Benthic foraminiferal stable isotope record for the equatorial Pacific

Stable oxygen and carbon isotope (d18O and d13C) values measured in foraminiferal calcite are one of the primary tools used in paleoceanography. Diagenetic recrystallization of foraminiferal calcite can act to reset primary isotopic values, but its effects are typically poorly quantified. Here we test the impact of early stage diagenesis on stable isotope records generated from a suite of drill sites in the equatorial Pacific Ocean recovered during Ocean Drilling Program Leg 199 and Integrated Ocean Drilling Program Expedition 320. Our selected sites form paleowater and burial depth transects, with excellent stratigraphic control allowing us to confidently correlate our records. We observe large intersite differences in the preservation state of benthic foraminiferal calcite, implying very different recrystallization histories, but negligible intersite offsets in benthic d18O and d13C values. We infer that diagenetic alteration of benthic foraminiferal calcite (in sedimentary oozes) must predominantly occur at shallow burial depths (<100 m) where offsets in both the temperature and isotopic composition of waters in which the foraminifera calcified and pore waters in which diagenesis occurs are small. Our results suggest that even extensive recrystallization of benthic foraminiferal calcite results in minimal shifts from primary d18O and d13C values. This finding supports the long-held suspicion that diagenetic alteration of foraminiferal calcite is less problematic in benthic than in planktic foraminifera and that in deep-sea sediments routinely employed for paleoceanographic studies benthic foraminifera are robust recorders of stable isotope values in the fossil record.

Age models and stable isotope record of sediment cores from the Atlantic Ocean

The high-resolution delta18O and delta13C records of benthic foraminifera from a 150,000-year long core from the Caribbean Sea indicate that there was generally high delta13C during glaciations and low delta13C during interglaciations. Due to its 1800-m sill depth, the properties of deep water in the Caribbean Sea are similar to those of middepth tropical Atlantic water. During interglaciations, the water filling the deep Caribbean Sea is an admixture of low delta13C Upper Circumpolar Water (UCPW) and high delta13C Upper North Atlantic Deep Water (UNADW). By contrast, only high delta13C UNADW enters during glaciations. Deep ocean circulation changes can influence atmospheric CO2 levels (Broecker and Takahashi, 1985; Boyle, 1988 doi:10.1029/JC093iC12p15701; Keir, 1988 doi:10.1029/PA003i004p00413; Broecker and Peng, 1989 doi:10.1029/GB003i003p00215). By comparing delta13C records of benthic foraminifera from cores lying in Southern Ocean Water, the Caribbean Sea, and at several other Atlantic Ocean sites, the thermohaline state of the Atlantic Ocean (how close it was to a full glacial or full interglacial configuration) is characterized. A continuum of circulation patterns between the glacial and interglacial extremes appears to have existed in the past. Subtracting the deep Pacific (~mean ocean water) delta13C record from the Caribbean delta13C record yields a record which describes large changes in the Atlantic Ocean thermohaline circulation. The delta13C difference varies as the vertical nutrient distribution changes. This new proxy record bears a striking resemblance to the 150,000-year-long atmospheric CO2 record (Barnola et al., 1987 doi:10.1038/329408a0). This favorable comparison between the new proxy record and the atmospheric CO2 record is consistent with Boyle's (1988a) model that vertical nutrient redistribution has driven large atmospheric CO2 changes in the past. Changes in the relative contribution of NADW and Pacific outflow water to the Southern Ocean are also consistent with Broecker and Peng's (1989) recent model for atmospheric CO2 changes.

Stable carbon isotope record of sediment core Bass_River_Site

A thick, apparently continuous section recording events of the latest Paleocene thermal maximum in a neritic setting was drilled at Bass River State Forest, New Jersey as part of ODP Leg 174AX [Miller, Sugarman, Browning et al., 1998]. Integrated nannofossil and magneto-stratigraphy provides a firm chronology supplemented by planktonic foraminiferal biostratigraphy. This chronologic study indicates that this neritic section rivals the best deep-sea sections in providing a complete record of late Paleocene climatic events. Carbon and oxygen isotopes measured on benthic foraminifera show a major (4.0% in carbon, 2.3% in oxygen) negative shift correlative with the global latest Paleocene carbon isotope excursion (CIE). A sharp increase in kaolinite content coincides with the isotope shift in the Bass River section, analogous to increases found in several other records. Carbon and oxygen isotopes remain low and kaolinite content remains high for the remainder of the depositional sequence above the CIE (32.5 ft, 9.9 m), which we estimate to represent 300-500 k.y. We interpret these data as indicative of an abrupt shift to a warmer and wetter climate along the North American mid-Atlantic coast, in concert with global events associated with the CIE.

