Calcite saturation and yield and Mg/Ca, Mn/Ca, Al/Ca, Fe/Ca for four species of planktic foraminifera cleaned using Mg-cleaning and Cd-cleaning methods

Four species of planktic foraminifera from core-tops spanning a depth transect on the Ontong Java Plateau were prepared for Mg/Ca analysis both with (Cd-cleaning) and without (Mg-cleaning) a reductive cleaning step. Reductive cleaning caused etching of foraminiferal calcite, focused on Mg-rich inner calcite, even on tests which had already been partially dissolved at the seafloor. Despite corrosion, there was no difference in Mg/Ca of Pulleniatina obliquiloculata between cleaning methods. Reductive cleaning decreased Mg/Ca by an average (all depths) of ~ 4% for Globigerinoides ruber white and ~ 10% for Neogloboquadrina dutertrei. Mg/Ca of Globigerinoides sacculifer (above the calcite saturation horizon only) was 5% lower after reductive cleaning. The decrease in Mg/Ca due to reductive cleaning appeared insensitive to preservation state for G. ruber, N. dutertrei and P. obliquiloculata. Mg/Ca of Cd-cleaned G. sacculifer appeared less sensitive to dissolution than that of Mg-cleaned. Mg-cleaning is adequate, but SEM and contaminants (Al/Ca, Fe/Ca and Mn/Ca) show that Cd-cleaning is more effective for porous species. A second aspect of the study addressed sample loss during cleaning. Lower yield after Cd-cleaning for G. ruber, G. sacculifer and N. dutertrei confirmed this to be the more aggressive method. Strongest correlations between yield and Delta[CO3^2-] in core-top samples were for Cd-cleaned G. ruber (r = 0.88, p = 0.020) and Cd-cleaned P. obliquiloculata (r = 0.68, p = 0.030). In a down-core record (WIND28K) correlation, r, between yield values > 30% and dissolution index, XDX, was -0.61 (p = 0.002). Where cleaning yield < 30% most Mg-cleaned Mg/Ca values were biased by dissolution.

Barium/Calcium and Cadmium/Calcium ratios of sediment core RC13-229

A new benthic foraminiferal Ba/Ca and Cd/Ca data set from core RC13-229 in the deep Cape Basin indicates only small variations in bottom water nutrient concentrations in Circumpolar Deep Water (CPDW) over the last 450 kyr. Variability in the Ba record is characterized by somewhat higher values during glacial periods, consistent with a reduction in the flux of Ba-depleted North Atlantic Deep Water to the Southern Ocean during glacial periods. The small changes in the Ba and Cd records contrast with the large and systematic increase in CPDW nutrients during glacial periods implied by the benthic delta13C record. This discrepancy, essentially an extension of the well-known Southern Ocean Cd-delta13C conflict, is evaluated by transforming RC13-229 paleochemical data into carbonate parameters using the modern oceanic relationships between delta13C, Cd, and SumCO2 and between Ba and alkalinity. Calculations using Cd/Ca to estimate past variations in CPDW SumCO2 and Ba/Ca to estimate past variations in CPDW alkalinity yield carbonate ion concentrations that exceed calcite saturation throughout the record length, with generally higher carbonate ion values associated with glacial intervals (opposite in sense to the RC13-229 %CaCO3 record). Substituting delta13C to estimate SumCO2 leads to extreme calcite undersaturation at this site during glacial periods, clearly inconsistent with the preservation of calcite throughout the length of RC13-229. Accepting the carbon isotope record as a direct measure of past variations in CPDW SumCO2 concentrations requires that both the Cd and Ba evidence for limited nutrient and alkalinity changes be disregarded.

