Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9°50’N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54’N, 155°15’W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50’N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Ge fluid-basalt up to 1.15 ‰ at EPR 9°50’N and 1.64 ‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 ± 0.6 ‰ (2sd), and a maximum value of -3.6 ± 0.6 ‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50’N also demonstrates that Ge isotopes are fractionated by approximately -5.6 ± 0.6 ‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

Geochemistry and mineralogy of a silica chimney from an inactive seafloor hydrothermal field (East Pacific Rise, 18°S)

An inactive vent field comprised of dead chimneys was discovered on the ultrafast East Pacific Rise (EPR) at 18°S during the research campaign NAUDUR with the R/V Le Nadir in December 1993. One of these chimneys was sampled, studied and found to be largely composed of silica-mineralized bacterial-like filaments. The filaments are inferred to be the result of microbial activity leading to silica (± Fe-oxyhydroxide) precipitation. The chimney grew from the most external layer (precipitated 226 ± 4 yr. B.P.) towards the central chimney conduit. Hydrothermal activity ceased 154 ± 13 yr. B.P. and the chimney conduit was completely sealed. Mixing between an end-member hydrothermal fluid and seawater explains the Sr–Nd isotopic composition of the chimney. Seawater was the major source of Sr to the chimney, whereas the dominant Nd source was the local mid-ocean ridge basalt (MORB) leached by the hydrothermal fluids. The mixing scenarios point to a dynamic hydrothermal system with fluctuating fluid compositions. The proportion of seawater within the venting fluid responsible for the precipitation of the silica chimney layers varied between 94 and 85%. Pb-isotope data indicates that all of the Pb in the chimney was derived from the underlying MORB. The precipitation temperatures of the chimney layers varied between 55 and 71 °C, and were a function of the seawater/end-member hydrothermal fluid mixing ratio. δ30Si correlates with the temperature of precipitation implying that temperature is one of the major controls of the Si-isotope composition of the chimney. Concentrations of elements across the chimney wall were a function of this mixing ratio and the composition of the end-member hydrothermal fluid. The inward growth of the chimney wall and accompanying decrease in wall permeability resulted in an inward decrease in the seawater/hydrothermal fluid mixing ratio, which in turn exerted a control on the concentrations of the elements supplied mainly by the hydrothermal fluids. The silica chimney is significantly enriched in U, likely a result of bacterial concentration of U from the seawater-dominated vent fluid. The chimney is poor in rare earth elements (REE). It inherited its REE distribution patterns from the parent end-member hydrothermal fluids. The dilution of the hydrothermal fluid with over 85% seawater could not obliterate the particular REE features (positive Eu anomaly) of the hydrothermal fluids.

Hydrothermal activity along the slow-spreading Lucky Strike ridge segment (Mid-Atlantic Ridge): Distribution, heatflux, and geological controls

We have reviewed available visual information from the seafloor, and recently acquired microbathymetry for several traverses across the Lucky Strike segment, to evaluate the distribution of hydrothermal activity. We have identified a new on-axis site with diffuse flow, Ewan, and an active vent structure ∼1.2 km from the axis, Capelinhos. These sites are minor relative to the Main field, and our total heatflux estimate for all active sites (200–1200 MW) is only slightly higher than previously published estimates. We also identify fossil sites W of the main Lucky Strike field. A circular feature ∼200 m in diameter located on the flanks of a rifted off-axis central volcano is likely a large and inactive hydrothermal edifice, named Grunnus. We find no indicator of focused hydrothermal activity elsewhere along the segment, suggesting that the enhanced melt supply and the associated melt lenses, required to form central volcanoes, also sustain hydrothermal circulation to form and maintain large and long-lived hydrothermal fields. Hydrothermal discharge to the seafloor occurs along fault traces, suggesting focusing of hydrothermal circulation in the shallow crust along permeable fault zones.

