Cathodoluminescence of authigenic albite

Authigenic albites in carbonate rocks typically grow in a high-grade diagenetic to low-grade metamorphic environment and often show Roc-Tourné-twinning sensu Füchtbauer. Based on an investigation of four Middle to South European occurrences, they show Mn²⁺- and Fe³⁺-activated cathodoluminescence (CL), as revealed by combined high resolution spectroscopy of cathodoluminescence emission (HRS-CL), electron paramagnetic resonance (EPR), and proton-induced X-ray emission (μPIXE).     

Quantitative aspects of Mn-activated cathodoluminescence of natural and synthetic aragonite

The cathodoluminescence analyses of the trigonal carbonates calcite and dolomite have been applied intensively in sedimentary petrology for a long time and the properties of these minerals are well-known, but much less attention has been paid to aragonite. In this study, the cathodoluminescence behaviour and the trace element composition of natural and synthetic aragonite have been studied employing trace element analyses (proton induced X-ray emission) and luminescence spectroscopy. Aragonite doped with Mn²⁺ has been synthesized in a NH₄⁺–Mg²⁺–Ca²⁺–Cl⁻ solution in contact with a CO₂–H₂O–NH₃ atmosphere. The low effective distribution coefficients indicate a rapid growth of the crystals of millimetre size which occurred within hours or days. The natural aragonite samples contain Mn, Fe and Sr in different concentrations. The Mn-bearing aragonites exhibit a bright green luminescence which is caused by a strong emission band at 575 nm with a half-width of about 84 nm. The luminescence intensity shows a strong positive correlation with Mn in aragonite when Fe and Mn do not exceed 2000 p.p.m. The intensity is depressed if the concentration of these elements exceeds the critical values. In the shell of a recent Unio sp., the luminescence intensity deviates from the linear correlation, although the trace element contents are not too high; this is probably an effect of quenching by organic material between the crystallites of the biogenic aragonite.     

Water content in natural eclogite and implication for water transport into the deep upper mantle

Infrared spectroscopy and ion micro-probe measurements showed that the major constituent minerals of eclogites from the Kokchetav massif, which have been subducted to 180 km depths, contain significant amounts of water up to 870 ppm H₂O (by weight) in omphacite, 130 ppm H₂O in garnet and 740 ppm H₂O in rutile. Omphacite shows three hydroxyl absorption bands at 3440–3460, 3500–3530 and 3600–3625 cm^− 1, garnet has a single band at 3580–3630 cm^− 1 and rutile has a single sharp band at 3280 cm^− 1. The hydroxyl absorbance at these wavenumbers changes with the crystal orientation in polarized infrared radiation, indicating that the water is structurally incorporated in these minerals. The water contents in omphacite and garnet increase systematically with the metamorphic pressure of the host eclogites. The partitioning coefficient of the water content between coexisting garnet and omphacite is similar in different eclogites, D^Grt/Omp0.1–0.2, but decreases slightly at high pressure. Based on the mineral proportions of the eclogites, we estimate bulk-rock water content in the eclogites ranging from 3070 to 300 ppm H₂O (by weight). Although hydrous minerals are absent in the diamond-grade eclogite (60 kbar and 1000 °C), trace amounts of water are incorporated in the nominally anhydrous minerals such as omphacite and garnet. The presence of significant water in these minerals implies that the subducting oceanic crust can transport considerable amounts of water into the deep upper mantle beyond the stability of hydrous minerals. Such water may be stored in the deep upper mantle and have an important influence on dynamics in the Earth's interior.     

Mineralogy of primary carbonate-bearing hypabyssal kimberlite, Lac de Gras, Slave Province, Northwest Territories, Canada

