Planktonic foraminifera, nannofossils and stable isotope record across tghe Paleocene-Eocene thermal maximum of ODP Hole 113-690B

The carbonate saturation profile of the oceans shoaled markedly during a transient global warming event known as the Paleocene-Eocene thermal maximum (PETM) (circa 55 Ma). The rapid release of large quantities of carbon into the ocean-atmosphere system is believed to have triggered this intense episode of dissolution along with a negative carbon isotope excursion (CIE). The brevity (120-220 kyr) of the PETM reflects the rapid enhancement of negative feedback mechanisms within Earth's exogenic carbon cycle that served the dual function of buffering ocean pH and reducing atmospheric greenhouse gas levels. Detailed study of the PETM stratigraphy from Ocean Drilling Program Site 690 (Weddell Sea) reveals that the CIE recovery period, which postdates the CIE onset by ~80 kyr, is represented by an expanded (~2.5 m thick) interval containing a unique planktic foraminiferal assemblage strongly diluted by coccolithophore carbonate. Collectively, the micropaleontological and sedimentological changes preserved within the CIE recovery interval reflect a transient state when ocean-atmosphere chemistry fostered prolific coccolithophore blooms that suppressed the local lysocline to relatively deeper depths. A prominent peak in the abundance of the clay mineral kaolinite is associated with the CIE recovery interval, indicating that continental weathering/runoff intensified at this time as well (Robert and Kennett, 1994). Such parallel stratigraphic changes are generally consonant with the hypothesis that enhanced continental weathering/runoff and carbonate precipitation helped sequester carbon during the PETM recovery period (e.g., Dickens et al., 1997, doi:10.1130/0091-7613(1997)025<0259:ABOGIT>2.3.CO;2 ; Zachos et al., 2005, doi:10.1126/science.1109004).

Isotopic and chemical compositions of rocks and minerals from the TAG hydrothermal mound, ODP Site 957

Strontium- and oxygen-isotopic measurements of samples recovered from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound during Leg 158 of the Ocean Drilling Program provide important constraints on the nature of fluid-rock interactions during basalt alteration and mineralization within an active hydrothermal deposit. Fresh Mid-Ocean Ridge Basalt (MORB), with a 87Sr/86Sr of 0.7026, from the basement beneath the TAG mound was altered at both low and high temperatures by seawater and altered at high temperature by near end-member black smoker fluids. Pillow breccias occurring beneath the margins of the mound are locally recrystallized to chlorite by interaction with large volumes of conductively heated seawater (>200°C). The development of a silicified, sulfide-mineralized stockwork within the basaltic basement follows a simple paragenetic sequence of chloritization followed by mineralization and the development of a quartz+pyrite+paragonite stockwork cut by quartz-pyrite veins. Initial alteration involved the development of chloritic alteration halos around basalt clasts by reaction with a Mg-bearing mixture of upwelling, high-temperature (>300°C), black smoker-type fluid with a minor (<10%) proportion of seawater. Continued high-temperature (>300°C) interaction between the wallrock and these Mg-bearing fluids results in the complete recrystallization of the wallrock to chlorite+quartz+pyrite. The quartz+pyrite+paragonite assemblage replaces the chloritized basalts, and developed by reaction at 250-360°C with end-member hydrothermal fluids having 87Sr/86Sr ~0.7038, similar to present-day vent fluids. The uniformity of the 87Sr/86Sr ratios of hydrothermal assemblages throughout the mound and stockwork requires that the 87Sr/86Sr ratio of end-member hydrothermal fluids has remained relatively constant for a time period longer than that required to change the interior thermal structure and plumbing network of the mound and underlying stockwork. Precipitation of anhydrite in breccias and as late-stage veins throughout most of the mound and stockwork, down to at least 125 mbsf, records extensive entrainment of seawater into the hydrothermal deposit. 87Sr/86Sr ratios indicate that most of the anhydrite formed from ~2:1 mixture of seawater and black smoker fluids (65%±15% seawater). Oxygen-isotopic compositions imply that anhydrite precipitated at temperatures between 147°C and 270°C and require that seawater was conductively heated to between 100°C and 180°C before mixing and precipitation occurred. Anhydrite from the TAG mound has a Sr-Ca partition coefficient Kd ~0.60±0.28 (2 sigma). This value is in agreement with the range of experimentally determined partition coefficients (Kd ~0.27-0.73) and is similar to those calculated for anhydrite from active black smoker chimneys from 21°N on the East Pacific Rise. The d18O (for SO4) of TAG anhydrite brackets the value of seawater sulfate oxygen (~9.5?). Dissolution of anhydrite back into the oceans during episodes of hydrothermal quiescence provides a mechanism of buffering seawater sulfate oxygen to an isotopically light composition, in addition to the precipitation and dissolution of anhydrite within the oceanic basement during hydrothermal recharge at the mid-ocean ridges.

