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Tungstorhenate heteropolyanions. 2. Synthesis and characterization of enneatungstorhenates(V), -(VI), and -(VII)

The tungstorhenate(V) heteropolyanion [W 9 ReO 32 ] 5 - has been isolated as guanidinium and cesium salts from reaction of [ReO 2 (PPh 3 )(py) 3 ] + with sodium tungstate. Crystallographic analysis of black Cs 5 [W 9 ReO 32 ]·3H 2 O [triclinic, P 1 or P 1̄; a = 10.194(1), b = 11.503(2), c = 9.682(1) Å; α = 100.55(1), β = 115.81(1), γ = 99.13(1)°; Z = 1], based on 3743 reflections, shows the anion to be isostructural with decatungstate, [W 10 O 32 ] 4 - . Refinement in P 1̄ led to reliability indices R = 0.084, R w = 0.046. Electrochemical investigation revealed the existence of Re VI and Re VII analogues, which were hydrolytically unstable in aqueous solution but which were isolated as crystalline tetra- n -butylammonium and tetra- n -heptylammonium salts, respectively, from nonaqueous solvents. The tetra- n -butylammonium salts of [W 9 Re VI O 32 ] 4 - and [W 10 O 32 ] 4 - were shown to be isomorphous by X-ray powder diffraction. Simulation of the Q-band ESR spectrum of [W 9 Re VI O 32 ] 4 - (polycrystalline solid solution in [W 10 O 32 ] 4 - ) gave g x = 1.69(1), g y = 1.66(1), g z = 1.730(2) and 10 4 A x ( 185,187 Re, I = 5 / 2 ) = (−)252(10), 10 4 A y = (−)398(10), 10 4 A z = (−)653(5) cm - 1 . The orthorhombic ESR spectrum proves that the Re atom occupies one of the eight equivalent “equatorial” sites in the decatungstate structure.

Inorganic Chemistry↗

Temperature dependence of polyhedral cage volumes in clathrate hydrates

The polyhedral cage volumes of structure I (sI) (carbon dioxide, methane, trimethylene oxide) and structure II (sII) (methane-ethane, propane, tetrahydrofuran, trimethylene oxide) hydrates are computed from atomic positions determined from neutron powder-diffraction data. The ideal structural formulas for sI and sII are, respectively, S2L6 ?? 46H2O and S16L???8 ?? 136H2O, where S denotes a polyhedral cage with 20 vertices, L a 24-cage, and L??? a 28-cage. The space-filling polyhedral cages are defined by the oxygen atoms of the hydrogen-bonded network of water molecules. Collectively, the mean cage volume ratio is 1.91 : 1.43 : 1 for the 28-cage : 24-cage : 20-cage, which correspond to equivalent sphere radii of 4.18, 3.79, and 3.37 A??, respectively. At 100 K, mean polyhedral volumes are 303.8, 227.8, and 158.8 A??3 for the 28-cage, 24-cage, and 20-cage, respectively. In general, the 20-cage volume for a sII is larger than that of a sI, although trimethylene oxide is an exception. The temperature dependence of the cage volumes reveals differences between apparently similar cages with similar occupants. In the case of trimethylene oxide hydrate, which forms both sI and sII, the 20-cages common to both structures contract quite differently. From 220 K, the sII 20-cage exhibits a smooth monotonic reduction in size, whereas the sI 20-cage initially expands upon cooling to 160 K, then contracts more rapidly to 10 K, and overall the sI 20-cage is larger than the sII 20-cage. The volumes of the large cages in both structures contract monotonically with decreasing temperature. These differences reflect reoriented motion of the trimethyelene oxide molecule in the 24-cage of sI, consistent with previous spectroscopic and calorimetric studies. For the 20-cages in methane hydrate (sI) and a mixed methane-ethane hydrate (sII), both containing methane as the guest molecule, the temperature dependence of the 20-cage volume in sII is much less than that in sI, but sII is overall larger in volume.

Canadian Journal of Physics↗

Mineralogy and petrology of the Cretaceous- Tertiary boundary clay bed and adjacent clay-rich rocks, Raton Basin, New Mexico and Colorado.