A suite of fresh, Late Cretaceous to Eocene hypabyssal kimberlites from the Lac de Gras field were studied in order to understand better carbonate, silicate and oxide paragenesis. The samples have excellent preservation of textures and primary mineralogy and are archetypal or Group 1 kimberlite. Five kimberlite localities are identified as calcite-bearing based on the presence of high Sr–Ba calcite as phenocrysts, microphenocrysts and in segregations. Three kimberlite localities are identified as dolomite-bearing based on the presence of mixed calcite–dolomite segregations containing oscillatory and banded textures of calcite–dolomite solid solution and dolomite (±magnesite). Sr–Ba calcite are characterized by high X_Ca (>0.95) and are enriched in Sr (4900–11,100 ppm) and Ba (3200–14,200 ppm). The calcite–dolomite and dolomite–magnesite solid solution compositions span the X_Ca range from 0.42 to 0.95, and typically have Sr and Ba contents in the range of 1000–4000 ppm. The carbonate, silicate and oxide mineral compositions suggest that the origin of the calcite-bearing versus dolomite-bearing kimberlites studied is related to subtle differences in parent magma composition, in particular, the CO₂/H₂O ratio. Formation of the carbonates reflects the latter part of a protracted magmatic crystallization sequence, in which Sr–Ba calcite precipitates from an evolved kimberlite melt. Subsequently, calcite–dolomite solid solution and dolomite is precipitated from localized, Mg-rich carbonate fluids at relatively high temperatures (higher than serpentine stability).     

Melting of the subcontinental lithospheric mantle by the Emeishan mantle plume; evidence from the basal alkaline basalts in Dongchuan, Yunnan, Southwestern China

The Emeishan continental flood basalt (ECFB) sequence in Dongchuan, SW China comprises a basal tephrite unit overlain by an upper tholeiitic basalt unit. The upper basalts have high TiO₂ contents (3.2–5.2 wt.%), relatively high rare-earth element (REE) concentrations (40 to 60 ppm La, 12.5 to 16.5 ppm Sm, and 3 to 4 ppm Yb), moderate Zr/Nb and Nb/La ratios (9.3–10.2 and 0.6–0.9, respectively) and relatively high _{Nd (t)} values, ranging from − 0.94 to 2.3, and are comparable to the high-Ti ECFB elsewhere. The tephrites have relatively high P₂O₅ (1.3–2.0 wt.%), low REE concentrations (e.g., 17 to 23 ppm La, 4 to 5.3 ppm Sm, and 2 to 3 ppm Yb), high Nb/La (2.0–3.9) ratios, low Zr/Nb ratios (2.3–4.2), and extremely low _{Nd (t)} values (mostly ranging from − 10.6 to − 11.1). The distinct compositional differences between the tephrites and the overlying tholeiitic basalts cannot be explained by either fractional crystallization or crustal contamination of a common parental magma. The tholeiitic basalts formed by partial melting of the Emeishan plume head at a depth where garnet was stable, perhaps > 80 km. We propose that the tephrites were derived from magmas formed when the base of the previously metasomatized, volatile-mineral bearing subcontinental lithospheric mantle was heated by the upwelling mantle plume.     

Isotope stratigraphy of Neoproterozoic cap carbonates in the Araras Group, Brazil

The Neoproterozoic carbonate sequence on the southeastern border of the Amazon Craton is divided into three lithostratigraphic units: a basal cap dolomite, an intermediate limestone, limestone-mudstone unit, and an upper dolarenite-dolorudite unit. Sections of the cap-carbonate were measured from the inner shelf to the outer shelf. Carbon isotope ratios (relative to PDB) vary between − 10.5 and − 1.7‰ in cap dolomite, and between − 5.4 and + 0.1‰ in laminated limestone and mud-limestone. Limestones and mud-limestones exhibit ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.70740 to 0.70780. A comparative isotope stratigraphy between the inner-shelf and the middle-shelf basin shows differences in carbon isotope ratios: The cap dolomite and limestones have lower δ¹³C ratios on the border of the basin (inner shelf) than in the middle shelf of the basin. These lower values can be related to shallower environmental conditions and to a stronger influence of the continental border. The ⁸⁷Sr/⁸⁶Sr ratios are the same in both areas, and are consistent with seawater composition at around 600 Ma.     

Marginal mafic intrusions as indicators of downslope draining of dense residual melts in anorthositic diapirs?

