Spatial distribution of isotopic compositions of Globigerina bulloides and Neogloboquadrina pachyderma (dex.) and the faunal assemblages of planktic foraminifera in surface sediment samples along the Chilean continental slope between 23°S and 44°S

We report on the spatial distribution of isotopic compositions of the two planktic foraminifera species Globigerina bulloides and Neogloboquadrina pachyderma (dex.), and the faunal assemblages of planktic foraminifera in 91 surface sediment samples along the Chilean continental slope between 23°S and 44°S. Both d13C and d18O data of N. pachyderma (dex.) show little variability in the study area. North of 39°S, the isotopic values of N. pachyderma (dex.) are heavier than those of G. bulloides, whereas south of 39°S, this relation inverses. This is indicative for a change from a well-mixed, deep thermocline caused by coastal upwelling north of 39°S to well-stratified water masses in a non-upwelling environment south of 39°S. In addition, the faunal composition of planktic foraminifera marks this change by transition from an upwelling assemblage north of 39°S to a high-nutrient-non-upwelling assemblage south of 39°S, which is characterized by decreased contributions of upwelling indicators such as G. bulloides, N. pachyderma (sin.), and Globigerinita glutinata. In general, we can conclude that food and light rather than temperature are the primary control of the planktic foraminiferal assemblage between 23°S and 44°S off Chile. Our data point to higher marine productivity at upwelling centers north of 25°S and at 30-33°S. South of 39°S, significant supply of nutrients by fluvial input most likely boosts the productivity.

Atmospheric nitrate concentrations and isotope composition for samples collected in the marine boundary layer in 2006 and 2007

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the d15N of nitrate mostly deriving from anthropogenically emitted NOx is found to be significantly different (from 0 to 6 per mil) from nitrate sampled in locations influenced by natural NOx sources (-4 ± 2) per mil. The effects on d15N(NO3-) of different NOx sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (D17O = d17O - 0.52 × d18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NOx sinks. Different D17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low d15N values (down to -40 per mil) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NOx from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

Nd and Sr isotope compositions, REE concentrations and Al/Ca ratios of different phases of surface sediments in the South Pacific

The radiogenic isotope composition of neodymium (Nd) and strontium (Sr) are useful tools to investigate present and past oceanic circulation or input of terrigenous material. We present Nd and Sr isotope compositions extracted from different sedimentary phases, including early diagenetic Fe-Mn coatings, "unclean" foraminiferal shells, fossil fish teeth, and detritus of marine surface sediments (core-tops) covering the entire midlatitude South Pacific. Comparison of detrital Nd isotope compositions to deep water values from the same locations suggests that "boundary exchange" has little influence on the Nd isotope composition of western South Pacific seawater. Concentrations of Rare Earth Elements (REE) and Al/Ca ratios of "unclean" planktonic foraminifera suggest that this phase is a reliable recorder of seawater Nd isotope composition. The signatures obtained from fish teeth and "nondecarbonated" leachates of bulk sediment Fe-Mn oxyhydroxide coatings also agree with "unclean" foraminifera. Direct comparison of Nd isotope compositions extracted using these methods with seawater Nd isotope compositions is complicated by the low accumulation rates yielding radiocarbon ages of up to 24 kyr, thus mixing the signal of different ocean circulation modes. This suggests that different past seawater Nd isotope compositions have been integrated in authigenic sediments from regions with low sedimentation rates. Combined detrital Nd and Sr isotope signatures indicate a dominant role of the Westerly winds transporting lithogenic material from South New Zealand and Southeastern Australia to the open South Pacific. The proportion of this material decreases toward the east, where supply from the Andes increases and contributions from Antarctica cannot be ruled out.

