Carbon chemistry of oceanic crust

Carbonate mineral precipitation in the upper oceanic crust during low-temperature, off-axis, hydrothermal circulation is investigated using new estimates of the bulk CO2 content of seven DSDP/ODP drill cores. In combination with previously published data these new data show: (i) the CO2 content of the upper ~ 300 m of the crust is substantially higher in Cretaceous than in Cenozoic crust and (ii) for any age of crust, there is substantially more CO2 in Atlantic (slow-spreading) than Pacific (intermediate- to fast-spreading) crust. Modelling the Sr-isotopic composition of the carbonates suggests that > 80% of carbonate mineral formation occurs within < 20 Myr of crust formation. This means that the higher CO2 content of Cretaceous crust reflects a secular change in the rate of CO2 uptake by the crust. Oxygen isotope derived estimates of carbonate mineral precipitation temperatures show that the average and minimum temperature of carbonate precipitation was ~10 °C higher temperatures in the Cretaceous than in the Cenozoic. This difference is consistent with previous estimates of secular change in bottom seawater temperature. Higher fluid temperature within the crust will have increased reaction rates potentially liberating more basaltic Ca and hence enhancing carbonate mineral precipitation. Additionally, if crustal fluid pH is controlled by fluid-rock reaction, the higher Ca content of the Cretaceous ocean will also have enhanced carbonate mineral precipitation. New estimates of the rate of CO2 uptake by the upper ocean crust during the Cenozoic are much lower than previous estimates.

Trace metal concentration and age model of ODP Hole 165-1002C sediments

Titanium and iron concentration data from the anoxic Cariaco Basin, off the Venezuelan coast, can be used to infer variations in the hydrological cycle over northern South America during the past 14,000 years with subdecadal resolution. Following a dry Younger Dryas, a period of increased precipitation and riverine discharge occurred during the Holocene 'thermal maximum'. Since ~5400 years ago, a trend toward drier conditions is evident from the data, with high-amplitude fluctuations and precipitation minima during the time interval 3800 to 2800 years ago and during the 'Little Ice Age'. These regional changes in precipitation are best explained by shifts in the mean latitude of the Atlantic Intertropical Convergence Zone (ITCZ), potentially driven by Pacific-based climate variability. The Cariaco Basin record exhibits strong correlations with climate records from distant regions, including the high-latitude Northern Hemisphere, providing evidence for global teleconnections among regional climates.

Sea surface reconstruction of sediment cores off West Spitsbergen

Two sediment cores from the West Spitsbergen area, Euro-Arctic margin, MD99-2304 and MD99-2305, have been investigated for paleoceanographic proxies, including benthic and planktonic foraminifera, benthic foraminiferal stable isotopes and ice rafted debris. Core MD99-2304 is located on the upper continental margin, reflecting variations in the influx of Atlantic Water in the West Spitsbergen Current. Core MD99-2305 is located in Van Mijenfjord, picturing variations in tidewater glacier activity as well as fjord-ocean circulation changes. Surface water warmer than today, was present on the margin as soon as the Van Mijenfjord was deglaciated by 11,200 cal. years BP. Relatively warm water invaded the fjord bottom almost immediately after the deglaciation. A relatively warm early Holocene was followed by an abrupt cooling at 8800 cal. years BP on the continental margin. Another cooling in the fjord record, 8000-4000 cal. years BP, is documented by an increase in ice rafted debris and an increase in benthic foraminiferal delta18O. The IRD-record indicates that central Spitsbergen never was completely deglaciated during the Holocene. Relatively cool and stable conditions similar to the present were established about 4000 cal. years BP.

The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Occurence and thickness of flood layers in varved sediments of Lake Ammersee

