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.

Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Synergistic effects of pCO2 and iron availability on nutrient consumption ratio of the Bering Sea phytoplankton community

Little is known concerning the effect of CO2 on phytoplankton ecophysiological processes under nutrient and trace element-limited conditions, because most CO2 manipulation experiments have been conducted under elements-replete conditions. To investigate the effects of CO2 and iron availability on phytoplankton ecophysiology, we conducted an experiment in September 2009 using a phytoplankton community in the iron limited, high-nutrient, low-chlorophyll (HNLC) region of the Bering Sea basin . Carbonate chemistry was controlled by the bubbling of the several levels of CO2 concentration (180, 380, 600, and 1000 ppm) controlled air, and two iron conditions were established, one with and one without the addition of inorganic iron. We demonstrated that in the iron-limited control conditions, the specific growth rate and the maximum photochemical quantum efficiency (Fv/Fm) of photosystem (PS) II decreased with increasing CO2 levels, suggesting a further decrease in iron bioavailability under the high-CO2 conditions. In addition, biogenic silica to particulate nitrogen and biogenic silica to particulate organic carbon ratios increased from 2.65 to 3.75 and 0.39 to 0.50, respectively, with an increase in the CO2 level in the iron-limited controls. By contrast, the specific growth rate, Fv/Fm values and elemental compositions in the iron-added treatments did not change in response to the CO2 variations, indicating that the addition of iron canceled out the effect of the modulation of iron bioavailability due to the change in carbonate chemistry. Our results suggest that high-CO2 conditions can alter the biogeochemical cycling of nutrients through decreasing iron bioavailability in the iron-limited HNLC regions in the future.

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.

U and Th concentrations and isotope ratios of samples from ODP Leg 166

Constraining the history of seawater (234U/238U) is important because this ratio is used to assess the validity of U/Th ages, and because it provides information about the past rate of physical weathering on the continents. This study makes use of U-rich slope sediments from the Bahamas in an attempt to reconstruct seawater (234U/238U) for the last 800 kyr. For the last 360 kyr, U/Th dating of these sediments provides ages and initial (234U/238U) values. Sixty-seven samples, largely from marine highstands, have initial (234U/238U) which scatter somewhat about the modern seawater value (~1.145) but neither this scatter nor the average value increases with age of sample. These data contrast with published coral data and suggest that seawater (234U/238U) has remained within 15? of the modern value for the last 360 kyr. This confirms the rejection of coral U/Th ages where the initial (234U/238U) is significantly different from modern seawater. Data from older highstands, dated with delta18O stratigraphy or by the presence of the Brunhes/Matuyama (B/M) reversal at 780 kyr, allow seawater (234U/238U) to be assessed prior to the range of the 230Th chronometer. Unfortunately, diagenetic scatter in the data between the B/M reversal and 360 kyr is rather large, probably relating to low U concentrations for these samples. But there is no indication of a trend in seawater (234U/238U) with age. High U samples from close to the B/M reversal show less diagenetic scatter and an initial (234U/238U) that averages 1.102. This lower value can be explained by lower seawater (234U/238U) at the time of the B/M reversal, or by progressive loss of 234U from the sediment by alpha-recoil. A simple box model is presented to illustrate the response of seawater (234U/238U) to variations in riverine input, such as might be caused by changes in continental weathering. Comparison of the Bahamas (234U/238U) data with model results indicates that riverine (234U/238U) has not varied by more than 65? for any 100 kyr period during the last 360 kyr. It also indicates that the ratio of physical to chemical weathering on the continents has not been higher than at present for any extended period during the last 800 kyr.

Altered neurotransmitter function in CO2-exposed stickleback (Gasterosteus aculeatus): a temperate model species for ocean acidification research

Studies on the consequences of ocean acidification for the marine ecosystem have revealed behavioural changes in coral reef fishes exposed to sustained near-future CO2 levels. The changes have been linked to altered function of GABAergic neurotransmitter systems, because the behavioural alterations can be reversed rapidly by treatment with the GABAA receptor antagonist gabazine. Characterization of the molecular mechanisms involved would be greatly aided if these can be examined in a well-characterized model organism with a sequenced genome. It was recently shown that CO2-induced behavioural alterations are not confined to tropical species, but also affect the three-spined stickleback, although an involvement of the GABAA receptor was not examined. Here, we show that loss of lateralization in the stickleback can be restored rapidly and completely by gabazine treatment. This points towards a worrying universality of disturbed GABAA function after high-CO2 exposure in fishes from tropical to temperate marine habitats. Importantly, the stickleback is a model species with a sequenced and annotated genome, which greatly facilitates future studies on underlying molecular mechanisms.

Seawater carbonate chemistry, calcification and respiration duirng experiments with a pteropod Creseis acicula, 2010

Among marine calcifiers, shelled pteropods are expected to be particularly sensitive to ocean acidification, generated by the uptake of anthropogenic CO2 by the ocean, and the associated decrease of the seawater saturation state with respect to aragonite (omega aragonite). The few available studies have mostly focused on polar species although pteropods are also important components of temperate and tropical ecosystems. It is also unknown which parameter of the carbonate system controls calcification. Specimens of the temperate Mediterranean species Creseis acicula were maintained under seven different conditions of the carbonate chemistry, obtained by manipulating pH and total alkalinity, with the goal to disentangle the effects of pH and omega aragonite. Respiration, excretion as well as rates of net and gross calcification were not directly affected by a decrease in pH but decreased significantly with a decrease of omega aragonite. The decrease of gross calcification rates is consistent with that reported for polar species. Although the organisms were apparently able to maintain gross calcification rates under slightly undersaturated aragonite conditions, the clear net dissolution signal observed below saturation suggests that they are not able to build a shell in seawater corrosive to aragonite. The decrease in respiration and excretion, and the low O:N molar ratio, could be due to the short time that the organisms were allowed to acclimatize to their new environment.

