# Paleo-pCO2 Database ODP999 4.6 Million Year Boron Isotope and CO2 Data #----------------------------------------------------------------------- # World Data Service for Paleoclimatology, Boulder # and # NOAA Paleoclimatology Program # National Centers for Environmental Information (NCEI) #----------------------------------------------------------------------- # Template Version 3.0 # Encoding: UTF-8 # NOTE: Please cite Publication, and Online_Resource and date accessed when using these data. # If there is no publication information, please cite Investigators, Title, and Online_Resource and date accessed. # # Online_Resource: https://www.ncdc.noaa.gov/paleo/study/23590 # Description: NOAA Landing Page # Online_Resource: https://www1.ncdc.noaa.gov/pub/data/paleo/climate_forcing/trace_gases/Paleo-pCO2/boron_isotopes_Bartoli_2011.txt # Description: NOAA location of the template # # Original_Source_URL: # Description: # # Description/Documentation lines begin with # # Data lines have no # # # Archive: Climate Forcing # # Dataset DOI: # # Parameter_Keywords: carbon dioxide #-------------------- # Contribution_Date # Date: 2018-03-10 #-------------------- # File_Last_Modified_Date # Date: 2020-02-25 #-------------------- # Title # Study_Name: Paleo-pCO2 Database ODP999 4.6 Million Year Boron Isotope and CO2 Data #-------------------- # Investigators # Investigators: Bartoli, G.; Hönisch, B.; Zeebe, R.E. #-------------------- # Description_Notes_and_Keywords # Description: Paleo-CO2 derived from boron isotope measurements on marine sediment core ODP999A for the past 4.6 million years, contributed to the Paleo-pCO2 Database. # File updated February 2020 - new Paleo-pCO2 Database format #-------------------- # Publication # Authors: Gretta Bartoli, Bärbel Hönisch, Richard E. Zeebe # Published_Date_or_Year: 2011-11-16 # Published_Title: Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations # Journal_Name: Paleoceanography # Volume: 26 # Edition: # Issue: 4 # Pages: # Report_Number: # DOI: 10.1029/2010PA002055 # Online_Resource: https://agupubs.onlinelibrary.wiley.com/doi/abs/10.1029/2010PA002055 # Full_Citation: # Abstract: Several hypotheses have been put forward to explain the onset of intensive glaciations on Greenland, Scandinavia, and North America during the Pliocene epoch between 3.6 and 2.7 million years ago (Ma). A decrease in atmospheric CO2 may have played a role during the onset of glaciations, but other tectonic and oceanic events occurring at the same time may have played a part as well. Here we present detailed atmospheric CO2 estimates from boron isotopes in planktic foraminifer shells spanning 4.6-2.0 Ma. Maximal Pliocene atmospheric CO2 estimates gradually declined from values around 410 uatm to early Pleistocene values of 300 uatm at 2.0 Ma. After the onset of large-scale ice sheets in the Northern Hemisphere, maximal pCO2 estimates were still at 2.5 Ma +90 uatm higher than values characteristic of the early Pleistocene interglacials. By contrast, Pliocene minimal atmospheric CO2 gradually decreased from 310 to 245 uatm at 3.2 Ma, coinciding with the start of transient glaciations on Greenland. Values characteristic of early Pleistocene glacial atmospheric CO2 of 200 uatm were abruptly reached after 2.7 Ma during the late Pliocene transition. This trend is consistent with the suggestion that ocean stratification and iron fertilization increased after 2.7 Ma in the North Pacific and Southern Ocean and may have led to increased glacial CO2 storage in the oceanic abyss after 2.7 Ma onward. #------------------ # Funding_Agency # Funding_Agency_Name: # Grant: #------------------ # Site_Information # Site_Name: ODP999A # Location: Ocean>Atlantic Ocean>North Atlantic Ocean>Caribbean Sea # Country: # Northernmost_Latitude: 12.74 # Southernmost_Latitude: 12.74 # Easternmost_Longitude: -78.74 # Westernmost_Longitude: -78.74 # Elevation: -2839 m #------------------ # Data_Collection # Collection_Name: Bartoli2011ODP999boron # Earliest_Year: 4580295 # Most_Recent_Year: 1975132 # Time_Unit: Cal. Year BP # Core_Length: # Notes: #------------------ # Chronology_Information # Chronology: # #---------------- # Variables # # Data variables follow are preceded by "##" in columns one and two. # Data line variables format: one per line, shortname-tab-variable components (what, material, error, units, seasonality, data type,detail, method, C or N for Character or Numeric data, free text) # # #---------------- # Data: # Data lines follow (have no #) # Data line format - tab-delimited text, variable short name as header # Missing Values: # Basic Info REFERENCE AND CONTACT INFORMATION SAMPLE IDENTIFICATION AGE CONSTRAINTS ANALYTICAL SPECIFICATIONS VITAL EFFECT CALCULATED d11Bborate ACCESSORY INPUTS METHOD OF TEMPERATURE DETERMINATION ALTERNATIVE METHOD OF TEMPERATURE RECONSTRUCTION SEAWATER COMPOSITION AQUEOUS BORON ISOTOPE FRACTIONATION PARAMETERIZATION OF CO2 CALCULATION SECOND PARAMETER OF THE CARBONATE SYSTEM CALCULATED PARAMETERS OF THE CARBONATE SYSTEM alternative Age (in case different models are available) d11B (relative to SRM 951) d11Bc/d11Bborate calibration slope d11Bc/d11Bborate calibration intercept pressure (i.e. depth of foraminifer habitat) Temperature Mg/Ca e.g., Alkenone UK'37, TEX 86 Salinity [Ca] of seawater at S=35 [Mg] of seawater at S=35 [SO4] of seawater at S=35 [B]T of seawater at S=35 d11Bsw pKB aB3-B4 if applicable proxy first_author_last_name publication_year doi age_ka Age_uncertainty_pos_ka Age_uncertainty_neg_ka CO2_ppm CO2_uncertainty_pos_ppm CO2_uncertainty_neg_ppm Name of individual entering the data Contact email Reference of the data product DOI link to reference Site (DSDP/ODP/IODP or other site number) Hole Core Section top cm bottom cm core depth below seafloor (meters, specify CSF-A or CSF-B where applicable, original IODP record)a core composite depth below seafloor (meters, CCSF)a reference for composite depth Location (e.g., Atlantic, Carribbean, South China Sea etc.) Modern Latitude (decimal degree, south negative) Modern Longitude (decimal degree, west negative) Paleo Latitude (decimal degree, south negative) Paleo Longitude (decimal degree, west