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Quantitative microscopic analyses of sediment trap samples collected in the Ross Sea between January 1990 and February 1992 reveal striking temporal and spatial differences in algal bloom composition and size. Trap samples from the southwestern Ross Sea (site A, 76°30′S, 167°30′E) were dominated by the diatom Fragilariopsis curia (maximum of 92%), a species associated with both sea ice and the retreating ice edge in the Ross Sea. This species was probably seeded by melting congelation ice. Highest flux of diatom valves to both upper and lower traps in the 1991–1992 season occurred as a distinct event in mid-February 1991, after which flux decreased by 1 to 3 orders of magnitude. As overall flux decreased, an increase in relative abundance of Chaetoceros resting spores and the open water species Thalassiosira antarctica was observed in the lower trap, suggesting some localized lateral advection. In the south central Ross Sea (site B, 76°30′, S 175°W), algal diversity was much higher, with a greater contribution of nondiatom material. The prymnesiophyte Phaeocystis antarctica, dinoflagellates, and cysts of unknown affinity were much more common than at site A, as were the diatoms Fragilariopsis cylindrus, Fragilariopsis kerguelensis, and Thalassiosira gracilis. Highest diatom flux occurred later (February 20 to March 6,1991) at this site and was an order of magnitude lower as compared to maximum flux at site A. Distinct differences in bloom size and composition between sites A and B may be a function of upper water column structure, differences in the amount of sea ice melting, and the type of sea ice present at the time of ice breakout (congelation versus pack ice). Despite rich surface productivities, lower silica flux to the seafloor at site B results from the higher proportion of nonsiliceous algae. At site C (72°30′S, 172°30′E), in the northwestern Ross Sea, diatoms again dominated algal flux; however, assemblage composition differed from that observed at both sites A and B. Relative abundance of F. curta was lower, averaging 60–70%, while the remainder of the assemblage was made up of F. cylindrus, other more robust species of Fragilariopsis, and Chaetoceros resting spores. Algal flux at site C is intermediate in style between sites A and B. Significantly, spatial differences in diatom assemblages noted above appear to be reflected in seafloor surface sediments, suggesting that downcore diatom data provide an interpretable record of paleoproductivity in the Ross Sea.

We examined the cycling of organic carbon and biogenic silica in the water column and upper sediments of the Ross Sea, seeking to understand the processes leading to the formation of opal-rich, organic-poor sediments over much of the Southern Ocean. Between January, 1990 and December, 1994 we conducted three cruises, performing tracer incubation studies (14C, 15N, 30Si, 32Si) to measure rates of primary production, nitrate-based “new” production, biogenic silica production and biogenic silica dissolution in the upper 50 m over most of the Ross Sea shelf in spring, mid summer and late summer. We deployed sediment traps from January, 1990 to early March, 1992 to measure the mid-water (250 m) and near-bottom gravitational fluxes of particulate organic carbon, nitrogen and biogenic silica year-round at three sites, and obtained sediment cores at 15 sites to assess the accumulation rates of organic carbon and biogenic silica in all known sediment regimes on the shelf. At 9 of those sites we also measured nutrient efflux from the sediments, enabling us to calculate benthic recycling fluxes of organic matter and opal. These data permit estimates of the annual production, near-surface recycling, vertical sinking flux, delivery to the seabed, benthic regeneration and long-term burial of both organic and siliceous material, integrated over a 3.3 × 105 km2 area that covers 75–80% of the Ross Sea shelf. The resulting annual budgets for carbon and silica indicate highly selective preservation of biogenic silica over organic carbon between 50 and 250 m in the water column, as well as in the upper seabed. Selective preservation of silica within the upper 50 m is not indicated, and both organic matter and silica are transported from 250 m to the sea floor with virtually 100% efficiency. The SiO2/C mass ratios for surface-layer production, 250-m sinking flux, delivery to the seabed and long-term burial are approximately 0.85, 6.1, 6.2 and 27, respectively. This progressive enrichment in silica results in long-term burial of 5.8% of the biogenic silica and 0.17% of the organic carbon produced by phytoplankton in the surface layer, a factor of 30 greater preservation efficiency for silica than for carbon. Nevertheless, the ratio of opal burial to opal production in the Ross Sea is only about twice the apparent global average of 3% and

The Ross Sea, Antarctica, with its high rates of primary productivity and biogenic accumulation, provides an important location to test the validity of a one-dimensional particle-settling model. As part of an interdisciplinary field project performed from 1990 to 1992 to examine cycling and accumulation of biogenic matter in the Ross Sea, water-column particulate and current data were collected at three sites. At each of the sites, a current meter and sediment trap were placed 240 m below the water surface, and a similar set of instruments was located 40 m above the seabed. The moorings were deployed for 1- to 2-years duration. The current-meter records showed that the speed of flow in the southwestern Ross Sea is relatively slow ( 50 cm s−1) and least variability in direction. To examine the validity of a one-dimensional approximation for fluxes of biogenic material, two models were developed to determine the net displacement of particles settling through the water column. Current-meter data and particle-settling characteristics were incorporated in both models. One model produced a time-varying, linearly interpolated current field between the moorings in which particle advection was evaluated. The second model used time-averaged progressive-vector plots to estimate lateral particle advection. Results show that particles are displaced the least at the southwestern site ( 50 km). The pattern in displacement trends correlates well with observed sediment types and accumulation rates at each site. A one-dimensional model for the settling of biogenic material is most applicable at the southwestern site and least applicable at the northwestern site.

A 2-year (1993-1994) study was conducted in the Galapagos Islands (Ecuador) to determine the relationship between δ18O in skeletal carbonate and sea surface temperature (SST) in three species of reef-building corals: Pavona clavus, Pavona gigantea, and Porites lobata. Coral samples were grown at 3, 10, and 3 m depth at Bartolome Island, Champion iIsland, and Urvina Bay (Isabela Island), respectively. Hourly measurements of SST and sea surface salinity (SSS) were taken at each site immediately adjacent to colonies which were stained biannually to establish the chronology of growth. In addition, surface waters were sampled periodically (bimonthly to monthly) at each site to determine variation in δ18O seawater. Results indicate the mean annual SSTs were similar between sites, varying from 22.9°C at Champion to 23.8°C at Urvina Bay. Comparisons of monthly SST averages between instrumental and remote sensing (satellite, 1° × 1° grid) data show a high correspondence (r2 ranging from 0.84 to 0.94), indicating that remote sensing data are useful for interpreting the δ18O record in corals when instrumental data are lacking. Here δ18Ocoral analyses of eight specimens show that coralline aragonite is a reliable indicator of SST in Galapagos. In general, higher-resolution coral sampling/year resolved more of the monthly variation in SST, up to 97% at a sampling resolution of 1.4 samples per millimeter of linear skeletal growth. Comparisions of the δ18Ocoral signal among and between species at the same site showed consistent seasonal patterns of variation closely tracking SST. In addition, comparisons between sites were highly concordant, with some differences reflecting local variation in SST. Seasonal patterns, however, were essentially the same over the entire region. Thus we conclude that the δ18Ocoral signal from coral skeletons in Galapagos can be used to interpret regional changes in SST variation.

