Mineralogical and geochemical investigations of pyrite-rich mine waste from a kyanite mine in Central Virginia with comments on recycling

A pyrite-rich waste stream is one of three types generated from a kyanite mine in central Virginia near the town of Dillwyn, Buckingham County. Currently, ore consists of approximately 3% pyrite waste and an estimated 382,000 tons of this waste stream has been generated over the past 60 years. The mineralogy of the waste stream consists of variable amounts of pyrite (70–>99%), talc (1–20%), quartz (1–10%), kyanite (0.5–5%) with minor or trace amounts of magnetite, hematite, galena, anorthite and rare earth phosphate. Energy dispersive spectroscopy analysis indicates that talc has minor amounts of Al up to 1.57 wt% and Fe up to 4.29 wt% and pyrite grains have no impurities above detection limit of approximately 0.1 wt%. Bulk chemical analysis of selected elements using inductively coupled plasma-mass spectrometry analysis indicate that Zn (28.82–367.71 ppm), As (8.94–18.26 ppm), Se (44.62–64.50 ppm), Cd (0.19–1.03 ppm), Hg (0.87–35.91 ppm), and Pb (65.10–189.66 ppm) occur at levels of some environmental concern. Au and Ag concentrations are negligible. Currently the waste stream is well managed and sold, but for a low price. Talc is of sufficient quality to be of interest for recycling but the estimated 540 tons generated per year is not a suitable quantity to be economically viable. Currently, the waste stream is not viable for recycling for higher monetary value; however, the characteristics of the pyrite may enable such recycling in the future for solar energy technologies. This and other associated waste streams show long term promise for integrated recycling and may play important economic roles in an economically disadvantaged region.     

An investigation of aspects of mine waste from a kyanite mine,Central Virginia,USA

Kyanite Mining Corporation, located in Dillwyn, Virginia has been in operation for over 50 years and their local operation is the largest kyanite mine in the world. As part of the processing at this location, a magnetic separate is generated and a minimum estimation of 3.57 million tons of waste has accumulated. Currently no use for the magnetic separate has been identified. We investigated eight representative samples of the magnetic mine waste which varied in color from a dark tan to black, to determine if the waste could be recycled as an ore or could be used as an environmental media. Mineralogical investigations indicate the composition of the magnetic mine waste is dominated by magnetite, kyanite, lesser amounts of hematite and charcoal. Magnetite occurs as fine grained crystals and as inclusions in kyanite. Hematite occurs largely as botryoidal textures, as discrete grains, and as coatings on kyanite grains. Fe-oxide spheres ranging in diameter from approximately 5–100 μm are common and may compose up to 10% in some samples. Titanium dioxide was rarely observed as coatings on silicate mineral grains. Energy dispersive spectroscopy analysis on magnetite crystals indicates they have end-member compositions. Bulk property investigations indicate that grain size distributions of samples are primarily unimodal with 20–40% of material being between 0.600 and 0.250 mm. Hydraulic conductivity values of samples investigated vary between 0.0036 and 0.0077 cm/s and are broadly consistent with those expected of sands with similar grain size distributions. In addition to the magnetic waste stream a light blue, water soluble, amorphous Cu sulfate occurs as a coating on surfaces of boulders. The coating is composed of rounded interlocking particles 5–60 μm in diameter. This material is of some environmental concern for freshwater invertebrates, but can be managed using sorption media. Hyperspectral data were gathered of the magnetic separate, kyanite ore samples, and the light blue Cu sulfate. The signatures of the kyanite ore, the blue mineral coating, and a mixture of the two provide spectral fingerprints that an imaging spectrometer could exploit for rapid detection and subsequent environmental monitoring.     

Metasomatized lithospheric mantle beneath Turkana depression in southern Ethiopia (the East Africa Rift): geochemical and Sr–Nd–Pb isotopic characteristics

Mantle xenoliths entrained in Quaternary alkaline basalts from the Turkana Depression in southern Ethiopia (the East Africa Rift) were studied for their geochemical and Sr–Nd–Pb isotopic compositions to constrain the evolution of the lithosphere. The investigated mantle xenoliths are spinel lherzolites in composition with a protogranular texture. They can be classified into two types: anhydrous and hydrous spinel lherzolites; the latter group characterized by the occurrences of pargasite and phlogopite. The compositions of whole-rock basaltic component (CaO = 3.8–5.6 wt%, Al₂O₃ = 2.5–4.1 wt%, and MgO = 34.7–38.1 wt%), spinel (Cr# = 0.062–0.117, Al₂O₃ = 59.0–64.4 wt%) and clinopyroxene (Mg# = 88.4–91.7, Al₂O₃ = 5.2–6.7 wt%) indicate that the lherzolites are fertile and have not experienced significant partial melting. Both types are characterized by depleted ⁸⁷Sr/⁸⁶Sr (0.70180–0.70295) and high ¹⁴³Nd/¹⁴⁴Nd (0.51299–0.51348) with wide ranges of ²⁰⁶Pb/²⁰⁴Pb (17.86–19.68) isotopic compositions. The variations of geochemical and isotopic compositions can be explained by silicate metasomatism induced by different degree of magma infiltrations from ascending mantle plume. The thermobarometric estimations suggest that the spinel lherzolites were derived from depths of 50–70 km (15.6–22.2 kb) and entrained in the alkaline magma at 847–1,052°C. Most of the spinel lherzolites from this study record an elevated geotherm (60–90 mW/m²) that is related to the presence of rising mantle plume in an active tectonic setting. Sm–Nd isotopic systematic gives a mean T_DM model age of 0.95 Ga, interpreted as the minimum depletion age of the subcontinental lithosphere beneath the region.     

