Extraction and distribution of soil organic and inorganic selenium in coal mine environments of Wyoming, USA

 Selenium (Se), an animal toxicant and aquifer contaminant, occurs in coal mine environments of Wyoming. There is a paucity of information on solution-phase Se speciation in mine soils. The objectives of this study were to compare Se extraction efficiencies of various reagents and to characterize SeO^2– ₃ (selenite), SeO^2– ₄ (selenate) and organic Se components in these extracts. Forty coal mine soils were extracted using DI (deionized) water, hot water (0.1% CaCl₂), AB-DTPA, NaOH, and KH₂PO₄. Each solution was analyzed for total dissolved Se, and inorganic and organic Se fractions. Both inorganic and organic Se fractions were detected in the soil extracts. The order of Se (total, inorganic, and organic) extraction efficiency for different reagents was DI water < hot water < AB-DTPA < NaOH < KH₂PO₄. The inorganic–organic Se ratios in DI water, hot water, AB-DTPA, NaOH, and KH₂PO₄ extracts were 60 : 40, 26 : 74, 61 : 39, 87 : 13, and 52 : 48, respectively, indicating predominance of inorganic Se in all but the hot water extract. Selenite was the dominant inorganic species in AB-DTPA and KH₂PO₄ extracts, while SeO^2– ₄ was the major Se species in the DI water, hot water, and NaOH extracts. Significant correlations (P<0.01) were observed among extractable inorganic Se [NaOH and KH₂PO₄ (r=0.95); hot water and AB-DTPA (r=0.89)], total soluble Se [DI water with hot water (r=0.98) and AB-DTPA (r=0.95)], and Se species [SeO^2– ₃ in AB-DTPA with SeO^2– ₄ in NaOH (r=0.94) and SeO^2– ₃ in KH₂PO₄ (r=0.88)]. These correlations are indicative of Se extraction efficiency, thermodynamically predicted chemical transformations (such as oxidation of SeO^2– ₃ to SeO^2– ₄), and probable interconversions between the organic and inorganic Se fractions (r=0.70 in KH₂PO₄ extracts); as a whole the correlations can be used as statistical validations of possible geochemical processes. Received: 21 August 1995 · Accepted: 16 October 1995     

Selenium speciation and partitioning within Burkholderia cepacia biofilms formed on α-Al2O3 surfaces

The distribution and speciation of Se within aerobic Burkholderia cepacia biofilms formed on α-Al₂O₃ (1-102) surfaces have been examined using grazing-angle X-ray spectroscopic techniques. We present quantitative information on the partitioning of 10⁻⁶ M to 10⁻³ M selenate and selenite between the biofilms and underlying alumina surfaces derived from long-period X-ray standing wave (XSW) data. Changes in the Se partitioning behavior over time are correlated with microbially induced reduction of Se(VI) and Se(IV) to Se(0), as observed from X-ray absorption near edge structure (XANES) spectroscopy.Selenite preferentially binds to the alumina surfaces, particularly at low [Se], and is increasingly partitioned into the biofilms at higher [Se]. When B. cepacia is metabolically active, B. cepacia rapidly reduces a fraction of the SeO₃²⁻ to red elemental Se(0). In contrast, selenate is preferentially partitioned into the B. cepacia biofilms at all [Se] tested due to a lower affinity for binding to the alumina surface. Rapid reduction of SeO₄²⁻ by B. cepacia to Se(IV) and Se(0) subsequently results in a vertical segregation of Se species at the B. cepacia/α-Al₂O₃ interface. Elemental Se(0) accumulates within the biofilm with Se(VI), whereas Se(IV) intermediates preferentially sorb to the alumina surface.B. cepacia/α-Al₂O₃ samples incubated with SeO₄²⁻ and SeO₃²⁻ when the bacteria were metabolically active result in a significant reduction in the mobility of Se vs. X-ray treated biofilms. Remobilization experiments show that a large fraction of the insoluble Se(0) produced within the biofilm is retained during exchange with Se-free solutions. In addition, Se(IV) intermediates generated during Se(VI) reduction are preferentially bound to the alumina surface and do not fully desorb. In contrast, Se(VI) is rapidly and extensively remobilized.     

