Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Surface in situ measurements of atmospheric CO, CH4, and CO2 combined with selected meteorological measurements at the University of Wollongong, Australia

Wollongong, Australia is an urban site at the intersection of anthropogenic, biomass burning, biogenic and marine sources of atmospheric trace gases. The location offers a valuable opportunity to study drivers of atmospheric composition in the Southern Hemisphere. Here, a record of surface carbon monoxide (CO), methane (CH4) and carbon dioxide (CO2) was measured with an in situ Fourier transform infrared trace gas analyser between April 2011 and August 2014. Clean air was found to arrive at Wollongong in approximately 10% of air masses. Biomass burning influence was evident in the average annual cycle of clean air CO during austral spring. A significant negative short-term trend was found in clean air CO (-1.5 nmol/mol/a), driven by a reduction in northern Australian biomass burning. Significant short-term positive trends in clean air CH4 (5.4 nmol/mol/a) and CO2 (1.9 ?mol/mol/a) were consistent with the long-term global average trends. Polluted Wollongong air was investigated using wind-direction/wind-speed clustering, which revealed major influence from local urban and industrial sources from the south. High values of CH4, with anthropogenic DCH4/DCO2 enhancement ratio signatures, originated from the northwest, in the direction of local coal mining. A pollution climatology was developed for the region using back trajectory analysis and DO3/DCO enhancement ratios. Ozone production environments in austral spring and summer were associated with anticyclonic meteorology on the east coast of Australia, while ozone depletion environments in autumn and winter were associated with continental transport, or fast moving trajectories from southern latitudes. This implies the need to consider meteorological conditions when developing policies for controlling air quality.

Platinum group elements and geochemistry of altered oceanic crust of ODP Hole 140-504B

Primary chemical heterogeneity in the sheeted dike complex in Deep Sea Drilling Project Hole 504B makes these rocks unsuitable for conventional mass balance calculations in determining element mobility associated with hydrothermal alteration. Due to the original heterogeneity and variable degrees of fractionation in the dikes, an appropriate reference sample on which calculations can be based is difficult to find. Therefore, the use of incompatible element ratios is developed to evaluate geochemical changes during alteration(s). For example, on a Zr/Yb-La/Yb plot, scatter along a straight line suggests tapping of a variably depleted mantle source and deviation from the line suggests element mobility (gain or loss). Using this method, our data indicates that the hydrothermal evolution of the sheeted dike complex was accompanied by significant loss of Cu, Zn, and Ti and some loss of La. The sheeted dike complex has low platinum group element (PGE) concentrations and steep PGE patterns, typical of mid-ocean ridge basalts (MORBs) on the global scale. We propose that the unusual PGE patterns of MORBs cannot be entirely generated by a partial melting and sulfide segregation model; instead, these patterns in part must have been inherited from their mantle source. The Au data show no evidence for mobilization during hydrothermal alteration of the dikes.

Element concentrations and Osmium, Platinum and Rhenium isotope ratios of ODP Site 153-920 abyssal peridotites

Abyssal peridotites are normally thought to be residues of melting of the mid-ocean ridge basalt (MORB) source and are presumably a record of processes affecting the upper mantle. Samples from a single section of abyssal peridotite from the Kane Transform area in the Atlantic Ocean were examined for 190Pt-186Os and 187Re-187Os systematics. They have uniform 186Os/188Os ratios with a mean of 0.1198353 +/- 7, identical to the mean of 0.1198340 +/-12 for Os-Ir alloys and chromitites believed to be representative of the upper mantle. While the Pt/Os ratios of the upper mantle may be affected locally by magmatic processes, these data show that the Pt/Os ratio for the bulk upper mantle has not deviated by more than about +/- 30% from a chondritic Pt/Os ratio over 4.5 billion years. These observations are consistent with the addition of a chondritic late veneer after core separation as the primary control on the highly siderophile element budget of the terrestrial upper mantle. The 187Os/188Os of the samples range from 0.12267 to 0.12760 and correlate well with Pt and Pt/Os, but not Re/Os. These relationships may be explained by variable amounts of partial melting with changing D(Re), reflecting in part garnet in the residue, with a model-dependent melting age between about 600 and 1700 Ma. A model where the correlation between Pt/Os and 187Os/188Os results from multiple ancient melting events, in mantle peridotites that were later juxtaposed by convection, is also consistent with these data. This melting event or events are evidently unrelated to recent melting under mid-ocean ridges, because recent melting would have disturbed the relationship between Pt/Os and 187Os/188Os. Instead, this section of abyssal peridotite may be a block of refractory mantle that remained isolated from the convecting portions of the upper mantle for 600 Ma to >1 Ga. Alternatively, Pt and Os may have been sequestered during more recent melting and possibly melt/rock reaction processes, thereby preserving an ancient melting history. If representative of other abyssal peridotites, then the rocks from this suite with subchondritic 187Os/188Os are not simple residues of recent MORB source melting at ridges, but instead have a more complex history. This suite of variably depleted samples projects to an undepleted present-day Pt/Os of about 2.2 and 187Os/188Os of about 0.128-0.129, consistent with estimates for the primitive upper mantle.