Chemical composition of spinel from Uralian-Alaskan-type Mafic–Ultramafic complexes and its petrogenetic significance

Uralian-Alaskan-type mafic–ultramafic complexes are recognized as a distinct class of intrusions regarding lithologic assemblage, mineral chemistry and petrogenetic setting. In the present study, we discuss new data on the distribution of major elements in minerals of the spinel group in rocks from Uralian-Alaskan-type complexes in the Ural Mountains, Russia. Cr-rich spinel (Cr₂O₃ = 20–53 wt%) in dunite with interstitial clinopyroxene and in wehrlite cumulates indicate that it reacted with interstitial liquid resulting in the progressive substitution of Al₂O₂ and Cr₂O₃ by Fe₂O₃ and TiO₂. A distinct change in the spinel chemistry in dunite (Cr₂O₃ = 47–53 wt%), towards Al₂O₃- and Cr₂O₃-poor but Fe₂O₃-rich compositions monitors the onset of clinopyroxene fractionation in wehrlite (Cr₂O₃ = 15–35 wt%, Al₂O₃ = 1–8 wt%, Fe₂O₃ = 25–55 wt%). In more fractionated mafic rocks, the calculated initial composition of exsolved spinel traces the sustained crystallization of clinopyroxene by decreasing Cr₂O₃ and increasing FeO, Fe₂O₃ and fO₂. Finally, the initiation of feldspar crystallization buffers the Al₂O₃ content in most of the spinels in mafic rocks at very low Cr₂O₃ contents (<5 wt%). The fractionation path all along and the reaction with interstitial liquid are accompanied by increasing Fe₂O₃ contents in the spinel. This likely is caused by a significant increase in the oxygen fugacity, which suggests closed system fractionation processes. Spinel with Cr₂O₃ < 27 wt% is exsolved into a Fe₂O₃-rich and an Al₂O₃-rich phase forming a variety of textures. Remarkably, exsolved spinel in different lithologies from complexes 200 km apart follows one distinct solvus line defining a temperature of ca. 600°C. This indicates that the parental magmas were emplaced and eventually cooled at similar levels in the lithosphere, likely near the crust–mantle boundary. Eventually, these 600°C hot bodies were rapidly transported into colder regions of the upper crust during a regional tectonic event, probably during the major active phase of the Main Uralian Fault.     

Andalusite and Na- and Li-rich cordierite in the La Costa pluton, Sierras Pampeanas, Argentina: textural and chemical evidence for a magmatic origin

The La Costa pluton in the Sierra de Velasco (NW Argentina) consists of S-type granitoids that can be grouped into three igneous facies: the alkali-rich Santa Cruz facies (SCF, SiO₂ ~67 wt%) distinguished by the presence of andalusite and Na- and Li-rich cordierite (Na₂O = 1.55–1.77 wt% and Li₂O = 0.14–0.66 wt%), the Anillaco facies (SiO₂ ~74 wt%) with a significant proportion of Mn-rich garnet, and the Anjullón facies (SiO₂ ~75 wt%) with abundant albitic plagioclase. The petrography, mineral chemistry and whole-rock geochemistry of the SCF are compatible with magmatic crystallization of Na- and Li-rich cordierite, andalusite and muscovite from the peraluminous magma under moderate P–T conditions (~1.9 kbar and ca. 735°C). The high Li content of cordierite in the SCF is unusual for granitic rocks of intermediate composition.     

High-Mg# andesitic lavas of the Shisheisky Complex,Northern Kamchatka: implications for primitive calc-alkaline magmatism

