Fe-catalyzed sulfide oxidation in hydrothermal plumes is a source of reactive oxygen species to the ocean.

Historically, the production of reactive oxygen species (ROS) in the ocean has been attributed to photochemical and biochemical reactions. However, hydrothermal vents emit globally significant inventories of reduced Fe and S species that should react rapidly with oxygen in bottom water and serve as a heretofore unmeasured source of ROS. Here, we show that the Fe-catalyzed oxidation of reduced sulfur species in hydrothermal vent plumes in the deep oceans supported the abiotic formation of ROS at concentrations 20 to 100 times higher than the average for photoproduced ROS in surface waters. ROS (measured as hydrogen peroxide) were determined in hydrothermal plumes and seeps during a series of Alvin dives at the North East Pacific Rise. Hydrogen peroxide inventories in emerging plumes were maintained at levels proportional to the oxygen introduced by mixing with bottom water. Fenton chemistry predicts the production of hydroxyl radical under plume conditions through the reaction of hydrogen peroxide with the abundant reduced Fe in hydrothermal plumes. A model of the hydroxyl radical fate under plume conditions supports the role of plume ROS in the alteration of refractory organic molecules in seawater. The ocean's volume circulates through hydrothermal plumes on timescales similar to the age of refractory dissolved organic carbon. Thus, plume-generated ROS can initiate reactions that may affect global ocean carbon inventories.

High 3He/4He in central Panama reveals a distal connection to the Galápagos plume.

It is well established that mantle plumes are the main conduits for upwelling geochemically enriched material from Earth's deep interior. The fashion and extent to which lateral flow processes at shallow depths may disperse enriched mantle material far (>1,000 km) from vertical plume conduits, however, remain poorly constrained. Here, we report He and C isotope data from 65 hydrothermal fluids from the southern Central America Margin (CAM) which reveal strikingly high 3He/4He (up to 8.9RA) in low-temperature (≤50 °C) geothermal springs of central Panama that are not associated with active volcanism. Following radiogenic correction, these data imply a mantle source 3He/4He >10.3RA (and potentially up to 26RA, similar to Galápagos hotspot lavas) markedly greater than the upper mantle range (8 ± 1RA). Lava geochemistry (Pb isotopes, Nb/U, and Ce/Pb) and geophysical constraints show that high 3He/4He values in central Panama are likely derived from the infiltration of a Galápagos plume-like mantle through a slab window that opened ∼8 Mya. Two potential transport mechanisms can explain the connection between the Galápagos plume and the slab window: 1) sublithospheric transport of Galápagos plume material channeled by lithosphere thinning along the Panama Fracture Zone or 2) active upwelling of Galápagos plume material blown by a "mantle wind" toward the CAM. We present a model of global mantle flow that supports the second mechanism, whereby most of the eastward transport of Galápagos plume material occurs in the shallow asthenosphere. These findings underscore the potential for lateral mantle flow to transport mantle geochemical heterogeneities thousands of kilometers away from plume conduits.

Modeling and forecasting of monthly PM2.5 emission of Paris by periodogram-based time series methodology.

In this study, monthly particulate matter (PM2.5) of Paris for the period between January 2000 and December 2019 is investigated by utilizing a periodogram-based time series methodology. The main contribution of the study is modeling the PM2.5 of Paris by extracting the information purely from the examined time series data, where proposed model implicitly captures the effects of other factors, as all their periodic and seasonal effects reside in the air pollution data. Periodicity can be defined as the patterns embedded in the data other than seasonality, and it is crucial to understand the underlying periodic dynamics of air pollutants to better fight pollution. The method we use successfully captures and accounts for the periodicities, which could otherwise be mixed with seasonality under an alternative methodology. Upon the unit root test based on periodograms, it is revealed that the investigated data has periodicities of 1 year and 20 years, so harmonic regression is utilized as an alternative to Box-Jenkins methodology. As the harmonic regression displayed a better performance both in and out-of-sample forecasts, it can be considered as a powerful alternative to model and forecast time series with a periodic structure.

Distinct patterns of sedimentary phosphorus fractionation and mobilization in the seafloor of the Black Sea, Marmara Sea and Mediterranean Sea.

