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The geochemistry of tropical coral skeletons is widely used in paleoclimate reconstructions. However, sub‐aerially exposed corals may be affected by diagenesis, altering the aragonite skeleton through partial dissolution, or infilling of secondary minerals like calcite. We analyzed the impact of intra‐skeletal calcite on the geochemistry (δ¹⁸O, Sr/Ca, Mg/Ca, Li/Mg, Li/Ca, U/Ca, B/Ca, Ba/Ca, and Mn/Ca) of a sub‐aerially exposedPoritessp. coral. Each micro‐milled coral sample was split into two aliquots for geochemistry and X‐ray diffraction (XRD) analysis to quantify the direct impact of calcite on geochemistry. We modified the sample loading technique for XRD to detect low calcite levels (1%–2%; total uncertainty = 0.33%, 2σ) in small samples (∼7.5 mg). Calcite content ranged from 0% to 12.5%, with higher percentages coinciding with larger geochemical offsets. Sr/Ca, Li/Mg, Li/Ca, and δ¹⁸O‐derived sea‐surface temperature (SST) anomalies per 1% calcite were +0.43°C, +0.24°C, +0.11°C, and +0.008°C, respectively. A 3.6% calcite produces a Sr/Ca‐SST signal commensurate with local SST seasonality (∼1.5°C), which we propose as the cut‐off level for screening calcite diagenesis in paleo‐temperature reconstructions. Inclusion of intra‐skeletal calcite decreases B/Ca, Ba/Ca, and U/Ca values, and increases Mg/Ca values, and can therefore impact reconstructions of paleoclimate and the carbonate chemistry of the semi‐isolated calcifying fluid in corals. This study emphasizes the importance of quantifying fine‐scale calcite diagenesis to identify coral preservation levels and assure robust paleoclimate reconstructions.

Corals nucleate and grow aragonite crystals, organizing them into intricate skeletal structures that ultimately build the world’s coral reefs. Crystallography and chemistry have profound influence on the material properties of these skeletal building blocks, yet gaps remain in our knowledge about coral aragonite on the atomic scale. Across a broad diversity of shallow-water and deep-sea scleractinian corals from vastly different environments, coral aragonites are remarkably similar to one another, confirming that corals exert control on the carbonate chemistry of the calcifying space relative to the surrounding seawater. Nuances in coral aragonite structures relate most closely to trace element chemistry and aragonite saturation state, suggesting the primary controls on aragonite structure are ionic strength and trace element chemistry, with growth rate playing a secondary role. We also show how coral aragonites are crystallographically indistinguishable from synthetic abiogenic aragonite analogs precipitated from seawater under conditions mimicking coral calcifying fluid. In contrast, coral aragonites are distinct from geologically formed aragonites, a synthetic aragonite precipitated from a freshwater solution, and mollusk aragonites. Crystallographic signatures have future applications in understanding the material properties of coral aragonite and predicting the persistence of coral reefs in a rapidly changing ocean.

Metal sulfide minerals, including mercury sulfides (HgS), are widespread in hydrothermal vent systems where sulfur‐oxidizing microbes are prevalent. Questions remain as to the impact of mineral composition and structure on sulfur‐oxidizing microbial populations at deep‐sea hydrothermal vents, including the possible role of microbial activity in remobilizing elemental Hg from HgS. In the present study, metal sulfides varying in metal composition, structure, and surface area were incubated for 13 days on and near a diffuse‐flow hydrothermal vent at 9°50′N on the East Pacific Rise. Upon retrieval, incubated minerals were examined by scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (SEM‐EDS), X‐ray diffraction (XRD), and epifluorescence microscopy (EFM). DNA was extracted from mineral samples, and the 16S ribosomal RNA gene sequenced to characterize colonizing microbes. Sulfur‐oxidizing genera common to newly exposed surfaces (Sulfurimonas, Sulfurovum, and Arcobacter) were present on all samples. Differences in their relative abundance between and within incubation sites point to constraining effects of the immediate environment and the minerals themselves. Greater variability in colonizing community composition on off‐vent samples suggests that the bioavailability of mineral‐derived sulfide (as influenced by surface area, crystal structure, and reactivity) exerted greater control on microbial colonization in the ambient environment than in the vent environment, where dissolved sulfide is more abundant. The availability of mineral‐derived sulfide as an electron donor may thus be a key control on the activity and proliferation of deep‐sea chemosynthetic communities, and this interpretation supports the potential for microbial dissolution of HgS at hydrothermal vents.

In the marine environment, the reactive oxygen species (ROS) superoxide is produced through a diverse array of light‐dependent and light‐independent reactions, the latter of which is thought to be primarily controlled by microorganisms. Marine superoxide production influences organic matter remineralization, metal redox cycling, and dissolved oxygen concentrations, yet the relative contributions of different sources to total superoxide production remain poorly constrained. Here we investigate the production, steady‐state concentration, and particle‐associated nature of light‐independent superoxide in productive waters off the northeast coast of North America. We find exceptionally high levels of light‐independent superoxide in the marine water column, with concentrations ranging from 10 pM to in excess of 2,000 pM. The highest superoxide concentrations were particle associated in surface seawater and in aphotic seawater collected meters off the seafloor. Filtration of seawater overlying the continental shelf lowered the light‐independent, steady‐state superoxide concentration by an average of 84%. We identify eukaryotic phytoplankton as the dominant particle‐associated source of superoxide to these coastal waters. We contrast these measurements with those collected at an off‐shelf station, where superoxide concentrations did not exceed 100 pM, and particles account for an average of 40% of the steady‐state superoxide concentration. This study demonstrates the primary role of particles in the production of superoxide in seawater overlying the continental shelf and highlights the importance of light‐independent, dissolved‐phase reactions in marine ROS production.