High-temperature thermal expansion of lime, periclase, corundum and spinel

The high-temperature cell parameters of lime (CaO), periclase (MgO), corundum (Al₂O₃), and spinel (MgAl₂O₄) have been determined from 300 up to 3000 K through X-ray diffraction experiments with synchrotron radiation. The good agreement found with dilatometric results suggests that vacancy-type defects do not make a large contribution to thermal expansion for these oxides, even near the melting point, justifying the use of X-ray diffraction for determining volume properties up to very high temperatures. Thermal expansion coefficients were determined from the measured cell volumes with equations of the form α=α₀ + α₁ T + α₂/T ². Along with available isobaric heat capacity and compressibility data, these derived coefficients clearly show that anharmonic effects contribute little to the isochoric heat capacities (C _v ) of CaO, MgO, and Al₂O₃, which do not depart appreciably from the 3nR Dulong and Petit limit. Received: 31 March 1999 / Revised, accepted: 23 June 1999     

Hydrothermal synthesis of pumpellyite–okhotskite series minerals

Summary ?Hydrothermal experiments to synthesize pumpellyite group minerals of the pumpellyite–okhotskite series and to investigate their stability have been carried out at 200, 300 and 400 MPa P _fluid and 250–500 °C by using cold-seal pressure vessels and solid buffers of MnO₂–Mn₂O₃, Cu₂O–CuO and Cu₂O–Cu buffer assemblages. Okhotskite and pumpellyite rich in the okhotskite component crystallized from an oxide mixture starting material of Ca₄MgMn³⁺ ₃Al₂Si₆O_24.5-oxide+excess H₂O at P _fluid of 200, 300 and 400 MPa and temperatures of 300 and 400 °C. However, a single phase of okhotskite was not produced, and associated piemontite, hausmannite, wollastonite, clinopyroxene, corundum, braunite–neltnerite solid solution and alleghanyite also formed. Mn-pumpellyite of the okhotskite–pumpellyite join occurs as aggregates of needle crystals, rounded grains or flaky crystals. Chemical compositions are variable and range from pumpellyite-(Mn²⁺) to okhotskite: 31–36 SiO₂, 13–21 Al₂O₃, 12–25 total Mn₂O₃, 0.6–4 MgO and 20–24 wt.% CaO. Reconnaissance experiments using a starting material of synthetic Ca₂Mn³⁺Al₂Si₃O₁₂(OH)-piemontite at 300 MPa and temperatures of 250, 300, 400 and 500 °C indicate that Mn-rich pumpellyite can crystallize from piemontite at lower temperatures than the stability field of piemontite. The Mn-rich pumpellyite was accompanied by garnet, wollastonite and alleghanyite. The chemical compositions of the Mn-pumpellyites are 32–36 SiO₂, 18–27 Al₂O₃, 8–18 total Mn₂O₃ and 20–23 wt.% CaO. This study shows that the stability fields of piemontite, piemontite+Mn-pumpellyite, and Mn-pumpellyite range in this order with decreasing temperature under high fO₂ conditions. The maximum stability temperature of Mn-rich pumpellyite lies between 400 and 500 °C at 200–400 MPa in high fO₂ conditions. Received March 3, 2000; revised version accepted December 28, 2001     

IIb trioctahedral chlorite from the Barberton greenstone belt: crystal structure and rock composition constraints with implications to geothermometry

