Late Pliocene carbonate mineralogy of ODP Hole 133-818B

Shedding of shallow carbonate material toward the deep slopes and basin floors is clearly tied to the position of the carbonate bank tops relative to the photic zone. The onset of bank shedding in periplatform sediments can record either the flooding of the bank tops within the photic zone during a rise in sea level following a period of exposure, referred to in the literature as the "highstand shedding" scenario, or the reentry of the bank tops into the photic zone during a lowering of sea level following a period of drowning, referred to as the "lowstand shedding" scenario. Results from Leg 133 post-cruise research on the Pliocene sequences, drilled in six sites within different slope settings of the Queensland Plateau, seem to point out that the latter "lowstand shedding" scenario can be applied to this particular carbonate system. At the Queensland Plateau sites, the early Pliocene (5.2-3.5 Ma) and the earliest part of the late Pliocene (3.5-2.9 Ma) age sequences were characterized, especially in the ôdeepö Sites 811 and 817, by pelagic sediments (foraminifers and coccoliths) and by typically pelagic sedimentation rates not exceeding 20 mm/k.y. The earliest part of the late Pliocene age section was characterized by well-developed hardgrounds in the "shallow" Sites 812 and 814 and by normal pelagic sediments mixed with reworked phosphatized planktonic foraminifers in Site 813. Finally, the early part of the late Pliocene (2.9-2.4 Ma) section was characterized by high sedimentation rates, related to the shedding and admixture into the pelagic sediments of bank-derived materials. These bank-derived materials consist of either diagenetically unaltered fine aragonite with traces of dolomite in Site 818 or micritic calcite resulting from seafloor and/or shallow burial alteration in the deepest Sites 817 and 811. The highest sedimentation rates (163 mm/k.y.) were recorded in Site 818, drilled nearest the modern carbonate bank of Tregrosse Reef. The sedimentation rates decrease with increasing distance from Tregrosse Reef - 120 mm/k.y. in Site 817 and 47.5 mm/k.y. in Site 811. The initial appearance of fine aragonite in Site 818, corresponding to the transition from pelagic to periplatform sedimentation rates, has been dated at 2.9 Ma. This Pliocene sediment pattern on the Queensland Plateau is different from the pattern observed in sediments from two earlier ODP legs (i.e., Leg 101 in the Bahamas and in Leg 115 in the Maldives), where aragonite-rich sediments, characterized by high periplatform sedimentation rates, were observed in the lower Pliocene section (5.2-3.5 Ma), whereas the upper Pliocene (3.5-1.6 Ma) sediments are more pelagic in nature and are characterized by low sedimentation rates or major hiatuses. These Pliocene periplatform sequences in the Bahamas and in the Maldives and late Quaternary age periplatform sequences worldwide have pointed out that "highstand shedding" was the typical response of carbonate platforms to fluctuations in sea level, just opposite to a "lowstand shedding" response to sea-level fluctuations, typical of siliciclastic shelves. Assuming that the envelope of Haq et al.'s (1987) sea-level curve, showing a well-defined lowering of sea level between 3.5 and 2.9 Ma, can also be applied to the southwest Pacific Ocean, based on a high-resolution Pliocene d18O record from the Ontong Java Plateau recently published by Jansen et al. (1993, doi:10.2973/odp.proc.sr.130.028.1993), the Pliocene periplatform sequences on the Queensland Plateau would have recorded the reentry of the bank tops into the photic zone during a general lowering of sea level, following an interval characterized by high sea level, during which the shallow carbonate system on the Queensland Plateau was drowned. The early Pliocene age (5.2-3.5 Ma) sediments deposited on the Queensland Plateau, an established interval of eustatic sea-level highstand, are typically pelagic in character. In addition, relatively cold surface temperatures (estimated to have ranged from 18° to 20°C by Isern et al. [this volume]) might have also stressed the reefs during early Pliocene time and contributed to the drowning of the Queensland Plateau carbonate system during the late Miocene and early Pliocene. Differential and relatively high subsidence rates, inferred by variations in paleodepth of water (based upon benthic foraminifer assemblages; Katz and Miller, this volume) may also have influenced the drowning of the carbonate bank tops on the Queensland Plateau during the late Miocene and early Pliocene. The sediments of early late Pliocene age (2.9-2.4 Ma), a well-established interval of lowering of sea level, are clearly periplatform and cyclic in nature. High-frequency (~40 k.y.) aragonite cycles, well-developed between 2.9 and 2.45 Ma, correlate with the planktonic high-resolution Pliocene d18O record from the Ontong Java Plateau, a good sea-level proxy (Jansen et al., in press). Contrary to late Quaternary age aragonite cycles from the Bahamas, the Nicaragua Rise, the Maldives, and the Queensland Plateau, the late Pliocene aragonite cycles in Hole 818B display high levels of aragonite during glacial stages and, therefore, lowstands of sea level. In addition, sediments deposited during the earliest part of the late Pliocene (3.5-2.9 Ma), transition between the early Pliocene highstand and the late Pliocene lowering in sea level, have recorded the first evidence of a fall in sea level, by (1) the occurrence of synchronous submarine hardgrounds in the two shallowest sites (Sites 812 and 814), (2) the deposition of reworked material from the shallower part of the slope into the intermediate Sites 813 and 818, and (3) the deposition of pelagic sediments in the deepest Sites 817 and 817. In summary, contrary to previous findings, the Pliocene periplatform sediments on the Queensland Plateau appear to have recorded a regional shedding of shallow carbonate bank tops during an interval of sea-level lowering, a good illustration of the "carbonate lowstand shedding" scenario, occurring during the reentry of previously drowned carbonate bank tops into the photic zone related to a decrease in sea level.

