Barite Crystals Research Articles

Phase Analysis and Crystal Morphology of Barium Sulphate Precipitated from The Laminar Flowing Water

Barium sulphate (BaSO4) is common scale deposits precipitated in pipes which can hinder the flow rate and lower heat transfer efficiency. Therefore, there is a need to address the understanding of scale formation in pipes. In this paper, the formation of BaSO4 scale in the laminar flowing water was investigated in the laboratory rig of scale formation. The scale forming solution was prepared by BaCl2 and Na2SO4 with Ba2+ concentrations in equimolar ppm of 2500, 3000, and 3500. The pH solution was set up in the values of 6, 8, and 10. The crystals were deposited on the four coupons pipes made of copper inside the pipes. The scale deposited from the flowing water was then characterized by using SEM equipped by EDX for crystal morphology and elemental analysis. XRD method was used for the crystalline phase analysis. The results showed that BaSO4 crystals with star-like morphology can be observed from SEM imaging. The pure crystal barite can be obtained from the experiments as can be confirmed by XRD analysis. It is obvious that the barite crystals can be easily formed in the basic solution.

Genetic aspects of barite mineralization related to rocks of the teschenite association in the Silesian Unit, Outer Western Carpathians, Czech Republic

AbstractBarite is a relatively uncommon phase in vein and amygdule mineralizations hosted by igneous rocks of the teschenite association in the Silesian Unit (Western Carpathians). In macroscopically observable sizes, it has been reported from 10 sites situated only in the Czech part of the Silesian Unit. Microscopic barite produced by the hydrothermal alteration of rock matrix and also by the supergene processes is more abundant. We examined four samples of barite by mineralogical and geochemical methods. Electron microprobe analyses proved pure barites with up to 0.038 apfu Sr and without remarkable internal zonation. Fluid inclusion and sulphur isotope data suggests that multiple sources of fluid components have been involved during barite crystallization. Barite contains primary and secondary aqueous all-liquid (L) or less frequent two-phase (L+V) aqueous fluid inclusions with variable salinity (0.4-2.9 wt. % NaCl eq.) and homogenization temperatures between 77 and 152 °C. The higher-salinity fluid endmember was probably Cretaceous seawater and the lower-salinity one was probably diagenetic water derived from surrounding flysch sediments during compaction and thermal alteration of clay minerals. The δ34S values of barite samples range between -1.0 ‰ and +16.4 ‰ CDT suggesting participation of two sources of sulphate, one with a near-zero δ34S values probably derived from wall rocks and another with high δ34S values being most probably sulphate from the Cretaceous seawater. All results underline the role of externally derived fluids during post-magmatic alteration of bodies of rock of the teschenite association.

Oriented Crystallization of Barium Sulfate Confined in Hierarchical Cellular Structures

Biomineralization involves the controlled formation of inorganic matter within hierarchical biological scaffolds. Mimicking the crystallization of biominerals in such confinement is an important goal in the field of crystal engineering. Natural porous materials offer an interesting platform for studying mineral morphogenesis and texturing through template-directed mineralization. In this paper, we precipitate barium sulfate from aqueous salt solutions in the constrained micro- and nanoenvironment of pristine wood cells and cell walls. By employing spatially resolved characterization techniques, such as scanning electron microscopy (SEM), Raman spectroscopic imaging, and scanning wide-angle X-ray scattering (WAXS), we gain important insights into the deposition pattern, morphology, and crystallographic orientation of Barite crystals in the plant cell anatomy. The experimental findings suggest directed crystallization of BaSO4 at different hierarchical levels. SEM shows elongated, dendritic BaSO4 crystals g...