The Cretaceous-Tertiary (K-T) boundary is preserved in a sequence of coal-bearing, fluvial rocks in the lower part of the Raton Formation (Late Cretaceous and Paleocene) at several sites in the east-central part of the Raton Basin. The K-T boundary occurs at the top of a kaolinitic claystone layer, commonly referred to as the "boundary clay layer," in an interval of coal and carbonaceous shale. The boundary is defined by the disappearance of certain fossil-pollen taxa. The boundary clay layer also contains shocked quartz grains and abundance anomalies of iridium, chromium, and other elements. Each of these characteristics support the hypothesis of an asteroid impact at the end of the Cretaceous. Small goyazite spheres were also found in the boundary clay bed; however, their origin is uncertain. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and thin-section petrography have shown that the boundary clay bed exhibits unique mineralogic and petrologic characteristics not possessed by other clay-rich beds in coal-bearing rocks of the Raton Basin. The boundary clay bed is composed primarily of well-crystallized kaolinite but also contains subordinate, randomly interstratified, mixed-layer illite/smectite, both of which appear to have been formed by the alteration of vitreous material in a coal-swamp environment. The bulk mineralogy of the boundary clay bed is similar to that of other kaolinite-rich clay beds (tonsteins) that altered in coal swamps from airfall volcanic ash. The alteration process and diagenetic products of the host material in the boundary clay bed, however, differed from those of the tonsteins, resulting in a unique petrographic fabric. The boundary clay bed is characterized by an overall imbricate fabric that may reflect an original vitreous material that included shards, bubbles, and spheres. The original fallout material of the boundary clay bed first altered to "cabbage-like" microspherules, indicating a halloysite or allophane precursor, and then to well-crystallized kaolinite; the well-crystallized kaolinite is the diagenetic stable phase for these rocks at their maximum burial conditions. In comparison, the vitreous components of the tonsteins were altered directly to coarse vermicular and platey kaolinite. Alteration of the original fallout material in the boundary bed was probably rapid, leading to hydrated, disordered, fine-grained clay minerals that formed into curled spherical or tubular shapes. The factors that produced these unique fabrics in the boundary clay bed existed at all K-T sites in the Raton Basin and were much different from those that formed the coarse platey and vermicular fabrics of ordinary tonsteins. The distinctive character of the boundary clay may be due to the unique nature and chemistry of the fallout material and (or) physical or chemical conditions existing shortly after its deposition.

Journal of Sedimentary Petrology↗

Vanadium chlorite from a sandstone-hosted vanadium-uranium deposit, Henry basin, Utah

An unusual vanadium chlorite precipitated during the formation of a vanadium-uranium ore deposit in the Henry Basin, southeastern Utah. The ore deposit formed by reduction and precipitation of U and V in the presence of organic matter at the interface between a stagnant brine and overlying, circulating meteoric water. Some samples of the vanadium chlorite (heated before analysis) contain > 10% V 2 O 5 . In fresh samples, most of the vanadium is in the trivalent oxidation state. X-ray powder diffraction data suggest that Fe and V are concentrated preferentially in the interlayer hydroxide sheets of the chlorite. A d(060) value of 1.52 Å indicates that the chlorite probably has a dioctahedral structure which is distended by the presence of octahedral Fe and V. The vanadium ore zone is flanked by peripheral zones containing perfectly ordered chlorite/smectite. This chlorite/smectite contains much less V than the pure chlorite. This chlorite may have formed by the progressive precipitation of vanadium-rich interlayer hydroxide sheets in the mixed-layer chlorite/smectite in the most reducing portion of the ore zone. The pure chlorite is a IIb polytype, which, for nonvanadiferous analogs, is ordinarily found in high-temperature environments; however, no evidence exists to show that these rocks have ever been exposed to elevated temperatures. In fact, the presence of unreacted smectite in a potassium-rich setting and the low vitrinite reflectance of coalified plant debris indicate a low-temperature history for these sediments.

Utah↗

Reassessment of the volkonskoite-chromian smectite nomenclature problem.

