Evaluation of the threat of marine CO2 leakage-associated acidification on the toxicity of sediment metals to juvenile bivalves

The effects of the acidification associated with CO2 leakage from sub-seabed geological storage was studied by the evaluation of the short-term effects of CO2-induced acidification on juveniles of the bivalve Ruditapes philippinarum. Laboratory scale experiments were performed using a CO2-bubbling system designed to conduct ecotoxicological assays. The organisms were exposed for 10 days to elutriates of sediments collected in different littoral areas that were subjected to various pH treatments (pH 7.1; pH 6.6; pH 6.1). The acute pH-associated effects on the bivalves were observed, and the dissolved metals in the elutriates were measured. The median toxic effect pH was calculated, which ranged from 6.33 and 6.45. The amount of dissolved Zn in the sediment elutriates increased in parallel with the pH reductions and was correlated with the proton concentrations. The pH, the pCO2 and the dissolved metal concentrations (Zn and Fe) were linked with the mortality of the exposed bivalves.

Composition of soil samples from injection location

CO2 leakage from subsurface storage sites is one of the main concerns connected with the CCS technology. As CO2 leakages into near surface formations appear to be very unlikely within pilot CCS projects, the aim of this work is to emulate a leakage by injecting CO2 into a near surface aquifer. The two main questions pursued by the injection test are (1) to investigate the impact of CO2 on the hydrogeochemistry of the groundwater as a base for groundwater risk assessment and (2) to develop and apply monitoring methods and monitoring concepts for detecting CO2 leakages in shallow aquifers. The presented injection test is planned within the second half of 2010, as a joint project of the University of Kiel (Germany), the Helmholtz-Centre for Environmental Research (Leipzig, Germany) and the Engineering Company GICON (Dresden, Germany). The test site has been investigated in detail using geophysical methods as well as direct-push soundings, groundwater well installation and soil and groundwater analyses. The present paper presents briefly the geological and hydrogeological conditions at the test site as well as the planned injection test design and monitoring concept.

(Table 1) GRACE-derived mass balance of the Greenland ice sheet 2002-2010

We re-evaluate the Greenland mass balance for the recent period using low-pass Independent Component Analysis (ICA) post-processing of the Level-2 GRACE data (2002-2010) from different official providers (UTCSR, JPL, GFZ) and confirm the present important ice mass loss in the range of -70 and -90 Gt/y of this ice sheet, due to negative contributions of the glaciers on the east coast. We highlight the high interannual variability of mass variations of the Greenland Ice Sheet (GrIS), especially the recent deceleration of ice loss in 2009-2010, once seasonal cycles are robustly removed by Seasonal Trend Loess (STL) decomposition. Interannual variability leads to varying trend estimates depending on the considered time span. Correction of post-glacial rebound effects on ice mass trend estimates represents no more than 8 Gt/y over the whole ice sheet. We also investigate possible climatic causes that can explain these ice mass interannual variations, as strong correlations between GRACE-based mass balance and atmosphere/ocean parallels are established: (1) changes in snow accumulation, and (2) the influence of inputs of warm ocean water that periodically accelerate the calving of glaciers in coastal regions and, feed-back effects of coastal water cooling by fresh currents from glaciers melting. These results suggest that the Greenland mass balance is driven by coastal sea surface temperature at time scales shorter than accumulation.

Heat flow measurements on METEOR cruise M86/5

Mud volcanoes (MV) are sources of mass and energy, transported from deeper levels of the sediment pile to the surface. Together with fluid and gas, thermal energy is emitted through these structures. Therefore heat flow determination is a sensible tool to detect and quantify the amount of convective flow. In the Gulf of Cadiz several mud volcanoes can be found along major tectonic lines (SWIM faults). We employ geothermal measurements to observe the activity of mud volcanoes and possible leakage at the faults apart from pronounced structures.

Sedimentology, foraminiferal assemblage, and isotope record of the Agulhas Bank region