negative) Modern elevation (m), below sea level negative Paleo elevation (m), below sea level negative reference and Method to determine Paleo position notes about any flags in the studied core section Age (ka) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s Age uncertainty pos (ka) 2s Age uncertainty neg (ka) Age Scale (GTS 20XX) age method (nannofossil biostratigraphy, radiolaria, magnetic polarity, radiometric etc.) reference to age model, if different from primary reference of data set Age (ka) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s Age uncertainty pos (ka) 2s Age uncertainty neg (ka) Age Scale (GTS 20XX) age method (nannofossil biostratigraphy, radiolaria, magnetic polarity, radiometric etc.) reference to age model, if different from primary reference of data set foraminifer species analyzed foraminifer size class (µm) number of foraminifera shells per sample total sample weight (mg) Reference for sample cleaning procedure Boron separation method (e.g., column chemistry, microsublimation) analytical Method (e.g., MC-ICP-MS, P-TIMS, N-TIMS etc) d11B of individual replicate measurements of the same solution; separate by commas n of replicate measurements 2se of replicates ( [ 2* (sd/sqrt(n))] ) d11B (‰, average of replicates) type of uncertainty (e.g., set value, normal distribution, specify whether uncertainty is presented as standard deviation or standard error) 2s uncertainty (report internal or external reproducibility, whichever is larger) slope value type of uncertainty (e.g., set value, normal distribution) 2s uncertainty intercept value type of uncertainty (e.g., set value, normal distribution) 2s uncertainty Reference for calibration slope Notes (e.g., shell size corrected?) d11Bborate (‰) type of uncertainty (e.g., set value, normal distribution) 2s uncertainty notes about uncertainty estimate: e.g., included calibration slope and intercept Error propagation method depth habitat (m) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty temperature (°C) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s temperature pos (°C) 2s temperature neg (°C) Mg/Ca of individual replicate measurements; separate replicates by commas Mg/Ca (mmol/mol, average of replicates) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s Mg uncertainty pos (mmol/mol) 2s Mg/Ca uncertainty neg (mmol/mol) temperature calibration equation reference for temperature calibration equation Mg/Casw correction Mg/Casw correction reference salinity correction (list reference if applied) dissolution correction (list reference if applied) pH correction (list reference if applied) proxy value of individual replicate measurements; separate replicates by commas average proxy value (please specify units) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty temperature calibration equation reference for temperature calibration equation used same sample material as for d11B analyses? If not, provide details Salinity (unit-less) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty method of salinity estimation (list reference if applicable) [Ca] (mol/kg) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty reference for [Ca] of seawater value [Mg] (mol/kg) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty reference for [Mg] of seawater value [SO4] (mol/kg) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty reference for [SO4] of seawater value [B]T (µmol/kg) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty reference for [B]T value d11Bsw (‰) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty reference for d11Bsw reference for pKB and for correction of major ion composition, if applied reference for pressure effect on pKB value for aB3-B4 type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty reference for aB3-B4 equation for temperature correction of aB3-B4 (if applied) reference for temperature correction of aB3-B4 (if applied) CO2 calculation program and version, e.g. CO2SYS, seacarb, other (please specify) reference for pK0 and for correction of major ion composition, if applied reference for pK1 and for correction of major ion composition, if applied reference for pK2 and for correction of major ion composition, if applied reference for pKHSO4 reference for pKspcalcite and pKsparagonite and for correction of major ion composition, if applied reference for pressure effect on pKspcalcite and pKsparagonite Parameter used (e.g., alkalinity, DIC, [CO32-] Method for deriving 2nd parameter (e.g., CCD, W, LOSCAR, GENIE, code can be submitted as supplement) Reference for second parameter (if not primary reference of data set) central value (µmol/kg) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty pos (µmol/kg) 2s uncertainty neg (µmol/kg) Wcalcite (if used as a constraint) type of uncertainty (e.g., set value, normal distribution, +/- range) 2s uncertainty pos 2s uncertainty neg pH pH scale reported (e.g., total scale, seawater scale) 2s uncertainty pos 2s uncertainty neg Aqueous pCO2 (µatm) Air-sea pCO2 disequilibrium (µatm) Notes about air-sea disequilibrium: what is the estimate based on; are there assumptions on seasonality? bAtmospheric pCO2 (i.e. after correction for any modern air-sea disequilibrium, µatm) 2s pCO2 uncertainty pos 2s pCO2 uncertainty neg Error propagation method (code can be provided in supplement) parameters included in the error propagation (e.g., calibration uncertainty, d11Bsw, T, S, second parameter of the carbonate system) cAlkalinity (µmol/kg, if not used as an input parameter) 2s alkalinity uncertainty pos 2s alkalinity uncertainty neg DIC (µmol/kg, if not used as an input parameter 2s DIC uncertainty pos 2s DIC uncertainty neg Wcalcite, if not used as an input parameter 2s uncertainty Wcalcite pos 2s uncertainty Wcalcite neg Waragonite, if not used as an input parameter 2s uncertainty Waragonite pos 2s uncertainty Waragonite neg boron isotopes Bartoli 2011 10.1029/2010PA002055 1975.13 6 6 201.6 45.7 51.9 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 7 7 64 66 64.74 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 1975.1 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 38.8 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.45, 21.89, 21.55, 21.59, 21.62 5 0.15 21.62 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.70 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.03 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.010664 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0510631 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." likely variable but data no longer available NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 269.5 normal distribution 25 25 NA NA NA NA 8.23 total scale 0.03 0.03 219 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 201.6 46 52 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2026.54 6 6 244.7 51.5 59.4 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 8 2 47 49 66.57 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2026.5 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 35.