Limpets counteract ocean acidification induced shell corrosion by thickening of aragonitic shell layers

Specimens of the patellogastropod limpet Patella caerulea were collected within (pHlow-shells) and outside (pHn-shells) a CO2 vent site at Ischia, Italy. Four pHlow-shells and four pHn-shells were sectioned transversally and scanned for polymorph distribution by means of confocal Raman microscopy. The pHlow-shells displayed a twofold increase in aragonite area fraction and size-normalised aragonite area. Size-normalised calcite area was halved in pHlow-shells. Taken together with the increased apical and the decreased flank size-normalised thickness of the pHlow-shells, these data led us to conclude that low-pH-exposed P. caerulea specimens counteract shell dissolution by enhanced shell production. This is different from normal elongation growth and proceeds through addition of aragonitic parts only, while the production of calcitic parts is confined to elongation growth. Therefore, aragonite cannot be regarded as a disadvantageous polymorph per se under ocean acidification conditions.

Sr/Ca ratios and oxygen isotopes from sclerosponges

We investigate aragonitic skeletons of the Caribbean sclerosponge Ceratoporella nicholsoni from Jamaica, 20 m below sea level (mbsl), and Pedro Bank, 125 mbsl. We use d18O and Sr/Ca ratios as temperature proxies to reconstruct the Caribbean mixed layer and thermocline temperature history since 1400 A.D. with a decadal time resolution. Our age models are based on U/Th dating and locating of the radiocarbon bomb spike. The modern temperature difference between the two sites is used to tentatively calibrate the C. nicholsoni Sr/Ca thermometer. The resulting calibration points to a temperature sensitivity of Sr/Ca in C. nicholsoni aragonite of about -0.1 mmol/mol/K. Our Sr/Ca records reveal a pronounced warming from the early 19th to the late 20th century, both at 20 and 125 mbsl. Two temperature minima in the shallow water record during the late 17th and early 19th century correspond to the Maunder and Dalton sunspot minima, respectively. Another major cooling occurred in the late 16th century and is not correlatable with a sunspot minimum. The temperature contrast between the two sites decreased from the 14th century to a minimum in the late 17th century and subsequently increased to modern values in the early 19th century. This is interpreted as a long-term deepening and subsequent shoaling of the Caribbean thermocline. The major trends of the Sr/Ca records are reproduced in both specimens but hardly reflected in the d18O records.

Inorganic major, minor, and trace element geochemistry and clay mineralogy of sediments from the Deep Sea Drilling Project Leg 96, Gulf of Mexico

Sediment samples collected at DSDP Leg 96 Mississippi Fan Sites 615, 616, 620, 621, and 623, Orca Basin Site 618, and Pigmy Basin Site 619 were analyzed for 22 major, minor, and trace elements. This study was undertaken to document the downhole variability in inorganic geochemistry between sites. The mineralogy of the clays, including those from Sites 614, 617, and 622 on the fan, was determined by X-ray diffraction to define the principal clay minerals present at the sites, examine any downhole trends in clay mineralogy, and aid in the interpretation of the geochemical signature of the sediments. Clay mineral composition at all the sites is smectite:illite:chlorite:kaolinite in the approximate percentage ratio 50:20:20:10. Geochemical results indicate only slight variation between and within the sites, with the exception of a discrete unit of carbonates that occurs near the bottom of Site 615. Variation in the major, minor, and trace element composition can be explained by a change in the relative abundance of quartz, clay minerals, and carbonates.

