Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater.Mg isotopes are significantly(up to 5%)fractionated during carbonate precipitation by preferential incorporation of ^(24)Mg,while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of^( 26)Mg.Thus,the marine Mg cycle could be reflected by seawater Mg isotopic composition(δ^(26)Mg_(sw)),which might be recorded in marine carbonate.However,carbonates are both texturally and compositionally heterogeneous,and it is unclear which carbonate component is the most reliable for reconstructing δ^(26)Mg_(sw).In this study,we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China.Based on petrographic studies,four carbonate components were recognized:micrite,marine cement,brachiopod shell,and mixture.The four components had distinct δ^(26)Mg:(1)micrite samples ranged from -2.86% to -2.97%;(2)pure marine cements varied from -3.40% to -3.54%,while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range(-3.27% to-3.75%);(3)values for the mixture component were-3.17% and -3.49%;and (4)brachiopod shells ranged from -2.20% to -3.07%,with the thickened hinge area enriched in ^( 24)Mg.Due to having multiple carbonate sources,neither the micrite nor the mixture component could be used to reconstruct δ^(26)Mg_(sw).In addition,the marine cement was homogenous in Mg isotopes,but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ^(26)Mg_(sw).Furthermore,brachiopod shells had heterogeneous C and Mg isotopes,suggesting a significant vital effect during growth.Overall,the heterogeneous δ^(26)Mg of the Huangjin limestone makes it difficult to reconstruct δ^(26)Mg_(sw)using bulk carbonate/calcareous sediments.Finally,δ^(26)Mg_(sw)was only slightly affected by the faunal composition of carbonate-secreting organisms,even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range(0.2%–4.8%)of fractionation during biogenic carbonate formation.

Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle

The continent is the second largest carbon sink on Earth’s surface.With the diversification of vascular land plants in the late Paleozoic,terrestrial organic carbon burial is represented by massive coal formation,while the development of soil profiles would account for both organic and inorganic carbon burial.As compared with soil organic carbon,inorganic carbon burial,collectively known as the soil carbonate,would have a greater impact on the long-term carbon cycle.Soil carbonate would have multiple carbon sources,including dissolution of host calcareous rocks,dissolved inorganic carbon from freshwater,and oxidation of organic matter,but the host calcareous rock dissolution would not cause atmospheric CO2drawdown.Thus,to evaluate the potential effect of soil carbonate formation on the atmospheric p CO2level,different carbon sources of soil carbonate should be quantitatively differentiated.In this study,we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop,consisting of limestone of the early Paleogene Guanzhuang Group in North China.Based on the C and Mg isotope data,we developed a numerical model to quantify the carbon source of calcite veins.The modeling results indicate that4–37 wt%of carbon in these calcite veins was derived from atmospheric CO2.The low contribution from atmospheric CO2might be attributed to the host limestone that might have diluted the atmospheric CO2sink.Nevertheless,taking this value into consideration,it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2within 2000 years,i.e.,soil carbonate alone would sequester all atmospheric CO2within 1 million years.Finally,our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.

Revisiting the Mg isotopic systematics of siliciclastic components of sediments and sedimentary rocks:A new geochemical proxy of continental weathering in Earth's history

