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The linkage between the variation of the seawater Mg budget and the long-term carbon cycle can be elucidated by seawater Mg isotope composition (δ26Mg). However, obtaining primary seawater δ26Mg signatures from marine archives is challenging due to the widespread alteration of diagenesis. Aragonite, a common primary marine carbonate, can effectively record seawater δ26Mg but is prone to alteration and transformation into calcite during early diagenesis. Therefore, a comprehensive understanding of Mg isotope behavior during the aragonite–calcite transition is essential to enhance the applicability of aragonite δ26Mg. In this study, we investigate the variation of aragonite δ26Mg during diagenesis with a limited supply of Mg by conducting a series of well-controlled aragonite–calcite transition experiments in a closed system. The experimental conditions encompass temperatures of 60 and 90 °C, the presence of Ca and Na in the solution, varying Na concentrations, as well as the presence of calcite seed. Results demonstrate that the significant decrease of bulk carbonate δ26Mg is accompanied by a substantial amount of Mg released into the solution during the aragonite–calcite transition, and the amount of released Mg is controlled by fluid chemistry via altering Mg partitioning in calcite. Furthermore, Mg isotope fractionation during calcite precipitation is influenced by temperature, ionic strength, and the presence of calcite seed, while kinetics played a negligible role in our experiments. Combined with previous experiments, the temperature-dependent Mg isotope fractionation during calcite precipitation in unseeded experiments is Δ26Mg cal-sol = (−0.13 ± 0.06) × 106/T2 – (0.47 ± 0.68). This fractionation is systematically higher than that of seeded experiments by 0.3–0.6 ‰ from 15 to 90 °C and can mainly be attributed to differences in surface free energy between homogeneous and heterogeneous calcite nucleation. These findings offer fundamental understandings of the Mg isotope behavior during the aragonite–calcite transformation, providing useful insights for interpreting the variation of δ26Mg in experimental and natural carbonates and facilitating ancient seawater δ26Mg reconstruction. [ABSTRACT FROM AUTHOR]

Mg isotopic composition of river water is dominantly controlled by the dissolution of both silicate and carbonate sources and a series of biogeochemical processes. However, the relative importance of source and isotopic fractionation control at basin/global scale is poorly constrained. This study presents the Mg isotopic composition of river water and suspended load in river draining silicate rocks in the southeastern coastal region of China. The fractionation effect of silicate weathering on Mg isotopes is documented in both dissolved and solid phases. Mg isotopic composition of rivers draining silicate rocks exhibit ∼0.3‰ δ26Mg difference, the release of Mg from Mg‐rich minerals and formation of clays are the dominant processes controlling Mg isotopic composition of river water. The variation of Mg isotopic compositions of suspended load is closely related to the species of secondary clays (illite and chlorite); the fractionation direction during illite and chlorite formation contrasts, isotopically heavy Mg preferentially incorporates into illite while light Mg incorporates into chlorite. Furthermore, the negative correlation between 1/Mg and Mg isotopic compositions of river water indicates the Mg re‐distribution and isotope fractionation between weathering solutions and secondary clays during silicate weathering. Such isotope fractionation‐induced Mg isotope variations could be employed to estimate the contribution of Mg from silicate weathering at basin/continental scale. Key Points: The δ26Mg values of Southeast Coastal Rivers draining silicate rocks exhibit ∼0.3% difference due to isotope fractionationThere is a clay control on δ26Mg values of suspended loadThe Mg isotope fractionation is coupled with Mg re‐distribution during silicate weathering [ABSTRACT FROM AUTHOR]

Abstract Mg isotopic composition of river water is dominantly controlled by the dissolution of both silicate and carbonate sources and a series of biogeochemical processes. However, the relative importance of source and isotopic fractionation control at basin/global scale is poorly constrained. This study presents the Mg isotopic composition of river water and suspended load in river draining silicate rocks in the southeastern coastal region of China. The fractionation effect of silicate weathering on Mg isotopes is documented in both dissolved and solid phases. Mg isotopic composition of rivers draining silicate rocks exhibit ∼0.3‰ δ26Mg difference, the release of Mg from Mg‐rich minerals and formation of clays are the dominant processes controlling Mg isotopic composition of river water. The variation of Mg isotopic compositions of suspended load is closely related to the species of secondary clays (illite and chlorite); the fractionation direction during illite and chlorite formation contrasts, isotopically heavy Mg preferentially incorporates into illite while light Mg incorporates into chlorite. Furthermore, the negative correlation between 1/Mg and Mg isotopic compositions of river water indicates the Mg re‐distribution and isotope fractionation between weathering solutions and secondary clays during silicate weathering. Such isotope fractionation‐induced Mg isotope variations could be employed to estimate the contribution of Mg from silicate weathering at basin/continental scale.