(Fig. 1) Stable carbon and oxygen isotope ratios of foraminifera of ODP Hole 113-690B

A remarkable oxygen and carbon isotope excursion occurred in Antarctic waters near the end of the Palaeocene (~57.33 Myr ago), indicating rapid global warming and oceanographic changes that caused one of the largest deep-sea benthic extinctions of the past 90 million years. In contrast, the oceanic plankton were largely unaffected, implying a decoupling of the deep and shallow ecosystems. The data suggest that for a few thousand years, ocean circulation underwent fundamental changes producing a transient state that, although brief, had long-term effects on environmental and biotic evolution.

(Table 1) Stable carbon and oxygen isotope ratios of benthic foraminifera of ODP Hole 184-1148A

Changes in intermediate and deep ocean circulation likely played a significant role in global carbon cycling and meridional heat/moisture transport during the middle Miocene climate transition (~14 Ma). High-resolution middle Miocene (16-13 Ma) benthic foraminifer stable isotope records from the South China Sea reveal a reorganization of regional bottom waters, which preceded the globally recognized middle Miocene ~1 per mil d18O increase (13.8 Ma) by 100,000 years. An observed reversal of the benthic foraminifera d13C gradient between ODP Sites 1146 (2092 m) and 1148 (3294 m; 13.9-13.5 Ma) is interpreted to reflect an increase in the southward flux of low d13C deep (> 2000 m) Pacific Ocean waters (Flower and Kennett, 1993, doi:10.1029/93PA02196; Shevenell and Kennett, 2004). Large-scale changes in Pacific intermediate and deep ocean circulation, coupled with enhanced global carbon cycling at the end of the Monterey Carbon Isotope excursion, likely acted as internal feedbacks to the Earth's climate system. These feedbacks reduced the sensitivity of Antarctica to lower latitude-derived heat/moisture and facilitated the transition of the Earth's climate system to a new, relatively stable glacial state.

Layer description, carbon and nitrogen content and stable isotope record of bulk sedimentary organic matter from Laguna Potrok Aike

An investigation of stable isotope (d13C TOC and d15N TN) and elemental parameters (TOC, TN contents and TOC/TN ratios) of bulk organic matter (<200 µm) from sediment cores recovered from the Patagonian lake Laguna Potrok Aike (Argentina) in the framework of the ICDP deep drilling project PASADO provided insights into past changes in lake primary productivity and environmental conditions in South Patagonia throughout the last Glacial-Interglacial transition. Stratigraphically constrained cluster analyses of all proxy parameters suggest four main phases. From ca 26,100 to 17,300 cal. years BP, lacustrine phytoplankton was presumably the predominant organic matter source in an aquatic environment with low primary productivity rates. At around 17,300 cal. years BP, abrupt and distinct shifts of isotopic and elemental values indicate that the lacustrine system underwent a rapid reorganization. Lake primary productivity (phytoplankton and aquatic macrophytes) shows higher levels albeit with large variations during most of the deglaciation until 13,000 cal. years BP. The main causes for this development can be seen in improved growing conditions for primary producers because of deglacial warming in combination with expedient availability of nutrients and likely calm wind conditions. After 13,000 cal. years BP, decreased d13C TOC values, TOC, TN contents and TOC/TN ratios indicate that the lake approached a new state with reduced primary productivity probably induced by unfavourable growing conditions for primary producers like strengthened winds and reduced nutrient availability. The steady increase in d15N TN values presumably suggests limitation of nitrate supply for growth of primary producers resulting from a nutrient shortage after the preceding phase with high productivity. Nitrate limitation and consequent decreased lacustrine primary productivity continued into the early Holocene (10,970-8400 cal. years BP) as reflected by isotopic and elemental values.

Stable oxygen isotope record of foraminifera from the Ontong Java Plateau

We provide a reconstruction of atmospheric CO2 from deep-sea sediments, for the past 625000 years (Milankovitch chron). Our database consists of a Milankovitch template of sea-level variation in combination with a unique data set for the deep-sea record for Ontong Java plateau in the western equatorial Pacific. We redate the Vostok ice-core data of Barnola et al. (1987, doi:10.1038/329408a0). To make the reconstructions we employ multiple regression between deep-sea data, on one hand, and ice-core CO2 data in Antarctica, on the other. The patterns of correlation suggest that the main factors controlling atmospheric CO2 can be described as a combination of sea-level state and sea-level change. For best results squared values of state and change are used. The square-of-sea-level rule agrees with the concept that shelf processes are important modulators of atmospheric CO2 (e.g., budgets of shelf organic carbon and shelf carbonate, nitrate reduction). The square-of-change rule implies that, on short timescales, any major disturbance of the system results in a temporary rise in atmospheric CO2.

