ni value) of the metal sulfides, implies that the Mo isotope signatures of sulfides in the hydrothermal stage were not inherited from component signatures of the magmatic phase or contamination of surrounding rocks. Our study proposes that heterogeneous partitioning and transportation of heavy/light Mo isotopes into progressively precipitated metal sulfides as a result of changes in the redox-driven metallogenic setting and differential geochemical behaviors of Mo species contribute to the observed δ98Mo variations and that the heavier and strongly variable Mo isotopic signatures correspond to the dominant metallogenic stage of the deposit. Such fractionation may be explained by the Rayleigh fractionation model, whereby 95Mo is preferentially partitioned into isotopically light molybdenite, and the subsequent precipitation of pyrite, chalcopyrite and pyrrhotite from the residual 98Mo-rich ore-forming fluids manifests heavier isotopic compositions. We therefore highlight that the Mo isotopes of metal sulfides provide valuable insights into the precipitation of metal-rich fluids, the identification of favorable mineralization zones, and the ability to trace the evolution of sophisticated magmatic-hydrothermal systems.

Mo isotopes record recycling of anoxic sediment in a Paleo-oceanic subduction zone

Mafic arc igneous rocks with oceanic crust-derived fluids in their mantle sources generally show heavy Mo isotope compositions. However, these rocks may exhibit variable Mo isotope compositions due to involvement of seafloor sediments under different redox conditions. Thus, it is intriguing how Mo isotope recycles with sediment subduction and how Mo isotope fractionation occurs during this process. Here we report Mo isotope data for Paleozoic mafic arc igneous rocks from the Qinling-Tongbai orogenic belt in Central China. The Qinling mafic rocks have δ98Mo values of −0.03 to 0.40‰, and the Tongbai mafic rocks have δ98Mo values of −0.26 to 0.17‰. These values are considerably higher than the normal mantle values of −0.20 ± 0.01‰. In combination with low Mo/Ce ratios, enriched SrNd isotope compositions, and high melt-mobile incompatible trace element contents for these rocks, the high δ98Mo values suggest that anoxic sediment-derived melts with heavy Mo isotopes were incorporated by oceanic subduction into the mantle sources. The high δ98Mo values of the mafic rocks indicate the limited Mo isotope fractionation during subduction of the anoxic sediment. This inference is further verified by modeling of Mo isotope fractionation under reducing conditions in the subduction zone. In this regard, Mo isotopes can be used to identify the recycling of sediments in different types and thus provide geochemical constraints on the redox conditions of oceanic subduction zones.

Different B[sbnd]Mo isotopic fractionation processes controlled by redox conditions in the subduction zone

The control of redox conditions on the geochemical recycling process in subduction zones is still poorly understood due to large uncertainties in oxygen fugacity (fO2) for subducted slabs. We present the first systematic geochemical and B-Mo-Sr-Nd-Hf-Pb isotopic data for continental arc basalts (CABs) and back-arc basalts (BABs) from Sumatra to investigate the relationships between oxygen fugacity and BMo isotopic fractionation processes during subduction. The Sumatran CABs and BABs yield high FeOT/MgO ratios and low K2O contents (0.48–1.42 wt%) and can be classified as tholeiitic. They have variable Sr-Nd-Hf-Pb isotopic compositions, consistent with the input of different amounts of melt from subducted terrigenous sediments into mantle sources. The BAB samples show much lower δ11B (−9.0‰ to −7.3‰) values than the CABs (δ11B = −7.0‰ to +0.17‰), reflecting significant B isotopic fractionation during multistage melting of subducted sediments. This is distinct from the similar δ98/95Mo values for the Sumatran CABs (−0.21‰ to −0.01‰) and BABs (−0.17‰ to −0.08‰), suggesting limited Mo isotopic fractionation during subduction. The Sumatran CABs show low V/Yb ratios, suggesting that melts from subducted sediments were possibly generated at fO2 values lower than FMQ + 1.5. The limited Mo isotopic fractionation could be induced by the relatively low fO2 during melting of subducted sediments, which would significantly decrease the mobility of Mo but have no influence on B. Alternatively, rocks from highly oxidized arcs, such as the Izu arc (e.g., >FMQ + 3), exhibit across-arc lightening trends for both B and Mo isotopes, which is consistent with enhanced Mo isotopic fractionation due to elevation of fO2 during subduction. Thus, the BMo isotopes of arc rocks could provide diagnostic indicators for distinct geochemical recycling processes controlled by changes in redox conditions in subduction zones.