Geochemistry of neritic carbonates of ODP Hole 134-831B

Drilling at Bougainville Guyot (Ocean Drilling Program Site 831), New Hebrides Island Arc during Leg 134 revealed that 727.5 m of carbonate overlies an andesite basement. The carbonate cap at Site 831 consists of 20 m of pelagic carbonate overlying 707.5 m of neritic carbonates. The neritic section consists of ~230 m of largely unaltered aragonite sediment that overlies ~497 m of totally calcitized limestone. The deeper portion of the calcitized interval has been pervasively altered by diagenesis. Prior to this study the age distribution of sediments at Bougainville Guyot was poorly known because age diagnostic fossils are sparsely and discontinuously distributed in the sequence. We have used Sr isotopes to provide temporal constraints on the deposition of carbonates at Site 831; these constraints are critical in reconstructing the vertical movement of Bougainville Guyot before its collision with the New Hebrides Island Arc. Overall, the chronostratigraphy of Bougainville Guyot can be subdivided into three intervals: (1) a Pleistocene interval (102.4 to 391.11 meters below sea floor [mbsf]); (2) a Miocene interval (410.31 to 669.53 mbsf); and (3) an Oligocene interval (678.83 to 727.50 mbsf). Strontium isotopic ages of samples increase with increasing depth in the carbonate sequence, except near the bottom of the sequence, where several samples exhibit a consistent reversed age vs. depth trend. Such age reversals are most likely the product of post-depositional rock-water interaction. Preliminary stable isotope data are consistent with diagenetic alteration in the marine and meteoric environments. Several abrupt decreases in d87Sr, and hence age, of sediments are recognized in the carbonate cap at Bougainville Guyot. These disconformities are most likely the product of subaerial exposure in response to relative sea-level fall. Indeed, Sr-isotope ages indicate that 2 to 9 m.y. of sediment deposition is missing across these d87Sr disconformities.

Mineralogical-sedimentological and chemical investigation of sediments from Cross Bank off Florida

The sediments of a core of.1.55 m length taken on the windward side of the Cross Bank, Florida Bay, are clearly subdivided into two portions, as shown by grain size analysis: silt-sized particles predominate in the relatively homogeneous lower two thirds of the core. This is succeeded abruptly by a thin layer of sand, containing fragments of Halimeda. They indicate a catastrophic event in the Florida Bay region, because Halimeda does not grow within Florida Bay. Above this layer, the amount of sand decreases at first and then continuously increases right to the present sediment-water-interface. The median and skewness increase simultaneously with the increase in the sand and granule portion. We assume that the changing grain size distribution was determined chiefly by the density of the marine flora: during the deposition of the lower two thirds of the core a dense grass cover acted as a sediment catcher for the fine-grained detritus washed out of the shallow basins of the Florida Bay, and simultaneously prohibited renewed reworking. Similar processes go on today on the surface of most mud banks of Florida Bay. The catastrophic event indicated by the sand layer probably changed the morphology of the bank to such an extent that the sampling point was shifted more to the windward side of the bank. This side is characterized by less dense plant growth. Therefore, less detritus could be caught and the material deposited could be reworked. The pronounced increase in skewness in the upper third of the core certainly indicates a strong washing out of the smaller-sized particles. The sediments are predominantly made up of carbonates, averagely 88.14 percent. The average CaCO3-content is 83.87 percent and the average MgCO3-content amounts to 4.27 percent. The chief carbonate mineral is aragonite making up 60.1 percent of the carbonate portion in the average, followed by high-magnesian calcite (33.8 percent) and calcite (6.1 percent). With increasing grain size the aragonite clearly increases at the cost of high-magnesian calcite in the upper third of the core. Chemically, this is shown by an increase of the CaCO3 : MgCO3-ratio. This increase is mainly caused by the more common occurrence of aragonitic fragments of mollusks in the coarse grain fractions. The bulk of the carbonates is made up of mollusks, foraminifera, ostracods, and - to a much lesser extent - of corals, worm-tubes, coccolithophorids, and calcareous algae, as shown by microscopic investigations. The total amount of the carbonate in the sediments is biogenic detritus with the possible exception of a very small amount of aragonite needles in the clay and fine silt fraction. The individual carbonate components of the gravel and sand fraction can be relatively easy identified as members of a particular animal or plant group. This becomes very difficult in the silt and clay fraction. Brownish aggregates are very common in the coarse and medium silt fraction. It was not always possible to clarify their origin (biogenic detritus, faecal pellets or carbonate particles cemented by carbonates or organic slime, etc.). Organic matter (plant fragments, rootlets), quartz, opal (siliceous sponge needles), and feldspar also occur in the sediments, besides carbonates. The lowermost part of the core has an age of 1365 +/- 90 years, as shown by 14C analysis.