A survey of corals from a variety of tropical settings reveals previously unseen seasonal variations in skeletal UCa. Based upon two corals from the Galapagos Islands, a comparison of UCa with δ180 suggests a possible temperature dependence of +3–4% per degree centigrade cooling. An overall range in UCa of 1.03–1.37 μmol U/mol Ca (2.45–3.25 ppm) between corals from warm and cool water settings supports this interpretation. An alternative control, however, cannot be ruled out. Changes in the carbonate ion content of surface waters are sufficient to drive comparable variations, provided uranium is incorporated as UO22+ or a carbonate complex thereof. In addition to these possible controls, we identify a probable salinity influence on coral UCa which suggests that uranium uptake depends upon [U]seawater and not [UCa]seawater. Within individual corals, artifacts associated with “vital” influences appear minimal. Extension/calcification rate effects as assessed via comparisons of contemporaneous growth trajectories in individual colonies appear small relative to typical seasonal UCa variations of 10–20%. Excluding corals from the Galapagos cool regime, five species from warmer tropical settings exhibit remarkably little variability in mean UCa (1.03–1.09 μmol U/mol Ca). Our findings suggest that the range of UCa in modern corals defined by published data reflects a combination of interspecific variability and environmental control. The possibility that coral UCa is associated with temperature, alkalinity, and salinity suggests many uses for this new paleotracer. Rapid and precise measurement of uranium by isotope dilution ICP-MS will expedite future development and application. Key among the next steps must be studies to isolate the influences of the above mentioned environmental parameters. Additionally, potential microsampling artifacts (e.g., caused by drilling) and an apparent 6% “leachable” uranium fraction in a single test coral should be investigated through further pretreatment studies.

In this study we measured stable oxygen and carbon isotope ratios in the skeletons of massive reef-building corals (Porites lobata and Pavona gigantea) at four widespread locations in the tropical eastern Pacific, each with a unique marine climate. Annual variation in sea surface temperature (SST) varied from 5–7°C at upwelling sites (Gulf of Panama and Galapagos Islands) to 2–3°C where upwelling was absent [Cano Isand (Costa Rica) and Gulf of Chiriqui (Panama)]. Annual range in salinity was high in the gulfs of Panama and Chiriqui (up to 15‰) and low at Cano Island and Galapagos (2–3‰). We characterize the isotopic signatures of recent (15–40 y long records) El Nino/Southern Oscillation (ENSO) events, particularly the very severe 1982–1983 event. Subannual sampling at 1–2 month resolution reveals that the δ18O signal at Cano Island records strong to very strong ENSOs. In the Gulf of Chiriqui, this signal is governed mainly (80%) by salinity and thus is a weak recorder of ENSO events: only the 1951–1952, 1957–1958 and 1972–1973 events appear as significant δ18O anomalies over the period 1940–1984. In the Gulf of Panama, high variation in both SST and salinity contribute to the δ18O signal. ENSO events at this site are poorly recorded, probably due to ameliorating effects of cool upwelled water during the early stage of the ENSO event. The δ18O record in Galapagos, however, shows a strong correlation with SST and accurately records all but the most severe 1982–1983 ENSO event. Thus, ENSOs are most clearly recorded at sites where salinity variation is minimal. At Cano only strong ENSOs are recorded while mild to strong events appear in the Galapagos record. Nowhere did the δ18O signal accurately record the full range of temperatures that occurred during the 1982–1983 ENSO; however, a stress band on the coral skeleton was evident at all sites. By comparing the δ18O records and skeletal features across sites it may be possible to identify the occurrence of strong to very severe ENSOs prior to instrumental records. The relationship between δ18O and δ13C was examined and found to be significantly positive and in phase (i.e., either depleted or enriched at the same time) at three of the four sites studied. Weak correlations at some sites may be explained by high variability in water column clarity leading to depleted δ13C when waters are cool and surface isolation high.

The Integrated Ocean Drilling Program Expedition 318 to the Wilkes Land margin of Antarctica recovered a sedimentary succession ranging in age from lower Eocene to the Holocene. Excellent stratigraphic control is key to understanding the timing of paleoceanographic events through critical climate intervals. Drill sites recovered the lower and middle Eocene, nearly the entire Oligocene, the Miocene from about 17 Ma, the entire Pliocene and much of the Pleistocene. The paleomagnetic properties are generally suitable for magnetostratigraphic interpretation, with well-behaved demagnetization diagrams, uniform distribution of declinations, and a clear separation into two inclination modes. Although the sequences were discontinuously recovered with many gaps due to coring, and there are hiatuses from sedimentary and tectonic processes, the magnetostratigraphic patterns are in general readily interpretable. Our interpretations are integrated with the diatom, radiolarian, calcareous nannofossils and dinoflagellate cyst (dinocyst) biostratigraphy. The magnetostratigraphy significantly improves the resolution of the chronostratigraphy, particularly in intervals with poor biostratigraphic control. However, Southern Ocean records with reliable magnetostratigraphies are notably scarce, and the data reported here provide an opportunity for improved calibration of the biostratigraphic records. In particular, we provide a rare magnetostratigraphic calibration for dinocyst biostratigraphy in the Paleogene and a substantially improved diatom calibration for the Pliocene. This paper presents the stratigraphic framework for future paleoceanographic proxy records which are being developed for the Wilkes Land margin cores. It further provides tight constraints on the duration of regional hiatuses inferred from seismic surveys of the region.

The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high d11B compositions ranging from 23.2‰ to 28.7‰. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pHcf), being elevated by ~0.6–0.8 units (?pH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower d11B composition of 15.5‰, with a corresponding lower ?pH value of ~0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pHT and shows an approximate linear correlation with ?pHDesmo = 6.43 - 0.71pHT (r2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where ?pHDesmo = 1.09 - 0.14Oarag (r2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pHcf, and consequently Ocf, of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+-ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (d11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium. We also show that the relatively strong up-regulation of pH and consequent elevation of the internal carbonate saturation state (Ocf ~8.5 to ~13) at the site of calcification by cold-water corals, facilitates calcification at or in some cases below the aragonite saturation horizon, providing a greater ability to adapt to the already low and now decreasing carbonate ion concentrations. Although providing greater resilience to the effects of ocean acidification and enhancing rates of calcification with increasing temperature, the process of internal pHcf up-regulation has an associated energetic cost, and therefore growth-rate cost, of ~10% per 0.1 pH unit decrease in seawater pHT. Furthermore, as the aragonite saturation horizon shoals with rapidly increasing pCO2 and Oarag < 1, increased dissolution of the exposed skeleton will ultimately limit their survival in the deep oceans.

Ocean acidification poses multiple challenges for coral reefs on molecular to ecological scales, yet previous experimental studies of the impact of projected CO2 concentrations have mostly been done in aquarium systems with corals removed from their natural ecosystem and placed under artificial light and seawater conditions. The Coral–Proto Free Ocean Carbon Enrichment System (CP-FOCE) uses a network of sensors to monitor conditions within each flume and maintain experimental pH as an offset from environmental pH using feedback control on the injection of low pH seawater. Carbonate chemistry conditions maintained in the −0.06 and −0.22 pH offset treatments were significantly different than environmental conditions. The results from this short-term experiment suggest that the CP-FOCE is an important new experimental system to study in situ impacts of ocean acidification on coral reef ecosystems.

Human impact on biodiversity usually is measured by reduction in species abundance or richness. Just as important, but much more difficult to discern, is the anthropogenic elimination of ecological interactions. Here we report on the persistence of a long ecological interaction chain linking diverse food webs and habitats in the near-pristine portions of a remote Pacific atoll. Using biogeochemical assays, animal tracking, and field surveys we show that seabirds roosting on native trees fertilize soils, increasing coastal nutrients and the abundance of plankton, thus attracting manta rays to native forest coastlines. Partnered observations conducted in regions of this atoll where native trees have been replaced by human propagated palms reveal that this complex interaction chain linking trees to mantas readily breaks down. Taken together these findings provide a compelling example of how anthropogenic disturbance may be contributing to widespread reductions in ecological interaction chain length, thereby isolating and simplifying ecosystems.