Spurious molybdenum isotope anomalies resulting from non-exponential mass fractionation

Mass-independent (nucleosynthetic) Mo isotope anomalies are uniquely useful for constraining genetic relationships among meteoritic and planetary materials and, by extension, the origin and nature of Earth's late-stage building blocks. The meaningful interpretation of such data, however, critically depends on the accurate correction of any natural and analytical mass-dependent isotope fractionation, which is commonly assumed to follow the ‘exponential law’. Here, using new high-precision Mo isotope data for a diverse set of terrestrial samples, we show that mass-dependent Mo isotope fractionation in nature typically does not adhere to this law, but is instead dominated by equilibrium and Rayleigh processes. We demonstrate that even moderate degrees of such non-exponential fractionation (i.e., mass-dependent isotope fractionation deviating from the exponential law) can result in significant spurious mass-independent Mo isotope anomalies that, when misinterpreted as nucleosynthetic anomalies, can lead to erroneous conclusions, particularly with respect to Earth's accretion history. Consequently, assessing the magnitude and origin of mass-dependent fractionation will be essential for future efforts to precisely determine the mass-independent Mo isotope composition of bulk silicate Earth and to identify potential nucleosynthetic isotope anomalies in terrestrial rocks.

Riverine molybdenum isotopic fractionation in small mountainous rivers of Taiwan: The effect of chemical weathering and lithology

The molybdenum (Mo) concentration and its isotopic composition from 25 major river catchments throughout Taiwan have been measured to better understand the geochemical behavior of Mo and the mechanism that controls Mo isotopic fractionation via weathering and erosion processes, in a tectonically active high-stand island. In addition, the Mo isotopic composition and its abundance in bedrock and riverine bedload sediments were also studied for source identification. The concentration of Mo in river water varies between 1.94 and 45.09 nM, and the δ98/95Mo ranges from −0.53‰ to +1.35‰, with an average of +0.70 ± 0.31‰ (1SD, n = 42) for the wet season. In the dry season, Mo concentration varies between 2.15 and 58.27 nM, and the δ98/95Mo ranges from −0.48‰ to +1.09‰, with an average of +0.74 ± 0.28‰ (1SD, n = 43). The seasonal variability of δ98/95Mo composition is very small in Taiwan river catchment.The dissolved riverine δ98/95Mo are heavier than those of the bedrock (∼ −0.72 to +1.03‰). These rivers flow through quite different lithologies and are thus difficult to identify a common cause responsible for the observed Mo isotopic fractionations. However, δ98/95Mo of riverine bedload sediments from three rivers show a negative trend with trace elements, e.g., Nb, Mn, and Ti, that are enriched in fine-grain residual Fe-Ti oxides, such as titanite, rutile, ilmenite, and niobite, important hosts for Mo. Consequently, the riverine bedload sediments may be the sink for light δ98/95Mo, which drives the riverine dissolved load towards a heavier δ98/95Mo isotopic signature through adsorption processes. In general, the rivers of Taiwan discharge a significant flux and a heavier mean δ98/95Mo (+0.75‰) to the oceans than that of the mean global rivers (∼ +0.55‰). While the results will help better constrain the global Mo cycle, short-term seasonal variations, e.g., precipitations, tend to have an insignificant effect on the Mo cycle in the oceans.