Termination II record, stable isotopes and trace elements of Stagamite MF-3 from Schafsloch Cave

The timing and nature of the penultimate deglaciation, also known as Termination II (T-II), is subject of controversial discussions due to the scarcity of precisely-dated palaeoclimate records. Here we present a new precisely-dated and highly-resolved multi-proxy stalagmite record covering T-II from the high alpine Schafsloch Cave in Switzerland, an area where climate is governed by the North Atlantic. The inception of stalagmite growth at 137.4 ± 1.4 kyr before present (BP) indicates the presence of drip water and cave air temperatures of above 0 °C, and is related to a climate-induced change in the thermal state (from cold-to warm-based) of the glacier above the cave. The cessation of stalagmite growth between 133.1 ± 0.7 and 131.9 ± 0.6 kyr BP is most likely related to distinct drop in temperature associated with Heinrich stadial 11. The resumption of stalagmite growth at 131.9 ± 0.6 kyr BP is accompanied by an abrupt increase in temperature and precipitation as indicated by distinct shifts in the oxygen and carbon isotopic composition as well as in trace element concentrations. The mid-point of T-II is around 131.8 ± 0.6 kyr BP in the Schafsloch Cave record is significantly earlier compared to the age of 129.1 ± 0.1 kyr BP in the Sanbao Cave record from China. The different ages between both records can be best explained by the competing effects of insolation and glacial boundary forcing on seasonality and snow cover extent in Eurasia.

Stable carbon and oxygen isotopes and Mg/Ca ratios of foraminifers from ODP Site 202-1241 sediments

A combination of stable isotope records and Mg/Ca temperature estimates of four different planktonic foraminiferal species from Ocean Drilling Program Site 1241 allows differentiation between temperature and salinity changes in the tropical east Pacific (TEP) upper water column during the Pliocene (~5.7-2.1 Ma). The deviation of d18O records and Mg/Ca temperature estimates from thermocline-dwelling planktonic foraminifers suggests that local changes in salinity exerted a much stronger control on Pliocene TEP upper ocean water mass signatures than previously assumed. The most pronounced Pliocene change in TEP upper ocean stratification was the shoaling of the thermocline from ~4.8 to 4.0 Ma that was possibly triggered by changes in the configuration of low-latitude ocean gateways. During this time interval, mixed-layer temperatures and salinities remained relatively constant in contrast to a pronounced temperature (~6°C) and salinity decrease at the bottom of the photic zone. This change led to a new state in the thermal structure of the TEP, as the thermocline remained relatively shallow until ~2.1 Ma.

Stable isotopes, PCBs and pesticide concentrations in zooplankton, seawater and POM from Kongsfjorden and Liefdefjorden, Svalbard

Differences in bioaccumulation of persistent organic pollutants (POPs) between fjords characterized by different water masses were investigated by comparing POP concentrations, patterns and bioaccumulation factors (BAFs) in seven species of zooplankton from Liefdefjorden (Arctic water mass) and Kongsfjorden (Atlantic water mass), Svalbard, Norway. No difference in concentrations and patterns of POPs was observed in seawater and POM; however higher concentrations and BAFs for certain POPs were found in species of zooplankton from Kongsfjorden. The same species were sampled in both fjords and the differences in concentrations of POPs and BAFs were most likely due to fjord specific characteristics, such as ice cover and timing of snow/glacier melt. These confounding factors make it difficult to conclude on water mass (Arctic vs. Atlantic) specific differences and further to extrapolate these results to possible climate change effects on accumulation of POPs in zooplankton. The present study suggests that zooplankton do biomagnify POPs, which is important for understanding contaminant uptake and flux in zooplankton, though consciousness regarding the method of evaluation is important.

d13C and d15N stable isotopes values, total nitrogen and C/N ratios of sediment core GeoB4801-1

