Laser ablation data of benthic foraminifera from surface sediments collected from the muddy intertidal flats near Dorum, Northwestern Germany in Autumn 2008

Biological activity introduces variability in element incorporation during calcification and thereby decreases the precision and accuracy when using foraminifera as geochemical proxies in paleoceanography. This so-called 'vital effect' consists of organismal and environmental components. Whereas organismal effects include uptake of ions from seawater and subsequent processing upon calcification, environmental effects include migration- and seasonality-induced differences. Triggering asexual reproduction and culturing juveniles of the benthic foraminifer Ammonia tepida under constant, controlled conditions allow environmental and genetic variability to be removed and the effect of cell-physiological controls on element incorporation to be quantified. Three groups of clones were cultured under constant conditions while determining their growth rates, size-normalized weights and single-chamber Mg/Ca and Sr/Ca using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Results show no detectable ontogenetic control on the incorporation of these elements in the species studied here. Despite constant culturing conditions, Mg/Ca varies by a factor of similar to 4 within an individual foraminifer while intra-individual Sr/Ca varies by only a factor of 1.6. Differences between clone groups were similar to the intra-clone group variability in element composition, suggesting that any genetic differences between the clone-groups studied here do not affect trace element partitioning. Instead, variability in Mg/Ca appears to be inherent to the process of bio-calcification itself. The variability in Mg/Ca between chambers shows that measurements of at least 6 different chambers are required to determine the mean Mg/Ca value for a cultured foraminiferal test with a precision of <= 10%

Summary of boron isotope and Mg/Ca data

Biological productivity and carbon export in the equatorial Atlantic are thought to have been dramatically higher during the last glacial period than during the Holocene. Here we reconstruct the pH and CO2 content of surface waters from the eastern equatorial Atlantic Ocean over the past ~30 k.y. using the boron isotope composition of Globigerinoides ruber (a mixed-layer-dwelling planktic foraminifera). Our new record, combined with previously published data, indicates that during the last glacial, in contrast to today, a strong west to east gradient existed in the extent of air:sea equilibrium with respect to pCO2 (DeltapCO2), with the eastern equatorial Atlantic acting as a significant source of CO2 (+100 µatm) while the western Atlantic remained close to equilibrium (+25 µatm). This pattern suggests that a fivefold increase in the upwelling rate of deeper waters drove increased Atlantic productivity and large-scale regional cooling during the last glacial, but the higher than modern DeltapCO2 in the east indicates that export production did not keep up with enhanced upwelling of nutrients. However, the downstream decline of DeltapCO2 provides evidence that the unused nutrients from the east were eventually used for biologic carbon export, thereby effectively negating the impact of changes in upwelling on atmospheric CO2 levels. Our findings indicate that the equatorial Atlantic exerted a minimal role in contributing to lower glacial-age atmospheric CO2.

(Table 1) Boron concentration and d11B ratios of ODP Hole 130-803D

The pH of the surface ocean is a sensitive function of its alkalinity and total inorganic carbon concentration, properties which also control the partial pressure of atmospheric carbon dioxide (Broecker and Peng, 1982). Thus, an accurate proxy for past ocean pH could yield information about variations in atmospheric CO2. Recently, it has been suggested that the boron isotopic composition of foraminiferal tests depends on the pH of sea water as well as its isotopic composition (Vengosh et al., 1991, doi:10.1016/0016-7037(91)90139-V; Hemming and Hanson, 1992, doi:10.1016/0016-7037(92)90151-8). Here we present boron isotope and elemental data for sedimentary pore fluids and isotope data for bulk foraminiferal samples from a deep-sea sediment core. The composition of the pore waters implies that sea water boron concentrations and isotopic composition have been constant during the past 21 Myr, allowing us to reconstruct past ocean pH directly from the foraminiferal isotope data. We find that 21 Myr ago, surface ocean pH was only 7.4 ±0.2, but it then increased to 8.2 ±0.2 (roughly the present value) about 7.5 Myr ago. This is consistent with suggestions (Popp et al., 1989; Cerling, 1991; Arthur et al., 1991) that atmospheric CO2 concentrations may have been much higher 21 Myr ago than today.

(Table 3) Boron and chlorine in atmospheric moisture and rain water collected on the shore of the Golubaya Bay in 1970

Boron and chlorine were determined in rain water and in atmospheric moisture condensed in a "Saratov" refrigerator. Ocean is the main source of boron on the earth surface. Boron evaporates from the ocean and enriches atmospheric precipitation: B/Cl ratio of ocean water (0.00024) increases by factor of 10-15. Assuming that the average Cl content in global river runoff is 7.8 mg/l and boron content 0.013 mgl, B/Cl ratio in this runoff is 0.0017. The average B/Cl ratio in rain water of the Golubaya (Blue) Bay (Gelendzhik, Black Sea region) is 0.0026 and in condensates of atmospheric moisture during onshore and offshore winds in the same region it averages from 0.0029 to 0.0033. The maximum boron content in the condensates of this region during onshore winds was 0.032 mg/l and the minimum during offshore winds, 0.004 mg/l. /Cl ratio in sea water over the Atlantic Ocean and in the Gelendzhik area of the Black Sea varied within narrow range, mostly from 0.0025 to 0.0035. Similar B/Cl ratio (0.0024) was found for atmospheric precipitation on the slope of the Terskei Ala-Tau near the Issyk-Kul Lake in 1969. Thus, although chemistries of boron and chlorine (in chlorides) are very different, the B/Cl ratio in the atmosphere is fairly constant. This can be taken as a confirmation of an assumption that salt composition of sea water passes into the atmosphere in molecularly dispersed state. Supposing that the ocean-atmosphere system is in equilibrium as regards to the boron budget, it can be assumed that the same amount of boron passes from the ocean into bottom sediments and from lithosphere rocks and soils into the hydrosphere.