IIb trioctahedral chlorite in the Barberton greenstone belt (BGB) metavolcanic rocks was formed during pervasive greenschist metamorphism. The chem‐ical composition of the chlorite is highly variable, with the Fe/(Fe+Mg) ratio ranging from 0.12 to 0.8 among 53 samples. The chemical variation of the chlorite results from the chemical diversity of the host rock, especially the MgO content of the rock, but major details of the variation pattern of the chlorite are due to the crystal structure of the chlorite. All major cation abundances in the chlorite are strongly correlated with each other. Sil‐icon increases with Mg and decreases with Fe, while Al^IV and Al^VI decrease with Mg and increase with Fe²⁺. A complex exchange vector explains over 90% of the chlorite compositional variation: Mg₄SiFe²⁺ ₋₃Al^VI ₋₁ Al^IV ₋₁, which has 3 parts Fe-Mg substitution coupled with one part tschermakite substitution. This ratio is required to maintain the charge and site balances and the dimensional fit between the tetrahedral and octahedral sheets. The subtle change in Al substitution in chlorite implies that Al^VI is preferentially ordered in the M(4) site, and about 84% of the Al^VI present is in the M(4) sites when they are nearly filled with Al^VI. Based on 47 analyzed chlorite-bearing rock samples, chlorite (Chl) composition is strongly correlated with the MgO content of the host rock. Calculated correlation coefficients are +0.91 for SiO_2Chl-MgO_Rock, −0.87 for Al₂O_3Chl-MgO_Rock, +0.89 for MgO_Chl-MgO_Rock, and −0.85 for FeO_Chl-MgO_Rock. Only weak correlations have been found between chlorite oxides and other oxides of rock (between same oxides in chlorite and rock: SiO₂−0.67, Al₂O₃ + 0.59, FeO −0.41). However, MgO_Chl is saturated at about 36 wt% in rocks that have MgO above 22 wt%.The MgO_Chl is about 5 wt% when the host rock approaches 0 wt% of MgO. This implies that Mg substituting into the chlorite is approximately limited to 1.5–9.2 Mg atoms per formula unit and 1.0–3.2 Al^IV. Chlorite geothermometers can not be applied to all BGB samples. However, the empirical chlorite geothermometer based on Al^IV of chlorite may be applicable to chlorites formed under metamorphic conditions because it can predict the chemical composition of the chlorite from basaltic and dacitic samples in this study. An estimated temperature of about 320°C for the greenschist metamorphism of the greenstone belt through this geothermometer is consistent with that obtained by other geothermometers. Received: 22 January 1996 / Accepted: 15 August 1996     

An assessment of selenate co-precipitation with gypsum

In this study, we assessed the co-precipitation of selenate (SeO₄²⁻) with gypsum (CaSO₄·2H₂O) in controlled laboratory experiments. Batch testing was used to quantify the ability of CaSO₄·2H₂O to co-precipitate dissolved SeO₄²⁻ over a range of dissolved SeO₄²⁻-Se concentrations (0–50 mg/L) and under slightly acidic (pH ∼5.5–6.1) and oxic (Eh ∼416−501 mV) conditions. Aqueous samples were analyzed using inductively coupled plasma optical emission spectrometry, solid samples using X-ray diffraction and Raman spectroscopy, and digests of selected CaSO₄·2H₂O precipitates using inductively coupled plasma-mass spectrometry. The concentration of Se co-precipitated in CaSO₄·2H₂O increased linearly with dissolved SeO₄²⁻-Se concentration. The aqueous analyses and calculations based on the CaSO₄·2H₂O digest data show between 14–19 % of the dissolved Se was removed during the co-precipitation experiments. The strong linear relationship between SeO₄²⁻-Se added to the test solutions and Se co-precipitated in CaSO₄·2H₂O can be used to estimate the concentration of co-precipitated SeO₄^2- if the concentration of SeO₄^2- in the associated porewater is known, and vice versa. Results indicate that <1% of SeO₄²-Se was removed from the test solutions during co-precipitation and the mass of Se in CaSO₄·2H₂O solids was low, ranging between 0−120 μg/g. These results were used in conjunction with field- and model-derived data to show co-precipitation of SeO₄^2- with CaSO₄·2H₂O should be a minor SeO₄^2- sequestration mechanism. The findings of this study should be applicable to mined rock dumps in North America and elsewhere.     