Primitive arc magmatism and mantle wedge processes are investigated through a petrologic and geochemical study of high-Mg# (Mg/Mg + Fe > 0.65) basalts, basaltic andesites and andesites from the Kurile-Kamchatka subduction system. Primitive andesitic samples are from the Shisheisky Complex, a field of Quaternary-age, monogenetic cones located in the Aleutian–Kamchatka junction, north of Shiveluch Volcano, the northernmost active composite volcano in Kamchatka. The Shisheisky lavas have Mg# of 0.66–0.73 at intermediate SiO₂ (54–58 wt%) with low CaO (<8.8%), CaO/Al₂O₃ (<0.54), and relatively high Na₂O (>3.0 wt%) and K₂O (>1.0 wt%). Olivine phenocryst core compositions of Fo90 appear to be in equilibrium with whole-rock ‘melts’, consistent with the sparsely phyric nature of the lavas. Compared to the Shisheisky andesites, primitive basalts from the region (Kuriles, Tolbachik, Kharchinsky) have higher CaO (>9.9 wt%) and CaO/Al₂O₃ (>0.60), and lower whole-rock Na₂O (<2.7 wt%) and K₂O (<1.1 wt%) at similar Mg# (0.66–0.70). Olivine phenocrysts in basalts have in general, higher CaO and Mn/Fe and lower Ni and Ni/Mg at Fo88 compared to the andesites. The absence of plagioclase phenocrysts from the primitive andesitic lavas contrasts the plagioclase-phyric basalts, indicating relatively high pre-eruptive water contents for the primitive andesitic magmas compared to basalts. Estimated temperature and water contents for primitive basaltic andesites and andesites are 984–1,143°C and 4–7 wt% H₂O. For primitive basalts they are 1,149–1,227°C and 2 wt% H₂O. Petrographic and mineral compositions suggest that the primitive andesitic lavas were liquids in equilibrium with mantle peridotite and were not produced by mixing between basalts and felsic crustal melts, contamination by xenocrystic olivine, or crystal fractionation of basalt. Key geochemical features of the Shisheisky primitive lavas (high Ni/MgO, Na₂O, Ni/Yb and Mg# at intermediate SiO₂) combined with the location of the volcanic field above the edge of the subducting Pacific Plate support a genetic model that involves melting of eclogite or pyroxenite at or near the surface of the subducting plate, followed by interaction of that melt with hotter peridotite in the over-lying mantle wedge. The strongly calc-alkaline igneous series at Shiveluch Volcano is interpreted to result from the emplacement and evolution of primitive andesitic magmas similar to those that are present in nearby monogenetic cones of the Shisheisky Complex.     

Petrogenetic and geotectonic significance of Neoproterozoic suprasubduction mantle as revealed by the Wizer ophiolite complex,Central Eastern Desert,Egypt

Ophiolite complexes, formed in a suprasubduction zone environment during Neoproterozoic time, are widely distributed in the Eastern Desert of Egypt. Their mantle sections provide important information on the origin and tectonic history of ocean basins these complexes represent. The geochemistry and mineralogy of the mantle section of the Wizer ophiolite complex, represented by serpentinites after harzburgite containing minor dunite bodies, are presented. Presence of antigorite together with the incipient alteration of chromite and absence of chlorite suggests that serpentinization occurred in the mantle wedge above a Neoproterozoic subduction zone. Wizer peridotites have a wide range of spinel compositions. Spinel Cr# [100Cr/(Cr + Al)] decrease gradually from dunite bodies (Cr# = 81–87) and their host highly depleted harzburgites (Cr# = 67–79) to the less depleted harzburgites (Cr# = 57–63). Such decreases in mantle refractory character are accompanied by higher Al and Ti contents in bulk compositions. Estimated parental melt compositions point to an equilibration with melts of boninitic composition for the dunite bodies (TiO₂ = ~<0.07–0.22 wt%; Al₂O₃ = 9.4–10.6 wt%), boninitic-arc tholeiite for the highly depleted harzburgites (TiO₂ = <0.09–0.28 wt%; Al₂O₃ = 11.2–14.1 wt%) and more MORB-like affinities for the less depleted harzburgites (TiO₂ = ~<0.38–0.51 wt%; Al₂O₃ = 14.5–15.3 wt%). Estimated equilibrium melts are found in the overlying volcanic sequence, which shows a transitional MORB–island arc geochemical signature with a few boninitic samples. Enrichment of some chromites in TiO₂ and identification of sulfides in highly depleted peridotites imply interaction with an impregnating melt. A two-stage partial melting/melt–rock reaction model is advocated, whereby, melting of a depleted mantle source by reaction with MORB-like melts is followed by a second stage melting by interaction with melts of IAT–boninitic affinities in a suprasubduction zone environment to generate the highly depleted harzburgites and dunite bodies. The shift from MORB to island arc/boninitic affinities within the mantle lithosphere of the Wizer ophiolite sequence suggests generation in a protoarc-forearc environment. This, together with the systematic latitudinal change in composition of ophiolitic lavas in the Central Eastern Desert (CED) of Egypt from IAT–boninitic affinities to more MORB-like signature, implies that the CED could represent a disrupted forearc-arc-backarc system above a southeast-dipping subduction zone.     

