Description: Hyperthermophilic iron reducers are common in hydrothermal chimneys found along the Endeavour Segment in the northeastern Pacific Ocean based on culture-dependent estimates. However, information on the availability of Fe(III) (oxyhydr) oxides within these chimneys, the types of Fe(III) (oxyhydr) oxides utilized by the organisms, rates and environmental constraints of hyperthermophilic iron reduction, and mineral end products is needed to determine their biogeochemical significance and are addressed in this study. Thin-section petrography on the interior of a hydrothermal chimney from the Dante edifice at Endeavour showed a thin coat of Fe(III) (oxyhydr) oxide associated with amorphous silica on the exposed outer surfaces of pyrrhotite, sphalerite, and chalcopyrite in pore spaces, along with anhydrite precipitation in the pores that is indicative of seawater ingress. The iron sulfide minerals were likely oxidized to Fe(III) (oxyhydr) oxide with increasing pH and Eh due to cooling and seawater exposure, providing reactants for bioreduction. Culture-dependent estimates of hyperthermophilic iron reducer abundances in this sample were 1740 and 10 cells per gram (dry weight) of material from the outer surface and the marcasite-sphalerite-rich interior, respectively. Two hyperthermophilic iron reducers, Hyperthermus sp. Ro04 and Pyrodictium sp. Su06, were isolated from other active hydrothermal chimneys on the Endeavour Segment. Strain Ro04 is a neutrophilic (pHopt 7–8) heterotroph, while strain Su06 is a mildly acidophilic (pHopt 5), hydrogenotrophic autotroph, both with optimal growth temperatures of 90–92 °C. Mössbauer spectroscopy of the iron oxides before and after growth demonstrated that both organisms form nanophase (〈12 nm) magnetite [Fe3O4] from laboratory-synthesized ferrihydrite [Fe10O14(OH)2] with no detectable mineral intermediates. They produced up to 40 mm Fe2+ in a growth-dependent manner, while all abiotic and biotic controls produced 〈3 mm Fe2+. Hyperthermophilic iron reducers may have a growth advantage over other hyperthermophiles in hydrothermal systems that are mildly acidic where mineral weathering at increased temperatures occurs.

Description: Rock and fluid samples were collected from three hydrothermal chimneys at the Endeavour Segment, Juan de Fuca Ridge to evaluate linkages among mineralogy, fluid chemistry, and microbial community composition within the chimneys. Mössbauer, midinfrared thermal emission, and visible-near infrared spectroscopies were utilized for the first time to characterize vent mineralogy, in addition to thin-section petrography, X-ray diffraction, and elemental analyses. A 282°C venting chimney from the Bastille edifice was composed primarily of sulfide minerals such as chalcopyrite, marcasite, and sphalerite. In contrast, samples from a 300°C venting chimney from the Dante edifice and a 321°C venting chimney from the Hot Harold edifice contained a high abundance of the sulfate mineral anhydrite. Geochemical modeling of mixed vent fluids suggested the oxic-anoxic transition zone was above 100°C at all three vents, and that the thermodynamic energy available for autotrophic microbial redox reactions favored aerobic sulfide and methane oxidation. As predicted, microbes within the Dante and Hot Harold chimneys were most closely related to mesophilic and thermophilic aerobes of the Betaproteobacteria and Gammaproteobacteria and sulfide-oxidizing autotrophic Epsilonproteobacteria. However, most of the microbes within the Bastille chimney were most closely related to mesophilic and thermophilic anaerobes of the Deltaproteobacteria, especially sulfate reducers, and anaerobic hyperthermophilic archaea. The predominance of anaerobes in the Bastille chimney indicated that other environmental factors promote anoxic conditions. Possibilities include the maturity or fluid flow characteristics of the chimney, abiotic Fe2+ and S2− oxidation in the vent fluids, or O2 depletion by aerobic respiration on the chimney outer wall.