Quaternary carbonate and stable isotope record of ODP Holes 133-817A and 133-818B

The Quaternary history of metastable CaCO3 input and preservation within Antarctic Intermediate Water (AAIW) was examined by studying sediments from ODP Holes 818B (745 mbsl) and 817A (1015 mbsl) drilled in the Townsville Trough on the southern slope of the Queensland Plateau. These sites lie within the core of modern AAIW, and near the aragonite saturation depth (~1000 m). Thus, they are well positioned to monitor chemical changes that may have occurred within this watermass during the past 1.6 m.y. The percent of fine aragonite content, percent of fine magnesian calcite content, and percent of whole pteropods (>355 µm) were used to separate the fine aragonite input signal from the CaCO3 preservation signal. Stable d18O and d13C isotopic ratios were determined for the planktonic foraminifer Globigerinoides sacculifer and, in Hole 818B, for the benthic foraminifer Cibicidoides spp. to establish the oxygen isotope stratigraphy and to study the relationship between intermediate and shallow water d13C of Sum CO2 and the relationship between benthic foraminiferal d13C and CaCO3 preservation within intermediate waters of the Townsville Trough. Data were converted from depth to age using oxygen isotope stratigraphy, nannostratigraphy, and foraminiferal biostratigraphy. Several long hiatuses and the absence of magnetostratigraphy did not permit time series analysis. The principal results of the CaCO3 preservation study include the following (1) a general increase in CaCO3 preservation between 0.9 and 1.6 Ma; (2) a CaCO3 dissolution maximum near 0.9 Ma, primarily expressed in the Hole 818B fine aragonite record; (3) an abrupt and permanent increase of fine aragonite content between 0.86 and 0.875 Ma in both Holes 818B and 817A probably reflecting a dramatic increase of fine carbonate sediment production on the Queensland Plateau; (4) an improvement in CaCO3 preservation near 0.87 Ma, which accompanied the increase of sediment input, indicated by the first appearance of whole pteropods in the deeper Hole 817A and a "spike" in the percent whole pteropods in Hole 818B; (5) a period of strong CaCO3 dissolution during the mid-Brunhes Chron from 0.36 to 0.41 Ma; and (6) a complex CaCO3 preservation pattern between 0.36 Ma and the present characterized by a general increase in CaCO3 preservation through time with good preservation during interglacial stages and poor preservation during glacial stages. The long-term aragonite preservation histories for Holes 818B and 817A appear to be similar in general shape, although different in detail, to CaCO3 preservation records from the deep Indian and central equatorial Pacific oceans as well as from intermediate water sites in the Bahamas and the Maldives. All of these areas have experienced CaCO3 dissolution at about 0.9 Ma and during the mid-Brunhes Chron. However, the late Quaternary (0 to 0.36 Ma) glacial to interglacial preservation pattern in Holes 818B and 817A is out of phase with CaCO3 preservation records for sediments deposited in Pacific deep and bottom waters. The sharp increase in bank production and export from the Queensland Plateau and the coincident improvement of CaCO3 preservation between 0.86 and 0.875 Ma may have been synchronous with the initiation of the Great Barrier Reef and roughly coincides with an increase in carbonate accumulation on the Bahama banks, in the western North Atlantic Ocean, and on Mururoa atoll, in the central South Pacific Ocean. The development of these reef systems during the middle Quaternary may be related to the transition in the frequency and amplitude of global sea level change from 41 k.y. low amplitude cycles prior to 0.9 Ma to 100 k.y. high amplitude cycles after 0.73 Ma. Carbon isotopic analyses show that benthic foraminiferal d13C values (Cibicidoides spp.) have been heavier than planktonic foraminiferal d13C values (G. sacculifer) throughout most of the last 0.54 m.y., which may indicate that 13C-enriched intermediate water (AAIW) occupied the Townsville Trough during much of the late Quaternary. Furthermore, both planktonic and benthic foraminiferal d13C values are often observed to be heaviest during interglacial to glacial transitions, and lightest during glacial to interglacial transitions. We suggest that this pattern is the result of changes in the preformed d13C of Sum CO2 of AAIW and may reflect changes in nutrient utilization by primary producers in Antarctic surface waters, changes in the d13C of upwelled Circumpolar Deep Water, or changes in the extent and/or temperature of equilibration between surface water and atmospheric CO2 within the Antarctic Polar Frontal Zone (the source area for AAIW). Finally, the poor correlation between percent of whole pteropods (aragonite preservation) and d13C of Cibicidoides spp. may be the result of a decoupling of d13C from CO2 due to the numerous and complex variables that combine to produce the preformed d13C of AAIW.