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.23, 21.46, 20.96, 21.30, 21.02 5 0.18 21.20 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.70 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 33.84 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0106739 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0510187 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 266.9 normal distribution 25 25 NA NA NA NA 8.19 total scale 0.03 0.03 262 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 244.7 51 59 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2078.09 6 6 228.7 49.3 56.6 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 8 3 103 105 68.63 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2078.1 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 43.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.38, 21.41, 21.80, 21.46 4 0.19 21.52 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.70 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 36.60 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0106838 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0509743 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 294.7 normal distribution 25 25 NA NA NA NA 8.21 total scale 0.03 0.03 246 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 228.7 49 57 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2161.01 6 6 204.2 46.0 52.4 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 8 5 71 73 71.31 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2161.0 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 50.3 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.78, 21.54, 21.76, 21.70 4 0.11 21.70 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.70 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.78 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0106997 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0509029 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 284.8 normal distribution 25 25 NA NA NA NA 8.23 total scale 0.03 0.03 221 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 204.2 46 52 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2166.04 6 6 365.6 69.1 81.5 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 8 5 87 89 71.47 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2166.0 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 48.0 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.58, 20.00, 20.60, 20.50, 20.58 5 0.23 20.45 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.70 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.28 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0107006 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0508986 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 279.6 normal distribution 25 25 NA NA NA NA 8.10 total scale 0.04 0.04 383 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 365.6 69 81 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2201.94 6 6 368.8 69.5 82.1 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 8 6 49 51 72.59 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2201.9 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 42.2 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.64, 19.96, 20.46, 20.31, 20.29, 20.65 6 0.21 20.38 normal distribution, standard error 0.28 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.70 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.85 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0107075 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0508677 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 285 normal distribution 25 25 NA NA NA NA 8.09 total scale 0.03 0.03 386 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 368.8 70 82 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2304.67 6 6 220.6 48.2 55.2 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 9 1 127 129 75.37 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2304.7 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 43.5 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.65, 21.60, 21.35, 21.59 4 0.13 21.55 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 26.11 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.68 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0107272 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0507797 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 281.5 normal distribution 25 25 NA NA NA NA 8.21 total scale 0.03 0.03 238 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 220.6 48 55 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2502.94 6 6 350.4 66.8 78.6 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 9 6 64 66 82.24 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2502.9 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 53.0 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.65, 20.44, 20.89, 20.50, 20.47 5 0.17 20.59 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.13 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.51 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0107651 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0506104 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 277.4 normal distribution 25 25 NA NA NA NA 8.12 total scale 0.04 0.04 367 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 350.4 67 