Description: Fe 2+ - and Mn 2+ -rich tourmalines were used to test whether Fe 2+ and Mn 2+ substitute on the Z site of tourmaline to a detectable degree. Fe-rich tourmaline from a pegmatite from Lower Austria was characterized by crystal-structure refinement, chemical analyses, and Mössbauer and optical spectroscopy. The sample has large amounts of Fe 2+ (~2.3 apfu), and substantial amounts of Fe 3+ (~1.0 apfu). On basis of the collected data, the structural refinement and the spectroscopic data, an initial formula was determined by assigning the entire amount of Fe 3+ (no delocalized electrons) and Ti 4+ to the Z site and the amount of Fe 2+ and Fe 3+ from delocalized electrons to the Y-Z ED doublet (delocalized electrons between Y-Z and Y-Y ): X (Na 0.9 Ca 0.1 ) Y (Fe 2+ 2.0 Al 0.4 Mn 2+ 0.3 Fe 3+ 0.2 ) Z (Al 4.8 Fe 3+ 0.8 Fe 2+ 0.2 Ti 4+ 0.1 ) T (Si 5.9 Al 0.1 )O 18 (BO 3 ) 3 V (OH) 3 W [O 0.5 F 0.3 (OH) 0.2 ] with a = 16.039(1) and c = 7.254(1) Å. This formula is consistent with lack of Fe 2+ at the Z site, apart from that occupancy connected with delocalization of a hopping electron. The formula was further modified by considering two ED doublets to yield: X (Na 0.9 Ca 0.1 ) Y (Fe 2+ 1.8 Al 0.5 Mn 2+ 0.3 Fe 3+ 0.3 ) Z (Al 4.8 Fe 3+ 0.7 Fe 2+ 0.4 Ti 4+ 0.1 ) T (Si 5.9 Al 0.1 )O 18 (BO 3 ) 3 V (OH) 3 W [O 0.5 F 0.3 (OH) 0.2 ]. This formula requires some Fe 2+ (~0.3 apfu) at the Z site, apart from that connected with delocalization of a hopping electron. Optical spectra were recorded from this sample as well as from two other Fe 2+ -rich tourmalines to determine if there is any evidence for Fe 2+ at Y and Z sites. If Fe 2+ were to occupy two different 6-coordinated sites in significant amounts and if these polyhedra have different geometries or metal-oxygen distances, bands from each site should be observed. However, even in high-quality spectra we see no evidence for such a doubling of the bands. We conclude that there is no ultimate proof for Fe 2+ at the Z site, apart from that occupancy connected with delocalization of hopping electrons involving Fe cations at the Y and Z sites. A very Mn-rich tourmaline from a pegmatite on Elba Island, Italy, was characterized by crystal-structure determination, chemical analyses, and optical spectroscopy. The optimized structural formula is X (Na 0.6 0.4 ) Y (Mn 2+ 1.3 Al 1.2 Li 0.5 ) Z Al 6 T Si 6 O 18 (BO 3 ) 3 V (OH) 3 W [F 0.5 O 0.5 ], with a = 15.951(2) and c = 7.138(1) Å. Within a 3 error there is no evidence for Mn occupancy at the Z site by refinement of Al Mn, and, thus, no final proof for Mn 2+ at the Z site, either. Oxidation of these tourmalines at 700–750 °C and 1 bar for 10–72 h converted Fe 2+ to Fe 3+ and Mn 2+ to Mn 3+ with concomitant exchange with Al of the Z site. The refined Z Fe content in the Fe-rich tourmaline increased by ~40% relative to its initial occupancy. The refined Y Fe content was smaller and the 〈 Y -O〉 distance was significantly reduced relative to the unoxidized sample. A similar effect was observed for the oxidized Mn 2+ -rich tourmaline. Simultaneously, H and F were expelled from both samples as indicated by structural refinements, and H expulsion was indicated by infrared spectroscopy. The final species after oxidizing the Fe 2+ -rich tourmaline is buergerite. Its color had changed from blackish to brown-red. After oxidizing the Mn 2+ -rich tourmaline, the previously dark yellow sample was very dark brown-red, as expected for the oxidation of Mn 2+ to Mn 3+ . The unit-cell parameter a decreased during oxidation whereas the c parameter showed a slight increase.

Description: Measurements of Fe 3+ /Fe in geological materials have been intractable because of lack of access to appropriate facilities, the time-consuming nature of most analyses, and the lack of precision and reproducibility in most techniques. Accurate use of bulk Mössbauer spectroscopy is limited by largely unconstrained recoilless fraction ( f ), which is used to convert spectral peak area ratios into valid estimates of species concentrations and is unique to different mineral groups and compositions. Use of petrographic-scale synchrotron micro-XANES has been handicapped by the lack of a consistent model to relate spectral features to Fe 3+ /Fe. This paper addresses these two deficiencies, focusing specifically on a set of garnet group minerals. Variable-temperature Mössbauer spectra of the Fe 2+ -bearing almandine and Fe 3+ -bearing andradite end-members are used to characterize f in garnets, allowing Fe 3+ /Fe to be measured accurately. Mössbauer spectra of 19 garnets with varying composition were acquired and fit, producing a set of garnet-specific standards for Fe 3+ analyses. High-resolution XANES data were then acquired from these and 15 additional previously studied samples to create a calibration suite representing a broad range of Fe 3+ and garnet composition. Several previously proposed techniques for using simple linear regression methods to predict Fe 3+ /Fe were evaluated, along with the multivariate analysis technique of partial least-squares regression (PLS). Results show that PLS analysis of the entire XANES spectral region yields the most accurate predictions of Fe 3+ in garnets with both robustness and generalizability. Together, these two techniques present reliable choices for bulk and microanalysis of garnet group minerals.