Temporal and spatial variation in temperature experienced by macrofauna at main endeavour Hydrothermal vent field

A significant focus of hydrothermal vent ecological studies has been to understand how species cope with various stressors through physiological tolerance and biochemical resistance. Yet, the environmental conditions experienced by vent species have not been well characterized. This objective requires continuous observations over time intervals that can capture environmental variability at scales that are relevant to animals. We used autonomous temperature logger arrays (four roughly parallel linear arrays of 12 loggers spaced every 10–12 cm) to study spatial and temporal variations in the thermal regime experienced by hydrothermal vent macrofauna at a diffuse flow vent. Hourly temperatures were recorded over eight months from 2010 to 2011 at Grotto vent in the Main Endeavour vent field on the Juan de Fuca Ridge, a focus area of the Ocean Networks Canada cabled observatory. The conspicuous animal assemblages in video footage contained Ridgeia piscesae tubeworms, gastropods (primarily Lepetodrilus fucensis), and polychaetes (polynoid scaleworms and the palm worm Paralvinella palmiformis). Two dimensional spatial gradients in temperature were generally stable over the deployment period. The average temperature recorded by all arrays, and in some individual loggers, revealed distinctive fluctuations in temperature that often corresponded with the tidal cycle. We postulate that this may be related to changes in bottom currents or fluctuations in vent discharge. A marked transient temperature increase lasting over a period of days was observed in April 2011. While the distributions and behavior of Juan de Fuca Ridge vent invertebrates may be partially constrained by environmental temperature and temperature tolerance, except for the one transient high-temperature event, observed fluid temperatures were generally similar to the thermal preferences for some species, and typically well below lethal temperatures for all species. Average temperatures of the four arrays ranged from 4.1 to 11.0 °C during the deployment, indicating that on an hourly timescale the temperature conditions in this tubeworm community were fairly moderate and stable. The generality of these findings and behavioural responses of vent organisms to predictable rhythmicity and non-periodic temperature shifts are areas for further investigation

Biogeographical distribution of Rimicaris exoculata resident gut epibiont communities along the Mid-Atlantic Ridge hydrothermal vent sites

Rimicaris exoculata is a deep-sea hydrothermal vent shrimp which enlarged gill chamber houses a complex trophic epibiotic community. Its gut harbours an autochthonous and distinct microbial community. This species dominates hydrothermal ecosystems megafauna along the Mid-Atlantic Ridge, regardless of contrasted geochemical conditions prevailing in them. Here, the resident gut epibiont community at four contrasted hydrothermal vent sites (Rainbow/TAG/Logatchev/Ashadze) was analysed and compiled with previous data to evaluate the possible influence of site location, using 16S rRNA surveys and microscopic observations (TEM, SEM and FISH analyses). Filamentous epibionts inserted between the epithelial cells microvilli were observed on all examined samples. Results confirmed resident gut community affiliation to Deferribacteres, Mollicutes, Epsilonproteobacteria and to a lesser extent Gammaproteobacteria lineages. Still a single Deferribacteres phylotype was retrieved at all sites. Four Mollicutes-related OTUs were distinguished, one being only identified on Rainbow specimens. The topology of ribotypes median-joining networks illustrated a community diversification possibly following demographic expansions, suggesting a more ancient evolutionary history and/or a larger effective population size at Rainbow. Finally, the gill chamber community distribution was also analysed through ribotypes networks based on sequences from R. exoculata collected at Rainbow/Snake Pit/TAG/Logatchev/Ashadze sites. Results allow refining hypotheses on the epibiont role and transmission pathways.