Barite scale formation and inhibition in laminar and turbulent flow: A rotating cylinder approach

Turbulent flow in oilfield pipes is very common, especially around chokes, tubing joints, and safety values. However the flow is generally laminar in laboratory tests for mineral scale formation and evaluation of scale inhibitors. The objective of this study is to investigate mineral scale formation and inhibition under laminar and turbulent conditions. A novel testing method of rotating cylinder apparatus has been developed to generate flow that spans from laminar to turbulent regimes (Reynolds number from 176 to 11,249) under field temperature of 70°C. Barite scale formation and inhibition by several typical inhibitors were investigated under different hydrodynamic conditions. Barite precipitation kinetics experiments showed no significant difference in precipitation kinetics between laminar and turbulent flow without scale inhibitors. However in the presence of scale inhibitors, precipitation kinetics was slower under turbulent condition. Barite precipitate was collected at the end of the experiment and examined by scanning electron microscope (SEM). SEM images display major difference in barite size and morphology between different flow regimes - highly crystalline barite with an average size of 10µm in laminar flow and amorphous barite of much smaller size in turbulent flow. Adsorption kinetics experiments of scale inhibitors on barite shows faster kinetics in turbulent flow than that in laminar flow possibly due to enhanced mass transfer in turbulence. It is proposed that the slower barite precipitation kinetics with inhibitors in turbulent flow is due to enhanced adsorption of scale inhibitor on barite crystals, and the mechanisms of enhanced adsorption include larger specific surface area and faster mass transfer rate. These results indicate that scale inhibitors may be more effective under some turbulent conditions, as opposed to previous observations. The insights presented in this work will help to understand scale control in oilfield pipes especially under turbulent conditions, and develop optimal doses of scale inhibitors with regard to flow regimes.

Preparation and characterization of SO3-doped barium borosilicate glass-ceramics containing zirconolite and barite phases

In order to improve the solubility of actinides and sulfate in the glass matrix, barium borosilicate glass-ceramics containing zirconolite and barite crystalline phases were developed. The effects of SO3 addition (0–8wt%) on crystalline phases, microstructure, and chemical durability of glass-ceramics belonging to SiO2-B2O3-Na2O-BaO-CaO-TiO2-ZrO2-Nd2O3-SO3 system were mainly studied. The results show that glass transformation temperature decreases slightly with increasing SO3 content. The main crystalline phase is zirconolite for all of the samples. When the addition SO3 content is higher or equal to 4wt%, rice-shaped barite crystals appear in the bulk of glass-ceramics. Barite phase was formed during the melting stage. X-ray fluorescence analysis indicates that about 1.3wt% of SO3 can be incorporated in the glass-ceramics when the addition content of SO3 is 6wt%. S element mainly distributes in the barite crystals. The decomposition of sulfate mainly occurs during the melting process. Moreover, the addition of a certain content (≤6wt%) of sulfate has no significant influence on the chemical durability of barium borosilicate glass-ceramics.

The 3.2Ga marine environment inferred from sulfur isotope ratio of barite crystals in Pilbara, Western Australia

The 3.2Ga marine environment inferred from sulfur isotope ratio of barite crystals in Pilbara, Western Australia

Multi-stage barite crystallization in partially melted UHP eclogite from the Sulu belt, China

Barite inclusions in rock-forming and accessory minerals and in multiphase solid inclusions (MSI) in ultrahigh pressure (UHP) eclogites have been controversially interpreted to record the presence of high-salinity oxidizing fluids1 close to the peak of metamorphism. A detailed petrographic and microstructural study of barite in partially melted UHP eclogite from Yangkou, in the central Sulu belt of China demonstrates that barite precipitation is a multi-stage process. The different generations of barite provide insight into the evolution of fluid systems as P-T conditions evolved through the late prograde stage of subduction to the peak of UHP metamorphism and subsequently during exhumation. Five microstructural types of barite are recognized in this study. Type I barite (variable high to low Sr/Ba) occurs as equant primary inclusions with rutile in garnet and omphacite within coesite-bearing eclogite. Zr-in-rutile thermometry on the primary inclusions of rutile yields T = 658–699 °C at P = 2.5–4.5 GPa. Thus, barite inclusions were likely precipitated from an internally buffered fluid during the late prograde evolution. Type II barite (low Sr/Ba) occurs in MSI located toward the rims of garnet and omphacite. Since peak pressure was above the second critical endpoint for basaltic compositions, the MSI are inferred to represent aliquots of a silica-rich supercritical fluid trapped during the late prograde evolution close to the metamorphic peak. Type III barite (low Sr/Ba) occurs in pseudomorphs after phengite inclusions in garnet. The replacement phase assemblage formed during exhumation, by in situ melting of phengite. Type IV barite (low Sr/Ba) forms coarse-grained patches associated with sub-solidus replacement of omphacite by hornblende and albite symplectites along grain boundaries. Type V barite (low Sr/Ba) occurs as grain-boundary veinlets, intergranular grains, and closed rings around pyrite that is partly replaced by hematite and goethite. We interpret the types IV and V barite to have precipitated from an internally generated grain-boundary aqueous fluid, which is expected to be a response to H 2 O exsolving from garnet and omphacite during low-pressure amphibolite facies conditions. Therefore, barite precipitated during the late prograde subduction and the retrograde exhumation of UHP eclogite yields information about the mobility of Ba, Sr, and S during the metamorphic evolution.

