ALBERT

Description: Methane seepage from the upper continental slopes of Western Svalbard has previously been attributed to gas hydrate dissociation induced by anthropogenic warming of ambient bottom waters. Here we show that sediment cores drilled off Prins Karls Foreland contain freshwater from dissociating hydrates. However, our modeling indicates that the observed pore water freshening began around 8 ka BP when the rate of isostatic uplift outpaced eustatic sea-level rise. The resultant local shallowing and lowering of hydrostatic pressure forced gas hydrate dissociation and dissolved chloride depletions consistent with our geochemical analysis. Hence, we propose that hydrate dissociation was triggered by postglacial isostatic rebound rather than anthropogenic warming. Furthermore, we show that methane fluxes from dissociating hydrates were considerably smaller than present methane seepage rates implying that gas hydrates were not a major source of methane to the oceans, but rather acted as a dynamic seal, regulating methane release from deep geological reservoirs.

Description: Anthropogenic impacts are perturbing the global nitrogen cycle via warming effects and pollutant sources such as chemical fertilizers and burning of fossil fuels. Understanding controls on past nitrogen inventories might improve predictions for future global biogeochemical cycling. Here we show the quantitative reconstruction of deglacial bottom water nitrate concentrations from intermediate depths of the Peruvian upwelling region, using foraminiferal pore density. Deglacial nitrate concentrations correlate strongly with downcore δ13C, consistent with modern water column observations in the intermediate Pacific, facilitating the use of δ13C records as a paleo-nitrate-proxy at intermediate depths and suggesting that the carbon and nitrogen cycles were closely coupled throughout the last deglaciation in the Peruvian upwelling region. Combining the pore density and intermediate Pacific δ13C records shows an elevated nitrate inventory of 〉10% during the Last Glacial Maximum relative to the Holocene, consistent with a δ13C-based and δ15N-based 3D ocean biogeochemical model and previous box modeling studies.

Description: Monthly time-series data (1998–2009) of bottom water oxygen, nitrate and nitrite concentrations from the outer shelf (150 m water depth) in the oxygen minimum zone offshore Peru were coupled to a layered biogeochemical sediment model to investigate benthic-pelagic coupling over multi-annual time scales. The model includes the mineralization of four reactive pools of particulate organic carbon (POC) with lifetimes of 0.13, 1.3, 20, and 1700 year that were constrained using empirical data. Total POC rain rates to the seafloor were derived from satellite based estimates of primary production. Solute fluxes and concentrations in sediment porewater showed highly dynamic behavior over the course of a typical year. Conversion of fixed N to N2 by denitrification varied from 1.1 mmol m−2 d−1 of N in winter to 1.8 mmol m−2 d−1 of N in summer with a long term mean N loss for the shelf of 1.5 mmol m−2 d−1 of N. Fixed N loss across the whole time-series agreed very well with a previously-published vertically-integrated sediment model for coupling the benthic and pelagic N cycle in regional and global models. Dissimilatory nitrate reduction to ammonium (DNRA) emerges as a major process in the benthic N cycle, producing on average 1.9 mmol m−2 d−1 of ammonium: more than twice the rate of ammonification of organic nitrogen. The model predicts sulfide emissions from the sediment of up to 1 mmol m−2 d−1 when POC rain rate exceeds 20 mmol m−2 d−1, in agreement with past observations of benthic sulfide fluxes and sulfide plume distributions in the water column. This study demonstrates that sediments on the Peruvian shelf are not static repositories that are independent of changes taking place in the water column. Our results strongly suggest the shelf sediments must exert an important feedback on biogeochemical processes in the overlying waters, and should be considered in regional model studies.

Description: Our study presents a basin-scale 3D modeling solution, quantifying and exploring gas hydrate accumulations in the marine environment around the Green Canyon (GC955) area, Gulf of Mexico. It is the first modeling study that considers the full complexity of gas hydrate formation in a natural geological system. Overall, it comprises a comprehensive basin re-construction, accounting for depositional and transient thermal history of the basin, source rock maturation, petroleum components generation, expulsion and migration, salt tectonics and associated multi-stage fault development. The resulting 3D gas hydrate distribution in the Green Canyon area is consistent with independent borehole observations. An important mechanism identified in this study and leading to high gas hydrate saturation (〉 80 vol. %) at the base of the gas hydrate stability zone (GHSZ), is the recycling of gas hydrate and free gas enhanced by high Neogene sedimentation rates in the region. Our model predicts the rapid development of secondary intra-salt mini-basins situated on top of the allochthonous salt deposits which leads to significant sediment subsidence and an ensuing dislocation of the lower GHSZ boundary. Consequently, large amounts of gas hydrates located in the deepest parts of the basin dissociate and the released free methane gas migrates upwards to recharge the GHSZ. In total, we have predicted the gas hydrate budget for the Green Canyon area that amounts to ∼3,256 Mt of gas hydrate which is equivalent to ∼340 Mt of carbon (∼7 x 1011 m3 of CH4 at STP conditions), and consists mostly of biogenic hydrates.

