(Appendix) Oxygen isotope record and carbonate mineralogy of the top part of ODP Hole 101-633A

Hole 633A was drilled in the southern part of Exuma Sound on the toe-of-slope of the southeastern part of Great Bahama Bank during ODP Leg 101. The top 55 m, collected as a suite of six approximately 9.5-m-long hydraulic piston cores, represents a Pliocene-Pleistocene sequence of periplatform carbonate ooze, a mixture of pelagic calcite (foraminifer and coccolith tests), some pelagic aragonite (pteropod tests), and bank-derived fine aragonite and magnesian calcite. A 1.6-m.y.-long hiatus was identified at 43.75 mbsf using calcareous nannofossil biostratigraphy and magnetostratigraphy. The 43.75-m-thick periplatform sequence above the hiatus is a complete late Pliocene-Quaternary record of the past 2.15 m.y. The d18O curve, primarily based on Globigerinoides sacculifera, clearly displays high-frequency/low-amplitude cycles during the early Pleistocene and low-frequency/high-amplitude cycles during the middle and late Pleistocene. Variations in aragonite content in the fine fraction of the periplatform ooze show a cyclic pattern throughout the Pleistocene, as previously observed in piston cores of the upper Pleistocene. These variations correlate well with the d18O record: high aragonite corresponds to light interglacial d18O values, and vice versa. Comparison of the d18O record and the aragonite curve helps to identify 23 interglacial and glacial oxygen-isotope stages, corresponding to 10.5 aragonite cycles (labeled A to K) commonly established during the middle and late Pleistocene (0.9 Ma-present). Strictly based on the aragonite curve, another 11 aragonite cycles, labeled L to V, were identified for the early Pleistocene (0.9 to 1.6 Ma). Mismatches between the d18O record and the aragonite curve occur mainly at some of the glacial-to-interglacial transitions, where aragonite increases usually lag behind d18O depletion. When one visually connects the minima on the Pleistocene aragonite curve, low-frequency (0.4 to 0.5 m.y.) supercycles seem to be superimposed on the high-frequency cycles. The timing of this supercycle roughly matches the timing of the Pleistocene carbonate preservation supercycles described in the Pacific, Indian, and Atlantic oceans. Mismatches between aragonite and d18O cycles are even more obvious for the late Pliocene (1.6 to 2.15 Ma). Irregular aragonite variations are observed for the late Pliocene, although after the onset of late Pleistocene-like glaciations in the North Atlantic Ocean 2.4 m.y. ago the d18O record has shown a mode of high-frequency/low-amplitude cycles. Initiation of climatically induced aragonite cycles occurs only at the Pliocene-Pleistocene transition, 1.6 m.y. ago. After that time, aragonite cycles are fully developed throughout the Quaternary. The 11-m-thick periplatform sequence below the hiatus represents a lower Pliocene interval between 3.75 and 4.45 Ma. The bottom half (4.25-4.45 Ma) has a fairly constant, high aragonite content (averaging 60%) and high sedimentation rates (28 m/m.y.) and corresponds to the end of the prolonged early Pliocene interglacial interval (4.1-5.0 Ma), established as a worldwide high sea-level stand. The second half (3.75-4.25 Ma), in which aragonite content decreases by successive steps, paralleled by a gradual 5180 enrichment in Globigerinoides sacculifera and low sedimentation rates (10 m/m.y), corresponds to the climatic deterioration established worldwide between 4.1 and 3.8 Ma, to a decrease of carbonate preservation observed in the equatorial Pacific Ocean, and to a global sea-level decline. Dolomite, a ubiquitous secondary component in the lower Pliocene, is interpreted as being authigenic and possibly related to diagenetic transformation of primary bank-derived fine magnesian calcite. Transformation of the primary mineralogical composition of the periplatform ooze was evidently minor, as the sediments have retained a detailed record of the Pliocene-Pleistocene climatic evolution. Clear evidence of diagenetic transformations in the periplatform ooze includes (1) the disappearance of magnesian calcite in the upper 20 m of Hole 633A, (2) the occurrence of calcite overgrowths on foraminiferal tests and microclasts at intermittent chalky core levels, and (3) the ubiquitous presence of authigenic dolomite in the lower Pliocene.

