Seawater carbonate chemistry during a Ishigaki Island (Japan) coral reef seasonal observations, 2005

Monitoring seawater CO2 for a full year with seasonal observations of community metabolism in Ishigaki Island, Japan, revealed seasonal variation and anomalous values owing to the bleaching event in 1998. The daily average pCO2 showed a seasonal pattern on an annual scale, 280 to 320 ?atm in winter and 360 to 400 ?atm in summer, which was determined primarily by the seasonal change in seawater temperature. By contrast, the range in the diel variation in pCO2, 400 to 500 ?atm in summer 200 to 300 ?atm in winter, was attributed to the seasonal variation in community metabolism: Gross primary production (P g ) and respiration (R) were high in summer and low in winter. During the 1998 bleaching event, although P g and R increased, community excess organic production (E) decreased by three quarters compared with the same month in 1999, when the coral community showed high recovery. This change in metabolism led to large diel range and increased average value of pCO2 levels in the seawater on the reef flat. The decrease in the range and increase in the average value of pCO2 were observed by monitoring the Palau barrier reef flat, where overall mortality of corals occurred after the bleaching. All the metabolic parameters, P g , R, E and calcification (G) were reduced by half after the bleaching, which increased the average pCO2 value by 10 ?atm and decreased its diel range from 200-400 ?atm to 100-200 ?atm. Bleaching and resultant mortality of coral reefs led to degradation of their metabolic performance, and thus resulted in the loss of their active interaction with the carbon cycle.

Paleomagnetic of the Cobb Mountin event sections

Detailed paleomagnetic investigations are reported for 283 specimens, sampled from three closely spaced Ocean Drilling Program Leg 135 cores from the Lau Basin. These specimens cover three rather similar records of the reversed Cobb Mountain short polarity event, having an age of about 1.12 m.y. On the basis of a very detailed subsampling every 0.6 cm, we found that the transition times for the Cobb Mountain geomagnetic polarity event, as seen in the three Lau Basin sediment records, appear to have been as short as 0.6-1.0 k.y., although the duration of the normal-polarity event itself lasted only about 17 ± 4 k.y. The older (R to N) transition as well as the younger (N to R) transition show virtual geomagnetic paths roughly along the Americas, but shifted some 30° ± 10° to the east. These paths conflict with Cobb Mountain transition paths recorded in sediments from the Labrador Sea and the North Atlantic, but they are in fair accordance with sediment records from the Celebes and Sulu seas when corrected for differences in site longitude, suggesting that the transitional fields are dominated by nonaxial, high-order spherical harmonics.

The Cenomanian/Turronian Boundary Event at ODP Hole 103-641A

Drilling at ODP Site 641 (on the western margin of Galicia Bank, off northwestern Spain) revealed a thin, but pronounced, interval of black shale and gray-green claystone. Our high-resolution study combines the sedimentology, micropaleontology (palynomorphs and others), organic and inorganic geochemistry, and isotopic values of this layer to demonstrate the distinct nature of the sediment and prove that the sequence represents the local sedimentary expression of the global Cenomanian/Turonian Oceanic Anoxic Event (OAE) of Schlanger and Jenkyns (1976), Arthur and Schlanger (1979), and Jenkyns (1980), also called the Cenomanian/Turonian Boundary Event (CTBE). The most striking evidence is that the strong positive d13C excursion characterizing the CTBE sequences in shallow areas can be traced into a pronounced deep-sea expression, thus providing a good stratigraphic marker for the CTBE in various paleosettings. The isotopic excursion at Site 641 coincides with an extremely enriched trace metal content, with values that were previously unknown for the Cretaceous Atlantic. Similar to other CTBE occurrences, the organic carbon content is high (up to 11%) and the organic matter is of dominantly marine origin (kerogen type II). The bulk mineralogy of the CTBE sediments does not differ significantly from the general trend of Cretaceous North Atlantic sediments (dominance of smectite and zeolite with minor amounts of illite and scattered palygorskite, kaolinite, and chlorite); thus, no evidence for either increased volcanic activity nor a drastic climatic change in the borderlands was found. Results from Site 641 are compared with the CTBE section found at Site 398, DSDP Leg 47B (Vigo Seamount at the southern end of the Galicia Bank).

