Stabilization of arsenic-contaminated mine tailings using natural and calcined oyster shells

Natural oyster shells (NOS) and calcined oyster shells (COS) were used to immobilize arsenic (As) from contaminated mine tailings. In addition, a blend of Portland cement (PC)/cement kiln dust (CKD) was used as a stabilizing agent. The Korean Standard Test (KST) method (1 N HCl extraction) was used to evaluate the effectiveness of the treatment. The experimental results showed that COS effectively immobilized As in treated mine tailings. Specifically, an As concentration less than 1 mg L⁻¹ was obtained following COS treatment at 25 and 30 wt%. However, all the samples subjected to NOS treatments failed the Korean warning standard of 1.2 mg L⁻¹ after 28 days of curing. All of the COS-PC treatments were successful meeting the Korean warning standard after 7 days of curing. However, the PC-only treatment failed to meet the Korean warning standard. Similarly, the CKD-only treatment was failed to meet the Korean warning standard after 7 days of curing. However, the COS-CKD treatment showed that when the COS content was greater than 20 wt%, less than 1 mg L⁻¹ of As leachability was obtained. Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDX) showed needle-like and torpedo-like Ca–As phases in the COS-treated samples suggesting that As was strongly associated with Ca and O. X-ray absorption near edge structure (XANES) analyses confirmed that As(V) was prevalent in the tailings and that there were no changes in As speciation following NOS or COS treatment.     

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.     

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.     

Mineralogical and geochemical investigations of silicate-rich mine waste from a kyanite mine in central Virginia: implications for mine waste recycling

A kyanite mine in central Virginia produces a silicate-rich waste stream which accumulates at a rate of 450,000–600,000 tons per year. An estimated 27 million tons of this waste stream has accumulated over the past 60 years. Grain size distribution varies between 1.000 and 0.053 mm, and is commonly bimodal with modes typically being 0.425 and 0.250 mm and uniformity coefficients vary from 2.000 to 2.333. Hydraulic conductivity values vary from 0.017 to 0.047 cm/s. Mineralogy of the waste stream consists of quartz, muscovite, kyanite and hematite. Muscovite grains have distinct chemical compositions with significant Na₂O content (1.12–2.66 wt%), TiO₂ content (0.63–1.68 wt% TiO₂) and Fe content, expressed as Fe₂O₃ (up to 1.37 wt%). Major element compositions of samples were dominated by SiO₂ (87.894–90.997 wt%), Al₂O₃ (6.759–7.741 wt%), Fe₂O₃ (1.136–1.283 wt%), and K₂O (0.369–0.606 wt%) with other components being <1.000 wt%. Elements of environmental concern (V, Cr, Ni, Cu, Zn, As, Ag, Sn, Sb, Ba, Hg, Tl, and Pb) were detected; however, the concentrations of all elements except Ni were below that of the kyanite quartzites in the region from which the waste is derived. Both major and trace element compositions indicate minimal variation in composition. The waste stream has potential for recycling. Muscovite is suitable for recycling as a paint pigment or other industrial applications. Muscovite and hematite are commonly intergrown and are interpreted to be material where much of the elements of environmental concern are concentrated. Reprocessing of the waste stream to separate muscovite from other components may enable the waste stream to be used as constructed wetland media for Virginia and nearby states. Recycling of this mine waste may have a positive impact on the local economy of Buckingham County and aid in mitigation of wetland loss.     

Chalcophile element geochemistry and petrogenesis of high-Ti and low-Ti magmas in the Permian Emeishan large igneous province,SW China