Geochemical and isotopic investigation of three small mafic intrusions (Løyning: 1250 × 150 m, Hogstad: 2000 × 200 m, Koldal: 1250 × 500 m) in the marginal zones of the Egersund-Ogna (Løyning, Koldal) and Åna-Sira massif-type anorthosites (Hogstad) (Rogaland Anorthositic Province, south Norway: 930 Ma) provides new insights into the late evolution of anorthositic diapirs. These layered mafic intrusions are essentially of norite, gabbronorite as well as leuconorite and display conspicuous evidence of subsolidus recrystallization. In Løyning and Hogstad, the modal layering is parallel to the subvertical foliation in the enclosing anorthosite. The northern part of the Koldal intrusion cuts across the foliation of the anorthosite, whereas in its southern part the subvertical layering is parallel to the anorthosite's foliation. The regularity of the layered structures suggests that the layering was initially acquired horizontally and later tilted during the final movements of the diapirs.

The least differentiated compositions of plagioclase and orthopyroxene in the three intrusions (An₅₉–En₆₈ in Løyning, An₄₉–En₆₄ in Hogstad and An₄₄–En₆₁ in Koldal) and the REE contents in apatite (Hogstad) indicate that their parent magmas were progressively more differentiated in the sequence Løyning–Hogstad–Koldal. Isotopic data (Løyning: ⁸⁷Sr/⁸⁶Sr: 0.70376–0.70457, ε_Ndt: + 6.8 to + 2.7; Hogstad: ⁸⁷Sr/⁸⁶Sr: 0.70537–0.70588, ε_Ndt: + 2.1 to − 0.5; Koldal: ⁸⁷Sr/⁸⁶Sr: 0.70659–0.70911, ε_Ndt: + 3.5 to − 1.6) also indicate that in this sequence, parent magmas were characterized by a progressively more enriched Sr and Nd isotopic signature. In Løyning, the parent magma was slightly more magnesian and anorthitic than a primitive jotunite; in Hogstad, it is a primitive jotunite; and, in Koldal, an evolved jotunite. Given that plagioclase and orthopyroxene of the three intrusions display more differentiated compositions than the orthopyroxene and plagioclase megacryts of the enclosing anorthosites, it is suggested that the parent magmas of the small intrusions are residual melts after anorthosite formation which were entrained in the anorthositic diapir during its rise from lower crustal chambers.

Calculated densities of primitive jotunites (2.73–2.74 at FMQ, 0.15% H₂O, 200 ppm CO₂, 435 ppm F, 1150 °C, 3 kb) and evolved jotunites (2.75–2.76 at FMQ, 0.30% H₂O, 400 ppm CO₂, 870 ppm F, 1135 °C, 3 kb) demonstrate that they are much denser than the plagioclase of the surrounding anorthositic crystal mush (2.61–2.65). Efficient migration and draining of dense residual melts through the anorthositic crystal mush could have taken place along sloping floors (zones of lesser permeability in the mush), which occur along the margins of the rising anorthositic diapirs. This process takes into account the restricted occurrence of the mafic intrusions in the margins of the massif anorthosites. In a later stage, when the anorthosite was nearly consolidated, the residual melts were more differentiated (evolved jotunites) and could have been extracted into extensional fractures in the cooling and contracting anorthositic body in a similar way as aplitic dikes are emplaced in granitic plutons. As in the Rogaland Anorthositic Province, these dikes are much more abundant than the small mafic intrusions, collection and transport along dikes was probably more efficient than draining through the crystal mush.     

Perspectives on basaltic magma crystallization and differentiation: Lava-lake blocks erupted at Mauna Loa volcano summit, Hawaii

Explosive eruptions at Mauna Loa summit ejected coarse-grained blocks (free of lava coatings) from Moku'aweoweo caldera. Most are gabbronorites and gabbros that have 0–26 vol.% olivine and 1–29 vol.% oikocrystic orthopyroxene. Some blocks are ferrogabbros and diorites with micrographic matrices, and diorite veins (≤ 2 cm) cross-cut some gabbronorites and gabbros. One block is an open-textured dunite.

The MgO of the gabbronorites and gabbros ranges  7–21 wt.%. Those with MgO > 10 wt.% have some incompatible-element abundances (Zr, Y, REE; positive Eu anomalies) lower than those in Mauna Loa lavas of comparable MgO; gabbros (MgO < 10 wt.%) generally overlap lava compositions. Olivines range Fo_83–58, clinopyroxenes have Mg#s  83–62, and orthopyroxene Mg#s are 84–63 — all evolved beyond the mineral-Mg#s of Mauna Loa lavas. Plagioclase is An_75–50. Ferrogabbro and diorite blocks have  3–5 wt.% MgO (TiO₂ 3.2–5.4%; K₂O 0.8–1.3%; La 16–27 ppm), and a diorite vein is the most evolved (SiO₂ 59%, K₂O 1.5%, La 38 ppm). They have clinopyroxene Mg#s 67–46, and plagioclase An_57–40. The open-textured dunite has olivine  Fo_83.5. Seven isotope ratios are ⁸⁷Sr/⁸⁶Sr 0.70394–0.70374 and ¹⁴³Nd/¹⁴⁴Nd 0.51293–0.51286, and identify the suite as belonging to the Mauna Loa system.