Chemical composition of mineral phases of serpentinized and steatized peridotite from the Mid Atlantic Ridge (15°20'N Fracture Zone, ODP Leg209)

Serpentinization of abyssal peridotites is known to produce extremely reducing conditions as a result of dihydrogen (H2,aq) release upon oxidation of ferrous iron in primary phases to ferric iron in secondary minerals by H2O.We have compiled and evaluated thermodynamic data for Fe-Ni-Co-O-S phases and computed phase relations in fO2,g-fS2,g and aH2,aq-aH2S,aq diagrams for temperatures between 150 and 400°C at 50MPa.We use the relations and compositions of Fe-Ni-Co-O-S phases to trace changes in oxygen and sulfur fugacities during progressive serpentinization and steatitization of peridotites from the Mid-Atlantic Ridge in the 15°20'N Fracture Zone area (Ocean Drilling Program Leg 209). Petrographic observations suggest a systematic change from awaruite- magnetite-pentlandite and heazlewoodite-magnetite-pentlandite assemblages forming in the early stages of serpentinization to millerite-pyrite-polydymite-dominated assemblages in steatized rocks. Awaruite is observed in all brucite-bearing partly serpentinized rocks. Apparently, buffering of silica activities to low values by the presence of brucite facilitates the formation of large amounts of hydrogen, which leads to the formation of awaruite. Associated with the prominent desulfurization of pentlandite, sulfide is removed from the rock during the initial stage of serpentinization. In contrast, steatitization indicates increased silica activities and that highsulfur-fugacity sulfides, such as polydymite and pyrite-vaesite solid solution, form as the reducing capacity of the peridotite is exhausted and H2 activities drop. Under these conditions, sulfides will not desulfurize but precipitate and the sulfur content of the rock increases. The co-evolution of fO2,g-fS2,g in the system follows an isopotential of H2S,aq, indicating that H2S in vent fluids is buffered. In contrast, H2 in vent fluids is not buffered by Fe-Ni-Co-O-S phases, which merely monitor the evolution of H2 activities in the fluids in the course of progressive rock alteration.The co-occurrence of pentlandite- awaruite-magnetite indicates H2,aq activities in the interacting fluids near the stability limit of water. The presence of a hydrogen gas phase would add to the catalyzing capacity of awaruite and would facilitate the abiotic formation of organic compounds.

Mineral and oxygen isotopic compositions in a profile through the altered lower oceanic crust, ODP Hole 176-735B

ODP Hole 735B located on the Southwest Indian Ridge at 57°E is an in situ sampled long, continuous section of lower oceanic crust. Oxygen isotope compositions of constituent minerals of Leg 176 gabbros have been measured by UV-laser oxygen isotope microprobe. Together with existing data from Leg 118, a complete oxygen isotope profile through the lower oceanic crust has been obtained. Most clinopyroxenes and olivines have normal mantle values of ~5.5 per mil and ~5.2 per mil, respectively, while plagioclases show slight d18O enrichment relative to its mantle value of 6.1per mil. Down-hole variations of Hole 735B gabbro indicate a downward decreasing d18O profile, with a kink at a depth of about 800 m below sea floor. Above this depth, gabbros are depleted in 18O relative to unaltered basalts, while below ~800 m they show nearly unmodified d18O values. Abundant seawater penetration appears to be limited to the upper part of the lower crust at ODP site 735 (~800 m into the gabbroic layer and ~2-2.5 km into the oceanic crust from the top of pillow basalts). Mass balance calculations show that the lower crust formed under this ultra-slow-spreading ridge has an average d18O value of 5.5 per mil. The whole crust at Site 735 has an overall 18O enrichment with d18O values of 6.0 per mil to 7.8 per mil, depending on the possible variation of the d18O values of the upper pillow basalts and sheeted dykes. The apparent difference in oxygen isotope compositions of ocean crusts formed with different spreading rates has important implications on the buffering of ocean water over geological time, as well as on the oxygen recycling between crust and mantle through subduction. The difference of seawater penetration between fast- and slow-spreading ridges could be related to their particular magmatic-tectonic history during the formation and aging of the crust. However, more analyses on continuous sections through oceanic and ophiolitic crust in different tectonic settings are required to derive any predictive models.