Ocean acidification poses multiple challenges for coral reefs on molecular to ecological scales, yet previous experimental studies of the impact of projected CO2 concentrations have mostly been done in aquarium systems with corals removed from their natural ecosystem and placed under artificial light and seawater conditions. The Coral–Proto Free Ocean Carbon Enrichment System (CP-FOCE) uses a network of sensors to monitor conditions within each flume and maintain experimental pH as an offset from environmental pH using feedback control on the injection of low pH seawater. Carbonate chemistry conditions maintained in the −0.06 and −0.22 pH offset treatments were significantly different than environmental conditions. The results from this short-term experiment suggest that the CP-FOCE is an important new experimental system to study in situ impacts of ocean acidification on coral reef ecosystems.

[1] Observations from November 2006 in the southwestern Ross Sea indicate that stratification developed in a localized fashion, proximal to upper ocean fronts. These regions were hotspots for biological productivity, exhibiting greater drawdown of CO2 and accumulation of oxygen, indicative of enhanced photosynthesis and air-sea gas exchange. While the effect of stratification is clear, the reasons for its development was not; air temperatures were unseasonably cold, sea-ice melt and sea surface warming were not significant. By comparing a one-dimensional mixed layer model with two-dimensional numerical simulations that include horizontal density gradients characteristic of the region, it is shown that Ekman advection is critical to structuring early season stratification. Where fronts are forced by winds that oppose the surface frontal current, Ekman advection displaces lighter water over dense. As biological productivity is light limited in the Ross Sea, and thus sensitive to the depth of the mixed layer, Ekman restratification plays an important role in determining the spatial distribution and development of the annual phytoplankton bloom in the region. The presence of fronts is therefore of first-order importance to the restratification and bloom dynamics of the Ross Sea in the early spring. Citation: Long, M. C., L. N. Thomas, and R. B. Dunbar (2012), Control of phytoplankton bloom inception in the Ross Sea, Antarctica, by Ekman restratification, Global Biogeochem. Cycles, 26, GB1006, doi:10.1029/2010GB003982.

The influence of Antarctica and the Southern Ocean on Late Pliocene global climate reconstructions has remained ambiguous due to a lack of well-dated Antarctic-proximal, paleoenvironmental records. Here we present ice sheet, sea-surface temperature, and sea ice reconstructions from the ANDRILL AND-1B sediment core recovered from beneath the Ross Ice Shelf. We provide evidence for a major expansion of an ice sheet in the Ross Sea that began at similar to 3.3 Ma, followed by a coastal sea surface temperature cooling of similar to 2.5 degrees C, a stepwise expansion of sea ice, and polynya-style deep mixing in the Ross Sea between 3.3 and 2.5 Ma. The intensification of Antarctic cooling resulted in strengthened westerly winds and invigorated ocean circulation. The associated northward migration of Southern Ocean fronts has been linked with reduced Atlantic Meridional Overturning Circulation by restricting surface water connectivity between the ocean basins, with implications for heat transport to the high latitudes of the North Atlantic. While our results do not exclude low-latitude mechanisms as drivers for Pliocene cooling, they indicate an additional role played by southern high-latitude cooling during development of the bipolar world.

A reconstruction of late Pleistocene surface water carbon isotopic (δ13C) variability is presented from Ocean Drilling Program (ODP) site 769 in the Sulu Sea in the western tropical Pacific. The Sulu Sea is a shallowly silled back arc basin with a maximum sill depth of 420 m. Site 769 was drilled on a bathymetric high in 3643 m of water and has average late Pleistocene sedimentation rates of 8.5 cm/kyr. The oxygen isotope record (δ18O) of Globigerinoides ruber at site 769 shows a strong correlation with the SPECMAP stacked δ18O record, attesting to the continuity of sediment archive at the site. Surface δ13C displays consistent glacial-interglacial variability which averages ∼0.9‰ and has varied from 0.75 to 1.1‰ over the last 800 kyr. Comparison to surface water δ13C records in the South China Sea and western tropical Pacific suggests that the glacial-interglacial surface δ13C variability is regional in scale. Planktonic δ13C data from ODP site 677 in the eastern Pacific is also coherent with the site 769. Additionally, we have found that the site 769 surface δ13C record is coherent at periods of 100 and 41 kyr with deepwater δ13C records from the Pacific. The highest correlation occurs with the deep eastern Pacific, where benthic δ13C data from cores RC13-110 and ODP site 677 closely match the Sulu Sea surface water record. We evaluate several possible controls of surface water δ13C in the Sulu Sea that may explain the coherent timing with Pacific deepwater δ13C records. These include variations in terrestrial organic matter flux to the basin, the upwelling of subsurface water and productivity changes, and the influx of western Pacific intermediate water to the Sulu Sea. Our preferred explanation involves a region of upper intermediate water upwelling in the far western Pacific which has been shown to outgas CO2 from subsurface waters into surface waters. Upwelling also occurs in the area of Panama Basin site 677. These equatorial upwelling zones could potentially provide a route by which Pacific intermediate water can modulate the δ13C composition of certain Pacific surface water locations. Future reconstructions of late Pleistocene surface water δ13C variability in the western Pacific and Indonesian seas will be required to further evaluate the source of the glacial-interglacial surface water δ13C change.

We measured stable oxygen isotope ratios and skeletal growth rates in the massive corals Pavona clavus and P. gigantea from the west coast of Isabela Island, Galapagos, to assess interannual to decadal climate variability in the eastern Pacific. Comparisons of instrumental data sets show that sea surface temperatures (SST) in the Galapagos region are representative of a broad portion of the eastern equatorial Pacific. The site is especially well-suited for long-term studies of the El Nino/Southern Oscillation (ENSO) phenomenon, as it lies within the eastern Pacific “center of action” for thermal anomalies associated with ENSO. The P. gigantea isotope record is nearly monthly in resolution, spans the period 1961–1982, and shows strong correlation with a Galapagos instrumental SST record (r = −0.90 for annual averages). Cross-spectral analysis shows that SST can explain greater than 80% of the variance in δ18O at both the annual cycle and within the high-frequency portion of the ENSO band (3-5 years). The P. clavus record is annual in resolution, extends from 1587 to 1953 A.D., and was obtained from a 10-m diameter colony preserved within the Urvina Bay uplift. Because seawater δ18O variations in the region are very small, we interpret the Urvina Bay coral δ18O record in terms of annual average SST. The isotopic record appears to be a very good, but not perfect, indicator of ENSO events and shows good correspondence with the historical ENSO reconstruction of Quinn et al. (1987). A number of low δ18O excursions that we observe during the 17th and 18th centuries very likely represent ENSO events that are missing from the historical tabulations. Most interannual δ18O variations between 1607 and 1953 A.D. represent annual average temperature excursions of 1° to 2.5°C. During the Little Ice Age, the annual δ18O series correlates well with many North American tree ring records and shows low temperatures during the early 1600s and early 1800s, and relatively warmer conditions during the 1700s. Unlike most northern hemisphere tree ring and instrumental records, we see no evidence at this site for warming between 1880 and 1940 but rather observe a slight cooling ( 28% of the total variance. The main ENSO mode is centered at 4.6 years and accounts for 12% of the total variance. Additional significant oscillations occur at periods of 3.3, 6, 8, 11, 17, 22, and 34 years. Both annual growth rate and δ18O show variance at periods equivalent to the solar and solar magnetic periods (e.g., 11 and 22 years, respectively). In addition, the amplitude of the 11-year δ18O cycle generally varies with the amplitude of the solar cycle, supporting previous suggestions that the solar cycle may modulate interannual to decadal climate variability in the tropics. The dominant oscillatory modes, both within the ENSO and interdecadal frequency bands, shift to shorter periods from the early to middle 1700s and again from the middle to late 1800s. This may reflect major reorganizations within the tropical ocean-atmosphere system and suggests that tropical Pacific climate variability is linked across timescales ranging from years to decades.