Chemical and isotope composition of carbonate nodules and host bottom sediments from Core DM9-666, Gulf of California

Results of mineralogical and isotopic analyzes of sulfur and carbon in carbonate nodules and host bottom sediments and results of 14C measurement in carbonate nodules are reported. It is proved that the carbonate nodules formed 11-22 thousand years ago in anaerobic diagenesis of bottom sediments rich in organic matter. Isotopic light metabolic carbon dioxide was a source of carbonate for nodules. It formed during microbial degradation of organic matter of bottom sediments.

Concentrations and accumulation rates of chemical elements and sediment components in sediments of central equatorial Pacific, DSDP data

Accumulation rates of Mg, Al, Si, Mn, Fe, Ni, Cu, Zn, opal, and calcium carbonate have been calculated from their concentrations in samples from equatorial Deep Sea Drilling Project sites. Maps of element accumulation rates and of Q-mode factors derived from raw data indicate that the flux of trace metals to equatorial Pacific sediments has varied markedly through time and space in response to changes in the relative and absolute influence of several depositional influences: biogenic, detrital, authigenic, and hydrothermal sedimentation. Biologically derived material dominates the sediment of the equatorial Pacific. The distributions of Cu and Zn are most influenced by surface-water biological activity, but Ni, Al, Fe, and Mn are also incorporated into biological material. All of these elements have equatorial accumulation maxima similar to those of opal and calcium carbonate at times during the past 50 m.y. Detritus distributed by trade winds and equatorial surface circulation contributes Al, non-biogenic Si, Fe, and Mg to the region. Detrital sediment is most important in areas with a small supply of biogenic debris and low bulk-accumulation rates. Al accumulation generally increases toward the north and east, indicating its continental source and distribution by the northeast trade winds. Maxima in biological productivity during middle Eocene and latest Miocene to early Pliocene time and concomitant well-developed surface circulation contributed toward temporal maxima in the accumulation rates of Cu, Zn, Ni, and Al in sediments of those ages. Authigenic material is also important only where bulk-sediment accumulation rates are low. Ni, Cu, Zn, and sometimes Mn are associated with this sediment. Fe is almost entirely of hydrothermal origin. Mn is primarily hydrothermal, but some is probably scavenged from sea water by amorphous iron hydroxide floes along with other elements concentrated in hydrothermal sediments, Ni, Cu, and Zn. During the past 50 m.y. all of these elements accumulated over the East Pacific Rise at rates nearly an order of magnitude higher than those at non-rise-crest sites. In addition, factor analysis indicates that some of this material is carried substantial distances to the west of the rise crest. Accumulation rates of Fe in basal metalliferous sediments indicate that the hydrothermal activity that supplied amorphous Fe oxides to the East Pacific Rise areas was most intense during middle Eocene and late Miocene to early Pliocene time.

Mineral dust deposition in interglacial and glacial climate conditions: model results

The global aerosol/climate model ECHAM5-HAM is used in order to investigate the dust cycle for four interglacial and one glacial climate conditions. The 20-year time-slices are the pre-industrial control (CTRL), mid-Holocene (6000 years BP), last glacial inception (115000 years BP), Eemian (126000 years BP) and Last Glacial Maximum (LGM) (21000 years BP) time intervals. The study is focused on the Antarctic region. The model is able to reproduce the magnitude order of dust deposition globally for the pre-industial and LGM climates. Correlation coefficient of the natural logarithm of the observed and modeled values is 0.78 for the CTRL and 0.81 for the LGM. For the pre-industrial simulation the model overestimates observed values in Antarctica by a factor of about 2-3 due to overestimation of the Australian dust source and too high wet deposition in the Antarctica interior. In the LGM, the model underestimates dust deposition in eastern Antarctica by a factor of about 4-5 due to underestimation of the South American dust source. More records are needed to validate dust deposition for the past interglacial time-slices. The modeled results show that dust deposition in Antarctica in the past interglacial time-slices is higher than in the CTRL simulation. The largest increase of dust deposition in Antarctica is simulated for the LGM, showing about 10-fold increase compared to CTRL.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Geochemistry of Cretaceous sediments from Argo and Gascoyne Abyssal Plains

