The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ∼380,000 m³ of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS₂; arsenopyrite, FeAsS; berthierite, FeSb₂S₄) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As⁵⁺). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As₂O₅ and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As⁵⁺. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.     

Surface complexation modeling of Co(II) adsorption on mixtures of hydrous ferric oxide, quartz and kaolinite

Co sorption was measured as a function of pH, ionic strength (0.001-0.1 M NaNO₃) and sorbate/sorbent ratio on pure quartz, HFO and kaolinite and on binary and ternary mixtures of the three solids. Sorption data measured for the pure solids were used to derive internally-consistent diffuse layer surface complexation model (DLM) stability constants for Co sorption. Co sorption on HFO could be adequately modeled over a broad range of ionic strengths and sorbate/sorbent ratios with a two variable-charge site model. Fits based on a single variable-charge site model were reasonable, but were improved by using ionic-strength dependent stability constants. A single variable-charge site model with an additional permanent ion exchange site produced the best fit to Co edges measured on kaolinite over a range of ionic strength and sorbate/sorbent ratios. These DLM fits were also improved by using ionic-strength dependent stability constants. The DLM approach could not adequately describe the slope of Co sorption edges on quartz. This study demonstrates that for accurate prediction of Co sorption over wide ranges of ionic strength and sorbate/sorbent ratio, the DLM may require ionic-strength dependent stability constants. DLM stability constants for Co sorption derived for the pure solids were used to predict sorption as a function of pH and solid concentration on binary and ternary mixtures of the three solids. Discrepancies between predictions and measurements were quantitatively similar to those observed for the pure mineral systems. Thus, a simple component additivity approach provides useful predictions of metal sorption in the mixed solid systems.     

Surface complexation modeling of Cu(II) adsorption on mixtures of hydrous ferric oxide and kaolinite

Background  

The application of surface complexation models (SCMs) to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids.     

Electrical conductivity of hydrous basaltic melts: implications for partial melting in the upper mantle

The Earth’s uppermost asthenosphere is generally associated with low seismic wave velocity and high electrical conductivity. The electrical conductivity anomalies observed from magnetotelluric studies have been attributed to the hydration of mantle minerals, traces of carbonatite melt, or silicate melts. We report the electrical conductivity of both H₂O-bearing (0–6 wt% H₂O) and CO₂-bearing (0.5 wt% CO₂) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO₂ hardly affects conductivity at such a concentration level. The effect of water on the conductivity of basaltic melt is markedly larger than inferred from previous measurements on silicate melts of different composition. The conductivity of basaltic melts with more than 6 wt% of water approaches the values for carbonatites. Our data are reproduced within a factor of 1.1 by the equation log σ = 2.172 − (860.82 − 204.46 w ^0.5)/(T − 1146.8), where σ is the electrical conductivity in S/m, T is the temperature in K, and w is the H₂O content in wt%. We show that in a mantle with 125 ppm water and for a bulk water partition coefficient of 0.006 between minerals and melt, 2 vol% of melt will account for the observed electrical conductivity in the seismic low-velocity zone. However, for plausible higher water contents, stronger water partitioning into the melt or melt segregation in tube-like structures, even less than 1 vol% of hydrous melt, may be sufficient to produce the observed conductivity. We also show that ~1 vol% of hydrous melts are likely to be stable in the low-velocity zone, if the uncertainties in mantle water contents, in water partition coefficients, and in the effect of water on the melting point of peridotite are properly considered.     

Tourmaline from the rare-element Pinilla pegmatite, (Central Iberian Zone, Zamora, Spain): chemical variation and implications for pegmatitic evolution

Summary Tourmaline is an ubiquitous constituent in the Pinilla de Fermoselle rare-element pegmatite (Zamora, Spain), as well as in barren pegmatitic and quartz–tourmaline veins inside the associated leucogranite. The rare-element pegmatite shows internal zoning, evolving from a barren facies, in the lower border zone, in contact with the leucogranite, to a Li-rich facies in the upper border zone, close to the host-rocks.Tourmalines from the veins within the leucogranite have highest Mg contents, and belong to the schorl–dravite series. The tourmalines from the rare-element pegmatite mostly belong to the schorl–elbaite series, with chemical compositions within the range of the end-members, whereas the tourmalines associated with the most evolved zone in the pegmatite belong to the elbaite–rossmanite series. The broad compositional range shown by the tourmalines correlates quite well with the pegmatite zoning. The most plausible substitution mechanism for the chemical evolution of tourmalines during crystallization seems to be Mg_–1Fe²⁺₁, [X]_–1^YAl_–1^XNa_–1^YFe²⁺₁, for the foitite–schorl series; ^YFe²⁺_–3^YAl_1.5^YLi_1.5, for the schorl–elbaite vector; ^XNa_–1^YLi_–0.5[X]₁^YAl_0.5, for the elbaite–rossmanite series; and, (OH)₁F₁ for all the tourmalines except the pink elbaites. This chemical variation in tourmaline is consistent with a crystal fractionation model for the evolution of the Pinilla pegmatite.     