Gabbronorites and gabbros originated in solidification zones of Moku'aweoweo lava lakes where they acquired orthocumulate textures and incompatible-element depletions. These features suggest deeper and slower cooling lakes than the lava lake paradigm, Kilauea Iki, which is basalt and picrite. Clinopyroxene geobarometry suggests crystallization at < 1 kbar P. Highly evolved mineral Mg#s, < 75, are largely explained by cumulus phases exposed to evolving intercumulus liquids causing compositional ‘shifts.’ Ferrogabbro and diorite represent segregation veins from differentiated intercumulus liquids filter pressed into rigid zones of cooling lakes. Clinopyroxene geobarometry suggests < 300 bar P. Open-textured dunite represents olivine-melt mush, precursor to vertical olivine-rich bodies (as in Kilauea Iki). Its Fo_83.5 identifies the most primitive lake magma as  8.3 wt.% MgO. Mass balancing and MELTS show that such a magma could have yielded both ferrogabbro and diorite by ≥ 50% fractional crystallization, but under different fO₂: < FMQ (250 bar) led to diorite, and FMQ (250 bar) yielded ferrogabbro. These segregation veins, documented as similar to those of Kilauea, testify to appreciable volumes of ‘rhyolitic’ liquid forming in oceanic environments. Namely, SiO₂-rich veins are intrinsic to all shields that reached caldera stage to accommodate various-sized cooling, differentiating lava lakes.     

Kyanite eclogite xenolith from the orthogneiss terrane of the Tisza Megaunit, Jánoshalma area, crystalline basement of southern Hungary

New evidence for high-pressure, eclogite facies metamorphism in the crystalline basement of the Tisza Megaunit (southern Hungary) is reported. The retrogressed mafic eclogite forms a small lens in the orthogneiss and it was found in the borehole near Jánoshalma. The carbonated eclogite contains the peak metamorphic assemblage omphacite + garnet + phengite + kyanite + clinozoizite + rutile + K-feldspar + quartz. Omphacite (Xjd_0.40–0.41Xdio_0.52–0.53Xhd_0.05Xaug_1.55–2.85) occurs in the matrix and as inclusions in garnet (Xpy_0.37–0.38Xgrs_0.21–0.22Xalm_0.39–0.40Xsps_0–0.01Xadr_0–0.01) and kyanite. Thermobarometry based on net-transfer reactions between garnet, omphacite, kyanite and phengite yields P–T conditions of 710 ± 10 °C and 2.6 ± 0.75 GPa. Retrogression during decompression is manifested by formation of symplectites; the most typical are diopside + plagioclase after omphacite, corundum + spinel + plagioclase after kyanite and biotite + plagioclase after phengite. Carbonatization along the veins of the retrogressed eclogite was probably coeval with formation of these symplectites. At places where carbonate is absent the rock was completely hydrated and retrogressed down to the greenschist facies with the development of actinolite. Similar eclogites together with abundant orthogneisses occur mainly in the eastern parts of the Tisza Megaunit, suggesting the existence of an ancient (possibly Variscan) subduction/accretionary complex.     