Mineralogy and geochemistry at DSDP Leg 80 Holes

Cenozoic sediments recovered from Sites 548, 549, and 550 were the objects of mineralogical (bulk sample and <2 - µm fraction) and geochemical (HCl extract) studies. Thin sections of rock pebbles embedded in sediments (upper levels at Site 548, particularly) were examined on a polarizing microscope. This study outlines the vertical and lateral variation and evolution of the sedimentation. In the Paleocene and lower Eocene, the clay fraction is abundant and smectite is practically the sole existing clay mineral. High Mn, Al, Fe, Mg, and K contents were measured in HCl extracts. Through the middle Eocene, carbonates become more abundant - highly dominant at Site 548. Metal contents in HCl extracts are very low. The clay fraction, although dominated at all sites by smectites, becomes richer in illite and poorly crystallized chlorite. At the middle/upper Miocene boundary, a significant decrease in the smectite/(illite + chlorite) ratio occurs at all sites, and this decrease continues into the middle Pliocene. This decrease is marked by an abrupt increase of quartz at Site 548. At the two other sites, carbonates remain highly predominant; HCl extracts reflect the relative abundance of the clay and carbonate fractions. After a brief recurrence of smectite in a high-metal-content interval, illite and chlorite become the dominant clay minerals in the upper Pliocene and the Pleistocene, where numerous variations in mineralogical composition occur in the clay fraction (Sites 548 and 549) or in non-clay components (Site 548). Several pebbles of various nature and origin, encountered in different levels of this interval at Site 548, appear to have an ice-rafting origin. This study points out three main breaks in the general evolution of the sedimentation: the first, corresponding to the lower/middle Eocene boundary, is marked by the increase of carbonates and associated elements; the second, corresponding to the middle/upper Miocene boundary, is marked by a major decrease of the smectite/(illite + chlorite) ratio at all sites and by a massive appearance of quartz at Site 548; and the third, which occurred toward the late Pliocene, is marked by the dominance of primary clay minerals and the arrival of ice-rafted pebbles. Our interpretation of results considers paleohydrological and paleoclimatic phenomena. It is suggested that the major middle/late Miocene break was associated with an increase of the deep bottom-water circulation between the Norwegian Sea and the North Atlantic Ocean, and/or a climatic evolution: humidification and cooling of climate. The changes toward the late Pliocene appear to have been the first effects of the glaciations at the end of Cenozoic.

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Isotope ratios, trace elements and ultrastructure results of Mytilus galloprovincialis shells and experimental site data off Ischia (Italy)

Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island. Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

Sedimentology and origin of lower Cretaceous pelagic carbonates and redeposited clastics at DSDP Hole 76-534A

Drilling at Site 534 in the Blake-Bahama Basin recovered 268 m of Lower Cretaceous, Berriasian to Hauterivian, pelagic carbonates, together with volumetrically minor intercalations of claystone, black shales, and terrigenous and calcareous elastics. Radiolarian nannofossil pelagic carbonates accumulated in water depths of about 3300 to 3650 m, below the ACD (aragonite compensation depth) but close to the CCD (calcite compensation depth). Radiolarian abundance points to a relatively fertile ocean. In the Hauterivian and Barremian, during times of warm, humid climate and rising sea level, turbiditic influxes of both terrigenous and calcareous sediments, and minor debris flows were derived from the adjacent Blake Plateau. The claystones and black shales accumulated on the continental rise, then were redeposited onto the abyssal plain by turbidity currents. Dark organic-rich and pale organic-poor couplets are attributed to climatic variations on land, which controlled the input of terrigenous organic matter. Highly persistent, fine, parallel lamination in the pelagic chalks is explained by repeated algal "blooms." During early diagenesis, organic-poor carbonates remained oxygenated and were cemented early, whereas organic-rich intervals, devoid of burrowing organisms, continued to compact later in diagenesis. Interstitial dissolved-oxygen levels fluctuated repeatedly, but bottom waters were never static nor anoxic. The central western Atlantic in the Lower Cretaceous was thus a relatively fertile and wellmixed ocean basin.

Mineralogy and geochemistry of weathered serpentinites in DSDP Leg 84 sediments

At Sites 566, 567, and 570 of Leg 84, ophiolitic serpentinite basement was covered by a sequence of serpentinitic mud that was formed by weathering of the serpentinites under sea- or pore-water conditions. Several mineralogical processes were observed: (1) The serpentinitic mud that consists mainly of chrysotile was formed from the lizardite component of the serpentinites by alteration. (2) Slightly trioctahedral smectites containing nonexpandable mica layers, trioctahedral smectites containing nonexpandable chlorite layers, and swelling chlorites were presumably formed from detrital chlorite and/or serpentine. (3) The occurrence of tremolite, chlorite, analcime, and talc can be attributed to reworking of gabbroic ophiolite rocks. (4) Dolomite, aragonite, and Mg-calcite, all authigenic, occur in the serpentinitic mud.