Delta 44/40 Ca, Mg/Ca and Sr/Ca record of Globigerinoides sacculifer and calculated temperatures and salinity changes of ODP Hole 165-999A

The delta18O values of planktonic foraminifera increased in the Caribbean by about 0.5? relative to the equatorial East Pacific values between 4.6 and 4.2 Ma as a consequence of the closure of the Central American Gateway (CAG). This increase in delta18O can be interpreted either as an increase in Caribbean sea surface (mixed layer) salinity (SSS) or as a decrease in sea surface temperatures (SST). This problem represents an ideal situation to apply the recently developed paleotemperature proxy delta44/40Ca together with Mg/Ca and d18O on the planktic foraminifer Globigerinoides sacculifer from ODP Site 999. Although differences in absolute temperature calibration of delta44/40Ca and Mg/Ca exist, the general pattern is similar indicating a SST decrease of about 2-3 8C between 4.4 and 4.3 Ma followed by an increase in the same order of magnitude between 4.3 and 4.0 Ma. Correcting the delta18O record for this temperature change and assuming that changes in global ice volume are negligible, the salinity-induced planktonic delta18O signal decreased by about 0.4? between 4.4 and 4.3 Ma and increased by about 0.9? between 4.3 and 4.0 Ma in the Caribbean. The observed temperature and salinity trends are interpreted to reflect the restricted exchange of surface water between the Caribbean and the Pacific in response to the shoaling of the Panamanian Seaway, possibly accompanied by a southward shift of the Intertropical Convergence Zone (ITCZ) between 4.4 and 4.3 Ma. Differences in Mg/Ca- and delta44/40Ca-derived temperatures can be reconciled by corrections for secular variations of the marine Mg/Ca[sw] and delta44/40Ca, a salinity effect on the Mg/Ca ratio and a constant temperature offset of ~2.5 °C between both SST proxy calibrations.

Element concentrations of bulk sediment from the Southern Cape Basin

High-resolution records of Ca and Sr were obtained from shipboard XRF analyses of bulk sediments in five gravity cores from the southern Cape Basin, South Atlantic Ocean. Sr/Ca ratios display regular glacial/interglacial variations of 14-40% and reveal a close correlation with the SPECMAP record, minimum Sr/Ca ratios appearing during glacial (delta18 O) maxima, distinct increases during periods of deglaciation, and highest ratios in interstadials. Shifts in carbonate-producing phytoplankton and/or zooplankton assemblages over glacial/interglacial cycles are suggested to be the main cause for the observed variations in Sr/Ca patterns. Quick assessment of the relationship between Sr/Ca ratios and the SPECMAP record made it possible to easily transfer an age model to the newly collected cores already during the cruise.

Geochemistry of sheeted dike complex minerals of ODP Hole 140-504B

Diabases were recovered during Legs 137 and 140 at Hole 504B from depths between 1621.5 and 2000.4 meters below seafloor in the lower sheeted dike complex. The samples contain multiple generations of millimetric to centimetric veins. The orientation of the measured veins suggests that two main vein sets exist: one characterized by shallow dipping and the other by random trend. Thermal contraction during rock cooling is considered the main mechanism responsible for fracture formation. Vein infill is related to the circulation of hydrothermal fluids near the spreading axis. Some veins are surrounded by millimeter-sized alteration halos due to fluid percolation from the fractures through the host rock. Vein-filling minerals are essentially amphibole, chlorite, and zeolites. Amphibole composition is controlled by the microstructural site of the rock. Actinolite is the main amphibole occurring in the veins and also in the groundmass away from the halos. In the alteration halos, amphibole shows composition of actinolitic hornblende and Mg-hornblende. Late-stage tension gashes and interstitial spaces in some amphibole-bearing veins are filled with zeolites, suggesting that the veins likely suffered multiple opening stages that record the cooling history of the circulating fluids. Evidence of deformation recorded by the recovered samples seems to be restricted to veins that clearly represent elements of weakness of the rock. On the basis of vein geometry and microstructure we infer structural interpretations for the formation mechanism and for deformation of veins.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.