Rising stable nitrogen isotope ratios (d15N) in dated sediment records of the German Bight/SE North Sea track river-induced coastal eutrophication over the last 2 centuries. Fully exploiting their potential for reconstructions of pristine conditions and quantitative analysis of historical changes in the nitrogen cycle from these sediment records requires knowledge on processes that alter the isotopic signal in non-living organic matter (OM) of sinking particles and sediments. In this study, we analyze the isotopic composition of particulate nitrogen (PN) in the water column during different seasons, in surface sediments, and in sediment cores to assess diagenetic influences on the isotopic composition of OM. Amino acid (AA) compositions of suspended matter, surface sediments, and dated cores at selected sites of the German Bight serve as indicators for quality and degradation state of PN. The d15N of PN in suspended matter had seasonal variances caused by two main nitrate sources (oceanic and river) and different stages of nitrate availability during phytoplankton assimilation. Elevated d15N values (> 20 per mil) in suspended matter near river mouths and the coast coincide with a coastal water mass receiving nitrate with elevated isotope signal (d15N > 10 per mil) derived from anthropogenic input. Particulate nitrogen at offshore sites fed by oceanic nitrate having a d15N between 5 and 6 per mil had low d15N values (< 2 per mil), indicative of an incipient phytoplankton bloom. Surface sediments along an offshore-onshore transect also reflect the gradient of low d15N of nitrate in offshore sites to high values near river mouths, but the range of values is smaller than between the end members listed above and integrates the annual d15N of detritus. Sediment cores from the coastal sector of the gradient show an increasing d15N trend (increase of 2.5 per mil) over the last 150 years. This is not related to any change in AA composition and thus reflects eutrophication. The d15N signals from before AD 1860 represent a good estimation of pre-industrial isotopic compositions with minimal diagenetic overprinting. Rising d13C in step with rising d15N in these cores is best explained by increasing productivity caused by eutrophication.

(Table 1) Peak intensities and stable carbon and oxygen isotope ratios of various diagenetic carbonates of ODP Site 128-799

Abundant and various diagenetic carbonates were recovered from a 1084-m-thick, Quaternary to lower Miocene section at ODP Site 799 in the Japan Sea. Petrographic, XRD, SEM, EDS-chemical, and isotopic analyses revealed wide variations in occurrence and textural relations and complex mineralogy and chemistry. Diagenetic carbonates include calcite, calcium-rich rhodochrosite, iron- and manganese-rich magnesite, iron- and manganese-rich dolomite and ankerite, and iron- and manganeserich lansfordite (hydrous Mg-carbonate). Rhodochrosite commonly occurs as small, solid nodules and semi-indurated, thin layers in bioturbated, mottled sediments of Units I and II (late Miocene to Quaternary). Lansfordite occurs as unindurated nodules and layers in Unit II (late Miocene and Pliocene), whereas magnesite forms indurated beds a few centimeters thick in slightly bioturbated-to-faintly laminated sediments of Unit III (middle and late Miocene). Some rhodochrosite nodules have dark-colored, pyritic cores, and some pyrite-rhodochrosite nodules are overgrown by and included within magnesite beds. Dolomite and ankerite tend to form thick beds (>10 cm) in bedded to laminated sediments of Units III, IV, and V (early to late Miocene). Calcite occurs sporadically throughout the Site 799 sediments. The d18O values of carbonates and the interstitial waters, and the measured geothermal gradient indicate that almost all of the Site 799 carbonates are not in isotopic equilibrium with the ambient waters, but were precipitated in the past when the sediments were at shallower depths. Depths of precipitation obtained from the d18O of carbonates span from 310 to 510 mbsf for magnesite and from 60 to 580 mbsf for dolomite-ankerite. Rhodochrosite and calcite are estimated to have formed within sediments at depths shallower than 80 mbsf. Diagenetic history in the Site 799 sediments have been determined primarily by the environment of deposition; in particular, by the oxidation-reduction state of the bottom waters and the alkalinity level of the interstitial waters. Under the well-oxygenated bottom-water conditions in the late Miocene and Pliocene, manganese initially accumulated on the seafloor as hydrogenous oxides and subsequently was mobilized and reprecipitated as rhodochrosite within the shallow sulfate-reduction, sub-oxic zone. Precipitation of lansfordite occurred in the near-surface sediments with abundant organic carbon and an extremely high alkalinity during the latest Miocene and Pliocene. The lansfordite was transformed to magnesite upon burial in the depth interval 310 to 510 mbsf. Dolomite first precipitated at shallow depths in Mn-poor, anoxic, moderately biocalcareous sediments of early to late Miocene. With increasing temperature and depth, the dolomite recrystallized and reequilibrated with ambient waters at depths below about 400 mbsf.

Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis

Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. delta 13C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significantly lighter with increasing seawater pCO2. Together with a decrease in the difference between delta 13C values of both fractions at the higher pCO2 sites, these results indicate there is a greater net autotrophic input to the A. viridis carbon budget under high pCO2 conditions. delta 15N values and C/N ratios did not change in Symbiodinium and host tissue along the pCO2 gradient. Additional physiological parameters revealed anemone protein and Symbiodinium chlorophyll a remained unaltered among sites. Symbiodinium density was similar among sites yet their mitotic index increased in anemones under elevated pCO2. Overall, our findings show that A. viridis is characterized by a higher autotrophic/heterotrophic ratio as pCO2 increases. The unique trophic flexibility of this species may give it a competitive advantage and enable its potential acclimation and ecological success in the future under increased ocean acidification.