Phase relations and formation of sodium-rich majoritic garnet in the system Mg3Al2Si3O12–Na2MgSi5O12 at 7.0 and 8.5 GPa

The pseudo-binary system Mg₃Al₂Si₃O₁₂–Na₂MgSi₅O₁₂ modelling the sodium-bearing garnet solid solutions has been studied at 7 and 8.5 GPa and 1,500–1,950°C. The Na-bearing garnet is a liquidus phase of the system up to 60 mol% Na₂MgSi₅O₁₂ (NaGrt). At higher content of NaGrt in the system, enstatite (up to ∼80 mol%) and then coesite are observed as liquidus phases. Our experiments provided evidence for a stable sodium incorporation in garnet (0.3–0.6 wt% Na₂O) and its control by temperature and pressure. The highest sodium contents were obtained in experiments at P = 8.5 GPa. Near the liquidus (T = 1,840°C), the equilibrium concentration of Na₂O in garnet is 0.7–0.8 wt% (∼6 mol% Na₂MgSi₅O₁₂). With the temperature decrease, Na concentration in Grt increases, and the maximal Na₂MgSi₅O₁₂ content of ∼12 mol% (1.52 wt% Na₂O) is gained at the solidus of the system (T = 1,760°С). The data obtained show that most of natural diamonds, with inclusions of Na-bearing garnets usually containing <0.4 wt% Na₂O, could be formed from sodium-rich melts at pressures lower than 7 GPa. Majoritic garnets with higher sodium concentrations (>1 wt% Na₂O) may crystallize at a pressure range of 7.0–8.5 GPa. However the upper pressure limit for the formation of naturally occurring Na-bearing garnets is restricted by the eclogite/garnetite bulk composition.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Garnet-bearing tonalitic porphyry from East Kunlun,Northeast Tibetan Plateau: implications for adakite and magmas from the MASH Zone

A garnet-bearing tonalitic porphyry from the Achiq Kol area, northeast Tibetan Plateau has been dated by SHRIMP U-Pb zircon techniques and gives a Late Triassic age of 213 ± 3 Ma. The porphyry contains phenocrysts of Ca-rich, Mn-poor garnet (CaO > 5 wt%; MnO < 3 wt%), Al-rich hornblende (Al₂O₃ ~ 15.9 wt%), plagioclase and quartz, and pressure estimates for hornblende enclosing the garnet phenocrysts yield values of 8–10 kbar, indicating a minimum pressure for the garnet. The rock has SiO₂ of 60–63 wt%, low MgO (<2.0 wt%), K₂O (<1.3 wt%), but high Al₂O₃ (>17 wt%) contents, and is metaluminous to slightly peraluminous (ACNK = 0.89–1.05). The rock samples are enriched in LILE and LREE but depleted in Nb and Ti, showing typical features of subduction-related magmas. The relatively high Sr/Y (~38) ratios and low HREE (Yb < 0.8 ppm) contents suggest that garnet is a residual phase, while suppressed crystallization of plagioclase and lack of negative Eu anomalies indicate a high water fugacity in the magma. Nd–Sr isotope compositions of the rock (εNd_T = −1.38 to −2.33; ⁸⁷Sr/⁸⁶Sr_i = 0.7065–0.7067) suggest that both mantle- and crust-derived materials were involved in the petrogenesis, which is consistent with the reverse compositional zoning of plagioclase, interpreted to indicate magma mixing. Both garnet phenocrysts and their ilmenite inclusions contain low MgO contents which, in combination with the oxygen isotope composition of garnet separates (+6.23‰), suggests that these minerals formed in a lower crust-derived felsic melt probably in the MASH zone. Although the rock samples are similar to adakitic rocks in many aspects, their moderate Sr contents (<260 ppm) and La/Yb ratios (mostly 16–21) are significantly lower than those of adakitic rocks. Because of high partition coefficients for Sr and LREE, fractionation of apatite at an early stage in the evolution of the magma may have effectively decreased both Sr and LREE in the residual melt. It is suggested that extensive crystallization of apatite as an early phase may prevent some arc magmas from evolving into adakitic rocks even under high water fugacity.     

Mobilization of Ag,heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería,SE Spain)

We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerías mine in Almería (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg^–1), Ba (mean 2.5%), Fe (mean 114,000 mg kg^–1), Sb (mean 342.5 mg kg^–1), Pb (mean 1,229.8 mg kg^–1), Zn (mean 493 mg kg^–1), Mn (mean 4,321.1 mg kg^–1), Cd (mean 1.2 mg kg^–1) and Eu (mean 4.0 mg kg^–1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)₃, which controls the solubility of Eu in the pH–Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.     

Characterization of non-equilibrium and equilibrium occurrences of paragonite/muscovite intergrowths in an eclogite from the Sesia–Lanzo Zone (Western Alps, Italy)