The accumulation of organic matter, ferrous and pyrite iron, and the ratios of organic carbon/total sulfur and organic carbon/total phosphorus in the Lower Cretaceous sediments from the Argo and Gascoyne abyssal plains have been used as indicators of both the source and reactivity of organic matter in the sediments and the depositional environment. Total sulfur, used as an indicator of pyrite sulfur, is more abundant in sediments from the Gascoyne Abyssal Plain than in those from the Argo Abyssal Plain. Sulfur positively correlates with TOC at both sites (although poorly at the Argo Abyssal Plain site, R = 0.48), with an extension of the line of best-fit through the origin, indicating that pyrite (TOC <2 wt%) is diagenetic and deposited from normal marine conditions. The average ratio of C/S for samples of TOC <2 wt% is 5.4 at Argo Abyssal Plain (compared to the modern normal marine value of 2.8) indicating deposition of organic matter probably of mixed terrestrial and oxidized marine sources that is unreactive to the sulfate-reducing bacteria. One sample from the Aptian sediments is rich in TOC (5.1 wt%) and has a C/S ratio of 0.5. The average C/S ratio in Gascoyne Abyssal Plain sediments is 0.8 (R = 0.97), which indicates the formation of abundant pyrite in addition to burial and preservation of relatively fresh organic matter that is reactive to the sulfate-reducing bacteria. Organic carbon to phosphorus ratios (C/P) in the sediments indicate preferential remobilization of organic carbon over phosphorus with increasing water depth. Estimates of the degree of pyritization (DOP) increase with increasing TOC at both sites, indicating iron is not limiting and pyrite is formed diagenetically. The one sample with a TOC content of 5.1 wt%, from the Argo Abyssal Plain near the Barremian-Aptian boundary, is composed mostly of framboidal pyrite, finely laminated and not bioturbated, and hence may have been deposited during a brief period of anoxia in the overlying waters.

Sedimentation rate, bulk density, accumulation rate of terrigenous material and grain sizes of ODP Leg 167 sites

The terrigenous mineral fraction of sediments recovered by drilling during Ocean Drilling Program Leg 167 at Sites 1018 and 1020 is used to evaluate changes in the source and transport of fine-grained terrigenous sediment and its relation to regional climates and the paleoceanographic evolution of the California Current system during the late Pleistocene. Preliminary time scales developed by correlation of oxygen isotope stratigraphies with the global SPECMAP record show average linear sedimentation rates in excess of 100 m/m.y., which provide an opportunity for high-resolution studies of terrigenous flux, grain size, and mineralogy. The mass flux of terrigenous minerals at Site 1018 varies from 5 to 30 g/(cm**2 x k.y.) and displays a general trend toward increased flux during glacials. The terrigenous record at Site 1020 shows a similar pattern of increased glacial input, but overall accumulation rates are significantly lower. Spectral analysis demonstrates that most of this variability is concentrated in frequency bands related to orbital cycles of eccentricity, tilt, and precession. Detailed grain-size analysis performed on the isolated terrigenous mineral fraction shows that sediments from Site 1018 are associated with higher energy transport and depositional regimes than those found at Site 1020. Grain-size data are remarkably uniform throughout the last 500 k.y., with no discernible difference observed between glacial and interglacial size distributions within each site. X-ray diffraction analysis of the <2-µm clay component suggests that the deposition of minerals found at Site 1020 is consistent with transport from a southern source during intervals of increased terrigenous input.

Sm-Nd, Rb-Sr, and He isotopic composition and hydrocarbon gases in rocks and minerals from the Markov Deep, Mid-Atlantic Ridge rift valley

The paper presents characteristics of the Nd and Sr isotopic systems of ultrabasic rocks, gabbroids, plagiogranites, and their minerals as well as data on helium and hydrocarbons in fluid inclusions of the same samples. Materials presented in this publication were obtained by studying samples dredged from the MAR crest zone at 5°-6°N (U/Pb zircon dating, geochemical and petrological-mineralogical studies). It was demonstrated that variations in the isotopic composition of He entrapped in rocks and minerals were controlled by variable degrees of mixing of juvenile He, which is typical of basaltic glass for MAR (DM source), and atmospheric He. Increase in the atmospheric He fraction in plutonic rocks and, to a lesser degree, in their minerals reflects involvement of seawater or hydrated material of the oceanic crust in magmatic and postmagmatic processes. This conclusion finds further support in positive correlation between the fraction of mantle He (R ratio) and 87Sr/86Sr ratio. High-temperature hydration of ultrabasic rocks (amphibolization) was associated with increase in the fraction of mantle He, while their low-temperature hydration (serpentinization) was accompanied by drastic decrease in this fraction and significant increase in 87Sr/86Sr ratio. Insignificant variations in 143Nd/144Nd (close to 0.5130) and 87Sr/86Sr (0.7035) in most of gabbroids and plagiogranites as well as the fraction of mantle He in these rocks, amphibolites, and their ore minerals indicate that the melts were derived from the depleted mantle. Similar e-Nd values of gabbroids, plagiogranites, and fresh harzburgites (6.77-8.39) suggest that these rocks were genetically related to a single mantle source. e-Nd value of serpentinized lherzolites (2.62) likely reflects relations of these relatively weakly depleted mantle residues to another source. Aforementioned characteristics of the rocks generally reflect various degrees of mixing of depleted mantle components with crustal components (seawater) during metamorphic and hydrothermal processes that accompanied formation of the oceanic crust.