[1] We present corrections to uncertainty estimates of late 20th century (1972-1998) coral-based sea-surface temperature (SST) and salinity (SSS) trends from Palmyra, Fanning and Christmas Islands of the central tropical Pacific reported in Nurhati et al. [2009] (Geophysical Research Letters, 36, L21606, doi:10.1029/2009GL040270). In our original paper we had assigned relatively large error bars to coral Sr/Ca-based warming trends observed at all three islands, rendering those trends statistically insignificant with respect to the large errors. However, those large uncertainties originate from large errors associated with quantifying absolute SST at any given point, whereas the uncertainties for SST trends should reflect errors in quantifying relative changes, which are much lower. Late 20th century warming trends of 0.94–1.65°C at the three islands are statistically significant with the corrected error ranges of ±0.19–0.37°C (1σ; originally ±5.73–6.57°C). Freshening trends inferred from coral-based oxygen isotopic composition of seawater (δ18OSW) of −0.32‰ and −0.12‰ (1σ) at Palmyra and Fanning, respectively, are associated with corrected error ranges of ±0.07‰ and ±0.08‰ (1σ; originally ±0.08‰ for both), respectively. Christmas experienced an insignificant +0.03 ± 0.11‰ (1σ; originally also ±0.11‰) trend in δ18OSWover this period. With the new, lower uncertainty estimates, the coral-based SST and SSS trends are statistically significant, thereby strengthening Nurhati et al.'s (2009) conclusions that robust warming and freshening have occurred in the central tropical Pacific over the late 20th century. Our detailed uncertainty calculations presented below will be of value to the paleoclimate community, as the correct calculation of absolute errors and relative errors represents a key component of paleoclimatic reconstruction.

[1] The Ross Sea polynya is among the most productive regions in the Southern Ocean and may constitute a significant oceanic CO2 sink. Based on results from several field studies, this region has been considered seasonally iron limited, whereby a “winter reserve” of dissolved iron (dFe) is progressively depleted during the growing season to low concentrations (∼0.1 nM) that limit phytoplankton growth in the austral summer (December–February). Here we report new iron data for the Ross Sea polynya during austral summer 2005–2006 (27 December–22 January) and the following austral spring 2006 (16 November–3 December). The summer 2005–2006 data show generally low dFe concentrations in polynya surface waters (0.10 ± 0.05 nM in upper 40 m, n = 175), consistent with previous observations. Surprisingly, our spring 2006 data reveal similar low surface dFe concentrations in the polynya (0.06 ± 0.04 nM in upper 40 m, n = 69), in association with relatively high rates of primary production (∼170–260 mmol C m−2 d−1). These results indicate that the winter reserve dFe may be consumed relatively early in the growing season, such that polynya surface waters can become “iron limited” as early as November; i.e., the seasonal depletion of dFe is not necessarily gradual. Satellite observations reveal significant biomass accumulation in the polynya during summer 2006–2007, implying significant sources of “new” dFe to surface waters during this period. Possible sources of this new dFe include episodic vertical exchange, lateral advection, aerosol input, and reductive dissolution of particulate iron.

[1] We calculate net community production (NCP) during summer 2005–2006 and spring 2006 in the Ross Sea using multiple approaches to determine the magnitude and consistency of rates. Water column carbon and nutrient inventories and surface ocean O2/Ar data are compared to satellite-derived primary productivity (PP) estimates and 14C uptake experiments. In spring, NCP was related to stratification proximal to upper ocean fronts. In summer, the most intense C drawdown was in shallow mixed layers affected by ice melt; depth-integrated C drawdown, however, increased with mixing depth. ΔO2/Ar-based methods, relying on gas exchange reconstructions, underestimate NCP due to seasonal variations in surface ΔO2/Ar and NCP rates. Mixed layer ΔO2/Ar requires approximately 60 days to reach steady state, starting from early spring. Additionally, cold temperatures prolong the sensitivity of gas exchange reconstructions to past NCP variability. Complex vertical structure, in addition to the seasonal cycle, affects interpretations of surface-based observations, including those made from satellites. During both spring and summer, substantial fractions of NCP were below the mixed layer. Satellite-derived estimates tended to overestimate PP relative to 14C-based estimates, most severely in locations of stronger upper water column stratification. Biases notwithstanding, NCP-PP comparisons indicated that community respiration was of similar magnitude to NCP. We observed that a substantial portion of NCP remained as suspended particulate matter in the upper water column, demonstrating a lag between production and export. Resolving the dynamic physical processes that structure variance in NCP and its fate will enhance the understanding of the carbon cycling in highly productive Antarctic environments.

Downcore diatom data from a deep basin in Granite Harbor, Antarctica, provide new, high-resolution information concerning changes in oceanographic and depositional processes that have occurred during approximately the last 1250 years. The influence of global-scale climatic change, during the time of the Medieval Warm Period and possibly the Little Ice Age, is revealed by long-term changes in floral assemblages, as recorded by changes in the relative concentration of Nitzschia cylindrus. The diatom data suggest that Granite Harbor experienced less annual ice and pack ice cover during both these periods, possibly because of higher temperatures during the Medieval Warm Period and stronger offshore winds during the Little ice Age. The sedimentary record reveals several distinct, short-lived events, in which nearly monospecific blooms of Corethron criophilum and Chaetoceros spp. occurred, possibly the result of strong stabilization of the upper water column and were most likely a response to regional, rather than global conditions. Although short-lived, these events may play a significant role in the delivery of organic carbon and biogenic silica to the seafloor.

[1] We examined controls on the carbon isotopic composition of sea ice brines and organic matter during cruises to the Ross Sea, Antarctica in November/December 1998 and November/December 2006. Brine samples were analyzed for salinity, nutrients, total dissolved inorganic carbon (ΣCO2), and the 13C/12C ratio of ΣCO2 Particulate organic matter from sea ice cores was analyzed for percent particulate organic carbon (POC), percent total particulate nitrogen (TPN), and stable carbon isotopic composition (δ13CPOC). ΣCO2 in sea ice brines ranged from 1368 to 7149 μmol kg−1, equivalent to 1483 to 2519 μmol kg−1 when normalized to 34.5 psu salinity (sΣCO2), the average salinity of Ross Sea surface waters. Sea ice primary producers removed up to 34% of the available ΣCO2, an amount much higher than the maximum removal observed in sea ice free water. Carbonate precipitation and CO2 degassing may reduce sΣCO2 by a similar amount (e.g., 30%) in the most hypersaline sea ice environments, although brine volumes are low in very cold ice that supports these brines. Brine ranged from −2.6 to +8.0‰ while δ13CPOC ranged from −30.5 to −9.2‰. Isotopic enrichment of the ΣCO2 pool via net community production accounts for some but not all carbon isotopic enrichment of sea ice POC. Comparisons of sΣCO2, and δ13CPOC within sea ice suggest that ep (the net photosynthetic fractionation factor) for sea ice algae is ∼8‰ smaller than the ep observed for phytoplankton in open water regions of the Ross Sea. These results have implications for modeling of carbon uptake and transformation in the ice-covered ocean and for reconstruction of past sea ice extent based on stable isotopic composition of organic matter in sediment cores.

Recent studies provide seasonally and spatially resolved information on the isotopic characteristics of nitrate supply and N cycling in Southern Ocean surface waters. The new data improve our understanding of the nitrate supply to the Antarctic surface and its isotopic characteristics, especially with regard to the summertime subsurface minimum temperature (T min ) layer in the Antarctic. We use these findings to update and compile estimates of the N isotope effect of nitrate assimilation, e, in the Southern Ocean near Australia. A poleward decrease in e emerges, from 8-9‰ in the Subantarctic Zone (SAZ, 40-52°S) to similar to 5‰ in the Polar Antarctic Zone (PAZ, ~66°S). e is strongly correlated with mixed layer depth at the time of sampling. We hypothesize that the correlation is driven by the physiological response of diatoms to light availability, with light limitation leading to higher cellular efflux of nitrate and thus higher e.