 Coexisting muscovite and paragonite have been observed in an eclogite from the Sesia–Lanzo Zone (Western Alps, Italy). The P-T conditions of this eclogite reached 570–650 °C and 19–21 kbar and the rocks show several stages of mineral growth during their retrograde path, ranging from the subsequent lower-P eclogite facies to the blueschist facies and then the greenschist facies. Muscovite and paragonite are very common in these rocks and show two texturally different occurrences indicating equilibrium and non-equilibrium states between them. In one mode of occurrence they coexist in equilibrium in the lower-P eclogite facies. In the same rock muscovite ± albite also replaced paragonite during a greenschist-facies overprint, as evidenced by unique across – (001) layer boundaries. The chemical compositions of the lower-P eclogite-facies micas plot astride the muscovite – paragonite solvus, whereas the compositions of the greenschist-facies micas lie outside the solvus and indicate disequilibrium. The TEM observations of the textural relations of the greenschist-facies micas imply structural coherency between paragonite and muscovite along the layers, but there is a sharp discontinuity in the composition of the octahedral and tetrahedral sheets across the phase boundary. We propose that muscovite formed through a dissolution and recrystallization process, since no gradual variations toward the muscovite – paragonite interfaces occur and no intermediate, homogeneous Na-K phase has been observed. Because a solid-state diffusion mechanism is highly unlikely at these low temperatures (300–500 °C), especially with respect to octahedral and tetrahedral sites, it is assumed that H₂O plays an important role in this process. The across-layer boundaries are inferred to be characteristic of such non-equilibrium replacement processes. The characterization of these intergrowths is crucial to avoiding erroneous assumptions regarding composition and therefore about the state of equilibrium between both micas, which in turn may lead to misinterpretations of thermometric results. Received: 3 February 1999 / Accepted: 19 October 1999     

The geochemistry of mantle chromitites from the northern part of the Oman ophiolite: inferred parental melt compositions

Chromitites from a single section through the mantle in the Oman ophiolite are of two different types. Low-cr# chromitites, of MORB affinity are found in the upper part of the section, close to the Moho. High-cr# chromitites, with arc affinities are found deeper in the mantle. Experimental data are used to recover the compositions of the melts parental to the chromitites and show that the low-cr# chromitites were derived from melts with 14.5–15.4 wt% Al₂O₃, with 0.4 to 0.9 wt% TiO₂ and with a maximum possible mg# of 0.76. In contrast the high-cr# chromitites were derived from melts with 11.8–12.9 wt% Al₂O₃, 0.2–0.35 wt% TiO₂ and a maximum melt mg# of 0.785. Comparison with the published compositions of lavas from the Oman ophiolite shows that the low-cr# chromitites may be genetically related to the upper (Lasail, and Alley) pillow lava units and the high-cr# chromitites the boninites of the upper pillow lava Alley Unit. The calculated TiO₂–Al₂O₃ compositions of the parental chromitite magmas indicate that the high-cr# chromitites were derived from high-Ca boninitic melts, produced by melting of depleted mantle peridotite. The low-cr# chromitites were derived from melts which were a mixture of two end-members—one represented by a depleted mantle melt and the other represented by MORB. This mixing probably took place as a result of melt–rock reaction. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Compositional and thermal evolution of olivine-hosted melt inclusions in small-volume basaltic eruptions: a “simple” example from Dotsero Volcano,NW Colorado

Olivine-hosted melt inclusions have been analyzed from the young (4,150 ± 300 ybp) Dotsero basaltic (48.2 wt% SiO₂) lava flow in Northwest Colorado, USA. Silicate melt-inclusion compositions have a bimodal distribution (41–46 wt% SiO₂ and 47–50 wt% SiO₂). Low-Si melt inclusions record high pre-eruptive sulfur concentrations (>1,000 ppm S) and variations in their major- and trace-element compositions appears to be related to shallow assimilation of local basement sandstone. Whole-rock compositions are modeled as a contamination of low-Si inclusion compositions with ~10 wt% sandstone. Host olivine crystallization may have accompanied magma injection into a shallow storage chamber. In contrast to the low-Si melt inclusions, the high-Si population is relatively degassed and records late-stage rapid crystallization either during or post-eruption. Hopper or skeletal olivine grains in conjunction with the bimodal inclusion compositions suggest relatively rapid cooling rates at the time of eruption and inclusion entrapment. Inclusion compositions, in conjunction with mineral textures, therefore provide a more complete picture of shallow magma processes, coupling the relative timing of undercooling and crystallization, assimilation and melt compositional evolution. Most of the inclusion and host textural and compositional data indicates late and very shallow petrogenetic processes and does not appear to record deeper (mid-, lower-crustal) processes.     

Solubility of manganotantalite, zircon and hafnon in highly fluxed peralkaline to peraluminous pegmatitic melts