Serpentinite fluids and slab-melting in the Aleutian arc: Evidence from molybdenum isotopes and boron systematics

Mo isotope compositions have been increasingly used as a source tracer in magmatic systems. Here, we investigate the relative role of subducting oceanic crust, fluid-rich sources (e.g., serpentinite, altered oceanic crust – AOC), subducted sediments and upper mantle in the chemical composition of Aleutian arc magmas with Mo and B systematics. We present elemental and Mo isotope compositions (δ98/95Mo) and B concentrations on Aleutian lavas (n = 59), from Okmok Volcano in the east to the westernmost seamount Piip, showing absence of Mo isotope fractionation during magmatic differentiation. Additionally, we report Mo isotope systematics for serpentinized peridotites from the South-West Indian Ridge (SWIR) (n = 6), AOC (n = 2) and Pacific sediments (DSDP 183, ODP 886) (n = 5) outboard the Aleutian arc. Molybdenum isotope composition and B enrichment (e.g., B/Ce) patterns display a step-function increase along the arc, with low, MORB-like, δ98/95Mo and low B/Ce values in the western section of the arc (B/Ce = 0.15–1.07; δ98/95Mo =−0.38 to +0.01‰), that abruptly increase in the central-eastern volcanoes Korovin, Seguam and Yunaska (B/Ce = 1.20–2.60; δ98/95Mo = +0.03 to +0.30‰) near the intersection of the Amlia Fracture Zone (AFZ) with the trench, but decrease again farther east at Okmok (B/Ce = 0.76 and δ98/95Mo = −0.12‰ on average). These data patterns are interpreted to reflect an along-arc changing source in the Aleutian magmas. AOC and Pacific sediments have predominantly low δ98/95Mo (−0.47 to −0.32 and +0.17 to −1.9‰, respectively), while serpentinites have extremely high δ98/95Mo (up to +1.09‰) and high B/Ce (∼22000). Based on the low δ98/95Mo in sediments and AOC, and lack of correlation between along-arc δ98/95Mo and radiogenic sediment tracers, subducted sediments and AOC do not exert first-order controls on the observed Mo isotope compositions. Rather, low, MORB-like, δ98/95Mo but high Mo enrichments (e.g., Mo/Ce) in the western samples are consistent with slab melting under rutile-bearing eclogitic facies with near absent Mo isotope fractionation from the slab to the arc sources. In turn, the abrupt increase of δ98/95Mo and B/Ce in lavas near the AFZ are best explained by a serpentinite endmember (likely dehydration fluids) at the AFZ that is not evident elsewhere along the arc. Results from this study provide evidence for serpentinites as an additional heavy Mo isotope signature component in subduction zones and demonstrate that high δ98/95Mo coupled with B enrichments are a useful proxy for tracing serpentinite fluids in subduction zones.

Density Functional Theory Calculations of Equilibrium Mo Isotope Fractionation Factors among MoOxS4–x2– Species in the Aqueous Phase by the ONIOM Method

Molybdenum (Mo) is a redox-sensitive metal element. Its isotope composition (δ98Mo) has the potential to reconstruct oceanic oxygenation extent in deep time. To accurately reconstruct the bulk δ98Mo value of ancient seawater from sediment records, it is necessary to clarify the Mo isotope fractionation mechanism during the transformation among thiomolybdates (MoOxS4–x2–, x = 0∼4) in marine environments. For aqueous systems, predicting the equilibrium isotope fractionation factors theoretically needs careful treatment of solvent effects. The commonly used water-droplet or periodical boundary condition methods are not only troublesome but also time-consuming. We test the efficiency of the two-layer own N-layer integrated molecular orbital molecular mechanics (ONIOM) method in predicting the reduced partition function ratios (β factors) of the MoOxS42– species in aqueous phases. Compared to other methods, the ONIOM method can produce β factors with the same accuracy and considerably fewer computational resources. The predicted β factors are in the order MoO4(aq)2– > MoO3S(aq)2– > MoO2S2(aq)2– > MoOS3(aq)2– > MoS4(aq)2–, which are in line with previous laboratory experiments and field observations. The new results provide the basic data for reconstructing δ98Mo values in suboxic, ferruginous, and weakly euxinic sediments.