Phosphorus (P) is a key element to all life that is used for structural and functional component of all organisms. The cycling of sedimentary P may differ depending on the redox-conditions of the overlying waters affecting the dynamics, and distribution of P-fractions and the elements that are highly coupled to P cycle. Though biogeochemistry of water column in the three interconnected marine basins of Black, Marmara and Mediterranean Seas have been studied extensively, few studies were carried out to understand sedimentary P dynamics in these regions. In this study, therefore, the biogeochemical cycling of sedimentary P and related variables such as porewater nutrients, sedimentary organic carbon, nitrogen and reactive iron were studied in selected sites at the three interconnected marine basins: Black Sea, Marmara and Northeastern (NE) Mediterranean Sea. The pool of "potentially mobile P" was also determined for the studied sites. The study results showed that porewater and sediment biogeochemistry displayed great variability in the studied sites with the maximum concentrations of porewater phosphate, ammonium, reactive silicate, surface sediment organic carbon, nitrogen, phosphorus and total phosphorus (TP) measured in the hypoxic Marmara Sea and suboxic/anoxic Black Sea. The decline in the TP concentrations of all sediment core samples indicated P-mobilization to the overlying water. The pool of "potentially mobile P" varied between 0.023 and 0.148 mol/m2 in the studied sites with the maximum values recorded in suboxic and anoxic/sulfidic parts of the Black Sea. This study predicts that the deoxygenation and eutrophication would further lead to the preferential release of P in these three interconnected marine basins, hence changing the remineralization, N/P molar ratios and eventually transform the deep-water nutrient stocks with implications for internal N/P control on marine ecosystems.

Standard operating procedure for the analysis of major ions in hydrothermal fluids by ion chromatography.

This standard operating procedure (SOP) describes an ion chromatography (IC) procedure for the major cations and anions in hydrothermal fluids. Hydrothermal fluids are aqueous solutions with a wide range of temperature, salinity, pH and ion species that can be used by microbial metabolism as electron donors and electron acceptors. Due to the high variability of the environmental physical-chemical parameters in these samples, we have developed this protocol taking into account the special features of the matrices analyzed. An Eco IC Metrohm system equipped with a conductivity detector was used. Calibration curves are linear in the 0.1 to 10 mg/L concentration range for cations Ca 2+, Na +, K +, Mg 2+, NH 4 + and anions Cl -, Br -, NO 3 -, NO 2 -, SO 4 2- , PO 4 3-.

This manuscript details the standard operating procedure used for the determination of major cations and anions in hydrothermal fluids, which are characterized by a high variability of physico-chemical parameters. Due to the high variability of our samples, we customized the method to compensate for the variability on the physico-chemical parameters. The results are useful to interpret the geochemical processes and for understanding how these processes influence microbial diversity in geothermal systems.

Standard Operating Procedure for the determination of trace elements in hydrothermal fluids by Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

This standard operating procedure (SOP) validates an inductively coupled plasma mass spectrometry (ICP-MS) procedure for the determination of trace elements in hydrothermal fluids. Hydrothermal fluids are aqueous solutions with a wide range of temperature, salinity, pH and trace elements that can be used by a set of microbial proteins containing redox-sensitive transition metals as their catalytic core. Due to the high variability of these samples, we have developed this protocol taking into account the special features of the matrices analyzed. An ICP-MS 7900 Agilent system was used. Calibration curves are linear in the 0.01 to 100 µg/L concentration range.

This manuscript outlines the standard operating procedure used to determine trace elements in hydrothermal fluids, which are characterized by a high variability of physical-chemical parameters. Due to the high variability of our samples, we customized the method to compensate for the variability on the physico-chemical parameters. The obtained data on the distribution and abundance of trace elements in sediments and fluids can be used to track geochemical processes mobilizing the metals as well as their influence on the microbial diversity in geothermal systems.

Chemolithoautotroph distributions across the subsurface of a convergent margin.