79 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2558.58 6 6 292.7 58.3 68.0 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 9 7 67 69 83.77 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2558.6 set value 6 6 Pleistocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 NA Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.68, 21.15, 21.31 3 0.38 21.05 normal distribution, standard error 0.38 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 26.20 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.90 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0107758 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0505631 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 280.1 normal distribution 25 25 NA NA NA NA 8.15 total scale 0.05 0.05 310 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 292.7 58 68 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2600.86 6 6 185.6 43.6 49.3 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 1 127 129 84.87 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2600.9 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 46.9 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.53, 21.68, 21.41, 21.84, 21.42 5 0.16 21.58 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.42 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.11 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0107838 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0505272 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 262.4 normal distribution 25 25 NA NA NA NA 8.25 total scale 0.03 0.03 203 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 185.6 44 49 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2685.47 6 6 176.5 42.5 47.8 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 3 98 100 87.58 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2685.5 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 35.2 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.49, 21.61, 21.57 3 0.07 21.55 normal distribution, standard error 0.39 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 22.85 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 33.99 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0504555 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0195 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 260.8 normal distribution 25 25 NA NA NA NA 8.27 total scale 0.04 0.04 194 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 176.5 42 48 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2702.23 6 6 340.5 65.3 76.8 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 4 20 22 88.30 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2702.2 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 34.2 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.59, 20.49, 20.67, 20.45 4 0.10 20.55 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.27 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.46 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108032 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0504413 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 274.5 normal distribution 25 25 NA NA NA NA 8.13 total scale 0.04 0.04 358 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 340.5 65 77 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2705.51 6 6 297.0 58.9 68.8 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 4 35 37 88.45 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2705.5 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 48.0 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.87, 20.94, 20.58, 20.52, 20.64 5 0.17 20.71 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.93 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.24 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108038 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0504385 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 272.4 normal distribution 25 25 NA NA NA NA 8.16 total scale 0.03 0.03 314 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 297.0 59 69 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2708.11 6 6 221.3 48.3 55.3 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 4 47 49 88.57 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2708.1 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 29.9 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.40, 21.22, 21.16, 21.28 4 0.10 21.26 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.93 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.30 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108043 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0504363 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 273 normal distribution 25 25 NA NA NA NA 8.22 total scale 0.04 0.04 238 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 221.3 48 55 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2710.46 6 6 316.8 61.8 72.4 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 4 57 59 88.67 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2710.5 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 33.0 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.84, 20.92, 19.35, 21.04 4 0.82 20.54 normal distribution, standard error 0.82 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.35 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.91 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108047 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0504344 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0195 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 269.3 normal distribution 25 25 NA NA NA NA 8.15 total scale 0.10 0.10 334 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 316.8 62 72 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2751.56 6 6 282.7 56.8 66.2 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 5 4 6 89.64 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2751.6 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 35.6 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.91, 21.02, 20.71, 21.18, 20.88 5 0.16 20.94 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.23 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.02 