Late Quaternary variations in calcium carbonate preservation of deep-sea sediments in the northern Cape Basin: results from a multiproxy approach

In this study, we test various parameters in deep-sea sediments (bulk sediment parameters and changes in microfossil abundances and preservation character) which are generally accepted as indicators of calcium carbonate dissolution. We investigate sediment material from station GeoB 1710-3 in the northern Cape Basin (eastern South Atlantic), 280 km away from the Namibian coast, well outside today’s coastal upwelling. As northern Benguela upwelling cells were displaced westward and periodically preceded the core location during the past 245 kyr (Volbers et al., submitted), GeoB 1710-3 sediments reflect these changes in upwelling productivity. Results of the most commonly used calcium carbonate dissolution proxies do not only monitor dissolution within these calcareous sediments but also reflect changes in upwelling intensity. Accordingly, these conventional proxy parameters misrepresent, to some extent, the extent of calcium carbonate dissolution. These results were verified by an independent dissolution proxy, the Globigerina bulloides dissolution index (BDX′) (Volbers and Henrich, submitted). The BDX′ is based on scanning electronic microscope ultrastructural investigation of planktonic foraminiferal tests and indicates persistent good carbonate preservation throughout the past 245 kyr, with the exception of one pronounced dissolution event at early oxygen isotopic stage (OIS) 6.

The early OIS 6 is characterized by calcium carbonate contents, sand contents, and planktonic foraminiferal concentrations all at their lowest levels for the last 245 kyr. At the same time, the ratio of radiolarian to planktonic foraminiferal abundances and the ratio of benthic to planktonic foraminiferal tests are strongly increased, as are the rain ratio, the fragmentation index, and the BDX′. The sedimentary calcite lysocline rose above the core position and GeoB 1710-3 sediments were heavily altered, as attested to by the unusual accumulation of pellets, aggregates, sponge spicules, radiolaria, benthic foraminifera, and planktonic foraminiferal assemblages.

Solely the early OIS 6 dissolution event altered the coarse fraction intensely, and is therefore reflected by all conventional calcium carbonate preservation proxies and the BDX′. We attribute the more than 1000 m rise of the sedimentary calcite lysocline to the combination of two processes: (a) a prominent change in the deep-water mass distribution within the South Atlantic and (b) intense degradation of organic material within the sediment (preserved as maximum total organic carbon content) creating microenvironments favorable for calcium carbonate dissolution.     

Shell preservation of Limacina inflata (Pteropoda) in surface sediments from the Central and South Atlantic Ocean: a new proxy to determine the aragonite saturation state of water masses

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive “metabolic” aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and δ¹³C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO₂ release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.     

Influence of export rain ratio changes on atmospheric CO<Subscript>2</Subscript> and sedimentary calcite preservation

The responses of atmospheric pCO₂ and sediment calcite content to changes in the export rain ratio of calcium carbonate to organic carbon are examined using a diffusion-advection ocean biogeochemical model coupled to a one-dimensional sediment geochemistry model. Our model shows that a 25% reduction in rain ratio decreases atmospheric pCO₂ by 59 ppm. This is caused by alkalinity redistribution by a weakened carbonate pump and an alkalinity increase in the whole ocean via carbonate compensation with decreasing calcite burial. The steady state responses of sedimentary calcite content and calcite preservation efficiency are rather insensitive to the deepening of the saturation horizon of 1.9 km. This insensitivity is a result of the reduced deposition flux that decreases calcite burial, counteracting the saturation horizon deepening that increases calcite burial. However, in the first 10,000 years the effect of reduced calcite deposition on the burial change is more prominent; while after 10,000 years, the effect of saturation horizon deepening is more dominant. The lowering of sediment calcite content for the first 10,000 years is effectively decoupled from the 1.9 km downward shift of the saturation horizon. Our results are in part a consequence of the more dominant role that respiration CO₂ plays in sediment calcite dissolution over bottom water chemistry in our control run and support the decoupling of calcite lysocline depth and saturation horizon shifts, as suggested originally by Archer and Maier-Reimer (1994) and Archer et al. (2000).     

