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.

Average fluorescence and dissolved iron and Fe-binding ligand characteristics during POLARSTERN expedition ANT-XXIV/3 in 2008

Organic complexation of dissolved iron (dFe) was investigated in the Atlantic sector of the Southern Ocean in order to understand the distribution of Fe over the whole water column. The total concentration of dissolved organic ligands ([Lt]) measured by voltammetry ranged between 0.54 and 1.84 nEq of M Fe whereas the conditional binding strength (K') ranged between 10**21.4 and 10**22.8. For the first time, trends in Fe-organic complexation were observed in an ocean basin by examining the ratio ([Lt]/[dFe]), defined as the organic ligand concentration divided by the dissolved Fe concentration. The [Lt]/[dFe] ratio indicates the saturation state of the natural ligands with Fe; a ratio near 1 means saturation of the ligands leading to precipitation of Fe. Reversely, high ratios mean Fe depletion and show a high potential for Fe solubilisation. In surface waters where phytoplankton is present low dissolved Fe and high variable ligand concentrations were found. Here the [Lt]/[dFe] ratio was on average 4.4. It was especially high (5.6-26.7) in the HNLC (High Nutrient, Low Chlorophyll) regions, where Fe was depleted. The [Lt]/[dFe] ratio decreased with depth due to increasing dissolved Fe concentrations and became constant below 450 m, indicating a steady state between ligand and Fe. Relatively low [Lt]/[dFe] ratios (between 1.1 and 2.7) existed in deep water north of the Southern Boundary, facilitating Fe precipitation. The [Lt]/[dFe] ratio increased southwards from the Southern Boundary on the Zero Meridian and from east to west in the Weddell Gyre due to changes both in ligand characteristics and in dissolved iron concentration. High [Lt]/[dFe] ratio expresses Fe depletion versus ligand production in the surface. The decrease with depth reflects the increase of [dFe] which favours scavenging and (co-) precipitation, whereas a horizontal increase in the deep waters results from an increasing distance from Fe sources. This increase in the [Lt]/[dFe] ratio at depth shows the very resistant nature of the dissolved organic ligands.

Biogenic silica and silicic acid benthic fluxes of a North-eastern Atlantic Abyssal Locality

Within the framework of the EU-funded BENGAL programme, the effects of seasonality on biogenic silica early diagenesis have been studied at the Porcupine Abyssal Plain (PAP), an abyssal locality located in the northeast Atlantic Ocean. Nine cruises were carried out between August 1996 and August 1998. Silicic acid (DSi) increased downward from 46.2 to 213 µM (mean of 27 profiles). Biogenic silica (BSi) decreased from ca. 2% near the sediment-water interface to <1% at depth. Benthic silicic acid fluxes as measured from benthic chambers were close to those estimated from non-linear DSi porewater gradients. Some 90% of the dissolution occurred within the top 5.5 cm of the sediment column, rather than at the sediment-water interface and the annual DSi efflux was close to 0.057 mol Si/m**2/yr. Biogenic silica accumulation was close to 0.008 mol Si/m**2/yr and the annual opal delivery reconstructed from sedimentary fluxes, assuming steady state, was 0.065 mol Si/m**2/yr. This is in good agreement with the mean annual opal flux determined from sediment trap samples, averaged over the last decade (0.062 mol Si/m**2/yr). Thus ca. 12% of the opal flux delivered to the seafloor get preserved in the sediments. A simple comparison between the sedimentation rate and the dissolution rate in the uppermost 5.5 cm of the sediment column suggests that there should be no accumulation of opal in PAP sediments. However, by combining the BENGAL high sampling frequency with our experimental results on BSi dissolution, we conclude that non-steady state processes associated with the seasonal deposition of fresh biogenic particles may well play a fundamental role in the preservation of BSi in these sediments. This comes about though the way seasonal variability affects the quality of the biogenic matter reaching the seafloor. Hence it influences the intrinsic dissolution properties of the opal at the seafloor and also the part played by non-local mixing events by ensuring the rapid transport of BSi particles deep into the sediment to where saturation is reached.

