ALBERT

Description: Highlights • Seafloor massive sulphides vary in mineralogy and oxidise at different rates. • Galvanic cells play a role in increasing dissolution rates. • SMS deposits that have been inactive for some time may have lost economic value. • The geochemistry of oxidation products has potential to be an exploration tool. • Potential for anthropogenic release of heavy metals during seafloor mining. • Any risk needs addressing by the ISA prior to the formation of mining regulations. The weathering process of seafloor massive sulphide (SMS) deposits can be considered analogous to weathering of terrestrial volcanogenic massive sulphides (VMS) deposits. However, in the context of SMS deposits, the process occurs in chemically buffered waters of near neutral pH, resulting in the formation of insoluble Fe oxy-hydroxide minerals including goethite and hematite as well as sulphates such as jarosite. As a result of this precipitation, it is commonly assumed that any SMS deposit is unlikely to exhibit a significant loss of metals (dissolution and release of heavy metals) into the water column. However, galvanic interactions have never been considered in this seafloor context, whilst they have already been shown to have the ability to increase dissolution significantly in terrestrial deposits. If heavy metal release is not temporally balanced by precipitation of oxide phases, there is the potential that these metal occurrences lose economic value. This is specifically significant if there is an industrial focus on exploiting deposits associated with hydrothermal vents that have been inactive for some time. Not only this, but the geochemistry of weathering products – ‘gossans’ – that are formed have the potential to be used as tools for exploration. Furthermore, it is unknown what impact galvanic coupling may have with regards to anthropogenic release of heavy metals during seafloor mining of deposits associated with either active or inactive vents (disturbance of sediment, plume generation and dewatering process). This environmental impact needs to be addressed prior to the formulation of regulations for deep-sea mining by the International Seabed Authority. The present review examines our current understanding of oxidation and dissolution of a mixed sulphide ore, bringing together lines of evidence from a range of literature sources. Based on this review, different seafloor sulphide ore deposits will dissolve by oxidation and release a variety of different metals (economic and/or toxic), all at different rates, with galvanic cells playing a role by increasing dissolution rates. While precipitation of oxide and oxy-hydroxide phases will occur, it is unknown in both a natural weathering and anthropogenic (mining) context whether heavy metal release (including economic and toxic metals) is temporally balanced by this precipitation and any subsequent adsorption. Based on our current understanding, certain sites will be more predisposed to oxidation as a result of their mineralogy (those containing significant pyrrhotite, marcasite, galena and secondary copper sulphides) and/or environment (higher temperatures and oxygen concentrations, lower pH's). Furthermore, certain sites pose more of an environmental risk (in terms of toxicity) than others, with arc-related SMS deposits associated with higher concentrations of As, Pb, Sb, Cd and Hg and ultra-mafic hosted SMS deposits associated with high concentrations of Co and Ni. The review highlights the need for subsequent studies that investigate the natural weathering process of seafloor sulphide ore deposits, including how this process impacts their economic value and consequent geochemical signature of oxides that are produced over time. Moreover, this review underlines the necessity for experiments to elucidate the oxidative dissolution of ore throughout any mining process.

Description: The response of the marine carbon cycle to changes in atmospheric CO2 concentrations will be determined, in part, by the relative response of calcifying and non-calcifying organisms to global change. Planktonic foraminifera are responsible for a quarter or more of global carbonate production, therefore understanding the sensitivity of calcification in these organisms to environmental change is critical. Despite this, there remains little consensus as to whether, or to what extent, chemical and physical factors affect foraminiferal calcification. To address this, we directly test the effect of multiple controls on calcification in culture experiments and core-top measurements of Globigerinoides ruber. We find that two factors, body size and the carbonate system, strongly influence calcification intensity in life, but that exposure to corrosive bottom waters can overprint this signal post mortem. Using a simple model for the addition of calcite through ontogeny, we show that variable body size between and within datasets could complicate studies that examine environmental controls on foraminiferal shell weight. In addition, we suggest that size could ultimately play a role in determining whether calcification will increase or decrease with acidification. Our models highlight that knowledge of the specific morphological and physiological mechanisms driving ontogenetic change in calcification in different species will be critical in predicting the response of foraminiferal calcification to future change in atmospheric pCO2.