Tab. 1 Mole % CO2 and 13C values of CO2 at baseline and at the final monitoring event for the eight observation wells

During CO2 storage operations in mature oilfields or saline aquifers it is desirable to trace the movement of injected CO2 for verification and safety purposes. We demonstrate the successful use of carbon isotope abundance ratios for tracing the movement of CO2 injected at the Cardium CO2 Storage Monitoring project in Alberta between 2005 and 2007. Injected CO2 had a d13C value of -4.6±1.1 per mil that was more than 10 per mil higher than the carbon isotope ratios of casing gas CO2 prior to CO2 injection with average d13C values ranging from -15.9 to -23.5 per mil. After commencement of CO2 injection, d13C values of casing gas CO2 increased in all observation wells towards those of the injected CO2 consistent with a two-source end-member mixing model. At four wells located in a NE-SW trend with respect to the injection wells, breakthrough of injected CO2 was registered chemically (>50 mol % CO2) and isotopically 1-6 months after commencement of CO2 injection resulting in cumulative CO2 fluxes exceeding 100000 m**3 during the observation period. At four other wells, casing gas CO2 contents remained below 5 mol % resulting in low cumulative CO2 fluxes (<2000 m**3) throughout the entire observation period, but carbon isotope ratios indicated contributions between <30 and 80% of injected CO2. Therefore, we conclude that monitoring the movement of CO2 in the injection reservoir with geochemical and isotopic techniques is an effective approach to determine plume expansion and to identify potential preferential flow paths provided that the isotopic composition of injected CO2 is constant and distinct from that of baseline CO2.

Paleomegnetic and geochemistry of sediments from the early Aptian Oceanic Anoxic Event

The early Aptian Oceanic Anoxic Event (OAE1a, 120 Ma) represents a geologically brief time interval in the mid-Cretaceous greenhouse world that is characterized by increased organic carbon accumulation in marine sediments, sudden biotic changes, and abrupt carbon-isotope excursions indicative of significant perturbations to global carbon cycling. The brevity of these drastic environmental changes (< 10**6 year) and the typically 10**6 year temporal resolution of the available chronologies, however, represent a critical gap in our knowledge of OAE1a. We have conducted a high-resolution investigation of three widely distributed sections, including the Cismon APTICORE in Italy, Santa Rosa Canyon in northeastern Mexico, and Deep Sea Drilling Project (DSDP) Site 398 off the Iberian margin in the North Atlantic Ocean, which represent a range of depositional environments where condensed and moderately expanded OAE1a intervals are recorded. The objectives of this study are to establish orbital chronologies for these sections and to construct a common, high-resolution timescale for OAE1a. Spectral analyses of the closely-spaced (corresponding to ~5 to 10 kyr) measurements of calcium carbonate content of the APTICORE, magnetic susceptibility (MS) and anhysteretic remanent magnetization (ARM) of the Santa Rosa samples, and MS, ARM and ARM/IRM, where IRM is isothermal remanent magnetization, of Site 398 samples reveal statistically significant cycles. These cycles exhibit periodicity ratios and modulation patterns similar to those of the mid-Cretaceous orbital cycles, suggesting that orbital variations may have modulated depositional processes. Orbital control allows us to estimate the duration of unique, globally identifiable stages of OAE1a. Although OAE1a had a duration of ~1.0 to 1.3 Myr, the initial perturbation represented by the negative carbon-isotope excursion was rapid, lasting for ~27-44 kyr. This estimate could serve as a basis for constraining triggering mechanisms for OAE1a.

Grazing rate of microzooplankton measured experimentally in the North Atlantic during the Maria S. Merian cruise MSM26, spring 2013

The microzooplankton grazing dilution experiments were conducted at stations 126, 127, 131 and 133-137, following Landry & Hassett (1982). Seawater samples (whole seawater - WSW) were taken via Niskin bottles mounted on to a CTD Rosette out of the chlorophyll maximum at each station. Four different dilution levels were prepared with WSW and GF/F filtered seawater - 100% WSW, 75% WSW, 50% WSW and 25% WSW. The diluted WSW was filled in 2.4 L polycarbonate bottles (two replicates for every dilution level). Three subsamples (250 - 500 mL depending on in situ chlorophyll) of the 100% WSW were filtered on to GF/F filters (25 mm diameter) and chlorophyll was extracted in 5 mL 96% ethanol for 12-24 hours. Afterwards it was measured fluorometrically before and after the addition of HCl with a Turner fluorometer according to Jespersen and Christoffersen (1987) on board of the ship. In addition, one 250 mL subsample of the 100% WSW was fixed in 2% Lugol (final concentration), to determine the microzooplankton community when back at the Institute for Hydrobiology and Fisheries Science in Hamburg. Also, one 50 mL subsample of the 100% WSW was fixed in 1 mL glutaraldehyde, to quantify bacteria abundance. The 2.4 L bottles were put in black mesh-bags, which reduced incoming radiation to approximately 50% (to minimize chlorophyll bleaching). The bottles were incubated for 24 hours in a tank on deck with flow-through water, to maintain in situ temperature. An additional experiment was carried out to test the effect of temperature on microzooplankton grazing in darkness. Therefore, 100% WSW was incubated in the deck tank and in two temperature control rooms of 5 and 15°C in darkness (two bottles each). The same was done with bottles where copepods were added (five copepods of Calanus finmarchicus in each bottle; males and females were randomly picked and divided onto the bottles). In addition, two 100% WSW bottles with five copepods each were incubated at in situ temperature at 100% light level (without mesh-bags). All experiments were incubated for 24 hours and afterwards two subsamples of each bottle were filtered on to GF/F filters (25 mm diameter); 500 - 1000 mL depending on in situ chlorophyll. One 250 mL subsample of one of the two replicates of each dilution level and each additional experiment (temperature and temperature/copepods) was fixed in 5 mL lugol for microzooplankton determination. One 50 mL subsample of one of the two 100% WSW bottles as well as of one of the additional experiments without copepods was fixed in 1 mL glutaraldehyde for bacteria determination later on. Copepods were fixed in 4% formaldehyde for length measurements and sex determination.

