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A significant proportion of marine calcium carbonate sediments are comprised of metastable minerals that are susceptible to diagenetic alterations during burial. These reactions can reset the geochemical signature of sediments and pore fluids and influence elemental cycling in the ocean. However, the timing and mechanisms by which these reactions take place are poorly constrained. This study uses cores drilled on the slope of the Great Bahama Bank to provide quantitative constraints on important diagenetic reactions; namely respiration-driven dissolution, authigenic carbonate mineral formation, and conversion of aragonite to low Mg calcite (LMC). We perform detailed mineralogical characterization using newly acquired, high resolution X-ray diffraction (XRD) data and over 1000 reanalyzed XRD scans, characterize sediments texturally and elementally using electron microprobe data, calculate pore fluid saturation state with respect to aragonite using a Pitzer ion interaction approach, and use pore fluid chemistry and experimental distribution coefficients to predict authigenic carbonate compositions. These data suggest that aerobic organic matter oxidation, enabled by the advection of oxygenated seawater throughout the upper ∼ 30 m interval of sediment, causes undersaturation and thus dissolution of biogenic high Mg calcite (HMC) and aragonite. Deeper, anaerobic organic matter oxidation takes over and causes supersaturation, promoting authigenic precipitation in the form of HMC, which in turn decreases pore fluid Mg/Ca and promotes aragonite conversion to LMC. One novel aspect of this study is the identification of three types of calcites using the newly acquired XRD and electron microprobe data. Based on their unique crystallographic characteristics and chemical compositions, these types of calcites are interpreted to represent pelagic biogenic LMC, bank-derived biogenic HMC, and authigenic HMC precipitated from pore fluids. Notably, the composition of the authigenic calcite matches that predicted to precipitate from pore fluids using an empirical Mg partition coefficient in calcite. Calcites that form authigenically and from aragonite via replacement are suggested to recrystallize with burial as evidenced by the decrease in Mg content and micro-strain. This process-based geochemical framework assigns diagenetic processes to a specific depth window within the sediment column and paves the way for a mechanistic understanding of carbonate diagenesis, one that is rooted in thermodynamic and kinetic bases. [ABSTRACT FROM AUTHOR]

The balance between alkalinity generation by carbonate and silicate weathering and sulfuric acid generation by sulfide weathering controls the effect of weathering on atmospheric p CO 2 over geologic timescales. How this balance varies across environmental gradients remains poorly constrained. Here, we analyze this balance across an erosional gradient of two orders of magnitude in the Three Rivers (Yangtze, Mekong, and Salween Rivers) Headwater Region (TRHR), eastern Qinghai-Tibet Plateau (QTP). By employing major element chemistry and multiple isotopes (δ34S SO 4 , δ18O SO 4 , and δ18O H 2 O) coupled with forward and inverse approaches, we unmix contributions of silicates, carbonates, evaporites, and sulfides to the total weathering budget. Across the TRHR, riverine SO 4 2– is derived mainly from a mixture of an evaporite source with uniform values of δ34S SO 4 and δ18O SO 4 , and a sulfide source that contributes highly variable values of δ34S (−12.2 ‰ to +4.1 ‰) and δ18O (−17.7 ‰ to −1.6 ‰). Contributions of sulfide oxidation to riverine SO 4 2– vary from 16 % to 94 %, and sulfuric acid consumes 6 % to 63 % of the alkalinity produced by weathering. The fractions of weathering alkalinity derived from carbonate weathering range from 36 % to 98 % relative to silicate weathering. The combination of silicate, carbonate, and sulfide weathering suggests that the instantaneous weathering fluxes of most sampled catchments in the TRHR act as a sink of atmospheric CO 2 over timescales shorter than marine carbonate burial (∼104 years), but as a carbon source over timescales longer than carbonate burial and shorter than sulfide burial (∼107 years). The spatial variability of the balance between alkalinity and acid generation, and, thus, the relationship between chemical weathering and atmospheric p CO 2 , are largely dependent on lithology. However, within comparable lithologic settings, sulfide and carbonate weathering rates rise with increasing erosion, whereas silicate weathering rates remain constant. Consequently, plateau weathering shifts from a sink to a source of atmospheric CO 2 with increasing erosion. These findings suggest that sulfide weathering is more sensitive to erosion than carbonate and silicate weathering, and that it could play an important role in the long-term carbon cycle during mountain building. [ABSTRACT FROM AUTHOR]