The name volkonskoite was first used in 1830 to describe a bright blue-green, chromium-bearing clay material from the Okhansk region, west of the Ural Mountains, U.S.S.R. Since that time, the name has been applied to numerous members of the smectite group of clay minerals, although the reported chromium content has ranged from 1% to about 30% Cr 2 O 3 . The name has also been applied to some chromian chlorites. Because volkonskoite has been used for materials that differ not only in their chromium content but also in their basic structure, the species status of the mineral has been unclear. To resolve this uncertainty, two specimens of volkonskoite from (1) Mount Efimiatsk, the type locality in the Soviet Union (USNM 16308) and (2) the Okhansk region in the Perm Basin, U.S.S.R. (USNM R4820), were examined by several mineralogical techniques. Neotype sample 16308 has the following structural formula: (Ca 0.11 Mg 0.11 Fe 2+ 0.03 K 0.02 )(Cr 1.18 Mg 0.78 Fe 3+ 0.29 Ca 0.02 )(Si 3.50 Al 0.51 )O 10 (OH) 2 ⋅3.64H 2 O. Sample R4820 has the following structural formula: (Ca 0.25 Mg 0.05 Fe 2+ 0.01 K 0.03 Mn 0.01 )(Cr 1.07 Mg 0.75 Fe 3+ 0.35 (Si 3.59 Al 0.43 )O 10 (OH) 2 ⋅4.22H 2 O. Mössbauer spectroscopy indicates that 91% and 98% of the iron is present as Fe 3+ in samples 16308 and R4820, respectively. X-ray powder diffraction patterns of both samples have broad lines corresponding to minerals of the smectite group. On the basis of these data, volkonskoite appears to be a dioctahedral member of the smectite group that contains chromium as the dominant cation in the octahedral layer. Smectites containing less than this amount of octahedral chromium should not be called volkonskoite, but should be named by chemical element adjectives, e.g., chromian montmorillonite, chromian nontronite.

Clays and Clay Minerals↗

Considerations and applications of the illite/smectite geothermometer in hydrocarbon-bearing rocks of Miocene to Mississippian age

Empirical relationships between clay mineral transformations and temperature provide a basis for the use of clay minerals as geothermometers. Clay-mineral geothermometry has been applied mainly to diagenetic, hydrothermal, and contact- and burial-metamorphic settings to better understand the thermal histories of migrating fluids, hydrocarbon source beds, and ore and mineral formation. Quantitatively, the most important diagenetic clay mineral reaction in sedimentary rocks is the progressive transformation of smectite to illite via mixed-layer illite/smectite (I/S). Changes in both the illite/smectite ratio and ordering of I/S, as determined from X-ray powder diffraction profiles, correlate with changes in temperature due to burial depth. Although the smectite-to-illite reaction may be influenced by several factors, reaction progress appears to be strongly controlled by temperature. Studies show that the model proposed by Hoffman and Hower in 1979 is applicable in burial diagenetic settings from about 5 to 330 Ma, and includes most rocks about Miocene to Mississippian in age. Reliability of the I/S geothermometer is, however, dependent upon a good understanding of the rock's original clay-mineral composition. Changes in the ordering of I/S are particularly useful in the exploration for hydrocarbons because of the common coincidence between the temperatures for the conversion from random-to-ordered I/S and those for the onset of peak, or main phase, oil generation. Here, the utility of the I/S geothermometer is reviewed in hydrocarbon-bearing rocks of Miocene to Mississippian age. Using three common applications, the I/S geothermometer is compared to other mineral geothermometers, organic maturation indices, and grades of indigenous hydrocarbons. Good agreement between changes in ordering of I/S and calculated maximum burial temperatures or hydrocarbon maturity suggests that I/S is a reliable semiquantitative geothermometer and an excellent measures of thermal maturity.

Clays and Clay Minerals↗

Characterization of microbially Fe(III)-reduced nontronite: Environmental cell-transmission electron microscopy study

Microstructural changes induced by the microbial reduction of Fe(III) in nontronite by Shewanella oneidensis were studied using environmental cell (EC)-transmission electron microscopy (TEM), conventional TEM, and X-ray powder diffraction (XRD). Direct observations of clays by EC-TEM in their hydrated state allowed for the first time an accurate and unambiguous TEM measurement of basal layer spacings and the contraction of layer spacing caused by microbial effects, most likely those of Fe(III) reduction. Non-reduced and Fe(III)-reduced nontronite, observed by EC-TEM, exhibited fringes with mean d 001 spacings of 1.50 nm (standard deviation, σ = 0.08 nm) and 1.26 nm (σ = 0.10 nm), respectively. In comparison, the same samples embedded with Nanoplast resin, sectioned by microtome, and observed using conventional TEM, displayed layer spacings of 1.0–1.1 nm (non-reduced) and 1.0 nm (reduced). The results from Nanoplast-embedded samples are typical of conventional TEM studies, which have measured nearly identical layer spacings regardless of Fe oxidation state. Following Fe(III) reduction, both EC- and conventional TEM showed an increase in the order of nontronite selected area electron diffraction patterns while the images exhibited fewer wavy fringes and fewer layer terminations. An increase in stacking order in reduced nontronite was also suggested by XRD measurements. In particular, the ratio of the valley to peak intensity ( v/p ) of the 1.7 nm basal 001 peak of ethylene glycolated nontronite was measured at 0.65 (non-reduced) and 0.85 (microbially reduced).

