Catabolic and anabolic energy for chemolithoautotrophs in deep-sea hydrothermal systems hosted in different rock types

Active deep-sea hydrothermal vents are hosted by a range of different rock types, including basalt, peridotite, and felsic rocks. The associated hydrothermal fluids exhibit substantial chemical variability, which is largely attributable to compositional differences among the underlying host rocks. Numerical models were used to evaluate the energetics of seven inorganic redox reactions (potential catabolisms of chemolithoautotrophs) and numerous biomolecule synthesis reactions (anabolism) in a representative sampling of these systems, where chemical gradients are established by mixing hydrothermal fluid with seawater. The wide ranging fluid compositions dictate demonstrable differences in Gibbs energies (ΔG_r) of these catabolic and anabolic reactions in three peridotite-hosted, six basalt-hosted, one troctolite-basalt hybrid, and two felsic rock-hosted systems. In peridotite-hosted systems at low to moderate temperatures (<∼45 °C) and high seawater:hydrothermal fluid (SW:HF) mixing ratios (>10), hydrogen oxidation yields the most catabolic energy, but the oxidation of methane, ferrous iron, and sulfide can also be moderately exergonic. At higher temperatures, and consequent SW:HF mixing ratios <10, anaerobic processes dominate the energy landscape; sulfate reduction and methanogenesis are more exergonic than any of the aerobic respiration reactions. By comparison, in the basalt-hosted and felsic rock-hosted systems, sulfide oxidation was the predominant catabolic energy source at all temperatures (and SW:HF ratios) considered. The energetics of catabolism at the troctolite-basalt hybrid system were intermediate to these extremes. Reaction energetics for anabolism in chemolithoautotrophs—represented here by the synthesis of amino acids, nucleotides, fatty acids, saccharides, and amines—were generally most favorable at moderate temperatures (22-32 °C) and corresponding SW:HF mixing ratios (∼15). In peridotite-hosted and the troctolite-basalt hybrid systems, ΔG_r for primary biomass synthesis yielded up to ∼900 J per g dry cell mass. The energetics of anabolism in basalt- and felsic rock-hosted systems were far less favorable. The results suggest that in peridotite-hosted (and troctolite-basalt hybrid) systems, compared with their basalt (and felsic rock) counterparts, microbial catabolic strategies—and consequently variations in microbial phylotypes—may be far more diverse and some biomass synthesis may yield energy rather than imposing a high energetic cost.     

Identification of potential sites for aquifer storage and recovery (ASR) in coastal areas using ASR performance estimation methods

Performance of freshwater aquifer storage and recovery (ASR) systems in brackish or saline aquifers is negatively affected by lateral flow, density effects, and/or dispersive mixing, causing ambient groundwater to enter ASR wells during recovery. Two recently published ASR performance estimation methods are applied in a Dutch coastal area, characterized by brackish-to-saline groundwater and locally high lateral-flow velocities. ASR performance of existing systems in the study area show good agreement with the predicted performance using the two methods, provided that local vertical anisotropy ratios are limited (<3). Deviations between actual and predicted ASR performance may originate from simplifications in the conceptual model and uncertainties in the hydrogeological and hydrochemical input. As the estimation methods prove suitable to predict ASR performance, feasibility maps are generated for different scales of ASR to identify favorable ASR sites. Successful small-to-medium-scale ASR varies spatially in the study area, emphasizing the relevance of reliable a priori spatial mapping.     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Occurrence and use of mineral and thermal waters in Poland

Mineral and thermal waters are defined according to Polish geological and mining law. Their occurrence in particular hydrogeological provinces of the country is characterized. Besides their use in balneotherapeutics, their role as a heat carrier and source of chemical raw materials is stressed. Topics mentioned requiring further research are: the origin of saline formation waters and the origin of CO₂ in carbonated waters.     

UHP metamorphism recorded by kyanite-bearing eclogite in the Seve Nappe Complex of northern Jämtland,Swedish Caledonides

The first evidence for ultrahigh-pressure (UHP) metamorphism in the Seve Nappe Complex of the Scandinavian Caledonides is recorded by kyanite-bearing eclogite, found in a basic dyke within a garnet peridotite body exposed close to the lake Friningen in northern Jämtland (central Sweden). UHP metamorphic conditions of ~ 3 GPa and 800 °C, within the stability field of coesite, are constrained from geothermobarometry and calculated phase equilibria for the peak-pressure assemblage garnet + omphacite + kyanite + phengite. A prograde metamorphic evolution from a lower P–T (1.5–1.7 GPa and 700–750 °C) stage during subduction is inferred from inclusions of pargasitic amphibole, zoisite and kyanite in garnet cores. The post-UHP evolution is constrained from breakdown textures, such as exsolutions of kyanite and silica from the Ca-Eskola clinopyroxene. Near isothermal decompression of eclogite to lower crustal levels (~ 0.8–1.0 GPa ) led to formation of sapphirine, spinel, orthopyroxene and diopside at granulite facies conditions. Published age data suggest a Late Ordovician (460–445 Ma) age of the UHP metamorphism, interpreted to be related to subduction of Baltoscandian continental margin underneath an outboard terrane, possibly outermost Laurentia, during the final stages of closure of the Iapetus Ocean. The UHP rocks were emplaced from the hinterland collision zone during Scandian thrusting of the nappes onto the Baltoscandian foreland basin and platform. The record of P–T conditions and geochonological data from UHP rocks occurring within the allochthonous units of the Scandinavian Caledonides indicate that Ordovician UHP events may have affected much wider parts of the orogen than previously thought, involving deep subduction of the continental crust prior to final Scandian collision between Baltica and Laurentia.     

Chemical and structural relations of epitaxial xenotime and zircon substratum in sedimentary and hydrothermal environments: a TEM study

Xenotime overgrowths on detrital zircon in siliciclastic sediments have been reported in numerous studies. However, in natural samples, solid solution of zircon and xenotime is limited to near-end-member compositions. In order to characterize the interface region between both minerals and to draw inferences on the growth mechanisms of authigenic xenotime, we studied xenotime overgrowths on detrital zircon grains from two Phanerozoic sandstone samples with contrasting post-depositional histories. In one sample, the small (≤10 μm), pyramidal xenotime overgrowths are of diagenetic origin and grew without major discontinuity on the detrital zircon grain. The second sample shows up to >50-μm-wide, porous and inclusion-rich, hydrothermal xenotime overgrowths on detrital zircon, whereas the transition zone between both minerals is accompanied by large pore volume. Chemical compositions of the xenotime precipitates from the two samples differ particularly in Y, REE, Th and Sc concentrations, whereas high MREE availability in the diagenetic sample and the presence of Sc in the hydrothermal sample, respectively, appear to have promoted xenotime growth. Transmission electron microscopy on electron-transparent foils cut from the interface region shows that both the diagenetic xenotime and the hydrothermal xenotime are crystalline and grew in optical and crystallographic continuity to their detrital zircon substrata. Only a narrow transition zone (≤90 nm—diagenetic sample, 200–300 nm—hydrothermal sample) between zircon and xenotime is in part made up of nanometre-scale crystalline domains that are slightly distorted and may have formed from dissolution–re-precipitation processes at the zircon rim along with precipitation from the respective fluid.