Seawater carbonate chemistry and calcification in the tropical urchin Echinometra viridis in a laboratory experiment

Atmospheric carbon dioxide (pCO2) has risen from approximately 280 to 400 ppm since the Industrial Revolution, due mainly to the combustion of fossil fuels, deforestation, and cement production. It is predicted to reach as high as 900 ppm by the end of this century. Ocean acidification resulting from the release of anthropogenic CO2 has been shown to impair the ability of some marine calcifiers to build their shells and skeletons. Here, we present the results of ocean acidification experiments designed to assess the effects of an increase in atmospheric pCO2 from ca. 448 to 827 ppm on calcification rates of the tropical urchin Echinometra viridis. Experiments were conducted under the urchin's winter (20 °C) and summer (30 °C) water temperatures in order to identify seasonal differences in the urchin's response to ocean acidification. The experiments reveal that calcification rates decreased for urchins reared under elevated pCO2, with the decline being more pronounced under wintertime temperatures than under summertime temperatures. These results indicate that the urchin E. viridis will be negatively impacted by CO2-induced ocean acidification that is predicted to occur by the end of this century. These results also suggest that impact of CO2-induced ocean acidification on urchin calcification will be more severe in the winter and in cooler waters.

Sedimentary record of the western Amundsen Sea Embayment after the last glacial maximum

Reliable dating of glaciomarine sediments deposited on the Antarctic shelf since the Last Glacial Maximum (LGM) is very challenging because of the general absence of calcareous (micro-) fossils and the recycling of fossil organic matter. As a consequence, radiocarbon (14C) ages of the acid-insoluble organic fraction (AIO) of the sediments bear uncertainties that are very difficult to quantify. In this paper we present the results of three different chronostratigraphic methods to date a sedimentary unit consisting of diatomaceous ooze and diatomaceous mud that was deposited following the last deglaciation at five core sites on the inner shelf in the western Amundsen Sea (West Antarctica). In three cores conventional 14C dating of the AIO in bulk sediment samples yielded age reversals down-core, but at all sites the AIO 14C ages obtained from diatomaceous ooze within the diatom-rich unit yielded similar uncorrected 14C ages ranging from 13,517±56 to 11,543±47 years before present (yr BP). Correction of these ages by subtracting the core-top ages, which are assumed to reflect present-day deposition (as indicated by 21044 Pb dating of the sediment surface at one core site), yielded ages between ca. 10,500 and 8,400 calibrated years before present (cal yr BP). Correction of the AIO ages of the diatomaceous ooze by only subtracting the marine reservoir effect (MRE) of 1,300 years indicated deposition of the diatom-rich sediments between 14,100 and 11,900 cal yr BP. Most of these ages are consistent with age constraints between 13.0 and 8.0 ka BP for the diatom-rich unit, which we obtained by correlating the relative palaeomagnetic intensity (RPI) records of three of the sediment cores with global and regional reference curves for palaeomagnetic intensity. As a third dating technique we applied conventional 53 radiocarbon dating of the AIO included in acid-cleaned diatom hard parts that were extracted from the diatomaceous ooze. This method yielded uncorrected 14C ages of only 5,111±38 and 5,106±38 yr BP, respectively. We reject these young ages, because they are likely to be overprinted by the adsorption of modern atmospheric carbon dioxide onto the surfaces of the extracted diatom hard parts prior to sample graphitisation and combustion for 14C dating. The deposition of the diatom-rich unit in the western Amundsen Sea suggests deglaciation of the inner shelf before ca. 13 ka BP. The deposition of diatomaceous oozes on other parts of the Antarctic shelf around the same time, however, seems to be coincidental rather than directly related.

Heavy metals and carbon isotope concentrations in recent Baltic Sea sediments

Recent sediment cores of the western Baltic Sea were analyzed for heavy metal and carbon isotope contents. The sedimentation rate was determined from radiocarbon dates to be 1.4 mm/yr. The 'recent age' of the sediment was about 850 yr. Within the upper 20 cm of sediment, certain heavy metals became increasingly enriched towards the surface; Cd, Pb, Zn and Cu increased 7-, 4-, 3- and 2-fold, respectively, whereas Fe, Mn, Ni and Co remained unchanged. Simultaneously, the radiocarbon content decreased by about 14 per cent. The enrichment in heavy metals as well as the decrease in the 14C-concentration during the last 130 ± 30yr parallels industrial growth as reflected in European fossil fuel consumption within that same period of time. The near-surface sediments are affected by residues released from fossil fuels at the rate of about 30 g/m**2 yr for the past two decades. The residues have a pronounced effect on the heavy metal and carbon isotope composition of the most Recent sediments allowing estimates to be made for sedimentation, erosion and heavy metal pollution.