Ocean acidification is driven by increasing atmospheric CO 2 and represents a key threat to the Great Barrier Reef (GBR) and other coral reefs globally. Previous investigations have depended on studies in aquaria that are compromised by reduced ecological complexity and buffering capacity, and problems associated with containment. These aquaria studies also include artifacts such as artificial flow, light, temperature, and water quality conditions. In order to avoid these issues a new technology was needed for in situ science. This need was the driver behind development of the Free Ocean Carbon Enrichment (FOCE) approach. FOCE is similar in approach to the Free Air Carbon Enrichment (FACE) experiments pursued on land for almost two decades. FOCE as a systems concept was developed at the Monterey Bay Aquarium Research Institute (MBARI) to perform controlled in situ studies on the effects of increased carbon dioxide on ocean environments. FOCE systems inject carbon dioxide enriched water into the desired control volume to lower the environmental pH to a specified value.

Plant introductions and subsequent community shifts are known to affect nutrient cycling, but most such studies have focused on nutrient enrichment effects. The nature of plant-driven nutrient depletions and the mechanisms by which these might occur are relatively poorly understood. In this study we demonstrate that the proliferation of the commonly introduced coconut palm, Cocos nucifera , interrupts the flow of allochthonous marine subsidies to terrestrial ecosystems via an indirect effect: impact on birds. Birds avoid nesting or roosting in C. nucifera , thus reducing the critical nutrient inputs they bring from the marine environment. These decreases in marine subsidies then lead to reductions in available soil nutrients, decreases in leaf nutrient quality, diminished leaf palatability, and reduced herbivory. This nutrient depletion pathway contrasts the more typical patterns of nutrient enrichment that follow plant species introductions. Research on the effects of spatial subsidy disruptions on ecosystems has not yet examined interruptions driven by changes within the recipient community, such as plant community shifts. The ubiquity of coconut palm introductions across the tropics and subtropics makes these observations particularly noteworthy. Equally important, the case of C. nucifera provides a strong demonstration of how plant community changes can dramatically impact the supply of allochthonous nutrients and thereby reshape energy flow in ecosystems.

The Santa Barbara Basin (SBB) record of laminated sediment, well known for its excellent time resolution, shows the presence of an unusual once-in-a-millenium event, in the period 1835–1840, at a depth of 55–57 cm below the surface of the seafloor. This “Macoma Event” is the brief flourishing of a macrofaunal community in the deep center of the SBB, from which large organisms are normally excluded by the lack of oxygen. Shells of the pelecypodMacoma leptonoidea Dall and associated fossils, which congregate in a thin layer dated at 1840, provide evidence for a sudden local extinction of macrobenthos by suffocation. Various stratigraphic evidence suggests thatM. leptonoidea colonized the basin floor for a few years prior to 1840 as a result of temporarily decreased productivity and increased oxygen content in the water spilling over the sill into the basin. Historical eyewitness reports indicate unusually severe winter storms from southeasterly directions during the 1830s in the SBB. We suggest that coastal upwelling was severely reduced during 1835–1839 with the effect of reducing the intensity of the oxygen minimum layer. TheMacoma Event apparently is one manifestation of large-scale climatic anomalies felt throughout North America, and which were possibly linked to the major volcanic eruption of Cosiguina, Nicaragua, in 1835.

[1] Global climate models and analyses of instrumental datasets provide a wide range of scenarios for future tropical Pacific climate change, limiting the accuracy of regional climate projections. Coral records provide continuous reconstructions of tropical Pacific climate trends that are difficult to quantify using the short, sparse instrumental datasets available from the tropical Pacific. Here, we present coral-based reconstructions of late 20th century sea-surface temperature and salinity trends from several islands in the central tropical Pacific. The coral data reveal warming trends that increase towards the equator, implying a decrease in equatorial upwelling in the last decades. Seawater freshening trends on the southern edge of the Inter-Tropical Convergence Zone suggest a strengthening and/or an equatorward shift of the convergence zone. Together, the new coral records support a late 20th century trend towards “El Nino-like” conditions in the tropical Pacific, in line with the majority of coupled global climate model projections.

[1] We report nitrate nitrogen (N) and oxygen (O) isotope measurements from the seasonally sea ice covered Polar Antarctic Zone (PAZ) south of the Southern Antarctic Circumpolar Front. The 15N/14N and 18O/16O ratios of nitrate both increase into the summertime surface mixed layer, in strong correlation with the upward decrease in nitrate concentration, the expected result of nitrate assimilation by phytoplankton. Culture studies indicate that algal assimilation of nitrate fractionates the nitrate N and O isotopes equally, while previous field studies suggest that nitrate N and O isotope behavior can be decoupled by euphotic zone nitrification. Our data for the PAZ show strong coupling of the dual isotopes of nitrate, and a numerical model of Antarctic summertime surface layer N cycling fits our observations (including isotopic compositions of both nitrate and suspended particulate N) if the nitrification rate is no more than 6% of the nitrate assimilation rate by phytoplankton. The model estimates that the N isotope effect of nitrate assimilation is 5.0 ± 0.7‰. This estimate lacks some of the uncertainties associated with previous studies within the Antarctic Circumpolar Current, and it is at the low end of most recent estimates from the Southern Ocean, the range of which we speculatively attribute to an effect of mixed layer depth on the amplitude of isotope discrimination.

This paper presents the results of an effort to label calcium carbonates formed by marine organisms with stable isotopes to obtain information about the biomineralization processes. The growing skeleton of the scleractinian coral Porites porites was labeled three times with enhanced abundances of Sr-86. The distribution of Sr-86 in the skeleton was imaged with the NanoSIMS ion microprobe with a spatial resolution of similar to 200 nm and combined with images of the skeletal ultra-structure. Importantly, the distribution of the Sr-86 label in the P. porites skeleton was found to be strongly heterogeneous. This constrains the physical dimensions of the hypothetical Extracellular Calcifying Fluid (ECF) reservoir at the surface of the growing skeleton, which is implicit in most geochemical models for coral biomineralization. These new experimental capabilities allow for a much more detailed view of the growth dynamics for a wide range of marine organisms that biomineralize carbonate structures. Citation: Houlbreque, F., A. Meibom, J.-P. Cuif, J. Stolarski, Y. Marrocchi, C. Ferrier-Pages, I. Domart-Coulon, and R. B. Dunbar ( 2009), Strontium-86 labeling experiments show spatially heterogeneous skeletal formation in the scleractinian coral Porites porites, Geophys. Res. Lett., 36, L04604, doi: 10.1029/2008GL036782.

Paleoclimate records from southern South America can be used to address important questions regarding the timing and nature of late-Holocene climate variability. During the last 30 years, many areas of southern South America have experienced rapid climatic and ecological changes that are driven by global and hemispheric-scale ocean-atmosphere processes. In order to place these recent changes in a longer-term context, we first present an overview of the modern climate processes relevant for the interpretation of paleoclimate records in southern South America, and then review records that have been developed from various archives that span the last two thousand years. Multiple paleoclimate records provide evidence for an overall decrease in temperature and an increase in westerly wind intensity that culminates in the last few hundred years during the time of the European Little Ice Age. We also find evidence for aridity generally coincident with the Medieval Climate Anomaly in several paleoclimate archives. Although much work has been done in this region, high-resolution well-dated archives are still needed from sensitive locations to improve our understanding of past and present climate change. From the paleoclimate records that we have compiled, we infer that warming, retreat of glaciers, and reconfiguration of precipitation patterns during the past century is unique within the context of the last 2000 years.