Porosity, permeability, trace elements, and carbon-oxygen isotopes at DSDP Hole 77-536

Talus deposits recovered from Site 536 show evidence of aragonite dissolution, secondary porosity development, and calcite cementation. Although freshwater diagenesis could account for the petrographic features of the altered talus deposits, it does not uniquely account for isotopic or trace-element characteristics. Also, the hydrologic setting required for freshwater alteration is not easily demonstrated for the Campeche Bank. A mixing-zone model does not account for the available trace-element data, but does require somewhat less drastic assumptions about the size of the freshwater lens. Although a seawater (bottom-water) alteration model requires no hydrologic difficulties, unusual circumstances are required to account for the geochemical characteristics of the talus deposits using this model.

Seawater carbonate chemistry during experiments with Patella vulgata, 2010

The effect of short-term (5 days) exposure to CO2-acidified seawater (year 2100 predicted values, ocean pH = 7.6) on key aspects of the function of the intertidal common limpet Patella vulgata (Gastropoda: Patellidae) was investigated. Changes in extracellular acid-base balance were almost completely compensated by an increase in bicarbonate ions. A concomitant increase in haemolymph Ca2+ and visible shell dissolution implicated passive shell dissolution as the bicarbonate source. Analysis of the radula using SEM revealed that individuals from the hypercapnic treatment showed an increase in the number of damaged teeth and the extent to which such teeth were damaged compared with controls. As radula teeth are composed mainly of chitin, acid dissolution seems unlikely, and so the proximate cause of damage is unknown. There was no hypercapnia-related change in metabolism (O2 uptake) or feeding rate, also discounting the possibility that teeth damage was a result of a CO2-related increase in grazing. We conclude that although the limpet appears to have the physiological capacity to maintain its extracellular acid-base balance, metabolism and feeding rate over a 5 days exposure to acidified seawater, radular damage somehow incurred during this time could still compromise feeding in the longer term, in turn decreasing the top-down ecosystem control that P. vulgata exerts over rocky shore environments.

Secondary calcification and dissolution respond differently to future ocean conditions

Climate change threatens both the accretion and erosion processes that sustain coral reefs. Secondary calcification, bioerosion, and reef dissolution are integral to the structural complexity and long-term persistence of coral reefs, yet these processes have received less research attention than reef accretion by corals. In this study, we use climate scenarios from RCP 8.5 to examine the combined effects of rising ocean acidity and sea surface temperature (SST) on both secondary calcification and dissolution rates of a natural coral rubble community using a flow-through aquarium system. We found that secondary reef calcification and dissolution responded differently to the combined effect of pCO2 and temperature. Calcification had a non-linear response to the combined effect of pCO2 and temperature: the highest calcification rate occurred slightly above ambient conditions and the lowest calcification rate was in the highest temperature-pCO2 condition. In contrast, dissolution increased linearly with temperature-pCO2 . The rubble community switched from net calcification to net dissolution at +271 µatm pCO2 and 0.75 °C above ambient conditions, suggesting that rubble reefs may shift from net calcification to net dissolution before the end of the century. Our results indicate that (i) dissolution may be more sensitive to climate change than calcification and (ii) that calcification and dissolution have different functional responses to climate stressors; this highlights the need to study the effects of climate stressors on both calcification and dissolution to predict future changes in coral reefs.