Description: Understanding of Fe site occupancy across the Ca-Fe-Mg pyroxene quadrilateral requires knowledge of space groups and appreciation of the diversity of site geometries across Ca-Mg-Fe composition space. Most commonly, site occupancies are measured using some combination of single-crystal structure refinements (SREF) from X-ray diffraction data and Mössbauer spectroscopy for bulk measurements. The vast majority of previous Mössbauer studies have been hampered by the lack of differential recoil-free fraction data that describe how the Fe 2+ and Fe 3+ cations are bonded in the M1 and M2 sites in pyroxene. To remedy this situation, this paper examines 658 Mössbauer spectra acquired from 64 synthetic samples covering the pyroxene quadrilateral in roughly 10 mol% increments, and determines their fundamental Mössbauer parameters as a function of composition. Results show variations in all the Mössbauer parameters studied: center shift (), quadrupole splitting (), area, recoil-free fraction ( f ), Mössbauer temperature ( M ), and intrinsic isomer shift ( I ). The most systematic variations with composition are seen for and f , while small variations are seen for , M , and I . These data are then related to characteristics of the pyroxene crystal structure to examine the relationship between site geometry and recoil-free fraction. In general, smaller bond lengths (e.g., in the M1 site along the enstatite-ferrosilite join) result in higher f values. As Ca is added to the structure and Mg is removed, the f value for M1 increases as the site becomes larger and more regular. Larger sites with lower bond strengths result in lower values of f because the cation is less tightly bound in the crystal structure and thus encounters more recoil. This result is in keeping with theoretical expectations, but has not previously been clearly demonstrated for minerals with experimental data. Values of recoil-free fraction determined in this study will facilitate more accurate determinations of cation site occupancies in pyroxenes from Mössbauer data and lend insights into the geometries of the M1 and M2 sites.

Description: The ferric oxyhydroxide minerals akaganéite and schwertmannite are associated with acidic environments and iron alteration on Earth and may be present on Mars as well. These minerals have a tunnel structure and are crystallographically related. The extended visible region reflectance spectra of these minerals are characterized by a broad Fe 3+ electronic transition centered near 0.92 μm, a reflectance maximum near 0.73 μm, and a shoulder near 0.59 μm. The near-infrared (NIR) reflectance spectra of each of these minerals are dominated by broad overtones and combinations of the H 2 O vibration features. These occur near 1.44–1.48 and 1.98–2.07 μm (~6750–6950 and 4830–5210 cm –1 ) in akaganéite spectra, while in schwertmannite spectra they occur at 1.44–1.48 and 1.95–2.00 μm (~6750–6950 and 5005–5190 cm –1 ). Additional bands due to OH vibrational overtones are found near 1.42 μm (~7040 cm –1 ) in akaganéite and schwertmannite spectra and due to OH combination bands in akaganéite spectra at 2.46 μm (4070 cm –1 ) with weaker components at 2.23–2.42 μm (4134–4492 cm –1 ). A strong and broad band is observed near 2.8–3.1 μm (~3300–3600 cm –1 ) in reflectance and transmittance spectra of akaganéite and schwertmannite due to overlapping OH and H 2 O stretching vibrations. H 2 O bending vibrations occur near 1620 cm –1 (~6.17 μm) in akaganéite spectra and near 1630 cm –1 (~6.13 μm) in schwertmannite spectra with additional bands at lower frequencies due to constrained H 2 O molecules. OH bending vibrations occur near 650 and 850 cm –1 (~15.4 and 11.8 μm) in akaganéite spectra and near 700 cm –1 (~14.3 μm) in schwertmannite spectra. Sulfate vibrations are observed for schwertmannite as a 3 triplet at 1118, 1057, and 1038 cm –1 (~8.9, 9.5, and 9.6 μm), 1 at 982 cm –1 (~10.2 μm), 4 near 690 cm –1 (~14.5 μm), and 2 at 608 cm –1 (~16.5 μm). Fe-O bonds occur near 410–470 cm –1 (μm) for akaganéite and schwertmannite. Both minerals readily absorb H 2 O molecules from the environment and adsorb them onto the mineral surfaces and incorporate them into the tunnels. If akaganéite and schwertmannite were present on the surface of Mars they could enable transport of H 2 O from the near-surface to the atmosphere as the partial pressure of H 2 O varies diurnally.