Rapid hydrothermal cooling above the axial melt lens at fast-spreading mid-ocean ridge

Axial melt lenses sandwiched between the lower oceanic crust and the sheeted dike sequences at fast-spreading mid-ocean ridges are assumed to be the major magma source of oceanic crust accretion. According to the widely discussed "gabbro glacier'' model, the formation of the lower oceanic crust requires efficient cooling of the axial melt lens, leading to partial crystallization and crystal-melt mush subsiding down to lower crust. These processes are believed to be controlled by periodical magma replenishment and hydrothermal circulation above the melt lens. Here we quantify the cooling rate above melt lens using chemical zoning of plagioclase from hornfelsic recrystallized sheeted dikes drilled from the East Pacific at the Integrated Ocean Drilling Program Hole 1256D. Weestimate the cooling rate using a forward modelling approach based on CaAl-NaSi interdiffusion in plagioclase. The results show that cooling from the peak thermal overprint at 1000-10506 degrees C to 6006 degrees C are yielded within about 10-30 years as a result of hydrothermal circulation above melt lens during magma starvation. The estimated rapid hydrothermal cooling explains how the effective heat extraction from melt lens is achieved at fast-spreading mid-ocean ridges.

A comparison of in situ vs. ex situ filtration methods on the assessment of dissolved and particulate metals at hydrothermal vents

The objective of this study was to assess the impact of the filtration method (in situ vs. ex situ) on the dissolved/particulate partitioning of 12 elements in hydrothermal samples collected from the Lucky Strike vent field (Mid-Atlantic Ridge; MAR). To do so, dissolved ( <0.45 mu m) and particulate Mg, Li, Mn, U, V, As, Ba, Fe, Zn, Cd, Pb and Cu were measured using different techniques (HR-ICP-MS, ICP-AES and CCSA). Using in situ filtration as a baseline, we showed that ex situ filtration (on-board and on shore after freezing) resulted in an underestimation of the dissolved pool, which was counterbalanced by an overestimation of the particulate pool for almost all the elements studied. We also showed that on-board filtration was acceptable for the assessment of dissolved and particulate Mn, Mg, Li and U for which the measurement bias for the dissolved fraction did not exceed 3%. However, in situ filtration appeared necessary for the accurate assessment of the dissolved and particulate concentrations of V, As, Fe, Zn, Ba, Cd, Pb and Cu. In the case of Fe, on-board filtration underestimated the dissolved pool by up to 96%. Laboratory filtration (after freezing) resulted in a large bias in the dissolved and particulate concentrations, unambiguously discounting this filtration method for deep-sea chemical speciation studies. We discuss our results in light of the precipitation processes that can potentially affect the accuracy of ex situ filtration methods.

Enzymatic hydrolysis and fermentation of ultradispersed wood particles after ultrasonic pretreatment

Background: A study of the correlation between the particle size of lignocellulosic substrates and ultrasound pretreatment on the efficiency of further enzymatic hydrolysis and fermentation to ethanol. Results: Themaximumconcentrations of glucose and, to a lesser extent, di- and trisaccharideswere obtained in a series of experiments with 48-h enzymatic hydrolysis of pine rawmaterials ground at 380–400 rpm for 30min. The highest glucose yield was observed at the end of the hydrolysis with a cellulase dosage of 10 mg of protein (204 ± 21 units CMCase per g of sawdust). The greatest enzymatic hydrolysis efficiency was observed in a sample that combined two-stage grinding at 400 rpm with ultrasonic treatment for 5–10 min at a power of 10 W per kg of sawdust. The glucose yield in this case (35.5 g glucose l−1) increased twofold compared to ground substrate without further preparation. Conclusions: Using a mechanical two-stage grinding of lignocellulosic raw materials with ultrasonication increases the efficiency of subsequent enzymatic hydrolysis and fermentation.