Carbonate mineralogy and stable isotope composition of cool-water bryozoans from sediments of ODP Leg 182 sites

The carbon and oxygen isotopic compositions of selected bryozoan skeletons from upper Pleistocene bryozoan mounds in the Great Australian Bight (Ocean Drilling Program Leg 182; Holes 1129C, 1131A, and 1132B) were determined. Cyclostome bryozoans, Idmidronea spp. and Nevianipora sp., have low to intermediate magnesian calcite skeletons (1.5-10.0 and 0.9-6.4 molar percentage [mol%] MgCO3, respectively), but a considerable number include marine cements. The cheilostome Adeonellopsis spp. are biminerallic, principally aragonite, with some high magnesian calcite (HMC) (6.6-12.1 mol% MgCO3). The HMC fraction of Adeonellopsis has lower d13C and similar d18O values compared with the aragonite fraction. Reexamination of modern bryozoan isotopic composition shows that skeletons of Adeonellopsis spp. and Nevianipora sp. form close to oxygen isotopic equilibrium with their ambient water. Therefore, changes in glacial-interglacial oceanographic conditions are preserved in the oxygen isotopic profiles. The bryozoan oxygen isotopic profiles are correlated well with marine isotope Stages 1-8 in Holes 1129C and 1132B and to Stages 1-4(?) in Hole 1131A. The horizons of the bryozoan mounds that yield skeletons with heavier oxygen isotopic values can be correlated with isotope Stages 2, 4(?), 6, and 8 in Hole 1129C; Stages 2 and 4(?) in Hole 1131A; and Stages 2, 4, 6, and 8 in Hole 1132B. These results provide supporting evidence for a model for bryozoan mound formation, in which the mounds were formed during intensified upwelling and increased trophic resources during glacial periods.

Late Quaternary siliciclastic/carbonate sedimentation in the Cabricorn Channel

A model is presented for hemipelagic siliciclastic and carbonate sedimentation during the last glacial-interglacial cycle in the Capricorn Channel, southern Great Barrier Reef (GBR). Stable isotope ratios, grainsize, carbonate content and mineralogy were analysed for seven cores in a depth transect from 166 to 2892 m below sea level (mbsl). Results show variations in the flux of terrigenous, neritic and pelagic sediments to the continental slope over the last sea level cycle. During the glacial lowstand terrigenous sediment influenced all the cores down to 2000 mbsl. The percentages of quartz and feldspar in the cores decreased with water depth, while the percentage of clay increased. X-ray diffraction analysis of the glacial lowstand clay mineralogy suggests that the siliciclastic sediment was primarily sourced from the Fitzroy River, which debouched directly into the northwest sector of the Capricorn Channel at this time. The cores also show a decrease in pelagic calcite and an increase in aragonite and high magnesium calcite (HMC) during the glacial. The influx of HMC and aragonite is most likely from reworking of coral reefs exposed on the continental shelf during the glacial, and also from HMC ooids precipitated at the head of the Capricorn Channel at this time. Mass accumulation rates (MARs) are high (13.5 g/cm**/kyr) during the glacial and peak at ~20 g/cm** 3/kyr in the early transgression (16-14 ka BP). MARs then decline with further sea level rise as the Fitzroy River mouth retreats from the edge of the continental shelf after 13.5 ka BP. MARs remain low (4 g/cm**3/kyr) throughout the Holocene highstand. Data for the Holocene highstand indicate there is a reduction in siliciclastic influx to the Capricorn Channel with little quartz and feldspar below 350 mbsl. However, fine-grained fluvial sediments, presumably from the Fitzroy River, were still accumulating on the mid slope down to 2000 mbsl. The proportion of pelagic calcite in the core tops increases with water depth, while HMC decreases, and is present only in trace amounts in cores below 1500 mbsl. The difference in the percentage of HMC in the deeper cores between the glacial and Holocene may reflect differences in supply or deepening of the HMC lysocline during the glacial. Sediment accumulation rates also vary between cores in the Capricorn Channel and do not show the expected exponential decrease with depth. This may be due to intermediate or deep water currents reworking the sediments. It is also possible that present bathymetry data are too sparse to detect the potential role that submarine channels may play in the distribution and accumulation of sediments. Comparison of the Capricorn Channel MARs with those for other mixed carbonate/siliciclastic provinces from the northeast margin of Australia indicates that peak MARs in the early transgression in the Capricorn Channel precede those from the central GBR and south of Fraser Island. The difference in the timing of the carbonate and siliciclastic MAR peaks along the northeast margin is primarily related to differences in the physiography and climate of the provinces. The only common trend in the MARs from the northeast margin of Australia is the near synchronicity of the carbonate and siliciclastic MAR peaks in individual sediment cores, which supports a coeval sedimentation model.