Miocene microflora and palaeoclimatic estimates of the Stetten section (Austria)

Pollen analyses have been proven to possess the possibility to decipher rapid vegetational and climate shifts in Neogene sedimentary records. Herein, a c. 21-kyr-long transgression-regression cycle from the Lower Austrian locality Stetten is analysed in detail to evaluate climatic benchmarks for the early phase of the Middle Miocene Climate Optimum and to estimate the pace of environmental change. Based on the Coexistence Approach, a very clear signal of seasonality can be reconstructed. A warm and wet summer season with c. 204-236 mm precipitation during the wettest month was opposed by a rather dry winter season with precipitation of c. 9-24 mm during the driest month. The mean annual temperature ranged between 15.7 and 20.8 °C, with about 9.6-13.3 °C during the cold season and 24.7-27.9 °C during the warmest month. In contrast, today's climate of this area, with an annual temperature of 9.8 °C and 660 mm rainfall, is characterized by the winter season (mean temperature: -1.4 °C, mean precipitation: 39 mm) and a summer mean temperature of 19.9 °C (mean precipitation: 84 mm). Different modes of environmental shifts shaped the composition of the vegetation. Within few millennia, marshes and salt marshes with abundant Cyperaceae rapidly graded into Taxodiaceae swamps. This quick but gradual process was interrupted by swift marine ingressions which took place on a decadal to centennial scale. The transgression is accompanied by blooms of dinoflagellates and of the green alga Prasinophyta and an increase in Abies and Picea. Afterwards, the retreat of the sea and the progradation of estuarine and wetland settings were a gradual progress again. Despite a clear sedimentological cyclicity, which is related to the 21-kyr precessional forcing, the climate data show little variation. This missing pattern might be due to the buffering of the precessional-related climate signal by the subtropical vegetation. Another explanation could be the method-inherent broad range of climate-parameter estimates that could cover small scale climatic changes.

Acid-base balance and changes in haemolymph properties of the South African rock lobsters, Jasus lalandii, a palinurid decapod, during chronic hypercapnia

Few studies exist reporting on long-term exposure of crustaceans to hypercapnia. We exposed juvenile South African rock lobsters, Jasus lalandii, to hypercapnic conditions of pH 7.3 for 28 weeks and subsequently analysed changes in the extracellular fluid (haemolymph). Results revealed, for the first time, adjustments in the haemolymph of a palinurid crustacean during chronic hypercapnic exposure: 1) acid-base balance was adjusted and sustained by increased bicarbonate and 2) quantity and oxygen binding properties of haemocyanin changed. Compared with lobsters kept under normocapnic conditions (pH 8.0), during prolonged hypercapnia, juvenile lobsters increased bicarbonate buffering of haemolymph. This is necessary to provide optimum pH conditions for oxygen binding of haemocyanin and functioning of respiration in the presence of a strong Bohr Effect. Furthermore, modification of the intrinsic structure of the haemocyanin molecule, and not the presence of molecular modulators, seems to improve oxygen affinity under conditions of elevated pCO2.

Stable isotopes and element concentrations of samples from the Wadi Bih, United Arab Emirates

Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.

Carbon sources in the North Sea evaluated by means of carbon isotope tracers

A multitracer approach is applied to assess the impact of boundary fluxes (e.g., benthic input from sedi- ments or lateral inputs from the coastline) on the acid-base buffering capacity, and overall biogeochemistry, of the North Sea. Analyses of both basin-wide observations in the North Sea and transects through tidal basins at the North-Frisian coastline, reveal that surface distributions of the d13C signature of dissolved inorganic carbon (DIC) are predominantly controlled by a balance between biological production and respiration. In particular, variability in metabolic DIC throughout stations in the well-mixed southern North Sea indi- cates the presence of an external carbon source, which is traced to the European continental coastline using naturally occurring radium isotopes (224Ra and 228Ra). 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (AT) compared to the more conventional use of salinity. Coastal inputs of meta- bolic DIC and AT are calculated on a basin-wide scale, and ratios of these inputs suggest denitrification as a primary metabolic pathway for their formation. The AT input paralleling the metabolic DIC release prevents a significant decline in pH as compared to aerobic (i.e., unbuffered) release of metabolic DIC. Finally, long- term pH trends mimic those of riverine nitrate loading, highlighting the importance of coastal AT production via denitrification in regulating pH in the southern North Sea.