Environmental impacts of heavy metals (Co, Cu, Pb, Zn) in surficial sediments of estuary in Daliao River and Yingkou Bay (northeast China): concentration level and chemical fraction

Heavy metal pollution in the surficial sediments derived from the estuary in Daliao River and Yingkou Bay is investigated to assess environmental quality, pollution level, bioavailability and toxicity. The ranges of Pb, Co, Zn and Cu concentrations in the surficial sediments are: 16.57–39.18, 3.61–16.02, 16.53–39.18, 2.77–43.80 mg/kg. Results of the geoaccumulation index (I _geo) show that the pollution levels of four metals are in the “unpolluted” class except for Pb in 15 sampling sites. The pollution level of the study area assessed by pollution load index (PLI) shows that except for the moderately polluted region of sites 1, 2, 3, 8, 12 and 13, other sites belong to unpolluted state. The sequence of pollution extent of different heavy metals is: Pb > Zn > Co > Cu. At all sampling sites, the grades of potential ecological risk of Co, Cu, Pb and Zn are “light”. The order of potential ecological risk is: Pb > Co > Cu > Zn. Sequential extraction of the metals indicates that the states of Pb, Cu, Co and Zn in the sediment are relatively stable at most sites of the estuary in Daliao River and Yingkou Bay, which means that there is a low source of pollution arriving in this area. While only at several sites, Co, Pb and Zn are labile, which are considered as anthropogenically originated.     

Changes in the composition of bitumen extracts and chemical structure of kerogen during hydrous pyrolysis

The paper presents data on the composition of biomarkers from bitumen extracts and the chemical structure of kerogen from C_org-rich sedimentary rocks before and after hydrothermal treatment in an autoclave at 300°C. Samples selected for this study are kukersite and Ordovician Dictyonema shale from the Baltics, Domanik oil shale from the Ukhta region, Upper Permian brown coal from the Pre-Ural foredeep, carbonaceous shale from the Oxfordian horizon of the Russian plate, and Upper Jurassic oil shales from the Sysola oil shale bearing region. The rocks contain type I, II, III, and II-S kerogens. The highest yield of extractable bitumen is achieved for Type II-S kerogen, whereas Type III kerogen produces the lowest amount of bitumen. The stages of organic matter thermal maturation achieved during the experiments correspond to a transition from PC_2–3 to MC_1–2. The ¹³C NMR data on kerogen indicate that the aromatic structures of geopolymers underwent significant changes.     

Contrasting compositional trends of rocks and olivine-hosted melt inclusions from Cerro Negro volcano (Central America): implications for decompression-driven fractionation of hydrous magmas

Melt inclusions in olivine Fo_83–72 from tephras of 1867, 1971 and 1992 eruptions of Cerro Negro volcano represent a series of basaltic to andesitic melts of narrow range of MgO (5.6–8 wt %) formed by ~46 wt % fractional crystallization of olivine (~6 wt %), plagioclase (~27 wt %), pyroxene (~13 wt %) and magnetite (<1 wt %) from primitive basaltic melt (average SiO₂ = 49 wt %, MgO = 7.6 wt %, H₂O = 6 wt %) as it ascended to the surface from the depth of about 14 km. The crystallization occurred at increasing liquidus temperature from 1,050 to 1,090 °C in the pressure range from 400 to 50 MPa and was induced by release of mixed H₂O–CO₂ fluid from the melt at decreasing pressure. Matrix glass compositions fall at the high-Si end of the melt inclusion trend and represent the final stage of melt crystallization during and after eruption. The bulk compositions of erupted Cerro Negro magmas (tephras and lavas) range from high- to low-MgO (3–10 wt %) basalts, which form a compositional array crossing the trend of melt inclusions so that virtually no rock from Cerro Negro has composition akin to true melt represented by the inclusions. The variations of the bulk magma (rocks) and melt (melt inclusions) compositions can be generated in a dyke connecting a deep primitive magma reservoir with the Cerro Negro edifice. While the melt inclusions represent the compositional trend of instantaneous melts along the magma pathway at decreasing pressure and H₂O content, occurrence of low-Mg to high-Mg basalts reflects the process of phenocryst re-distribution in progressively evolving melt. The crystallization scenario is anticipated to operate everywhere in dykes feeding basaltic volcanoes and can explain the predominance of plagioclase-rich high-Al basalts in island arc as well as typical compositional variations of magmas during single eruptions.     