Stable isotope and Mg/Ca record of IODP Site 339-U1385

Although millennial-scale climate variability (<10 ka) has been well studied during the last glacial cycles, little is known about this important aspect of climate in the early Pleistocene, prior to the Middle Pleistocene Transition. Here we present an early Pleistocene climate record at centennial resolution for two representative glacials (marine isotope stages (MIS) 37-41 from approximately 1235 to 1320 ka) during the "41 ka world" at Integrated Ocean Drilling Program Site U1385 (the "Shackleton Site") on the southwest Iberian margin. Millennial-scale climate variability was suppressed during interglacial periods (MIS 37, MIS 39, and MIS 41) and activated during glacial inceptions when benthic d18O exceeded 3.2 per mil. Millennial variability during glacials MIS 38 and MIS 40 closely resembled Dansgaard-Oeschger events from the last glacial (MIS 3) in amplitude, shape, and pacing. The phasing of oxygen and carbon isotope variability is consistent with an active oceanic thermal bipolar see-saw between the Northern and Southern Hemispheres during most of the prominent stadials. Surface cooling was associated with systematic decreases in benthic carbon isotopes, indicating concomitant changes in the meridional overturning circulation. A comparison to other North Atlantic records of ice rafting during the early Pleistocene suggests that freshwater forcing, as proposed for the late Pleistocene, was involved in triggering or amplifying perturbations of the North Atlantic circulation that elicited a bipolar see-saw response. Our findings support similarities in the operation of the climate system occurring on millennial time scales before and after the Middle Pleistocene Transition despite the increases in global ice volume and duration of the glacial cycles.

Mg/Ca ratio of Globorotalia tumida and subsurface temperature reconstruction for ODP Site 130-806

The tropical Pacific thermocline strength, depth, and tilt are critical to tropical mean state and variability. During the early Pliocene (~3.5 to 4.5 Ma), the Eastern Equatorial Pacific (EEP) thermocline was deeper and the cold tongue was warmer than today, which resulted in an mean state with a reduced zonal sea surface temperature gradient, or El Padre. However, it is unclear whether the deep thermocline was a local feature of the EEP or a basin-wide condition with global implications. Our measurements of Mg/Ca of Globorotalia tumida in a western equatorial Pacific site indicate Pliocene subsurface temperatures warmer than today; thus, El Padre included a basin-wide thermocline that was relatively warm, deep, and weakly tilted. At ~4 Ma, thermocline steepening was coupled to cooling of the cold tongue. Since ~4 Ma, the basin-wide thermocline cooled/shoaled gradually, with implications for thermocline feedbacks in tropical dynamics and the interpretation of TEX86-derived temperatures.

Geological investigation of a section at Kulyumbe river in Siberia

An integrated, high-resolution chemostratigraphic (C, O and Sr isotopes) and magnetostratigraphic study through the upper Middle Cambrian - lowermost Ordovician shallow-marine carbonates of the northwestern margin of the Siberian Platform is reported. The interval was analysed at the Kulyumbe section, which is exposed along the Kulyumbe River: an eastern tributary of the Enisej River. It comprises the upper Ust'-Brus, Labaz, Orakta, Kulyumbe, Ujgur, and lower Iltyk formations and includes the Steptoean positive carbon isotopic excursion (SPICE) studied here in detail from upper Cambrian carbonates of the Siberian Platform for the first time. The peak of the excursion, showing d13C positive values as high as +4.6? and least-altered 87Sr/86Sr ratios of 0.70909, is reported herein from the Yurakhian Horizon of the Kulyumbe Formation. The stratigraphic position of the SPICE excursion does not support traditional correlation of the boundary between the Orakta and Labaz formations at Kulyumbe River with its supposedly equivalent level in Australia, Laurentia, South China, and Kazakhstan, where the Glyptagnostus stolidotus and G. reticulatus biozones are known to immediately precede the SPICE excursion and span the Middle-Upper Cambrian boundary. The Cambrian-Ordovician boundary is probably situated in the middle Nyajan Horizon of the Iltyk Formation, in which carbon isotope values show a local maximum below a decrease in the upper part of the Nyajan Horizon, attributed herein to the Tremadocian. A refined magnetic polarity sequence shows that the geomagnetic reversal frequency was very high during the Middle Cambrian at 5-10 reversals per Ma, assuming a total duration of ~10 Ma and up to 100 magnetic intervals in the Middle Cambrian. By contrast, the sequence attributed herein to the Upper Cambrian on chemostratigraphic grounds contains only 10-11 magnetic intervals. Preprint in Open Access hdl:10013/epic.30209.d001

Annotated record and chemical analyses of a polygenetic manganese nodule (slab) from the Scott Plateau, Indian Ocean (core VA-16-13KD)

A large manganese nodule (manganese slab) was dredged from 2100 m on the Scott Plateau by R.V. Valdivia in 1977. It is an irregular ellipsoid, with a maximum dimension of 28 cm, parallel to the sea floor. Chemical analyses show that Mn and Fe proportions are comparable, and total Ni + Cu + Co content averages 0.7%. The nodule has a complex growth history which started with radial upward growth leading to coalescing into a continuous crust. The crust was coated with horizontal layers. After fracturing and infilling of cracks with calcareous sediment, further layers encased the nodule.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

Zn/Sr record of the Last Interglacial Transition in South Atlantic Ocean sediments

We examined the zinc content of diatom frustules as an indicator of past changes in surface seawater Zn2+ concentration. Zn/Si data of samples from three cores located in the South Atlantic sector of the Southern Ocean spanning the last interglacial-glacial transition are presented. Changes in the Zn/Si record are linked to changes in the surface water Zn2+ concentration. The source of variation in Zn2+ concentration appears to be via changes in deep water upwelling and circulation. We rule out changes in phytoplankton productivity and aeolian dust input as a source of variation in the Zn/Si record. Likewise, the Zn/Si data are not linked to shifts in the diatom species composition of the sediment or sediment preservation effects. The Zn/Si results presented do not support the zinc hypothesis. There is no link between the uptake of CO2 by phytoplankton, as inferred from the d13C record, and the Zn/Si record.