Microfacies analyses and X-ray fluorescence scanning (µ-XRF) at sub-mm resolution were conducted on the varved Mid- to Late Holocene interval of two sediment profiles from pre-alpine Lake Ammersee (southern Germany). The coring sites are located in a proximal (AS10prox) and distal (AS10dist) position towards the main tributary River Ammer, in 1.8 km distance from each other. To shed light on sediment distribution within the lake, particular emphasis was (1) the detection of intercalated detrital layers and their micro-sedimentological features, and (2) intra-basin correlation of these event deposits. Detrital layers were dated by microscopic varve counting, verified by accelerator mass spectrometry 14C dating of terrestrial plant macrofossils. Since ~5500 varve years (vyr) BP, in total 1573 detrital layers were detected in either one or both of the investigated sediment profiles. Based on their microfacies, geochemistry, and proximal-distal deposition pattern, detrital layers were interpreted as River Ammer flood deposits. Earlier studies on flood layer seasonality have proven that flood layer deposition occurs predominantly during spring and summer, the flood season at Lake Ammersee. Most prominent features of the record are the onset of regular flood layer deposition at ~5500 vyr BP in AS10prox and ~ 2800 vyr BP in AS10dist as well as three major increases in mean flood layer thickness at ~5500, 2800, and 400 vyr BP. Integrating information from both sediment profiles allowed to interpret these changes in terms of shifts towards higher mean flood intensity. Proposed triggering mechanisms are gradual reduction in Northern Hemisphere orbital summer forcing and superimposed centennial-scale solar activity minima. Likely responses to this forcing are enhanced equator-to-pole temperature gradients and changes in synoptic-scale atmospheric circulation. The consequences for the Ammersee region are more intense cyclones leading to extremer rainfall and flood events in spring and summer.

1.2 Ma stacked benthic foraminiferal carbon isotope record

Pleistocene stable carbon isotope (d13C) records from surface and deep dwelling foraminifera in all major ocean basins show two distinct long-term carbon isotope fluctuations since 1.00 Ma. The first started around 1.00 Ma and was characterised by a 0.35 per mil decrease in d13C values until 0.90 Ma, followed by an increase of 0.60 per mil lasting until 0.50 Ma. The subsequent fluctuation started with a 0.40 per mil decrease between 0.50 and 0.25 Ma, followed by an increase of 0.30 per mil between 0.25 and 0.10 Ma. Here, we evaluate existing evidence and various hypotheses for these global Pleistocene d13C fluctuations and present an interpretation, where the fluctuations most likely resulted from concomitant changes in the burial fluxes of organic and inorganic carbon due to ventilation changes and/or changes in the production and export ratio. Our model indicates that to satisfy the long-term 'stability' of the Pleistocene lysocline, the ratio between the amounts of change in the organic and inorganic carbon burial fluxes would have to be close to a 1:1 ratio, as deviations from this ratio would lead to sizable variations in the depth of the lysocline. It is then apparent that the mid-Pleistocene climate transition, which, apart from the glacial cycles, represents the most fundamental change in the Pleistocene climate, was likely not associated with a fundamental change in atmospheric pCO2. While recognising that high frequency glacial/interglacial cycles are associated with relatively large (100 ppmv) changes in pCO2, our model scenario (with burial changes close to a 1:1 ratio) produces a maximum long-term variability of only 20 ppmv over the fluctuation between 1.00 and 0.50 Ma.

Geochemistry of Central American Volcanic Arc basement samples

The Central American Volcanic Arc (CAVA) has been the subject of intensive research over the past few years, leading to a variety of distinct models for the origin of CAVA lavas with various source components. We present a new model for the NW Central American Volcanic Arc based on a comprehensive new geochemical data set (major and trace element and Sr-Nd-Pb-Hf-O isotope ratios) of mafic volcanic front (VF), behind the volcanic front (BVF) and back-arc (BA) lava and tephra samples from NW Nicaragua, Honduras, El Salvador and Guatemala. Additionally we present data on subducting Cocos Plate sediments (from DSDP Leg 67 Sites 495 and 499) and igneous oceanic crust (from DSDP Leg 67 Site 495), and Guatemalan (Chortis Block) granitic and metamorphic continental basement. We observe systematic variations in trace element and isotopic compositions both along and across the arc. The data require at least three different endmembers for the volcanism in NW Central America. (1) The NW Nicaragua VF lavas require an endmember with very high Ba/(La, Th) and U/Th, relatively radiogenic Sr, Nd and Hf but unradiogenic Pb and low d18O, reflecting a largely serpentinite-derived fluid/hydrous melt flux from the subducting slab into a depleted N-MORB type of mantle wedge. (2) The Guatemala VF and BVF mafic lavas require an enriched endmember with low Ba/(La, Th), U/Th, high d18O and radiogenic Sr and Pb but unradiogenic Nd and Hf isotope ratios. Correlations of Hf with both Nd and Pb isotopic compositions are not consistent with this endmember being subducted sediments. Granitic samples from the Chiquimula Plutonic Complex in Guatemala have the appropriate isotopic composition to serve as this endmember, but the large amounts of assimilation required to explain the isotope data are not consistent with the basaltic compositions of the volcanic rocks. In addition, mixing regressions on Nd vs. Hf and the Sr and O isotope plots do not go through the data. Therefore, we propose that this endmember could represent pyroxenites in the lithosphere (mantle and possibly lower crust), derived from parental magmas for the plutonic rocks. (3) The Honduras and Caribbean BA lavas define an isotopically depleted endmember (with unradiogenic Sr but radiogenic Nd, Hf and Pb isotope ratios), having OIB-like major and trace element compositions (e.g. low Ba/(La, Th) and U/Th, high La/Yb). This endmember is possibly derived from melting of young, recycled oceanic crust in the asthenosphere upwelling in the back-arc. Mixing between these three endmember types of magmas can explain the observed systematic geochemical variations along and across the NW Central American Arc.