Description: [1] A new model is developed and applied to simulate the Phanerozoic evolution of seawater composition (dissolved Ca, Sr, dissolved inorganic carbon, alkalinity, pH, δ18O), marine carbonates (Sr/Ca, 87Sr/86Sr, δ13C, δ18O), atmospheric CO2 and surface temperature. The marine carbonate records (Sr/Ca, 87Sr/86Sr, δ13C) are used to reconstruct changes in volcanic/tectonic activity and organic carbon burial over the Phanerozoic. Seawater pH is calculated assuming saturation with respect to calcite and considering the changing concentration of dissolved Ca documented by brine inclusion data. The depth of calcite saturation is allowed to vary through time and the effects of changing temperature and pressure on the stability constants of the carbonate system are considered. Surface temperatures are calculated using the GEOCARB III approach considering also the changing flux of galactic cosmic radiation (GCR). It is assumed that GCR cools the surface of the Earth via enhanced cloud formation at low altitudes. The δ18O of marine carbonates is calculated considering the changing isotopic composition of seawater, the prevailing surface temperatures and seawater pH. Repeated model runs showed that the trends observed in the marine δ18O record can only be reproduced by the model if GCR is allowed to have a strong effect on surface temperature. The climate evolution predicted by the model is consistent with the geological record. Warm periods (Cambrian, Devonian, Triassic, Cretaceous) are characterized by low GCR levels. Cold periods during the late Carboniferous to early Permian and the late Cenozoic are marked by high GCR fluxes and low pCO2 values. The major glaciations occurring during these periods are the result of carbon cycling processes causing a draw-down of atmospheric CO2 and a coevally prevailing dense cloud cover at low-altitudes induced by strong GCR fluxes. The two moderately cool periods during the Ordovician - Silurian and Jurassic - early Cretaceous are characterized by both high pCO2 and GCR levels so that greenhouse warming compensated for the cooling effect of low-altitude clouds. The very high Jurassic δ18O values observed in the geological record are caused by low pH values in surface waters rather than cold surface conditions.

Description: The phosphorus budget of the pre-human modern ocean is constrained applying the most recent estimates of the natural riverine, eolian, and ice-rafted input fluxes, the phosphorus burial in marine sediments, and the hydrothermal removal of dissolved phosphate from the deep ocean. This review of current flux estimates indicates that the phosphorus budget of the ocean is unbalanced since the accumulation of phosphorus in marine sediments and altered oceanic crust exceeds the continental input of particulate and dissolved phosphorus. The phosphorus mass balance is further tested considering the dissolved phosphate distribution in the deep water column, the marine export production of particulate organic matter, rain rates of phosphorus to the seafloor, benthic dissolved phosphate fluxes, and the organic carbon to phosphorus ratios in marine particles. These independent data confirm that the phosphate and phosphorus budgets were not at steadystate in the pre-human global ocean. The ocean is losing dissolved phosphate at a rate of ≥ 11.6 x 1010 mol yr-1 corresponding to a decline in the phosphate inventory of ≥ 4.5 % kyr-1. Benthic data show that phosphate is preferentially retained in pelagic deep-sea sediments where extended oxygen exposure times favor the degradation of particulate organic matter and the up-take of phosphate in manganese and iron oxides and hydroxides. Enhanced C : P regeneration ratios observed in the deep water column (〉400 m water depth) probably reflect the preferential burial of phosphorus in pelagic sediments. Excess phosphate is released from continental margin sediments deposited in low-oxygen environments. The dissolved oxygen threshold value for the enhanced release of dissolved phosphate is ~20 μM. Benthic phosphate fluxes increase drastically when oxygen concentrations fall below this value.

Description: An empirical function is derived for predicting the rate-depth profile of particulate organic carbon (POC) degradation in surface marine sediments including the bioturbated layer. The rate takes the form of a power law analogous to the Middelburg function. The functional parameters were optimized by simulating measured benthic O2 and NO3− fluxes at 185 stations worldwide using a diagenetic model. The novelty of this work rests with the finding that the vertically-resolved POC degradation rate in the bioturbated zone can be determined using a simple function where the POC rain rate is the governing variable. Although imperfect, the model is able to fit 71 % of paired O2 and NO3− fluxes to within 50% of measured values. It further provides realistic geochemical concentration-depth profiles, NO3− penetration depths and apparent first-order POC mineralization rate constants. The model performs less well on the continental shelf due to the high heterogeneity there. When applied to globally resolved maps of rain rate, the model predicts a global denitrification rate of 182 ± 88 Tg yr−1 of N and a POC burial rate of 107 ± 52 Tg yr−1 of C with a mean carbon burial efficiency of 6.1%. These results are in very good agreement with published values. Our proposed function is conceptually simple, requires less parameterization than multi-G type models and is suitable for non-steady state applications. It provides a basis for more accurately simulating benthic nutrient fluxes and carbonate dissolution rates in Earth system models.