Foraminiferal shell-weight evidence for sedimentary calcite dissolution above the lysocline

Shell-weight measurements were carried out on planktonic foraminifera G. sacculifer and G. ruber specimens from coretop depth transects in the Atlantic, Indian and Pacific Ocean to investigate calcite dissolution above the lysocline. The results suggest that foraminifera deposited in sediments overlain by supersaturated bottom water undergo considerable dissolution at the sediment–water interface and that the calcite saturation state at the interface is considerably offset from that of bottom water. Also, the extent of exposure to undersaturated conditions at the interface is not constant. Rather, it increases towards the surface ocean, i.e. towards shallow marine sediments where the organic matter flux is expected to be higher. It is proposed that the benthic fluff layer at the sediment–water interface represents a zone of undersaturation through which the foraminifera pass prior to deeper burial, and that the residence time of foraminifera within this zone of intense organic matter respiration is long enough to result in significant decreases in shell weight.     

Deep-water carbonate concentrations in the southwest Pacific

We have compiled carbonate chemistry and sedimentary CaCO₃% data for the deep-waters (>1500 m water depth) of the southwest (SW) Pacific region. The complex topography in the SW Pacific influences the deep-water circulation and affects the carbonate ion concentration ([CO₃2−]), and the associated calcite saturation horizon (CSH, where ??_calcite=1). The Tasman Basin and the southeast (SE) New Zealand region have the deepest CSH at ∼3100 m, primarily influenced by middle and lower Circumpolar Deep Waters (m or lCPDW), while to the northeast of New Zealand the CSH is ∼2800 m, due to the corrosive influence of the old North Pacific deep waters (NPDW) on the upper CPDW (uCPDW). The carbonate compensation depth (CCD; defined by a sedimentary CaCO₃ content of <20%), also varies between the basins in the SW Pacific. The CCD is ∼4600 m to the SE New Zealand, but only ∼4000 m to the NE New Zealand. The CaCO₃ content of the sediment, however, can be influenced by a number of different factors other than dissolution; therefore, we suggest using the water chemistry to estimate the CCD. The depth difference between the CSH and CCD (??Z_CSH−CCD), however, varies considerably in this region and globally. The global ??Z_CSH−CCD appears to expand with increase in age of the deep-water, resulting from a shoaling of the CSH. In contrast the depth of the chemical lysocline (??_calcite=0.8) is less variable globally and is relatively similar, or close, to the CCD determined from the sedimentary CaCO₃%. Geochemical definitions of the CCD, however, cannot be used to determine changes in the paleo-CCD. For the given range of factors that influence the sedimentary CaCO₃%, an independent dissolution proxy, such as the foraminifera fragmentation % (>40%=foraminiferal lysocline) is required to define a depth where significant CaCO₃ dissolution has occurred back through time. The current foraminiferal lysocline for the SW Pacific region ranges from 3100-3500 m, which is predictably just slightly deeper than the CSH. This compilation of sediment and water chemistry data provides a CaCO₃ dataset for the present SW Pacific for comparison with glacial/interglacial CaCO₃ variations in deep-water sediment cores, and to monitor future changes in [CO₃2−] and dissolution of sedimentary CaCO₃ resulting from increasing anthropogenic CO₂.     

Signatures of different water masses in δ<Superscript>18</Superscript>O values,relative abundance of <Emphasis Type="Italic">G. Bulloides</Emphasis> and total planktonic foraminiferal assemblage across the Indian Ocean sector of the southern ocean: Initial results

Nineteen surface sediment samples, collected onboard ORV Sagar Kanya during the 199C and 200th (the pilot expedition to Southern Ocean) cruises along a north-south transect between 1.92° S to 55.01° S latitude and 67.88° E and 44.89° E longitude, were studied for total planktonic foraminiferal assemblage, relative abundance and the oxygen isotopic values of the indicator planktic species Globigerina bulloides. These profiles were compared with the latitudinal variations in the average salinity and nutrient (phosphate) contents of the top 100 meters water column. The initial results have traced the signatures of salinity linked variations of different water masses in the study region. The influence of Australian Mediterranean Water (AAMW) has been noticed in the present dataset.     

Late Quaternary carbonate sedimentation at the Sierra Leone Rise (eastern equatorial Atlantic Ocean)

In the eastern equatorial Atlantic Ocean, changes in the concentration of carbonate in Late Quaternary sediments resulted from reduced production of carbonate in surface waters and increased dilution with non-carbonate sediments during glacial maxima. During glacial stages, production of carbonate in surface water (measured as its accumulation rate in shallow, undissolved cores) decreased by one half. The glacial accumulation rate of non-carbonate components increased 1.5 to 4 times over Holocene values; the greatest increases occurred in the deepest cores.