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108126 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0503996 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 269 normal distribution 25 25 NA NA NA NA 8.16 total scale 0.03 0.03 300 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 282.7 57 66 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2772.86 6 6 386.5 72.2 85.4 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 5 50 52 90.10 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2772.9 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 36.1 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.78, 20.39, 20.04, 20.47, 20.46 5 0.24 20.43 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 26.02 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.15 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108166 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0503816 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 269.7 normal distribution 25 25 NA NA NA NA 8.09 total scale 0.04 0.04 404 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 386.5 72 85 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2778.72 6 6 401.3 74.5 88.2 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 5 77 79 90.37 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2778.7 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 37.1 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.26, 20.33, 20.28, 20.16, 20.27 5 0.06 20.26 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.74 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.66 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108178 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0503767 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 265.3 normal distribution 25 25 NA NA NA NA 8.09 total scale 0.04 0.04 418 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 401.3 74 88 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2781.41 6 6 298.8 59.2 69.1 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 5 92 94 90.52 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2781.4 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 36.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.78, 20.90, 20.97, 20.40, 20.72 5 0.20 20.75 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.99 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.98 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108183 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0503744 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 268.3 normal distribution 25 25 NA NA NA NA 8.15 total scale 0.03 0.03 316 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 298.8 59 69 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2795.49 6 6 297.4 59.0 68.8 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 10 6 20 22 91.30 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2795.5 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 36.8 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.04, 20.85, 20.56, 21.00 4 0.22 20.86 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.23 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.34 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108209 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0503625 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 271.6 normal distribution 25 25 NA NA NA NA 8.15 total scale 0.04 0.04 314 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 297.4 59 69 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 2918.77 6 6 224.1 48.6 55.8 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 11 1 117 119 94.27 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 2918.8 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 35.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.21, 20.75, 21.45, 21.38 4 0.31 21.20 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.26 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.17 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108444 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0502587 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0195 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 269 normal distribution 25 25 NA NA NA NA 8.22 total scale 0.04 0.04 241 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 224.1 49 56 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3000.57 6 6 336.8 64.7 76.1 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 11 3 77 79 96.87 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3000.6 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 31.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.21, 20.46, 20.33, 20.23, 20.58 5 0.14 20.36 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.55 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 33.49 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.01086 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.05019 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 251.7 normal distribution 25 25 NA NA NA NA 8.13 total scale 0.04 0.04 354 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 336.8 65 76 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3073.92 6 6 247.5 51.9 59.9 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 11 5 57 59 99.67 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3073.9 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 48.1 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.46, 21.08, 21.23, 21.17, 21.01 5 0.28 20.99 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.16 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.28 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108739 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0501285 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 258 normal distribution 25 25 NA NA NA NA 8.19 total scale 0.04 0.04 265 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 247.5 52 60 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3081.38 6 6 393.6 73.3 86.8 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 11 5 80 82 99.90 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3081.4 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 