Molecular identification and localization of filamentous symbiotic bacteria associated with the hydrothermal vent annelid Alvinella pompejana

Alvinella pompejana is a polychaetous annelid that inhabits high temperature environments associated with active deep-sea hydrothermal vents along the East Pacific Rise. A unique and diverse epibiotic microflora with a prominent filamentous morphotype is found associated with the worm's dorsal integument. A previous study established the taxonomic positions of two epsilon proteobacterial phylotypes, 13B and 5A, which dominated a clone library of 16S rRNA genes amplified by PCR from the epibiotic microbial community of an A. pompejana specimen. In the present study deoxyoligonucleotide PCR primers specific for phylotypes 13B and 5A were used to demonstrate that these phylotypes are regular features of the bacterial community associated with A. pompejana. Assaying of other surfaces around colonies of A. pompejana revealed that phylotypes 13B and 5A are not restricted to A. pompejana. Phylotype 13B occurs on the exterior surfaces of other invertebrate genera and rock surfaces, and phylotype 5A occurs on a congener, Alvinella caudata. The 13B and 5A phylotypes were identified and localized on A. pompejana by in situ hybridization, demonstrating that these two phylotypes are, in fact, the prominent filamentous bacteria on the dorsal integument of A. pompejana. These findings indicate that the filamentous bacterial symbionts of A. pompejana are epsilon Proteobacteria which do not have an obligate requirement for A. pompejana.

Hydrothermal-vent alvinellid polychaete dispersal in the eastern Pacific .1. Influence of vent site distribution, bottom currents, and biological patterns

Deep-sea hydrothermal-vent habitats are typically linear, discontinuous, and short-lived. Some of the vent fauna such as the endemic polychaete family Alvinellidae are thought to lack a planktotrophic larval stage and therefore not to broadcast-release their offspring. The genetic evidence points to exchanges on a scale that seems to contradict this type of reproductive pattern. However, the rift valley may topographically rectify the bottom currents, thereby facilitating the dispersal of propagules between active vent sites separated in some cases by 10s of kilometers or more along the ridge axis. A propagule flux model based on a matrix of intersite distances, long-term current-meter data, and information on the biology and ecology of Alvinellidae was developed to test this hypothesis. Calculations of the number of migrants exchanged between two populations per generation (N-m) allowed comparisons with estimates obtained from genetic studies. N, displays a logarithmic decrease with increasing dispersal duration and reaches the critical value of 1 after 8 d when the propagule Aux model was run in standard conditions. At most, propagule traveling time cannot reasonably exceed 15-30 d, according to the model, whereas reported distances between sites would require longer lasting dispersal abilities. Two nonexclusive explanations are proposed. First, some aspects of the biology of Alvinellidae have been overlooked and long-distance dispersal does occur. Second, such dispersal never occurs in Alvinellidae, but the spatial-temporal dynamics of vent sites over geological timescales allows short-range dispersal processes to maintain gene flow.

Lipid and lipid carbon stable isotope composition of the hydrothermal vent shrimp Mirocaris fortunata: evidence for nutritional dependence on photosynthetically fixed carbon