Crystal chemistry of selenates with mineral-like structures: VII. The structure of (H<Subscript>3</Subscript>O)[(UO<Subscript>2</Subscript>)(SeO<Subscript>4</Subscript>)(SeO<Subscript>2</Subscript>OH)] and some structural features of selenite-selenates

The crystal structure of a new compound, (H₃O)[(UO₂)(SeO₄)(SeO₂OH)] (monoclinic, P2₁/n, a = 8.6682(19), b = 10.6545(16), c = 9.846(2) Å, β = 97.881(17)°, V = 900.7(3) ų), was solved by direct methods and refined to R ₁ = 0.050. The structure contains two symmetrically different Se atoms. The Se1 site is coordinated by three O atoms as is characteristic of Se⁴⁺ cations. The Se2 site is coordinated by four O atoms and forms selenate anion SeO ₄ ^2? . The structure is based on selenite-selenate sheets [(UO₂)(SeO₄)(SeO₂OH)]^? linked by the interlayer H₃O^? ions. The sheets are parallel to (101). The structure is compared to that of schmiederite, Pb₂Cu₂(SeO₃)(SeO₄)(OH)₄.     

Abundances of F,Cl S and P in Volcanic Magmas and Their Evolution,Wudalianchi

F, Cl, S and P were determined, using electron microprobe, in magmatic inclusions trapped within minerals and glass mesostasis from Wudalianchi volcanic rocks. The initial volcanic magma from Wudalianchi corresponds to the basanitic magma crystallized near the surface ( pressure < 91 Mpa ). The potential H₂O content of this magma is in the range 2 — 4 wt. %. The initial composition of volcanic magmas varies regularly from early to late volcanic events. From the Middle Pleistocene to the recent eruptions (1719 – 1721 yr.), the basicity of volcanic magma tends to increase, as reflected by an increase in MgO and CaO contents and by a progressive decrease in SiO₂ and K₂O contents. Meanwhile. from early (Q₂ ) to late (Q₃) episodic eruptions of the Middle Pleistocene, the initial concentrations of chlorine in volcanic magmas range from 1430 – 1930 ppm to 1700 ppm and decrease to 700 — 970 ppm for the first episodic eruption during the Holocene (Q ₄ ¹ ). The chlorine concentrations of volcanic magmas of recent eruption (Q ₄ ² ) are increased again to 2600 – 2870 ppm. A parallel evolution trend for phosphorus and chlorine concentrations in magmas has been certified: 1500 – 5970 ppm (Q₂)→ 3500 – 4210 ppm (Q₃)→ 1100– 3500 ppm (Q ₄ ¹ )→ 6800– 7900 ppm (Q ₄ ² ). The fluorine contents of volcanic magmas, from early to late volcanic events, show the same trend: 770 – 2470 ppm → 200–700 ppm → 700 – 800 ppm. During the crystallization-evolution of volcanic magmas, fluorine and phosphorus tend to be enriched in residual magmas as a result of crystal-melt differentiation. for example. the fluorine contents reach 5000– 6800 ppm and the phosphorus contents, 2.93wt.% in residual magmas. An appreciable amount of chlorine may be lost from water rich volcanic magmas prior to eruption as a result of degassing. Apparently, water serves as a gas carrier for the chlorine. The chlorine contents of residual magmas may decrease to 100 – 300 ppm. The volcanic magmas from Wudalianchi are poor in sulfur, normally ranging from 200 to 400ppm. On account of the behavior of sulfur in magmas and the strontium and oxygen isotopic analyses ((⁸⁷Sr /⁸⁶Sr)_i=0.70503– 0.70589; δ¹⁸O = + 5.50 – + 6.89 ‰ ), it can be considered that the basanitic magmas in the Wudalianchi volcanic area came from the upper mantle and have not yet been contaminated probably by continental crust materials.     