The Mg isotopic compositions of siliciclastic components(δ^(26)Mg_(sili))of sediments and sedimentary rocks have been commonly used to constrain the intensity of continental weathering,based on observations of,(1)an upward enrichment of26Mg in modern weathering profiles,(2)preferential uptake of26Mg in soil clays,and(3)general positive correlations between weathering intensities andδ^(26)Mg_(sili)values.However,not all weathering profiles display an upward increase ofδ^(26)Mg_(sili),and not all soil clays enrich in26Mg,complicating the interpretations ofδ^(26)Mg_(sili)data of sediments and sedimentary rocks.To further explore the controls ofδ^(26)Mg_(sili)of sediments and sedimentary rocks,here we measuredδ^(26)Mg_(sili),mineralogical compositions and major element compositions of deep sea sediments from South China Sea(SCS)and carbonate rock samples from two late Paleozoic sections in South China.Carbonate samples show decreasing trends of both normalized Mg concentration(Mgnorm)andδ^(26)Mg_(sili)values with the increase of weathering intensity,while SCS sediments samples do not show any correlation between Mgnormorδ^(26)Mg_(sili)values and weathering intensity.A three-stages weathering model is developed to explain the observed Mgnorm andδ^(26)Mg_(sili)data.In the new model,weathering can be divided into three stages,(1)the preliminary weathering stage characterized by dissolution of primary minerals and formation of secondary clay minerals in saprolite,(2)the transitional stage with massive vermiculite and chlorite formation on the bottom of soil,and(3)the advanced stage showing dissolution of vermiculite and chlorite in the top of soil.The new model explains anδ^(26)Mg_(sili)increase and Mgnormdecrease with an increase weathering intensity in preliminary weathering stage and decrease of Mgnormandδ^(26)Mg_(sili)with increase weathering intensity in advanced weathering stage.The revised weathering model warrants the application of Mg isotope in the study of continental weathering in deep time.

Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion(SPICE) in the Jiangnan Basin, South China

Global occurrences of Steptoean Positive Carbon Isotope Excursion（SPICE） during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon（δ^（13）C） and organic carbon（δ^（13）C_（org）） isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate（CAS, δ^（34）S_（CAS）） and pyrite（δ^（34）S_（pyrite））, unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰ increase in δ^（13）C_（carb） of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions in δ^（34）S_（CAS） and δ^（34）S_（pyrite） have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound（VOSC, such as methanethiol and dimethyl sulfide） formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of ^（32）S from continental margins to open oceans, elevating δ^（34）S of seawater sulfate in continental margins. A simple box model indicates that about 35% to 75% of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

Sulfur and Oxygen Isotopes of Sulfate Extracted from Early Cambrian Phosphorite Nodules： Implications for Marine Redox Evolution in the Yangtze Platform

Phosphorite nodule beds are discovered in the black shale of basal Niutitang Formation throughout the Yangtze Platform in South China, recording an important phosphorite-generation event. Platform-wide phosphorite precipitation requires special oceanographic and geochemical conditions, thus the origin of the Niutitang phosphorite nodules may provide valuable information about the ocean chemistry in the Early Cambrian. In this study, we measured sulfur and oxygen isotopic compositions of sulfate extracted from phosphorite nodules collected from the basal Niutitang Formation. Phosphorite associated sulfate（PAS） is a trace amount of sulfate that incorporates into crystal lattice during phosphorite precipitation, accordingly PAS records the geochemical signals during phosphorite nodule formation. Sulfur isotopic composition of PAS（δ^（34）S_（PAS）） ranges from-1.16‰ to ＋24.48‰（mean=＋8.19‰, n=11）, and oxygen isotopic value（δ^（18）O_（PAS）） varies between-5.3‰ and ＋26.3‰（mean=＋7.0‰, n=8）. Most phosphorite nodules have low δ^（34）SPAS and low δ^（18）O_（PAS） values, suggesting PAS mainly derived from anaerobic oxidation of H_2S within suboxic sediment porewater. We propose that phosphate was delivered to the Yangtze Platform by a series of upwelling events, and was scavenged from seawater with the precipitation of FeOOH. The absorbed phosphate was released into suboxic porewater by the reduction of FeOOH at the oxic-suboxic redox boundary in sediments, and phosphorite nodule precipitated by the reaction of phosphate with Ca^（2＋） diffused from the overlying seawater. The platform-wide deposition of phosphorite nodules in the basal Niutitang Formation implies the bottom water might be suboxic or even oxic, at least sporadically, in Early Cambrian. We speculate that the intensified ocean circulation as evident with frequent occurrences of upwelling events might be the primary reason for the episodic oxidation of the Yangtze Platform in Early Cambrian.