Sulfide-poor mafic layered intrusions, sills/dykes and lava flows in the Funing region, SW China, are part of the ~260 Ma Emeishan large igneous province. They belong to either a high-Ti group (TiO₂ = 1.6–4.4 wt%) with elevated Ti/Y ratios (351–1,018), or a low-Ti group (TiO₂ < 1.2 wt%) with low Ti/Y ratios (133–223). This study investigates the role of fractionation of olivine, chromite and sulfide on the distributions of chalcophile elements, Ni, Cu and PGE, of the high-Ti and low-Ti group rocks at Funing. The high-Ti group rocks contain 1.6–5.3 ppb Pt + Pd, 0.06–0.43 ppb Ir and 0.01–0.13 ppb Ru, and show relative constant (Cu/Pd)_PM ratios (4.0–9.7) and a negative correlation between Ni/Pd and Cu/Ir ratios. Fractionated IPGE/PPGE patterns and very negative Ru anomalies of the high-Ti group rocks, together with low Fo values (59–62 mol%) of olivine, indicate that the high-Ti magmas may have experienced fractionation of olivine and chromite under S-undersaturated condition. Based on the PGE concentrations, the low-Ti group rocks can be further divided into two subgroups; a high-PGE low-Ti subgroup and a low-PGE low-Ti subgroup. The high-PGE low-Ti group rocks are rich in MgO (10–20 wt%), but Fo values of olivine from the rocks are low (74–76 mol%). The rocks contain highly variable PGE (Pt + Pd = 1.7–88 ppb, Ir = 0.05–1.3 ppb), Ni (179 –1,380 ppm) and Cu (59–568 ppm). They have Cu/Zr ratios >1, low (Y/Pd)_PM ratios (0.2–7.1) and nearly constant (Cu/Pd)_PM ratios (1.5–3.8). The even and parallel chalcophile element patterns of the high-PGE low-Ti subgroup rocks are likely a result of olivine-dominated fractionation under S-undersaturated condition. The low-PGE low-Ti group rocks have low MgO (4.5–8.9 wt%) and very poor PGE (Pt + Pd 0.5–1.6 ppb, Ir 0.004–0.02 ppb) with low Cu/Zr ratios (0.1–0.5), high (Y/Pd)_PM (26–70) and variable (Cu/Pd)_PM ratios (2.8–14). The trough-like chalcophile element patterns of the low-PGE low-Ti subgroup rocks indicate that the magmas were sulfide saturation and sulfide melts were extracted from the magmas. The extracted sulfide melts might be potential Ni–Cu sulfide ores at depth in the Funing region.     

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.     

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.     

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.     

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.     

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.     

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.     

Zircon Hf isotope perspective on the origin of granitic rocks from eastern Bavaria, SW Bohemian Massif

The petrogenetic potential of in situ laser ablation Hf isotope data from melt precipitated zircons was explored through the analyses of about 700 individual crystals derived from about 20 different granitic intrusions covering the Variscan basement segment of eastern Bavaria, SE Germany. In combination with geochemical features, four major suites of granitic rocks can be distinguished: (1) NE Bavarian redwitzites (52–57 wt% SiO₂, intrusion ages around 323 Ma) have chondritic εHf(t) values (+0.8 to –0.4). The redwitzites are hybrid rocks and the Hf data are permissive of mixing of a mantle progenitor and crustal melts. (2) Various intermediate rock types (dioritic dyke, granodiorite, palite, 59–63 wt% SiO₂, 334–320 Ma) from the Bavarian Forest yield negative εHf(t) values between –3.4 and –5.1. These values which apparently contradict a mantle contribution fingerprint an enriched (metasomatized) mantle component that was mixed with crustal material. (3) Voluminous, major crust forming granites sensu stricto (67–75 wt% SiO₂, 328–298 Ma) are characterized by a range in εHf(t) values from –0.5 to –5.6. Different crustal sources and/or modification of crustal melts by various input of juvenile material can explain this variation. (4) Post-plutonic (c. 299 Ma) porphyritic dykes of dacitic composition (64–67 wt% SiO₂) from the southern Bavarian Forest have chondritic εHf(t) values (+0.6 to –1.1) and display large intergrain Hf isotope variation. The dykes form a separate petrogenetic group and the Hf data suggest that the zircons crystallized when a pristine mantle-derived parental melt was modified by infiltration of crustal material. The zircon Hf data form a largely coherent positive array with the whole-rock Nd data and both systems yield similar two-stage depleted mantle model ages (1.1–1.7 Ga).     

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.     