On the effects of circulation, sediment resuspension and biological incorporation by diatoms in an ocean model of aluminium, link to model data

The distribution of dissolved aluminium in the West Atlantic Ocean shows a mirror image with that of dissolved silicic acid, hinting at intricate interactions between the ocean cycling of Al and Si. The marine biogeochemistry of Al is of interest because of its potential impact on diatom opal remineralisation, hence Si availability. Furthermore, the dissolved Al concentration at the surface ocean has been used as a tracer for dust input, dust being the most important source of the bio-essential trace element iron to the ocean. Previously, the dissolved concentration of Al was simulated reasonably well with only a dust source, and scavenging by adsorption on settling biogenic debris as the only removal process. Here we explore the impacts of (i) a sediment source of Al in the Northern Hemisphere (especially north of ~ 40° N), (ii) the imposed velocity field, and (iii) biological incorporation of Al on the modelled Al distribution in the ocean. The sediment source clearly improves the model results, and using a different velocity field shows the importance of advection on the simulated Al distribution. Biological incorporation appears to be a potentially important removal process. However, conclusive independent data to constrain the Al / Si incorporation ratio by growing diatoms are missing. Therefore, this study does not provide a definitive answer to the question of the relative importance of Al removal by incorporation compared to removal by adsorptive scavenging.

(Appendix A) Dissolved manganese concentrations during POLARSTERN Cruise ARK-XXII/2

A total of 773 samples were analysed for dissolved manganese (Mn) in the Arctic Ocean aboard R.V. Polarstern during expedition ARK XXII/2 from 28 July until 07 October 2007 from Tromsø (Norway) to Bremerhaven. Concentrations of Mn were elevated in the surface layer with concentrations of up to 6 nM over the deep Basins and over 20 nM in the Laptev Sea. The general distribution of Mn through the water column is consistent with previous studies, but there are differences in the absolute concentrations that are most likely related to differences in sample area, sampling and filtration. The elevated concentrations of Mn in the surface layer are related to fresh water input. This was visible in the strong negative correlations observed between dissolved Mn and salinity. The correlation between Mn and salinity and the correlation between Mn and the quasi conservative trace water mass tracer PO4*, showed fluvial and melt water input and the Pacific and Atlantic origin of the surface waters. A large portion of the Mn delivered by the Arctic rivers is removed in the shelf seas and does not pass into the central basins. Most likely a benthic flux is at the origin of the elevated concentrations of Mn near the sediments in the Barents and Kara Seas. These elevated concentrations of Mn apparently affected the deep basins as well, as maxima in the concentrations of Mn were observed that corresponded with lowered transmission over the continental slope. A maximum in the concentration of Mn in the deep basin corresponded with anomalies in light transmission, potential temperature and dissolved iron, confirming the hydrothermal origin. The hydrothermal plume was observed throughout the Nansen Basin and over the deep Gakkel Ridge around 2500 m depth and a smaller plume was observed around 3200 m. The concentration of Mn at the Mn maximum around 2500 m depth decreased exponentially, consistent with a first order scavenging model. The concentrations of Mn were extremely low in the deep Makarov Basin (~0.05 nM) and slightly higher in the Eurasian Basin (~0.1 nM) outside the influence of the hydrothermal activity.

Dissolved aluminium measured on water bottle samples during POLARSTERN cruise ARK-XXII/2 (SPACE)

Concentrations of dissolved (0.2 µm filtered) aluminium (Al) have been determined for the first time in the Eurasian part of the Arctic Ocean over the entire water column during expedition ARK XXII/2 aboard R.V. Polarstern (2007). An unprecedented number of 666 samples was analysed for 44 stations along 5 ocean transects. Dissolved Al in surface layer water (SLW) was very low, close to 1 nM, with lowest SLW concentrations towards the Canadian part of the Arctic Ocean and higher values adjacent to and in the shelf seas. The low SLW concentrations indicate no or little influence from aeolian dust input. Dissolved Al showed a nutrient-type increase with depth up to 28 nM, but large differences existed between the different deep Arctic basins. The differences in concentrations of Al between water masses and basins could largely be related to the different origins of the water masses. In the SLW and intermediate water layers, Atlantic and Pacific inflows were of importance. Deep shelf convection appeared to influence the Al distribution in the deep Eurasian Basin. The Al distribution of the deep Makarov Basin provides evidence for Eurasian Basin water inflow into the deep Makarov Basin. A strong correlation between Al and Silicon (Si) was observed in all basins. This correlation and the nutrient-like profile indicate a strong biological influence on the cycling and distribution of Al. The biological influence can be direct by the incorporation of Al in biogenic silica, indirect by preferential scavenging of Al onto biogenic siliceous particles, or by a combination of both processes. From the slope of the overall Al-Si relationship in the intermediate water layer (AIDW; ~ 200-2000 m depth), an Al/Si ratio of 2.2 atoms Al per 1000 atoms Si was derived. This ratio is consistent with the range of previously reported Al/Si uptake ratio in biogenic opal frustules of diatoms. In the deepest waters (>2000 m depth) a steeper slope of the Al-Si relationship of 7.4 to 13 atoms Al per 1000 atoms Si likely results from entrainment of cold shelf water into the deep basins, carrying the signal of dissolution of terrigenous particles with a much higher Al:Si ratio of crustal abundance. Only a small enrichment with such crustal Al and Si component may readily account for the higher Al:Si slope in the deepest waters.