Carbonate dissolution during stages 2, 3 and 4 increased the proportion of foraminiferal fragments and decreased the accumulation rate of susceptible species in the deep sites. In shallow sites, slightly increased dissolution can be detected during stage 3 while greatly increased dissolution occurred during stage 4. Bathymetric profiles of foraminiferal fragmentation and accumulation document a shoaling of the foraminiferal lysocline by 1000 m during glacial isotopic stages. We present a mass balance model of sediment accumulation for carbonate and insoluble components and from this model we estimate the rate of downslope transport and dissolution of carbonate at the Sierra Leone Rise. Our results show that during stage 4 the rate of carbonate loss to dissolution was greater than the rate observed today or during other interglacial stages. The calculated rates of dissolution for stages 2 and 3 are not significantly different from those calculated for stage 1.     

Occurrence of an exceptional carbonate dissolution episode during early glacial isotope stage 6 in the Southeastern Atlantic

Concentration and mass accumulation rate profiles from Southeastern Atlantic sediment cores located off Namibia show that an exceptional episode in benthic carbonate dissolution occurred during early glacial isotope stage 6 (substages 6.6 and 6.5) between about 186 000 and 170 000 yr BP. Although this episode is restricted to or is more pronounced in this region than in other areas of the Atlantic Ocean, its exceptional character with respect to older and younger climatic episodes at the same site cannot be fully explained by local factors alone, but requires a combination of local and global influences. The onset of the carbonate dissolution episode is related to a more efficient transfer of organic matter from surface eutrophic areas to the lower and is due to low sea level, while its termination relates to a change in either global ocean alkalinity or bottom water circulation. An evaluation of the magnitude of this local carbonate dissolution episode suggests that its contribution to a global alkalinity change may have been significant. Carbonate dissolution was probably amplified by stronger upwelling activity of the Benguela System linked to an exceptional northern excursion of the boreal summer ITCZ during early glacial isotope stage 6. This low latitude global linkage may explain how this carbonate dissolution event as well as other ‘anomalies’ observed for early stage 6, like an important Dole effect minimum or a ‘cold’ Mediterranean sapropel, are related.     

Oxygen isotope records of Globigerina bulloides across a north-south transect in the south-western Indian Ocean

Along a north-south transect (9.69°N to 55.01°S) in the southwestern Indian Ocean during the Indian Pilot Expedition to Southern Ocean (PESO), the oxygen isotopic analysis of planktic foraminifera (Globigerina bulloides) from 23 surface sediment samples was carried out to assess the relationship between isotopic composition of G. bulloides and the prevailing physical (seawater temperature and salinity) conditions of the ambient seawater. An increasing trend in the δ¹⁸O value is noticed towards higher latitude. Apparently such an increase in δ¹⁸O values is inversely related to the temperature changes along the transect. However, slight mismatch is observed at a few stations due to calcification out of optimum conditions or due to the salinity changes. The preliminary results of the present study, if extended to the subsurface sediments coupled with other parameters, may contribute to the reconstruction of the paleohydrography of the region, especially the position of various seawater fronts during the geologic past albeit with areal limitation.     

南海东北部表层沉答中微体化石与碳酸盐溶跃面和补偿深度

通过对南海东北部(12°～22°N,116°～122°E)表层沉积中的浮游有孔虫、底栖有孔虫、钙质超微化石、硅质与钙质生物丰度和比值的定量分析以及碳酸盐含量的测定,发现碳酸盐含量、浮游有孔虫、钙质超微化石丰度以及钙质生物比值随水深的增大迅速减小,而底栖有孔虫占有孔虫全群的比值和硅质生物比值以及底栖有孔虫胶结质壳类的百分含量却随水深的增大迅速增加.研究表明,调查区内微体化石丰度和比值以及碳酸钙含量的高低,与碳酸盐溶跃面(lysocline)和碳酸盐补偿深度密切相关,碳酸盐溶跃面和碳酸盐补偿深度南、北还存在一定差异,碳酸盐溶跃面南部较北部深,南部在2600m上下,北部则在2200m上下;碳酸盐补偿深度也是南部的较深,南部为3 600 m上下,而北部在3 400 m上下。     