Incubation experiments to examine the production and loss of CH3I in surface seawater

In order to investigate production pathways of methyl iodide and controls on emissions from the surface ocean, a set of repeated in-vitro incubation experiments were performed over an annual cycle in the context of a time-series of in-situ measurements in Kiel Fjord (54.3 N, 10.1E). The incubation experiments revealed a diurnal variation of methyl iodide in samples exposed to natural light, with maxima during day time and losses during night hours. The amplitude of the daily accumulation varied seasonally and was not affected by filtration (0.2µm), consistent with a photochemical pathway for CH3I production. The methyl iodide loss rate during night time correlated with the concentration accumulated during daytime. Daily (24 hour) net production (Pnet) was similar in magnitude between in vitro and in situ mass balances. However, the estimated gross production (Pgross) of methyl iodide ranged from -0.07 to 2.24 pmol/day and were 5 times higher in summer than Pnet calculated from the in-situ study [Shi et al., 2014]. The large excess of Pgross over Pnet revealed by the in-vitro (incubation) experiments in summer is a consequence of large losses of CH3I by as-yet uncharacterized processes (e.g. biological degradation or chemical pathways other than Cl- substitution).

Halogen deposition in polar snow and ice

The atmospheric chemistry of iodine and bromine in polar regions is of interest due to the key role of halogens in many atmospheric processes, particularly tropospheric ozone destruction. Bromine is emitted from the open ocean but is enriched above first-year sea ice during springtime bromine explosion events, whereas iodine is emitted from biological communities hosted by sea ice. It has been previously demonstrated that bromine and iodine are present in Antarctic ice over glacial-interglacial cycles. Here we investigate seasonal variability of bromine and iodine in polar snow and ice, to evaluate their emission, transport and deposition in Antarctica and the Arctic and better understand potential links to sea ice. We find that bromine enrichment (relative to sea salt content) and iodine concentrations in polar ice do vary seasonally in Arctic snow and Antarctic ice and we relate such variability to satellite-based observations of tropospheric halogen concentrations. Peaks of bromine enrichment in Arctic snow and Antarctic ice occur in spring and summer, when sunlight is present. Iodine concentrations are largest in winter Antarctic ice strata, contrary to contemporary observations of summer maxima in iodine emissions.

(Table 1) Concentrations of Os, Ir, Pt and 187Os/188Os ratio in ODP Hole 130-806C samples