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.     

Experiments on silicate melt immiscibility in the system Fe2SiO4–KAlSi3O8–SiO2–CaO–MgO–TiO2–P2O5 and implications for natural magmas

The effect of CaO and MgO, with or without TiO₂ and P₂O₅, on the two-melt field in the simplified system Fe₂SiO₄–KAlSi₃O₈–SiO₂ has been experimentally determined at 1,050°–1,240°C, 400 MPa. Despite the suppressing effect of MgO, CaO, and pressure on silicate melt immiscibility, our experiments show that this process is still viable at mid-crustal pressures when small amounts (0.6–2.0 wt%) of P₂O₅ and TiO₂ are present. Our data stress that the major element partition coefficients between the two melts are highly correlated with the degree of polymerisation (nbo/t) of the SiO₂-rich melt, whatever temperature, pressure, or exact composition. Experimental immiscible melt compositions in natural systems at 0.1 MPa from the literature (lunar and tholeiitic basalts) plot on similar but distinct curves compared to the simplified system. These relations between melt polymerisation and partition coefficients, which hold for a large range of compositions and fO₂, are extended to various volcanic and plutonic rocks. This analysis strengthens the proposal that silicate melt immiscibility can be important in volcanic rocks of various compositions (from tholeiitic basalts to lamprophyres). However, the majority of proposed immiscible compositions in plutonic rocks are at least not coexisting melts, but may have suffered accumulation of early crystallized minerals.     

Pressure dependence of electrical conductivity of (Mg,Fe)SiO<Subscript>3</Subscript> ilmenite

The electrical conductivity of (Mg_0.93Fe_0.07)SiO₃ ilmenite was measured at temperatures of 500–1,200 K and pressures of 25–35 GPa in a Kawai-type multi-anvil apparatus equipped with sintered diamond anvils. In order to verify the reliability of this study, the electrical conductivity of (Mg_0.93Fe_0.07)SiO₃ perovskite was also measured at temperatures of 500–1,400 K and pressures of 30–35 GPa. The pressure calibration was carried out using in situ X-ray diffraction of MgO as pressure marker. The oxidation conditions of the samples were controlled by the Fe disk. The activation energy at zero pressure and activation volume for ilmenite are 0.82(6) eV and −1.5(2) cm³/mol, respectively. Those for perovskite were 0.5(1) eV and −0.4(4) cm³/mol, respectively, which are in agreement with the experimental results reported previously. It is concluded that ilmenite conductivity has a large pressure dependence in the investigated P–T range.     

Abundances of chemical elements of the granitoids in different geotectonic units of China and their characteristics

On the basis of actual analytical data of 767 composited samples collected mainly from about 750 large to middle representative granitoid bodies all over China, the average chemical compositions and element abundances of about 70 chemical elements of SiO₂, Al₂O₃, Fe₂O₃, FeO, MgO, CaO, Na₂O, K₂O, H₂O⁺, CO₂, TFe₂O₃, Ag, As, Au, B, Ba, Be, Bi, Cd, Cl, Co, Cr, Cs, Cu, F, Ga, Ge, Hf, Hg, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, S, Sb, Sc, Se, Sn, Sr, Ta, Th, Ti, Tl, U, V, W, Zn, Zr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y in alkalifeldspar granite, syenogranite and adamellite in 7 geotectonic units in China such as Tianshan-Xing’an orogenic series, Sino-Korean metaplatform, Kunlun-Qilian-Qinling orogenic series, Yunnan-Tibet orogenic series, Yangtze metaplatform, South China-Youjiang orogenic zone and Himalayan orogenic belt, are calculated and presented in this paper. In addition, the characteristics of petrochemical parameters, trace element contents and rare earth element distributions of different rock types of the granitoids in different geotectonic units are also sufficiently discussed. Translated from Acta Geologica Sinica, 2007, 81(1): 47–59 [译自: 地质学报]     