Seawater carbonate chemistry and concentration boundary layers around complex assemblages of macroalgae in a laboratory experiment

Metabolic processes have the potential to modulate the effects of ocean acidification (OA) in nearshore macroalgal beds. We investigated whether natural mixed assemblages of the articulate coralline macroalgae Arthrocardia corymbosa and understory crustose coralline algae (CCA) altered pH and O2 concentrations within and immediately above their canopies. In a unidirectional flume, we tested the effect of water velocity (0-0.1 m/s), bulk seawater pH (ambient pH 8.05, and pH 7.65), and irradiance (photosynthetically saturating light and darkness) on pH and O2 concentration gradients, and the derived concentration boundary layer (CBL) thickness. At bulk seawater pH 7.65 and slow velocities (0 and 0.015 m/s), pH at the CCA surface increased to 7.90-8.00 in the light. Although these manipulations were short term, this indicates a potential daytime buffering capacity that could alleviate the effects of OA. Photosynthetic activity also increased O2 concentrations at the surface of the CCA. However, this moderating capacity was flow dependent; the CBL thickness decreased from an average of 26.8 mm from the CCA surface at 0.015 m/s to 4.1 mm at 0.04 m/s. The reverse trends occurred in the dark, with respiration causing pH and O2 concentrations to decrease at the CCA surface. At all flow velocities the CBL thicknesses (up to 68 mm) were much greater than those previously published, indicating that the presence of canopies can alter the CBL substantially. In situ, the height of macroalgal canopies can be an order of magnitude larger than those used here, indicating that the degree of buffering to OA will be context dependent.

Diffusion boundary layers ameliorate the negative effects of ocean acidification on the temperate coralline macroalga Arthrocardia corymbosa

Anthropogenically-modulated reductions in pH, termed ocean acidification, could pose a major threat to the physiological performance, stocks, and biodiversity of calcifiers and may devalue their ecosystem services. Recent debate has focussed on the need to develop approaches to arrest the potential negative impacts of ocean acidification on ecosystems dominated by calcareous organisms. In this study, we demonstrate the role of a discrete (i.e. diffusion) boundary layer (DBL), formed at the surface of some calcifying species under slow flows, in buffering them from the corrosive effects of low pH seawater. The coralline macroalga Arthrocardia corymbosa was grown in a multifactorial experiment with two mean pH levels (8.05 'ambient' and 7.65 a worst case 'ocean acidification' scenario projected for 2100), each with two levels of seawater flow (fast and slow, i.e. DBL thin or thick). Coralline algae grown under slow flows with thick DBLs (i.e., unstirred with regular replenishment of seawater to their surface) maintained net growth and calcification at pH 7.65 whereas those in higher flows with thin DBLs had net dissolution. Growth under ambient seawater pH (8.05) was not significantly different in thin and thick DBL treatments. No other measured diagnostic (recruit sizes and numbers, photosynthetic metrics, %C, %N, %MgCO3) responded to the effects of reduced seawater pH. Thus, flow conditions that promote the formation of thick DBLs, may enhance the subsistence of calcifiers by creating localised hydrodynamic conditions where metabolic activity ameliorates the negative impacts of ocean acidification.

Seawater carbonate chemistry and maximum growth rates of Skeletonema marinoi and Alexandrium ostenfeldii, toxin composition of Alexandrium ostenfeldii in a laboratory experiment

Phytoplankton populations can display high levels of genetic diversity that, when reflected by phenotypic variability, may stabilize a species response to environmental changes. We studied the effects of increased temperature and CO2 availability as predicted consequences of global change, on 16 genetically different isolates of the diatom Skeletonema marinoi from the Adriatic Sea and the Skagerrak (North Sea), and on eight strains of the PST (paralytic shellfish toxin)-producing dinoflagellate Alexandrium ostenfeldii from the Baltic Sea. Maximum growth rates were estimated in batch cultures of acclimated isolates grown for five to 10 generations in a factorial design at 20 and 24 °C, and present day and next century applied atmospheric pCO2, respectively. In both species, individual strains were affected in different ways by increased temperature and pCO2. The strongest response variability, buffering overall effects, was detected among Adriatic S. marinoi strains. Skagerrak strains showed a more uniform response, particularly to increased temperature, with an overall positive effect on growth. Increased temperature also caused a general growth stimulation in A. ostenfeldii, despite notable variability in strain-specific response patterns. Our data revealed a significant relationship between strain-specific growth rates and the impact of pCO2 on growth-slow growing cultures were generally positively affected, while fast growing cultures showed no or negative responses to increased pCO2. Toxin composition of A. ostenfeldii was consistently altered by elevated temperature and increased CO2 supply in the tested strains, resulting in overall promotion of saxitoxin production by both treatments. Our findings suggest that phenotypic variability within populations plays an important role in the adaptation of phytoplankton to changing environments, potentially attenuating short-term effects and forming the basis for selection. In particular, A. ostenfeldii blooms may expand and increase in toxicity under increased water temperature and atmospheric pCO2 conditions, with potentially severe consequences for the coastal ecosystem.