Benthic foraminifera of the Red Sea

The distribution of living (Rose Bengal-stained), dead and fossil benthic foraminifera was investigated in six short cores (multicores, 30-32 cm total length) recovered from the central Red Sea. The ecological preferences as well as the relationship between the live and dead/fossil assemblages (preserved down-core) were examined. The sites, located along a W-E profile and between the depth of 366 and 1782 m, extend from the center of the oxygen minimum zone (OMZ, ~200-650 m), through its margin at ~600 m, and down to the well-aerated deep-water environment. Live (Rose-Bengal stained) and coexisting dead foraminifera were studied in the upper 5 cm of each of the sites, and the fossil record was studied down to ~32 cm. Q-mode Principal Component Analysis was used and four distinct foraminiferal fossil assemblages were determined. These assemblages follow different water mass properties. In the center of the OMZ, where the organic carbon content is highest and the oxygen concentration is lowest (<=0.5 ml O2/l), the Bolivina persiensis-Bulimina marginata-Discorbinella rhodiensis assemblage dominates. The slightly more aerated and lower organic-carbon-content seafloor, at the margin of the OMZ, is characterized by the Neouvigerina porrecta-Gyroidinoides cf. G. soldanii assemblage. The transitional environment, between 900-1200 m, with its well-aerated and oligotrophic seafloor, is dominated by the Neouvigerina ampullacea-Cibicides mabahethi assemblage. The deeper water (>1500 m), characterized by the most oxygenated and oligotrophic seafloor conditions, is associated with the Astrononion sp. A-Hanzawaia sp. A assemblage. Throughout the Red Sea extremely high values of temperature and salinity are constant below ~200 m depth, but the flux of organic matter to the sea floor varies considerably with bathymetry and appears to be the main controlling factor governing the distribution pattern of the benthic foraminifera. Comparison between live and the dead/fossil assemblages reveals a large difference between the two. Processes that may control this difference include species-specific high turnover rates, and preferential predation and loss of fragile taxa (either by chemical or microbial processes). Significant variations in the degree of loss of the organic-cemented agglutinants were observed down core. This group is preserved down to 5-10 cm at the shallow OMZ sites and down to greater depths at well-aerated and oligotrophic sites. The lower rate of disintegration of these forms, in the deeper locations of the Red Sea, may be related to low microbial activity. This results in the preservation of increasing numbers of organic-cemented shells down-core.

Late Quaternary deep sea sedimentation off the Niger delta

The oxygen isotopes ratios of benthic foraminifera and detailed radiocarbon ages of the organic matter of an over 15 m long sediment core from the outer Niger delta allow us to date the oxygen isotope stage boundaries 1/2 to 11500 (+/- 650) years BP, 2/3 to approximately 23000 (+/- 2000) years BP. The composition of the predominantly terrigenous clays and accessory pelagic fossils reflects the evolution of the climate over the southwestern Sahel zone and the response of the Eastern Tropical Atlantic to these climatic fluctuations during the Late Quaternary. The dilution of the pelagic fossil concentrations by the terrigenous material and the oxygen isotopes ratios of planktonic foraminifera indicate large fluctuations in the freshwater discharge from the Niger, with high precipitations over the drainage area of this river from 4500 (+/- 300) to 11500 (+/- 650) years BP and from 11800 (+(- 600) to 13000 (+/- 600) years BP while the time intervals in between were as dry as today. Relative increase of kaolinite during wet phases and the association of smectite, chlorite and attapulgite during dry ones characterize the response of the weathering in the Niger drainage basins to the climatic fluctuations. The occurrence of 10-14 A mixed-layers prior to 26000 years BP is correlated with moderate alteration of the crystalline substratum outcrops from the middle-lower part of the Niger Basin. High quartz concentrations are particularly typical for the transition between oxygen isotope stages 1 and 2 at the inception of heavy precipitations in the southern Sahel zone. Sedimentation rates were quite constant, 30-35 cm/1000 years; they became unusually large at the beginning of the Holocene from 10900 (+/- 650) to 11500 (+/- 650) years BP where they reached more than 600 cm/1000 years. Bottom waters around 1100 m depth in the Gulf of Guinea responded to changes in paleo-oceanography of the entire Atlantic Ocean as well as to local influences. Abnormal carbon isotopes ratios and the drastic changes from a highly diversified fauna (during stages 2 and 3. and during the last part of stage 1 after approx. 7000 years BP) to a poorly diversified fauna in the intervenin time span point to the development of a local benthic environment which cannot easily be compared with the corresponding continental and slope environments of the entire Atlantic Ocean.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

(Table 3, page 264), Composition of a manganese micronodule found in a fossil red clay bed from Western Timor

Chemical analyses are presented for two Cretaceous clays from Noil Tobee, Timor. Mineralogical examination has shown that they consist principally of quartz, feldspar, illite and chlorite, together with minor amounts of montmorillonite. Both chemically and mineralogically the clays are very similar to the recent argillaceous deep-sea sediments of the Pacific and Indian Oceans, which confirms Molengraaff's theory (1921) that they are of deep-sea origin. Further confirmation of this theory is provided by comparison of the composition of micromanganese nodules, separated from one of these clays, with that of manganese nodules from the Pacific Ocean.