楚科奇海与白令海表层沉积中的钙质和硅质微体化石研究

通过对北冰洋楚科奇海和令海41个表层沉积样品中的有孔虫、介形类等钙质微体化石和硅藻、放射虫、海绵骨针等硅质微体化石的定量分析，发现表层沉积中浮游有孔虫几乎缺失，这可能与该区表层生产力相对低、碳酸盐溶解作用较强有关，而底栖有孔虫和硅质微体化石的丰度分布则明显受表层沉积物类型、表层初级生物生产力和碳酸盐溶解作用所控制。其中，北冰洋楚科奇海陆架区有孔虫丰度和分异度低，含少量浅水介形类，放射虫在陆架浅水区缺失，但含有较多硅藻和海绵骨针等其它硅质微体化石，反映该区由于海冰、表层海水温度较冷而导致表歧初级生产力相对低。白令海陆坡区底栖有孔虫丰度比较科奇海高一个数量级，底栖有孔虫分异度也相对高，硅藻、放射虫、海绵骨针等硅质微体化石的丰度与钙质化石一样，其丰度比楚科奇海明显高，反映表层初级生产力相对高。根据白令海陆坡区底栖有孔虫和硅质微体化石丰度、底栖有孔虫胶结质壳比值的水深变化，推测该区碳酸盐溶跃层和补偿深度（CCD）相对浅，分别位于水深2000m和3800m处。     

东海2万年来碳酸盐溶解作用变化:翼足类的记录

对东海84个表层沉积样品和5个重力柱状样中的翼足类和浮游有孔虫丰度、浮游有孔虫碎壳率和底栖有孔虫群中胶结质类的比例等进行了定量分析,确定了东海现代文石补偿深度（ACD）位于约600 m处,碳酸盐溶跃面在约1 400 m处.末次冰期时随着碳酸盐溶解作用的显著减弱,ACD大幅度下降至现代的1 000 m之下.     

Surface sediment carbonate mineralogy and water column chemistry: Nicaragua Rise versus the Bahamas

Periplatform surface sediments were studied for carbonate mineralogy in conjunction with analyses of the water column for carbonate chemistry on the eastern Northern Nicaragua Rise (NNR) in the Caribbean Sea. The results show a strong correspondence between variations and disappearance, with increasing water depth, of metastable carbonate minerals (fine aragonite and magnesian calcite) and their respective saturation levels in the overlying waters. Similar correspondence between variations in sediment proportions of fine aragonite and magnesian calcite and their respective saturation levels has previously been established in the Bahamas. There are, however, significant differences between the two areas. The sharp decrease in aragonite content and the measured aragonite saturation level occur at 4000 m in the Bahamas, compared to 1800 m on the eastern NNR. In both areas, magnesian calcite minima correspond to the in situ PCO₂ maxima in the water column. The magnesian calcite minimum, however, is at 950 m in the Bahamas and 750 m on the eastern NNR. Magnesian calcite disappears in the Bahamas at 3800 m and at 2000 m on the eastern NNR. These results demonstrate the importance of the influence of overlying water chemistry on the preservation of metastable carbonate minerals in off-bank periplatform sediments, and they clearly demonstrate the difference in terms of carbonate preservation between the poorly ventilated waters of the Caribbean Sea and the well-oxygenated waters of the adjacent Atlantic Ocean. They also open the possibility of obtaining paleoceanographic information on the depth of the CO₂ maximum (O₂ minimum) and its separation from the aragonite saturation depth in at least some areas.     

Transfer of organic carbon on the Moroccan Atlantic continental margin (NW Africa): productivity and lateral advection

Land—ocean transfer of sediment and organic matter along the Moroccan Atlantic margin (NW Africa) seems to have been very effective during the last 130 ka. In a marine core from this region, we found total organic carbon (TOC) values ranging from 0.3 to 1.7 dry wt% of bulk sediments. These relatively high values are fairly unusual, as the core was recovered from an open-ocean environment that is currently oligotrophic. In order to explain this trend, more typical of an upwelling eutrophic setting, three processes were evaluated: (1) in situ primary production associated with the extension of the Cape Ghir upwelling filament, (2) bottom water conditions that may favour organic carbon preservation and (3) lateral organic carbon advection. The site occasionally experienced more eutrophic conditions, especially during termination I; here, we recorded a relative high abundance of the planktonic foraminifer Globigerina bulloides, suggesting high primary production. However, given the absence of correlation between TOC and G. bulloides records, high TOC storage cannot be attributed exclusively to primary production. Preservation factors such as bottom water ventilation are also ruled out. Lateral TOC advection seems to be the most plausible process. Today, lateral advection and offshore transport of nutrients and organic matter characterize the study region. However, the triggering mechanisms deserve further investigation. Different controlling factors influencing the mobilization and advection of organic carbon from coastal upwelling sites to the deep basin are discussed. The correlation found between down-core TOC and sea-level changes suggests sea-level fluctuations as the most effective mechanism driving nepheloid layer detachment and seaward material transport.     