Seawater carbonate chemistry during experiments with Stylophora pistillata, 2008

The decrease in the saturation state of seawater, following seawater acidification, is believed to be the main factor leading to a decrease in the calcification of marine organisms. To provide a physiological explanation for this phenomenon, the effect of seawater acidification was studied on the calcification and photosynthesis of the scleractinian tropical coral Stylophora pistillata. Coral nubbins were incubated for 8 days at three different pH (7.6, 8.0, and 8.2). To differentiate between the effects of the various components of the carbonate chemistry (pH, CO32, HCO3, CO2), tanks were also maintained under similar pH, but with 2-mM HCO3 added to the seawater. The addition of 2-mM bicarbonate significantly increased the photosynthesis in S. pistillata, suggesting carbon-limited conditions. Conversely, photosynthesis was insensitive to changes in pH and pCO2. Seawater acidification decreased coral calcification by ca. 0.1-mg CaCO3 g-1 d-1 for a decrease of 0.1 pH units. This correlation suggested that seawater acidification affected coral calcification by decreasing the availability of the CO32 substrate for calcification. However, the decrease in coral calcification could also be attributed either to a decrease in extra- or intracellular pH or to a change in the buffering capacity of the medium, impairing supply of CO32 from HCO3.

Regulation of intracellular pH in cnidarians: response to acidosis in Anemonia viridis

The regulation of intracellular pH (pHi) is a fundamental aspect of cell physiology that has received little attention in studies of the phylum Cnidaria, which includes ecologically important sea anemones and reef-building corals. Like all organisms, cnidarians must maintain pH homeostasis to counterbalance reductions in pHi, which can arise because of changes in either intrinsic or extrinsic parameters. Corals and sea anemones face natural daily changes in internal fluids, where the extracellular pH can range from 8.9 during the day to 7.4 at night. Furthermore, cnidarians are likely to experience future CO2-driven declines in seawater pH, a process known as ocean acidification. Here, we carried out the first mechanistic investigation to determine how cnidarian pHi regulation responds to decreases in extracellular and intracellular pH. Using the anemone Anemonia viridis, we employed confocal live cell imaging and a pH-sensitive dye to track the dynamics of pHi after intracellular acidosis induced by acute exposure to decreases in seawater pH and NH4Cl prepulses. The investigation was conducted on cells that contained intracellular symbiotic algae (Symbiodinium sp.) and on symbiont-free endoderm cells. Experiments using inhibitors and Na-free seawater indicate a potential role of Na/H plasma membrane exchangers (NHEs) in mediating pHi recovery following intracellular acidosis in both cell types. We also measured the buffering capacity of cells, and obtained values between 20.8 and 43.8 mM per pH unit, which are comparable to those in other invertebrates. Our findings provide the first steps towards a better understanding of acid-base regulation in these basal metazoans, for which information on cell physiology is extremely limited.

Boron, carbonate carbon and oxygen isotope analyses of samples from the Yangtze Platform (China), Congo craton (Namibia), and Karatau microcontinent (Kazakhstan) of the Marinoan glaciation

Boron isotope patterns preserved in cap carbonates deposited in the aftermath of the younger Cryogenian (Marinoan, ca. 635 Ma) glaciation confirm a temporary ocean acidification event on the continental margin of the southern Congo craton, Namibia. To test the significance of this acidification event and reconstruct Earth's global seawater pH states at the Cryogenian-Ediacaran transition, we present a new boron isotope data set recorded in cap carbonates deposited on the Yangtze Platform in south China and on the Karatau microcontinent in Kazakhstan. Our compiled d11B data reveal similar ocean pH patterns for all investigated cratons and confirm the presence of a global and synchronous ocean acidification event during the Marinoan deglacial period, compatible with elevated postglacial pCO2 concentrations. Differences in the details of the ocean acidification event point to regional distinctions in the buffering capacity of Ediacaran seawater.