29.1 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.46, 20.25, 20.08, 20.15 4 0.17 20.24 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.93 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.93 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108753 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0501223 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 274.1 normal distribution 25 25 NA NA NA NA 8.10 total scale 0.04 0.04 411 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 393.6 73 87 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3104.91 6 6 231.9 49.7 57.1 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 11 6 5 6 100.65 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3104.9 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 40.2 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.90, 21.08, 21.19, 21.16, 21.09, 20.82 6 0.12 21.04 normal distribution, standard error 0.27 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.35 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 33.57 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108798 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0501026 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 250.8 normal distribution 25 25 NA NA NA NA 8.20 total scale 0.03 0.03 249 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 231.9 50 57 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3155.92 6 6 215.7 47.5 54.3 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 11 7 17 19 102.27 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3155.9 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 44.5 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.47, 20.61, 21.53, 21.30, 21.93 5 0.43 21.37 normal distribution, standard error 0.43 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.36 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.86 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0108894 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.05006 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 262 normal distribution 25 25 NA NA NA NA 8.21 total scale 0.05 0.05 233 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 215.7 48 54 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3218.57 6 6 224.9 48.8 55.9 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 12 1 50 52 103.10 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3218.6 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 45.8 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.32, 21.15, 21.37 3 0.10 21.28 normal distribution, standard error 0.39 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.26 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.13 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109013 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0500077 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 254.2 normal distribution 25 25 NA NA NA NA 8.20 total scale 0.04 0.04 242 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 224.9 49 56 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3239.17 6 6 313.4 61.3 71.8 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 12 1 90 92 103.50 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3239.2 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 39.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.65, 20.54, 20.97, 20.99, 20.37, 20.42 6 0.22 20.66 normal distribution, standard error 0.27 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.50 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 33.97 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109052 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0499906 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 252.4 normal distribution 25 25 NA NA NA NA 8.13 total scale 0.03 0.03 330 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 313.4 61 72 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3259.15 6 6 234.5 50.1 57.6 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 12 2 20 22 104.30 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3259.1 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 32.4 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.19, 21.15, 21.35 3 0.12 21.23 normal distribution, standard error 0.39 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.70 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.93 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.010909 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0499739 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 261.2 normal distribution 25 25 NA NA NA NA 8.19 total scale 0.03 0.03 252 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 234.5 50 58 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3321.60 6 6 256.6 53.1 61.5 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 12 3 90 92 106.50 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3321.6 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 52.5 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.04, 20.85, 20.89, 20.91 4 0.08 20.92 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.16 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.08 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109208 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.049922 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 252.9 normal distribution 25 25 NA NA NA NA 8.18 total scale 0.04 0.04 274 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 256.6 53 61 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3403.24 6 6 237.8 50.5 58.1 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 12 5 12 14 108.72 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3403.2 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 41.1 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.21, 21.21, 21.36, 20.93, 20.80 5 0.21 21.10 normal distribution, standard error 0.30 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.92 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.38 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109363 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0498542 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 254.4 normal distribution 25 25 NA NA NA NA 8.19 total scale 0.03 0.03 255 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 237.8 51 58 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3406.73 6 6 233.5 49.9 57.4 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 12 5 20 22 108.80 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3406.7 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 42.