Analysis of an ancient global warming event, the Paleocene-Eocene thermal maximum, under examination from ODP Holes 113-689B and 113-690B

Spatiotemporal patterns of carbonate dissolution provide a critical constraint on carbon input during an ancient (~55.5 Ma) global warming event known as the Paleocene-Eocene thermal maximum (PETM), yet the magnitude of lysocline shoaling in the Southern Ocean is poorly constrained due to limited spatial coverage in the circum-Antarctic region. This shortcoming is partially addressed by comparing patterns of carbonate sedimentation at the Site 690 PETM reference section to those herein reconstructed for nearby Site 689. Biochemostratigraphic correlation of the two records reveals that the first ~36 ka of the carbon isotope excursion (CIE) signaling PETM conditions is captured by the Site 689 section, while the remainder of the CIE interval and nearly all of the CIE recovery are missing due to a coring gap. A relatively expanded stratigraphy and higher carbonate content at mid-bathyal Site 689 indicate that dissolution was less severe than at Site 690. Thus, the bathymetric transect delimited by these two PETM records indicates that the lysocline shoaled above Site 689 (~1,100 m) while the calcite compensation depth remained below Site 690 (~1,900 m) in the Weddell Sea region. The ensuing recovery of carbonate sedimentation conforms to a bathymetric trend best explained by gradual lysocline deepening as negative feedback mechanisms neutralized ocean acidification. Further, biochemostratigraphic evidence indicates the tail end of the CIE recovery interval at both sites has been truncated by a hiatus most likely related to vigorous production and advection of intermediate waters.

Occurrence and Range-through database of functional diversity of marine ecosystems after the Late Permian mass extinction event

The Late Permian mass extinction event about 252 million years ago was the most severe biotic crisis of the past 500 million years and occurred during an episode of global warming. The loss of around two-thirds of marine genera is thought to have had substantial ecological effects, but the overall impacts on the functioning of marine ecosystems and the pattern of marine recovery are uncertain. Here we analyse the fossil occurrences of all known benthic marine invertebrate genera from the Permian and Triassic periods, and assign each to a functional group based on their inferred lifestyle. We show that despite the selective extinction of 62-74% of these genera, all but one functional group persisted through the crisis, indicating that there was no significant loss of functional diversity at the global scale. In addition, only one new mode of life originated in the extinction aftermath. We suggest that Early Triassic marine ecosystems were not as ecologically depauperate as widely assumed. Functional diversity was, however, reduced in particular regions and habitats, such as tropical reefs; at these smaller scales, recovery varied spatially and temporally, probably driven by migration of surviving groups. We find that marine ecosystems did not return to their pre-extinction state, and by the Middle Triassic greater functional evenness is recorded, resulting from the radiation of previously subordinate groups such as motile, epifaunal grazers.

Planktic foraminiferal sieve size specific d13C and d18O values and maximum test diameter from ODP sites 171-1051 and 120-748

Many genera of modern planktic foraminifera are adapted to nutrient-poor (oligotrophic) surface waters by hosting photosynthetic symbionts, but it is unknown how they will respond to future changes in ocean temperature and acidity. Here we show that ca. 40 Ma, some fossil photosymbiont-bearing planktic foraminifera were temporarily 'bleached' of their symbionts coincident with transient global warming during the Middle Eocene Climatic Optimum (MECO). At Ocean Drilling Program (ODP) Sites 748 and 1051 (Southern Ocean and mid-latitude North Atlantic, respectively), the typically positive relationship between the size of photosymbiont-bearing planktic foraminifer tests and their carbon isotope ratios (d13C) was temporarily reduced for ~100 k.y. during the peak of the MECO. At the same time, the typically photosymbiont-bearing planktic foraminifera Acarinina suffered transient reductions in test size and relative abundance, indicating ecological stress. The coincidence of minimum d18O values and reduction in test size-d13C gradients suggests a link between increased sea-surface temperatures and bleaching during the MECO, although changes in pH and nutrient availability may also have played a role. Our findings show that host-photosymbiont interactions are not constant through geological time, with implications for both the evolution of trophic strategies in marine plankton and the reliability of geochemical proxy records generated from symbiont-bearing planktic foraminifera.

Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.