The behavior of tantalum and zirconium in pegmatitic systems has been investigated through the determination of Ta and Zr solubilities at manganotantalite and zircon saturation from dissolution and crystallization experiments in hydrous, Li-, F-, P- and B-bearing pegmatitic melts. The pegmatitic melts are synthetic and enriched in flux elements: 0.7–1.3 wt% Li₂O, 2–5.5 wt% F, 2.8–4 wt% P₂O₅ and 0–2.8 wt% B₂O₃, and their aluminum saturation index ranges from peralkaline to peraluminous (ASI_Li = Al/[Na + K + Li] = 0.8 to 1.3) with various K/Na ratios. Dissolution and crystallization experiments were conducted at temperatures varying between 700 and 1,150°C, at 200 MPa and nearly water-saturated conditions. For dissolution experiments, pure synthetic, end member manganotantalite and zircon were used in order to avoid problems with slow solid-state kinetics, but additional experiments using natural manganotantalite and zircon of relatively pure composition (i.e., close to end member composition) displayed similar solubility results. Zircon and manganotantalite solubilities considerably increase from peraluminous to peralkaline compositions, and are more sensitive to changes in temperature or ASI of the melt than to flux content. A model relating the enthalpy of dissolution of manganotantalite to the ASI_Li of the melt is proposed: ∆H _diss (kJ/mol) = 304 × ASI_Li − 176 in the peralkaline field, and ∆H _diss (kJ/mol) = −111 × ASI_Li + 245 in the peraluminous field. The solubility data reveal a small but detectable competitivity between Zr and Ta in the melt, i.e., lower amounts of Zr are incorporated in a Ta-bearing melt compared to a Ta-free melt under the same conditions. A similar behavior is observed for Hf and Ta. The competitivity between Zr (or Hf) and Ta increases from peraluminous to peralkaline compositions, and suggests that Ta is preferentially bonded to non-bridging oxygens (NBOs) with Al as first-neighbors, whereas Zr is preferentially bonded to NBOs formed by excess alkalies. As a consequence Zr/Ta ratios, when buffered by zircon and manganotantalite simultaneously, are higher in peralkaline melts than in peraluminous melts.     

The high PT stability of apatite and Cl partitioning between apatite and hydrous potassic phases in peridotite: an experimental study to 19 GPa with implications for the transport of P,Cl and K in the upper mantle

High PT experiments were performed in the range 2.5–19 GPa and 800–1,500°C using a synthetic peridotite doped with trace elements and OH-apatite or with Cl-apatite + phlogopite. The aim of the study was (1) to investigate the stability and phase relations of apatite and its high PT breakdown products, (2) to study the compositional evolution with P and T of phosphate and coexisting silicate phases and (3) to measure the Cl-OH partitioning between apatite and coexisting calcic amphibole, phlogopite and K-richterite. Apatite is stable in a garnet-lherzolite assemblage in the range 2.5–8.7 GPa and 800–1,100°C. The high-P breakdown product of apatite is tuite γ-Ca₃ (PO₄)₂, which is stable in the range 8–15 GPa and 1,100–1,300°C. Coexisting apatite and tuite were observed at 8 GPa/1,050°C and 8.7 GPa/1,000°C. MgO in apatite increases with P from 0.8 wt% at 2.5 GPa to 3.2 wt% at 8.7 GPa. Both apatite and tuite may contain significant Na, Sr and REE with a correlation indicating 2 Ca²⁺=Na⁺ + REE³⁺. Tuite has always higher Sr and REE and lower Fe and Mg than apatite. Phosphorus in the peridotite phases decreases in the order P_melt ≫ P_grt ≫ P_Mg2SiO4 > P_cpx > P_opx. The phosphate-saturated P₂O₅ content of garnet increases from 0.07 wt% at 2.5 GPa to 1.5 wt% at 12.8 GPa. Due to the low bulk Na content of the peridotite, ^[8]Na^[4]P^[8]M²⁺ ₋₁ ^[4]Si₋₁ only plays a minor role in controlling the phosphorus content of garnet. Instead, element correlations indicate a major contribution of ^[6]M^2+[4]P^[6]M³⁺ ₋₁ ^[4]Si₋₁. Pyroxenes contain ~200–500 ppm P and olivine has 0.14–0.23 wt% P₂O₅ in the P range 4–8.7 GPa without correlation with P, T or X_Mg. At ≥12.7 GPa, all Mg₂SiO₄ polymorphs have <200 ppm P. Coexisting olivine and wadsleyite show an equal preference for phosphorus. In case of coexisting wadsleyite and ringwoodite, the latter fractionates phosphorus. Although garnet shows by far the highest phosphorus concentrations of any peridotite silicate phase, olivine is no less important as phosphorus carrier and could store the entire bulk phosphorus budget of primitive mantle. In the Cl-apatite + phlogopite-doped peridotite, apatite contains 0.65–1.35 wt% Cl in the PT range 2.5–8.7 GPa/800–1,000°C. Apatite coexists with calcic amphibole at 2.5 GPa, phlogopite at 2.5–5 GPa and K-richterite at 7 GPa, and all silicates contain between 0.2 and 0.6 wt% Cl. No solid potassic phase is stable between 5 and 8.7 GPa. Cl strongly increases the solubility of K in hydrous fluids. This may lead to the breakdown of phlogopite and give rise to the local presence in the mantle of fluids strongly enriched in K, Cl, P and incompatible trace elements. Such fluids may get trapped as micro-inclusions in diamonds and provide bulk compositions suitable for the formation of unusual phases such as KCl or hypersilicic Cl-rich mica.     

