Description: Studies that focus on meiofaunal assemblages of deep-sea mud volcanoes show an unpredictable abundance and diversity in a clear response to the different environmental conditions of the seeped sediment. The mud volcanoes Abzu, Tiamat and M. Ivanov (ATI), are located along the SWIM1 fracture zone, in front of the accretionary wedge of the Gulf of Cadiz (AWGC). The geological setting and the fluid geo- chemical characteristics of the ATI mud volcanoes are differ- ent from those located within the AWGC. The main aim of this study is to describe and compare the spatial and vertical distributions of the meiofauna and nematode assemblage s from the ATI mud volcanoes, the Porto mud volcano located in the AWGC, and a non-seep site (Site 2) as reference. The pore-water on the uppermost sediment layers has composi- tions close to the near-bottom seawater. The meiofauna abun- dances were generally lower and the vertical distribution of the assemblages showed a typical pattern, gradually decreas- ing towards depth. The lack of spatial patterns of the standing stocks contrasts with the spatial variability of diversity and biomass, related to the differences in the nematode assem- blages that are distinct between ATI, Site 2 and the Porto mud volcano. The ATI and Site 2 assemblages are similar to deep-sea non-seep habitats, and are clearly coupled with the environmental conditions of the bottom seawater. No evi- dence of seep conditions favouring the development of specialised fauna were found. The lower diversity and the presence of higher dominance species could be driven by dis- tinct seepage conditions of the Porto mud volcano.

Description: Molybdenum (Mo) concentrations and isotope compositions in sediments and shales are commonly used as proxies for anoxic and sulfidic (i.e., euxinic) conditions in the water column of paleo-marine systems. A basic assumption underlying this practice is that the proxy signal extracted from the geological record is controlled by long-term (order of decades to millennia) Mo scavenging in the euxinic water column rather than Mo deposition during brief episodes or events (order of weeks to months). To test whether this assumption is viable we studied the biogeochemical cycling of Mo and its isotopes in sediments of the intermittently euxinic Gotland Deep in the central Baltic Sea. Here, multiannual to decadal periods of euxinia are occasionally interrupted by inflow events during which well‑oxygenated water from the North Sea penetrates into the basin. During these events manganese (Mn) (oxyhydr)oxide minerals are precipitated in the water column, which are known to scavenge Mo. We present sediment and pore water Mo and Mo isotope data for sediment cores which were taken before and after a series of inflow events between 2014 and 2016. After seawater inflow, pore water Mo concentrations in anoxic surface sediments exceed the salinity-normalized concentration by more than two orders of magnitude and coincide with transient peaks of dissolved Mn. A fraction of the Mo liberated into the pore water is transported by diffusion in a downward direction and sequestered by organic matter within the sulfidic zone of the sediment. Diffusive flux calculations as well as a mass balance that is based on the sedimentary Mo isotope composition suggest that about equal proportions of the Mo accumulating in the basin are delivered by Mn (oxyhydr)oxide minerals during inflow events and Mo scavenging with hydrogen sulfide during euxinic periods. Since the anoxic surface sediment where Mo is released from Mn (oxyhydr)oxides are separated by several centimeters from the deeper sulfidic layers where Mo is removed, the solid phase record of Mo concentration and isotope composition would be misinterpreted if steady state Mo accumulation was assumed. Based on our observations in the Gotland Deep, we argue that short-term redox fluctuations need to be considered when interpreting Mo-based paleo-records.

Description: Because of anthropogenic global warming, the world ocean is currently losing oxygen. This trend called ocean deoxygenation is particularly pronounced in low-latitude upwelling-related oxygen minimum zones (OMZs). In these areas, the temperature-related oxygen drawdown is additionally modulated by biogeochemical feedback mechanisms between sedimentary iron (Fe) and phosphorus release, water column nitrogen cycling and primary productivity. Similar feedbacks were likely active during past periods of global warming and ocean deoxygenation. However, their integrated role in amplifying or mitigating climate change-driven ocean anoxia has not been evaluated in a systematic fashion. Moreover, many studies on past (de)oxygenation events emphasize anoxic-sulfidic (i.e., euxinic) basins such as the Black Sea rather than upwelling-related OMZs as modern analogue systems. In this review, I summarize the current state of knowledge on biogeochemical processes in the water column and sediments of OMZs. Nitrate-reducing (i.e., nitrogenous) to weakly sulfidic conditions in the water column and Fe-reducing (i.e., ferruginous) to sulfidic conditions in the surface sediment are identified as key-features of anoxic OMZs in the modern ocean. A toolbox of paleo-redox proxies is proposed that can be used to identify OMZ-type biogeochemical cycling in the geological record. By using a generalized model of sedimentary Fe release and trapping, I demonstrate that the extent of Fe mobilization and transport in modern OMZs is comparable to that inferred for the euxinic Black Sea and ferruginous water columns in Earth history. Based on this result, I suggest that many sedimentary Fe enrichments in the geological record are broadly consistent with OMZ-type redox conditions in the water column and surface sediment, especially if enhanced chemical weathering and reactive Fe supply to the ocean during past periods of global warming are taken into account. Future studies on paleo-(de)oxygenation events with a combined focus on Fe, sulfur and nitrogen cycling may reveal that OMZ-type redox conditions were an important feature of the ocean through Earth's history.