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.25, 20.94, 20.94 3 0.20 21.04 normal distribution, standard error 0.39 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.97 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.22 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109369 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0498513 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 253.3 normal distribution 25 25 NA NA NA NA 8.20 total scale 0.04 0.04 251 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 233.5 50 57 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3471.47 6 6 274.6 55.7 64.7 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 12 6 57 59 110.67 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3471.5 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 48.9 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.82, 21.04, 20.71, 20.73 4 0.15 20.83 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.02 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.64 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109492 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0497977 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 256 normal distribution 25 25 NA NA NA NA 8.16 total scale 0.04 0.04 292 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 274.6 56 65 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3542.53 6 6 312.3 61.1 71.6 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 13 1 77 79 112.87 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3542.5 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 29.3 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.72, 20.69, 20.75 3 0.03 20.72 normal distribution, standard error 0.39 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.56 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.98 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109626 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.049739 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 258.1 normal distribution 25 25 NA NA NA NA 8.13 total scale 0.04 0.04 329 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 312.3 61 72 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3590.77 6 6 265.2 54.3 63.0 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 13 2 57 59 114.17 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3590.8 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 26.1 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.81, 21.00, 20.71, 20.86 4 0.12 20.84 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.38 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.40 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109717 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0496992 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 252.5 normal distribution 25 25 NA NA NA NA 8.17 total scale 0.04 0.04 282 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 265.2 54 63 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3716.06 6 6 292.8 58.3 68.0 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 13 4 117 119 117.77 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3716.1 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 46.5 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.04, 20.61, 20.60, 20.68 4 0.21 20.73 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.46 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.21 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0109953 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0495961 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 258.5 normal distribution 25 25 NA NA NA NA 8.15 total scale 0.04 0.04 310 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 292.8 58 68 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3792.18 6 6 270.5 55.1 64.0 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 13 6 48 50 120.08 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3792.2 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 45.7 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 21.07, 21.12, 21.08 3 0.03 21.09 normal distribution, standard error 0.39 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.66 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 36.39 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0110097 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0495337 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0193 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 268.3 normal distribution 25 25 NA NA NA NA 8.17 total scale 0.04 0.04 288 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 270.5 55 64 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3870.13 6 6 390.9 72.9 86.3 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 14 1 48 50 122.08 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3870.1 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 53.0 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.32, 20.22, 19.96, 20.18 4 0.15 20.17 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 23.10 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 35.87 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0110243 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0494699 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0195 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 263.3 normal distribution 25 25 NA NA NA NA 8.10 total scale 0.04 0.04 408 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 390.9 73 86 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 3961.07 6 6 277.5 56.1 65.2 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 14 3 7 9 124.67 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 3961.1 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 