Subducting oceanic crusts release fluids rich in biologically relevant compounds into the overriding plate, fueling subsurface chemolithoautotrophic ecosystems. To understand the impact of subsurface geochemistry on microbial communities, we collected fluid and sediments from 14 natural springs across a ~200 km transect across the Costa Rican convergent margin and performed shotgun metagenomics. The resulting 404 metagenome-assembled genomes (MAGs) cluster into geologically distinct regions based on MAG abundance patterns: outer forearc-only (25% of total relative abundance), forearc/arc-only (38% of total relative abundance), and delocalized (37% of total relative abundance) clusters. In the outer forearc, Thermodesulfovibrionia, Candidatus Bipolaricaulia, and Firmicutes have hydrogenotrophic sulfate reduction and Wood-Ljungdahl (WL) carbon fixation pathways. In the forearc/arc, Anaerolineae, Ca. Bipolaricaulia, and Thermodesulfovibrionia have sulfur oxidation, nitrogen cycling, microaerophilic respiration, and WL, while Aquificae have aerobic sulfur oxidation and reverse tricarboxylic acid carbon fixation pathway. Transformation-based canonical correspondence analysis shows that MAG distribution corresponds to concentrations of aluminum, iron, nickel, dissolved inorganic carbon, and phosphate. While delocalized MAGs appear surface-derived, the subsurface chemolithoautotrophic, metabolic, and taxonomic landscape varies by the availability of minerals/metals and volcanically derived inorganic carbon. However, the WL pathway persists across all samples, suggesting that this versatile, energy-efficient carbon fixation pathway helps shape convergent margin subsurface ecosystems.

Soluble, Colloidal, and Particulate Iron Across the Hydrothermal Vent Mixing Zones in Broken Spur and Rainbow, Mid-Atlantic Ridge.

The slow-spreading Mid-Atlantic Ridge (MAR) forms geological heterogeneity throughout the ridge system by deep crustal faults and their resultant tectonic valleys, which results in the existence of different types of hydrothermal vent fields. Therefore, investigating MAR hydrothermal systems opens a gate to understanding the concentration ranges of ecosystem-limiting metals emanating from compositionally distinct fluids for both near-field chemosynthetic ecosystems and far-field transport into the ocean interiors. Here, we present novel data regarding onboard measured, size-fractionated soluble, colloidal, and particulate iron concentrations from the 2018 R/V L'Atalante - ROV Victor research expedition, during which samples were taken from the mixing zone of black smokers using a ROV-assisted plume sampling. Iron size fractionation (<20, 20-200, and >200nm) data were obtained from onboard sequential filtering, followed by measurement via ferrozine assay and spectrophotometric detection at 562nm. Our results showed the persistent presence of a nanoparticulate/colloidal phase (retained within 20-200nm filtrates) even in high-temperature samples. A significant fraction of this phase was retrievable only under treatment with HNO3 - a strong acid known to attack and dissolve pyrite nanocrystals. Upon mixing with colder bottom waters and removal of iron in the higher parts of the buoyant plume, the larger size fractions became dominant as the total iron levels decreased, but it was still possible to detect significant (micromolar) levels of nanoparticulate Fe even in samples collected 5m above the orifice in the rising plume. The coolest sample (<10°C) still contained more than 1µM of only nitric acid-leachable nanoparticle/colloidal, at least 200 times higher than a typical Fe concentration in the non-buoyant plume. Our results support previous reports of dissolved Fe in MAR vent plumes, and we propose that this recalcitrant Fe pool - surviving immediate precipitation - contributes to maintaining high hydrothermal iron fluxes to the deep ocean.

Iron and sulfide nanoparticle formation and transport in nascent hydrothermal vent plumes.

Deep-sea hydrothermal vents are a significant source of dissolved metals to the global oceans, producing midwater plumes enriched in metals that are transported thousands of kilometers from the vent source. Particle precipitation upon emission of hydrothermal fluids controls metal speciation and the magnitude of metal export. Here, we document metal sulfide particles, including pyrite nanoparticles, within the first meter of buoyant plumes from three high-temperature vents at the East Pacific Rise. We observe a zone of particle settling 10-20 cm from the orifice, indicated by stable sulfur isotopes; however, we also demonstrate that nanoparticulate pyrite (FeS2) is not removed from the plume and can account for over half of the filtered Fe (≤0.2 µm) up to one meter from the vent orifice. The persistence of nanoparticulate pyrite demonstrates that it is an important mechanism for near-vent Fe stabilisation and highlights the potential role of nanoparticles in element transport.