Chemical composition of nyerereite and gregoryite from natrocarbonatites of Oldoinyo Lengai volcano,Tanzania

Alkali carbonates nyerereite, ideally Na₂Ca(CO₃)₂ and gregoryite, ideally Na₂CO₃, are the major minerals in natrocarbonatite lavas from Oldoinyo Lengai volcano, northern Tanzania. They occur as pheno- and microphenocrysts in groundmass consisting of fluorite and sylvite; nyerereite typically forms prismatic crystals and gregoryite occurs as round, oval crystals. Both minerals are characterized by relatively high contents of various minor elements. Raman spectroscopy data indicate the presence of sulfur and phosphorous as (SO₄)²⁻ and (PO₄)³⁻ groups. Microprobe analyses show variable composition of both nyerereite and gregoryite. Nyerereite contains 6.1–8.7 wt % K₂O, with subordinate amounts of SrO (1.7–3.3 wt %), BaO (0.3–1.6 wt %), SO₃ (0.8–1.5 wt %), P₂O₅ (0.2–0.8 wt %) and Cl (0.1–0.35 wt %). Gregoryite contains 5.0–11.9 wt % CaO, 3.4–5.8 wt % SO₃, 1.3–4.6 wt % P₂O₅, 0.6–1.0 wt % SrO, 0.1–0.6 wt % BaO and 0.3–0.7 wt % Cl. The content of F is below detection limits in nyerereite and gregoryite. Laser ablation ICP-MS analyses show that REE, Mn, Mg, Rb and Li are typical trace elements in these minerals. Nyerereite is enriched in REE (up to 1080 ppm) and Rb (up to 140 ppm), while gregoryite contains more Mg (up to 367 ppm) and Li (up to 241 ppm) as compared with nyerereite.     

辽西黄半吉沟早白垩世义县组高镁安山岩的成因

利用橄榄石和熔体包裹体,结合全岩的方法对辽西地区早白垩世义县组黄半吉沟火山岩的成因进行了研究。黄半吉沟火山岩SiO_2=53.41%~53.74%,MgO=8.15%~8.23%,Mg#=~70(Mg#=mol Mg/(Mg+Fe2+)),为高镁安山岩;全岩在TAS图解上,落在玄武安山岩范围内,属于亚碱性系列;它们具有较高Ni(119×10-6~125×10-6)和高Cr(467×10-6~521×10-6),显示幔源岩浆特征;在微量元素组成上,黄半吉沟高镁安山岩Sr=920×10-6~930×10-6,Y=16.1×10-6~16.4×10-6,Sr/Y=57~58;在微量元素原始地幔标准化蛛网图上,黄半吉沟高镁安山岩显示轻重稀土分异,明显的Nb-Ta-Ti和弱的Zr-Hf负异常,Ba、Sr和Pb正异常,这些特征与大陆下地壳非常相似。熔体包裹体MgO为6.5%~9.7%,SiO_2为51%~53%,不符合典型高镁安山岩的定义;在TAS图解上它们落在玄武粗安岩内,属于碱性系列;MgO与其它主量元素成分呈明显或者弱的负相关关系,说明它们的成分主要受控于橄榄石结晶分离过程。黄半吉沟高镁安山岩的橄榄石Fo值为75~91;CaO含量为0.10%~0.18%,NiO为0.05%~0.41%,Fe/Mn比值为60~80。黄半吉沟高镁安山岩的全岩和熔体包裹体成分存在显著差异,如熔体包裹体具有更高的Al2O3和更低的SiO_2。结合全岩微量元素特征,我们认为黄半吉沟高镁安山岩在地壳深度的岩浆演化过程中加入了来自下地壳的酸性熔体,是壳幔相互作用的结果。全岩较低Ni高Mg#,熔体包裹体低CaO并落在CATS-Olivine-Quartz相图的热障碍边界线富硅一侧,以及橄榄石低Ca和陡倾的Fo-Ni关系,指示黄半吉沟高镁安山岩的幔源岩浆是来自以斜方辉石为主辉石岩的源区。我们认为广泛发育于辽西地区的早白垩世义县组高镁安山岩可能经历了壳幔相互作用,因而不能作为拆沉作用导致岩石圈大规模减薄的重要证据。     