Mineralogy and interstitial-water chemistry of ODP Leg 101 sites

Concentrations of dissolved Ca2+, Sr2+, Mg2+, SO4[2-], and alkalinity were measured in pore waters squeezed from sediments taken from ODP Holes 626C and 626D in the Florida Straits; Holes 627A and 627B, 628A, and 630A and 630C north of Little Bahama Bank; Holes 631 A, 632A and 632B, and 633A in Exuma Sound; and Holes 634A and 635A and 635B in Northeast Providence Channel. These data are compared with the mineralogy and strontium content of the sediments from which the waters were squeezed. Contrasts in the geochemical profiles suggest that significantly different processes govern pore-water signatures at each group of sites. In Little Bahama Bank, strong positive Ca2+ gradients are correlated with weak negative Mg2+ profiles. These trends are analogous to those seen at DSDP sites where carbonate deposits immediately overlie mafic basement, but as the depth to basement may be in excess of 5000 m, we suggest that diffusion gradients are initiated by an underlying sedimentary unit. In contrast, Ca2+ and Mg2+ gradients in Exuma Sound are not developed to any appreciable extent over similar thicknesses of sediment. We suggest that the pore-water chemistry in these deposits is principally controlled by diagenetic reactions occurring within each sequence. The location and extent of carbonate diagenesis can be estimated from dissolved Sr2+ profiles. In Little Bahama Bank and Exuma Sound, Sr2+ concentrations reach a maximum value of between 700 and 1000 µmol/L. Although the depths at which these concentrations are achieved are different for the two areas, the corresponding age of the sediment at the dissolved Sr2+ maximum is similar. Consequently, the diffusive flux of Sr2+ and the calculated rates of recrystallization in the two areas are likewise of a similar magnitude. The rates of recrystallization we calculate are lower than those found in some DSDP pelagic sites. As the waters throughout most of the holes are saturated with respect to SrSO4, celestite precipitation may cause erroneously low Sr2+ production rates and, consequently, low calculated rates of recrystallization. We therefore encourage only the discriminate use of Sr2+ profiles in the quantification of diagenetic processes.

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.

Age analysis, aragonite and high magnesium calcite content from different IODP Holes from Exp 310

The widespread occurrence of microbialites in the last deglacial reef frameworks (16-6 Ka BP) implies that the accurate study of their development patterns is of prime importance to unravel the evolution of reef architecture through time and to reconstruct the reef response to sea-level variations and environmental changes. The present study is based on the sedimentological and chronological analysis (14C AMS dating) of drill cores obtained during the IODP Expedition #310 "Tahiti Sea Level" on the successive terraces which typify the modern reef slopes from Tahiti. It provides a comprehensive data base to investigate the microbialite growth patterns (i.e. growth rates and habitats), to analyze their roles in reef frameworks and to reconstruct the evolution of the reef framework architecture during sea-level rise. The last deglacial reefs from Tahiti are composed of two distinctive biological communities: (1) the coralgal communities including seven assemblages characterized by various growth forms (branching, robust branching, massive, tabular and encrusting) that form the initial frameworks and (2) the microbial communities developed in the primary cavities of those frameworks, a few meters (1.5 to 6 m) below the living coral reef surface, where they heavily encrusted the coralgal assemblages to form microbialite crusts. The dating results demonstrate the occurrence of two distinctive generations of microbialites: the "reefal microbialites" which developed a few hundred years after coralgal communities in shallow-water environments, whereas the "slope microbialites" grew a few thousands of years later in significantly deeper water conditions after the demise of coralgal communities. The development of microbialites was controlled by the volume and the shape of the primary cavities of the initial reef frameworks determined by the morphology and the packing of coral colonies. The most widespread microbialite development occurred in frameworks dominated by branching, thin encrusting, tabular and robust branching coral colonies which built loose and open frameworks typified by a high porosity (> 50%). In contrast, their growth was minimal in compact coral frameworks formed by massive and thick encrusting corals where primary cavities yielded a low porosity (~ 30%) and could not host a significant microbialite expansion.

(Table 1) Isotopes, calcite, aragonite and sample descriptions at DSDP Hole 55-433C

Calcite in the cavities and veins of igneous rocks has long been recognized as an alteration by-product (Dana, 1892). Elementary mineralogy textbooks report that the most common occurrence of aragonite is in the cavities of basalts and andesites (e.g., Kerr, 1977). Therefore, it is not surprising to find both carbonate minerals in association with the moderately to extensively altered basalt flows recovered during deep sea drilling on Suiko Seamount in the Emperor Seamount chain (DSDP Leg 55, Hole 433C). The thickness and vesicularity of the flows, along with the presence of oxidized flow tops, indicate that the basalt erupted subaerially (Site 433 Report, 1980). The stable isotopic contents of the carbonate phases filling and lining the veins and vesicles denote the environment of alteration. An isotopic study was undertaken to secure supportive evidence for a subaerial period in the development of the seamount. Also, the subsequent alteration history after submergence may be interpreted from this isotopic record.