Formation of Zn- and Fe-sulfides near hydrothermal vents at the Eastern Lau Spreading Center: implications for sulfide bioavailability to chemoautotrophs.

BACKGROUND: The speciation of dissolved sulfide in the water immediately surrounding deep-ocean hydrothermal vents is critical to chemoautotrophic organisms that are the primary producers of these ecosystems. The objective of this research was to identify the role of Zn and Fe for controlling the speciation of sulfide in the hydrothermal vent fields at the Eastern Lau Spreading Center (ELSC) in the southern Pacific Ocean. Compared to other well-studied hydrothermal systems in the Pacific, the ELSC is notable for unique ridge characteristics and gradients over short distances along the north-south ridge axis. RESULTS: In June 2005, diffuse-flow (< 50 degrees C) and high-temperature (> 250 degrees C) vent fluids were collected from four field sites along the ELSC ridge axis. Total and filtered Zn and Fe concentrations were quantified in the vent fluid samples using voltammetric and spectrometric analyses. The results indicated north-to-south variability in vent fluid composition. In the high temperature vent fluids, the ratio of total Fe to total Zn varied from 39 at Kilo Moana, the most northern site, to less than 7 at the other three sites. The concentrations of total Zn, Fe, and acid-volatile sulfide indicated that oversaturation and precipitation of sphalerite (ZnS(s)) and pyrite (FeS2(s)) were possible during cooling of the vent fluids as they mixed with the surrounding seawater. In contrast, most samples were undersaturated with respect to mackinawite (FeS(s)). The reactivity of Zn(II) in the filtered samples was tested by adding Cu(II) to the samples to induce metal-exchange reactions. In a portion of the samples, the concentration of labile Zn2+ increased after the addition of Cu(II), indicating the presence of strongly-bound Zn(II) species such as ZnS clusters and nanoparticles. CONCLUSION: Results of this study suggest that Zn is important to sulfide speciation at ELSC vent habitats, particularly at the southern sites where Zn concentrations increase relative to Fe. As the hydrothermal fluids mix with the ambient seawater, Zn-sulfide clusters and nanoparticles are likely preventing sulfide oxidation by O2 and reducing bioavailability of S(-II) to organisms.

Ecological Succession of Sulfur-Oxidizing Epsilon- and Gammaproteobacteria During Colonization of a Shallow-Water Gas Vent.

In this study, we integrated geochemical measurements, microbial diversity surveys and physiological characterization of laboratory strains to investigate substrate-attached filamentous microbial biofilms at Tor Caldara, a shallow-water gas vent in the Tyrrhenian Sea. At this site, the venting gases are mainly composed of CO2 and H2S and the temperature at the emissions is the same as that of the surrounding water. To investigate the composition of the total and active fraction of the Tor Caldara biofilm communities, we collected established and newly formed filaments and we sequenced the 16S rRNA genes (DNA) and the 16S rRNA transcripts (cDNA). Chemoautotrophic sulfur-oxidizing members of the Gammaproteobacteria (predominantly Thiotrichales) dominate the active fraction of the established microbial filaments, while Epsilonproteobacteria (predominantly Sulfurovum spp.) are more prevalent in the young filaments. This indicates a succession of the two communities, possibly in response to age, sulfide and oxygen concentrations. Growth experiments with representative laboratory strains in sulfide gradient medium revealed that Sulfurovum riftiae (Epsilonproteobacteria) grew closer to the sulfide source than Thiomicrospira sp. (Gammaproteobacteria, Thiotrichales). Overall, our findings show that sulfur-oxidizing Epsilonproteobacteria are the dominant pioneer colonizers of the Tor Caldara biofilm communities and that Gammaproteobacteria become prevalent once the community is established. This succession pattern appears to be driven - among other factors - by the adaptation of Epsilon- and Gammaproteobacteria to different sulfide concentrations.

Microbial Sulfide Filter along a Benthic Redox Gradient in the Eastern Gotland Basin, Baltic Sea.