Nano-structural features of barite crystals observed by electron microscopy and atom probe tomography

For the first time a barite sample was investigated by applying electron microscopy and atom probe tomography in a complementary approach to characterize its inner microstructure. Pores covering the size range from a few nanometers to a few micrometers were identified inside particles of a commercially available high purity barite. The barite matrix appeared to be a single crystal. A particular feature of the observed porous structure is a system of layers containing a high number of homogeneously distributed nano-scale pores, alternating with layers containing a limited number of larger pores. High-resolution chemical analyses indicate that the pores contain a solution of water and sodium chloride. The filling of these nano-scale inclusions was interpreted as residua of the initial supersaturated solution used for particle growth by precipitation. These findings explain the high reactivity observed in previous Ra uptake studies on the same type of barite and provide further implications for the interpretation of these results. Our results offer a new analytical approach and necessary reference data for future investigations on changes of the internal barite structure during these Ra uptake experiments.

Novel Barite Chimneys at the Loki's Castle Vent Field Shed Light on Key Factors Shaping Microbial Communities and Functions in Hydrothermal Systems.

In order to fully understand the cycling of elements in hydrothermal systems it is critical to understand intra-field variations in geochemical and microbiological processes in both focused, high-temperature and diffuse, low-temperature areas. To reveal important causes and effects of this variation, we performed an extensive chemical and microbiological characterization of a low-temperature venting area in the Loki's Castle Vent Field (LCVF). This area, located at the flank of the large sulfide mound, is characterized by numerous chimney-like barite (BaSO4) structures (≤ 1 m high) covered with white cotton-like microbial mats. Results from geochemical analyses, microscopy (FISH, SEM), 16S rRNA gene amplicon-sequencing and metatranscriptomics were compared to results from previous analyses of biofilms growing on black smoker chimneys at LCVF. Based on our results, we constructed a conceptual model involving the geochemistry and microbiology in the LCVF. The model suggests that CH4 and H2S are important electron donors for microorganisms in both high-temperature and low-temperature areas, whereas the utilization of H2 seems restricted to high-temperature areas. This further implies that sub-seafloor processes can affect energy-landscapes, elemental cycling, and the metabolic activity of primary producers on the seafloor. In the cotton-like microbial mats on top of the active barite chimneys, a unique network of single cells of Epsilonproteobacteria interconnected by threads of extracellular polymeric substances (EPS) was seen, differing significantly from the long filamentous Sulfurovum filaments observed in biofilms on the black smokers. This network also induced nucleation of barite crystals and is suggested to play an essential role in the formation of the microbial mats and the chimneys. Furthermore, it illustrates variations in how different genera of Epsilonproteobacteria colonize and position cells in different vent fluid mixing zones within a vent field. This may be related to niche-specific physical characteristics. Altogether, the model provides a reference for future studies and illustrates the importance of systematic comparative studies of spatially closely connected niches in order to fully understand the geomicrobiology of hydrothermal systems.