The Agulhas Bank region, south of Africa, is an oceanographically important and complex area. The leakage of warm saline Indian Ocean water into the South Atlantic around the southern tip of Africa is a crucial factor in the global thermohaline circulation. Foraminiferal assemblage, stable isotope and sedimentological data from the top 10 m of core MD962080, recovered from the western Agulhas Bank Slope, are used to indicate changes in water mass circulation in the southeastern South Atlantic for the last 450 kyr. Sedimentological and planktonic foraminiferal data give clear signals of cold water intrusions. The benthic stable isotope record provides the stratigraphic framework and indicates that the last four climatic cycles are represented (i.e. down to marine isotope stage (MIS) 12). The planktonic foraminiferal assemblages bear a clear transitional to subantarctic character with Globorotalia inflata and Neogloboquadrina pachyderma (dextral) being the dominant taxa. Input of cold, subantarctic waters into the region by means of leakage through the Subtropical Convergence, as part of Agulhas ring shedding, and a general cooling of surface waters is suggested by increased occurrence of the subantarctic assemblage during glacial periods. Variable input of Indian Ocean waters via the Agulhas Current is indicated by the presence of tropical/subtropical planktonic foraminiferal species Globoquadrina dutertrei, Globigerinoides ruber (alba) and Globorotalia menardii with maximum leakage occurring at glacial terminations. The continuous presence of G. menardii throughout the core suggests that the exchange of water from the South Indian Ocean to the South Atlantic Ocean was never entirely obstructed in the last 450 kyr. The benthic carbon isotope record and sediment textural data reflect a change in bottom water masses over the core location from North Atlantic Deep Water to Upper Southern Component Water. Planktonic foraminiferal assemblages and sediment composition indicate a profound change in surface water conditions over the core site approximately 200-250 kyr BP, during MIS 7, from mixed subantarctic and transitional water masses to overall warmer surface water conditions.

Oxygen and carbon isotope data for benthic foraminifera from DSDP Site 94-608 and ODP Site 208-1264

Small biserial foraminifera were abundant in the early Miocene (ca. 18.9-17.2 Ma) in the eastern Atlantic and western Indian Oceans, but absent in the western equatorial Atlantic Ocean, Weddell Sea, eastern Indian Ocean, and equatorial Pacific Ocean. They have been assigned to the benthic genus Bolivina, but their high abundances in sediments without evidence for dysoxia could not be explained. Apertural morphology, accumulation rates, and isotopic composition show that they were planktic (genus Streptochilus). Living Streptochilus are common in productive waters with intermittent upwelling. The widespread early Miocene high Streptochilus abundances may reflect vigorous but intermittent upwelling, inducing high phytoplankton growth rates. However, export production (estimated from benthic foraminiferal accumulation rates) was low, possibly due to high regeneration rates in a deep thermocline. The upwelled waters may have been an analog to Subantarctic Mode Waters, carrying nutrients into the eastern Atlantic and western Indian Oceans as the result of the initiation of a deep-reaching Antarctic Circumpolar Current, active Agulhas Leakage, and vigorous vertical mixing in the Southern Oceans.

Age models for sediment cores in the eastern tropical Pacific

We present new high-resolution N isotope records from the Gulf of Tehuantepec and the Nicaragua Basin spanning the last 50-70 ka. The Tehuantepec site is situated within the core of the north subtropical denitrification zone while the Nicaragua site is at the southern boundary. The d15N record from Nicaragua shows an 'Antarctic' timing similar to denitrification changes observed off Peru-Chile but is radically different from the northern records. We attribute this to the leakage of isotopically heavy nitrate from the South Pacific oxygen minimum zone (OMZ) into the Nicaragua Basin. The Nicaragua record leads the other eastern tropical North Pacific (ETNP) records by about 1000 years because denitrification peaks in the eastern tropical South Pacific (ETSP) before denitrification starts to increase in the Northern Hemisphere OMZ, i.e., during warming episodes in Antarctica. We find that the influence of the heavy nitrate leakage from the ETSP is still noticeable, although attenuated, in the Gulf of Tehuantepec record, particularly at the end of the Heinrich events, and tends to alter the recording of millennial timescale denitrification changes in the ETNP. This implies (1) that sedimentary d15N records from the southern parts of the ETNP cannot be used straightforwardly as a proxy for local denitrification and (2) that denitrification history in the ETNP, like in the Arabian Sea, is synchronous with Greenland temperature changes. These observations reinforce the conclusion that on millennial timescales during the last ice age, denitrification in the ETNP is strongly influenced by climatic variations that originated in the high-latitude North Atlantic region, while commensurate changes in Southern Ocean hydrography more directly, and slightly earlier, affected oxygen concentrations in the ETSP. Furthermore, the d15N records imply ongoing physical communication across the equator in the shallow subsurface continuously over the last 50-70 ka.