Systematic study of hydrogen incorporation into Fe-free wadsleyite

The H₂O content of wadsleyite were measured in a wide pressure (13–20 GPa) and temperature range (1,200–1,900°C) using FTIR method. We confirmed significant decrease of the H₂O content of wadsleyite with increasing temperature and reported first systematic data for temperature interval of 1,400–1,900°C. Wadsleyite contains 0.37–0.55 wt% H₂O at 1,600°C, which may be close to its water storage capacity along average mantle geotherm in the transition zone. Accordingly, water storage capacity of the average mantle in the transition zone may be estimated as 0.2–0.3 wt% H₂O. The H₂O contents of wadsleyite at 1,800–1,900°C are 0.22–0.39 wt%, indicating that it can store significant amount of water even under the hot mantle environments. Temperature dependence of the H₂O content of wadsleyite can be described by exponential equation C_{\textH2 \textO} = 6 3 7.0 7 \texte ^{- 0.00 4 8T} , C_{{{\text{H}}_{2} {\text{O}}}} = 6 3 7.0 7 {\text{e}}^{ - 0.00 4 8T} , where T is in °C. This equation is valid for temperature range 1,200–2,100°C with the coefficient of determination R ² = 0.954. Temperature dependence of H₂O partition coefficient between wadsleyite and forsterite (D _wd/fo) is complex. According to our data apparent D_wd/fo decreases with increasing temperature from D _wd/fo = 4–5 at 1,200°C, reaches a minimum of D _wd/fo = 2.0 at 1,400–1,500°C, and then again increases to D _wd/fo = 4–6 at 1,700–1,900°C.     

Melting of iron–silicon alloy up to the core–mantle boundary pressure: implications to the thermal structure of the Earth’s core

The melting temperature of Fe–18 wt% Si alloy was determined up to 119 GPa based on a change of laser heating efficiency and the texture of the recovered samples in the laser-heated diamond anvil cell experiments. We have also investigated the subsolidus phase relations of Fe–18 wt% Si alloy by the in-situ X-ray diffraction method and confirmed that the bcc phase is stable at least up to 57 GPa and high temperature. The melting curve of the alloy was fitted by the Simon’s equation, P(GPa)/a = (T _m(K)/T ₀) ^c , with parameters, T ₀ = 1,473 K, a = 3.5 ± 1.1 GPa, and c = 4.5 ± 0.4. The melting temperature of bcc Fe–18 wt% Si alloy is comparable with that of pure iron in the pressure range of this work. The melting temperature of Fe–18 wt% Si alloy is estimated to be 3,300–3,500 K at 135 GPa, and 4,000–4,200 K at around 330 GPa, which may provide the lower bound of the temperatures at the core–mantle boundary and the inner core–outer core boundary if the light element in the core is silicon.     

Hydrous peridotites with Ti-rich chromian spinel as a low-temperature forearc mantle facies: evidence from the Happo-O’ne metaperidotites (Japan)

The Happo-O’ne peridotite complex is situated in the northeastern part of the Hida Marginal Tectonic Zone, central Japan, characterized by the high-P/T Renge metamorphism, and is considered as a serpentinite mélange of Paleozoic age. Peridotitic rocks, being massive or foliated, have been subjected to hydration and metamorphism. Their protoliths are mostly lherzolites to harzburgites with subordinate dunites. We found a characteristic mineral assemblage, olivine + orthopyroxene + tremolite + chlorite + chromian spinel, being stable at low-T, from 650 to 750°C, and high-P, from 16 to 20 kbar, tremolite–chlorite peridotites of the tremolite zone. Olivines are Fo₈₈–Fo_91, and orthopyroxenes (Mg# = 0.91) show low and homogenous distributions of Al₂O₃ (up to 0.25 wt%), Cr₂O₃ (up to 0.25 wt%), CaO (up to 0.36 wt%) and TiO₂ (up to 0.06 wt%) due to the low equilibration temperature. Chromian spinels, which are euhedral and enclosed mainly in the orthopyroxenes, have high TiO_2, 3.1 wt% (up to 5.7 wt%) on average, and high Cr# [=Cr/(Cr + Al) atomic ratio], 0.95 on average but low Fe³⁺ [=Fe³⁺/(Cr + Al + Fe³⁺) atomic ratio, <0.3]. The bulk-rock chemistry shows that the Happo-O’ne metaperidotites with this peculiar spinel are low in TiO₂ (0.01–0.02 wt%), indicating no addition of TiO₂ from the outside source during the metamorphism; the high TiO₂ of the peculiar spinel has been accomplished by Ti release from Ti-bearing high-T pyroxenes during the formation of low-T, low-Ti silicates (<0.1 wt% TiO₂) during cooling. Some dunites are intact from hydration: their olivine is Fo₉₂ and spinel shows high Cr#, 0.72. The Happo-O’ne metaperidotites (tremolite–chlorite peridotites), being in the corner of the mantle wedge, are representative of a hydrous low-T, high-P mantle peridotite facies transitional from a higher T anhydrous peridotite facies (spinel peridotites) formed by in situ retrograde metamorphism influenced by fluids from the subducting slab. They have suffered from low-T (<600°C) retrogressive metamorphism to form antigorite and diopside during exhumation of the Renge metamorphic belt.     

