Mg/Ca ratios in planktonic foraminifera

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.

(Table 4) Seasonal variation of sea spray sodium concentrations during 2004-2007 at Concordia Station, Antarctica

From November 2004 to December 2007, size-segregated aerosol samples were collected all-year-round at Dome C (East Antarctica) by using PM10 and PM2.5 samplers, and multi-stage impactors. The data set obtained from the chemical analysis provided the longest and the most time-resolved record of sea spray aerosol (sea salt Na+) in inner Antarctica. Sea spray showed a sharp seasonal pattern. The highest values measured in winter (Apr-Nov) were about ten times larger than in summer (Dec-Mar). For the first time, a size-distribution seasonal pattern was also shown: in winter, sea spray particles are mainly submicrometric, while their summer size-mode is around 1-2 µm. Meteorological analysis on a synoptic scale allowed the definition of atmospheric conditions leading sea spray to Dome C. An extreme-value approach along with specific environmental based criteria was taken to yield stronger fingerprints linking atmospheric circulation (means and anomalies) to extreme sea spray events. Air mass back-trajectory analyses for some high sea spray events allowed the identification of two major air mass pathways, reflecting different size distributions: micrometric fractions for transport from the closer Indian-Pacific sector, and sub-micrometric particles for longer trajectories over the Antarctic Plateau. The seasonal pattern of the SO4**2- /Na+ ratio enabled the identification of few events depleted in sulphate, with respect to the seawater composition. By using methanesulphonic acid (MSA) profile to evaluate the biogenic SO4**2- contribution, a more reliable sea salt sulphate was calculated. In this way, few events (mainly in April and in September) were identified originating probably from the "frost flower" source. A comparison with daily-collected superficial snow samples revealed that there is a temporal shift between aerosol and snow sea spray trends. This feature could imply a more complex deposition processes of sea spray, involving significant contribution of wet and diamond dust deposition, but further work has to be carried out to rule out the effect of wind re-distribution and to have more statistic significance.