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.

(Table 1) Boron, carbon, magnesium and calcium isotope data, post-Marinoan Neoproterozoic carbonate sections, Namibia

A marked ocean acidification event and elevated atmospheric carbon dioxide concentrations following the extreme environmental conditions of the younger Cryogenian glaciation have been inferred from boron isotope measurements. Calcium and magnesium isotope analyses offer additional insights into the processes occurring during this time. Data from Neoproterozoic sections in Namibia indicate that following the end of glaciation the continental weathering flux transitioned from being of mixed carbonate and silicate character to a silicate-dominated one. Combined with the effects of primary dolomite formation in the cap dolostones, this caused the ocean to depart from a state of acidification and return to higher pH after climatic amelioration. Differences in the magnitude of stratigraphic isotopic changes across the continental margin of the southern Congo craton shelf point to local influences modifying and amplifying the global signal, which need to be considered in order to avoid overestimation of the worldwide chemical weathering flux.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Iodine and boron concentrations in pore fluids, ultramafic clasts and interstitial serpentinite mud of ODP Hole 125-779A and Site 195-1200

Iodine and boron were analyzed in pore fluids, serpentinized ultramafic clasts, and the serpentinized mud matrix of the South Chamorro Seamount mud volcano (Ocean Drilling Program Leg 195 Site 1200) to determine the distribution of these elements in deep forearc settings. Similar analyses of clasts and muds from the Conical Seamount mud volcano (Leg 125 Site 779) were also carried out. Interstitial pore fluids are enriched in boron and iodine without appreciable change in chloride concentration relative to seawater. Both the ultramafic clasts and the associated serpentinized mud present the highest documented iodine concentrations for all types of nonsedimentary rocks (6.3-101.7 µmol/kg). Such high iodine concentrations, if commonplace in marine forearc settings, may constitute a significant, previously unknown reservoir of iodine. This serpentinized forearc mantle reservoir may potentially contribute to the total crustal iodine budget and provide a mechanism for its recycling at convergent plate margins. Both clasts and mud show concurrent enrichments in boron and iodine, and the similarity in pore fluid profiles also suggests that these two incompatible, fluid-mobile elements behave similarly at convergent plate margins.

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.

Carbon, boron and oxygen isotope ratios of sediments from the Moresby Seamount

We report results from boron, carbon and oxygen stable isotope analyses of faulted and veined rocks recovered by scientific ocean drilling during ODP Leg 180 in the western Woodlark Basin, off Papua New Guinea. In this area of active continental extension, crustal break-up and incipient seafloor spreading, a shallow-dipping, seismically active detachment fault accommodates strain, defining a zone of mylonites and cataclasites, vein formation and fluid infiltration. Syntectonic microstructures and vein-fill mineralogy suggest frictional heating during slip during extension and exhumation of Moresby Seamount. Low carbon and oxygen isotope ratios of calcite veins indicate precipitation from hydrothermal fluids (delta13C PDB down to -17?; delta18O PDB down to -22?) formed by both dehydration and decarbonation. Boron contents are low (<7 ppm), indicating high-grade metamorphic source rock for the fluids. Some of the delta11B signatures (17-35?; parent solutions to calcite vein fills) are low when compared to deep-seated waters in other tectonic environments, likely reflecting preferential loss of 11B during low-grade metamorphism at depth. Pervasive devolatilization and flux of CO2-rich fluids are evident from similar vein cement geochemistry in the detachment fault zone and splays further updip. Multiple rupture-and-healing history of the veins suggests that precipitation may be an important player in fluid pressure evolution and, hence, seismogenic fault movement.

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.

The alkali element and boron geochemistry of ODP Site 169-1038 in the Escanaba Trough, East Pacific

A suite of conjugate pore fluid and sediment samples were collected during Leg 169 of the ODP from within the clastic sedimentary sequences which host massive sulphides at Central Hill, Escanaba Trough (ODP Site 1038). We report the alkali element and boron, and Li and B isotope data for these samples. Relative to a reference site (Site 1037) located outside the zone of high heat flow, pore fluids from Site 1038 show a wide variation in Cl (300-800 mM), and have far higher concentrations of Li (up to 6.2 mM), B (up to 9.7 mM), Cs (up to 5.0 mM), and Rb (up to 97 mM). We show that the pore fluids are derived from hydrothermal circulation that has extended into the basement oceanic crust, with input of the alkali elements and B as the rising hydrothermal fluids interact geochemically with the overlying clastic sediments. There is, however, no marked depletion of these elements in the conjugate sediments, suggesting that there has been advective transport of fluids away from the primary hydrothermal reaction site. This is supported by modelling of the Li and B isotope systematics of the pore fluids, which shows that they record extensive formation of secondary minerals during cooling of the fluids from ~350 to ~20ºC. Precipitation of metal-rich sulphides would have occurred prior to the formation of these minerals, thus, the pore fluid Li and B isotope data can place important constraints on the locus of sulphide deposition beneath the seafloor at Escanaba.

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.