The sediment-water interface is an important site for material exchange in marine systems and harbor unique microbial habitats. The flux of nutrients, metals, and greenhouse gases at this interface may be severely dampened by the activity of microorganisms and abiotic redox processes, leading to the "benthic filter" concept. In this study, we investigate the spatial variability, mechanisms and quantitative importance of a microbially-dominated benthic filter for dissolved sulfide in the Eastern Gotland Basin (Baltic Sea) that is located along a dynamic redox gradient between 65 and 173 m water depth. In August-September 2013, high resolution (0.25 mm minimum) vertical microprofiles of redox-sensitive species were measured in surface sediments with solid-state gold-amalgam voltammetric microelectrodes. The highest sulfide consumption (2.73-3.38 mmol m-2 day-1) occurred within the top 5 mm in sediments beneath a pelagic hypoxic transition zone (HTZ, 80-120 m water depth) covered by conspicuous white bacterial mats of genus Beggiatoa. A distinct voltammetric signal for polysulfides, a transient sulfur oxidation intermediate, was consistently observed within the mats. In sediments under anoxic waters (>140 m depth), signals for Fe(II) and aqueous FeS appeared below a subsurface maximum in dissolved sulfide, indicating a Fe(II) flux originating from older sediments presumably deposited during the freshwater Ancylus Lake that preceded the modern Baltic Sea. Our results point to a dynamic benthic sulfur cycling in Gotland Basin where benthic sulfide accumulation is moderated by microbial sulfide oxidation at the sediment surface and FeS precipitation in deeper sediment layers. Upscaling our fluxes to the Baltic Proper; we find that up to 70% of the sulfide flux (2281 kton yr-1) toward the sediment-seawater interface in the entire basin can be consumed at the microbial mats under the HTZ (80-120 m water depth) while only about 30% the sulfide flux effuses to the bottom waters (>120 m depth). This newly described benthic filter for the Gotland Basin must play a major role in limiting the accumulation of sulfide in and around the deep basins of the Baltic Sea.

Diversity and Distribution of Prokaryotes within a Shallow-Water Pockmark Field.

Pockmarks are crater-like depression on the seafloor associated with hydrocarbon ascent through muddy sediments in continental shelves around the world. In this study, we examine the diversity and distribution of benthic microbial communities at shallow-water pockmarks adjacent to the Middle Adriatic Ridge. We integrate microbial diversity data with characterization of local hydrocarbons concentrations and sediment geochemistry. Our results suggest these pockmarks are enriched in sedimentary hydrocarbons, and host a microbial community dominated by Bacteria, even in deeper sediment layers. Pockmark sediments showed higher prokaryotic abundance and biomass than surrounding sediments, potentially due to the increased availability of organic matter and higher concentrations of hydrocarbons linked to pockmark activity. Prokaryotic diversity analyses showed that the microbial communities of these shallow-water pockmarks are unique, and comprised phylotypes associated with the cycling of sulfur and nitrate compounds, as well as numerous know hydrocarbon degraders. Altogether, this study suggests that shallow-water pockmark habitats enhance the diversity of the benthic prokaryotic biosphere by providing specialized environmental niches.

Nitrate and Nitrite Variability at the Seafloor of an Oxygen Minimum Zone Revealed by a Novel Microfluidic In-Situ Chemical Sensor.

Microfluidics, or lab-on-a-chip (LOC) is a promising technology that allows the development of miniaturized chemical sensors. In contrast to the surging interest in biomedical sciences, the utilization of LOC sensors in aquatic sciences is still in infancy but a wider use of such sensors could mitigate the undersampling problem of ocean biogeochemical processes. Here we describe the first underwater test of a novel LOC sensor to obtain in situ calibrated time-series (up to 40 h) of nitrate+nitrite (ΣNOx) and nitrite on the seafloor of the Mauritanian oxygen minimum zone, offshore Western Africa. Initial tests showed that the sensor successfully reproduced water column (160 m) nutrient profiles. Lander deployments at 50, 100 and 170 m depth indicated that the biogeochemical variability was high over the Mauritanian shelf: The 50 m site had the lowest ΣNOx concentration, with 15.2 to 23.4 µM (median=18.3 µM); while at the 100 site ΣNOx varied between 21.0 and 30.1 µM over 40 hours (median = 25.1 µM). The 170 m site had the highest median ΣNOx level (25.8 µM) with less variability (22.8 to 27.7 µM). At the 50 m site, nitrite concentration decreased fivefold from 1 to 0.2 µM in just 30 hours accompanied by decreasing oxygen and increasing nitrate concentrations. Taken together with the time series of oxygen, temperature, pressure and current velocities, we propose that the episodic intrusion of deeper waters via cross-shelf transport leads to intrusion of nitrate-rich, but oxygen-poor waters to shallower locations, with consequences for benthic nitrogen cycling. This first validation of an LOC sensor at elevated water depths revealed that when deployed for longer periods and as a part of a sensor network, LOC technology has the potential to contribute to the understanding of the benthic biogeochemical dynamics.

