Description: Increasing interest in deep-sea mineral resources, such as polymetallic nodules, calls for environmental research about possible impacts of mineral exploitation on the deep-sea ecosystem. So far, little geochemical comparisons of deep-sea sediments before and after mining induced disturbances have been made, and thus long-term environmental effects of deep-sea mining are unknown. Here we present geochemical data from sediment cores from an experimental disturbance area at 4,100 m water depth in the Peru Basin. The site was revisited in 2015, 26 years after a disturbance experiment mimicking nodule mining was carried out and compared to sites outside the experimental zone which served as a pre-disturbance reference. We investigated if signs of the disturbance are still visible in the solid phase and the pore water after 26 years or if pre-disturbance conditions have been re-established. Additionally, a new disturbance was created during the cruise and sampled 5 weeks later to compare short- and longer-term impacts. The particulate fraction and pore water were analyzed for major and trace elements to study element distribution and processes in the surface sediment. Pore water and bottom water samples were also analyzed for oxygen, nitrate, dissolved organic carbon, and dissolved amino acids, to examine organic matter degradation processes. The study area of about 11 km2 was found to be naturally more heterogeneous than expected, requiring an analysis of spatial variability before the disturbed and undisturbed sites can be compared. The disturbed sites exhibit various disturbance features: some surface sediments were mixed through, others had the top layer removed and some had additional material deposited on top. Pore water constituents have largely regained pre-disturbance gradients after 26 years. The solid phase, however, shows clear differences between disturbed and undisturbed sites in the top 20 cm so that the impact is still visible in the plowed tracks after 26 years. Especially the upper layer, usually rich in manganese-oxide and associated metals, such as Mo, Ni, Co, and Cu, shows substantial differences in metal distribution. Hence, it can be expected that disturbances from polymetallic nodule mining will have manifold and long-lasting impacts on the geochemistry of the underlying sediment.

Description: The knowledge of the phase behavior of carbon dioxide (CO2)-rich mixtures is a key factor to understand the chemistry and migration of natural volcanic CO2 seeps in the marine environment, as well as to develop engineering processes for CO2 sequestration coupled to methane (CH4) production from gas hydrate deposits. In both cases, it is important to gain insights into the interactions of the CO2-rich phase—liquid or gas—with the aqueous medium (H2O) in the pore space below the seafloor or in the ocean. Thus, the CH4-CO2 binary and CH4-CO2-H2O ternary mixtures were investigated at relevant pressure and temperature conditions. The solubility of CH4 in liquid CO2 (vapor-liquid equilibrium) was determined in laboratory experiments and then modelled with the Soave–Redlich–Kwong equation of state (EoS) consisting of an optimized binary interaction parameter kij(CH4-CO2) = 1.32 × 10−3 × T − 0.251 describing the non-ideality of the mixture. The hydrate-liquid-liquid equilibrium (HLLE) was measured in addition to the composition of the CO2-rich fluid phase in the presence of H2O. In contrast to the behavior in the presence of vapor, gas hydrates become more stable when increasing the CH4 content, and the relative proportion of CH4 to CO2 decreases in the CO2-rich phase after gas hydrate formation.

Description: This article presents gas hydrate experimental measurements for mixtures containing methane (CH4), carbon dioxide (CO2) and nitrogen (N2) with the aim to better understand the impact of water (H2O) on the phase equilibrium. Some of these phase equilibrium experiments were carried out with a very high water-to-gas ratio that shifts the gas hydrate dissociation points to higher pressures. This is due to the significantly different solubilities of the different guest molecules in liquid H2O. A second experiment focused on CH4-CO2 exchange between the hydrate and the vapor phases at moderate pressures. The results show a high retention of CO2 in the gas hydrate phase with small pressure variations within the first hours. However, for our system containing 10.2 g of H2O full conversion of the CH4 hydrate grains to CO2 hydrate is estimated to require 40 days. This delay is attributed to the shrinking core effect, where initially an outer layer of CO2-rich hydrate is formed that effectively slows down the further gas exchange between the vapor phase and the inner core of the CH4-rich hydrate grain.