Seawater carbonate chemistry, Mg/Ca, Sr/Ca, oxygen production and calcification rate during experiments with coral Pocillopora damicornis, 2011

The Sr/Ca of aragonitic coral skeletons is a commonly used palaeothermometer. However skeletal Sr/Ca is typically dominated by weekly-monthly oscillations which do not reflect temperature or seawater composition and the origins of which are currently unknown. To test the impact of transcellular Ca2+ transport processes on skeletal Sr/Ca, colonies of the branching coral, Pocillopora damicornis, were cultured in the presence of inhibitors of Ca-ATPase (ruthenium red) and Ca channels (verapamil hydrochloride). The photosynthesis, respiration and calcification rates of the colonies were monitored throughout the experiment. The skeleton deposited in the presence of the inhibitors was identified (by 42Ca spike) and analysed for Sr/Ca and Mg/Ca by secondary ion mass spectrometry. The Sr/Ca of the aragonite deposited in the presence of either of the inhibitors was not significantly different from that of the solvent (dimethyl sulfoxide) control, although the coral calcification rate was reduced by up to 66% and 73% in the ruthenium red and verapamil treatments, respectively. The typical precision (95% confidence limits) of mean Sr/Ca determinations within any treatment was <±1% and differences in skeletal Sr/Ca between treatments were correspondingly small. Either Ca-ATPase and Ca channels transport Sr2+ and Ca2+ in virtually the same ratio in which they are present in seawater or transcellular processes contribute little Ca2+ to the skeleton and most Ca is derived from seawater transported directly to the calcification site. Variations in the activities of Ca-ATPase and Ca-channels are not responsible for the weekly-monthly Sr/Ca oscillations observed in skeletal chronologies, assuming that the specificities of Ca transcellular transport processes are similar between coral genera.

(Table S1) Stable oxygen isotopic values and Mg/Ca ratios of Globigerinoides ruber w from sediment core AAS9_21

Variations in sea surface temperature (SST), d18O of sea water (?18Ow), and salinity were reconstructed for the past 68 ka using a sediment core (AAS9/21) from the eastern Arabian Sea (EAS) in order to understand the changes in evaporation and precipitation associated with the monsoon system. The Mg/Ca-derived SST record varies by ~4°C; it shows that marine isotope stage (MIS) 4 was warmer than MIS 3, that the Last Glacial Maximum was 4°C cooler than the present, and that there was a 2°C increase within the Holocene. MIS 4 records higher d18Ow and salinity values than MIS 2, suggesting variable flow of low-salinity Bay of Bengal flow into the EAS during glacial periods. The transition from MIS 4 to MIS 3 was marked with a conspicuous shift from higher to lower d18Ow values, which reflects a decrease in the evaporation-precipitation budget in the EAS, perhaps due to the strengthening of southwest monsoon. Monsoon reconstructions based on d18Ow reveal that monsoon-driven precipitation was higher during MIS 3 and MIS 1 and was lower during MIS 2 and MIS 4. This is consistent with earlier monsoon reconstructions based on upwelling indices from the western Arabian Sea. However, the amplitude of monsoon fluctuations derived through upwelling indices and d18Ow varies significantly, which may indicate spatial variability of monsoon rainfall.

Mineralogical, geochemical and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic)

Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes.

(Table 3, Page 417) Table 3. The concentrations of Zn, Cu, Pb, Cd, Ni, Co, Ag, Mn and Fe in a soluble in 1M HCl fraction of ferromanganese nodules of Slupsk Furrow in the southern Baltic sea

The concentration of Zn, Cu, Pb, Cd, Ni, Co, Ag, Mn, Fe, Ca, Mg, K and Na in molluscs Macoma balthica, Mya arenaria, Cardium glaucum, Mytilus edulis and Astarte borealis from the southern Baltic was determined. The surface sediments and ferromanganese concretions associated with the molluscs were also analysed for concentration of these metals. Species- and region-dependent differences in the metal levels of the organisms were observed. The properties of molluscs analysed which have a tendency toward elevated biological tolerance of selected trace metals were specified. The interelement relationship between metal concentrations in the soft tissue and the shell was estimated and was discussed.