Description: Highlights • Lusi crater waters represent a regional geochemical anomaly. • Erupted waters are the result of a complex mix of sedimentary and hydrothermal fluids. • Lusi is not a typical mud volcano but a sediment-hosted hydrothermal system. • The neighbouring volcanic complex feeds hydrothermal fluids for the Lusi eruption. Abstract The spectacular Lusi mud-eruption started in northeast Java the 29th of May 2006. Despite extensive research, the origin of the erupted water remains elusive and poorly constrained. Here we present a comprehensive study of the geochemistry of Lusi waters compared with those collected from surrounding areas, all collected between 2006 and 2013, including data from mud volcanoes and volcano-hosted hydrothermal springs. Within this broad context, the geochemical characteristics of the fluids expelled in the Lusi region suggest that we can classify the waters in three groups: 1) meteoric waters expelled in cold springs and artesian wells, 2) hydrothermal waters typically mixed with meteoric waters, and 3) formation water from marine sediments altered by diagenetic processes such as clay-mineral dehydration. Samples collected from the Lusi crater are Cl and Na dominated (up to 527 mM and 471.7 mM, respectively) similar to seawater indicating that altered sedimentary formation waters are predominant in this system. In addition they are enriched in Sr (up to 808.4 μM) and other elements commonly associated with hydrothermal systems, such as Li (up to 877.6 μM compared to 26 μM in seawater). Some of these elements are up to ten times enriched compared to seawater values. High-temperature fluid mineral interactions in the subsurface appear to have facilitated the transfer of Li and other mobile elements into the fluids. High temperature fluid-mineral interaction reactions are also supported by Si concentrations significantly higher compared to other sampled mud volcanoes in the island. Crater samples also show the highest δ18O values (+5‰ after correction for evaporation compared to +1‰ at the MV localities). 87Sr/86Sr ratios vary between of 0.7077 and 0.7083 and seem to reflect a general mixture of fluids from clay-mineral dehydration, carbonate recrystallization, alteration of volcanic rocks and hydrothermal imprint. Eight years of geochemical monitoring indicate that the composition of the deep-sourced Lusi fluids remain fairly constant through time. Thus our findings show that the Lusi crater waters represent a regional geochemical anomaly, and we suggest that a combination of high temperatures in the source region, and fluid-rock interactions with silicates and, possibly, carbonate-rich lithologies can explain the data. This is consistent with a model where the emitted gases migrate from a deep-seated (〉4 km) source region, likely associated with the presence of hot igneous intrusions and/or high T reactions related to the presence of neighbouring active volcanoes.

Description: The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 µg g−1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the ‘anomalously’ high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

Description: Magmatic sill intrusions into organic-rich sediments cause the release of thermogenic CH4 and CO2. Pore fluids from the Guaymas Basin (Gulf of California), a sedimentary basin with recent magmatic activity, were investigated to constrain the link between sill intrusions and fluid seepage as well as the timing of sill-induced hydrothermal activity. Sampling sites were close to a hydrothermal vent field at the northern rift axis and at cold seeps located up to 30km away from the rift. Pore fluids close to the active hydrothermal vent field showed a slight imprint by hydrothermal fluids and indicated a shallow circulation system transporting seawater to the hydrothermal catchment area. Geochemical data of pore fluids at cold seeps showed a mainly ambient diagenetic fluid composition without any imprint related to high temperature processes at greater depth. Seep communities at the seafloor were mainly sustained by microbial methane, which rose along pathways formed earlier by hydrothermal activity, driving the anaerobic oxidation of methane (AOM) and the formation of authigenic carbonates. Overall, our data from the cold seep sites suggest that at present, sill-induced hydrothermalism is not active away from the ridge axis, and the vigorous venting of hydrothermal fluids is restricted to the ridge axis. Using the sediment thickness above extinct conduits and carbonate dating, we calculated that deep fluid and thermogenic gas flow ceased 28 to 7kyr ago. These findings imply a short lifetime of hydrothermal systems, limiting the time of unhindered carbon release as suggested in previous modeling studies. Consequently, activation and deactivation mechanisms of these systems need to be better constrained for the use in climate modeling approaches.