Extreme Mo isotope variations recorded in high-SiO2 granites: Insights into magmatic differentiation and melt–fluid interaction

The Mo stable isotope system has been used to trace material recycling during subduction-related processes, but the behavior of Mo isotopes during magmatic evolution (e.g., crystal–melt fractionation and melt–fluid interaction) remains contentious, especially in high-SiO2 granites. This study addresses the issue of Mo isotope variation in high-SiO2 granites by measuring bulk-rock and mineral Mo isotopes of biotite granites (BGs) and garnet-bearing two-mica granites (GBGs) from the well-characterized Zhengga granite pluton (southern Tibet, China). The GBGs have similar Sr–Nd–O isotope compositions to those of the BGs but show higher SiO2 and lower TiO2, MgO, total Fe2O3, and CaO contents, and represent the products of advanced fractionation of the BG magmas. The BGs have lower Mo contents (0.02–0.07 ppm) and higher δ98/95Mo values (−0.54‰ to 0.22‰) compared with the GBGs (0.029–2.121 ppm and −0.97‰ to −0.41‰, respectively). Analysis of major silicate minerals suggests that substantial segregation of biotite and feldspar with high δ98/95Mo values of 0.00‰ to 0.38‰ and −1.06‰ to 0.57‰ (most within −0.58‰ to 0.13‰) could have driven the GBGs and the late-stage crystalline phase of garnet (−1.22‰ to −0.98‰) towards very low δ98/95Mo values. However, the trend of decreasing δ98/95Mo with indices of magma differentiation is not linear: one group of GBGs show increasing Mo contents and decreasing δ98/95Mo values with decreasing Y, Ho, and Dy contents; while the other group display increasing Mo contents and slightly decreasing δ98/95Mo values with respect to the increasing contents of Y, Ho, and Dy. These two contrasting behaviors can be ascribed to further crystal fractionation and melt–fluid interaction in a closed magmatic–hydrothermal system. This is also evidenced by the formation of two types of garnets with different contents of Mo and rare earth elements in these two groups of GBGs. Closed-system fluid saturation is inferred to have driven the silicate melt to be enriched in 98Mo, which limited the decrease in melt δ98/95Mo caused by crystal fractionation. These observations are supported by quantitative geochemical modeling. We conclude that both fractional crystallization and melt–fluid interaction control Mo isotope fractionation in high-SiO2 granites and that Mo isotopes are useful for tracing the evolution of high-SiO2 igneous rocks.

The influence of crustal recycling on the molybdenum isotope composition of the Earth's mantle