40Ar-39Ar dating and isotopic composition of groundmass and felspar samples from core AND-2A

The AND-2A drillcore (Antarctic Drilling Program-ANDRILL) was successfully completed in late 2007 on the Antarctic continental margin (Southern McMurdo Sound, Ross Sea) with the aim of tracking ice proximal to shallow marine environmental fluctuations and to document the 20-Ma evolution of the Erebus Volcanic Province. Lava clasts and tephra layers from the AND-2A drillcore were investigated from a petrographic and stratigraphic point of view and analyzed by the 40Ar-39Ar laser technique in order to constrain the age model of the core and to gain information on the style and nature of sediment deposition in the Victoria Land Basin since Early Miocene. Ten out of 17 samples yielded statistically robust 40Ar-39Ar ages, indicating that the AND-2A drillcore recovered <230 m of Middle Miocene (~128-358 m below sea floor, ~11.5-16.0 Ma) and >780 m of Early Miocene (~358-1093 m below sea floor, ~16.0-20.1 Ma). Results also highlight a nearly continuous stratigraphic record from at least 358 m below sea floor down hole, characterized by a mean sedimentation rate of ~19 cm/ka, possible oscillations of no more than a few hundreds of ka and a break within ~17.5-18.1 Ma. Comparison with available data from volcanic deposits on land, suggests that volcanic rocks within the AND-2A core were supplied from the south, possibly with source areas closer to the drill site for the upper core levels, and from 358 m below sea floor down hole, with the 'proto-Mount Morning' as the main source.

Down-core sedimentary Sr-Nd isotope records from two Cape Basin sediment cores in the South Atlantic: GeoB3603-2 (Meteor cruise M34/1) and MD02-2594 (Marion Dufresne cruise MD128)

We report down-core sedimentary Nd isotope (epsilon Nd) records from two South Atlantic sediment cores, MD02-2594 and GeoB3603-2, located on the western South African continental margin. The core sites are positioned downstream of the present-day flow path of North Atlantic Deep Water (NADW) and close to the Southern Ocean, which makes them suitable for reconstructing past variability in NADW circulation over the last glacial cycle. The Fe-Mn leachates epsilon Nd records show a coherent decreasing trend from glacial radiogenic values towards less radiogenic values during the Holocene. This trend is confirmed by epsilon Nd in fish debris and mixed planktonic foraminifera, albeit with an offset during the Holocene to lower values relative to the leachates, matching the present-day composition of NADW in the Cape Basin. We interpret the epsilon Nd changes as reflecting the glacial shoaling of Southern Ocean waters to shallower depths combined with the admixing of southward flowing Northern Component Water (NCW). A compilation of Atlantic epsilon Nd records reveals increasing radiogenic isotope signatures towards the south and with increasing depth. This signal is most prominent during the Last Glacial Maximum (LGM) and of similar amplitude across the Atlantic basin, suggesting continuous deep water production in the North Atlantic and export to the South Atlantic and the Southern Ocean. The amplitude of the epsilon Nd change from the LGM to Holocene is largest in the southernmost cores, implying a greater sensitivity to the deglacial strengthening of NADW at these sites. This signal impacted most prominently the South Atlantic deep and bottom water layers that were particularly deprived of NCW during the LGM. The epsilon Nd variations correlate with changes in 231Pa/230Th ratios and benthic d13C across the deglacial transition. Together with the contrasting 231Pa/230Th: epsilon Nd pattern of the North and South Atlantic, this indicates a progressive reorganization of the AMOC to full strength during the Holocene.