Internal vascularity of the dermal plates of Stegosaurus (Ornithischia, Thyreophora)

X-ray computed tomography and petrographic thin sectioning were used to study internal features of the plates of the thyreophoran dinosaur Stegosaurus and the osteoderms of Alligator. Infrared thermographic imaging of basking caimans was used to examine possible differential blood flow to osteoderms and other parts of the skin. Multiple large openings in the Stegosaurus plate base lead to a linear, mesiodistally oriented vestibule, which in turn apically sends off multiply branching “pipes”. The pipes are best developed in the basal half of the plate, and communicate with cancellous regions (some of which presumably were vascular spaces) throughout the plate interior. Some internal vascular features also connect with vascular pits and grooves on the plate surface. Alligator osteoderms show a similar internal vascularity. In crocodylians, the osteoderms serve as armor and help to stiffen the back for terrestrial locomotion, but their vascularity enables them to be used as sources of calcium for egg shelling, as sites of lactate sequestration, and possibly for heat exchange with the external environment, as suggested by our infrared thermographic imaging of basking caimans. Thyreophoran osteoderms presumably had multiple functions as well. In Stegosaurus the potential thermoregulatory role of the plates may have been greater than in other thyreophorans, by virtue of their extensive external and internal vascularity, their large size, thin cross-sections above the plate base, dorsal position, and alternating arrangement.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

鄂西-黔中陆缘坻磷块岩迁移沉积及控矿(成矿)模型

鄂西-黔中陆缘坻是扬子地块东南缘晚震旦世陡山沱期磷块岩沉积成矿的构造古地理单元,其形态是向南东凸出的弧形,来自SE方向上升洋流抵达陆缘坻后,分成向NW和SW向两个方向洋流,磷块岩两个工业矿层随洋流方向发生有规律的迁移沉积,这在同一矿集区的不同矿段也表现出清晰的迁移沉积规律。由于陆缘坻本身古构造和古地形特点,决定了磷块岩成矿的具体位置,构成了不同的控矿模型,特别陆缘坻基底隆起迎向洋流的一侧是磷块岩大规模成矿的最佳地段,往往形成成群的大中小矿床,甚至形成超大型矿床。     

Formation, reactivity, and aging of ferric oxide particles formed from Fe(II) and Fe(III) sources: Implications for iron bioavailability in the marine environment

Freshly formed amorphous ferric oxides (AFO) in the water column are potentially highly reactive, but with reactivity declining rapidly with age, and have the capacity to partake in reactions with dissolved species and to be a significant source of bioavailable iron. However, the controls on reactivity in aggregated oxides are not well understood. Additionally, the mechanism by which early rapid aging occurs is not clear. Aging is typically considered in terms of changes in crystallinity as the structure of an iron oxide becomes more stable and ordered with time thus leading to declining reactivity. However, there has been recognition of the role that aggregation can play in determining reactivity, although it has received limited attention. Here, we have formed AFO in seawater in the laboratory from either an Fe(II) or Fe(III) source to produce either AFO(II) or AFO(III). The changes in reactivity of these two oxides following formation was measured using both ligand-promoted dissolution (LPD) and reductive dissolution (RD). The structure of the two oxides was examined using light scattering and X-ray adsorption techniques. The dissolution rate of AFO(III) was greater than that of AFO(II), as measured by both dissolution techniques, and could be attributed to both the less ordered molecular structure and smaller primary particle size of AFO(III). From EXAFS analysis shortly (90 min) following formation, AFO(II) and AFO(III) were shown to have the same structure as aged lepidocrocite and ferrihydrite respectively. Both oxides displayed a rapid decrease in dissolution rate over the first hours following formation in a pattern that was very similar when normalised. The early establishment and little subsequent change of crystal structure for both oxides undermined the hypothesis that increasing crystallinity was responsible for early rapid aging. Also, an aging model describing this proposed process could only be fitted to the data with kinetic parameters that were inconsistent with such a mechanism. The similar aging patterns and existence of diffusion limited cluster aggregation (DLCA) suggested that loss of Fe centre accessibility due to aggregation is the likely cause of early rapid aging of AFO. A simple model describing the loss of surface area during the aggregate growth, measured using dynamic light scattering (DLS), produced aging patterns that matched the reactivity loss of AFO(III) measured using RD but not LPD. The difference between the two measures of dissolution rate could not be explained, but indicated that different measures of reactivity respond differentially to various parameters controlling reactivity. Analysis of aggregate structure using aggregation kinetics and static light scattering (SLS) suggested that restructuring during aggregation was occurring at an aggregate level for AFO(III), but only minimally so for AFO(II). While our investigations support the contention that aggregation is responsible for early rapid aging, the role of aggregate structure is remains unclear.     