Activity variations attending tungsten skarn formation,Pine Creek,California

An integrated geochemical analysis of the well-exposed Pine Creek, California tungsten skarn deposit has been undertaken to evaluate changes in chemical gradients across various lithologies. Thermodynamic calculations using available experimental and thermodynamic data allow limits to be assigned to the activities of important chemical components in the metasomatic environment. Quantifiable changes in “non-volatile” component activites (CaO, MgO, Al₂O₃, Fe₂O₃, WO₃) and in fugacities (O₂, F₂) have been traced across the system. The activities of Al₂O₃, Fe₂O₃ and WO₃ generally increase from the marble (<10², <10⁻⁶, <10⁻⁵ respectively), through the outer skarn zone and into the massive garnet skarn (10^−1.7±0.3, 10^−3.4±0.4, 10^−4.8±0.1) While CaO and MgO activities decrease for the same traverse from 10⁻⁵ and 10^−2.1±1 respectively, to <10^−5.7 and <10⁻³. Calculated oxygen fugacities are 10^−23.5+1.0 at T=800 K (527° C), about one log unit below QFM, and more reducing than that required by Mt-Py-Po. The high variance of the garnet-pyroxene-quartz assemblages adds sufficient uncertainty to the calculated activities for individual specimens that only the large-scale trends survive the small-scale scatter. None of the chemical variables emerge as major independent or controlling factors for the mineralogy or phase compositions. Changes in the activity of one component may be offset by compensatory changes in another resulting in an environment that, while different from Pine Creek, could still host scheelite mineralization. Mass balance calculations indicate that the exposed endoskarn cannot have supplied the necessary chemical components to convert the country rock to skarn.     

The role of acidity–basicity in evaporating refractory inclusions in chondrites

When melts of Ca–Al inclusions in chondrites, which are dominated by the oxides SiO₂, MgO, CaO, and Al₂O₃, evaporate at high temperatures, the SiO₂ and MgO fugacities are inverted: SiO₂, which is more volatile than MgO, becomes less volatile when melts rich in refractory CaO and Al₂O₃ evaporate. This fugacity inversion can be realistically explained within the framework of D.S. Korzhinskii’s theory of acid–base interaction between components in silicate melts. According to this theory, an increase in CaO concentration in the melt increases its basicity, and this, in turn, increases the activity (and hence, also fugacity) of MgO and decreases those of SiO₂. In the real compositions of the Ca–Al inclusions in chondrites, the MgO/SiO₂ ratio systematically decreases with an increase in the CaO concentration under the effect of acid–base interaction.     

Oxyphlogopite K(Mg,Ti,Fe)3[(Si,Al)4O10](O,F)2: A new mineral species of the mica group