High-resolution planktic stable isotope and trace element record of ODP Hole 161-976

Multi-decadal to centennial planktic d18O and Mg/Ca records were generated at ODP976 in the Alboran Sea. The site is in the flow path of Atlantic inflow waters entering the Mediterranean and captured North Atlantic signals through the surface inflow and the atmosphere. The records reveal similar climatic oscillations during the last two glacial-to-interglacial transitions, albeit with a different temporal pacing. Glacial termination 1 (T1) was marked by Heinrich event 1 (H1), post-H1 Bolling/Allerod (B/A) warming and Younger Dryas (YD) cooling. During T2 the H11 d18O anomaly was twice as high and lasted 30% longer than during H1. The post-H11 warming marked the start of MIS5e while the subsequent YD-style cooling occurred during early MIS5e. The post-H11 temperature increase at ODP976 matched the sudden Asian Monsoon Termination II at 129 ka BP. Extending the 230Th-dated speleothem timescale to ODP976 suggests glacial conditions in the Northeast Atlantic region were terminated abruptly and interglacial warmth was reached in less than a millennium. The early-MIS5e cooling and freshening at ODP976 coincided with similar changes at North Atlantic sites suggesting this was a basin-wide event. By analogy with T1 we argue that this was a YD-type event that was shifted into the early stages of the last interglacial period. This scenario is consistent with evidence from northern North Atlantic and Nordic Sea sites that the continuing disintegration of the large Saalian Stage (MIS6) ice sheet in Eurasia delayed the advection of warm North Atlantic waters and full-strength convective overturn until later stages of MIS5e.

Lavas from the Elbrus volcano, Greater Caucasus

Comprehensive geochronological and isotope-geochemical studies showed that the Late Quaternary Elbrus Volcano (Greater Caucasus) experienced long (approximately 200 ka) discrete evolution with protracted periods of igneous quiescence (approximately 50 ka) between large-scale eruptions. Volcanic activity of Elbrus is subdivided into three phases: Middle Neopleistocene (225-170 ka), Late Neopleistocene (110-70 ka), and Late Neopleistocene - Holocene (earlier than 35 ka). Petrogeochemical and isotope (Sr-Nd-Pb) signatures of Elbrus lavas point to their mantle-crustal origin. It was shown that hybrid parental magmas of the volcano formed due to mixing and/or contamination of deep-seated mantle melts by Paleozoic upper crustal material of the Greater Caucasus. Mantle reservoir that participated in genesis of Elbrus lavas as well as most other Neogene-Quaternary magmatic rocks of Caucasus was represented by the lower mantle "Caucasus" source. Primary melts generated by this source in composition corresponded to K-Na subalkali basalts with the following isotopic characteristics: 87Sr/86Sr = 0.7041+/-0.0001, e-Nd = +4.1+/-0.2, 147Sm/144Nd = 0.105-0.114, 206Pb/204Pb = 18.72, 207Pb/204Pb = 15.62, and 208Pb/204Pb = 38.78. Temporal evolution of isotope characteristics for lavas of the Elbrus Volcano is well described by a Sr-Nd mixing hyperbole between "Caucasus" source and estimated average composition of the Paleozoic upper crust of the Greater Caucasus. It was shown that, with time, proportions of mantle material in parental magmas of Elbrus gently increased: from ~60% at the Middle-Neopleistocene phase of activity to ~80% at the Late Neopleistocene - Holocene phase, which indicates an increase of activity of a deep-seated source at decreasing input of crustal melts or contamination with time. Unraveled evolution of the volcano with discrete eruption events, lacking signs of cessation of the Late Neopleistocene - Holocene phase, increasing contribution of the deep-seated mantle source in genesis of Elbrus lavas with time as deduced from isotope-geochemical data, as well as numerous geophysical and geological evidence indicate that Elbrus is a potentially active volcano and its eruptions may be resumed. Possible scenarios were proposed for evolution of the volcano, if its eruptive activity continued.