Seawater carbonate chemistry, productivity and calcification of Marginopora vertebralis in a laboratory experiment

Changes in the seawater carbonate chemistry (ocean acidification) from increasing atmospheric carbon dioxide (CO2 ) concentrations negatively affect many marine calcifying organisms, but may benefit primary producers under dissolved inorganic carbon (DIC) limitation. To improve predictions of the ecological effects of ocean acidification, the net gains and losses between the processes of photosynthesis and calcification need to be studied jointly on physiological and population levels. We studied productivity, respiration, and abundances of the symbiont-bearing foraminifer species Marginopora vertebralis on natural CO2 seeps in Papua New Guinea and conducted additional studies on production and calcification on the Great Barrier Reef (GBR) using artificially enhanced pCO2 . Net oxygen production increased up to 90% with increasing pCO2 ; temperature, light, and pH together explaining 61% of the variance in production. Production increased with increasing light and increasing pCO2 and declined at higher temperatures. Respiration was also significantly elevated (~25%), whereas calcification was reduced (16-39%) at low pH/high pCO2 compared to present-day conditions. In the field, M. vertebralis was absent at three CO2 seep sites at pHTotal levels below ~7.9 (pCO2 ~700 µatm), but it was found in densities of over 1000 m(-2) at all three control sites. The study showed that endosymbiotic algae in foraminifera benefit from increased DIC availability and may be naturally carbon limited. The observed reduction in calcification may have been caused either by increased energy demands for proton pumping (measured as elevated rates of respiration) or by stronger competition for DIC from the more productive symbionts. The net outcome of these two competing processes is that M. vertebralis cannot maintain populations under pCO2 exceeding 700 µatm, thus are likely to be extinct in the next century.

Geochemistry of recent sediments of the East African continental margin, Arabian Sea

Chemical analyses have been carried out on 40 samples from the sediment surface and 210 samples from cores that were taken from the edge of the African continental block at the Arabian Sea (coasts of Somalia and Kenya, from Cape Guardafui to Mombasa) on the occasion of the Indian Ocean Expedition of the German research vessel "Meteor" during the years 1964/65. The carbonate content shows its maximum on the northern part of the continental shelf of Africa, where fossil reef debris furnish the detritic portion of carbonate. In the southern part of the continental shelf of Africa the portion of carbonate is low, as it is heavily diluted by the non-carbonatic detritus. It is also in the deep-sea that a lower carbonate content is encountered below the calcite compensation depth. Trace elements in the carbonates: On the shelf and in its vicinity Sr and Mg are enriched. The enrichment has been brought about by the portion of reef debris, as this latter contains aragonite (enrichment of Sr) as well as high-magnesium calcite. The greatest part of the slope contains carbonates that are poor in trace elements and mainly made up of foraminifera (and of coccoliths). Below the carbonate compensation depth another enrichment of Mg takes place in the carbonates, which is probably due to a selective dissolution of calcite in comparison to dolomite. The iron and manganese contents of the carbonates are high (iron higher in coast proximity, manganese higher in the depth), but not genuine, as they come about in the course of the extraction of the carbonates as a result of the dissolution of authigenic Mn-Fe-minerals. Non-carbonatic portion of the sediments: In coast proximity an enrichment of quartz comes about. Within the quartz-rich zone it is the elements V, Cr, Fe, Ti, and B that have been enriched in the non-carbonatic components. This enrichment must be attributed to an elevated content of heavy minerals. In the case of Ti and Fe the preliminary enrichment brought about by processes of lateritisation on the continent plays a certain role. Toward the deep-sea an enrichment of the elements Mn Ni, Cu, and Zn takes place; these enrichments must be explained by authigenic Mn-Fe-minerals. Within the Mn-rich zone a belt running parallel to the coast stands out that shows an increased Mn-enrichment. However, this increase in enrichment does not apply to the elements Ni, Cu, and Zn. It is probable that this latter increased enrichment comes about as a result of the migration of manganese to the sediment surface. (Within the sediments there prevail reductive conditions, in the presence of which Mn is capable of migration, whereas at the sediment surface its precipitation comes about under oxidizing conditions). The quantity of organic matter mainly is dependent on grain size and on the rate of sedimentation. On the shelf an impoverishment of organic matter is to be encountered, as the sediments are coarse-grained. In the depth the impoverishment must be explained on the strength of a small rate of sedimentation. Between those two ranges organic substance is enriched. P and N show an enrichment in comparison to Corg with this applying all the more the smaller the absolute quantity of Corg is. In this particular case one has to do with an enrichment coming about during the diagenetic processes of organic matter. A comparison with the sediments from the Indian and Pakistani continental border in Arabian Sea shows as follows: on the African continental border the coarse detrital material has been transported farther out to deep-sea, which has something to do with the greater inclination of the surface of sedimentation. Carbonate is found in greater abundance on the African side. Its chemical composition is influenced by reef-debris which is missing by Indian-Pakistani side. The content of organic matter is lower on the African side. Contrary to that, the enrichments of N and P compared to organic matter are of an equal order of magnitude on both sides of the Arabian Sea.