Sulfur isotope geochemistry and mineralogy of Balcilar vein type barite-sulphide mineralization, Biga peninsula, NW Turkey

The Balcilar (Canakkale) barite-galena mineralization is a typical example of the vein type barite-lead-zinc deposits in the Biga Peninsula. The lithologic units in the study area are Akcaalan andesite, Eocene, Adadagi pyroclastics, Oligocene, Dededag dacite, Miocene, Karaomerler basalt, Plio-Quaternary and alluvium Quaternary. Barite-galena veins occurred along the faults developed within the andesites. Barite, quartz and galena are main minerals and are accompanied by minor amounts of sphalerite, pyrite, chalcopyrite, covellite and marcasite. The earliest barite (barite I) occurs as coarse-grained subhedral-euhedral crystals and the later (barite II) as small tabular crystals in between the earlier coarse crystals. Quartz occurs as fine-grained crystals with the later small barite crystals. Galena, sphalerite, chalcopyrite, pyrite, marcasite and covellite occur open spaces within the earlier barite (barite I) crystals. Sulfur isotopes indicate that in galena the reduced sulfur from bacterially or inorganically reduced sulphate, or from an isotopically light reduced S-source. The δ34SH2S values calculated from the barite-H2S and galena-H2S fractionation factors, in the same samples, indicate a temperature of between 200 and 300 °C. Relatively lower δ34S values of barites than dissolved sulphate in modern oceans or Eocene sea waters have been evaluated as the ore forming hydrothermal fluids were derived from interacting throughout the magmatic host-rocks.

Precipitation and growth of barite within hydrothermal vent deposits from the Endeavour Segment, Juan de Fuca Ridge

Hydrothermal vent deposits form on the seafloor as a result of cooling and mixing of hot hydrothermal fluids with cold seawater. Amongst the major sulfide and sulfate minerals that are preserved at vent sites, barite (BaSO4) is unique because it requires the direct mixing of Ba-rich hydrothermal fluid with sulfate-rich seawater in order for precipitation to occur. Because of its extremely low solubility, barite crystals preserve geochemical fingerprints associated with conditions of formation. Here, we present data from petrographic and geochemical analyses of hydrothermal barite from the Endeavour Segment of the Juan de Fuca Ridge, northeast Pacific Ocean, in order to determine the physical and chemical conditions under which barite precipitates within seafloor hydrothermal vent systems. Petrographic analyses of 22 barite-rich samples show a range of barite crystal morphologies: dendritic and acicular barite forms near the exterior vent walls, whereas larger bladed and tabular crystals occur within the interior of chimneys. A two component mixing model based on Sr concentrations and 87Sr/86Sr of both seawater and hydrothermal fluid, combined with 87Sr/86Sr data from whole rock and laser-ablation ICP-MS analyses of barite crystals indicate that barite precipitates from mixtures containing as low as 17% and as high as 88% hydrothermal fluid component, relative to seawater. Geochemical modelling of the relationship between aqueous species concentrations and degree of fluid mixing indicates that Ba2+ availability is the dominant control on mineral saturation. Observations combined with model results support that dendritic barite forms from fluids of less than 40% hydrothermal component and with a saturation index greater than ∼0.6, whereas more euhedral crystals form at lower levels of supersaturation associated with greater contributions of hydrothermal fluid. Fluid inclusions within barite indicate formation temperatures of between ∼120°C and 240°C during barite crystallization. The comparison of fluid inclusion formation temperatures to modelled mixing temperatures indicates that conductive cooling of the vent fluid accounts for 60–120°C reduction in fluid temperature. Strontium zonation within individual barite crystals records fluctuations in the amount of conductive cooling within chimney walls that may result from cyclical oscillations in hydrothermal fluid flux. Barite chemistry and morphology can be used as a reliable indicator for past conditions of mineralization within both extinct seafloor hydrothermal deposits and ancient land-based volcanogenic massive sulfide deposits.