Clays and Clay Minerals↗

Ferromanganese micronodules from the surficial sediments of Georges Bank

Ferromanganese micronodules have been found on Georges Bank, off the U.S. northeast coast, distributed throughout the surficial sediments within an area about 125 km long and at least 12 km wide. These coarse, sand-sized concretions have precipitated from metal-rich interstitial waters and contain many of the textural and structural features common to other neritic nodules. Most of the nodules have accreted around detrital grains, and X-ray powder diffraction analyses indicate the presence of geothite and vernadite (  -MnO 2 ) in the ferromanganese layers. Chemical analyses of the micronodules, when compared with similar data on deep-sea manganese nodules, reveal lower Mn/Fe ratios, significantly higher concentrations of V and As, comparable values of Mo, and an order of magnitude less of Co, Ni, Ce and most other metals.

Georges Bank↗

Ordonezite from the Theodoso Soto Mine, Sapioris, Durango, Mexico: New data and structure refinement

A new occurrence of the rare mineral species ordonezite has been found at the Theodoso Soto tin mine, near Sapioris, Durango, Mexico. The average composition of the samples is (Zn 0.98 Fe 0.02 ) Σ1.00 Sb 2.00 O 6 ; the core of the crystals is slightly richer in Fe than the rim. The mineral is uniaxial (+), with all n greater than 2.30 (n calc is 2.38 at 589 nm); D obs 6.66 g/cm 3 , D calc 6.67 g/cm 3 . It is isostructural with ferrotapiolite, with a 4.668(2), c 9.269(6) A (from powder-diffraction data), space group P4 2 /mnm, and is twinned on {103}. Its crystal structure, refined to R=4.1, wR=4.3% using 163 observed reflections, is fully cation-ordered.

Durango↗

Nevadaite, (Cu2+, Al, V3+)6 [Al8 (PO4)8 F8] (OH 2 (H2O)22, a new phosphate mineral species from the Gold Quarry mine, Carlin, Eureka County, Nevada: Description and crystal structure