Description: The circulation and internal structure of the oceans exert a strong influence on Earth’s climate because they control latitudinal heat transport and the segregation of carbon between the atmosphere and the abyss. Circulation change, particularly in the Atlantic Ocean, is widely suggested to have been instrumental in the intensification of Northern Hemisphere glaciation when large ice sheets first developed on North America and Eurasia during the late Pliocene, approximately 2.7 million years ago. Yet the mechanistic link and cause/effect relationship between ocean circulation and glaciation are debated. Here we present new records of North Atlantic Ocean structure using the carbon and neodymium isotopic composition of marine sediments recording deep water for both the Last Glacial to Holocene (35–5 thousand years ago) and the late Pliocene to earliest Pleistocene (3.3–2.4 million years ago). Our data show no secular change. Instead we document major southern-sourced water incursions into the deep North Atlantic during prominent glacials from 2.7 million years ago. Our results suggest that Atlantic circulation acts as a positive feedback rather than as an underlying cause of late Pliocene Northern Hemisphere glaciation. We propose that, once surface Southern Ocean stratification and/or extensive sea-ice cover was established, cold-stage expansions of southern-sourced water such as those documented here enhanced carbon dioxide storage in the deep ocean, helping to increase the amplitude of glacial cycles.

Description: Bulk properties of the Denmark Strait overflow (DSO) plume observed in velocity and hydrography surveys undertaken in 1997 and 1998 are described. Despite the presence of considerable short-term variability, it is found that the pathway and evolution of the plume density anomaly are remarkably steady. Bottom stress measurements show that the pathway of the plume core matches well with a rate of descent controlled by friction. The estimated entrainment rate diagnosed from the rate of plume dilution with distance shows a marked increase in entrainment at approximately 125 km from the sill, leading to a net dilution consistent with previous reports of a doubling of overflow transport measured by current meter arrays. The entrainment rate increase is likely related to the increased topographic slopes in the region, compounded by a decrease in interface stratification as the plume is diluted and enters a denser background.

Description: Heinrich events are intervals of rapid iceberg-sourced freshwater release to the high latitude North Atlantic Ocean that punctuate late Pleistocene glacials. Delivery of fresh water to the main North Atlantic sites of deep water formation during Heinrich events may result in major disruption to the Atlantic Meridional Overturning Circulation (AMOC), however, the simple concept of an AMOC shutdown in response to each freshwater input has recently been shown to be overly simplistic. Here we present a new multi-proxy dataset spanning the last 41,000 years that resolves four Heinrich events at a classic mid-depth North Atlantic drill site, employing four independent geochemical tracers of water mass properties: boron/calcium, carbon and oxygen isotopes in foraminiferal calcite and neodymium isotopes in multiple substrates. We also report rare earth element distributions to investigate the fidelity by which neodymium isotopes record changes in water mass distribution in the northeast North Atlantic. Our data reveal distinct geochemical signatures for each Heinrich event, suggesting that the sites of fresh water delivery and/or rates of input played at least as important a role as the stage of the glacial cycle in which the fresh water was released. At no time during the last 41 kyr was the mid-depth northeast North Atlantic dominantly ventilated by southern-sourced water. Instead, we document persistent ventilation by Glacial North Atlantic Intermediate Water (GNAIW), albeit with variable properties signifying changes in supply from multiple contributing northern sources.

Description: Poleward heat transport in the oceans generate global-scale electric currents and associated Lorentz forces in the Earth's core. We make a first estimate of this effect using a simple zonally averaged model from which we obtain analytical/numerical solutions. The results indicate that the poleward heat transport in the presence of Main field reversals having periods of 10,000 to 10 million years lead to large-scale electric currents in the core of order 10-11 to 10-13 A/m2 which although extremely small, imply poleward forces in the core which are likely to have acted systematically throughout the history of the planet.