Approximately 550 measurements of Mn/Ca ratios in three corals from the western Galapagos Islands have been performed to reconstruct a 380-year history of surface ocean variability with respect to this trace element. The time period studied encompasses 1600 A.D. to 1978. Manganese is inferred to be lattice-bound in coralline aragonite at 10–50% of its seawater proportion to calcium; uncertainty about the distribution coefficient stems from inherent variability of oceanic Mn in nearshore settings. Interannual variations at Urvina Bay, Isabela Island are generally small, with the exception of a few decades during the nineteenth century. A large positive Mn/Ca anomaly found between 1821–1830 is hypothesized to have resulted from a major volcanic eruption on nearby Fernandina Island in 1825. On intrannual timescales a pronounced cycle occurs in response to seasonal upwelling. Quarterly changes in Mn/Ca are six months out-of-phase with Cd/Ca variations-a reflection of the opposite distributions of these metals in the upper waters of the eastern Pacific. High frequency reconstructions over brief time intervals from the 17th, 18th, and 20th century reveal that the seasonal onset of warm and cool phases near Galapagos has persisted for at least 340 years. A quantitative assessment of historical changes in upwelling intensity is complicated by offsets in background Mn levels recorded by different corals. One apparent longterm feature is an overall decline in skeletal Mn concentrations from 1600–1978 which results in a net decrease of 20–30%. Several possible explanations exist for this trend, ranging from accumulation of a persistent diagenetic Mn phase in fossil aragonite to a temporal shift in oceanic/atmospheric Mn fluxes reaching the surface waters of the Galapagos Islands.

Geological evidence shows that the ice sheet and climate in Antarctica has changed considerably since the onset of glaciation around 34 million years ago. By analysing this evidence, important information concerning processes responsible for ice sheet growth and decay can be determined, which is vital for appreciating future changes in Antarctica. Geological records are diverse and their analyses require a variety of techniques. They are, however, essential for the establishment of hypotheses regarding past Antarctic changes. Numerical models of ice and climate are useful for testing such hypotheses, and in recent years there have been several advances in our knowledge relating to ice sheet history gained from these tests. This paper documents five case studies, employing a full range of techniques, to exemplify recent insights into Antarctic climate evolution from modelling ice sheet inception in the earliest Oligocene to quantifying Neogene ice sheet fluctuations and process-led investigations of recent (last glacial) changes.

Precisely dated Antarctic continental margin and Southern Ocean geological records show that the early Pleistocene interglacial Marine Isotope Stage 31 (MIS-31) was characterized by warmer than present surface waters with reduced sea-ice and enhanced high latitude marine carbonate production. Micropaleontologic, isotopic, and paleomagnetic evidence from drill cores at 77°S (Cape Roberts Project-1) and 53°S (ODP Site 1094) indicate circumantarctic changes in sea surface temperature and water mass stratification that are in phase with high southern latitude insolation changes during MIS-31. These changes imply a significant, though as yet unquantifiable reduction in Antarctic ice volume. This study supports the hypothesis that the interhemispheric antiphased relationship of the precession cycle attenuates a potentially significant Antarctic ice volume signal in the deep sea oxygen isotope record. The implications are that Antarctic marine ice sheets may be more susceptible to warming and high insolation driven retreat than has been widely recognized.

The Southern Hemisphere westerly winds influence the spatial distribution of precipitation in southern South America and play a significant role in the global carbon cycle, yet little is known about how this important atmospheric circulation feature has varied in the past. Here, we present a sediment core record of late Holocene variability from Lago Guanaco, a small closed-basin lake located in Torres del Paine National Park, Chilean Patagonia. The park is located in the core of the modern wind field and variations in the intensity of the atmospheric circulation directly influence the hydrology of this region. We combine stable isotopic measurements of biogenic carbonate and bulk organic matter to identify two periods of increased evaporation between 900–550 and ∼400–50 calendar years before present (cal yr BP). The first interval is coincident with the Medieval Climate Anomaly (MCA) while the more recent period is broadly coincident with the timing of the Little Ice Age (LIA). During the LIA interval, we observe simultaneous monotonic increases in the δ 18 O of biogenic carbonate and Nothofagus dombeyi -type pollen, which we interpret as indicative of significant changes in the intensity of the southern westerlies during the last millennium. The isotopic and palynological variations in the Guanaco record are coincident with geochemical variations found in an Antarctic ice core record from Siple Dome, suggesting that the signal preserved in Lago Guanaco is regional rather than local, and that the LIA intensification was accompanied by a poleward shift in the southern margin of the westerlies. In addition, we interpret four periods of increased lake productivity centered on 900, 650, 500, and 200 cal yr BP from simultaneous increases in the δ 13 C of bulk organic material and biogenic carbonate. These increases in lake productivity are most likely tied to increases in summer temperatures.

The central and northern Peruvian margin consists of a series of 8 paired forearc basins which may be separated into an inner set of shelf basins and a seaward set of slope basins. We have examined the Cenozoic stratigraphy of the onshore portions of the Sechura Basin (5–7°S) and Pisco Basin (13–16°S), two shelf basins which have accumulated marine sediment discontinuously since the mid to late Eocene. Cenozoic sediments in the Pisco Basin were deposited during at least three major transgressive cycles. Each sequence is preserved as a similar vertical progression of facies including coarse nearshore bioclastic conglomerates and sandstones grading upwards into sandy siltstones and mudstones, and capped by biogenic deposits including diatomites, diatomaceous mudstones, dolomitic horizons, and phosphate deposits. Stratigraphic nomenclature for the Pisco Basin has recently evolved; a stratigraphy presented here includes the Eocene Caballas Fm., upper Eocene Los Choros fm., upper Eocene to lowermost Oligocene Yumaque fm., uppermost Oligocene to middle Miocene Chilcatay fm., and upper Miocene to Pliocene Pisco Fm. Major hiatuses in the Pisco Basin span the Late Cretaceous to middle Eocene, early to late Oligocene, middle Miocene, and late Pliocene/Pleistocene to Recent. Cenozoic sediments of the Sechura Basin were deposited within at least 4 major transgressive cycles with hiatuses during the Paleocene to middle Eocene, Oligocene, early to middle Miocene, and late Miocene. Based on recent biostratigraphic studies, sediments enriched in biogenic components accumulated between about 40-36 Ma, 24-16 Ma, and 11-3 Ma in the Pisco Basin and between 40-37 Ma and 8.5-4.5 Ma in the Sechura Basin. In both basins, the most diatomaceous sediments are restricted to the Late Eocene and Late Miocene through Pliocene. The temporal distribution of biogenic sediments suggests that high productivity conditions linked to coastal upwelling have occurred episodically since at least the Late Eocene. The occurrence of diatomites and phosphorites is diachronous between the Pisco and Sechura Basins and between the Peruvian forearc and other circum-Pacific Monterey Formation analogs, a reflection of the strong influence of local tectonism on sedimentation patterns. The volume of Neogene sediments along the Peruvian forearc is nearly twice that of the Monterey Fm.; despite basin-to-basin facies diachroneity, these deposits very likely contributed to fluctuations of the late Miocene carbon/CO 2 system by acting as large carbon sinks.