Bulk and clay mineral composition of ODP Leg 189 sites

Bulk and clay mineral investigations were conducted on ~750 samples from four sites drilled during Ocean Drilling Program Leg 189 on the western Tasmanian margin (Site 1168), the South Tasman Rise (Sites 1170 and 1171), and the East Tasman Plateau (Site 1172). The mineralogy of the bulk sediment is very similar at all sites, and major changes coincide with the boundaries of the three main lithologic units described in the Leg 189 Initial Reports volume. The clay mineral assemblages show significant regional differences, but their major variations coincide at all sites and with major changes in regional tectonics and climate.

Skeletal density of Porites

Paleotemperature estimates based on coral Sr/Ca have not been widely accepted because the reconstructed glacial-Holocene shift in tropical sea-surface temperature (~4-6°C) is larger than that indicated by foraminiferal Mg/Ca (~2-4°C). We show that corals over-estimate changes in sea-surface temperature (SST) because their records are attenuated during skeletogenesis within the living tissue layer. To quantify this process, we microprofiled skeletal mass accumulation within the tissue layer of Porites from Australasian coral reefs and laboratory culturing experiments. The results show that the sensitivity of the Sr/Ca and d18O thermometers in Porites will be suppressed, variable, and dependent on the relationship between skeletal growth rate and mass accumulation within the tissue layer. Our findings help explain why d18O-SST sensitivities for Porites range from -0.08 per mil/°C to -0.22 per mil/°C and are always less than the value of -0.23 per mil/°C established for biogenic aragonite. Based on this observation, we recalibrated the coral Sr/Ca thermometer to determine a revised sensitivity of -0.084 mmol/mol/°C. After rescaling, most of the published Sr/Ca-SST estimates for the Indo-Pacific region for the last ~14,000 years (-7°C to +2°C relative to modern) fall within the 95% confidence envelope of the foraminiferal Mg/Ca-SST records. We conclude that two types of calibration scales are required for coral paleothermometry; an attenuated Porites-specific thermometer sensitivity for studies of seasonal to interannual change in SST and, importantly, the rescaled -0.084 mmol/mol/°C Sr/Ca sensitivity for studies of 20th-century trends and millennial-scale changes in mean SST. The calibration-scaling concept will apply to the development of transfer functions for all geochemical tracers in corals.