Description: Petroleum is one of the most complex naturally occurring organic mixtures. The physical and chemical properties of petroleum in a reservoir depend on its molecular composition and the reservoir conditions (temperature, pressure). The composition of petroleum varies greatly, ranging from the simplest gas (methane), condensates, conventional crude oil to heavy oil and oil sands bitumen with complex molecules having molecular weights in excess of 1000 daltons (Da). The distribution of petroleum constituents in a reservoir largely depends on source facies (original organic material buried), age (evolution of organisms), depositional environment (dysoxic versus anoxic), maturity of the source rock (kerogen) at time of expulsion, primary/secondary migration, and in-reservoir alteration such as biodegradation, gas washing, water washing, segregation, and/or mixing from different oil charges. These geochemical aspects define the physical characteristics of a petroleum in the reservoir, including its density and viscosity. When the petroleum is released from the reservoir through an oil exploration accident like in the case of the Deepwater Horizon event, several processes are affecting the physical and chemical properties of the petroleum from the well head into the deep sea. A better understanding of these properties is crucial for the development of near-field oil spill models, oil droplet and gas bubble calculations, and partitioning behavior of oil components in the water. Section 3.1 introduces general aspects of the origin of petroleum, the impact of geochemical processes on the composition of a petroleum, and some molecular compositional and physicochemical background information of the Macondo well oil. Section 3.2 gives an overview over experimental determination of all relevant physicochemical properties of petroleum, especially of petroleum under reservoir conditions. Based on the phase equilibrium modeling using equations of state (EOS), a number of these properties can be predicted which is presented in Sect. 3.3 along with a comparison to experimental data obtained with methods described in Sect. 3.2.

Description: Mineral-bound Fe(II) species represent important natural reductants of pollutants in the anaerobic subsurface. At clay minerals, three types of Fe(II) species in fundamentally different chemical environments may be present simultaneously, i.e., structural Fe(II), Fe(II) complexed by surface hydroxyl groups, and Fe(II) bound by ion exchange. We investigated the accessibility and reactivity of these three types of Fe(II) species in suspensions of two different clay minerals containing either ferrous iron-bearing nontronite or iron-free hectorite. Nitroaromatic compounds (NACs) exhibiting different sorption behavior on clays were used to probe the reactivity of the various types of reduced iron species. The clay treatment allowed for a preparation of nontronite and hectorite surfaces with Fe(II) adsorbed by surface hydroxyl groups at the edge surfaces. Furthermore, hectorite suspensions with additional Fe(II) bound to the ion exchange sites at the basal siloxane surfaces were set up. We found that both structural Fe(II) and Fe(II) complexed by surface hydroxyl groups of nontronite reduced the NACs to anilines. An electron balance revealed that more than 10% of the total iron in nontronite was reactive Fe(II). Fe(II) bound by ion exchange did not contribute to the observed reduction of NACs. Reversible adsorption of the NACs at the basal siloxane surface of the clays strongly retarded NAC reduction, even in the presence of high concentrations of Fe(II) bound by ion exchange to the basal siloxane surfaces. Our work shows that in natural systems a fraction of the total Fe(II) present on clays may contribute to the pool of highly reactive Fe(II) species in the subsurface. Furthermore, this work may help to distinguish between Fe(II) species of different reactivity regarding pollutant reduction. Although structural iron in clays represents only a small fraction of the total iron pool in soils and aquifers, reactive Fe(II) species originating from the reduction of structural Fe(III) in clays may contribute significantly to the biogeochemical cycling of electrons in the subsurface since it is not subject to depletion by reductive dissolution.

Description: Due to the strong interest in geochemical CO2-fluid-rock interaction in the context of geological storage of CO2 a growing number of research groups have used a variety of different experimental ways to identify important geochemical dissolution or precipitation reactions and – if possible – quantify the rates and extent of mineral or rock alteration. In this inter-laboratory comparison the gas-fluid-mineral reactions of three samples of rock-forming minerals have been investigated by 11 experimental labs. The reported results point to robust identification of the major processes in the experiments by most groups. The dissolution rates derived from the changes in composition of the aqueous phase are consistent overall, but the variation could be reduced by using similar corrections for changing parameters in the reaction cells over time. The comparison of experimental setups and procedures as well as of data corrections identified potential improvements for future gas-fluid-rock studies.