Diatom abundances in sediment core CESAR_83-006

The modern Arctic Ocean is regarded as a barometer of global change and amplifier of global warming (Graversen et al., 2008, doi:10.1038/nature06502) and therefore records of past Arctic change are critical for palaeoclimate reconstruction. Little is known of the state of the Arctic Ocean in the greenhouse period of the Late Cretaceous epoch (65-99 million years ago), yet records from such times may yield important clues to Arctic Ocean behaviour in near-future warmer climates. Here we present a seasonally resolved Cretaceous sedimentary record from the Alpha ridge of the Arctic Ocean. This palaeo-sediment trap provides new insight into the workings of the Cretaceous marine biological carbon pump. Seasonal primary production was dominated by diatom algae but was not related to upwelling as was previously hypothesized (Kitchell and Clark, 1982, doi:10.1016/0031-0182(82)90087-6). Rather, production occurred within a stratified water column, involving specially adapted species in blooms resembling those of the modern North Pacific subtropical gyre (Dore et al., 2008, doi:10.1016/j.pocean.2007.10.002), or those indicated for the Mediterranean sapropels (Kemp et al., 1999, doi:10.1038/18001). With increased CO2 levels and warming currently driving increased stratification in the global ocean (Sarmiento et al., 1998, doi:10.1038/30455), this style of production that is adapted to stratification may become more widespread. Our evidence for seasonal diatom production and flux testify to an ice-free summer, but thin accumulations of terrigenous sediment within the diatom ooze are consistent with the presence of intermittent sea ice in the winter, supporting a wide body of evidence for low temperatures in the Late Cretaceous Arctic Ocean (Falcon-Lang et al., 2004, doi:10.1016/j.palaeo.2004.05.016; Amiot et al., 2004, doi:10.1016/j.epsl.2004.07.015; Otto-Bliesner et al., 2002, doi:10.1029/2001JD000821), rather than recent suggestions of a 15 °C mean annual temperature at this time (Jenkyns et al., 2004, doi:10.1038/nature03143).

Late Pleistocene sediment record of the Maldives carbonate platform

A piston core from the Maldives carbonate platform was investigated for carbonate mineralogy, grain-size distributions, calcium carbonate content and organic carbon. The sedimentary record was linked to Late Pleistocene sea-level variations, using an age model based on oxygen isotopes obtained from planktonic foramanifera, nannofossil biostratigraphy and 14C age determinations. The correlation between the sedimentary record and Late Pleistocene sea-level showed that variations in aragonite and mud during the past 150 000 years were clearly related to flooding and sea floor exposure of the main lagoons of the atolls of the Maldives carbonate platform. Platform flooding events were characterized by strongly increased deposition of aragonite and mud within the Inner Sea of the Maldives. Exposure events, in contrast, can be recognized by rapid decreases in the values of both proxy records. The results show that sediments on the Maldives carbonate platform contain a continuous record of Pleistocene sea-level variations. These sediments may, therefore, contribute to a better understanding of regional and even global sea-level changes, and yield new insights into the interplay between ocean currents and carbonate platform morphology.

Influence of sediment acidification and water flow on sediment acceptance and dispersal of juvenile soft-shell clams (Mya arenaria L.)

Although ocean acidification is expected to reduce carbonate saturation and yield negative impacts on open-ocean calcifying organisms in the near future, acidification in coastal ecosystems may already be affecting these organisms. Few studies have addressed the effects of sedimentary saturation state on benthic invertebrates. Here, we investigate whether sedimentary aragonite saturation (Omega aragonite) and proton concentration ([H+]) affect burrowing and dispersal rates of juvenile soft-shell clams (Mya arenaria) in a laboratory flume experiment. Two size classes of juvenile clams (0.5-1.5 mm and 1.51-2.5 mm) were subjected to a range of sediment Omega aragonite and [H+] conditions within the range of typical estuarine sediments (Omega aragonite 0.21-1.87; pH 6.8-7.8; [H+] 1.58 × 10**-8-1.51 × 10**- 7) by the addition of varying amounts of CO2, while overlying water pH was kept constant ~ 7.8 (Omega aragonite ~ 1.97). There was a significant positive relationship between the percent of juvenile clams burrowed in still water and Omega aragonite and a significant negative relationship between burrowing and [H+]. Clams were subsequently exposed to one of two different flow conditions (flume; 11 cm/s and 23 cm/s) and there was a significant negative relationship between Omega aragonite and dispersal, regardless of clam size class and flow speed. No apparent relationship was evident between dispersal and [H+]. The results of this study suggest that sediment acidification may play an important role in soft-shell clam recruitment and dispersal. When assessing the impacts of open-ocean and coastal acidification on infaunal organisms, future studies should address the effects of sediment acidification to adequately understand how calcifying organisms may be affected by shifting pH conditions.