Strontium isotopes, ages and carbonate content of sediments from the Agulhas Current

The Agulhas Leakage represents a significant portion of the warm, surface return flow of the global overturning circulation and thus may be an important feedback in the ocean climate system. Models indicate that reduced leakage could be caused by a stronger Agulhas Current and/or a more upstream (eastward) Agulhas Retroflection, while a weaker Agulhas Current would result in a more westward retroflection and increased leakage. However, data for the Last Glacial Maximum support both a weaker Agulhas Current and less leakage, implying a possible displacement of the retroflection. We present new 87Sr/86Sr results for modern sediments within this region, confirming that the modern pathway of the Agulhas Current, Retroflection, and Leakage can be traced by terrigenous sediment provenance using Sr isotopes. New 87Sr/86Sr data from sediments deposited during the Last Glacial Maximum suggest that the glacial Agulhas Current and Retroflection followed nearly their modern trajectory. The provenance data appear to rule out both a stronger Agulhas Current and a more upstream Agulhas Retroflection. We conclude that the reduced glacial leakage was caused by the weakened Agulhas Current, with no significant change in the retroflection position. This is inconsistent with the model predictions and thus emphasizes the need for further work in this region.

Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.

Geochemistry of tropical Atlantic sediments of Marine Isotope Stage 4

Antarctic Intermediate Water (AAIW) and Subantarctic Mode Water (SAMW) are the main conduits for the supply of dissolved silicon (silicic acid) from the deep Southern Ocean (SO) to the low-latitude surface ocean and therefore have an important control on low-latitude diatom productivity. Enhanced supply of silicic acid by AAIW (and SAMW) during glacial periods may have enabled tropical diatoms to outcompete carbonate-producing phytoplankton, decreasing the relative export of inorganic to organic carbon to the deep ocean and lowering atmospheric pCO2. This mechanism is known as the "silicic acid leakage hypothesis" (SALH). Here we present records of neodymium and silicon isotopes from the western tropical Atlantic that provide the first direct evidence of increased silicic acid leakage from the Southern Ocean to the tropical Atlantic within AAIW during glacial Marine Isotope Stage 4 (~60-70 ka). This leakage was approximately coeval with enhanced diatom export in the NW Atlantic and across the eastern equatorial Atlantic and provides support for the SALH as a contributor to CO2 drawdown during full glacial development.

Study on the last deglaciation section of sediment core GeoB6211-2

The North Atlantic Ocean underwent an abrupt temperature increase of 9 °C at high latitudes within a couple of decades during the transition from Heinrich event 1 (H1) to the Bølling warm event, but the mechanism responsible for this warming remains uncertain. Here we address this issue, presenting high-resolution last deglaciation planktic and benthic foraminiferal records of temperature and oxygen isotopic composition of seawater (d18OSW) for the subtropical South Atlantic. We identify a warming of ~6.5 °C and an increase in d18Osw of 1.2 per mil at the permanent thermocline during the transition, and a simultaneous warming of ~3.5 °C with no significant change in d18Osw at intermediate depths. Most of the warming can be explained by tilting the South Atlantic east-west isopycnals from a flattened toward a steepened position associated with a collapsed (H1) and strong (Bølling) Atlantic meridional overturning circulation (AMOC). However, this zonal seesaw explains an increase of just 0.3 per mil in permanent thermocline d18Osw. Considering that d18Osw at the South Atlantic permanent thermocline is strongly influenced by the inflow of salty Indian Ocean upper waters, we suggest that a strengthening in the Agulhas leakage took place at the transition from H1 to the Bølling, and was responsible for the change in d18Osw recorded in our site. Our records high-light the important role played by Indian-Atlantic interocean exchange as the trigger for the resumption of the AMOC and the Bølling warm event. of the AMOC and the Bølling warm event.

High resolution study of sediment core GeoB3606-1

Based on a high-resolution analysis of the diatom signal and biogenic bulk components at site GeoB3606-1 (25°S, off Namibia), we describe rapid palaeoceanographic changes in the Benguela Upwelling System (BUS) from early MIS 3 through to the early Holocene (55 000 to 7 000 14C yr BP). Coastal upwelling strongly varied at 25°S from MIS 3 through to MIS 2. The abrupt decrease in the accumulation rate of biogenic silica and diatoms from MIS 3 into MIS 2 records rapid oceanographic changes in the BUS off Namibia. During MIS 3, leakage of excess H4SiO4 acid from the Southern Ocean into low-latitude surface waters, as indicated by the occurrence of Antarctic diatoms, enhanced the production of spores of Chaetoceros at the expense of calcareous phytoplankton. Furthermore, shallower Antarctic Intermediate Water (AAIW) would have enriched the thermocline off Namibia with silicate transported from the Southern Ocean. The strong decrease of the siliceous signal throughout MIS 2 represents a decrease in the nutrient input to the BUS, even though the diatom assemblage is still dominated by spores of the upwelling-associated diatom genus Chaetoceros. Depletion of silicate in the thermocline from the onset of MIS 2 through to the early Holocene reflects the shutdown of AAIW injection from the Southern Ocean into the BUS, causing upwelled waters to become reduced in silicate, hence less favourable for diatom production. The deglaciation and early Holocene are characterised by the replacement of the upwelling-associated flora by a non-upwelling-related diatom community, reflecting weakened upwelling, retraction of the seaward extension of the chlorophyll filament off Lüderitz, and dominance of warmer waters.

