Benthic foraminifera accumulation rate and benthic foraminiferal productivity proxies at ODP Site 165-999 in the Caribbean (Appendix A)

This study tests the hypothesis that the late Miocene to early Pliocene constriction and closure of the Central American Seaway (CAS), connecting the tropical Atlantic and East quatorial Pacific (EEP), caused a decrease in productivity in the Caribbean, due to decreased coastal upwelling and an end to the connection with high-productivity tropical Pacific waters. The present study compared paleoceanographic proxies for the interval between 8.3 and 2.5 Ma in 47 samples from south Caribbean ODP Site 999 with published data on EEP DSDP Site 503. Proxies for Site 999 include the relative abundance of benthic foraminiferal species representing bottom current velocity and the flux of organic matter to the sea floor, the ratio of infaunal/epifaunal benthic foraminiferal species and benthic foraminifer accumulation rates (BFARs). In addition, we calculated % resistant planktic foraminifers species and used the previously published % sand fraction and benthic carbon isotope values from Site 999. During early shoaling of the Isthmus (8.3-7.9 Ma) the Caribbean was under mesotrophic conditions, with little ventilation of bottom waters and low current velocity. The pre-closure interval (7.6-4.2 Ma) saw enhanced seasonal input of phytodetritus with even more reduced ventilation, and enhanced dissolution between 6.8 and 4.8 Ma. During the post-closure interval (4.2-2.5 Ma) in the Caribbean, paleoproductivity decreased, current velocity was reduced, and ventilation improved, while the seasonality of phytodetrital input was reduced dramatically, coinciding with the establishment of the Atlantic-Pacific salinity contrast at 4.2 Ma. Our data support the hypothesis that late Miocene constriction of the CAS at 7.9 Ma and its closure at 4.2 Ma caused a gradual decrease in paleoproductivity in the Caribbean, consistent with decreased current velocity and seasonality of the phytodetrital input.

Total organic carbon, delta13C, biomarker, diatom distributions in sediment core JM11-FI-19PC

In the light of rapidly diminishing sea ice cover in the Arctic during the present atmospheric warming, it is imperative to study the distribution of sea ice in the past in relation to rapid climate change. Here we focus on glacial millennial scale climatic events (Dansgaard/Oeschger events) using the new sea ice proxy IP25 in combination with phytoplankton proxy data and quantification of diatom species in a record from the SE Norwegian Sea. We demonstrate that expansion and retreat of sea ice varied consistently in pace with the rapid climate changes 90 ka to present, and with this present the first IP25 sea ice proxy record resolving the D/O cyclicity going back in time into Marine Isotope Stage 5a. Sea ice retreated abruptly at the start of warm interstadials, but spread rapidly during the cooling phase of the interstadials and became near-perennial and perennial during cold stadials and Heinrich events, respectively. Low salinity surface water and the sea ice edge spread to the Greenland-Scotland Ridge, and during the largest Heinrich events, probably far into the Atlantic Ocean.

Dissolved organic carbon concentrations, amino sugar concentrations and highly significantly correlating FT-ICR mass peak magnitudes obtained from solid phase extracted marine dissolved organic matter during POLARSTERN cruise ANT-XXV/1

Dissolved organic matter (DOM) was extracted with solid phase extraction (SPE) from 137 water samples from different climate zones and different depths along an Eastern Atlantic Ocean transect. The extracts were analyzed with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI). D14C analyses were performed on subsamples of the SPE-DOM. In addition, the amount of dissolved organic carbon was determined for all water and SPE-DOM samples as well as the yield of amino sugars for selected samples. Linear correlations were observed between the magnitudes of 43% of the FT-ICR mass peaks and the extract D14C values. Decreasing SPE-DOM D14C values went along with a shift in the molecular composition to higher average masses (m/z) and lower hydrogen/carbon (H/C) ratios. The correlation was used to model the SPE-DOM D14C distribution for all 137 samples. Based on single mass peaks a degradation index was developed to compare the degradation state of marine SPE-DOM samples analyzed with FT-ICR MS. A correlation between D14C, degradation index, DOC values and amino sugar yield supports that SPE-DOM analyzed with FT-ICR MS reflects trends of bulk DOM. A relative mass peak magnitude ratio was used to compare aged SPE-DOM and fresh SPE-DOM regarding single mass peaks. The magnitude ratios show a continuum of different reactivities for the single compounds. Only few of the compounds present in the FT-ICR mass spectra are expected to be highly degraded in the oldest water masses of the Pacific Ocean. All other compounds should persist partly thermohaline circulation. Prokaryotic (bacterial) production, transformation and accumulation of this very stable DOM occurs probably primarily in the upper ocean. This DOM is an important contribution to very old DOM, showing that production and degradation are dynamic processes.

