Boron isotopes, pH and pCO2 calculation for one Fiji coral specimen Porites (1898-1998), 2012

delta11B results and deduced pH, pCO2 and omega values obtained for a tropical coral specimen Porites collected in 1998 at Yasawa (16°48'S- 177°27'E) on the western side of the Fiji archipelago, location in the north western part of the Pacific Warm Pool. Such Porites specimen grew during the XXth century (1898-1998). Boron isotopes results allowed the reconstruction of surface ocean acidification in the vincinity of Fiji Islands with strong interdecadal influence of the ENSO at regional scale. pHT calculation parameters (Hönisch et al., 2007): a=0 PER MIL; alpha=0.9804; delta11B=39.5 PER MIL; salinity=35.02; pKB from Dickson (1990). pCO2 and omega calculation parameters: TA= 2350 µM; Ca= 10.2 mM; Dickson et al.(2007); Mucci 1983.

(Table 1) Boron-isotope measurements of shallow-dwelling planktonic foraminifera of ODP Holes 144-817A, 144-872C and 143-865C

Knowledge of the evolution of atmospheric carbon dioxide concentrations throughout the Earth's history is important for a reconstruction of the links between climate and radiative forcing of the Earth's surface temperatures. Although atmospheric carbon dioxide concentrations in the early Cenozoic era (about 60 Myr ago) are widely believed to have been higher than at present, there is disagreement regarding the exact carbon dioxide levels, the timing of the decline and the mechanisms that are most important for the control of CO2 concentrations over geological timescales. Here we use the boron-isotope ratios of ancient planktonic foraminifer shells to estimate the pH of surface-layer sea water throughout the past 60 million years, which can be used to reconstruct atmospheric CO2 concentrations. We estimate CO2 concentrations of more than 2,000 p.p.m. for the late Palaeocene and earliest Eocene periods (from about 60 to 52 Myr ago), and find an erratic decline between 55 and 40 Myr ago that may have been caused by reduced CO2 outgassing from ocean ridges, volcanoes and metamorphic belts and increased carbon burial. Since the early Miocene (about 24 Myr ago), atmospheric CO2 concentrations appear to have remained below 500 p.p.m. and were more stable than before, although transient intervals of CO2 reduction may have occurred during periods of rapid cooling approximately 15 and 3 Myr ago.

Carbonate system of surface sediments from the South Pacific

B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].

Characteristics and aldehyde concentrations of diamond dust events near Barrow, Alaska

Diamond dust (DD) refers to tiny ice crystals that form frequently in the Polar troposphere under clear sky conditions. They provide surfaces for chemical reactions and scatter light. We have measured the specific surface area (SSA) of DD at Barrow in March-April 2009. We have also measured its chemical composition in mineral and organic ions, dissolved organic carbon (DOC), aldehydes, H2O2, and the absorption spectra of water-soluble chromophores. Mercury concentrations were also measured in spring 2006, when conditions were similar. The SSA of DD ranges from 79.9 to 223 m**2/kg . The calculated ice surface area in the atmosphere reaches 11000 (±70%) µm**2/cm**3, much higher than the aerosol surface area. However, the impact of DD on the downwelling and upwelling light fluxes in the UV and visible is negligible. The composition of DD is markedly different from that of snow on the surface. Its concentrations in mineral ions are much lower, and its overall composition is acidic. Its concentrations in aldehydes, DOC, H2O2 and mercury are much higher than in surface snows. Our interpretation is that DOC from the oceanic surface microlayer, coming from open leads in the ice off of Barrow, is taken up by DD. Active chemistry in the atmosphere takes place on DD crystal surfaces, explaining its high concentrations in aldehydes and mercury. After deposition, active photochemistry modifies DD composition, as seen from the modifications in its absorption spectra and aldehyde and H2O2 content. This probably leads to the emissions of reactive species to the atmosphere.

Seawater carbonate chemistry and zooxanthellate coral Cladocora caespitosa boron isotopic and elemental systematics during experiments, 2011

Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 > 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.