Several studies have suggested that the Earth's upper mantle is slightly enriched in light molybdenum isotopes relative to bulk Earth, defined by chondrites, but there is no consensus on the presence of this subtle but potentially notable signature. To establish better whether or not the 98Mo/95Mo of Earth's upper mantle is indeed sub-chondritic, we have analysed hand-picked glasses of depleted (i.e. chondrite normalised La/Sm<1) mid-ocean ridge basalts (MORB) from the Pacific, Atlantic and Indian ocean basins. The mean Mo isotope composition of our depleted MORB relative to reference NIST SRM 3134 (δ98/95MoNIST SRM 3134) is −0.22±0.03‰ (95% confidence interval, c.i.) compared to a value of −0.15±0.01‰ (95% c.i.) for bulk Earth. Our high precision analyses of the 234U/238U activity ratios of these samples are within uncertainty of unity, which rules out the effect of possible secondary, sea-floor processes as the dominant cause of their low δ98/95MoNIST SRM 3134. We further report experimental data showing that sulphide liquid has δ98/95MoNIST SRM 3134 0.25±0.01‰ lower than basaltic silicate liquid at 1400°C. This fractionation is too small to significantly alter the Mo isotope composition of basalts relative to their sources during melting or differentiation.Our MORB data show that resolvably sub-chondritic Mo isotope compositions are common in the upper mantle. Moreover, an appropriately weighted average δ98/95MoNIST SRM 3134 of depleted and enriched MORB, taken from this study and the literature, yields an estimated mantle value of −0.20±0.01‰, indicating that the upper mantle as a whole is sub-chondritic. Since prior work demonstrates that core formation will not create a residual silicate reservoir with a sub-chondritic δ98/95MoNIST SRM 3134, we propose that this feature is a result of recycling oceanic crust with low δ98/95MoNIST SRM 3134 because of Mo isotope fractionation during subduction dehydration. Such an origin is in keeping with the sub-chondritic Th/U and low Ce/Pb of the depleted mantle, features which cannot be explained by simple melt extraction. We present mass balance models of the plate tectonic cycle that quantitatively illustrate that the δ98/95MoNIST SRM 3134 of the Earth's mantle can be suitably lowered by such oceanic crustal recycling. Our Mo isotope study adds to the notion that the depleted mantle has been substantially modified by geodynamic cycling of subduction-processed oceanic crust.

Molybdenum isotope variation mechanism and ore-genesis of Niutoushan Pb–Zn sulfide orebodies in the Xiangshan volcanic basin, South China

Niutoushan Pb–Zn sulfide orebodies are found in the western part of the Xiangshan volcanic basin; however, genesis of the mineralization is highly debated. To appropriately constrain the mineralization process and genesis of the Niutoushan Pb–Zn sulfide orebodies present in the volcanic rocks in the Xiangshan volcanic basin, we investigate Mo isotope compositions of sulfide minerals (pyrite and sphalerite) from the Niutoushan Pb–Zn sulfide orebodies and those of the volcanic and subvolcanic rocks (the least-altered porphyritic lava and granitic porphyry rocks) from the Xiangshan volcanic-subvolcanic complex.The δ98Mo values (normalized to NIST3134 of 0.25 ‰) of the Xiangshan volcanic-subvolcanic rocks, including the least-altered granitic porphyry (0.20 ‰–0.26 ‰) and porphyritic lava rocks (0.40 ‰–0.51 ‰), are similar to those of the bulk continental crust (0.1 ‰–0.35 ‰, Willbold and Elliott, 2017). The δ98Mo values of sulfides from the Niutoushan Pb–Zn sulfide orebodies (pyrite: −0.95 ‰ to 0.30 ‰, sphalerite: −0.94 ‰ to −0.59 ‰) are mostly lower than those of the continental crust and span a wide range. After examining potential factors that may cause δ98Mo variation, it is concluded that the wide δ98Mo range of the Niutoushan Pb–Zn sulfide orebodies resulted mainly from the hydrothermal fluid evolution through Rayleigh fractionation in the mineralization process than from changes in other factors of the fluid, such as temperature, redox, and fluid boiling process.Further, based on this conclusion, the δ98Mo value of the initial hydrothermal fluid finally forming the Niutoushan sulfide orebodies was estimated to be 0.46 ‰ by combining the lowest δ98Mo value of the sulfides and the Mo isotope fractionation between the fluid and molybdenite. The initial hydrothermal ore-forming fluid with such a δ98Mo value was most likely derived from the Xiangshan subvolcanic magmas. This study highlights the potential of Mo isotope composition as a novel tool for tracking origin and evolution of ore-forming hydrothermal fluids and metals in case of Pb–Zn sulfide mineralization associated with igneous activities.