Fluid-assisted retrogression of garnet and P–T history of metapelites from HP/UHP metamorphic terrane (Pohorje Mountains, Eastern Alps)

Fluid inclusions in garnet combined with element X-ray mapping, phase equilibrium modelling and conventional thermobarometry have been used to constrain the metamorphic evolution of metapelitic gneiss from the HP/UHP metamorphic terrane of Pohorje Mountains in the Eastern Alps, Slovenia. Retrograde P–T trajectory from ~2.75 GPa and 780°C is constrained by the composition of matrix phengite (6.66 apfu Si) coexisting with garnet cores, kyanite and quartz. The intersection of the X _Prp = 0.25 isopleth for the garnet with the upper stability boundary for K-feldspar in the matrix indicates near-isothermal decompression to ~0.9 GPa at 720°C. Temperatures over 650°C during this stage are corroborated by the high degree of ordering of graphite inclusions associated with Zn, Mg-rich staurolite and phlogopite in the Mg-rich (X _Prp = 0.22–0.25) garnet cores. Majority of garnet porphyroblasts are depleted in Mg (down to X _Prp = 0.09) and enriched in Mn (up to X _Sps = 0.12) along cracks and at their margins. The associated retrograde mineral assemblage comprises Zn, Mg-poor staurolite, muscovite, biotite–siderophyllite, sillimanite and quartz. The onset of the retrogression and the compositional modification of the garnet porphyroblasts were accompanied by the addition of fluid-deposited graphite around older graphite inclusions, probably due to removal of water from a graphite-buffered COH fluid by dissolution in partial silicic melt. Instantaneous expulsion of water near the melt solidus (640°C, max. 0.45 GPa) caused dissolution of the graphite at redox conditions corresponding to 0.25–1.25 logfO₂ units below the QFM buffer, giving rise to a H₂O–CO₂–CH₄ fluid trapped in primary inclusions in Mn-rich, Mg-poor, almandine garnet that reprecipitated within the retrogressed domains. The absence of re-equilibration textures and consistent densities of the fluid inclusions reflect a near-isochoric cooling postdating the near-isothermal decompression. Bulk water content in the metapelite attained 2 wt% during this stage. The low-degree partial melting and extensive hydration due to the release of the internally derived, low-pressure aqueous fluids led to the reset of peak-pressure mineral assemblage.     

Stable isotope and fluid inclusion evidence for the origin of the Brandberg West area Sn–W vein deposits, NW Namibia

The Brandberg West region of NW Namibia is dominated by poly-deformed turbidites and carbonate rocks of the Neoproterozoic Damara Supergoup, which have been regionally metamorphosed to greenschist facies and thermally metamorphosed up to mid-amphibolite facies by Neoproterozoic granite plutons. The meta-sedimentary rocks host Damaran-age hydrothermal quartz vein-hosted Sn–W mineralization at Brandberg West and numerous nearby smaller deposits. Fluid inclusion microthermometric studies of the vein quartz suggests that the ore-forming fluids at the Brandberg West mine were CO₂-bearing aqueous fluids represented by the NaCl–CaCl₂–H₂O–CO₂ system with moderate salinity (mean=8.6 wt% NaCl_equivalent).Temperatures determined using oxygen isotope thermometry are 415–521°C (quartz–muscovite), 392–447°C (quartz–cassiterite), and 444–490°C (quartz–hematite). At Brandberg West, the oxygen isotope ratios of quartz veins and siliciclastic host rocks in the mineralized area are lower than those in the rocks and veins of the surrounding areas suggesting that pervasive fluid–rock interaction occurred during mineralization. The O- and H-isotope data of quartz–muscovite veins and fluid inclusions indicate that the ore fluids were dominantly of magmatic origin, implying that mineralization occurred above a shallow granite pluton. Simple mass balance calculations suggest water/rock ratios of 1.88 (closed system) and 1.01 (open system). The CO₂ component of the fluid inclusions had similar δ ¹³C to the carbonate rocks intercalated with the turbidites. It is most likely that mineralization at Brandberg West was caused by a combination of an impermeable marble barrier and interaction of the fluids with the marble. The minor deposits in the area have quartz veins with higher δ ¹⁸O values, which is consistent with these deposits being similar geological environments exposed at higher erosion levels.     

Petrogenesis of early cretaceous carbonatite and ultramafic lamprophyres in a diatreme in the Batain Nappes,Eastern Oman continental margin

