Shallow-water carbonate sediments constitute the bulk of sedimentary carbonates in the geologic record and are widely used archives of Earth's chemical and climatic history. One of the main limitations in interpreting the geochemistry of ancient carbonate sediments is the potential for post-depositional diagenetic alteration. In this study, we use paired measurements of calcium (44 Ca/ 40 Ca) and magnesium (26 Mg/ 24 Mg) isotope ratios in sedimentary carbonates and associated pore-fluids as a tool to understand the mineralogical and diagenetic history of Neogene shallow-water carbonate sediments from the Bahamas and southwest Australia. We find that the Ca and Mg isotopic composition of bulk carbonate sediments at these sites exhibits systematic stratigraphic variability that is related to both mineralogy and early marine diagenesis. The observed variability in bulk sediment Ca isotopes is best explained by changes in the extent of fluid-dominated early marine diagenesis in both platform and slope sediments. Our results indicate that this process, together with variations in carbonate mineralogy (aragonite, calcite, and dolomite), likely plays a fundamental and underappreciated role in determining the regional and global stratigraphic expressions of geochemical tracers (d 13 C, d 18 O, major, minor, and trace elements) in shallow water carbonate sediments in the geologic record.

Ongoing (1996-present) volcanic unrest near South Sister, Oregon, is accompanied by a striking set of hydrothermal anomalies, including elevated temperatures, elevated major ion concentrations, and 3 He/ 4 He ratios as large as 8.6 R A in slightly thermal springs. These observations prompted the US Geological Survey to begin a systematic hydrothermal-monitoring effort encompassing 25 sites and 10 of the highest-risk volcanoes in the Cascade volcanic arc, from Mount Baker near the Canadian border to Lassen Peak in northern California. A concerted effort was made to develop hourly, multiyear records of temperature and/or hydrothermal solute flux, suitable for retrospective comparison with other continuous geophysical monitoring data. Targets included summit fumarole groups and springs/streams that show clear evidence of magmatic influence in the form of high 3 He/ 4 He ratios and/or anomalous fluxes of magmatic CO 2 or heat. As of 2009-2012, summit fumarole temperatures in the Cascade Range were generally near or below the local pure water boiling point; the maximum observed superheat was <2.5°C at Mount Baker. Variability in ground temperature records from the summit fumarole sites is temperature-dependent, with the hottest sites tending to show less variability. Seasonal variability in the hydrothermal solute flux from magmatically influenced springs varied from essentially undetectable to a factor of 5-10. This range of observed behavior owes mainly to the local climate regime, with strongly snowmelt-influenced springs and streams exhibiting more variability. As of the end of the 2012 field season, there had been 87 occurrences of local seismic energy densities approximately ≥ 0.001 J/m 3 during periods of hourly record. Hydrothermal responses to these small seismic stimuli were generally undetectable or ambiguous. Evaluation of multiyear to multidecadal trends indicates that whereas the hydrothermal system at Mount St. Helens is still fast-evolving in response to the 1980-present eruptive cycle, there is no clear evidence of ongoing long-term trends in hydrothermal activity at other Cascade Range volcanoes that have been active or restless during the past century (Baker, South Sister, and Lassen). Experience gained during the Cascade Range hydrothermal-monitoring experiment informs ongoing efforts to capture entire unrest cycles at more active but generally less accessible volcanoes such as those in the Aleutian arc.

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