Oxyphlogopite is a new mica-group mineral with the idealized formula K(Mg,Ti,Fe)₃[(Si,Al)₄O₁₀](O,F)₂. The holotype material came from a basalt quarry at Mount Rothenberg near Mendig at the Eifel volcanic complex in Rhineland-Palatinate, Germany. The mineral occurs as crystals up to 4 × 4 × 0.2 mm in size encrusting cavity walls in alkali basalt. The associated minerals are nepheline, plagioclase, sanidine, augite, diopside, and magnetite. Its color is dark brown, its streak is brown, and its luster is vitreous. D _meas = 3.06(1) g/cm³ (flotation in heavy liquids), and D _calc = 3.086 g/cm³. The IR spectrun does not contain bands of OH groups. Oxyphlogopite is biaxial (negative); α = 1.625(3), β = 1.668(1), and γ = 1.669(1); and 2V _meas = 16(2)° and 2V _calc = 17°. The dispersion is strong; r < ν. The pleochroism is medium; X > Y > Z (brown to dark brown). The chemical composition is as follows (electron microprobe, mean of 5 point analyses, wt %; the ranges are given in parentheses; the H₂O was determined using the Alimarin method; the Fe²⁺/Fe³⁺ was determined with X-ray emission spectroscopy): Na₂O 0.99 (0.89–1.12), K₂O 7.52 (7.44–7.58), MgO 14.65 (14.48–14.80), CaO 0.27 ((0.17–0.51), FeO 4.73, Fe₂O₃ 7.25 (the range of the total iron in the form of FeO is 11.09–11.38), Al₂O₃ 14.32 (14.06–14.64), Cr₂O₃ 0.60 (0.45–0.69), SiO₂ 34.41 (34.03–34.66), TiO₂ 12.93 (12.69–13.13), F 3.06 (2.59–3.44), H₂O 0.14; O=F₂ −1.29; 99/58 in total. The empirical formula is (K_0.72Na_0.14Ca_0.02)(Mg_1.64Ti_0.73Fe_0.30²⁺ Fe_0.27³⁺Cr_0.04)_Σ2.98(Si_2.59Al_1.27Fe_0.14³⁺ O₁₀) O_1.20F_0.73(OH)_0.07. The crystal structure was refined on a single crystal. Oxyphlogopite is monoclinic with space group C2/m; the unit-cell parameters are as follows: a = 5.3165(1), b = 9.2000(2), c = 10.0602(2) ?, β = 100.354(2)°. The presence of Ti results in the strong distortion of octahedron M(2). The strongest lines of the X-ray powder diffraction pattern [d, ? (I, %) [hkl]] are as follows: 9.91(32) [001], 4.53(11) 110], 3.300(100) [003], 3.090(12) [112], 1.895(21) [005], 1.659(12) [−135], 1.527(16) [−206, 060]. The type specimens of oxyphlogopite are deposited at the Fersman Mineralogical Museum in Moscow, Russia; the registration numbers are 3884/2 (holotype) and 3884/1 (cotype).     

Petrography and major elements geochemistry of microgranular enclaves and neoproterozoic granitoids of south Khasi,Meghalaya: Evidence of magma mixing and alkali diffusion

Neoproterozoic (690±19 Ma) felsic magmatism in the south Khasi region of Precambrian northeast Indian shield, referred to as south Khasi granitoids (SKG), contains country-rock xenoliths and microgranular enclaves (ME). The mineral assemblages (pl-hbl-bt-kf-qtz-mag) of the ME and SKG are the same but differ in proportions and grain size. Modal composition of ME corresponds to quartz monzodiorite whereas SKG are quartz monzodiorite, quartz monzonite and monzogranite. The presence of acicular apatite, fine grains of mafic-felsic minerals, resorbed maficfelsic xenocrysts and ocellar quartz in ME strongly suggest magma-mixed and undercooled origin for ME. Molar Al₂O₃/CaO+Na₂O+K₂O (A/CNK) ratio of ME (0.68–0.94) and SKG (0.81–1.00) suggests their metaluminous (I-type) character. Linear to sub-linear variations of major elements (MgO, Fe₂O₃ ^t, P₂O₅, TiO₂, MnO and CaO against SiO₂) of ME and SKG and two-component mixing model constrain the origin of ME by mixing of mafic and felsic magmas in various proportions, which later mingled and undercooled as hybrid globules into cooler felsic (SKG) magma. However, rapid diffusion of mobile elements from felsic to mafic melt during mixing and mingling events has elevated the alkali contents of some ME.     

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.