Description: Remote sensing observations have identified aluminate spinel, in the absence of measureable olivine and pyroxene, as a globally distributed component of the lunar crust. Earlier remote sensing observations and returned samples did not indicate the presence of this component, leaving its geologic significance unclear. Here, we report visible to mid-infrared (V-IR) reflectance (300–25 000 nm) and Mössbauer spectra of aluminate spinels, synthesized at lunar-like oxygen fugacity ( f O 2 ), that vary systematically in Fe abundance. Reflectance spectra of particulate (〈45 mm), nominally stoichiometric aluminate spinels display systematic behavior, with bands at 700, 1000, 2000, and 2800 nm increasing in strength with increasing bulk Fe content. The especially strong bands at 2000 and 2800 are discernible for all spinel compositions and saturate at 〈15 Fe# [Fe/(Mg+Fe) x 100, molar]. Absorption bands at 700 and 1000 nm, collectively referred to as the 1000 nm bands, are weaker and become observable at 〉6 Fe#. Although the 2000 and 2800 nm bands are assigned to Fe 2+ IV electronic transitions, spectra of aluminate spinels with excess Al 2 O 3 demonstrate that the strengths of the 1000 nm bands are related to the abundance of Fe 2+ VI . The abundance of Fe 2+ VI depends on bulk Fe content as well as factors that control the degree of structural order-disorder, such as cooling rate. Consequently the strength of the 1000 nm bands are useful for constraining the Fe content and cooling rate of remotely sensed spinel. Controlling for cooling rate, particle size, and f O 2 , we conclude that spinels with 〉12 Fe# (〈88 Mg#) have observable 1000 nm bands under ambient lunar conditions and that only very Mg-rich spinels lack 1000 nm bands in their spectra. This links remote observations of spinel anorthosite to Mg-Suite magmatism. The combined effects of Fe oxidation state, abundance of coexisting plagioclase, and space weathering have not been explored here, and may add additional constraints. The relative strengths of the distinctive 1000 and 2000 nm bands of the spinels associated with pyroclastic deposits at Sinus Aestuum suggest fast cooling rates, possibly in the absence of an extensive vapor cloud.

Description: Microanalysis of Fe 3+ /Fe in geological samples using synchrotron-based X-ray absorption spectroscopy has become routine since the introduction of standards and model compounds. Existing calibrations commonly use least-squares linear combinations of pre-edge data from standard reference spectra with known coordination number and valence state acquired on powdered samples to avoid preferred orientation. However, application of these methods to single mineral grains is appropriate only for isometric minerals and limits their application to analysis of in situ grains in thin sections. In this work, a calibration suite developed by acquiring X-ray absorption near-edge spectroscopy (XANES) data from amphibole single crystals with the beam polarized along the major optical directions (X, Y, and Z) is employed. Seven different methods for predicting %Fe 3+ were employed based on (1) area-normalized pre-edge peak centroid, (2) the energy of the main absorption edge at the location where the normalized edge intensity has the highest R 2 correlation with Fe 3+ /Fe, (3) the ratio of spectral intensities at two energies determined by highest R 2 correlation with Fe 3+ /Fe, (4) use of the slope (first derivative) at every channel to select the best predictor channel, (5 and 6) partial least-squares models with variable and constant numbers of components, and (7) least absolute shrinkage and selection operator models. The latter three sophisticated multivariate analysis techniques for predicting Fe 3+ /Fe show significant improvements in accuracy over the former four types of univariate models. Fe 3+ /Fe can be measured in randomly oriented amphibole single crystals with an accuracy of ±5.5–6.2% absolute. Multivariate approaches demonstrate that for amphiboles main edge and EXAFS regions contain important features for predicting valence state. This suggests that in this mineral group, local structural changes accommodating site occupancy by Fe 3+ vs. Fe 2+ have a pronounced (and diagnostic) effect on the XAS spectra that can be reliably used to precisely constrain Fe 3+ /Fe.