Late Triassic granitoids of the eastern margin of the Tibetan Plateau: Geochronology, petrogenesis and implications for tectonic evolution

Late Triassic granitoids in the Songpan-Garzê Fold Belt (SGFB), on the eastern margin of the Tibetan Plateau, formed at 230 to 220 Ma and can be divided into two groups. Group 1 are high-K calc-alkaline rocks with adakitic affinities (K-adakites), with Sr > 400 ppm, Y < 11 ppm, strongly fractionated REE patterns ((La/Yb)_N = 32–105) and high K₂O/Na₂O (≈ 1). Group 2 are ordinary high-K calc-alkaline I-types with lower Sr (< 400 ppm), higher Y (> 18 ppm) and weakly fractionated REE patterns ((La/Yb)_N < 20). Rocks of both groups have similar negative Eu anomalies (Eu/Eu = 0.50 to 0.94) and initial ⁸⁷Sr/⁸⁶Sr (0.70528 to 0.71086), but group 1 rocks have higher ε_Nd(t) (− 1.01 to − 4.84) than group 2 (− 3.11 to − 6.71). Calculated initial Pb isotope ratios for both groups are: ²⁰⁶Pb/²⁰⁴Pb = 18.343 to 18.627, ²⁰⁷Pb/²⁰⁴Pb = 15.610 to 15.705 and ²⁰⁸Pb/²⁰⁴Pb = 38.269 to 3759. Group 1 magmas were derived through partial melting of thickened and then delaminated TTG-type, eclogitic lower crust, with some contribution from juvenile enriched mantle melts. Group 2 magmas were generated by partial melting of shallower lower crustal rocks. The inferred magma sources of both groups suggest that the basement of the SGFB was similar to the exposed Kangding Complex, and that the SGFB was formed in a similar manner to the South China basement. Here, passive margin crust was greatly thickened and then delaminated, all within a very short time interval ( 20 Myr). Such post-collisional crustal thickening could be the tectonic setting for the generation of many adakitic magmas, especially where there is no spatial and temporal association with subduction.     

The influence of the limestone-quarry Čertovy schody (Czech Republic) on the precipitation chemistry and atmospheric deposition

Atmospheric precipitation samples were collected in the Bohemian Karst (30 km SW from Prague, Czech Republic) at six localities in the vicinity of the limestone-quarry Čertovy schody during years 1996–2003. Samples were analyzed for major components (Na⁺, K⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₃⁻, HCO₃⁻, SO₄²⁻) and trace metals (Cu, Mn, Fe, Zn, Pb, Be, As, Sr, Cd, Al, Cr). Deposition fluxes were calculated from more than 10 000 elemental analyses of samples collected monthly. The fluxes of monitored substances show temporal and spatial variability. The most marked attribute is the strong affection by local emission sources confirmed by the investigation of seasonal variability, temporal trend and correlation analysis.     

Distribution of diagenetic alterations in fluvial and paralic deposits within sequence stratigraphic framework: Evidence from the Petrohan Terrigenous Group and the Svidol Formation, Lower Triassic, NW Bulgaria

Elucidation of diagenetic alterations in the Petrohan Terrigenous Group (fluvial; highstand systems tract HST) sandstones and Svidol Formation (tide-dominated deltaic and tidal flat, transgressive systems tract TST and highstand systems tract HST, respectively) sandstones and calcarenite, Lower Triassic, NW Bulgaria was constrained within a sequence stratigraphic framework. Eogenetic alterations in the fluvial HST sandstones include (i) formation of grain-coating infiltrated clays as a result of percolation of mud-rich surface waters into underlying coarse-grained and permeable channel-fills and crevasse splay sandstones; (ii) formation of pseudomatrix by mechanical compaction of mud intraclasts that were incorporated into the coarse-grained channel sandstones during their lateral avulsion; and (iii) cementation by calcite (δ¹⁸O_VPDB = − 6.5‰ to − 3‰; δ¹³C_VPDB = − 5.1‰ to + 0.6‰) and dolomite (δ¹⁸O_VPDB = − 6.1‰ to − 0.3‰; δ¹³C_VPDB = − 7.2‰ to − 5.8‰) in the crevasse splay and floodplain sediments. Mesogenetic alterations that are encountered in the fluvial HST sandstones include (i) illitization of grain-coating clays, mud intraclasts, and mica, possibly because of simultaneous albitization of feldspars; (ii) cementation by calcite (δ¹⁸O_VPDB = − 14.5‰ to − 8.4‰; δ¹³C_VPDB = − 7.7‰ to + 0.6‰) and dolomite (δ¹⁸O_VPDB = − 15.8‰ to − 5‰; δ¹³C_VPDB = − 7.9‰ to + 1.5‰); and (iii) limited amounts of quartz overgrowths in the channel sandstones owing to occurrence of thick grain-coating clays.