Barium measured on water bottle samples during POLARSTERN cruise ARK-XXII/2 (SPACE)

Dissolved barium has been shown to have the potential to distinguish Eurasian from North American (NA) river runoff. As part of the ARK-XXII/2 Polarstern expedition in summer 2007, Ba was analyzed in the Barents, Kara, Laptev seas, and the Eurasian Basins as well as the Makarov Basin up to the Alpha and Mendeleyev Ridges. By combining salinity, d18O and initial phosphate corrected for mineralization with oxygen (PO4*) or N/P ratios we identified the water mass fractions of meteoric water, sea ice meltwater, and marine waters of Atlantic as well as Pacific origin in the upper water column. In all basins inside the lower halocline layer and the Arctic intermediate waters we find Ba concentrations close to those of the Fram Strait branch of the lower halocline (41-45 nM), reflecting the composition of the incoming Atlantic water. A layer of upper halocline water (UHW) with higher Ba concentrations (45-55 nM) is identified in the Makarov Basin. Atop of the UHW, the Surface Mixed Layer (SML), including the summer and winter mixed layers, has high concentrations of Ba (58-67 nM). In the SML of the investigated area of the central Arctic the meteoric fraction can be identified by assuming a conservative behavior of Ba to be primarily of Eurasian river origin. However, in productive coastal regions biological removal compromises the use of Ba to distinguish between Eurasian and NA rivers. As a consequence, the NA river water fraction is underestimated in productive surface waters or waters that have passed a productive region, whereas this fraction is overestimated in subsurface waters containing remineralised Ba, particularly when these waters have passed productive shelf regions. Especially in the Laptev Sea and small regions in the Barents Sea, Ba concentrations are low in surface waters. In the Laptev Sea exceptionally high Ba concentrations in shelf bottom waters indicate that Ba is removed from surface waters to deep waters by biological activity enhanced by increasing ice-free conditions as well as by scavenging by organic matter of terrestrial origin. We interpret high Ba concentrations in the UHW of the Makarov Basin to result from enrichment by remineralisation in bottom waters on the shelf of the Chukchi Sea and therefore the calculated NA runoff is an artefact. We conclude that no NA runoff can be demonstrated unequivocally anywhere during our expedition with the set of tracers considered here. Small contributions of NA runoff may have been masked by Ba depletion and could only be resolved by supportive tracers on the uptake history. We thus suggest that Ba has to be used with care as it can put limits but not yield quantitative water mass distributions. Only if the extra Ba inputs exceed the cumulative biological uptake the signal can be unequivocally attributed to NA runoff.

Dissolved iron measurements from 32 stations in the Central Arctic Ocean and Arctic Shelf Sea during POLARSTERN expedition ARK-XXII/2

Concentrations of dissolved (<0.2 µm) Fe (DFe) in the Arctic shelf seas and in the surface waters of the central Arctic Ocean are presented. In the Barents and Kara seas, near-surface DFe minima indicate depletion of DFe by phytoplankton growth. Below the surface, lower DFe concentrations in the Kara Sea (~0.4-0.6 nM) than in the Barents Sea (~0.6-0.8 nM) likely reflect scavenging removal or biological depletion of DFe. Very high DFe concentrations (>10 nM) in the bottom waters of the Laptev Sea shelf may be attributed to either sediment resuspension, sinking of brine or regeneration of DFe in the lower layers. A significant correlation (R2 = 0.60) between salinity and DFe is observed. Using d18O, salinity, nutrients and total alkalinity data, the main source for the high (>2 nM) DFe concentrations in the Amundsen and Makarov Basins is identified as (Eurasian) river water, transported with the Transpolar Drift (TPD). On the North American side of the TPD, the DFe concentrations are low (<0.8 nM) and variations are determined by the effects of sea-ice meltwater, biological depletion and remineralization and scavenging in halocline waters from the shelf. This distribution pattern of DFe is also supported by the ratio between unfiltered and dissolved Fe (high (>4) above the shelf and low (<4) off the shelf).