Beschreibung: 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.

Beschreibung: 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.

Beschreibung: 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.

Beschreibung: Although Fe-sulfate minerals occur only rarely on Earth as alteration products of sulfidic basalts or in hydrothermal systems, multiple lines of evidence point to the importance of Fe- (and other) sulfate minerals on the surface of Mars. One such martian data set comes from the MIMOS II Mössbauer spectrometers on the Mars Exploration Rovers, which acquired hundreds of spectra from the martian surface at two locations. Interpretation of those spectra has been limited by the lack of a comprehensive set of laboratory analog spectra of the broad range of naturally occurring sulfate minerals. Accordingly, this study reports Mössbauer data of 98 samples representing 47 different sulfate mineral species, all containing six- or higher-coordinated Fe. The resultant Mössbauer parameters are related to the local polyhedral environment around the Fe cation in each mineral to explain variations in spectral characteristics. Results show that the size of the coordination polyhedron is the best predictor of quadrupole splitting, which increases with both octahedral volume and mean bond length. Species within groups of structurally similar minerals are shown to have comparable spectral peaks that generally fall within small ranges. Although coordination polyhedron geometry is not necessarily unique to any particular mineral species or group, Mössbauer data can be used to help constrain mineral identifications from martian spectra. The number of mineral species is large, but the range of crystal structures and hyperfine parameters may be small, so that in many cases, individual minerals cannot be uniquely fingerprinted. Examples would include quenstedtite, coquimbite, kornelite, and lausenite, which have indistinguishable spectra, as do apjohnite, bilinite, dietrichite, and römerite. Overlap of Mössbauer parameters is a particular complication for identification of Fe 3+ -rich phases because the range of Mössbauer parameters for Fe 3+ in any coordination number is so small. Previous analyses of martian Mössbauer spectra reported the presence of jarosite ( Klingelhöfer et al. 2004 ; Morris et al. 2004 ) and an unspecific ferric sulfate ( Morris et al. 2008 ). New data presented here indicate that botryogen, metasideronatrite, and slavikite exhibit Mössbauer spectra similar to those attributed to jarosite at Meridiani Planum. Fibroferrite and rhomboclase have parameters similar to those observed at Arad Samra, and copiapite and parabutlerite could be present at Tyrone Mount Darwin and Berkner Island. Unique mineral identifications are generally not possible from Mössbauer data alone, particularly for paramagnetic phases, although combining Mössbauer results with other data sets enables a greater level of confidence in constraining mineralogy. This study provides a new expansive data set for future interpretation of iron sulfates on Mars.

Beschreibung: Visible to near-infrared (V-NIR) remote sensing observations have identified spinel in various locations and lithologies on the Moon. Experimental studies have quantified the FeO content of these spinels ( Jackson et al. 2014 ), however the chromite component is not well constrained. Here we present compositional and spectral analyses of spinel synthesized with varying chromium contents at lunar-like oxygen fugacity ( f O 2 ). Reflectance spectra of the chromium-bearing synthetic spinels (Cr# 1–29) have a narrow (~130 nm wide) absorption feature centered at ~550 nm. The 550 nm feature, attributed to octahedral Cr 3+ , is present over a wide range in iron content (Fe# 8–30) and its strength positively correlates with spinel chromium content [ln(reflectance min ) = –0.0295 Cr# – 0.3708]. Our results provide laboratory characterization for the V-NIR and mid-infrared (mid-IR) spectral properties of spinel synthesized at lunar-like f O 2 . The experimentally determined calibration constrains the Cr# of spinels in the lunar pink spinel anorthosites to low values, potentially Cr# 〈 1. Furthermore, the results suggest the absence of a 550 nm feature in remote spectra of the Dark Mantle Deposits at Sinus Aestuum precludes the presence of a significant chromite component. Combined, the observation of low chromium spinels across the lunar surface argues for large contributions of anorthositic materials in both plutonic and volcanic rocks on the Moon.

Beschreibung: 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.

Beschreibung: This study of the spectral properties of Ca-sulfates was initiated to support remote detection of these minerals on Mars. Gypsum, bassanite, and anhydrite are the currently known forms of Ca-sulfates. They are typically found in sedimentary evaporites on Earth, but can also form via reaction of acidic fluids associated with volcanic activity. Reflectance, emission, transmittance, and Raman spectra are discussed here for various sample forms. Gypsum and bassanite spectra exhibit characteristic and distinct triplet bands near 1.4–1.5 μm, a strong band near 1.93–1.94 μm, and multiple features near 2.1–2.3 μm attributed to H 2 O. Anhydrite, bassanite, and gypsum all have SO 4 combination and overtone features from 4.2–5 μm that are present in reflectance spectra. The mid-IR region spectra exhibit strong SO 4 3 and 4 vibrational bands near 1150–1200 and 600–680 cm –1 (~8.5 and 16 μm), respectively. Additional weaker features are observed near 1005–1015 cm –1 (~10 μm) for 1 and near 470–510 cm –1 (~20 μm) for 2 . The mid-IR H 2 O bending vibration occurs near 1623–1630 cm –1 (~6.2 μm). The visible/near-infrared region spectra are brighter for the finer-grained samples. In reflectance and emission spectra of the mid-IR region the 4 bands begin to invert for the finer-grained samples, and the 1 vibration occurs as a band instead of a peak and has the strongest intensity for the finer-grained samples. The 2 vibration is a sharp band for anhydrite and a broad peak for gypsum. The band center of the 1 vibration follows a trend of decreasing frequency (increasing wavelength) with increasing hydration of the sample in the transmittance, Raman, and reflectance spectra. Anhydrite forms at elevated temperatures compared to gypsum, and at lower temperature, salt concentration, and pH than bassanite. The relative humidity controls whether bassanite or gypsum is stable. Thus, distinguishing among gypsum, bassanite, and anhydrite via remote sensing can provide constraints on the geochemical environment.

Beschreibung: Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe 3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe 3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yield accurate results from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 x 1 μm pixel sizes.

Beschreibung: Experimental silicate glasses are often used as analog and calibration material for terrestrial and planetary materials. Measurements of Fe oxidation state using electron energy loss spectroscopy (EELS) in an aberration-corrected scanning transmission electron microscope (ac-STEM) show that a suite of experimental silicate (e.g., basaltic, andesitic, rhyolitic) glasses have spatially heterogeneous oxidation states at scales of tens of nanometers. Nano-crystals are observed in several of the glasses, indicating nucleation and incipient crystallization not seen at the scale of electron microprobe analysis (EMPA). Glasses prepared in air are uniformly oxidized while glasses prepared at the iron-wustite (IW) or quartz-fayalite-magnetite (QFM) buffers range from reduced to highly oxidized. EELS spectral shapes indicate that oxidized glasses have tetrahedral Fe 3+ . The nanoscale compositional and structural heterogeneities present in the experimental glasses mean that the suitability of such glasses as analogs for natural materials and calibration standards depends strongly on the scale of the measurements being done. The electron beam quickly damages silicate glass, but data showing changes in oxidation state among and within samples can be obtained with careful control of the beam current and dwell time. Determination of oxidation state in silicate glasses via STEM-EELS is very challenging, and accurate and reliable measurements of Fe 3+ /Fe require careful sample preparation and control of microscope conditions and benefit from comparison to complementary techniques.