Allochthonous carbonatite and ultramafic lamprophyre occur in a diatreme at the beach of the Asseelah village, northeastern Oman. The diatreme consists of heterogeneous deposits dominated by ‘diatreme facies’ pyroclastic rocks. These include aillikite and carbonatite, which intrude late Jurassic to early Cretaceous cherts and shales of the Wahra Formation within the Batain nappes. Both rock types are dominated by carbonate, altered olivine, Ti–Al–phlogopite and Cr–Al–spinel and contain varying amounts of apatite and rutile. The carbonatite occur as fine-grained heterolithic breccias with abundant rounded carbonatite xenoliths, glimmerite and crustal xenoliths. The aillikite consists of pelletal lapilli tuff with abundant fine-grained carbonatite autoliths and crustal xenoliths, which resemble those in the carbonatite breccia. The aillikite and carbonatite are characterized by low SiO₂ (11–24 wt%), MgO (9.5–12.4 wt%) and K₂O (<0.3 wt%), but high CaO (18–22 wt%), Al₂O₃ (4.75–7.04 wt%), Fe₂O_3tot (8.7–13.8 wt%) and loss-on-ignition (24–30 wt%). Higher CaO, Fe₂O_3total, Al₂O₃, MnO, TiO₂, P₂O₅ and lower SiO₂ and MgO content distinguish carbonatite from the aillikite. The associated carbonatite xenoliths and autoliths have intermediate composition between the aillikite and carbonatite. Mg number is variable and ranges between 58 and 66 in the carbonatite, 66 and 72 in the aillikite and between 48 to 64 in the carbonatite autoliths and xenoliths. The Asseelah aillikite, carbonatite, carbonatite xenoliths and autoliths overlap in most of their mineral parageneses, mineral composition and major and trace element chemistry and have variable but overlapping Sr, Nd and Pb isotopic composition, implying that these rocks are related to a common type of parental magma with variable isotopic characteristics. The Asseelah aillikite, carbonatite and carbonatites xenoliths are LREE-enriched and significantly depleted in HREE. They exhibit similar smooth, subparallel REE pattern and steep slopes with (La/Sm) _n of 6–10 and relative depletion in heavy rare earth elements (Lu = 3–10 chondrite). Initial ⁸⁷Sr/⁸⁶Sr ratios vary from 0.70409 to 0.70787, whereas initial ¹⁴³Nd/¹⁴⁴Nd ratios vary between 0.512603 and 0.512716 (εNd _i between 2.8 and 3.6). ²⁰⁶Pb/²⁰⁴Pb _i ratios vary between 18.4 and 18.76, ²⁰⁷Pb/²⁰⁴Pb _i ratios vary between 15.34 and 15.63, whereas ²⁰⁸Pb/²⁰⁴Pb _i varies between 38.42 and 39.05. Zircons grains extracted from the carbonatite have a mean age of 137 ± 1 Ma (95% confidence, MSWD = 0.49). This age correlates with large-scale tectonic events recorded in the early Indian Ocean at 140–160 Ma. Geochemical and isotopic signatures displayed by the Asseelah rocks can be accounted for by vein-plus-wall-rock model of Foley (1992) wherein veins are represented by phlogopite, carbonate and apatite and depleted peridotite constitutes the wall-rock. The carbonatite and aillikite magmatism is probably a distal effect of the breaking up of Gondwana, during and/or after the rift-to-drift transition that led to the opening of the Indian Ocean.     

Revisiting the compositions and volatile contents of olivine-hosted melt inclusions from the Mount Shasta region: implications for the formation of high-Mg andesites

Primitive chemical characteristics of high-Mg andesites (HMA) suggest equilibration with mantle wedge peridotite, and they may form through either shallow, wet partial melting of the mantle or re-equilibration of slab melts migrating through the wedge. We have re-examined a well-studied example of HMA from near Mt. Shasta, CA, because petrographic evidence for magma mixing has stimulated a recent debate over whether HMA magmas have a mantle origin. We examined naturally quenched, glassy, olivine-hosted (Fo_87–94) melt inclusions from this locality and analyzed the samples by FTIR, LA-ICPMS, and electron probe. Compositions (uncorrected for post-entrapment modification) are highly variable and can be divided into high-CaO (>10 wt%) melts only found in Fo > 91 olivines and low-CaO (<10 wt%) melts in Fo 87–94 olivine hosts. There is evidence for extensive post-entrapment modification in many inclusions. High-CaO inclusions experienced 1.4–3.5 wt% FeO^T loss through diffusive re-equilibration with the host olivine and 13–28 wt% post-entrapment olivine crystallization. Low-CaO inclusions experienced 1–16 wt% olivine crystallization with <2 wt% FeO^T loss experienced by inclusions in Fo > 90 olivines. Restored low-CaO melt inclusions are HMAs (57–61 wt% SiO₂; 4.9–10.9 wt% MgO), whereas high-CaO inclusions are primitive basaltic andesites (PBA) (51–56 wt% SiO₂; 9.8–15.1 wt% MgO). HMA and PBA inclusions have distinct trace element characteristics. Importantly, both types of inclusions are volatile-rich, with maximum values in HMA and PBA melt inclusions of 3.5 and 5.6 wt% H₂O, 830 and 2,900 ppm S, 1,590 and 2,580 ppm Cl, and 500 and 820 ppm CO₂, respectively. PBA melts are comparable to experimental hydrous melts in equilibrium with harzburgite. Two-component mixing between PBA and dacitic magma (59:41) is able to produce a primitive HMA composition, but the predicted mixture shows some small but significant major and trace element discrepancies from published whole-rock analyses from the Shasta locality. An alternative model that involves incorporation of xenocrysts (high-Mg olivine from PBA and pyroxenes from dacite) into a primary (mantle-derived) HMA magma can explain the phenocryst and melt inclusion compositions but is difficult to evaluate quantitatively because of the complex crystal populations. Our results suggest that a spectrum of mantle-derived melts, including both PBA and HMA, may be produced beneath the Shasta region. Compositional similarities between Shasta parental melts and boninites imply similar magma generation processes related to the presence of refractory harzburgite in the shallow mantle.