Seasonal fatty acid and fatty alcohol composition of Pseudocalanus minutus and Oithona similis in Kongsfjorden (Svalbard)

Seasonal lipid dynamics of various developmental stages were investigated in Pseudocalanus minutus and Oithona similis. For P. minutus, the dominance of 16:1(n?7), 16:4(n?3) and 20:5(n?3) fatty acids indicated a diatom-based nutrition in spring, whereas 22:6(n?3), 16:0, 18:2(n?6) and 18:1(n?9) pointed to a flagellate-based diet during the rest of the year as well as omnivorous/carnivorous low-level feeding during winter. The shorter-chain fatty alcohols 14:0 and 16:0 prevailed, also reflecting biosynthetic processes typical of omnivores or carnivores. Altogether, the lipid signatures characterized P. minutus as an opportunistic feeder. In contrast, O. similis had consistently high amounts of the 18:1(n?9) fatty acid in all stages and during all seasons pointing to a generally omnivorous/carnivorous/detritivorous diet. Furthermore, the fatty alcohol 20:1(n?9) reached high percentages especially in adult females and males, and feeding on Calanus faecal pellets is suggested. Fatty alcohols, as wax ester moieties, revealed significant seasonal variations in O. similis and a seasonal trend towards wax ester accumulation in autumn in P. minutus. P. minutus utilized its lipid deposits for development in the copepodite stages III and IV and for gonad maturation in CV and females during the dark season. However, CVs and females depended on the spring phytoplankton bloom for final maturation processes and reproduction. O. similis fueled gonad maturation and egg production for reproduction in June by wax esters, whereas reproduction in August/September co-occurred with the accumulation of new depot lipids. Both species revealed significantly higher wax ester levels in deeper (>50 m) as compared to surface (0-50 m) dwelling individuals related to a descent prior to overwintering.

Gel particles in the sea-surface microlayer during an experimental study

Since the early 80's, the sea-surface microlayer (SML) has been hypothesized as being a gelatinous film. Recent studies have confirmed this characteristic, which confers properties that mediate mass and energy fluxes between ocean and atmosphere, including the emission of primary organic aerosols from marine systems. We investigated SML thickness and composition in five replicate indoor experiments between September and December 2010. During each experiment, the SML and underlying seawater were sampled from four seawater tanks: one served as control, and three were inoculated with Thalassiosira weissflogii grown in chemostats at 180, 380 and 780 ppm pCO2. We examined organic material enrichment factors in each tank, paying particular attention to gel particles accumulation such as polysaccharidic Transparent Exopolymer Particles (TEP) and the proteinaceous Coomassie Stainable Particles (CSP). While previous studies have observed carbohydrates and TEP enrichment in the microlayer, little is yet known about proteinaceous gel particles in the SML. Our experiments show that CSP dominate the gelatinous composition of the SML. We believe that the enrichment in CSP points to the importance of bacterial activity in the microlayer. Bacteria may play a pivotal role in mediating processes at the air-sea interface thanks to their exudates and protein content that can be released through cell disruption.

(Table 1) Biological and chemical characteristics of surface water stations during Nathaniel B. Palmer cruise NBP06-08 to the Ross Sea

We present results from a field study of inorganic carbon (C) acquisition by Ross Sea phytoplankton during Phaeocystis-dominated early season blooms. Isotope disequilibrium experiments revealed that HCO3? was the primary inorganic C source for photosynthesis in all phytoplankton assemblages. From these experiments, we also derived relative enhancement factors for HCO3?/CO2 interconversion as a measure of extracellular carbonic anhydrase activity (eCA). The enhancement factors ranged from 1.0 (no apparent eCA activity) to 6.4, with an overall mean of 2.9. Additional eCA measurements, made using membrane inlet mass spectrometry (MIMS), yielded activities ranging from 2.4 to 6.9 U/[?g chl a] (mean 4.1). Measurements of short-term C-fixation parameters revealed saturation kinetics with respect to external inorganic carbon, with a mean half-saturation constant for inorganic carbon uptake (K1/2) of ~380 ?M. Comparison of our early springtime results with published data from late-season Ross Sea assemblages showed that neither HCO3? utilization nor eCA activity was significantly correlated to ambient CO2 levels or phytoplankton taxonomic composition. We did, however, observe a strong negative relationship between surface water pCO2 and short-term 14C-fixation rates for the early season survey. Direct incubation experiments showed no statistically significant effects of pCO2 (10 to 80 Pa) on relative HCO3? utilization or eCA activity. Our results provide insight into the seasonal regulation of C uptake by Ross Sea phytoplankton across a range of pCO2 and phytoplankton taxonomic composition.