Description: Fluor-schorl, NaFe 2+ 3 Al 6 Si 6 O 18 (BO 3 ) 3 (OH) 3 F, is a new mineral species of the tourmaline supergroup from alluvial tin deposits near Steinberg, Zschorlau, Erzgebirge (Saxonian Ore Mountains), Saxony, Germany, and from pegmatites near Grasstein (area from Mittewald to Sachsenklemme), Trentino, South Tyrol, Italy. Fluor-schorl was formed as a pneumatolytic phase and in high-temperature hydrothermal veins in granitic pegmatites. Crystals are black (pale brownish to pale greyish-bluish, if 〈0.3 mm in diameter) with a bluish-white streak. Fluor-schorl is brittle and has a Mohs hardness of 7; it is non-fluorescent, has no observable parting and a poor/indistinct cleavage parallel to {0001}. It has a calculated density of ~3.23 g/cm 3 . In plane-polarized light, it is pleochroic, O = brown to grey-brown (Zschorlau), blue (Grasstein), E = pale grey-brown (Zschorlau), cream (Grasstein). Fluor-schorl is uniaxial negative, = 1.660(2)–1.661(2), = 1.636(2)–1.637(2). The mineral is rhombohedral, space group R 3 m, a = 16.005(2), c = 7.176(1) Å, V = 1591.9(4) Å 3 (Zschorlau), a = 15.995(1), c = 7.166(1) Å, V = 1587.7(9) Å 3 (Grasstein), Z = 3. The eight strongest observed X-ray diffraction lines in the powder pattern [ d in Å ( I ) hkl ] are: 2.584(100)(051), 3.469(99)(012), 2.959(83)(122), 2.044(80)(152), 4.234(40)(211), 4.005(39)(220), 6.382(37)(101), 1.454(36)(514) (Grasstein). Analyses by a combination of electron microprobe, secondary-ion mass spectrometry (SIMS), Mössbauer spectroscopic data and crystal-structure refinement result in the structural formulae X (Na 0.82 K 0.01 Ca 0.01 0.16 ) Y (Fe 2+ 2.30 Al 0.38 Mg 0.23 Li 0.03 Mn 2+ 0.02 Zn 0.01 0.03 ) 3.00 Z (Al 5.80 Fe 3+ 0.10 Ti 4+ 0.10 ) T (Si 5.81 Al 0.19 O 18 ) (BO 3 ) 3 V (OH) 3 W [F 0.66 (OH) 0.34 ] (Zschorlau) and X (Na 0.78 K 0.01 0.21 ) Y (Fe 2+ 1.89 Al 0.58 Fe 3+ 0.13 Mn 3+ 0.13 Ti 4+ 0.02 Mg 0.02 Zn 0.02 0.21 ) 3.00 Z (Al 5.74 Fe 3+ 0.26 ) T (Si 5.90 Al 0.10 O 18 ) (BO 3 ) 3 V (OH) 3 W [F 0.76 (OH) 0.24 ] (Grasstein). Several additional, newly confirmed occurrences of fluor-schorl are reported. Fluor-schorl, ideally NaFe 2+ 3 Al 6 Si 6 O 18 (BO 3 ) 3 (OH) 3 F, is related to end-member schorl by the substution F -〉 (OH). The chemical compositions and refined crystal structures of several schorl samples from cotype localities for schorl (alluvial tin deposits and tin mines in the Erzgebirge, including Zschorlau) are also reported. The unit-cell parameters of schorl from these localities are slightly variable, a = 15.98–15.99, c = 7.15–7.16 Å, corresponding to structural formulae ranging from ~ X (Na 0.5 0.5 ) Y (Fe 2+ 1.8 Al 0.9 Mg 0.2 0.1 ) Z (Al 5.8 Fe 3+ 0.1 Ti 4+ 0.1 ) T (Si 5.7 Al 0.3 O 18 ) (BO 3 ) 3 V (OH) 3 W [(OH) 0.9 F 0.1 ] to ~ X (Na 0.7 0.3 ) Y (Fe 2+ 2.1 Al 0.7 Mg 0.1 0.1 ) Z (Al 5.9 Fe 3+ 0.1 ) T (Si 5.8 Al 0.2 O 18 ) (BO 3 ) 3 V (OH) 3 W [(OH) 0.6 F 0.4 ]. The investigated tourmalines from the Erzgebirge show that there exists a complete fluor-schorl–schorl solid-solution series. For all studied tourmaline samples, a distinct inverse correlation was observed between the X –O2 distance (which reflects the mean ionic radius of the X -site occupants) and the F content ( r 2 = 0.92). A strong positive correlation was found to exist between the F content and the 〈 Y –O〉 distance ( r 2 = 0.93). This correlation indicates that Fe 2+ -rich tourmalines from the investigated localities clearly tend to have a F-rich or F-dominant composition. A further strong positive correlation ( r 2 = 0.82) exists between the refined F content and the Y–W (F,OH) distance, and the latter may be used to quickly estimate the F content.