Iron patinas on alabaster surfaces (Santa Maria de Poblet Monastery, Tarragona, NE Spain)

Abstract Alabaster is a white and pure gypsum rock classically used in sculptures or for ornamental purposes, but its characteristic white colour is sometimes masked by the development of noticeable reddish stains over the surface of the rock. The main altarpiece of the Santa Maria de Poblet monastery (Tarragona, NE Spain; 16th century, Damia Forment) is the focus of this study. Red-to-ochre patinas with diameters of 2–20 cm are found on the alabaster surface of this altarpiece. The origin of such patinas are discussed, as they are the result of degradation processes of minerals present in alabaster rocks, contrary to what happens in the formation of most patinas. The patinas consist of two differentiated layers that may occur occasionally mixed. The Lower Layer contains iron compounds, which have precipitated around the gypsum crystals of the rocky support and have provided the characteristic red-to-ochre colour to the surface of the altarpiece. The formation of this layer was driven by the (bio)oxidation of the pyrite, which is disseminated over the alabaster surface. The formation of this film of iron-rich particles was conducted by a series of destructive and penetrative processes, promoting disaggregation and crystal reduction (mechanical and/or by dissolution) of the matrix minerals (gypsum, celestite, barite, calcite-dolomite…). The Upper Layer was grown by means of constructive (agglutination of particles by accretion) and destructive (destruction of the alabaster matrix and incorporation into the Lower Layer) mixed processes. Thus, the presence of small crystals (1–10 μm) of gypsum, quartz, calcite, celestite, barite, clay minerals and pyrite in this upper patina are mainly related to the residual products of the alabaster rocks. Moreover, some of the calcite, quartz and clay particles could also be considered atmospheric dust. Oxalates (weddellite and whewellite), portlandite and coal particles are not related to the formation of iron-rich patinas. Such studied patinas might date from the 19th century due to the partial destruction of the monastery after the approval of the Law of Confiscation of Religious Properties in Spain (1835) and no later than the end of the ninetieth century, when the monastery was abandoned. The entry of rainwater and presence of humidity inside the monastery would promote the pyrite oxidation processes. Currently the patinas seem to be stabilized, the pyrites are no longer in contact with water, which is needed for oxidation.

Growth Kinetics and Morphology of Barite Crystals Derived from Face-Specific Growth Rates

We investigate the growth kinetics and morphology of barite (BaSO4) crystals by measuring the growth rates of the (001), (210), (010), and (100) surfaces using vertical scanning interferometry. Solutions with saturation indices 1.1, 2.1, and 3.0 without additional electrolyte, in 0.7 M NaCl, or in 1.3 mM SrCl2 are investigated. Face-specific growth rates are inhibited in the SrCl2 solution relative to a solution without electrolyte, except for (100). Contrarily, growth of all faces is promoted in the NaCl solution. The variation of face-specific rates is solution-specific, which leads to a change of the crystal morphology and overall growth rate of crystals. The measured face-specific growth rates are used to model the growth of single crystals. Modeled crystals have a morphology and size similar to those grown from solution. Based on the model the time dependence of surface area and growth rates is analyzed. Growth rates change with time due to surface area normalization for small crystals and large grow...

Rare earth elements, S and Sr isotopes and origin of barite from Bahariya Oasis, Egypt: Implication for the origin of host iron ores