An evaluation of the effect of degassing on the oxidation state of hydrous andesite and dacite magmas: a comparison of pre- and post-eruptive Fe2+ concentrations

The bulk (post-eruptive) wt% FeO concentration in each of 11 phenocryst-poor (<5%) andesite and dacite (60–69 wt% SiO₂) lavas from different monogenetic vents in the Mexican arc has been measured by titration, in duplicate. The results match, within analytical error, the wt% FeO content of the magmas during phenocryst growth (pre-euptive), which were calculated on the basis of oxygen fugacity and temperature results from Fe–Ti two-oxide oxygen barometry. The average deviation between the pre- and post-eruptive FeO concentrations is ±0.15 wt%. Application of the plagioclase-liquid hygrometer shows that at the time of phenocryst growth, these 11 magmas contained from ~3–8 wt% H₂O, which was extensively degassed upon eruption. There is no evidence that degassing of ≤8 wt% H₂O changed the oxidation state of these magmas. Calculations of pre-eruptive and post-eruptive oxygen fugacity values relative to the Ni-NiO buffer (in terms of log₁₀ units) for the 11 samples span a similar range; pre-eruptive ∆NNO = −0.9 to +0.7 and post-eruptive ∆NNO = −0.4 to +0.8. The data further show that extensive groundmass (closed-system) crystallization had no affect on bulk Fe³⁺/Fe²⁺ ratios. Finally, there is no systematic variation in the range of pre-eruptive Fe³⁺/Fe^T values of the samples as a function of SiO₂ concentration (i.e., differentiation). Therefore, the results of this study indicate that the elevated Fe³⁺/Fe^T ratios of arc andesites and dacites, compared with magmas erupted in other tectonic settings, cannot be attributed to the effects of (1) degassing of H₂O, (2) closed-system crystallization, and/or (3) differentiation effects, but instead must be inherited from their parental source rocks (i.e., mantle-derived arc basalts).     

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.     

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.     

The Tarim picrite–basalt–rhyolite suite, a Permian flood basalt from northwest China with contrasting rhyolites produced by fractional crystallization and anatexis

We report major and trace element composition, Sr–Nd isotopic and seismological data for a picrite–basalt–rhyolite suite from the northern Tarim uplift (NTU), northwest China. The samples were recovered from 13 boreholes at depths between 5,166 and 6,333 m. The picritic samples have high MgO (14.5–16.8 wt%, volatiles included) enriched in incompatible element and have high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd isotopic ratios (εNd (t) = −5.3; Sr_i = 0.707), resembling the Karoo high-Ti picrites. All the basaltic samples are enriched in TiO₂ (2.1–3.2 wt%, volatiles free), have high FeOt abundances (11.27–15.75 wt%, volatiles free), are enriched in incompatible elements and have high Sr and low Nd isotopic ratios (Sr_i = 0.7049–0.7065; εNd (t) = −4.1 to −0.4). High Nb/La ratios (0.91–1.34) of basalts attest that they are mantle-derived magma with negligible crustal contamination. The rhyolite samples can be subdivided into two coeval groups with overlapping U–Pb zircon ages between 291 ± 4 and 272 ± 2 Ma. Group 1 rhyolites are enriched in Nb and Ta, have similar Nb/La, Nb/U, and Sr–Nd isotopic compositions to the associated basalts, implying that they are formed by fractional crystallization of the basalts. Group 2 rhyolites are depleted in Nb and Ta, have low Nb/La ratios, and have very high Sr and low Nd isotopic ratios, implying that crustal materials have been extensively, if not exclusively, involved in their source. The picrite–basalt–rhyolite suite from the NTU, together with Permian volcanic rocks from elsewhere Tarim basin, constitute a Large Igneous Province (LIP) that is characterized by large areal extent, rapid eruption, OIB-type chemical composition, and eruption of high temperature picritic magma. The Early Permian magmatism, which covered an area >300,000 km², is therefore named the Tarim Flood Basalt.