Age, 232Th, 230Th, 238U, CaCO3, organic carbon, lithogenic fraction and opal concentrations of 4 sediment cores from the southwest Pacific, with calculated 230Th-normalized mass flux

No clear scenario has yet been able to explain the full carbon drawdown that occurred during the Last Glacial Maximum (LGM); however, increased export production (EP) in the Subantarctic Zone (SAZ) of the Southern Ocean due to iron (Fe) fertilisation has been proposed to have provided a key mechanism affecting the air-sea partitioning of carbon. We chronicle changes in marine EP based on four sediment cores in Subtropical Waters (STW) and SAZ around New Zealand since the LGM. For the first time in this region, we present 230-Thorium normalised fluxes of biogenic opal, carbonate (CaCO3), excess Barium (xsBa), and organic Carbon (Corg). In STW and SAZ, these flux variations show that EP did not change markedly since the LGM. The only exception was a site in the SAZ close to the STF, where we suggest the STF shifted over the core site, driving increased EP. To understand why EP was mostly low and constant we investigated dust deposition changes by measuring lithogenic fluxes at the four sites. These data are coherent with an increased dust deposition in the southwest Pacific during the LGM. Additionally, we infer an increased lithogenic material discharge from erosion and glacier melts during the deglaciation, limited to the Campbell Plateau. Therefore, we propose that even though increased glacial dust deposition may have relieved Fe limitation within the SAZ, the availability of silicic acid (Si(OH)4) limited any resultant increase in carbon export during the LGM. Consequently, we infer low Si(OH)4 concentrations in the SAZ that have not significantly changed since the LGM. This result suggests that both Si(OH)4 and Fe co-limit EP in the SAZ around New Zealand, which would be consistent with modern process studies.

Total organic carbon content and isorenieratene concentrations from three holes of ODP Leg 160

Carotenoids were analysed in ca. 1-cm thick subsamples of three laterally time-equivalent sapropels from a west-east transect of the eastern Mediterranean Basin to study euxinic periods during Pliocene sapropel formation. The amount of intact isorenieratene (summed all-trans and cis isomers), ranged from non-detectable at the base and top of a sapropel up to 140 µg/g sediment in the central parts. Isorenieratene accumulation rates at the central and western site are remarkably similar and increase sharply to levels of up to 3.0 mg/m**2/ yr in the central part of the sapropel and then drop to low levels. This pattern indicates an expansion of euxinic conditions reaching into the photic zone, followed by deepening of the chemocline during deposition of this Pliocene sapropel. The sapropel from the easternmost site of the basin, which contains less organic carbon, shows much lower isorenieratene accumulation rates and even absence of isorenieratene in the central part of the sapropel. Ba/Al ratios indicate enhanced palaeoproductivity during sapropel formation, supporting previously proposed models, according to which increased productivity is the driving force for the generation of euxinic conditions.