Fig. S1. Loci of possible event locations based on differential ts - tp arrival times at the single functioning geophone

Geological storage of CO2 that has been captured at large, point source emitters represents a key potential method for reduction of anthropogenic greenhouse gas emissions. However, this technology will only be viable if it can be guaranteed that injected CO2 will remain trapped in the subsurface for thousands of years or more. A signi?cant issue for storage security is the geomechanical response of the reservoir. Concerns have been raised that geomechanical deformation induced by CO2 injection will create or reactivate fracture networks in the sealing caprocks, providing a pathway for CO2 leakage. In this paper, we examine three large-scale sites where CO2 is injected at rates of ab. 1 megatonne/y or more: Sleipner, Weyburn, and In Salah. We compare and contrast the observed geomechanical behavior of each site, with particular focus on the risks to storage security posed by geomechanical deformation. At Sleipner, the large, high-permeability storage aquifer has experienced little pore pressure increase over 15 y of injection, implying little possibility of geomechanical deformation. At Weyburn, 45 y of oil production has depleted pore pressures before increases associated with CO2 injection. The long history of the ?eld has led to complicated, sometimes nonintuitive geomechanical deformation. At In Salah, injection into the water leg of a gas reservoir has increased pore pressures, leading to uplift and substantial microseismic activity. The differences in the geomechanical responses of these sites emphasize the need for systematic geomechanical appraisal before injection in any potential storage site.

Late Pliocene age models of Agulhas Plateau sediment cores

An ensemble of new, high-resolution records of surface ocean hydrography from the Indian-Atlantic oceanic gateway, south of Africa, demonstrates recurrent and high-amplitude salinity oscillations in the Agulhas Leakage area during the penultimate glacial-interglacial cycle. A series of millennial-scale salinification events, indicating strengthened salt leakage into the South Atlantic, appear to correlate with abrupt changes in the North Atlantic climate and Atlantic Meridional Overturning Circulation (AMOC). This interhemispheric coupling, which plausibly involved changes in the Hadley Cell and midlatitude westerlies that impacted the interocean transport at the tip of Africa, suggests that the Agulhas Leakage acted as a source of negative buoyancy for the perturbed AMOC, possibly aiding its return to full strength. Our finding points to the Indian-to-Atlantic salt transport as a potentially important modulator of the AMOC during the abrupt climate changes of the Late Pleistocene.

Effects of elevated CO2 and temperature on an intertidal meiobenthic community

In the near future, the marine environment is likely to be subjected to simultaneous increases in temperature and decreased pH. The potential effects of these changes on intertidal, meiofaunal assemblages were investigated using a mesocosm experiment. Artificial Substrate Units containing meiofauna from the extreme low intertidal zone were exposed for 60 days to eight experimental treatments (four replicates for each treatment) comprising four pH levels: 8.0 (ambient control), 7.7 & 7.3 (predicted changes associated with ocean acidification), and 6.7 (CO2 point-source leakage from geological storage), crossed with two temperatures: 12 °C (ambient control) and 16 °C (predicted). Community structure, measured using major meiofauna taxa was significantly affected by pH and temperature. Copepods and copepodites showed the greatest decline in abundance in response to low pH and elevated temperature. Nematodes increased in abundance in response to low pH and temperature rise, possibly caused by decreased predation and competition for food owing to the declining macrofauna density. Nematode species composition changed significantly between the different treatments, and was affected by both seawater acidification and warming. Estimated nematode species diversity, species evenness, and the maturity index, were substantially lower at 16 °C, whereas trophic diversity was slightly higher at 16 °C except at pH 6.7. This study has demonstrated that the combination of elevated levels of CO2 and ocean warming may have substantial effects on structural and functional characteristics of meiofaunal and nematode communities, and that single stressor experiments are unlikely to encompass the complexity of abiotic and biotic interactions. At the same time, ecological interactions may lead to complex community responses to pH and temperature changes in the interstitial environment.