Characteristics and distribution of Neogene turbidites at ODP Site 108-657

Numerous and variable silty-sandy siliciclastic turbidites were observed in Neogene pelagic sediments (late Miocene to Holocene) at Site 657: (1) thick-bedded, coarse-grained and thin-bedded, fine-grained turbidites; and (2) turbidites composed of eolian dune sand and shallow-water bioclasts or of fluvial-sand or mixed sandy component assemblages. The stratigraphic distribution of these turbidites indicates five periods during which climatic conditions and material sources change. Turbidite occurrence prior to 6.2 Ma (late Miocene) is sparse; the deposits contain coarse and fine-grained turbidites with quartz grains of eolian or mixed origin suggesting the existence of arid conditions at about 8.5 and 6.5 Ma. A coarse-grained turbidite of fluvial origin, recording a humid climate, occurs at about 6.2 Ma. During the early Pliocene, turbidites are frequent (15/Ma); they contain only fine-grained sequences comprising material of mixed origin, which indicates a more humid climate perhaps. The late Pliocene starts with rare coarse-grained turbidites of wind-transported sand while the uppermost Pliocene deposits show a higher frequency of fine-grained sequences (10/0.7 Ma) composed mainly of fluvial material. During the early Pleistocene, similar high turbidite frequency was observed (20/1.3 Ma) but with a total lack of eolian supply. During the last 0.7 Ma, the frequency decreases and the sequences are characterized by highly variable sediment components that could be related to strong variations of climatic conditions. The sedimentary characteristics of turbidites are mainly controlled by sediment source and climate. The frequency must be influenced by sea-level variations, by cyclic processes of climatic origin, and possibly by variations in the continental slope morphology. Clay mineral assemblages suggest a south Saharan source of terrigenous material during the late Miocene and the Pliocene and a northwest Saharan source during the Pleistocene.

Fecal pellet ingestion rate and feeding behavior of Oithona similis, Calanus helgolandicus and Pseudocalanus elongatus from the North Sea

Studies of fecal pellet flux show that a large percentage of pellets produced in the upper ocean is degraded within the surface waters. It is therefore important to investigate these degradation mechanisms to understand the role of fecal pellets in the oceanic carbon cycle. Degradation of pellets is mainly thought to be caused by coprophagy (ingestion of fecal pellets) by copepods, and especially by the ubiquitous copepods Oithona spp. We examined fecal pellet ingestion rate and feeding behavior of O. similis and 2 other dominant copepod species from the North Sea (Calanus helgolandicus and Pseudocalanus elongatus). All investigations were done with fecal pellets as the sole food source and with fecal pellets offered together with an alternative suitable food source. The ingestion of fecal pellets by all 3 copepod species was highest when offered together with an alternative food source. No feeding behavior was determined for O. similis due to the lack of pellet capture in those experiments. Fecal pellets offered together with an alternative food source increased the filtration activity by C. helgolandicus and P. elongatus and thereby the number of pellets caught in their feeding current. However, most pellets were rejected immediately after capture and were often fragmented during rejection. Actual ingestion of captured pellets was rare (<37% for C. helgolandicus and <24% for P. elongatus), and only small pellet fragments were ingested unintentionally along with alternative food. We therefore suggest coprorhexy (fragmentation of pellets) to be the main effect of copepods on the vertical flux of fecal pellets. Coprorhexy turns the pellets into smaller, slower-sinking particles that can then be degraded by other organisms such as bacteria and protozooplankton.

(Table 1) Carbon and lipids at DSDP Hole 61-462

The lipids of a Pliocene and a Cretaceous sample from Site 462 were analyzed to assess their source and diagenetic history. Judging from the distributions of the n-alkanes, n-fatty acids, n-alkylcyclohexanes and molecular markers, they are autochthonous, of marine origin, and deposited under oxic paleoenvironmental conditions of sedimentation. The stereochemistry of the various molecular markers (e.g., triterpanes and steranes) of the Pliocene sample indicates that the lipids are geologically mature. This supports the hypothesis of sediment recycling from older formations by turbidite redistribution into the Nauru Basin