Organic geochemistry of two sediment cores from the Kara Sea

Within the Russian-German research project on "Siberian River Run-off (SIRRO)" devoted to the freshwater discharge and its influence on biological, geochemical, and geological processes in the Kara Sea, sedimentological and organic-geochemical investigations were carried-out on two well-dated sediment cores from the Yenisei Estuary area. The main goal of this study was to quantify the terrigenous organic carbon accumulation based on biomarker and bulk accumulation rate data, and its relationship to Yenisei river discharge and climate change through Holocene times. The biomarker data at both cores clearly indicate the predominance of terrigenous organic matter, reaching 70 to 100% and 50 to 80% of the total organic carbon within and directly north of the estuary, respectively. During the last about 9 Cal. kyrs. BP represented in the studied sediment section, siliciclastic sediment and (terrigenous) organic carbon input was strongly influenced by postglacial sea-level rise and climate-related changes in river discharge. The mid-Holocene Climatic Optimum is documented by maximum river discharge between 8.2 and 7.3 Cal. kyrs. BP. During the last 2000 years river discharge probably became reduced, and accumulation of both terrigenous and marine organic carbon increased due to increased coagulation of fine-grained material.

Radiochemical analyses and contents of organic carbon and CaCO3 in equatorial Pacific Ocean sediments

Uranium series nuclide concentrations have been measured on sediments from five box cores from an equatorial Pacific transect. 230Thexcess activities show discontinuities at the Holocene-glacial boundary as dated by 14C. The glacial sedimentation rates determined by 230Th and 14C are 2.5-3.0 cm/kyr. The Holocene rates from 230Th are much lower than those dated by 14C (1.9-2.3 cm/kyr) because of carbonate dissolution. 230Th sedimentation fluxes exceed water column supply by factors of 1.2-1.8 in the Holocene and 1.8-3.0 in the glacial sections. A number of models have been applied to calculate carbonate dissolution rates. The results show that carbonate dissolution rates in the Holocene (in g/cm**2 kyr) equal 1.5 * 10**-3 exp (1.4D) where D is water depth in kilometers. A point-by- point estimation of sediment fluxes through time show that clay accumulation rates in the area have been near constant at 0.1-0.2 g/cm**2 kyr over the past 20 kyr whereas carbonate accumulation rates have decreased dramatically from 0.6-1.0 g/cm**2 kyr in the glacial sections of the cores to 0.2-0.6 g/cm**2 kyr in the Holocene. The errors caused by the uncertainties in the age of the termination of the last glacial period have been investigated and results show that a range of 11-14 kyr leads to an error upper limit of about 30% in the estimation of CaCO3 dissolution rates. The response time of CaCO3 and 230Thex concentrations in the mixed layer of sediments due to an impulse of change in CaCO3 dissolution rate has also been discussed, showing that the observed changes in carbonate dissolution may be explained in terms of a single or a continuous change, depending upon the thickness of the mixed layer.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Arabian Sea

Concentrations of total organic carbon (TOC) were determined on samples collected during six cruises in the northern Arabian Sea during the 1995 US JGOFS Arabian Sea Process Study. Total organic carbon concentrations and integrated stocks in the upper ocean varied both spatially and seasonally. Highest mixed-layer TOC concentrations (80-100 µM C) were observed near the coast when upwelling was not active, while upwelling tended to reduce local concentrations. In the open ocean, highest mixed-layer TOC concentrations (80-95 µM C) developed in winter (period of the NE Monsoon) and remained through mid summer (early to mid-SW Monsoon). Lowest open ocean mixed-layer concentrations (65-75 µM C) occurred late in the summer (late SW Monsoon) and during the Fall Intermonsoon period. The changes in TOC concentrations resulted in seasonal variations in mean TOC stocks (upper 150 m) of 1.5-2 mole C/m**2, with the lowest stocks found late in the summer during the SW Monsoon-Fall Intermonsoon transition. The seasonal accumulation of TOC north of 15°N was 31-41 x 10**12 g C, mostly taking place over the period of the NE Monsoon, and equivalent to 6-8% of annual primary production estimated for that region in the mid-1970s. A net TOC production rate of 12 mmole C/m**2/d over the period of the NE Monsoon represented ~80% of net community production. Net TOC production was nil during the SW Monsoon, so vertical export would have dominated the export terms over that period. Total organic carbon concentrations varied in vertical profiles with the vertical layering of the water masses, with the Persian Gulf Water TOC concentrations showing a clear signal. Deep water (>2000 m) TOC concentrations were uniform across the basin and over the period of the cruises, averaging 42.3±1.4 µM C.