Seasonal variability in multi-elemental ratios and δ18O in planktonic foraminifera from the Cariaco Basin, Venezuela

Multi-elemental ratios (Mg/Ca, Mg/Li, Li/Ca, B/Ca, U/Ca, P/Ca, Cd/Ca, and Zn/Ca) of four planktonic foraminiferal species (Globigerinoides ruber, Globigerinoides sacculifer, Orbulina universa, and Globorotalia menardii) have been measure on a Thermo Element 2 inductively coupled plasma mass spectrometer (ICP-MS) and δ18O measurements have been taken on a GV ISOPRIME stable isotope ratio mass spectrometer. The material is from biweekly sediment trap samples collected in the Cariaco Basin, Venezuela (10o30’ N, 65o31’ W) between May 2003 and May 2004. The data are compared to local hydrography and water column chemistry to evaluate each proxy’s applicability in reconstructing past ocean conditions. The oxygen isotope results are consistent with known depth habitats for all five species. The surface dwelling G. ruber displays the lowest values of -0.84 and -1.76‰. G. sacculifer which lives in the upper 50m, displays slightly higher δ18O (-0.55 - -1.39‰) and the deeper dwelling O. universa and G. menardii have the highest δ18O, predominately ranging from 0.0 to -1.0‰. The G. ruber δ18O range equates to a temperature range of approximately 4.5 oC, which is equivalent to seasonal SST range (24.5-29 oC). Temperature estimates derived from species specific equations indicate that G. ruber most accurately tracks SST throughout the year. The temperature proxies, Mg/Ca (mmol/mol) and Mg/Li (mol/mmol), also reflect these different depth habitats (G. ruber: 4.1 - 6.9, 0.3 - 0.5; G. sacculifer: 2.9 - 4.3, 0.2 - 0.4; G. menardii: 1.9 - 4.3, 0.1 - 0.3) except that O. universa has a relatively high concentration of magnesium (7.1 - 13.1, 0.8 - 1.6). With these proxies, G. sacculifer most accurately reflects SST for both Mg/Ca and Mg/Li. For Li/Ca (µmol/mol) G. ruber has the highest ratios (13.2 - 18.5) and O. universa has the lowest (7.1 - 11.6). All of the species show an inverse relationship between temperature and Li/Ca with G. ruber most accurately recording SST. The pH proxy, B/Ca (µmol/mol), displays clear depth stratification with G. ruber having the highest B/Ca (246 - 360) and G. menardii and O. universa the lowest (102 - 230), consistent with a decrease in pH with depth. However, the other pH proxy, U/Ca shows no inter-species variation with all species having U/Ca values between 8 and 27 nmol/mol, which suggests that U incorporation is controlled by additional factors. All of the species display higher average values of the nutrient proxies P/Ca (mmol/mol), Cd/Ca (µmol/mol), and Zn/Ca (µmol/mol) during the winter upwelling than during non-upwelling, which is consistent with the nutrient distributions in the water column. None of the proxies show a significant relationship with measured phosphate concentrations; however this may be a result of uniformly low phosphate concentrations in the mixed layer.