Mineral and chemical compositions of hydrothermal ores and sediments from the Menez Gwen Hydrothermal Field, Mid-Atlantic Ridge

Mineralogy and geochemistry of sulfide-bearing rocks and ores discovered within the Menez Gwen Hydrothermal Field are studied. Samples were taken during Cruise 49 of R/V Akademik Mstislav Keldysh of the p.p. Shirshov Institute of Oceanology. Mineral composition of rocks and ores were studied by traditional methods of optical microscopy, scanning electron microscopy (CAMSCAN), and microprobe analysis (EPMA SX-50). Contents of trace elements were determined by laser ablation inductively coupled plasma - mass spectrometry (LA-ICP-MS). Zn-Cu ore comprises zonal sulfide chimney intergrowths. Numerous Se-rich copper ore fragments occur in volcanomictic layered gritstones and/or barite slabs. Mineral composition, zonality and association of trace elements in ore are typical of black smokers formed at the basalt base near the Azores Triple Junction in the MAR. Obtained results make it possible to reconstruct formation history of the Menez Gwen Hydrothermal Field into the high-temperature (Cu-Se association in ore clasts), medium-temperature (Zn-Cu-As association in ore), and recent (Ba-SiO2 association) stages.

Neodymium isotope composition of planktonic foraminifera from ODP Hole 121-758A

This study presents neodymium isotope and elemental data for cleaned planktonic foraminifera from ODP site 758 in the southernmost reaches of the Bay of Bengal in the north-east Indian Ocean. Cleaning experiments using oxidative-reductive techniques suggest that diagenetic Fe-Mn oxyhydroxide coatings can be effectively removed, and that the measured Nd isotope composition reflects the composition of seawater from which the foraminiferal calcium carbonate was precipitated. Modern core-top Pulleniatina obliquiloculata and Globorotalia menardii give epsilon-Nd values of 310.12 +/- 0.16 and 310.28 +/- 0.16, respectively, indistinguishable from recent direct measurements of surface seawater in this area. A high-resolution Nd isotope record obtained from G. menardii for the past 150 kyr shows systematic variations (Delta epsilon-Nd = 3) on glacial-interglacial timescales. The timing of those variations shows a remarkable correspondence with the global oxygen isotope record, which suggests a process controlling the Nd isotope composition that responds in phase with global climate cycles. Palaeoclimate reconstruction indicates that during the last glacial maximum changes in monsoon circulation resulted in a reduction in rainfall over the Indian subcontinent, and a decrease in the flux of river water delivered to the Bay of Bengal. Thus, changes in the riverine input of Nd, a change in either flux or composition, most likely caused the isotope variations, although changes in dust source or local ocean circulation may have also played a role. These results clearly establish a link between climate change and variations in radiogenic isotopes in the oceans, and illustrate the potential of Nd isotopes in foraminifera for highresolution palaeoceanographic reconstruction.

Thallium isotope composition in pyrites

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ~183 Ma) are compared with data from Late Neogene (<10 Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment-water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment-water interface. The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate. The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.

Calcium isotopic composition of planktonic foraminifera from ODP Site 154-925

An 18 million year record of the Ca isotopic composition (d44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. ?44/42Ca in this record averages +0.37+/-0.05 (1 sigma SD) and ranges from +0.21? to +0.52?. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25? lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their d44/42Ca (i.e., by 0.06+/-0.06? (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in d44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (d44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (D_sed) results in unrealistically large variations in the total mass of Ca2+ in the oceans over the Neogene. Alternatively, variations of +/-0.05? in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in d44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in D_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in d44/42Ca_w and D_sed have been established, modeling the Ca2+ content of seawater from Ca isotope curves should be approached cautiously.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Carbonate system of surface sediments from the South Pacific

B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].

Os isotope ratios of sediments from the Eocene-Oligocene boundary

Osmium (Os) isotope analyses of bulk sediments from the South Atlantic, Equatorial Pacific, and the Italian Apennines yield a well-dated and coherent pattern of 187Os/188Os variation from the late Eocene to the early Oligocene. The resulting composite record demonstrates the global character of two prominent features of the low-resolution LL44-GPC3 Os isotope record (Pegram and Turekian, 1999, doi:10.1016/S0016-7037(99)00308-7). These are: (1) a pronounced minimum in 187Os/188Os (0.22-0.27) in the late Eocene, between 34 and 34.5 Ma, and (2) a subsequent rapid increase in 187Os/188Os, to approximately 0.6 by 32 Ma. An ultramafic weathering event and an increased influx of extraterrestrial particles to the Earth are discussed as alternative explanations for the late Eocene 187Os/188Os minimum. Comparison of the 187Os/188Os to benthic foraminiferal oxygen isotope records demonstrates that the nearly three-fold increase in 187Os/188Os from the late Eocene minimum coincides with the growth and decay of the first large ice sheet of the Oligocene (Oi1 (Miller et al., 1991, doi:10.1029/90JB02015)). The fine structure of the Os isotope record indicates that enhanced release of radiogenic Os, unrelated to the recovery from late Eocene minimum, lagged the initiation of the Oi1 event by roughly 0.5 Myr. This record, in conjunction with weathering studies in modern glacial soils (Blum, in: W.F. Ruddiman (Ed.), Tectonic Uplift and Climate Change, Plenum Press, New York, 1997, pp. 259-288; Peucker-Ehrenbrink and Blum, 1998, doi:10.1016/S0016-7037(98)00227-0), suggests that exposure of freshly eroded material during deglaciation following Oi1 enhanced chemical weathering rates, and may have contributed to ice sheet stabilization by drawing down atmospheric carbon dioxide. The improved temporal resolution and age control of the refined Eocene-Oligocene Os isotope record also makes it possible to illustrate the late Eocene Os isotope excursion as a tool for global correlation of marine sediments.