Oxygen and carbon isotopic composition in Eocene and Oligocene planktonic and benthic foraminifera from DSDP sediments

Oxygen and carbon isotope ratios in Eocene and Oligocene planktonic and benthic foraminifera have been investigated from Atlantic, Indian, and Pacific Ocean locations. The major changes in Eocene-Oligocene benthic foraminiferal oxygen isotopes were enrichment of up to 1 per mil in 18O associated with the middle/late Eocene boundary and the Eocene/Oligocene boundary at locations which range from 1- to 4-km paleodepth. Although the synchronous Eocene-Oligocene 18O enrichment began in the latest Eocene, most of the change occurred in the earliest Oligocene. The earliest Oligocene enrichment in 18O is always larger in benthic foraminifera than in surface-dwelling planktonic foraminifera, a condition that indicates a combination of deep-water cooling and increased ice volume. Planktonic foraminiferal d18O does not increase across the middle/late Eocene boundary at our one site with the most complete record (Deep Sea Drilling Project Site 363, Walvis Ridge). This pattern suggests that benthic foraminiferal d18O increased 40 m.y. ago because of increased density of deep waters, probably as a result of cooling, although glaciation cannot be ruled out without more data. Stable isotope data are averaged for late Eocene and earliest Oligocene time intervals to evaluate paleoceanographic change. Average d18O of benthic foraminifera increased by 0.64 per mil from the late Eocene to the early Oligocene d18O maximum, whereas the average increase for planktonic foraminifera was 0.52 per mil. This similarity suggests that the Eocene/Oligocene boundary d18O increase was caused primarily by increased continental glaciation, coupled with deep sea cooling by as much as 2°C at some sites. Average d18O of surface-dwelling planktonic foraminifera from 14 upper Eocene and 17 lower Oligocene locations, when plotted versus paleo-latitude, reveals no change in the latitudinal d18O gradient. The Oligocene data are offset by ~0.45 per mil, also believed to reflect increased continental glaciation. At present, there are too few deep sea sequences from high latitude locations to resolve an increase in the oceanic temperature gradient from Eocene to Oligocene time using oxygen isotopes.

Sediment composition and stable isotopic ratio of Neogloboquadrina pachyderma from DSDP Site 94-609_Site, North Altlantic

Digitized records of optical desnity in many North Atlantic cores exihibt rapid changes from lighter to darker extrems, typically within less than 200 years, at the 5d/5e, 5b/5c and 4/5 boundaries. In cores from DSDP site 609 the changes from lighter to darker color coincide with increasing in relative abundance of Neogloboquadrina pachyderma (l.c.), with increases in abundances of lithic grains and with decreasing in carbonate content. The rapid changes to dark color, therefore, are climate-driven and correspond to a lowering of seas surface temperatures and to increases in amounts of ice rafted debris relative to biogenic carbonate. At the 5d&4c boundary, delta18O in N. pachyderma (l.c.) increases abruptly with the change to darker sediments as expected for cooler sea surface temperatures. At the 4/5 boundary, however, delta18O decreases with the change to darker sediment and cooler sea surface temperatures, suggesting that a layer of fresh surface water was present in the North Atlantic at that time.