Temporal and spatial constraints on community assembly during microbial colonization of wood in seawater.

Wood falls on the ocean floor form chemosynthetic ecosystems that remain poorly studied compared with features such as hydrothermal vents or whale falls. In particular, the microbes forming the base of this unique ecosystem are not well characterized and the ecology of communities is not known. Here we use wood as a model to study microorganisms that establish and maintain a chemosynthetic ecosystem. We conducted both aquaria and in situ deep-sea experiments to test how different environmental constraints structure the assembly of bacterial, archaeal and fungal communities. We also measured changes in wood lipid concentrations and monitored sulfide production as a way to detect potential microbial activity. We show that wood falls are dynamic ecosystems with high spatial and temporal community turnover, and that the patterns of microbial colonization change depending on the scale of observation. The most illustrative example was the difference observed between pine and oak wood community dynamics. In pine, communities changed spatially, with strong differences in community composition between wood microhabitats, whereas in oak, communities changed more significantly with time of incubation. Changes in community assembly were reflected by changes in phylogenetic diversity that could be interpreted as shifts between assemblies ruled by species sorting to assemblies structured by competitive exclusion. These ecological interactions followed the dynamics of the potential microbial metabolisms accompanying wood degradation in the sea. Our work showed that wood is a good model for creating and manipulating chemosynthetic ecosystems in the laboratory, and attracting not only typical chemosynthetic microbes but also emblematic macrofaunal species.

Sulfide production and consumption in degrading wood in the marine environment.

Woody debris is known to be transported to the seas and accumulate on the seafloor, however, little is known on the consequences of its degradation in the marine environment. In this study we monitored the degradation product sulfide with Au/Hg voltammetric microelectrodes on the surface and interior of an experimentally immersed wood for 200 d. After 5 weeks of immersion, the interior became sulfidic, and steady-state conditions were established after 13 weeks with sulfide concentration reaching about 300 µM. Although sulfide was briefly detected at the surface of wood, its concentration remained lower than 20 µM, indicating that this compound was effectively oxidized within the substrate. Fitting these data to a kinetic model lead to an estimated microbial sulfide production rate in the range of 19-28 µM d(-1) at steady state. As much as 24 µM d(-1) nitrate could be consumed by this process in the steady-state period. Before the establishment of the steady state conditions, steep fluctuations in sulfide concentration (between 1mM and several µM) were observed in the wood interior. This study is the first to document the temporal dynamics of this unsteady process, characterized by fast sulfide fluctuation and consumption. Our results point to the complex mechanisms driving the dynamics of wood biogeochemical transformations, and reveal the capacity of woody debris to generate sulfidic conditions and act as a possible sink for oxygen and nitrate in the marine environment.

Marine chemical technology and sensors for marine waters: potentials and limits.

A significant need exists for in situ sensors that can measure chemical species involved in the major processes of primary production (photosynthesis and chemosynthesis) and respiration. Some key chemical species are O2, nutrients (N and P), micronutrients (metals), pCO2, dissolved inorganic carbon (DIC), pH, and sulfide. Sensors need to have excellent detection limits, precision, selectivity, response time, a large dynamic concentration range, low power consumption, robustness, and less variation of instrument response with temperature and pressure, as well as be free from fouling problems (biological, physical, and chemical). Here we review the principles of operation of most sensors used in marine waters. We also show that some sensors can be used in several different oceanic environments to detect the target chemical species, whereas others are useful in only one environment because of various limitations. Several sensors can be used truly in situ, whereas many others involve water brought into a flow cell via tubing to the analyzer in the environment or aboard ship. Multi-element sensors that measure many chemical species in the same water mass should be targeted for further development.