Nevadaite, (Cu 2+ , □, Al, V 3+ ) 6 (PO 4 ) 8 F 8 (OH) 2 (H 2 O) 22 , is a new supergene mineral species from the Gold Quarry mine, near Carlin, Eureka County, Nevada, U.S.A. Nevadaite forms radiating clusters to 1 mm of prismatic crystals, locally covering surfaces more that 2 cm across; individual crystals are elongate on [001] with a length:width ratio of > 10:1 and a maximum diameter of ~30 μm . It also occurs as spherules and druses associated with colorless to purple-black fluellite, colorless wavellite, strengitevariscite, acicular maroon-to-red hewettite, and rare anatase, kazakhstanite, tinticite, leucophosphite, torbernite and tyuyamunite. Nevadaite is pale green to turquoise blue with a pale powder-blue streak and a vitreous luster; it does not fluoresce under ultra-violet light. It has no cleavage, a Mohs hardness of ~3, is brittle with a conchoidal fracture, and has measured and calculated densities of 2.54 and 2.55 g/cm 3 , respectively. Nevadaite is biaxial negative, with 1.540, β 1.548, γ 1.553, 2 V (obs.) = 76°, 2 V (calc.) = 76° , pleochroic with X pale greenish blue, Y very pale greenish blue, Z blue, and with absorption Z ≫ X > Y and orientation X = c, Y = a, Z = b. Nevadaite is orthorhombic, space group P 2 1 mn , a 12.123(2), b 18.999(2), c 4.961(1) Å, V 1142.8(2) Å 3 , Z = 1, a:b:c = 0.6391:1:0.2611 . The strongest seven lines in the X-ray powder-diffraction pattern [ d in Å(I)( hkl )] are: 6.077(10)(200), 5.618(9)(130), 9.535(8)(020), 2.983(6)(241), 3.430(4)(041), 2.661(4)(061), and 1.844(4)(352). A chemical analysis with an electron microprobe gave P 2 O 5 32.54, Al 2 O 3 27.07, V 2 O 3 4.24, Fe 2 O 3 0.07, CuO 9.24, ZnO 0.11, F 9.22, H 2 O (calc.) 23.48, OH ≡ F–3.88, sum 102.09 wt.% ; the valence states of V and Fe, and the amount of H 2 O , were determined by crystal-structure analysis. The resulting empirical formula on the basis of 63.65 anions ( including 21.65 H 2 O pfu ) is ( (Cu 2.00 2+ Zn 0.02 V 0.98 3+ Fe 0.01 3+ Al 1.15 ) ∑ 4.16 Al 8 P 7.90 O 32 [F 8.37 (OH) 1.63 ] ∑10 (H 2 O) 21.65 . The crystal structure of nevadaite was solved by direct methods and refined to an R index of 4.0% based on 1307 observed reflections collected on a four-circle diffractometer with Mo K α X-radiation . The structure consists of ordered layers of vertex-sharing octahedra and tetrahedra alternating with layers of disordered vertex-sharing and face-sharing octahedra in the b direction. [Alϕ 5 ] chains of octahedra are decorated by (PO 4 ) tetrahedra that share vertices with octahedra adjacent in the chain . These chains link in the c direction by sharing vertices between octahedra and tetrahedra to form an ordered layer of the form [Al 8 (PO 4 ) 8 F 8 (H 2 O) 8 ] . In the disordered layer, octahedra containing positionally disordered Cu 2+ , V 3+ , Al and □ (vacancy) share trans faces to form columns that link by sharing octahedron vertices to form ribbons extending in the c direction; the resulting layer has the form {(Cu 2 2+ □ 2 V 3+ ,Al) ∑6 (H 2 O) 12 (OH) 2 (H 2 O) x }, x ≈ 2 . The layers link in the b direction by sharing vertices between octahedra and tetrahedra. Although decorated chains topologically equivalent to that in nevadaite are common in many oxysalt minerals, its chain is geometrically distinct from those topologically equivalent chains. The M – M linkage along the [ M ϕ 5 ] chains in most minerals take place through trans vertices of the octahedra, with one example of linkage through cis vertices; in nevadaite, the M – M linkage involves both trans and cis vertices, as does the chain in slavíkite . In most of these decorated chains, alternate tetrahedra along the chain occur either in a trans or a cis arrangement. In nevadaite and slavíkite, the tetrahedra are arranged in both trans and cis arrangements; the arrangements in these two minerals are geometrically distinct, however.

Nevada↗

Terlinguacreekite, Hg2+3O2 Cl2, a new mineral species from the Perry pit, Mariposa mine, Terlingua mining district, Brewster County, Texas, U.S.A

Terlinguacreekite, ideally Hg 2+ 3 O 2 Cl 2 , has a very pronounced subcell that is orthorhombic, space-group choices Imam , Imcm , Ima 2 and I 2 cm , with unit-cell parameters refined from powder data: a 6.737(3), b 25.528(10), c 5.533(2) Å, V 951.6(6) Å 3 , a:b:c 0.2639:1:0.2167, Z = 8. The true symmetry, supercell unit-cell parameters, and details regarding the crystal structure are unknown. The strongest nine lines of the X-ray powder-diffraction pattern [ d in Å ( I )(subcell hkl )] are: 5.413(30)(011), 4.063(80)(121), 3.201(50)(080), 3.023(50)(161), 2.983(60)(240), 2.858(30)(211), 2.765(50)(002), 2.518(100b)(091, 251) and 2.026(30)(242). The mineral is found in an isolated area measuring approximately 1 × 0.5 m in the lower level of the Perry pit, Mariposa mine, Terlingua mining district, Brewster County, Texas (type locality), as mm-sized anhedral dark orange to reddish orange crusts of variable thickness on calcite, and rarely as 0.5 mm-sized aggregates of crystals of the same color. It has also been identified at the McDermitt mine, Humboldt County, Nevada, U.S.A., where it occurs with kleinite and calomel in silicified volcanic rocks and sediments. Terlinguacreekite is a secondary phase, most probably formed from the alteration of primary cinnabar or native mercury. At Terlingua, most crusts are thin, almost cryptocrystalline, with no discernable forms, and are resinous and translucent to opaque. Crystals are up to 0.2 mm in length, subhedral, acicular to prismatic, elongation [001], with a maximum length-to-width ratio of 4:1. They are vitreous, transparent, and some crystals have brightly reflecting faces, which may be {010} and {110}. The streak is yellow, and the mineral is brittle with an uneven fracture, no observable cleavage, and is soft, nonfluorescent under both long- and short-wave ultraviolet light. D (calc.) is 9.899 g/cm 3 (empirical formula). Material from the McDermitt mine is reversibly photosensitive, and turns from vivid orange to black in strong light. In reflected plane-polarized light, it is bluish grey, with very weak (in air) to distinct (in oil) bireflectance, nonpleochroic, and distinctly anisotropic, with colors masked by ubiquitous yellowish orange to orange internal reflections. Measured values of reflectance obtained in air and in oil are tabulated. Averaged results of electron-microprobe analysis give HgO 92.03, Cl 9.54, Br 1.22, sum 102.79, less O = Cl + Br 2.28, total 100.51 wt.%. The empirical formula is Hg 2+ 3.00 O 2.00 (Cl 1.90 Br 0.11 ) ∑2.01 , based on O + Cl + Br = 4 atoms per formula unit. The mineral name recalls the creek that flows through the Terlingua mining district and into the Rio Grande River.

