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1. The Brachiopod δ 11 B Record Across the Carboniferous‐Permian Climate Transition

   https://doi.org/10.1029/2019PA003838  

   Legett, S. A. ; Rasbury, E. T. ; Grossman, E. L. ; Hemming, N. G. ; Penman, D. E. ( September 2020 , Paleoceanography and Paleoclimatology)

   We present the δ¹¹B of well‐preserved brachiopod fossils coupled with geochemical modeling to examine how seawater boron responded to abrupt and dynamic climate changes in the Late Paleozoic. The Late Carboniferous, a time of major coal formation and glacioeustatic sea level changes, is characterized by relatively stable brachiopod δ¹¹B of 15–17‰, similar to values seen in modern brachiopods. Brachiopod δ¹¹B dropped by ~5‰ in the early Permian and then restabilized at a new value of 10‰ within a few million years. Mass balance models of seawater δ¹¹B reproduced the overall trends in our brachiopod data but failed to capture the large drop in δ¹¹B in the early Permian. Published seawater⁸⁷Sr/⁸⁶Sr and δ^44/40Ca data based on brachiopod shells also shift to lower values in the early Permian, suggesting a common control on all three seawater isotope systems. The Permian terrestrial record of evaporites and eolian deposits suggests a prolonged reduced delivery of dissolved weathering products to the ocean, accounting for the change in seawater⁸⁷Sr/⁸⁶Sr. This reduced weathering, in turn, led to increased atmospheric CO₂and lowered seawater pH, which may have significantly decreased major removal mechanisms for seawater calcium and boron leading to declines in both isotope systems. We propose that boron removal via coprecipitation in carbonates and adsorption onto clay minerals was significantly diminished due to a reduction in the availability of the borate aqueous species caused by lowered seawater pH.

    

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2. Uncovering the spatial heterogeneity of Ediacaran carbon cycling

   https://doi.org/10.1111/gbi.12222  

   Li, C. ; Hardisty, D. S. ; Luo, G. ; Huang, J. ; Algeo, T. J. ; Cheng, M. ; Shi, W. ; An, Z. ; Tong, J. ; Xie, S. ; et al ( December 2016 , Geobiology)

   Records of the Ediacaran carbon cycle (635–541 million years ago) include the Shuram excursion (SE), the largest negative carbonate carbon isotope excursion in Earth history (down to −12‰). The nature of this excursion remains enigmatic given the difficulties of interpreting a perceived extreme global decrease in the δ¹³C of seawater dissolved inorganic carbon. Here, we present carbonate and organic carbon isotope (δ¹³C_carband δ¹³C_org) records from the Ediacaran Doushantuo Formation along a proximal‐to‐distal transect across the Yangtze Platform of South China as a test of the spatial variation of theSE. Contrary to expectations, our results show that the magnitude and morphology of this excursion and its relationship with coexisting δ¹³C_orgare highly heterogeneous across the platform. Integrated geochemical, mineralogical, petrographic, and stratigraphic evidence indicates that theSEis a primary marine signature. Data compilations demonstrate that theSEwas also accompanied globally by parallel negative shifts of δ³⁴S of carbonate‐associated sulfate (CAS) and increased⁸⁷Sr/⁸⁶Sr ratio and coastalCASconcentration, suggesting elevated continental weathering and coastal marine sulfate concentration during theSE. In light of these observations, we propose a heterogeneous oxidation model to explain the high spatial heterogeneity of theSEand coexisting δ¹³C_orgrecords of the Doushantuo, with likely relevance to theSEin other regions. In this model, we infer continued marine redox stratification through theSEbut with increased availability of oxidants (e.g., O₂and sulfate) limited to marginal near‐surface marine environments. Oxidation of limited spatiotemporal extent provides a mechanism to drive heterogeneous oxidation of subsurface reduced carbon mostly in shelf areas. Regardless of the mechanism driving theSE, future models must consider the evidence for spatial heterogeneity in δ¹³C presented in this study.

    

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3. Dipole Response of Millennial Variability in Tropical South American Precipitation and δ18Op during the Last Deglaciation. Part I: Rainfall Response

   https://doi.org/10.1175/JCLI-D-22-0172.1  

   Bao, Yuntao ; Liu, Zhengyu ; He, Chengfei ( July 2023 , Journal of Climate)

   Oxygen isotope speleothems have been widely used to infer past climate changes over tropical South America (TSA). However, the spatial patterns of the millennial precipitation and precipitationδ¹⁸O (δ¹⁸O_p) response have remained controversial, and their response mechanisms are unclear. In particular, it is not clear whether the regional precipitation represents the intensity of the millennial South American summer monsoon (SASM). Here, we study the TSA hydroclimate variability during the last deglaciation (20–11 ka ago) by combining transient simulations of an isotope-enabled Community Earth System Model (iCESM) and the speleothem records over the lowland TSA. Our model reasonably simulates the deglacial evolution of hydroclimate variables and water isotopes over the TSA, albeit underestimating the amplitude of variability. North Atlantic meltwater discharge is the leading factor driving the TSA’s millennial hydroclimate variability. The spatial pattern of both precipitation andδ¹⁸O_pshow a northwest–southeast dipole associated with the meridional migration of the intertropical convergence zone, instead of a continental-wide coherent change as inferred in many previous works on speleothem records. The dipole response is supported by multisource paleoclimate proxies. In response to increased meltwater forcing, the SASM weakened (characterized by a decreased low-level easterly wind) and consequently reduced rainfall in the western Amazon and increased rainfall in eastern Brazil. A similar dipole response is also generated by insolation, ice sheets, and greenhouse gases, suggesting an inherent stability of the spatial characteristics of the SASM regardless of the external forcing and time scales. Finally, we discuss the potential reasons for the model–proxy discrepancy and pose the necessity to build more paleoclimate proxy data in central-western Amazon.