Recent ostracods in surface sediment samples from Admiralty Bay, King George Island, West Antarctica

Ostracods from Admiralty Bay on King George Island (South Shetland Islands) represent 29 podocopid species, belonging to 19 genera, one cladocopid and six myodocopid species. They were recovered from Recent marine and/or glacio-marine sediment samples from water depths of up to 520 m. These ostracods constitute a variable assemblage, which is overall typical for the Antarctic environment. Shallow-water assemblages tend to be more variable in terms of frequencies and species richness than deep-water assemblages. The later are low in numbers and remain relatively high diversities. Overall, no linear relation between ostracod assemblage-composition and environmental features analyzed was recognized.

Occurrence and isotopic composition (d18O, d13C) of benthic foraminifera in sediments from DSDP Leg 72

Changes in the vertical water mass structure of the Vema Channel during the Pliocene have been inferred from benthic foraminiferal assemblages and stable isotopic analyses from three sites of DSDP Leg 72 (South Atlantic). Faunal and isotopic results from Sites 516A and 518 suggest that a major change occurred in deep-water circulation patterns in the late Pliocene near 3.2 Ma. Benthic oxygen isotopic records from Sites 516A and 518 show a characteristic increase in d18O values near 3.2 Ma. This has been documented in numerous Pliocene isotopic records. The magnitude of the oxygen isotopic enrichment near 3.2 Ma appears to increase with water depth from an average enrichment of 0.34 per mil in Site 516A (1313 m) to an average enrichment of 0.58 per mil in Site 518 (3944 m). We suggest that this enrichment resulted partly from a change in deep-water circulation patterns which included a decrease in bottom-water temperatures. Planktonic d18O values near 3.2 Ma show no evidence of an enrichment which would be indicative of an increase in global ice volume. On the contrary, d18O values in Sites 517 and 518 become more depleted near 3.2 Ma, indicating a surface-water warming perhaps due to a change in the strength and/or position of the Brazil Current. An increase in the relative abundance of the benthic foraminifer Nuttalides umbonifera, which is associated with Antarctic Bottom Water (AABW) in the modern ocean, coincides with the benthic 18O enrichment in Site 518. At 3.2 Ma, oxygen and carbon isotopic gradients between Sites 518 (3944 m) and 516A (1313 m) show a marked increase such that Site 518 becomes enriched in 18O and depleted in 13C relative to Site 516A. This enrichment in d18O is interpreted as partly representing a temperature decrease at Site 518; the depletion in d13C indicates a corrosive water mass which is high in metabolic CO2. We suggest that benthic foraminiferal and stable isotopic changes in Site 518 resulted from a pulse-like increase in the formation of AABW near 3.2 Ma. The cause of this circulation event may have been linked to global cooling and/or the final closure of the Central American Seaway.

Stable oxygen and carbon isotope composition of benthic foraminifera from the western Mediterranean Sea

The influence of microhabitat, organic matter flux, and metabolism on the stable oxygen and carbon isotope composition of live (Rose Bengal stained) and dead (empty tests) deep-sea benthic foraminifera from the Gulf of Lions (western Mediterranean Sea) have been studied. The total range of observed foraminiferal isotope values exceeds 1.0 per mil for d18O and 2.2 per mil for d13C demonstrating a wide range of coexisting disequilibria relative to d18O of equilibrium calcite (d18OEQ) and d13C of bottom water dissolved inorganic carbon (d13CDIC). The mean d18O values reveal strongest disequilibria for the studied epifaunal to shallow infaunal species (Cibicidoides pachydermus, Uvigerina mediterranea, Uvigerina peregrina) while values approach equilibrium in deep infaunal species (Globobulimina affinis, Globobulimina pseudospinescens). The mean d13C values decrease with increasing average living depths of the different species, thus reflecting a dominant microhabitat (pore water) signal. At the axis of the Lacaze-Duthier Canyon a minimum d13CDIC pore water gradient of approximately -2.1 per mil is assessed for the upper 6 cm of the surface sediment. Although live individuals of U. mediterranea were found in different depth intervals their mean d13C values are consistent with calcification at an average living depth around 1 cm. The deep infaunal occurrence of U. mediterranea specimens suggests association with macrofaunal burrows creating a microenvironment with geochemical characteristics similar to the topmost centimeter. This also explains the excellent agreement between stable isotope signals of live and dead individuals. The ontogenetic enrichment in both d18O and d13C values of U. mediterranea suggests a slow-down of metabolic rates during test growth similar to that previously observed in planktic foraminifera. Enhanced organic carbon fluxes and higher proportion of resuspended terrestrial organic material at the canyon axis are reflected by d13C values of U. mediterranea on average 0.58 per mil lower than those from the open slope. These results demonstrate the general applicability of the d13C signal of this species for the reconstruction of past organic matter fluxes in the Mediterranean Sea. Further studies on live specimens are needed for a more quantitative paleoceanographic approach.