Extremely light molybdenum isotope signature of sediments in the Mariana Trench

Molybdenum (Mo) isotope signature (δ98/95Mo) of marine sediments is a powerful proxy for constraining marine redox conditions and early diagenetic processes. Oxic pelagic sediments have been increasingly acknowledged as an important sink for Mo in its global cycling, however, the mechanisms controlling Mo enrichment and isotope fractionation during early diagenesis in this environment are not fully understood. In this study, four sedimentary cores were sampled by full-ocean-depth lander system in the Mariana Trench, aiming to explore the processes controlling Mo partitioning in the sediments of the deepest ocean in the world. Sediments from four locations exhibit a wide range of authigenic Mo contents (Moauth, relative to continental crust), varying from 1.98 to 43 μg/g. A positive relation between Mo and Mn contents was identified for these sediments, which suggests that Mo are mainly hosted in Fe-Mn (oxyhydr)oxides. In addition, negative correlations between δ98/95Mo values and Mo/Mn ratios are found at each site. The δ98/95Mo values of the sediments vary from −1.71 ± 0.05 to −0.15 ± 0.04‰, revealing similar trends towards lighter values with burial depth from three sites. However, throughout the sediment core TY41 obtained from Mariana Trench, the δ98/95Mo values of sediment remain nearly constant around −0.55‰. Supported by the abundant Fe (oxyhydr)oxides throughout this site, it is likely the sediment is affected by enhanced fluid exchange across sediment-seawater interface, and the δ98/95Mo values of dissolved Mo in pore water resemble seawater signature. Therefore, the Mo isotopic offset between dissolved Mo and sediment is similar to the expected fractionation during the adsorption to Mn oxides (~ + 3.0‰) and hematite (~ + 2.2‰), which suggests that most of the dissolved Mo is scavenged by Mn oxides and/or hematite. The extremely light δ98/95 Mo values of sediments in deeper parts of the cores coincide with enhanced Mo accumulation. This indicates an even lighter isotope signature of dissolved Mo in pore water during the re-precipitation of Fe-Mn (oxyhydr)oxides upon an isotopic equilibrium for Mo adsorption to metal oxides. Both the patterns of both dissolved oxygen and nitrate suggest that the study sites are located within the nitrate reduction zone and Mn reduction occur at deeper depths below the studied interval. Therefore, the source of the isotopically light dissolved Mo in pore water was explained by the preferential release of isotopically lighter Mo from Fe-Mn (oxyhydr)oxides during the enhanced dissolution at deeper depth. In contrast, at the shallower depths of these cores (expect for core TY41), the higher δ98/95 Mo values towards seawater-sediment interface suggest the dissolved Mo is more impacted by the seawater exchange. This study provides a deeper insight into the diagenetic Mo cycling in trench environments, with Fe-Mn (oxyhydr)oxides rich sediments as an important sink for Mo.

Covariation between molybdenum and uranium isotopes in reducing marine sediments

The isotopic compositions of redox-sensitive elements such as uranium (U) and molybdenum (Mo) have been extensively used to track the evolution of redox conditions on Earth's surface. However, additional investigation of the behaviors of U and Mo in modern marine sediments—particularly in reducing sediments underlying oxic seawater—can bolster understanding and improve application of these systems as biogeochemical tracers. Here we present elemental and isotopic Mo and U data from reducing sediments from various sites in the Bering Sea where the extent of bioturbation is well characterized. Total Mo concentrations and total organic carbon contents (TOC) are positively correlated, as are authigenic Mo isotopic compositions and TOC, indicating the presence of authigenic Mo enrichments in these sediments. Similar to what has previously been observed in euxinic settings, we observe a positive correlation between authigenic U and Mo concentrations, and a negative correlation between the isotopic compositions of authigenic U and Mo (δ238Uauth and δ98Moauth). These patterns likely reflect close associations of U and Mo reduction to organic carbon degradation. Observed variation in δ98Moauth values could reflect variations in Mo removal efficiency or Mo isotopic fractionation between particles and seawater related to porewater H2S levels. Conversely, we interpret variation in δ238Uauth values in these Bering Sea samples to be related to varying extents of U reduction and removal, coupled with anaerobic carbon degradation. There is no significant correlation between the extent of bioturbation and Mo or U isotope values, suggesting that bioturbation would likely not have a significant influence on sedimentary Mo and U records. Further, the array of U and Mo isotopic data from these sediments is distinct from those observed in anoxic sediments below euxinic seawater—suggesting that a combination of U and Mo isotopic compositions could help to more accurately resolve the redox state of depositional environments from past intervals of Earth's history.