Sea Surface Temperature (SST) Mg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides

We generated a high-resolution SSTMg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides from the core MD99-2346 collected in the Gulf of Lion, and compared it to that obtained using modern analogue techniques applied to fossil foraminiferal assemblages (SSTMAT). The two temperature records display similar patterns during the last 28,000 years but the SSTMg/Ca estimates are several degrees warmer (~+4 °C) than SSTMAT. The temperature shift between SSTMg/Ca and SSTMAT remained relatively constant over time. This seems to exclude a bias on the Mg/Ca record associated with salinity or secondary Mg-rich calcite encrustation on the foraminiferal tests during early diagenesis. Therefore, anomalously high Mg/Ca suggests either: (1) the empirical equation for G. bulloides of Elderfield and Ganssen (2000) is incorrect; or (2) there is a specific Mediterranean genotypes of G. bulloides for which a specific Mg/Ca-temperature calibration is needed.

Recent benthic foraminifera of the Scotia Sea and Argentine Basin

We investigated 88 surface sediment samples taken with a multiple corer from the southwestern South Atlantic Ocean for their live (Rose Bengal stained) and dead benthic foraminiferal content. Using Q-Mode Principal Component Analysis six live and six dead associations are differentiated. Live and dead association distributions correspond fairly well; differences are mainly caused by downslope transport and selective test destruction. In addition, four potential fossil associations are calculated from the dead data set after removal of non-fossilizable species. These potential fossil associations are expected to be useful for paleoceanographic reconstructions. Environments are described in detail for the live and potential fossil associations and for selected species. Along the upper Argentine continental slope strong bottom currents control the occurrence of live, dead and potential fossil Angulogerina angulosa associations. Here, particles of a high organic carbon flux rate remain suspended. Below this high energy environment live, dead and potential fossil Uvigerina peregrina dominated associations correlate with enhanced sediment organic carbon content and still high organic carbon flux rates. The live A. angulosa and U. peregrina associations correlate with high standing crops. Furthermore, live and dead Epistominella exigua-Nuttallides umbonifer associations were separated. Dominance of a Nuttallides umbonifer potential fossil association relates to coverage by Antarctic Bottom Water (AABW) and Lower Circumpolar Deep Water (LCDW), above the Calcite Compensation Depth (CCD). Three associations of mainly agglutinated foraminifera occur in sediments bathed mainly by AABW or CDW. A Reophax difflugiformis association was found in mud-rich and diatomaceous sediments. Below the CCD, a Psammosphaera fusca association occurs in coarse sediments poor in organic carbon while a Cribrostomoides subglobosus-Ammobaculites agglutinans association covers a more variable environmental range with mud contents exceeding 30%. One single Eggerella bradyi-Martinottiella communis association poor in both species and individuals remains from the agglutinated associations below the CCD if only preservable species are considered for calculation.

Exploring the potential of clumped isotope thermometry on coccolith-rich sediments as a sea surface temperature proxy

Understanding past changes in sea surface temperatures (SSTs) is crucial; however, existing proxies for reconstructing past SSTs are hindered by unknown ancient seawater composition (foraminiferal Mg/Ca and d18O), or reflect subsurface temperatures (TEX86) or have a limited applicable temperature range (Uk'37). We examine clumped isotope (D47) thermometry to fossil coccolith-rich material as an SST proxy, as clumped isotopes are independent of original seawater composition and applicable to a wide temperature range and coccolithophores are widespread and dissolution resistant. The D47-derived temperatures from <63, <20, <10 and 2-5 µm size fractions of two equatorial Pacific late Miocene-early Pliocene sediment samples (c1; c2) range between ~18-29 {degree sign}C, with c1 temperatures consistently above c2. Removing the >63 µm fraction removes most non-mixed layer components; however, the D47-derived temperatures display an unexpected slight decreasing trend with decreasing size fraction. This unexpected trend could partly arise because larger coccoliths (5-12 µm) are removed during the size fraction separation process. The c1 and <63 µm c2 D47-derived temperatures are comparable to concurrent Uk'37 SSTs. The <20, <10 and 2-5 µm c2 D47-derived temperatures are consistently cooler than expected. The D47-Uk'37 temperature offset is probably caused by abiotic/diagenetic calcite present in the c2 2-5 µm fraction (~53% by area), which potentially precipitated at bottom water temperatures of ~6 {degree sign}C . Our results indicate that clumped isotopes on coccolith-rich sediment fractions have potential as an SST proxy, particularly in tropical regions, providing that careful investigation of the appropriate size fraction for the region and timescale is undertaken.