(Table 1) Boron-isotope measurements of foraminifera of ODP Hole 143-865C

The carbon dioxide content of the atmosphere [measured as the partial pressure of CO2 (pCO2)] affects the content of the surface ocean, which in turn affects seawater pH. The boron isotope composition (d11B) of contemporaneous planktonic foraminifera that calcified their tests at different water depths can be used to reconstruct the pH-depth profile of ancient seawater. Construction of a pH profile for the middle Eocene tropical Pacific Ocean shows that atmospheric pCO2 was probably similar to modern concentrations or slightly higher.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Calculated sea surface temperatures of two sediment cores

The reconstruction of ocean history employs a large variety of methods with origins in the biological, chemical, and physical sciences, and uses modern statistical techniques for the interpretation of extensive and complex data sets. Various sediment properties deliver useful information for reconstructing environmental parameters. Those properties that have a close relationship to environmental parameters are called ''proxy variables'' (''proxies'' for short). Proxies are measurable descriptors for desired (but unobservable) variables. Surface water temperature is probably the most important parameter for describing the conditions of past oceans and is crucial for climate modelling. Proxies for temperature are: abundance of microfossils dwelling in surface waters, oxygen isotope composition of planktic foraminifers, the ratio of magnesium or strontium to calcium in calcareous shells or the ratio of certain organic molecules (e.g. alkenones produced by coccolithophorids). Surface water salinity, which is important in modelling of ocean circulation, is much more difficult to reconstruct. At present there is no established method for a direct determination of this parameter. Measurements associated with the paleochemistry of bottom waters to reconstruct bottom water age and flow are made on benthic foraminifers, ostracodes, and deep-sea corals. Important geochemical tracers are d13C and Cd/Ca ratios. When using benthic foraminifers, knowledge of the sediment depth habitat of species is crucial. Reconstructions of productivity patterns are of great interest because of important links to current patterns, mixing of water masses, wind, the global carbon cycle, and biogeography. Productivity is reflected in the flux of carbon into the sediment. There are a number of fluxes other than those of organic carbon that can be useful in assessing productivity fluctuations. Among others, carbonate and opal flux have been used, as well as particulate barite. Furthermore, microfossil assemblages contain clues to the intensity of production as some species occur preferentially in high-productivity regions while others avoid these. One marker for the fertility of sub-surface waters (that is, nutrient availability) is the carbon isotope ratio within that water (13C/12C, expressed as d13C). Carbon isotope ratios in today's ocean are negatively correlated with nitrate and phosphate contents. Another tracer of phosphate content in ocean waters is the Cd/Ca ratio. The correlation between this ratio and phosphate concentrations is quite well documented. A rather new development to obtain clues on ocean fertility (nitrate utilization) is the analysis of the 15N/14N ratio in organic matter. The fractionation dynamics are analogous to those of carbon isotopes. These various ratios are captured within the organisms growing within the tagged water. A number of reconstructions of the partial pressure of CO2 have been attempted using d13C differences between planktic and benthic foraminifers and d13C values of bulk organic material or individual organic components. To define the carbon system in sea water, two elements of the system have to be known in addition to temperature. These can be any combination of total CO2 , alkalinity, or pH. To reconstruct pH, the boron isotope composition of carbonates has been used. Ba patterns have been used to infer the distribution of alkalinity in past oceans. Information relating to atmospheric circulationand climate is transported to the ocean by wind or rivers, in the form of minerals or as plant andanimal remains. The most useful tracers in this respect are silt-sized particles and pollen.

Seawater carbonate chemistry and boron incorporation of planktic foraminifer Orbulina universa during experiments, 2011

Culture experiments with living planktic foraminifers reveal that the ratio of boron to calcium (B/Ca) in Orbulina universa increases from 56 to 92 µmol mol-1 when pH is raised from 7.61 +/- 0.02 to 8.67 +/- 0.03 (total scale). Across this pH range, the abundances of carbonate, bicarbonate, and borate ions also change (+ 530, - 500, and + 170 µmol kg-1, respectively). Thus specific carbonate system control(s) on B/Ca remain unclear, complicating interpretation of paleorecords. B/Ca in cultured O. universa also increases with salinity (55-72 µmol mol-1 from 29.9-35.4 per mil) and seawater boron concentration (62-899 µmol mol-1 from 4-40 ppm B), suggesting that these parameters may need to be taken into account for paleorecords spanning large salinity changes (~ 2 per mil) and for samples grown in seawater whose boron concentration ([B]SW) differs from modern by more than 0.25 ppm. While our results are consistent with the predominant incorporation of the charged borate species B(OH)4 into foraminiferal calcite, the behavior of the partition coefficient KD (defined as [B/Ca]calcite/B(OH)4/HCO3seawater) cannot be explained by borate incorporation alone, and suggests the involvement of other pH-sensitive ions such as CO3 For a given increase in seawater B(OH)4, the corresponding increase in B/Ca is stronger when B(OH)4 is raised by increasing [B]SW than when it is raised by increasing pH. These results suggest that B incorporation controls should be reconsidered. Additional insight is gained from laser-ablation ICP-MS profiles, which reveal variable B/Ca distributions within individual shells.