   We want to reconcile the controversy on whether there is a coherent or heterogeneous response in millennial hydroclimate over tropical South America and to clearly understand the forcing mechanisms behind it. Our isotope-enabled transient simulations fill the gap in speleothem reconstructions to capture a complete picture of millennial precipitation/δ¹⁸O_pand monsoon intensity change. We highlight a heterogeneous dipole response in precipitation andδ¹⁸O_pon millennial and orbital time scales. Increased meltwater discharge shifts ITCZ southward and favors a wet condition in coastal Brazil. Meanwhile, the low-level easterly and the summer monsoon intensity reduced, causing a dry condition in the central-western Amazon. However, the millennial variability of hydroclimate response is underestimated in our model, together with the lack of direct paleoclimate proxies in the central-west Amazon, complicating the interpretation of changes in specific paleoclimate events and posing a challenge to constraining the spatial range of the dipole. Therefore, we emphasize the necessity to increase the source of proxies, enhance proxy interpretations, and improve climate model performance in the future.

    

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4. Ge and Si Isotope Behavior During Intense Tropical Weathering and Ecosystem Cycling

   https://doi.org/10.1029/2019GB006522  

   Baronas, J. Jotautas ; West, A. Joshua ; Burton, Kevin W. ; Hammond, Douglas E. ; Opfergelt, Sophie ; Pogge von Strandmann, Philip A. E. ; James, Rachael H. ; Rouxel, Olivier J. ( August 2020 , Global Biogeochemical Cycles)

   Chemical weathering of volcanic rocks in warm and humid climates contributes disproportionately to global solute fluxes. Geochemical signatures of solutes and solids formed during this process can help quantify and reconstruct weathering intensity in the past. Here, we measured silicon (Si) and germanium (Ge) isotope ratios of the soils, clays, and fluids from a tropical lowland rainforest in Costa Rica. The bulk topsoil is intensely weathered and isotopically light (mean ± 1σ:δ³⁰Si = −2.1 ± 0.3‰,δ⁷⁴Ge = −0.13 ± 0.12‰) compared to the parent rock (δ³⁰Si = −0.11 ± 0.05‰,δ⁷⁴Ge = 0.59 ± 0.07‰). Neoforming clays have even lower values (δ³⁰Si = −2.5 ± 0.2‰,δ⁷⁴Ge = −0.16 ± 0.09‰), demonstrating a whole‐system isotopic shift in extremely weathered systems. The lowland streams represent mixing of dilute local fluids (δ³⁰Si = 0.2 − 0.6‰,δ⁷⁴Ge = 2.2 − 2.6‰) with solute‐rich interbasin groundwater (δ³⁰Si = 1.0 ± 0.2‰,δ⁷⁴Ge = 4.0‰). Using a Ge‐Si isotope mass balance model, we calculate that91 ± 9% of Ge released via weathering of lowland soils is sequestered by neoforming clays,9 ± 9% by vegetation, and only0.2 ± 0.2% remains dissolved. Vegetation plays an important role in the Si cycle, directly sequestering39 ± 14% of released Si and enhancing clay neoformation in surface soils via the addition of amorphous phytolith silica. Globally, volcanic soilδ⁷⁴Ge closely tracks the depletion of Ge by chemical weathering (τ_Ge), whereasδ³⁰Si and Ge/Si both reflect the loss of Si (τ_Si). Because of the different chemical mobilities of Ge and Si, aδ⁷⁴Ge‐δ³⁰Si multiproxy system is sensitive to a wider range of weathering intensities than each isotopic system in isolation.

    

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5. Potassium isotopic compositions of enstatite meteorites

   https://doi.org/10.1111/maps.13358  

   Zhao, Chen ; Lodders, Katharina ; Bloom, Hannah ; Chen, Heng ; Tian, Zhen ; Koefoed, Piers ; Pető, Mária K. ; Wang ( July 2019 , Meteoritics & Planetary Science)

   Enstatite chondrites and aubrites are meteorites that show the closest similarities to the Earth in many isotope systems that undergo mass‐independent and mass‐dependent isotopic fractionations. Due to the analytical challenges to obtain high‐precision K isotopic compositions in the past, potential differences in K isotopic compositions between enstatite meteorites and the Earth remained uncertain. We report the first high‐precision K isotopic compositions of eight enstatite chondrites and four aubrites and find that there is a significant variation of K isotopic compositions among enstatite meteorites (from −2.34‰ to −0.18‰). However, K isotopic compositions of nearly all enstatite meteorites scatter around the bulk silicate earth (BSE) value. The average K isotopic composition of the eight enstatite chondrites (−0.47 ± 0.57‰) is indistinguishable from theBSEvalue (−0.48 ± 0.03‰), thus further corroborating the isotopic similarity between Earth's building blocks and enstatite meteorite precursors. We found no correlation of K isotopic compositions with the chemical groups, petrological types, shock degrees, and terrestrial weathering conditions; however, the variation of K isotopes among enstatite meteorite can be attributed to the parent‐body processing. Our sample of the main‐group aubriteMIL13004 is exceptional and has an extremely light K isotopic composition (δ⁴¹K = −2.34 ± 0.12‰). We attribute this unique K isotopic feature to the presence of abundant djerfisherite inclusions in our sample because this K‐bearing sulfide mineral is predicted to be enriched in³⁹K during equilibrium exchange with silicates.

    

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