Based on their occurrences and relation to the host iron ores, barites are classified into: (1) fragmented barite occurs as pebble to sand-size white to yellowish white barite along the unconformity between the Bahariya Formation and iron ores, (2) interstitial barite is present as pockets and lenses of large and pure crystals inside the iron ores interstitial barite inside the iron ores, and (3) disseminated barite occurs at the top of the iron ores of relatively large crystals of barite embedded in hematite and goethite matrix. In the current study, these barites have been analyzed for their rare earth elements (REE) as well as strontium and sulfur isotopes to assess their source and origin as well as the origin of host iron ores.Barite samples from the three types are characterized by low ΣREE contents ranging between 12 and 21ppm. Disseminated barite shows relatively lower ΣREE contents (12ppm) compared to the fragmented (19ppm) and interstitial (21ppm) barites. This is probably due to the relatively higher Fe2O3 in the disseminated barite that might dilute its ΣREE content. Chondrite-normalized REE patterns for the three barite mineralizations exhibit enrichment of light rare earth elements (LREE) relative to heavy rare earth elements (HREE) as shown by the high (La/Yb)N ratios that range between 14 and 45 as well as pronounced negative Ce anomalies varying between 0.03 and 0.18. The 87Sr/86Sr ratios in the analyzed samples vary between 0.707422 and 0.712237. These 87Sr/86Sr values are higher than the 87Sr/86Sr ratios of the seawater at the time of barite formation (Middle Eocene with 87Sr/86Sr ratios of 0.70773 to 0.70778) suggesting a contribution of hydrothermal fluid of high Sr isotope ratios. The δ34S values in the analyzed barites range between 14.39‰ and 18.92‰. The lower δ34S ratios in the studied barites compared with those of the seawater at the time of barite formation (Middle Eocene with δ34S ratios of 20–22‰) is attributed to a possible contribution of hydrothermal fluid of low δ34S values that lowered the δ34S values in the studied barites.Rare earth elements distribution and patterns, as well as strontium and sulfur isotopes suggest a mixing of seawater and a hydrothermal fluid as possible sources for barite mineralizations in the Bahariya Oasis. The seawater source is suggested from the low Ce/La ratios, “V” shape of the rare earth patterns and pronounced negative Ce anomalies. On the other hand, the hydrothermal fluid contribution is evident from the low concentrations of rare earth and the deviation in both S and Sr isotopic compositions from those of the seawater during the time of barites formation (Middle Eocene). The relatively heterogeneous Sr and S isotope ratios among the studied barites suggest the Bahariya Formation and Basement Complex as possible sources of the hydrothermal fluids. The similarity in the REE as well as S and Sr isotopic compositions of the three types of barite suggest that they form simultaneously.As the geology and occurrence of the barites suggest a genetic relationship between these barites and the host iron ores, the mixed seawater and hydrothermal sources model of the barites is still applicable for the source of the host iron ores.

Diagenetic barite deposits in the Yurtus Formation in Tarim Basin, NW China: Implications for barium and sulfur cycling in the earliest Cambrian

Barite concretions and bands are widely distributed in black shale–chert horizons in the Yurtus Formation of Lower Cambrian in Aksu area, northwestern Tarim Basin, NW China. They mainly consist of coarse-grained anhedral to euhedral barite crystals with minor dolomites and pyrites. Petrological features indicate these concretions grew from the porewater in unconsolidated sediments at shallow burial below sediment-water interface. The slight deviation of 87Sr/86Sr ratios (0.7083 to 0.7090) and significant elevated δ34S values (56.8–76.4‰ CDT) of barite samples with respect to those of the Early Cambrian seawater further support that barite deposits precipitated from the enclosed porewater in sediment column, which evolved from the penecontemporaneous seawater with weak interaction with the host fine-grained siliciclastic sediments and highly-depleted sulfate in response to prolonged strong bacterial sulfate reduction without necessary renewal. The abundant organic matters in the basal Yurtus Formation should have facilitated developing sulfate-depleted methanogenesis zone and sulfate–methane transition zone (SMTZ) slightly after deposition. Therefore, barite deposits in the Yurtus Formation most likely resulted from diagenetic barium cycling and persistently grew from the porewater in the static SMTZ with a low sedimentation rate in the Early Cambrian. In comparison with the distribution of sedimentary barites in geological records, we tentatively proposed that a transition in diagenetic barium cycling and associated mineralization may have occurred from the Precambrian to Cambrian periods; this scenario may be causally linked to the changes in marine ecology (the advent of mesozooplankton and associated faecal pellet) and geochemistry (the increase of seawater sulfate concentration). Thus, the occurrence of diagenetic barite deposits in the Yurtus Formation implies that diagenetic barium cycling and more effective scavenging of barium from CH4- and Ba-rich porewaters within sediments might have become an nonnegligible process in continental margin areas, at least, since the earliest Cambrian, which could have significantly impacted the marine barium cycling.