Re-assessment of the effect of fractional crystallization on Mo isotopes: Constraints from I-type granitoids and their enclosed mafic magmatic enclaves

In recent years, considerable progress has been made on the study of Mo isotopes in high-temperature geological processes. However, it is still controversial whether Mo isotope fractionation occurs during magmatic differentiation. Here we reassess the effect of magma differentiation on Mo isotope fractionation using published data in conjunction with our new analysis of Mo isotopes in well-characterized I-type granitoids and their enclosed mafic magmatic enclaves (MMEs) from two plutons in the North Qilian Orogen. The MMEs in each pluton, representing earlier cumulates with greater modal proportions of amphibole and biotite, show similar Mo elemental and isotopic compositions to their host granitoids. The absence of covariation of Mo isotopes with Dy/Dy*, Fe2O3 and K/Rb in both plutons further indicates that fractional crystallization of amphibole, biotite and Fe3+-rich minerals does not fractionate Mo isotopes in these granitoids. On the basis of re-assessment of published and our newly obtained Mo isotope data, we find that there is no clear evidence for Mo isotope fractionation during fractional crystallization in igneous rock. Instead, Mo isotopes of our samples correlate positively with Sr isotopes and Rb/La ratios, and negatively with Nd isotopes and Ce/Pb ratios, indicating clearly that magma source compositional variation controls the variation of Mo isotope compositions of these granitoids.

Molybdenum isotope-based redox deviation driven by continental margin euxinia during the early Cambrian

Oceanic redox changes may be a key environmental trigger for the “Cambrian explosion”. However, a hypothesized predominantly oxygenated early Cambrian ocean, inferred from high sedimentary molybdenum (Mo) isotope ratios, conflicts with other evidence for euxinic continental margins. Here, we demonstrate that seawater Mo isotope ratios like those of today’s predominantly well-oxygenated oceans can also occur in less oxygenated early Cambrian oceans. New and existing Mo isotope data from early Cambrian black shales in South China span a range of greater than 3‰, which can only be explained by multi-stage fractionation of Mo isotopes. The lowest Mo isotopes ratios likely reflect a Fe-Mn (oxyhydr)oxide shuttle that preferentially transferred the lighter Mo isotopes into weakly euxinic bottom waters where Fe-Mn (oxyhydr)oxide dissolution released isotopically light Mo that was then scavenged by organic matters and sulfide minerals. We use a novel isotope mass balance model to show that Fe-Mn (oxyhydr)oxide shuttle operating on euxinic continental margins would preferentially bury lighter-mass Mo isotopes to such an extent that early Cambrian seawater can become enriched in heavier Mo isotopes at levels comparable to modern seawater. Hence, widespread ocean oxygenation may not have occurred during the early Cambrian as previously thought. Based on this paradigm shift, reconsideration of sedimentary Mo isotope temporal trends suggests a stepwise and protracted oxidation of the oceans until the Late Devonian. Sporadic intervals with Mo isotope ratios spanning over 3‰ and often accompanied by dramatic change in biodiversity (e.g., Ediacaran-Cambrian and Permian-Triassic transitions) probably had euxinic continental margins. Links between fossil records and marine redox structures disclose the importance of spatiotemporal fluctuations in continental margin euxinia on biodiversity changes.