Formation of chemogenic calcite in super-anoxic seawater — Framvaren, southern Norway

Framvaren, a super-anoxic fjord in southern Norway, contains 7–8 mmoll⁻¹ of sulphide and a total carbonate concentration of 18.5 mmol kg⁻¹ in the bottom water. The chemistry of calcium has been studied, considering sources, biogenic and chemical processes and sedimentary sinks. Calcium associated with the bacteria biomass at the redox interface (18m depth) appears to be the primary source of dissolved calcium in the deep, anoxic water. Excess calcium and high total carbonate cause supersaturation of calcite, which is precipitated chemogenically. Calcite (and presumably some aragonite) is identified both in sediment trap material and the bottom sediments below the depth of supersaturation.     

南海北部表层沉积物中浮游有孔虫分布特征与环境意义

对南海北部12°以北海域表层沉积物中的浮游有孔虫丰度、属种数量与组合、碳酸盐含量以及硅质生物相对丰度等进行了分析和鉴定,结果表明:随水深的增加,浮游有孔虫的丰度降低、属种数量减少,碳酸盐含量降低,硅质生物相对丰度升高,浮游有孔虫优势种由易溶种转变为抗溶种。浮游有孔虫以及碳酸盐含量等的这些变化与深海碳酸盐的溶解作用密切相关,同时,浊流沉积作用和水团等环境因素也是影响浮游有孔虫丰度与组合以及碳酸盐含量变化的重要因子。     

Facies distribution and dissolution depths of surface sediment components from the Vema channel and the Rio Grande rise (southwest Atlantic Ocean)

Surface sediments from the Vema channel and from the Rio Grande rise (western extremity) contain less calcareous fossils with increasing water depth. The pteropodal (aragonite) lysocline corresponds to the 3200-m isobath. The pteropodal compensation depth is found above the lower boundary of the North Atlantic Deep Water: 3500 m. The planktonic foraminiferal lysocline (4050 m) seems to be very close to the abyssal thermocline and is therefore here the upper limit of the Antarctic Bottom Water. The foraminiferal and the coccolith compensation depths seem to coincide: 4500 m. Distribution and dissolution of calcareous sediment components are the same all around the western extremity of the Rio Grande rise (southern, western and northern flanks).     

Do changes in coiling directions in planktonic foraminifera correspond to dimorphic reproduction?

A total of 25 surface sediment samples, collected along a North-South transect (from 9.69° N to 55.01° S and from 80° E and 40° E) in the south western Indian Ocean, were used to study the coiling direction patterns in foraminifera planktonic species Neogloboquadrina pachyderma, Globigerinita glutinata and Globigerina bulloides. Comparison between the coiling direction and mean proloculus size (MPS) revealed that all these profiles along N-S transect were not in tandem and thus indicated non-existence of any relationship between the coiling direction and reproductive modes expressed in terms of mean proloculus size.     

Evidence of bioturbation in the Cap-Ferret Canyon in the deep northeastern Atlantic

In the sedimentary column, a combined quantification of burrows and macrobenthic community provides evidence of bioturbation features in the submarine canyon of Cap-Ferret between 2000 and 3000 m depth. An image-processing technique allows accurate quantification of burrow volumes with depth in the sedimentary column. The major bioturbation mode seems to be different in the channel compared to the interfluve. Macrobenthic activity is more inclined to mix the sediment in the channel in response to increased organic matter supplies. Sediment mixing leads to burrow destruction in the upper mixed layer of sediment in the canyon. Burrows are better preserved on the interfluve where mixing is slower. Under the mixed zone, the volume of recorded burrows is higher when sedimentation rate increases, as in the upper canyon. In this transition layer, the burrow volume is estimated to be between 3 and 64% of the total sediment volume depending on the sediment depth. The fill-down of numerous burrows with surface sediment by bioregeneration suggests that anaerobic degradation of fresh organic matter is dominant in this canyon. In the sedimentary column, the negative relationship between carbonate content and macrobenthic abundance confirms that carbonate dissolution is largely influenced by bioturbation.