Conversely, the tide-dominated deltaic TST sandstones and the tidal flat HST calcarenite were pervasively cemented by calcite (δ¹⁸O_VPDB = − 6.6‰ to − 3.1‰; δ¹³C_VPDB = − 5.1‰ to + 0.6‰) and siderite (δ¹⁸O_VPDB = − 7.2‰ to − 5.7‰; δ¹³C_VPDB = + 0.3‰ to + 0.9‰) particularly below marine and maximum flooding surfaces, due to the presence of abundant bioclasts and prolonged residence time of the sediments under certain geochemical conditions along these surfaces. The remaining open pores were cemented during mesodiagenesis by calcite (δ¹⁸O_VPDB = − 6.6‰ to − 3.1‰ and δ¹³C_VPDB = − 5.1‰ to + 0.6‰) and dolomite (δ¹⁸O_VPDB = − 6.6‰ to − 3.1‰ and δ¹³C_VPDB = − 5.1‰ to + 0.6‰).

This study shows that constructing a conceptual model for the distribution of diagenetic alterations is possible by integration of diagenesis with sequence stratigraphy. The model shows that tide-dominated deltaic TST sandstones and tidal flat HST calcarenite were pervasively cemented by carbonates during near-surface eodiagenesis, owing to the presence of abundant bioclasts. Conversely, fluvial LST sandstones remained poorly cemented during near-surface eodiagenesis due to the lack of bioclasts, but were cemented by mesogenetic calcite, dolomite and quartz overgrowths instead.     

Revealing hidden structures: The application of cathodoluminescence and back-scattered electron imaging to dating zircons from lower crustal xenoliths

The use of cathodoluminescence (CL) and/or back-scattered electron (BSE) imaging techniques with in situ ion probe analyses of zircons can help unravel complex crustal histories of metamorphic rocks that otherwise might remain elusive. Using these techniques we have imaged zircons from three lower crustal xenolith suites that have previously been dated by SHRIMP (sensitive high-resolution ion microprobe). In all three cases, the zircons are featureless in transmitted light but CL and BSE reveal internal structures that correlate with distinct growth events. Generally, CL and BSE images reveal similar structures, with CL showing finer detail. Neither imaging technique is capable of delineating all growth features in every sample and the best results are obtained using a combination of the two techniques. Igneous cores in zircons commonly emit a different color CL emission. In many cases zoning in the cores is truncated, indicating that the zircons either spent time in the supracrustal environment after their initial crystallization and prior to the granulite facies event (s) or that part of the core zircon was resorbed during the subsequent metamorphic event. Metamorphic rims, when present, are commonly 10 to 30 μm thick, and are nearly always unzoned and featureless.

Igneous cores and metamorphic overgrowths commonly have distinctive CL emission spectra and trace element concentrations. However, the CL spectra can only be used to qualify chemical differences, as a linear relationship has not been shown to exist between CL intensity and trace element concentration in natural zircons. In many cases the Hf, Y, P, U and the heavy rare-earth elements (HREEs) concentrations can be correlated to igneous and metamorphic growth using a combination of CL and BSE imaging techniques and in situ trace element analyses with either the electron microprobe or PIXE (particle induced X-ray emission).     

Petrography and geochemical characteristics of the sediments of the small River Hemavati, Southern India: Implications for provenance and weathering processes

Small rivers (≤ 100 km length) are likely to drain fewer rock types. Therefore, their solutes and sediments are good indicators of weathering environments typical of their basins and help constraining the nature of their source rocks. To understand this, the texture, mineralogy, major and trace element compositions of the sediments deposited by the River Hemavati, a northern upland tributary of the Cauvery River in southern India, are analyzed and discussed.

The Hemavati sediments are overall of fine sand size (mean 2–3), and have high concentrations of FeO (≤ 7 wt.%), TiO₂ (≤ 1.2 wt.%), Cr (≤ 350 ppm) and Ni (≤ 125 ppm). Major and trace element distribution call for a binary source for the sediments, and particularly point to contrasting climatic conditions of their provenances. The source areas in the upstream and downstream parts are exposed to sub-humid high relief and sub-arid low relief conditions, respectively, with distinct weathering characteristics. The CIA values (85–48) decrease from near the source to downstream, suggesting that the downstream rain-shadow part of the catchment suffered only minor chemical weathering.