Mirocaris fortunata were sampled from the Lucky Strike hydrothermal vent area (Eiffel Tower site) on the mid-Atlantic ridge during the French DIVA 2 cruise (June 1994). Small adults (17 to 22 mm total length), although morphologically identical, could be divided into 2 categories on the basis of pigmentation, lipid composition and C-13/C-12 stable isotope ratios of fatty acids. Highly pigmented small adults (8.6 to 9.2 mu g carotenoid shrimp(-1)) contained higher levels of total lipid than similar-sized individuals containing lower levels of pigment (0.9 to 2.9 mu g carotenoid shrimp(-1)). Lipid class analysis indicated that wax esters comprised 62.5% of total lipid in the former group. These pigmented shrimp also contained high proportions of polyunsaturated fatty acids (PUFA), particularly the phototrophic microplanktonic markers 20:5(n-3) and 22:6(n-3) (14.0 and 33.5% respectively). By contrast small adults (22 mm) and adult shrimp (25 to 26 mm) with low levels of carotenoid pigmentation contained lower amounts of total lipid, little or no wax ester and low levels of 20:5(n-3) and 22:6(n-3), but did contain 16:2(n-4) and 18:2(n-4) and the non-methylene interrupted dienes 20:2 Delta 5,13 and 22:2 Delta 7,15. GC-IRMS analysis of all fatty acids and fatty alcohols in the pigmented small adults indicated delta(13)C values of -18.2 to -27.7 parts per thousand, which is consistent with a photosynthetic carbon source for these compounds. The C-13/C-12 isotope composition of fatty acids from low-pigmented small adults and adults was more variable (-12.5 to -33.1 parts per thousand) and suggests a bimodal distribution which may be attributable to differing nutritional sources or the physiological/reproductive status of these shrimp. Samples of eggs, which are carried by the female on the pleopods, represented approximately 57% of total somatic lipid which indicates a substantial reproductive investment by this species. The egg lipids comprised high proportions of triacylglycerols (64.4 to 78.0% of total lipid) whilst the fatty acid composition was dominated by the monounsaturated fatty acids 16:1(n-7), 18:1(n-7) and 18:1(n-9), which accounted for 65.7 to 33.5% of total fatty acids. By contrast, PUFA were relatively minor components of egg lipids, particularly 20:5(n-3) and 22:6(n-3), which accounted for only 1.1 and 2.9% of total egg fatty acids respectively. This indicates that the reproductive investment by this species is supported mainly by material derived from bacterial chemosynthesis. The potential for M. fortunata hedge betting by producing larvae which either metamorphose at the vent site or adopt a bathypelagic lifestyle and delay metamorphosis to facilitate more widespread dispersal is discussed.

Evolution of strength and physical properties of ultramafic and carbonate rocks under hydrothermal conditions

Interaction of rocks with fluids can significantly change mineral assemblage and structure. This so-called hydrothermal alteration is ubiquitous in the Earth’s crust. Though the behavior of hydrothermally altered rocks can have planet-scale consequences, such as facilitating oceanic spreading along slow ridge segments and recycling volatiles into the mantle at subduction zones, the mechanisms involved in the hydrothermal alteration are often microscopic. Fluid-rock interactions take place where the fluid and rock meet. Fluid distribution, flux rate and reactive surface area control the efficiency and extent of hydrothermal alteration. Fluid-rock interactions, such as dissolution, precipitation and fluid mediated fracture and frictional sliding lead to changes in porosity and pore structure that feed back into the hydraulic and mechanical behavior of the bulk rock. Examining the nature of this highly coupled system involves coordinating observations of the mineralogy and structure of naturally altered rocks and laboratory investigation of the fine scale mechanisms of transformation under controlled conditions. In this study, I focus on fluid-rock interactions involving two common lithologies, carbonates and ultramafics, in order to elucidate the coupling between mechanical, hydraulic and chemical processes in these rocks. I perform constant strain-rate triaxial deformation and constant-stress creep tests on several suites of samples while monitoring the evolution of sample strain, permeability and physical properties. Subsequent microstructures are analyzed using optical and scanning electron microscopy. This work yields laboratory-based constraints on the extent and mechanisms of water weakening in carbonates and carbonation reactions in ultramafic rocks. I find that inundation with pore fluid thereby reducing permeability. This effect is sensitive to pore fluid saturation with respect to calcium carbonate. Fluid inundation weakens dunites as well. The addition of carbon dioxide to pore fluid enhances compaction and partial recovery of strength compared to pure water samples. Enhanced compaction in CO2-rich fluid samples is not accompanied by enhanced permeability reduction. Analysis of sample microstructures indicates that precipitation of carbonates along fracture surfaces is responsible for the partial restrengthening and channelized dissolution of olivine is responsible for permeability maintenance.