Mineralogical and chemical characterization of historical mortars from military fortifications in Lisbon harbour (Portugal)

Historical mortars from sixteenth to seventeenth century military forts located at the mouth of the Tagus River in Lisbon have been characterized by polarized light microscopy (PLM), thermal analysis (TG/DTA), X-ray diffractometry (XRD) and scanning electron microscopy + energy dispersive spectroscopy (SEM + EDS). The results indicate that the mortars used were all hydraulic lime-based. The presence of well-rounded lime lumps indicates a limited use of water during the lime hydration process. The detection of hydrated calcium chloroaluminate and carboaluminate compounds mostly at binder-aggregate interfaces provides evidence for the onset of pozzolanic reactions during mortar production as further confirmed by the presence of ceramic fragments in the aggregate fractions intentionally added by the fort builders to increase the hydraulic properties of the mortars. The higher mechanical strength and greater resistance to degradation processes imparted by these pozzolanic compounds could explain why, despite the extreme proximity of the investigated sites to the sea, salt weathering processes do not appear to have significantly affected the studied mortars.     

Structure and crystal chemistry of hydrous wadsleyite, Mg1.75SiH0.5O4: possible hydrous magnesium silicate in the mantle transition zone

The crystal structure of hydrous wadsleyite, Mg_1.75SiH_0.5O₄ synthesized in an MA 8-type apparatus at conditions of 1300°C and 15.5 GPa, has been analyzed and refined in space group Imma, using the X-ray intensities measured on a 60X60X10 μm single crystal. The composition (Z=8) and unit cell are Mg_1.74Si_0.97H_0.65O₄ by E.P.M.A. analysis and a=5.663(1) Å, b= 11.546(2) Å, c=8.247(4) Å, V=539.2(5) ų. The partial M-site occupancies were determined; vacancies associated with the incorporation of water are strongly concentrated on the Mg 3 site. The OH in the structure was confirmed by Raman and FTIR spectroscopies. The result of valence sum calculation based on the refined bond lengths indicates that O1 is a hydroxyl. The formula of hydrous wadsleyite can be expressed as Mg_2-xSiH_2xO₄, where 0≤x≤0.25. When x=0.25, all of the O1 site is hydroxyl and the maximum solubility of 3.3 wt% H₂O is realized. Structural relations to other dense hydrous phases are discussed.     

Sedimentology, geochemistry and origin of phosphatic chalks: the Upper Cretaceous deposits of NW Europe

Santonian-Lower Campanian and Lower Maastrichtian phosphatic chalks in northern France, southern England and Belgium are Europe's largest sedimentary phosphatc deposits. The stratigraphy, sediment-ology, petrography, mineralogy and geochemistry of the lithofacies are reviewed and new data presented. Depositional and diagenetic models for phosphatic chalk deposits are developed using published experimental work and from observations of modern high- and low-productivity phosphogenic systems. It is concluded that phosphatic chalks were deposited in well-oxygenated, current-swept environments. Phosphatization required a delicate balance to be maintained between moderate organic carbon and carbonate sedimentation rates, reduced bulk sediment accumulation rate and an enhanced rate of bioturbation. Precipitation of carbonate-fluorapatite (francolite) accompanied the bacterially mediated decomposition of organic matter, occurring within centimetres of the sediment-seawater interface, and taking place preferentially within microbial bodies and coatings. In addition to the organically derived component, pore water phosphate levels were enhanced by phosphate absorbed on ferric oxyhydroxides which was liberated during iron reduction. Mineralization was probably a dominantly post-oxic process, but occurred in a thick sediment mixed layer in which marine organic matter was undergoing intense mixed aerobic and anaerobic microbial degradation. Phosphogenesis occurred predominantly on the NE margins of the Anglo-Paris Basin where shallower sea floors and suitable palaeoceanographic conditions prevailed. Phosphogenic episodes were limited by sea level fluctuations'which controlled the effectiveness of the erosional currents that formed and maintained the phosphatic basins and may have stimulated local productivity.     