On the other hand, the REE distribution in the Hemavati sediments indicates contrasting lithologies in their provenance, and is not controlled by chemical weathering. On the basis of REE patterns, the sediments are divided into two compositional groups. The Type 1 sediments have a REE chemistry similar to the upper continental crust, and have been derived from the > 3.2 Ga composite peninsular gneisses occurring in the low-lying, semi-arid Mysore Plateau. The Type 2 sediments, however, have dominantly intermediate to mafic granulite contributions from the tectonically uplifted Western Ghats, weathered under sub-humid conditions. High concentrations of FeO, TiO₂, Cr and Ni in the sediments suggest mafic-dominated source lithologies in the upper catchment, a feature also confirmed by field observations and petrographic study.     

Mineral phase compositions in silica-undersaturated ‘leucite’ lamproites from the Bucak area, Isparta, SW Turkey

Ultrapotassic rocks in the Bucak area of Isparta Angle, SW Turkey, show unusually low SiO₂ (46.8–49.2 wt.%) and high MgO (10.4–11.6 wt.%) contents, and lamproitic affinity (K/Na, > 2.5; Mg#, 73–75; Al₂O₃, 9.2–11 wt.%, CaO 7.4–10.6 wt.%, Cr, 525–675 ppm; Ni, 442–615 ppm). They are made up by phlogopite (30–40 vol.%), leucite (25–30 vol.%), olivine (5–20 vol.%), which rarely contain Cr-spinel, clinopyroxene (5–10 vol.%), sanidine (5 vol.%) and richterite, with accessory apatite, magnetite and ilmenite. One sample also include negligible sodalite in groundmass, which is unusual mineral in lamproites. Mineral phase variation and textures record discrete phases of pre-eruptive crystallization: (1) early appearance of (Cr-spinel-bearing) olivine, Ti poor phlogopite ± apatite at pressures of ca. 1.0–2.0 GPa, at or close to the lithospheric Mechanical Boundary Layer (MBL), and (2) later appearance of Ti rich phlogopite, clinopyroxene, richterite, leucite, sanidine, and other minor phases, at pressures of ca. 0.1–1.0 GPa, indicating discrete, pressure-specific fractionation events. The Bucak silica poor ‘leucite’ lamproites were probably generated by partial melting of phlogopite-bearing, refractory peridotite at pressures of ca. 1.5–2 GPa, higher than those proposed for SiO₂-saturated ‘phlogopite’ lamproites (ca. 1–1.5 GPa) from Afyon, to the North. The depth (total pressure) of melt segregation probably dominates over volatile partial pressures (e.g. of CO₂, F, H₂O) in determining the SiO₂-undersaturated character of Bucak magmas.     

Cenozoic “radiobarite” occurrences in the Ohře (Eger) Rift, Bohemian Massif: Mineralogical and geochemical revision

Barite occurrences related to the Cenozoic (Late Alpine) low-temperature hydrothermal activity are present in the continental Ohře (Eger) Rift area. A specific, Ra-bearing type of barite has been known under the name “radiobarite” from this area since 1904. Revision of 12 localities revealed the presence of alleged radiobarite only in the Teplice (Lahošť–Jeníkov) and Karlovy Vary areas. Barite from other localities is radium-poor. Barite crystals showing concentric oscillation colour zoning totally prevail. Isomorphous substitution of Sr (X×10⁻¹ to X×wt%), Ca (X×10⁻² wt%) and Fe (X×10⁻¹ wt%) for Ba was proved. Average SrO contents of 0.4 wt% are markedly exceeded in some samples from Lahošť–Jeníkov (max. 3.2 wt%) and Karlovy Vary (max. 4.9 wt%). Besides inclusions of stoichiometric iron disulphide, the same samples also contain iron disulphides with unusual high contents of Co (max. 12.2 wt%) and Ni (max. to 8.4 wt%). Specific activity of ²³⁸U in the studied barites is very low while that of ²²⁶Ra reaches 8 Bq/g in several samples. Therefore, ²²⁶Ra is not in equilibrium with its parent uranium. These “radiobarites” or their parts must be therefore relatively young, not older than 10–15 ka. Very low uranium contents (<0.4 ppm) were also confirmed by neutron activation analyses of barite samples.

