Description: The primary Mg/Ca ratio of foraminiferal shells is a potentially valuable paleoproxy for sea surface temperature (SST) reconstructions. However, the reliable extraction of this ratio from sedimentary calcite assumes that we can overcome artifacts related to foraminiferal ecology and partial dissolution, as well as contamination by secondary calcite and clay. The standard batch method for Mg/Ca analysis involves cracking, sonicating, and rinsing the tests to remove clay, followed by chemical cleaning, and finally acid-digestion and single-point measurement. This laborious procedure often results in substantial loss of sample (typically 30-60%). We find that even the earliest steps of this procedure can fractionate Mg from Ca, thus biasing the result toward a more variable and often anomalously low Mg/Ca ratio. Moreover, the more rigorous the cleaning, the more calcite is lost, and the more likely it becomes that any residual clay that has not been removed by physical cleaning will increase the ratio. These potentially significant sources of error can be overcome with a flow-through (FT) sequential leaching method that makes time- and labor-intensive pretreatments unnecessary. When combined with time-resolved analysis (FT-TRA) flow-through, performed with a gradually increasing and highly regulated acid strength, produces continuous records of Mg, Sr, Al, and Ca concentrations in the leachate sorted by dissolution susceptibility of the reacting material. Flow-through separates secondary calcite from less susceptible biogenic calcite and clay, and further resolves the biogenic component into primary and more resistant fractions. FT-TRA reliably separates secondary calcite (which is not representative of original life habitats) from the more resistant biogenic calcite (the desired signal) and clay (a contaminant of high Mg/Ca, which also contains Al), and further resolves the biogenic component into primary and more resistant fractions that may reflect habitat or other changes during ontogeny. We find that the most susceptible fraction of biogenic calcite in surface dwelling foraminifera gives the most accurate value for SST and therefore best represents primary calcite. Sequential dissolution curves can be used to correct the primary Mg/Ca ratio for clay, if necessary. However, the temporal separation of calcite from clay in FT-TRA is so complete that this correction is typically 〈=2%, even in clay-rich sediments. Unlike hands-on batch methods, that are difficult to reproduce exactly, flow-through lends itself to automation, providing precise replication of treatment for every sample. Our automated flow-through system can process 22 samples, two system blanks, and 48 mixed standards in 〈12 hours of unattended operation. FT-TRA thus represents a faster, cheaper, and better way to determine Mg/Ca ratios in foraminiferal calcite.

Description: We integrate micropaleontological and geochemical records (benthic stable isotopes, neodymium isotopes, benthic foraminiferal abundances and XRF-scanner derived elemental data) from well-dated Pacific Ocean successions(15-12.7Ma) to monitor circulation changes during the middle Miocene transition into a colder climate mode with permanent Antarctic ice cover. Together with previously published records, our results show improvement in deepwater ventilation and strengthening of the meridional overturning circulation following major ice expansion at 13.9 Ma. Neodymium isotope data reveal, however, that the provenance of intermediate and deepwater masses did not change markedly between 15 and 12.7 Ma. We attribute the increased d13C gradient between Pacific deep and intermediate water masses between 13.6 and 12.7 Ma to more vigorous entrainment of PacificCentral Water into the wind-driven ocean circulation due to enhanced production of intermediate and deep waters in the Southern Ocean. Prominent 100 kyr ventilation cycles after 13.9 Ma reveal that the deep Pacific remained poorly ventilated during warmer intervals at high eccentricity, whereas colder periods (low eccentricity) were characterized by a more vigorous meridional overturning circulation with enhanced carbonate preservation. The long-term d13C decline in Pacific intermediate and deepwater sites between 13.5 and 12.7 Ma reflects a global trend, probably related to a re-adjustment response of the global carbon cycle following the last 400 kyr carbon maximum (CM6) of the ''Monterey Excursion''.