Low-temperature magnetic remanence and hysteresis measurements on sediment core GeoB4901-8 from the Niger deep-sea fan

Low-temperature (LT) magnetic remanence and hysteresis measurements, in the range 300-5 K, were combined with energy dispersive spectroscopy (EDS) in order to characterize the magnetic inventory of strongly diagenetically altered sediments originating from the Niger deep-sea fan. We demonstrate the possibility of distinguishing between different compositions of members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series on a set of five representative samples, two from the upper suboxic and three from the lower sulfidic anoxic zone of gravity core GeoB 4901. Highly sensitive LT magnetic measurements were performed on magnetic extracts resulting in large differences in the magnetic behavior between samples from the different layers. This emphasizes that both Fe-Ti oxide phases occur in different proportions in the two geochemical environments. Most prominent are variations in the coercivity sensitive parameter coercive field (BC). At room-temperature (RT) hysteresis loops for all extracts are narrow and yield low coercivities (6-13 mT). With decreasing temperature the loops become more pronounced and wider. At 5 K an approximately 5-fold increase in BC for the suboxic samples contrasts a 20-25-fold increase for the samples from the anoxic zone. We demonstrate that this distinct increase in BC at LT corresponds to the increasing proportion of the Ti-rich hemoilmenite phase, while Fe-rich (titano-)magnetite dominates the magnetic signal at RT. This trend is also seen in the room-temperature saturation isothermal remanent magnetization (RT-SIRM) cycles: suboxic samples show remanence curves dominated by Fe-rich mineral phases while anoxic samples display curves clearly dominated by Ti-rich particles. We show that the EDS intensity ratios of the characteristic Fe Kalpha and Ti Kalpha lines of the Fe-Ti oxides may be used to differentiate between members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series. Furthermore it is possible to calculate an approximate composition for each grain if the intensity ratios of natural particles are linked to well-known standards. Thus, element spectra with high Fe/Ti intensity ratios were found to be rather typical of titanomagnetite while low Fe/Ti ratios are indicative of hemoilmenite. The EDS analyses confirm the LT magnetic results, Fe-rich magnetic phases dominate in the upper suboxic environment whereas Ti-rich magnetic phases comprise the majority of particles in the lower anoxic domain: The mineral assemblage of the upper suboxic environments is composed of magnetite (~19%), titanomagnetite (~62%), hemoilmenite (~17%) and ~2% other particles. In the lower anoxic sediments, reductive diagenetic alteration has resulted in more extensive depletion of the (titano-)magnetite phase, resulting in a relative enrichment of the hemoilmenite phase (~66%). In these strongly anoxic sediments stoichiometric magnetite is barely preserved and only ~5% titanomagnetite was detected. The remaining ~28% comprises Ti-rich particles such as pseudobrookite or rutile.

Seawater carbonate chemistry, calcification rate, oxygen production, maximum quantum yield, symbiont density, chlorophyll concentration and crystal width of Halimeda macroloba, Halimeda cylindracea and Marginopora vertebralis during experiments, 2011

The effects of elevated CO2 and temperature on photosynthesis and calcification in the calcifying algae Halimeda macroloba and Halimeda cylindracea and the symbiont-bearing benthic foraminifera Marginopora vertebralis were investigated through exposure to a combination of four temperatures (28°C, 30°C, 32°C, and 34°C) and four CO2 levels (39, 61, 101, and 203 Pa; pH 8.1, 7.9, 7.7, and 7.4, respectively). Elevated CO2 caused a profound decline in photosynthetic efficiency (FV : FM), calcification, and growth in all species. After five weeks at 34°C under all CO2 levels, all species died. Chlorophyll (Chl) a and b concentration in Halimeda spp. significantly decreased in 203 Pa, 32°C and 34°C treatments, but Chl a and Chl c2 concentration in M. vertebralis was not affected by temperature alone, with significant declines in the 61, 101, and 203 Pa treatments at 28°C. Significant decreases in FV : FM in all species were found after 5 weeks of exposure to elevated CO2 (203 Pa in all temperature treatments) and temperature (32°C and 34°C in all pH treatments). The rate of oxygen production declined at 61, 101, and 203 Pa in all temperature treatments for all species. The elevated CO2 and temperature treatments greatly reduced calcification (growth and crystal size) in M. vertebralis and, to a lesser extent, in Halimeda spp. These findings indicate that 32°C and 101 Pa CO2, are the upper limits for survival of these species on Heron Island reef, and we conclude that these species will be highly vulnerable to the predicted future climate change scenarios of elevated temperature and ocean acidification.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.