Texas↗

Mg- and K-bearing borates and associated evaporites at Eagle Borax spring, Death Valley, California: A spectroscopic exploration

Efflorescent crusts at the Eagle Borax spring in Death Valley, California, contain an array of rare Mg and K borate minerals, several of which are only known from one or two other localities. The Mg- and/or K-bearing borates include aristarainite, hydroboracite, kaliborite, mcallisterite, pinnoite, rivadavite, and santite. Ulexite and probertite also occur in the area, although their distribution is different from that of the Mg and K borates. Other evaporite minerals in the spring vicinity include halite, thenardite, eugsterite, gypsum-anhydrite, hexahydrite, and bloedite. Whereas the first five of these minerals are found throughout Death Valley, the last two Mg sulfates are more restricted in occurrence and are indicative of Mg-enriched ground water.Mineral associations observed at the Eagle Borax spring, and at many other borate deposits worldwide, can be explained by the chemical fractionation of borate-precipitating waters during the course of evaporative concentration. The Mg sulfate and Mg borate minerals in the Eagle Borax efflorescent crusts point to the fractionation of Ca by the operation of a chemical divide involving Ca carbonate and Na-Ca borate precipitation in the subsurface sediments. At many other borate mining localities, the occurrence of ulexite in both Na borate (borax-kernite) and Ca borate (ulexite-colemanite) deposits similarly reflects ulexite's coprecipitation with Ca carbonate at an early concentration stage. Such ulexite may perhaps be converted to colemanite by later reaction with the coexisting Ca carbonate--the latter providing the additional Ca (super 2+) ions needed for the conversion. Mg and Ca-Mg borates are the expected late-stage concentration products of waters forming ulexite-colemanite deposits and are therefore most likely to occur in the marginal zones or nearby mud facies of ulexite-colemanite orebodies. Under some circumstances, Mg and Ca-Mg borates might provide a useful prospecting guide for ulexite-colemanite deposits, although the high solubility of Mg borate minerals may prevent their formation in lacustrine settings and certainly inhibits their geologic preservation. The occurrence of Mg borates in borax-kernite deposits is also related to fractionation processes and points to the operation of an Mg borate chemical divide, characterized by Mg borate precipitation ahead of Mg carbonate. All of these considerations imply that Mg is a significant chemical component of many borate-depositing ground waters, even though Mg borate minerals may not be strongly evident in borate orebodies.The Eagle Borax spring borates and other evaporite minerals were studied using spectroscopic and X-ray powder diffraction methods, which were found to be highly complementary. Spectral reflectance measurements provide a sensitive means for detecting borates present in mixtures with other evaporites and can be used to screen samples rapidly for X-ray diffraction analysis. The apparently limited occurrence of Mg and K borate minerals compared to Ca and Na borates may stem partly from the inefficiency of X-ray diffraction methods for delineating the mineralogy of large and complex deposits. Spectral reflectance measurements can be made in the laboratory, in the field, on the mine face, and even remotely. Reflectance data should have an important role in studies of existing deposit mineralogy and related chemical fractionation processes, and perhaps in the discovery of new borate mineral resources.