Role of bacteria in marine barite precipitation: A case study using Mediterranean seawater

Marine bacteria isolated from natural seawater were used to test their capacity to promote barite precipitation under laboratory conditions. Seawater samples were collected in the western and eastern Mediterranean at 250m and 200m depths, respectively, since marine barite formation is thought to occur in the upper water column. The results indicate that Pseudoalteromonas sp., Idiomarina sp. and Alteromonas sp. actually precipitate barite under experimental conditions. Barite precipitates show typical characteristics of microbial precipitation in terms of size, morphology and composition. Initially, a P-rich phase precipitates and subsequently evolves to barite crystals with low P contents. Under laboratory conditions barite formation correlates with extracellular polymeric substances (EPS) production. Barite precipitates are particularly abundant in cultures where EPS production is similarly abundant. Our results further support the idea that bacteria may provide appropriate microenvironments for mineral precipitation in the water column. Therefore, bacterial production in the past ocean should be considered when using Ba proxies for paleoproductivity reconstructions.

Grumiplucite from the Rudňany deposit, Slovakia: a second world-occurrence and new data

Grumiplucite, ideally HgBi2S4 was identified at the Droždiak vein, Rudňany deposit (Spissko-gemerske Rudohorie Mts., Slovakia). This rare Hg-sulfosalt forms metallic lead-grey to steel-grey, prismatic to acicular crystals up to 1 cm long, often grouped into irregular aggregates. It occurs in cavities of siderite with abundant cinnabar, Hg-rich tetrahedrite and chalcopyrite aggregates. Minor quartz or barite crystals and microscopic aggregates of Sb-rich bismuthinite to Birich antimonite were also observed. On the basis of chemical analyses, two types of grumiplucite were distinguished at the Rudňany deposit. The first is close to an ideal composition and has empirical formula Hg0.99Bi1.94S4.08 (based on 7 apfu). The second is characterized by regularly elevated contents of Sb ranging from 0.02 to 0.77 apfu. Grumiplucite is monoclinic, space group C2/m, with unit-cell parameters refined from X-ray powder data: a = 14.172(2), b = 4.0525(7), c = 13.975(1) A, β = 118.257(8)o and V = 707.0(2) A3 (Sb-free) and a = 14.183(1), b = 4.0538(5), c = 13.980(1) A, β = 118.239(1)o and V = 708.1(2) A3 (Sb-rich). Raman spectra for grumiplucite crystals with variable Sb contents are mutually well comparable. Therefore it seems that different Sb occupation does not affect the energy and intensity of Raman bands and they significantly differ from spectra of particularly structure-related mineral livingstonite, HgSb4S8. The dominant feature in the Raman spectra of grumiplucite is a series of spectral bands that corresponds to the stretching and bending vibrations of BiS5 polyhedra and Hg–S bonds.

Episodic Subseafloor Hydrothermal Activity Within the Eastern Manus Back-Arc Basin Determined by Uranium-Series Disequilibrium in Barite

The geochronology of seafloor hydrothermal activity from several mineralized, active and inactive vent fields at Suzette and Pual Ridge, eastern Manus back-arc basin, Bismarck Sea, Papua New Guinea, has been established using the 228Th/228Ra, 228Ra/226Ra, and 226Ra/Ba uranium-series disequilibrium methods for barite-rich samples. These hydrothermal systems underwent episodes of hydrothermal fluid circulation that produced barite over the last ~6,000 years. Precipitation of hydrothermal barite, disseminated within the host rock and lining fractures, vugs, and conduits, was controlled by decreasing temperatures and mixing of hydrothermal fluids with oxidized seawater. Repeated fluctuations in hydrothermal fluid temperature and chemistry resulted in complex sequences of barite and sulfide minerals lining vugs and conduits, whereas rapid cooling following fracture events led to precipitation of only barite and some Fe oxide coatings on barite crystals. A wide range in ages of barite within drill cores (i.e., 380–5,990 yrs before present (BP)) reflect repeated pulses of hydrothermal fluids through the altered volcanic and mineralized rocks that make up the hydrothermal mound structures, with the younger ages (i.e., 34–220 yrs BP), representing more recent barite-precipitating fluid circulation accessing fractures, veins, and vugs. Barite from chimney samples is mostly young (i.e., 23–1,680 yrs BP), with the majority precipitated between 23 to 41 yrs BP; reflecting the structural stability (standing life) of the chimneys and possible influences from varying hydrothermal fluid chemistry or reactivation of vent fields. Three generalized age groupings, representing major episodes of barite-precipitating hydrothermal fluid circulation, are resolved from the Suzette area (19–45, 810–1,900, and 3,740–4,710 yrs BP, including 1σ errors); with the most recent ages recorded from both the Suzette and Pual Ridge areas. Fast-spreading rates within the Manus basin, an abundance of faults and variable magmatic inputs are major factors controlling the frequency and longevity of these episodes of hydrothermal activity. Mineral resource models and comparisons indicate that the Cu-Zn-Ag-Au–rich Suzette deposit is small; however the measured age range is comparable to ages given for modeled (typical) seafloor massive sulfide deposits from back-arc and arc environments. We suggest that the scale of the Suzette deposit may have been limited during formation by a low hydrothermal fluid flux and/or inappropriate physical and chemical conditions for sufficient metal precipitation from hydrothermal fluids.