Data on temporal variability in Mg isotope ratios of atmospheric deposition and runoff are critical for decreasing the uncertainty associated with construction of isotope mass balances in headwater catchments, and statistical evaluation of isotope differences among Mg pools and fluxes. Such evaluations, in turn, are needed to distinguish between biotic and abiotic contributions to Mg2+ in catchment runoff. We report the first annual time‐series of δ26Mg values simultaneously determined for rainfall, canopy throughfall, soil water and runoff. The studied 55‐ha catchment, situated in western Czech Republic, is underlain by Mg‐rich amphibolite and covered by mature spruce stands. Between 1970 and 1996, the site received extremely high amounts of acid deposition and fly ash form nearby coal‐burning power plants. The δ26Mg values of open‐area precipitation (median of −0.79‰) at our study site were statistically indistinguishable from the δ26Mg values of throughfall (−0.73‰), but significantly different from the δ26Mg values of soil water (−0.55‰) and runoff (−0.55‰). The range of δ26Mg values during the observation period decreased in the order: open‐area precipitation (0.57‰) > throughfall (0.27‰) > runoff (0.21‰) > soil water (0.16‰). The decreasing variability in δ26Mg values of Mg2+ from precipitation to soil water and runoff reflected an increasing homogenization of atmospheric Mg in the catchment and its mixing with geogenic Mg. In addition to atmospheric Mg, runoff also contained Mg mobilized from the three major solid Mg pools, bedrock (δ26Mg of −0.32‰), soil (−0.28‰), and vegetation (−0.31‰). The drought of summer 2019 did not affect the nearly constant δ26Mg value of runoff. Collectively, our data show that within‐catchment processes buffer the Mg isotope variability of the atmospheric input. [ABSTRACT FROM AUTHOR]

To investigate the behavior of Mg isotopes during low-temperature alteration of oceanic crust and to further understand its role in the global Mg cycle, we measured the Mg isotopic compositions ( 25 Mg/ 24 Mg and 26 Mg/ 24 Mg) of a set of samples of altered oceanic crust (AOC) recovered from the Ocean Drilling Program Hole 801C, the reference site for old crust (∼170 Ma) subducting in the Pacific. The measured δ 26 Mg values range from −1.70‰ to 0.21‰, deviating from that of pristine oceanic basalts (−0.25 ± 0.07‰). Composite samples of volcanoclastic breccia that have experienced relatively intense alteration have larger variation in δ 26 Mg values (−1.01‰ to 0.15‰) than composite samples of massive basaltic flows (−0.53‰ to −0.04‰), indicating significant Mg isotope fractionation during low-temperature alteration of the oceanic crust. Moreover, the upper off-axis basement has on average lower δ 26 Mg values (−1.70‰ to −0.04‰) than the lower on-axis basement (−0.16‰ to 0.21‰). These findings, combined with the co-variations between MgO content and FeO ∗ /CaO ratio and between δ 26 Mg and FeO ∗ /CaO ratio, suggest that formation of Mg-bearing minerals (i.e., saponite and calcite) during low-temperature alteration of the oceanic crust accounts for the highly variable δ 26 Mg of AOC. Early formation of saponite under anoxic condition preferentially takes up heavy Mg isotopes and accounts for Mg enrichment and relatively high δ 26 Mg in the on-axis basement. Subsequent precipitation of carbonates results in the dilution of Mg and relatively low δ 26 Mg in the off-axis basement. In addition, accumulation of carbonate-rich interflow sediments in the upper basement may contribute further to the low δ 26 Mg. A weighted average δ 26 Mg value of 0.00 ± 0.09‰ is estimated for the AOC at Site 801, implying that low-temperature alteration of oceanic crust drives the ocean to a lighter Mg isotopic composition, and thus requires additional carbonate precipitation to maintain a steady-state Mg isotopic composition of seawater. A mass balance calculation suggests that the Mg output flux due to low-temperature alteration of the oceanic crust equals ∼12% of the annual Mg riverine input, indicating that AOC is a significant sink of Mg in seawater. Our study further highlights that recycling of AOC with highly variable δ 26 Mg along with overlying marine sediments into the mantle through subduction may generate Mg isotopic heterogeneity in the mantle at small scales. [ABSTRACT FROM AUTHOR]

In order to assess the effects of critical zone processes on Mg concentrations and isotopic signatures of tropical streams, we studied a well constrained, highly weathered andesitic volcaniclastic catchment in the Luquillo Critical Zone Observatory, Puerto Rico. Our results indicate that dissolved Mg concentrations and isotope ratios in the regolith pore water are mainly controlled by rain input, with weathering inputs being more important at sites with thinner regolith (2.7–0.9 m deep) and at depth (>8 m) on a thick ridgetop regolith (∼10 m). In addition to mixing of precipitation and weathering-sourced Mg, an isotopic fractionation process is taking place between dissolved Mg and the regolith, likely during dissolution or recrystallisation of Fe(III)-(hydro)oxides under alternating redox conditions. Bulk regolith is isotopically heavier than both the bedrock and the exchangeable fraction (δ 26 Mg regolith-bedrock = +0.03 to +0.47‰), consistent with the preferential incorporation of heavy 26 Mg into secondary minerals with some exchange of sorbed Mg with isotopically lighter pore water. Magnesium concentrations in the stream show a typical dilution behaviour during a storm event, but the [Mg] – δ 26 Mg pattern cannot be explained by mixing of rain and pore water; the data are best explained by a steady-state fractionation model with α = 1.00115. During baseflow the stream has δ 26 Mg = +0.01‰, higher than any of the water samples or the bedrock. In-situ analysis of the Mg isotopic composition of bedrock minerals points at the dissolution of Mg-rich chlorite (δ 26 Mg = +0.19‰) as the most likely source of this isotopically heavy Mg, with mass balance calculations indicating chlorite dissolution is also the main source of Mg to the stream. Overall, our study highlights the importance of atmospheric input of nutrients to the vegetation in tropical areas covered by thick, highly leached regolith, whereas the Mg flux and Mg isotopic signature of watershed exports are dominated by bedrock dissolution delivered to the stream through deeper, usually un-sampled critical zone pathways. [ABSTRACT FROM AUTHOR]