Economic Geology↗

Spectral reflectance properties (0.4-2.5 um) of secondary Fe-oxide, Fe-hydroxide, and Fe-sulfate-hydrate minerals associated with sulfide-bearing mine waste

Fifteen Fe-oxide, Fe-hydroxide, and Fe-sulphate-hydrate mineral species commonly associated with sulphide bearing mine wastes were characterized by using X-ray powder diffraction and scanning electron microscope methods. Diffuse reflectance spectra of the samples show diagnostic absorption features related to electronic processes involving ferric and/or ferrous iron, and to vibrational processes involving water and hydroxyl ions. Such spectral features enable field and remote sensing based studies of the mineral distributions. Because secondary minerals are sensitive indicators of pH, Eh, relative humidity, and other environmental conditions, spectral mapping of these minerals promises to have important applications to mine waste remediation studies. This report releases digital (ascii) spectra (spectral_data_files.zip) of the fifteen mineral samples to facilitate usage of the data with spectral libraries and spectral analysis software. The spectral data are provided in a two-column format listing wavelength (in micrometers) and reflectance, respectively.

Open-File Report↗

Origin of manganese deposits of Busuanga Island, Philippines

The manganese deposits of Busuanga Island, Palawan, are tabular and broadly lenticular bodies which lie conformably within a thick sequence of deformed abort beds. The purpose of this study is to determine the probable mode of origin of the deposits. Similar deposits in other parts of the world have been described by others as products of several different genetic processes. Field and laboratory methods of research were employed in the course of the investigation. Detailed geologic mapping was done on the surface and underground, and many samples of rocks and ores were obtained. Later, intensive study of samples from four typical deposits and from the rooks in the surrounding areas was undertaken, using a variety of laboratory techniques. Microscopic study of thin sections and polished surfaces was supplemented by X-ray and chemical work. More than one hundred X-ray diffraction powder photographs were made to identify minerals, and qualitative chemical studies were made of a number of aamples by use of the X-ray spectrograph. In addition, quantitative chemical analyses were made of certain samples. Finally, published accounts of the occurrence and geological behavior of manganese and silica were consulted to aid in interpretation of the data at hand. Oherty layers in the manganese deposits are lithologically similar to the chart wallrooks and country rook beds. Radiolarian fossils are common in the chart and are also found in some ore specimens. Manganese content of the wallrocks and the country rock beds, however, in essentially nil. The manganese deposits contain mostly psilomelane-type oxides in their near-surface parts, and in the deepest mines this ore grades downward into siliceous protore. In three of the deposits studied, the protore consists mainly of braanite and quartz; in the fourth deposit, hausmannite and the silicate alleghatvite make up the milk of the protore. Some of the protoro is massive, but cherty stones are commonly well layered parallel to the wall rock structure. Grain size is very small, but, like the silica in the chert beds, becomes relatively coarse where the rocks are much deformed. No evidence of large-scale replacement or cross-cutting veins is found in the protores. It is concluded that the original manganiferous deposits were largely non-clastic or oolloidal marine sediments laid down in a reducing environment. The protorea were developed from these beds by processes of diagenesis and low-grade regional metamorphism. The protores were in turn altered to black oxide ore by near-surface agencies during the present erosion cycle. Particular interest is attached to the occurrence of alleghanyite and traces of pyroxmangite and hubnerite(?) in the protorea.

Busuanga Island↗

Pb-Bi-Ag-Cu-(Hg) chemistry of galena and some associated sulfosalts. A review and some new data from Colorado California and Pennsylvania

Galena, associated with Pb-Bi-Ag sulfosalts and simple sulfides, contains varied amounts of Ag and Bi in the Dandy vein system, Idarado mine, Ouray, Colorado; the Jackass mine, Darwin District, California; and the Leadville district, Colorado. Silver- and bismuth-bearing galena associated with minor amounts of pyrite, chalcopyrite and sphalerite occur at the Pequea mine, Lancaster County, Pennsylvania. Ag and Bi contents in the Dandy suite of galena range from about 1.4 to 3.4 and 2.5 to 6.5 wt.% respectively, and are comparable or lower in galena from the other localities. Exsolved matildite is present in galena from the Dandy, Jackass and Leadville localities. The presence in significant amounts of both Ag and Bi in a Pb-rich sulfide system is necessary for formation of PbSss (galena solid-solution). If Ag (especially) and Bi (to a lesser extent) are absent, the galena formed will be essentially pure PbS. Some minor Sb may substitute for Bi. Compositional data for all of the galena samples are in agreement with a previously proposed linear relationship between a and Ag-Bi(Sb) content. Matildite and seven additional Pb-Bi-Ag-Cu sulfosalts have been identified from the Dandy vein system, based on electron-microprobe analyses and some X-ray powder-diffraction data.