[1] We investigate the functioning of the ocean’s biological pump by analyzing the vertical transfer efficiency of particulate organic carbon (POC). Data evaluated include globally distributed time series of sediment trap POC flux, and remotely sensed estimates of net primary production (NPP) and sea surface temperature (SST). Mathematical techniques are developed to compare these temporally discordant time series using NPP and POC flux climatologies. The seasonal variation of NPP is mapped and shows regional- and basin-scale biogeographic patterns reflecting solar, climatic, and oceanographic controls. Patterns of flux are similar, with more high-frequency variability and a subtropical-subpolar pattern of maximum flux delayed by about 5 days per degree latitude increase, coherent across multiple sediment trap time series. Seasonal production-to-flux analyses indicate during intervals of bloom production, the sinking fraction of NPP is typically half that of other seasons. This globally synchronous pattern may result from seasonally varying biodegradability or multiseasonal retention of POC. The relationship between NPP variability and flux variability reverses with latitude, and may reflect dominance by the large-amplitude seasonal NPP signal at higher latitudes. We construct algorithms describing labile and refractory flux components as a function of remotely sensed NPP rates, NPP variability, and SST, which predict POC flux with accuracies greater than equations typically employed by global climate models. Globally mapped predictions of POC export, flux to depth, and sedimentation are supplied. Results indicate improved ocean carbon cycle forecasts may be obtained by combining satellite-based observations and more mechanistic representations taking into account factors such as mineral ballasting and ecosystem structure.

We analyzed radiocarbon in annual coral bands from the Galapagos Islands in the tropical east Pacific to understand natural variability of past ocean circulation associated with climate change. Variability was observed on El Nino timescales (3–7 years) as well as at decadal and multi-decadal periods. Low radiocarbon levels persisted for ten years during the early 1600s and for sixteen years during the early 1800s, both coincident with periods of high volcanic aerosol loading in the atmosphere from massive eruptions. Intensification of tropical circulation at this time may be linked to climatically-controlled changes in the structure of the tropical thermocline that is responsible for delivering cool, upwelled waters to the tropical east Pacific.

Core JPC17B was collected from the Adelie-Drift, a nearly 300-m thick drift deposit at 140oE along the Indian Ocean sector of the Antarctic continental shelf. Sediments consist of nearly continuously laminated diatom mud and diatom ooze, with accumulation rates on the order of 20-21 m kyr -1 based on 10 AMS radiocarbon dates. Spectral analysis was performed on time series of opal content, d 13 Corg, Ti content, and Ba content. Strong decadal to century- scale variability is present in all proxies. Opal and Ti-time series show strong variance at periods of 11, 22 and 110- years, which are suggestive of solar forcing. Ba-time series exhibits strong variance at a period of 3-3.6-yr, consistent with possible El Nino-Southern-Oscillation (ENSO) forcing.

International audience; We investigated the oxygen isotope composition (d18O) of shell striae from juvenile Comptopallium radula (Mollusca; Pectinidae) specimens collected live in New Caledonia. Bottom-water temperature and salinity were monitored in-situ throughout the study period. External shell striae form with a 2-day periodicity in this scallop, making it possible to estimate the date of precipitation for each calcite sample collected along a growth transect. The oxygen isotope composition of shell calcite (d18Oshell calcite) measured at almost weekly resolution on calcite accreted between August 2002 and July 2003 accurately tracks bottom-water temperatures. A new empirical paleotemperature equation for this scallop species relates temperature and d18Oshell calcite: t(°C)=20.00(+/-0.61)-3.66(+/-0.39)x(d18Oshell calcite VPDB -d18Owater VSMOW) The mean absolute accuracy of temperature estimated using this equation is 1.0 °C at temperatures between 20 and 30 °C. Uncertainties regarding the precise timing of CaCO3 deposition and the actual variations in d18Owater at our study sites probably contribute to this error. Comparison with a previously published empirical paleotemperature equation indicates that C. radula calcite is enriched in 18O by ~0.7‰ relative to equilibrium. Given the direction of this offset and the lack of correlation between shell growth rate and d18Oshell calcite, this disequilibrium is unlikely to be related to kinetic isotope effects. We suggest that this enrichment reflects (1) a relatively low pH in the scallop's marginal extrapallial fluid (EPF), (2) an isotopic signature of the EPF different from that of seawater, or (3) Rayleigh fractionation during the biocalcification process. Relative changes in d18Oshell calcite reflect seawater temperature variability at this location and we suggest that the shell of C. radula may be useful as an archive of past seawater temperatures.

[1] We present analyses of major elements C and Ca and trace elements N, S, Mg and Sr in a Porites sp. exoskeleton with a spatial resolution better than similar to 150 nm. Trace element variations are evaluated directly against the ultrastructure of the skeleton and are ascribed to dynamic biological forcing. Individual growth layers in the bulk fibrous aragonite skeleton form on sub-daily timescales. Magnesium concentration variations are dramatically correlated with the growth layers, but are uncorrelated with Sr concentration variations. Observed (sub) seasonal relationships between water temperature and skeletal trace-element chemistry are secondary, mediated by sensitive biological processes to which classical thermodynamic formalism does not apply.

Understanding the temporal dynamics of present thermal and pH exposure on coral reefs is crucial for elucidating reef response to future global change. Diel ranges in temperature and carbonate chemistry parameters coupled with seasonal changes in the mean conditions define periods during the year when a reef habitat is exposed to anomalous thermal and/or pH exposure. Anomalous conditions are defined as values that exceed an empirically estimated threshold for each variable. We present a 200-day time series from June through December 2010 of carbonate chemistry and environmental parameters measured on the Heron Island reef flat. These data reveal that aragonite saturation state, pH, and pCO2 were primarily modulated by biologically-driven changes in dissolved organic carbon (DIC) and total alkalinity (TA), rather than salinity and temperature. The largest diel temperature ranges occurred in austral spring, in October (1.5 - 6.6°C) and lowest diel ranges (0.9 - 3.2°C) were observed in July, at the peak of winter. We observed large diel total pH variability, with a maximum range of 7.7 - 8.5 total pH units, with minimum diel average pH values occurring during spring and maximum during fall. As with many other reefs, the nighttime pH minima on the reef flat were far lower than pH values predicted for the open ocean by 2100. DIC and TA both increased from June (end of Fall) to December (end of Spring). Using this high-resolution dataset, we developed exposure metrics of pH and temperature individually for intensity, duration, and severity of low pH and high temperature events, as well as a combined metric. Periods of anomalous temperature and pH exposure were asynchronous on the Heron Island reef flat, which underlines the importance of understanding the dynamics of co-occurrence of multiple stressors on coastal ecosystems.

Biological control over coral skeletal composition is poorly understood but critically important to paleoenvironmental reconstructions. We present microanalytical measurements of trace-element abundances as well as oxygen and carbon isotopic compositions of individual skeletal components in the zooxanthellate coral Colpophyllia sp. Our data show that centers of calcification (COC) have higher trace element concentrations and distinctly lighter isotopic compositions than the fibrous components of the skeleton. These observations necessitate that COC and the fibrous skeleton are precipitated by different mechanisms, which are controlled by specialized domains of the calicoblastic cell-layer. Biological processes control the composition of the skeleton even at the ultrastructure level.

This study introduces a new method of tracing the history of nutrient loading in coastal oceans via delta(15)N analysis of organic nitrogen preserved in the skeleton of the massive Porites coral. Four coral cores were collected in Bali, Indonesia, from reefs exposed to high levels of fertilizers in agricultural run-off, from lagoonal corals impacted by sewage, and from a reef located 30 km offshore. Skeletal delta(15)N in the agriculturally exposed coral declined from 10.7+/-0.4 per thousand in 1970-1971, when synthetic fertilizers (-0.8 per thousand+/-0.2 per thousand) were introduced to Bali, to a depleted "anthropogenic" baseline of 3.5 per thousand+/-0.4% in the mid-1990s. delta(15)N values were negatively correlated with rainfall, suggesting that marine delta(15)N lowers during flood-bourn influxes of waste fertilizers. Reef cores exposed to untreated sewage in terrestrial discharge were enriched (7.8 and 7.3+/-0.4 per thousand), while the offshore core reflected background oceanic signals (6.2+/-0.4 per thousand). delta(15)N, N concentration, and C:N systematics indicate that the N isotopic composition of skeletal organic matter was generally well preserved over 30 years. We suggest that skeletal organic delta(15)N can serve as a recorder of past nitrogen sources. In Bali, this tracer suggests that the intensification of Western style agricultural practices since 1970 are contributing to the degradation of coastal coral reefs.