Stable strontium isotope fractionation in synthetic barite

The mineral barite (BaSO4) accommodates strontium (Sr) in its crystal structure, providing an archive of Sr-isotopes (87Sr/86Sr and δ88/86Sr) in the highly stable sulfate mineral. We investigated mass dependent stable Sr-isotope fractionation (Δ88/86Sr=δ88/86Srsolid−δ88/86Srsolution) during inorganic precipitation of barite from a barium-rich solution by addition of sulfate under controlled conditions and compared this to equilibrium isotopic fractionation calculated using Density Functional Theory modeling. Sr-substituted barite is predicted to have lower 88Sr/86Sr than any other studied species, and at 25°C will be about 0.6–0.7‰ lower than the two modeled Sr(H2O)82+-bearing salts that could approximate aqueous Sr2+. This agrees in direction and order of magnitude with experimental results that estimate equilibrium Sr-isotope fractionation in barite to be 0.3‰ lower than aqueous Sr2+ at ∼20°C. The high ionic strength of some of the precipitating solutions (up to 1M) and potential differences in the average coordination number of aqueous Sr2+ add to uncertainty in a direct comparison of the calculated equilibrium isotopic fractionation values with the experimental results.Stable Sr-isotope fractionation varied along with the distribution coefficient of Sr [Kd(Sr)=[Sr/Ba]barite/[Sr/Ba]solution], which is a function of both temperature and barite saturation state. However the relationship between mass dependent isotopic fractionation and Kd(Sr) is different for conditions of changing temperature versus barite saturation state. With increasing temperature (from 5 to 40°C), the barite phase became isotopically lighter (Δ88/86Sr=−0.29‰ to −0.41‰). Conversely, with increasing saturation state (saturation index of barite=3.0–4.3) the barite phase became isotopically heavier (Δ88/86Sr=−0.25‰ to −0.10‰). These observations suggest chemical kinetic effects control isotopic fractionation rather than equilibrium temperature effects. The relationship with saturation state indicates the potential presence of a diffusive boundary layer. Barite crystal morphology appears to be affected by the diffusion rate of solute (sulfate) to the growing crystal surface relative to the overall growth rate of barite crystals during precipitation.

Crystals of suspended marine barite in the eastern equatorial Pacific: processes of dissolution and effects on crystal morphology

Suspended particulate substances were sampled in the eastern equatorial Pacific in water column from surface to near bottom in five stations in 2005, from which 868 barite crystals were recovered. The barite crystals were examined under scanning electron microscopy. About 61% of the total barites crystals contained detectable Sr by energy dispersive X-ray spectrometry. Barite crystals could be classified into four groups based on their morphology: 1) bladed; 2) ovoid or rounded; 3) arrow-like; and 4) irregularly shaped. The arrow-like barite crystals in natural environment has never been reported before. In addition, about a half of the studied crystals showed features of dissolution as cavities or holes inside of the crystals or around their edges. We found that differential dissolution of barite crystals is consequence of heterogeneous Sr distribution in barite crystals. Our results would help in understanding the biogeochemical processes of marine barite formation and preservation in seawater and marine sediments.