Neodymium isotope record of ODP Site 177-1090

Age estimates for the opening of Drake Passage range from 49 to 17 million years ago (Ma), complicating interpretations of the relationship between ocean circulation and global cooling. Secular variations of neodymium isotope ratios at Agulhas Ridge (Southern Ocean, Atlantic sector) suggest an influx of shallow Pacific seawater approximately 41 Ma. The timing of this connection and the subsequent deepening of the passage coincide with increased biological productivity and abrupt climate reversals. Circulation/productivity linkages are proposed as a mechanism for declining atmospheric carbon dioxide. These results also indicate that Drake Passage opened before the Tasmanian Gateway, implying the late Eocene establishment of a complete circum-Antarctic pathway.

Sedimentation and mineral analysis on sediment cores from the Lena Delta

Core and outcrop analysis from Lena mouth deposits have been used to reconstruct the Late Quaternary sedimentation history of the Lena Delta. Sediment properties (heavy mineral composition, grain size characteristics, organic carbon content) and age determinations (14C AMS and IR-OSL) are applied to discriminate the main sedimentary units of the three major geomorphic terraces, which form the delta. The development of the terraces is controlled by complex interactions among the following four factors: (1) Channel migration. According to the distribution of 14C and IR-OSL age determinations of Lena mouth sediments, the major river runoff direction shifted from the west during marine isotope stages 5-3 (third terrace deposits) towards the northwest during marine isotope stage 2 and transition to stage 1 (second terrace), to the northeast and east during the Holocene (first terrace deposits). (2) Eustasy. Sea level rise from Last Glacial lowstand to the modern sea level position, reached at 6-5 ka BP, resulted in back-filling and flooding of the palaeovalleys. (3) Neotectonics. The extension of the Arctic Mid-Ocean Ridge into the Laptev Sea shelf acted as a halfgraben, showing dilatation movements with different subsidence rates. From the continent side, differential neotectonics with uplift and transpression in the Siberian coast ridges are active. Both likely have influenced river behavior by providing sites for preservation, with uplift, in particular, allowing accumulation of deposits in the second terrace in the western sector. The actual delta setting comprises only the eastern sector of the Lena Delta. (4) Peat formation. Polygenetic formation of ice-rich peaty sand (''Ice Complex'') was most extensive (7-11 m in thickness) in the southern part of the delta area between 43 and 14 ka BP (third terrace deposits). In recent times, alluvial peat (5-6 m in thickness) is accumulated on top of the deltaic sequences in the eastern sector (first terrace).

Stable isotopes, Mg/Ca ratios and sea surface temperatures on foraminifera from sediment cores off equatorial Peru during the last ~17kyr

The complex deglacial to Holocene oceanographic development in the Gulf of Guayaquil (Eastern Equatorial Pacific) is reconstructed for sea surface and subsurface ocean levels from (isotope) geochemical proxies based on marine sediment cores. At sea surface, southern sourced Cold Coastal Water and tropical Equatorial Surface Water/Tropical Surface Water are intimately related. In particular since ~10 ka, independent sea surface temperature proxies capturing different seasons emphasize the growing seasonal contrast in the Gulf of Guayaquil, which is in contrast to ocean areas further offshore. Cold Coastal Water became rapidly present in the Gulf of Guayaquil during the austral winter season in line with the strengthening of the Southeast Trades, while coastal upwelling off Peru gradually intensified and expanded northward in response to a seasonally changing atmospheric circulation pattern affecting the core locations intensively since 4 ka BP. Equatorial Surface Water, instead, was displaced and Tropical Surface Water moved northward together with the Equatorial Front. At subsurface, the presence of Equatorial Under Current-sourced Equatorial Subsurface Water was continuously growing, prominently since ~10-8 ka B.P. During Heinrich Stadial 1 and large parts of the Bølling/Allerød, and similarly during short Holocene time intervals at ~5.1-4 ka B.P. and ~1.5-0.5 ka B.P., the admixture of Equatorial Subsurface Water was reduced in response to both short-term weakening of Equatorial Under Current strength from the northwest and emplacement by tropical Equatorial Surface Water, considerably warming the uppermost ocean layers.