Description: During opening of a new ocean magma intrudes into the surrounding sedimentary basins. Heat provided by the intrusions matures the host rock creating metamorphic aureoles potentially releasing large amounts of hydrocarbons. These hydrocarbons may migrate to the seafloor in hydrothermal vent complexes in sufficient volumes to trigger global warming, e.g. during the Paleocene Eocene Thermal Maximum (PETM). Mound structures at the top of buried hydrothermal vent complexes observed in seismic data off Norway were previously interpreted as mud volcanoes and the amount of released hydrocarbon was estimated based on this interpretation. Here, we present new geophysical and geochemical data from the Gulf of California suggesting that such mound structures could in fact be edifices constructed by the growth of black-smoker type chimneys rather than mud volcanoes. We have evidence for two buried and one active hydrothermal vent system outside the rift axis. The vent releases several hundred degrees Celsius hot fluids containing abundant methane, mid-ocean-ridge-basalt (MORB)-type helium, and precipitating solids up to 300 m high into the water column. Our observations challenge the idea that methane is emitted slowly from rift-related vents. The association of large amounts of methane with hydrothermal fluids that enter the water column at high pressure and temperature provides an efficient mechanism to transport hydrocarbons into the water column and atmosphere, lending support to the hypothesis that rapid climate change such as during the PETM can be triggered by magmatic intrusions into organic-rich sedimentary basins.

Description: Dissolved silicon isotope compositions have been analysed for the first time in pore waters (δ30SiPW) of three short sediment cores from the Peruvian margin upwelling region with distinctly different biogenic opal content in order to investigate silicon isotope fractionation behaviour during early diagenetic turnover of biogenic opal in marine sediments. The δ30SiPW varies between +1.1‰ and +1.9‰ with the highest values occurring in the uppermost part close to the sediment–water interface. These values are of the same order or higher than the δ30Si of the biogenic opal extracted from the same sediments (+0.3‰ to +1.2‰) and of the overlying bottom waters (+1.1‰ to +1.5‰). Together with dissolved silicic acid concentrations well below biogenic opal saturation, our collective observations are consistent with the formation of authigenic alumino-silicates from the dissolving biogenic opal. Using a numerical transport-reaction model we find that approximately 24% of the dissolving biogenic opal is re-precipitated in the sediments in the form of these authigenic phases at a relatively low precipitation rate of 56 μmol Si cm−2 yr−1. The fractionation factor between the precipitates and the pore waters is estimated at −2.0‰. Dissolved and solid cation concentrations further indicate that off Peru, where biogenic opal concentrations in the sediments are high, the availability of reactive terrigenous material is the limiting factor for the formation of authigenic alumino-silicate phases.

Description: Seafloor seepage of hydrocarbon-bearing fluids has been identified in a number of marine forearcs. However, temporal variations in seep activity and the structural and tectonic parameters that control the seepage often remain poorly constrained. Subduction-zone earthquakes for example, are often discussed to trigger seafloor seepage but causal links that go beyond theoretical considerations have not yet been fully established. This is mainly due to the inaccessibility of offshore epicentral areas, the infrequent occurrence of large earthquakes, and challenges associated with offshore monitoring of seepage over large areas and sufficient time periods. Here, we report visual, geochemical, geophysical, and modelling results and observations from the Concepción Methane Seep Area (offshore Central Chile) located in the rupture area of the 2010 Mw. 8.8 Maule earthquake. High methane concentrations in the oceanic water column and a shallow sub-bottom depth of sulfate penetration indicate active methane seepage. The stable carbon isotope signature of the methane and hydrocarbon composition of the released gas indicate a mixture of shallow-sourced biogenic gas and a deeper sourced thermogenic component. Pristine fissures and fractures observed at the seafloor together with seismically imaged large faults in the marine forearc may represent effective pathways for methane migration. Upper-plate fault activity with hydraulic fracturing and dilation is in line with increased normal Coulomb stress during large plate-boundary earthquakes, as exemplarily modelled for the 2010 earthquake. On a global perspective our results point out the possible role of recurring large subduction-zone earthquakes in driving hydrocarbon seepage from marine forearcs over long timescales.