Geochemistry of ODP Site 145-882

Measurements of benthic foraminiferal cadmium:calcium (Cd/Ca) have indicated that the glacial-interglacial change in deep North Pacific phosphate (PO4) concentration was minimal, which has been taken by some workers as a sign that the biological pump did not store more carbon in the deep glacial ocean. Here we present sedimentary redox-sensitive trace metal records from Ocean Drilling Program (ODP) Site 882 (NW subarctic Pacific, water depth 3244 m) to make inferences about changes in deep North Pacific oxygenation - and thus respired carbon storage - over the past 150,000 yr. These observations are complemented with biogenic barium and opal measurements as indicators for past organic carbon export to separate the influences of deep-water oxygen concentration and sedimentary organic carbon respiration on the redox state of the sediment. Our results suggest that the deep subarctic Pacific water mass was depleted in oxygen during glacial maxima, though it was not anoxic. We reconcile our results with the existing benthic foraminiferal Cd/Ca by invoking a decrease in the fraction of the deep ocean nutrient inventory that was preformed, rather than remineralized. This change would have corresponded to an increase in the deep Pacific storage of respired carbon, which would have lowered atmospheric carbon dioxide (CO2) by sequestering CO2 away from the atmosphere and by increasing ocean alkalinity through a transient dissolution event in the deep sea. The magnitude of change in preformed nutrients suggested by the North Pacific data would have accounted for a majority of the observed decrease in glacial atmospheric pCO2.

Chemical and mineral compositions of altered peridotites from ODP Leg 209

Abyssal peridotite from the 15°20'N area of the Mid-Atlantic Ridge show complex geochemical variations among the different sites drilled during ODP Leg 209. Major element compositions indicate variable degrees of melt depletion and refertilization as well as local hydrothermal metasomatism. Strongest evidence for melt-rock interactions are correlated Light Rare Earth Element (LREE) and High Field Strength Element (HFSE) additions at Sites 1270 and 1271. In contrast, hydrothermal alteration at Sites 1274, 1272, and 1268 causes LREE mobility associated with minor HFSE variability, reflecting the low solubility of HFSE in aqueous solutions. Site 1274 contains the least-altered, highly refractory, peridotite with strong depletion in LREE and shows a gradual increase in the intensity of isochemical serpentinization; except for the addition of H2O which causes a mass gain of up to 20 g/100 g. The formation of magnetite is reflected in decreasing Fe(2+)/Fe(3+) ratios. This style of alteration is referred to as rock-dominated serpentinization. In contrast, fluid-dominated serpentinization at Site 1268 is characterized by gains in sulfur and development of U-shaped REE pattern with strong positive Eu anomalies which are also characteristic for hot (350 to 400°C) vent-type fluids discharging from black smoker fields. Serpentinites at Site 1268 were overprinted by talc alteration under static conditions due to interaction with high a_SiO2 fluids causing the development of smooth, LREE enriched patterns with pronounced negative Eu anomalies. These results show that hydrothermal fluid-peridotite and fluid-serpentinite interaction processes are an important factor regarding the budget of exchange processes between the lithosphere and the hydrosphere in slow spreading environments.

Neodymium isotopes from fossil fish teeth and detrital sediment, and oxygen isotopes from benthic forams from ODP Hole 119-738 B

Ephemeral polar glaciations during the middle-to-late Eocene (48-34 Ma) have been proposed based on far-field ice volume proxy records and near-field glacigenic sediments, although the scale, timing, and duration of these events are poorly constrained. Here we confirm the existence of a transient cool event within a new high-resolution benthic foraminiferal d18O record at Ocean Drilling Program (ODP) Site 738 (Kerguelen Plateau; Southern Ocean). This event, named the Priabonian oxygen isotope maximum (PrOM) Event, lasted ~140 kyr and is tentatively placed within magnetochron C17n.1n (~37.3 Ma) based on the correlation to ODP Site 689 (Maud Rise, Southern Ocean). A contemporaneous change in the provenance of sediments delivered to the Kerguelen Plateau occurs at the study site, determined from the <63 µm fraction of decarbonated and reductively leached sediment samples. Changes in the mixture of bottom waters, based on fossil fish tooth epsilon-Nd, were less pronounced and slower relative to the benthic d18O and terrigenous epsilon-Nd changes. Terrigenous sediment epsilon-Nd values rapidly shifted to less radiogenic signatures at the onset of the PrOM Event, indicating an abrupt change in provenance favoring ancient sources such as the Paleoproterozoic East Antarctic craton. Bottom water epsilon-Nd reached a minimum value during the PrOM Event, although the shift begins much earlier than the terrigenous epsilon-Nd excursion. The origin of the abrupt change in terrigenous sediment provenance is compatible with a change in Antarctic terrigenous sediment flux and/or source as opposed to a reorganization of ocean currents. A change in terrigenous flux and/or source of Antarctic sediments during the oxygen isotope maximum suggests a combination of cooling and ice growth in East Antarctica during the early late Eocene.