New osmium (Os) isotope and platinum group element (PGE) concentration data are used in conjunction with published 3He and Th isotope data to determine the relative proportions of lithogenic, extraterrestrial and hydrogenous iridium (Ir) in a Pacific pelagic carbonate sequence from the Ocean Drilling Program (ODP) Site 806 on the Ontong Java Plateau (OJP). These calculations demonstrate that lithogenic and extraterrestrial contributions to sedimentary Ir budget are minor, while hydrogenous Ir accounts for roughly 85% of the total Ir. Application of analogous partitioning calculations to previously reported data from a North Pacific red clay sequence (LL44-GPC3) yields very similar results. Total Ir burial fluxes at Site 806 and LL44-GPC3 are also similar, 45 and 30 pg/cm**2/kyr, respectively. Average Ir/3He and Ir/xs230Th_initial ratios calculated from the entire Site 806 data set are similar to those reported earlier for Pacific sites. In general, down-core profiles of Ir, 3He and xs230Th_initial, are not well correlated with one another. However, all three data sets show similar variance and yield sediment mass accumulation rate estimates that agree within a factor of two. While these results indicate that Ir concentration has potential as a point-paleoflux tracer in pelagic carbonates, Ir-based paleoflux estimates are likely subject to uncertainties that are similar to those associated with Co-based paleoflux estimates. Consequently, local calibration of Ir flux in space and time will be required to fully assess the potential of Ir as a point paleoflux tracer. Measured 187Os/188Os of the OJP sediments are systematically lower than the inferred 187Os/188Os of contemporaneous seawater and a clear glacial-interglacial 187Os/188Os variation is lacking. Mixing calculations suggest Os contributions from lithogenic sources are insufficient to explain the observed 187Os/188Os variations. The difference between the 187Os/188Os of bulk sediment and that of seawater is interpreted in terms of subtle contributions of unradiogenic Os carried by particulate extraterrestrial material. Down-core variations of 187Os/188Os with Pt/Ir and Os/Ir also point to contributions from extraterrestrial particles. Mixing calculations for each set of several triplicate analyses suggest that the unradiogenic Os end member cannot be characterized by primary extraterrestrial particles of chondritic composition. It is noteworthy that in efforts aimed at determining the effect of extraterrestrial contributions, 187Os/188Os of pelagic carbonates has greater potential compared to abundances of PGE. An attempt has been made for the first time to estimate sediment mass accumulation rates based on amount of extraterrestrial Os in the OJP samples and previously reported extraterrestrial Os flux. Throughout most of the OJP record, Os isotope-based paleoflux estimates are within a factor of two of those derived using other constant flux tracers. Meaningful flux estimates cannot be made during glacial maxima because the OJP sediments do not record the low 187Os/188Os reported previously. We speculate that this discrepancy may be related to focusing of extraterrestrial particles at the OJP, as has been suggested to explain down-core 3He variations.

(Table 1) Concentrations of CaCO3 and organic carbon, organic matter atomic C/N ratios and delta13C values of sediment samples from Site DSDP 594

CaCO3 and total organic carbon concentrations, organic matter C/N and carbon isotope ratios, and sediment accumulation rates in late Quaternary sediments from DSDP Site 594 provide information about glacial-interglacial variations in the delivery of organic matter to the Chatham Rise offshore of southeastern New Zealand. Low C/N ratios and nearly constant organic delta13C values of ?23? indicate that marine production dominates organic matter supply in both glacial and interglacial times during oxygen isotope stages 1 through 6 (0-140 ka) and 17 through 19 (660-790 ka). Increased organic carbon mass accumulation rates in isotope stages 2, 4, 6, and 18 record enhanced marine productivity during glacial maxima. Excursions of organic delta13C values to ca. ?29? in portions of isotope stage 2 suggest that the local concentration of dissolved CO2 was occasionally elevated during the last glacial maximum, probably as a result of short periods of lowered sea-surface temperature. Dilution of carbonates by clastic continental sediment generally increases at this location during glacial maxima, but enhanced delivery of land-derived organic matter does not accompany the increased accumulation of clastic sediments.

(Table 1) Age and sedimentation rates of Pleistocene/Holocene sequences at DSDP Sites 86-580 and 94-611

The recovery from the North Atlantic (Site 611) of a continuous Pleistocene sedimentary record with a siliceous microfaunal component made it possible to compare the high-latitude abundance pattern of the radiolarian species Cycladophora davisiana in the Atlantic with that produced from analyses of a high-latitude record (Site 580) from the northwest Pacific. Previous studies had shown that the late Pleistocene (0-0.45 Ma) abundance variations of this species in these high-latitude regions were similar. Cycladophora davisiana maxima in the North Atlantic record reach abundance levels three to four times higher than C. davisiana maxima registered in sediments from the northwest Pacific site. This difference in magnitude of abundance peaks is most likely an effect of the more northerly location of Site 611 (53°N) compared with that of Site 580 (42°N), since high-latitude time-slice studies have shown a direct relationship between increasing latitude and C. davisiana abundance. Discontinuous preservation of radiolarians in sediments from North Atlantic Site 611 allows only tentative correlation of the North Atlantic and northwest Pacific C. davisiana abundance curves. These correlations are confined to those portions of the cores where ages are tightly constrained by magnetic boundaries, and to intervals with comparable sedimentation rates.