Canadian Mineralogist↗

Crystal chemistry of the natural vanadium bronzes

The crystal chemistry of the natural vanadium bronze minerals is reviewed on the basis of published information and new studies (mainly by X-ray powder-diffraction methods) using type material wherever possible. The known V bronze minerals are divided into three categories: 1) the hewettite group, 2) the straczekite group, 3) other structure types including navajoite, schubnelite, fervanite, shcherbinaite, bannermanite, and melanovanadite. All known structures associated with the fibrous V bronzes (fiber spacing 3.6 A??) can be considered as various lateral linkages (into sheets or networks) of only two types of polyvanadate chains: 1) a divanadate chain (V2O6)n consisting of alternating square pyramids, and 2) a tetravanadate chain (V4O12)n consisting of four highly condensed single octahedral chains. -from Authors

American Mineralogist↗

Hogtuvaite, a new beryllian member of the aenigmatite group from Norway, with new X-ray data on aenigmatite

Hogtuvaite is a new beryllian member of the aenigmatite group that was discovered in Nordland County, Norway. It is a metamorphic mineral, hosted by Proterozoic granitic gneisses and mafic pegmatites of metamorphic origin. Compositional variations within and between gneiss-hosted samples of hogtuvaite are minimal; however, pegmatite-hosted samples of hogtuvaite are significantly different, containing less Al and Sn, and more Ti and Mn, than those from the gneisses. The mineralogical, optical and crystallographic properties of hogtuvaite are described. A new and uniquely indexed set of X-ray powder diffraction data for aenigmatite is presented. -from Authors

Canadian Mineralogist↗

Jensenite, Cu 3 Te (super 6+) O 6 .2H 2 O, a new mineral species from the Centennial Eureka Mine, Tintic District, Juab County, Utah

Jensenite, ideally Cu 3 Te (super 6+) O 6 .2H 2 O, is monoclinic, P2 1 /n (14), with unit-cell parameters refined from powder data: a 9.204(2), b 9.170(2), c 7.584(1) Aa, beta 102.32(3) degrees , V 625.3(3) Aa 3 , a:b:c 1.0037:1:0.8270, Z = 4. The strongest six reflections of the X-ray powder-diffraction pattern [d in Aa(I)(hkl)] are: 6.428(100)(101,110), 3.217(70)(202), 2.601(40)(202), 2.530(50)(230), 2.144(35)(331) and 1.750(35)(432). The mineral is found on the dumps of the Centennial Eureka mine, Juab County, Utah, where it occurs as isolated crystals or as groups of crystals on drusy white quartz. Associated minerals are mcalpineite, xocomecatlite and unnamed Cu(Mg,Cu,Fe,Zn) 2 Te (super 6+) O 6 .6H 2 O. Individual crystals of jensenite are subhedral to euhedral, and form simple rhombs that are nearly equant. Some crystals are slightly elongate [101], with a length-to-width ratio up to 2:1. The largest crystal is approximately 0.4 mm in size; the average size is between 0.1 and 0.2 mm. Cleavage {101} fair. Forms are: {101} major; {110} medium; {100} minor; {301}, {201}, {203}, {102}, {010} very small. The mineral is transparent, emerald green, with a less intense streak of the same color and an uneven fracture. Jensenite is adamantine, brittle and nonfluorescent; H (Mohs) 3-4; D (calc.) 4.78 for the idealized formula, 4.76 g/cm 3 for the empirical formula. In a polished section, jensenite is very weakly bireflectant and nonpleochroic. In reflected plane-polarized light in air, it is a nondescript grey, and in oil, it is a much darker grey in color with a brownish tint, with ubiquitous bright green internal reflections. Anisotropy is not detectable. Measured values of reflectance, in air and in oil, are tabulated. Electron-microprobe analyses yielded CuO 50.91, ZnO 0.31, TeO 3 38.91, H 2 O (calc.) [8.00], total [98.13] wt.%. The empirical formula, derived from crystal-structure analysis and electron-microprobe analyses, is (Cu (sub 2.92) Zn (sub 0.02) ) (sub Sigma 2.94) Te (super 6+) (sub 1.01) O (sub 5.97) .2.03H 2 O, based on O = 8. The mineral name honors Martin C. Jensen, Reno, Nevada, who discovered the mineral.

Canadian Mineralogist↗