[1] We investigate the environmental and biological controls on oxygen isotope ratios in the shells of modern Pecten maximus bivalves collected alive in the Bay of Brest (France). Seasonal δ18O profiles, obtained by drilling the daily calcite ridges deposited at the surface of the left valve, were compared with in situ measurements of temperature and salinity. We show that P. maximus δ18O values accurately track seasonal variations in bottom water temperature. Shell growth rate has no significant effect on shell δ18O values. Our study demonstrates that daily variations in water temperature can be reconstructed within about 0.5°C. Temperatures estimated with the paleotemperature equation established in this study were compared with temperatures derived from previously published equations. The comparison indicates that the most commonly used paleotemperature equation for biogenic calcite (Epstein et al., 1953) provides inaccurate temperature estimates, but the Kim and O'Neil (1997) equation, established from abiogenic calcite precipitation, provides results very similar to ours and should therefore be used for scallop individuals coming from populations where proper empirical calibration cannot be done. Pecten maximus bivalves precipitate calcite in isotopic equilibrium with seawater, produce large daily growth striae, are stenohaline, and are well preserved in archeological and geological deposits, making them an excellent high-frequency archive of paleoenvironmental change.

[1] Oceanic uptake and transport of bomb-produced radiocarbon is used as a diagnostic in global ocean models to test parameterizations of mixing and air-sea gas exchange between the ocean and atmosphere. A model's ability to simulate bomb-produced 14C is also a good indicator of its ability to predict uptake of anthropogenic CO2. We have conducted a model-data comparison of surface radiocarbon time series from coral records from the coasts of Kenya and Sumatra and a suite of dynamical three-dimensional ocean models that were included in the second phase of the Ocean Carbon-Cycle Model Intercomparison Project. The coral records comprise the first intrabasin record of surface water Δ14C variability in the equatorial Indian Ocean and provide an independent evaluation of model performance. Differing treatments of lateral subgrid scale mixing in different models appear to be less important than other, unknown factors in explaining differences in results between the models. Those models that include a dynamic vertical mixing scheme appear to be more capable of matching observed coral radiocarbon time series. However, among models with the same parameterization of lateral subgrid scale mixing, there is a large degree of variation, suggesting that at both sites, factors such as resolution, topography, physical forcing and horizontal advection are more important than mixing parameterization in explaining intermodel differences. None of the models reproduce the time lag in the rate of bomb 14C response between the Kenya and Sumatra coral sites. Future efforts are needed to improve model simulation of radiocarbon in surface waters in the equatorial Indian Ocean.

10 figures, 3 tables., The long-term history of glaciation along the East Antarctic Wilkes Land margin, from the time of the first arrival of the ice sheet to the margin, through the significant periods of Cenozoic climate change is inferred using an integrated geophysical and geological approach. We postulate that the first arrival of the ice sheet to the Wilkes Land margin resulted in the development of a large unconformity (WL-U3) between 33.42 and 30 Ma during the early Oligocene cooling climate trend. Above WL-U3, substantial margin progradation takes place with early glacial strata (e.g., outwash deposits) deposited as low-angle prograding foresets by temperate glaciers. The change in geometry of the prograding wedge across unconformity WL-U8 is interpreted to represent the transition, at the end of the middle Miocene “climatic optimum” (14–10 Ma), from a subpolar regime with dynamic ice sheets (i.e., ice sheets come and go) to a regime with persistent but oscillatory ice sheets. The steep foresets above WL-U8 likely consist of ice proximal sediments (i.e., water-lain till and debris flows) deposited when grounded ice-sheets extended into the shelf. On the continental rise, shelf progradation above WL-U3 results in an up-section increase in the energy of the depositional environment (i.e., seismic facies indicative of more proximal turbidite and of bottom contour current deposition from the deposition of the lower WL-S5 sequence to WL-S7). Maximum rates of sediment delivery to the rise occur during the development of sequences WL-S6 and WL-S7, which we infer to be of middle Miocene age. During deposition of the two uppermost sequences, WL-S8 and WL-S9, there is a marked decrease in the sediment supply to the lower continental rise and a shift in the depocenters to more proximal areas of the margin. We believe WL-S8 records sedimentation during the final transition from a dynamic to a persistent but oscillatory ice sheet in this margin (14–10 Ma). Sequence WL-S9 forms under a polar regime during the Pliocene–Pleistocene, when most sediment delivered to the margin is trapped in the outer shelf and slope-forming steep prograding wedges. During the warmer but still polar, Holocene, biogenic sediment accumulates quickly in deep inner-shelf basins during the high-stand intervals. These sediments contain an ultrahigh resolution (annual to millennial) record of climate variability. Validation of our inferences about the nature and timing of Wilkes Land glacial sequences can be achieved by deep sampling (i.e., using IODP-type techniques). The most complete record of the long-term history of glaciation in this margin can be obtained by sampling both (1) the shelf, which contains the direct (presence or no presence of ice) but low-resolution record of glaciation, and (2) the rise, which contains the distal (cold vs. warm) but more complete record of glaciation. The Wilkes Land margin is the only known Antarctic margin where the presumed “onset” of glaciation unconformity (WL-U3) can be traced from shelf to the abyssal plain, allowing links between the proximal and the distal records of glaciation to be established. Additionally, the eastern segment of the Wilkes Land margin may be more sensitive to climate change because the East Antarctic Ice Sheet (EAIS) is grounded below sea level. Therefore, the Wilkes Land margin is not only an ideal location to obtain the long-term EAIS history but also to obtain the shorter-term record of ice sheet fluctuations at times that the East Antarctic Ice Sheet is thought to have been more stable (after 15 Ma-recent)., This paper has been possible through a coordinated approach to understanding glacial history in the Wilkes Land margin. The approach has depended upon the considerable efforts of coproponents and contributors of site survey data for two IODP drilling proposals, Proposal #482 (Escutia et al.) and an IODP Ancillary Project Letter (Dunbar et al.). Besides the coauthors, coproponents and contributors include, in alphabetical order, Xavier Crosta, Eugene Domack, Takemi Ishihara, Amy Leventer, Rick Murray, Phil O'Brien, and Manabu Tanahashi. This manuscript was greatly improved thanks to the constructive reviews provided by Eugene Domack, German Leitchenkov, and Phil O'Brien.

[1] Deep-sea coral communities have long been recognized by fisherman as areas that support large populations of commercial fish. As a consequence, many deep-sea coral communities are threatened by bottom trawling. Successful management and conservation of this widespread deep-sea habitat requires knowledge of the age and growth rates of deep-sea corals. These organisms also contain important archives of intermediate and deep-water variability, and are thus of interest in the context of decadal to century-scale climate dynamics. Here, we present Δ14C data that suggest that bamboo corals from the Gulf of Alaska are long-lived (75–126 years) and that they acquire skeletal carbon from two distinct sources. Independent verification of our growth rate estimates and coral ages is obtained by counting seasonal Sr/Ca cycles and probable lunar cycle growth bands.

Ion micro-probe imaging of the aragonite skeleton of Pavona clavus, a massive reef-building coral, shows that magnesium and strontium are distributed very differently. In contrast to strontium, the distribution of magnesium is strongly correlated with the fine-scale structure of the skeleton and corresponds to the layered organization of aragonite fibers surrounding the centers of calcification, which have up to ten times higher magnesium concentration. This indicates a strong biological control over the magnesium composition of all structural components within the skeleton. Magnesium may be used by the coral to actively control the growth of the different skeletal crystal components.