Sedimentology and Th, Pa, U, and N isotopic composition of core MD84-527

High-resolution records of opal, carbonate, and terrigenous fluxes have been obtained from a high-sedimentation rate core (MD84-527: 43°50'S; 51°19'E; 3269 m) by normalization to 230Th. This method estimates paleofluxes to the seafloor on a point-by-point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents. We also measured sediment delta15N to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations. Our results show that opal accumulation rates on the seafloor during the Holocene and stage 3, based on 14C dating, were respectively tenfold and fivefold higher than the vertical rain rates, At this particular location, changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column. Correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230Th disclose important variations in opal rain rates. We found relatively high but variable opal paleoflux during stage 3, with two maxima centered at 36 and 30 kyr B.P., low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early Holocene, We interpret this record as reflecting variations in opal production rates associated with climate-induced latitudinal migration of the southern ocean frontal system. Sediments deposited during periods of high opal paleoflux also have high authigenic U concentrations, suggesting more reducing conditions in the sediment, and high Pa-231/Th-230 ratios, suggesting increased scavenging from the water column. Sediment delta15N is circa 1.5 per mil higher during isotopic stage 2 and deglaciation. The low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion. This suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column. Increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid, leading to lower nitrate supply rates to surface waters.

Composition of Eocene claystones of ODP Hole 105-647A

Authigenic carbonates were recovered in lower to middle Eocene claystones at Ocean Drilling Program Site 647 in the Labrador Sea. Detailed chemical, petrographic, and X-ray investigations reveal that these diagenetic carbonates have a complex mineralogical composition. At least five different carbonate phases are identified: calcium-rich rhodochrosite, rhodochrosite, manganosiderite, siderite, and calcite. Manganese carbonates are the dominant carbonate phases formed throughout the section. Textural analyses show two major generations of carbonate formation. Early cementation of micritic carbonate in burrow structures was followed by carbonate cementation forming microsparry to sparry crystals. At approximately 620 meters below seafloor (mbsf), three concretions of iron carbonates occur, which indicates a special pore-water chemistry. Thin section analyses from this level show (1) several generations of diagenetic carbonates, (2) widespread secondary cavity formation in burrow structures, and (3) various cement precipitations in voids. We suggest that this level represents a hiatus or highly condensed sequence, as indicated by (1) the low carbonate content in host sediments, (2) carbonate dissolution reflected by the high ratio of benthic to planktonic foraminifers, and (3) complex diagenetic alteration in the carbonate concretions. Iron and manganese enrichments observed in lithologic Unit IV may have been derived from a hydrothermal source at the adjacent, then active, Labrador Sea mid-ocean ridge. Authigenic smectites forming numerous pseudomorphs of siliceous microfossils are precipitated in burrow structures. We propose that diagenetic smectite formation from biogenic opal and iron oxyhydroxide (analogous to smectite formation in surface sediments of the East Pacific area) occurred in the Labrador Sea during the early and middle Eocene.