Description: Literature data on benthic dissolved iron (DFe) fluxes (µmol m−2 d−1), bottom water oxygen concentrations (O2BW, μM), and sedimentary carbon oxidation rates (COX, mmol m−2 d−1) from water depths ranging from 80 to 3700 m were assembled. The data were analyzed with a diagenetic iron model to derive an empirical function for predicting benthic DFe fluxes: inline image where γ (= 170 µmol m−2 d−1) is the maximum flux for sediments at steady state located away from river mouths. This simple function unifies previous observations that COX and O2BW are important controls on DFe fluxes. Upscaling predicts a global DFe flux from continental margin sediments of 109 ± 55 Gmol yr−1, of which 72 Gmol yr−1 is contributed by the shelf (〈200 m) and 37 Gmol yr−1 by slope sediments (200–2000 m). The predicted deep-sea flux (〉2000 m) of 41 ± 21 Gmol yr−1 is unsupported by empirical data. Previous estimates of benthic DFe fluxes derived using global iron models are far lower (approximately 10–30 Gmol yr−1). This can be attributed to (i) inadequate treatment of the role of oxygen on benthic DFe fluxes and (ii) improper consideration of continental shelf processes due to coarse spatial resolution. Globally averaged DFe concentrations in surface waters simulated with the intermediate-complexity University of Victoria Earth System Climate Model were a factor of 2 higher with the new function. We conclude that (i) the DFe flux from marginal sediments has been underestimated in the marine iron cycle and (ii) iron scavenging in the water column is more intense than currently presumed.

Description: A new model for the marine cycles of particulate organic carbon (POC), oxygen, nitrate, and phosphorus has been developed and applied to explore the controls and constraints on marine productivity and nutrient inventories. The coupled benthic-pelagic model uses a new approach for the simulation of the reactive phosphorus turnover (Preac corresponding to the sum of organic P, authigenic P, and adsorbed phosphate) in marine sediments. The simulated POC/Preac burial ratio in shelf, slope and rise, and deep-sea sediments increases under strongly reducing conditions in agreement with field observation. The model runs revealed that the spread of anoxia in bottom waters may enhance the productivity of the global ocean by one order of magnitude if sufficient nitrate is provided by N2-fixation. Thus anoxic bottom waters promote eutrophic conditions and vice versa. Additional model runs showed that the productivity and nutrient inventory of the glacial ocean were probably enhanced due to the falling sea level. Marine regression induced a narrowing of the depositional areas on the continental shelves and thereby an increase in the fraction of POC exported to the deep ocean. The accelerated POC delivery, in turn, decreased the oxygen contents of the deep water and thus favored the release of phosphate from deep-sea and rise sediments. Enhanced recycling of phosphate at the seafloor promoted further POC export in a positive feedback loop.

Description: We measured halogen concentrations and I-129/I ratios in five drilling sites of Integrated Ocean Drilling Program Expedition 311 (offshore Vancouver Island, Canada) in order to identify potential sources of fluids and methane in gas hydrate fields. Iodine is dominated by organic decomposition and transports with fluids in reducing environments and the presence of the cosmogenic radioisotope I-129 (T-1/2 = 15.7 Ma) allows the age determination of organic sources for iodine. Here we report halogen concentrations in 135 pore water samples, I concentrations in 48 sediment samples, and I-129/I ratios measured in a subset of 20 pore water samples. Most I-129/I ratios fall into a range around 500 x 10(-15), corresponding to a minimum age of 25 Ma and the lowest ratio of 188 x 10(-15) (T-min = 47 Ma) was observed at 208 m below sea floor (mbsf) in Site 1326. These ages are considerably older than that of the local sediments in the gas hydrate fields and that of the subducting sediments on the Juan de Fuca plate, indicating that old, accreted sediments in the accretionary wedge contribute a significant amount of iodide and, by association, of methane to the gas hydrate occurrences. A geochemical transport-reaction model was applied to simulate the advection of deeply sourced fluids and the release of iodide, bromide, and ammonia in the host sediments due to organic matter degradation. The model was first tested with data from two well studied areas, Ocean Drilling Program Site 1230 (Peru margin) and Site 1245 (Hydrate Ridge). The model results for the Expedition 311 sites indicate that the in situ release of young iodine is relatively minor in comparison to the contribution of migrating fluids, carrying large amounts of old iodine from deep sources. The comparison between the sites demonstrates that the total organic content has a strong effect on the rate of in situ iodine release and that lateral flows along fractures can have a significant influence on pore water chemistry, especially at the Cascadia margin. The iodine results indicate that mobilization and transport of methane from sources in the upper plate of active margins is an important process which can also play a substantial role in the formation of gas hydrate fields.