Structural and luminescent characterisation of uraniferous fluorapatite and haematite associated with phosphatic rocks of the Bijawar group in Sagar District,Madhya Pradesh (India)

The structural and spectroscopic characteristics of phosphatic ferruginous shale samples from the Bijawar Group rocks from Sagar District of Madhya Pradesh (India) have been probed for identification of uranium species. Fluorapatite (\(\hbox {Ca}_{5}\hbox {(PO}_{4})_{3}\hbox {F}\), FAP) and haematite (\(\upalpha \)-\(\hbox {Fe}_{2}\hbox {O}_{3}\)) were identified as the main phases in the separated mineral concentrates. The photoluminescence (PL) and X-ray absorption near edge spectroscopy (XANES) studies pointed to a strong experimental evidence of both U(IV) and U(VI) oxidation states in the mineral concentrate portion obtained from the same parent host rock. The PL spectrum has confirmed the charge transfer (f–d) transition bands in UV and near-UV regions with emission peaks at ca. 290, 313, 336, 399 and 416 nm, which has been attributed to the substitution of \(\hbox {Ca}^{2+}\) ions by U(IV) in FAP and broad structureless emission due to stabilisation of U(VI) as \(\hbox {UO}_{6}^{6-}\) in haematite. Time-resolved spectroscopy studies have revealed biexponential decay components lasting 2–5 ns for U(IV) species and \(10\,\upmu \hbox {s}\) for U(VI) species. These characterisations revealed the fundamental information about the oxidation state and form of uranium in this region. Remediation measures for the Bijawar region are also suggested.     

The effects of source rocks and chemical weathering on the petrogenesis of siliciclastic sand from the Neto River (Calabria, Italy): implications for provenance studies

Plutonic and gneissic rocks of the Sila Massif in the uppermost portion of the Neto drainage basin (Calabria, Southern Italy) weather and erode under a humid Mediterranean climate. During the development of weathering profiles, a combination of chemical weathering and granular disintegration processes occurred. Chemical weathering involves a loss of both plagioclase (mainly during grus generation) and K-feldspar (mainly during soil formation). This loss is attributed to transformation of plagioclase to clay minerals and to leaching and dissolution of K-feldspar. Sand composition is quartzofeldspathic and nearly homogeneous along the main channel of the Neto River, even where the river cuts across a blanket of sedimentary cover. Thus, fluvial transport does not alter sand composition within the Neto drainage basin. Petrographic indices are effective in (1) discriminating between contributions from similar (granite and gneiss) source rocks (Qm/F); (2) relating the provenance of plutoniclastic and gneissiclastic sand found in the headwaters to grus horizons (Qm/F; Q/Rg); and (3) distinguishing between upstream first-cycle and downstream multicycle sand (Q/Rg). This last distinction is further emphasized by considering both aphanitic and phaneritic varieties of rock fragments (RgRmRs diagram). Chemical weathering is the main sand producer within the regolithic environment in northern Calabria. In addition, rapid erosion resulting from steep slopes removes weathered products, and rapid and short transport leads to minimal sediment maturation. In general, the F/Q index is climate and relief dependent; thus, it should be used in conjunction with palaeoclimatic and palaeophysiographic evidence for provenance interpretations of ancient quartzofeldspathic sandstones.     

On the presence of hydrous defects in differently coloured wulfenites (PbMoO4): an infrared and optical spectroscopic study

Several samples of wulfenite, PbMoO₄, varying in colour from colourless to yellow, orange and red, have been characterised by means of IR and optical absorption spectroscopy and by microprobe analyses. A distinct pleochroic band group with absorption maxima centred at 3,380 and 3,150 cm^?1 can be seen in the IR spectra of wulfenite single-crystals, indicating the presence of hydroxyl groups. The pleochroic and thermal behaviour of the OH stretching bands along with deuteration experiments, as well as results obtained from synthetic flux-grown samples, exclude the presence of submicroscopic hydrous mineral inclusions as their primary origin. The pleochroic scheme and the band positions were used to postulate a model for the OH incorporation mode, based on the assumption of vacancies on Mo and Pb sites in the structure of this ‘nominally anhydrous mineral’. Optical absorption spectra of coloured natural samples show a broad and polarised band around 23,000–24,000 cm^?1, preceding the fundamental UV absorption edge, which has been identified as the reason for the colour of the mineral. The comparison with synthetic PbMoO₄ single-crystals, doped with variable amounts of Cr⁶⁺, yielded conclusive evidence that trace amounts of the CrO₄ ^2? anion group, substituting for MoO₄ ^2?, determine the variable colour. Besides, in one sample, trace amounts of Nd³⁺ have been spectroscopically identified.