50.4 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.60, 20.82, 20.80, 20.77 4 0.10 20.75 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 25.26 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 33.87 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0110414 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0493957 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 242.7 normal distribution 25 25 NA NA NA NA 8.15 total scale 0.04 0.04 295 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 277.5 56 65 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 4036.18 6 6 317.4 61.9 72.5 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 14 4 98 100 127.08 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 4036.2 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 40.8 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.80, 20.37, 20.46, 20.56 4 0.19 20.55 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.46 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.99 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0110556 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0493345 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 252.4 normal distribution 25 25 NA NA NA NA 8.13 total scale 0.04 0.04 334 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 317.4 62 73 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 4117.13 6 6 376.7 70.7 83.6 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 14 6 38 40 129.51 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 4117.1 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 39.8 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.86, 20.15, 19.84, 20.14, 20.57 5 0.36 20.31 normal distribution, standard error 0.36 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.95 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.82 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0110707 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0492687 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 249.7 normal distribution 25 25 NA NA NA NA 8.09 total scale 0.05 0.05 394 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 376.7 71 84 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA boron isotopes Bartoli 2011 10.1029/2010PA002055 4580.30 6 6 407.7 75.5 89.4 Bärbel Hönisch, Richard Zeebe hoenisch@ldeo.columbia.edu, zeebe@hawaii.edu Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. 10.1029/2010PA002055 ODP 999 A 16 1 18 20 140.78 NA NA Carribbean 12.911 78.833 NA NA -2838.9 NA NA NA 4580.3 set value 6 6 Pliocene NA LR04 benthic oxygen isotope stack: L. E. Lisiecki, M. E. Raymo, Paleoceanography 20, 10.1029/2004PA001071 (2005) NA NA NA NA NA NA NA Globigerinoides saculifer 425-500 30-80 50.1 Bartoli, G., B. Hönisch and R.E. Zeebe (2011) Atmospheric CO2 decline during the Pliocene intensification of Northern Hemisphere glaciations, Paleoceanography, 26 (4), PA4213. NA N-TIMS, Triton 20.14, 20.10, 20.22, 19.98 4 0.10 20.11 normal distribution, standard error 0.33 NA NA NA -4.2 NA none Hönisch, B., N.G. Hemming, D. Archer, M. Siddall and J.F. McManus (2009) Atmospheric Carbon Dioxide Concentration Across the Mid-Pleistocene Transition, Science, 324 (5934), 1551-1554. unlike newer d11B-calcite vs. d11B-borate calibrations, this one is based on the d11B-G. sacculifer vs. pH calibration, corrected for instrument offsets and gametogenic calcite NA NA NA NA NA 0 NA none 24.78 set value 1.00 1.00 "NA, data interpolated from Groeneveld, J. (2005), Effect of the Pliocene closure of the Panamanian Gateway on Caribbean and east Pacific sea surface temperatures and salinities by applying combined Mg/Ca and 18O measurements (5.6– 2.2 Ma), Ph.D. thesis, 161 pp., Univ. of Kiel, Kiel, Germany." NA NA NA NA NA NA NA NA none NA none NA NA NA NA NA NA NA 34.46 set value 1 "estimated from d18Osw corrected for changes in global ice volume, where d18Osw was estimated from the deconvolution of d18O measured on G. sacculifer and Mg/Ca SST, and ice volume was estimated from Mudelsee and Raymo [2005]" 0.0111574 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." 0.0488954 NA NA "as summarized in Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018." NA NA NA 0.0004326 NA NA Lee, K., T.-W. Kim, R.H. Byrne et al. (2010) The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochimica et Cosmochimica Acta, 74 (6), 1801-1811. 39.61 the original paper did a sensitivity study with different estimates, but no single uncertainty to this preferred scenario has been applied none Foster, G.L., P.A.E. Pogge von Strandmann and J.W.B. Rae (2010) Boron and magnesium isotopic composition of seawater, Geochemistry Geophysics Geosystems, 11 (8), Q08015. A. G. Dickson, Deep-Sea Res. 37, 755 (1990). NA, assumed surface habitat 1.0194 NA none Kakihana & Kotaka (1977) alpha = 1.0206-0.000049205*T (°C) Kakihana et al. (1977), Bull. Chem. Soc. Japan, Vol. 50, No. 1, p. 158-163. matlab csys by Zeebe & Wolf-Gladrow (2001): CO2 in Seawater: Equilibrium, kinetics, isotopes, Elsevier, 346 pp. Weiss, R. F., Marine Chemistry 2:203-215, 1974. "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Mehrbach et al., Limnol. Oceanogr. 18 (1973) 897– 907; refit by Lueker, T.J., A.G. Dickson and C.D. Keeling (2000) Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Marine Chemistry, 70 (1-3), 105-119." "Dickson, Chem. Thermodyn. 22 (1990) 113– 127." [CO32-] "LOSCAR, assuming CCD, [Ca] and [Mg] varied through time and affected K*1m K*2 and K*sp after Tyrrell, T., and R. E. Zeebe (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68(17), 3521–3530, doi:10.1016/j.gca.2004.02.018."", and modern glacial/interglacial average [CO32-]=315 µmol/kg " NA 241.2 normal distribution 25 25 NA NA NA NA 8.07 total scale 0.04 0.04 425 17 "Takahashi, T., S. C. Sutherland, and A. Kozyr (2007), Global Ocean Surface Water Partial Pressure of CO2 Database: Measurements Performed During 1968–2007 (Version 2007), http://cdiac.ornl.gov/oceans/ndp_ 088/index.html, Oak Ridge Natl. Lab., Oak Ridge, Tenn." 407.7 75 89 square root of the sum of the squared individual pCO2 uncertainties d11B-calcite, temperature, salinity, CO32- NA NA NA NA NA NA NA NA NA NA NA NA