Carbonate system data on the Molokai reef flat

The severity of the impact of elevated atmospheric pCO2 to coral reef ecosystems depends, in part, on how seawater pCO2 affects the balance between calcification and dissolution of carbonate sediments. Presently, there are insufficient published data that relate concentrations of pCO2 and CO3**2- to in situ rates of reef calcification in natural settings to accurately predict the impact of elevated atmospheric pCO2 on calcification and dissolution processes. Rates of net calcification and dissolution, CO3**2- concentrations, and pCO2 were measured, in situ, on patch reefs, bare sand, and coral rubble on the Molokai reef flat in Hawaii. Rates of calcification ranged from 0.03 to 2.30 mmol CaCO3/m**2/h and dissolution ranged from -0.05 to -3.3 mmol CaCO3/m**2/h. Calcification and dissolution varied diurnally with net calcification primarily occurring during the day and net dissolution occurring at night. These data were used to calculate threshold values for pCO2 and CO3**2- at which rates of calcification and dissolution are equivalent. Results indicate that calcification and dissolution are linearly correlated with both CO3**2- and pCO2. Threshold pCO2 and CO3**2- values for individual substrate types showed considerable variation. The average pCO2 threshold value for all substrate types was 654±195 µatm and ranged from 467 to 1003 µatm. The average CO3**2- threshold value was 152±24 µmol/kg, ranging from 113 to 184 µmol/kg. Ambient seawater measurements of pCO2 and CO3**2- indicate that CO3**2- and pCO2 threshold values for all substrate types were both exceeded, simultaneously, 13% of the time at present day atmospheric pCO2 concentrations. It is predicted that atmospheric pCO2 will exceed the average pCO2 threshold value for calcification and dissolution on the Molokai reef flat by the year 2100.

(Tables 1-3) Pb and Sr isotopic data for sediments and rocks from DSDP holes in the Mariana island-arc system

Analyses of the isotopic composition of Pb in (1) western Pacific Ocean sediments [Jurassic(?) to Pleistocene in age, including clays and biogenic oozes], (2) Pacific Ocean basaltic rocks, (3) Mariana frontal arc volcanic rocks (Eocene to Miocene), and (4) Mariana active arc volcanic rocks [Pliocene (?) to Holocene] indicate that Pacific Ocean sediments could not have been a significant component of the source material for the Mariana arc volcanic rocks. Calculations involving the average concentrations and isotopic compositions of Pb in oceanic sediments, sea-floor basaltic rocks, and the Mariana arc volcanic rocks suggest that the sediment component must have been less than 1 percent of this source material. The Pb isotopic compositions of the Mariana arc volcanic rocks lie, within experimental error, along the trend of available Pacific Ocean basalt analyses in versus 207Pb/204Pb versus 206Pb/204Pb and 208Pb/204Pb versus 206Pb/204Pb diagrams. Isotopic analyses of Pb in Pacific Ocean sediments do not lie along this trend; they have higher 207Pb/204Pb and 208Pb/204Pb values for comparable 206Pb/204Pb ratios. Clayey sediments generally have higher 208Pb/204Pb and 207Pb/204Pb ratios than biogenic oozes regardless of the age of the sediment. Comparison of combined Sr and Pb isotopic analyses for (1) mantle-derived materials erupted through oceanic crust, (2) altered ocean-floor basaltic rocks, and (3) volcanic rocks from oceanic island arcs suggests that the Mariana arc volcanic rocks were derived, at least in part, from altered Pacific lithosphere subducted beneath the Mariana arc. Unaltered basalts from the Mariana inter-arc basin (Mariana Trough) have Pb and Sr isotopic compositions that are very similar to those reported for some Hawaiian volcanic rocks but distinct from Mariana active and frontal arc compositions. These observations, in addition to existing major-and trace-element data, support a mantle origin for the interarc basin volcanic rocks. Dacites dredged from the Mariana remnant arc (South Honshu Ridge) have Pb isotopic compositions that are within experimental error of the active-arc analyses, consistent with a genetic relation.

(Table S1) Boron isotope and trace element data and reconstructed carbonate system parameters, ODP Holes 122-761B and 154-926A

The middle Miocene Climatic Optimum (17-15 Ma; MCO) is a period of global warmth and relatively high CO2 and is thought to be associated with a significant retreat of the Antarctic Ice Sheet (AIS). We present here a new planktic foraminiferal d11B record from 16.6 to 11.8 Ma from two deep ocean sites currently in equilibrium with the atmosphere with respect to CO2. These new data demonstrate that the evolution of global climate during the middle Miocene (as reflected by changes in the cyrosphere) was well correlated to variations in the concentration of atmospheric CO2. What is more, within our sampling resolution (~1 sample per 300 kyr) there is no evidence of hysteresis in the response of ice volume to CO2 forcing during the middle Miocene, contrary to what is understood about the Antarctic Ice Sheet from ice sheet modelling studies. In agreement with previous data, we show that absolute levels of CO2 during the MCO were relatively modest (350-400 ppm) and levels either side of the MCO are similar or lower than the pre-industrial (200-260 ppm). These new data imply the presence of either a very dynamic AIS at relatively low CO2 during the middle Miocene or the advance and retreat of significant northern hemisphere ice. Recent drilling on the Antarctic margin and shore based studies indicate significant retreat and advance beyond the modern limits of the AIS did occur during the middle Miocene, but the complete loss of the AIS was unlikely. Consequently, it seems that ice volume and climate variations during the middle Miocene probably involved a more dynamic AIS than the modern but also some component of land-based ice in the northern hemisphere.