Food-Web Complexity in Guaymas Basin Hydrothermal Vents and Cold Seeps

In the Guaymas Basin, the presence of cold seeps and hydrothermal vents in close proximity, similar sedimentary settings and comparable depths offers a unique opportunity to assess and compare the functioning of these deep-sea chemosynthetic ecosystems. The food webs of five seep and four vent assemblages were studied using stable carbon and nitrogen isotope analyses. Although the two ecosystems shared similar potential basal sources, their food webs differed: seeps relied predominantly on methanotrophy and thiotrophy via the Calvin-Benson-Bassham (CBB) cycle and vents on petroleum-derived organic matter and thiotrophy via the CBB and reductive tricarboxylic acid (rTCA) cycles. In contrast to symbiotic species, the heterotrophic fauna exhibited high trophic flexibility among assemblages, suggesting weak trophic links to the metabolic diversity of chemosynthetic primary producers. At both ecosystems, food webs did not appear to be organised through predator-prey links but rather through weak trophic relationships among co-occurring species. Examples of trophic or spatial niche differentiation highlighted the importance of species-sorting processes within chemosynthetic ecosystems. Variability in food web structure, addressed through Bayesian metrics, revealed consistent trends across ecosystems. Food-web complexity significantly decreased with increasing methane concentrations, a common proxy for the intensity of seep and vent fluid fluxes. Although high fluid-fluxes have the potential to enhance primary productivity, they generate environmental constraints that may limit microbial diversity, colonisation of consumers and the structuring role of competitive interactions, leading to an overall reduction of food-web complexity and an increase in trophic redundancy. Heterogeneity provided by foundation species was identified as an additional structuring factor. According to their biological activities, foundation species may have the potential to partly release the competitive pressure within communities of low fluid-flux habitats. Finally, ecosystem functioning in vents and seeps was highly similar despite environmental differences (e.g. physico-chemistry, dominant basal sources) suggesting that ecological niches are not specifically linked to the nature of fluids. This comparison of seep and vent functioning in the Guaymas basin thus provides further supports to the hypothesis of continuity among deep-sea chemosynthetic ecosystems.

Hydrothermal carbonization of lignocellulosic biomass: Effect of process conditions on hydrochar properties

Although hydrothermal carbonization of biomass components is known to be mainly governed by reaction temperature, consistent reports on the effect and statistical significance of process conditions on hydrochar properties are still lacking. The objective of this research was to determine the importance and significance of reaction temperature, retention time and solid load on the properties of hydrochar produced from an industrial lignocellulosic sludge residue. According to the results, reaction temperature and retention time had a statistically significant effect on hydrochar ash content, solid yield, carbon content, O/C-ratio, energy densification and energy yield as reactor solid load was statistically insignificant for all acquired models within the design range. Although statistically significant, the effect of retention time was 3–7 times lower than that of reaction temperature. Predicted dry ash-free solid yields of attained hydrochar decreased to approximately 40% due to the dissolution of biomass components at higher reaction temperatures, as respective oxygen contents were comparable to subbituminous coal. Significant increases in the carbon contents of hydrochar led to predicted energy densification ratios of 1–1.5 with respective energy yields of 60–100%. Estimated theoretical energy requirements of carbonization were dependent on the literature method used and mainly controlled by reaction temperature and reactor solid load. The attained results enable future prediction of hydrochar properties from this feedstock and help to understand the effect of process conditions on hydrothermal treatment of lignocellulosic biomass.

Heterogeneously catalyzed hydrothermal processing of C5-C6 sugars

Biomass has been long exploited as an anthropogenic energy source; however, the 21st century challenges of energy security and climate change are driving resurgence in its utilization both as a renewable alternative to fossil fuels and as a sustainable carbon feedstock for chemicals production. Deconstruction of cellulose and hemicellulose carbohydrate polymers into their constituent C5 and C6 sugars, and subsequent heterogeneously catalyzed transformations, offer the promise of unlocking diverse oxygenates such as furfural, 5-hydroxymethylfurfural, xylitol, sorbitol, mannitol, and gluconic acid as biorefinery platform chemicals. Here, we review recent advances in the design and development of catalysts and processes for C5-C6 sugar reforming into chemical intermediates and products, and highlight the challenges of aqueous phase operation and catalyst evaluation, in addition to process considerations such as solvent and reactor selection.