Unit-cell dimensions refined from X-ray powder diffraction data do not show any systematic variation with the measured chemical composition. Their values agree with the data given in the literature. Reflection half-widths, however, seem to correlate with chemistry. Peaks are wider in samples from Lahošť–Jeníkov and Karlovy Vary.

Sulphur and oxygen stable isotope compositions of the Cenozoic barite mineralization of Teplice area are very uniform (δ³⁴S values between 3.9‰ and 7.1‰ CDT, and δ¹⁸O values between 6.1‰ and 7.7‰ SMOW), while the barites of Děc˘ín area show more variable sulphur sources. Sulphate derived from sediments of the Tertiary Most Basin seems to dominate for the Teplice area, while Cretaceous sediments are a more probable sulphur source in the Děc˘ín area. Calculation of oxygen isotope composition of hydrothermal fluids based on fluid inclusion homogenization temperatures and barite δ¹⁸O data shows δ¹⁸O_fluid values in the range of meteoric waters or δ¹⁸O – shifted deep circulating meteoric or basinal waters.     

Compositional diversity among Late Devonian peraluminous granitoid intrusions in the Meguma Zone of Nova Scotia, Canada

Late Devonian (385−370 Ma) granitoid intrusions in the Meguma Zone of southwestern Nova Scotia represent two geographically separate magmatic suites that show subtly different lithological, geochemical and isotopic characteristics. “Central intrusions” crop out with satellite mafic-intermediate intrusions, range in composition from granodiorite to leucogranite, contain two micas, have exclusively peraluminous compositions (molar A/CNK 1.1-1.3), variably high values for FeO_T (0.4–6.0 wt.%), Ba (5–980 ppm), Y (6–50 ppm), Pb (2–50 ppm), Ga (11–53 ppm), ⁸⁷Sr/⁸⁶Sr_i (0.7081-0.7130), δ¹⁸O (9.8–13.0) and δ³⁴S (4.5–11.9), in conjunction with low values for εNd (−1 to −6.5). In contrast, “peripheral plutons” crop out with synplutonic mafic-intermediate intrusions, range in composition from tonalite to leucogranite, may contain minor hornblende, have dominantly peraluminous compositions (molar A/CNK 0.9-1.3), variably high concentrations of TiO₂ (0.1-1.1 wt.%), Al₂O₃ (12.0–19.7 wt.%), CaO (0.2–4.9 wt.%), Sr (7–720 ppm), Cr (3–111 ppm) and V (1–136 ppm), higher εNd values (−2.0 to 3.2), and lower values for ⁸⁷Sr/⁸⁶Sr_i (0.7040-0.7079), δ¹⁸⁸O (7.6–10.5) and δ³⁴S (0–4.6). Such regional diversity is explained by inferring that upper crustal contamination dominated the central granitoid compositions and mixing with mantle-derived mafic-intermediate magmas dominated peripheral granitoid compositions. However, additional contributions from heterogeneous lower crust cannot be excluded.     

Extracting olivine (Fo–Fa) compositions from Raman spectral peak positions

The dominant feature of the olivine Raman spectrum is a doublet that occurs in the spectral region of 815–825 cm⁻¹ (DB1) and 838–857 cm⁻¹ (DB2). These features arise from coupled symmetric and asymmetric stretching vibrational modes of the constituent SiO₄ tetrahedra. The frequencies of both peaks show monotonic shifts following cation substitution between forsterite and fayalite. We present a calibration for extracting olivine Fo contents (Fo = Mg/(Mg + Fe) molar ratio; Fo_0–100) from the peak positions of this doublet, permitting estimates of chemical composition from Raman spectra (acquired in the laboratory or field) as well as providing information on crystal structure (distinction of polymorphs). Eight samples spanning the compositional range from forsterite to fayalite were used to develop the calibration equations for the DB1 and DB2 peaks individually and together. The data indicate that the DB1 peak is more reliable for calculating the compositions of Fe-rich olivine but that the DB2 peak is better for magnesian compositions. The two-peak calibration overcomes the limitations of the single-peak calibrations and is capable of calculating olivine compositions to within ±10 Fo units.     

方解石-白云石-菱镁矿的中远红外光谱学特征研究

利用拉曼光谱和红外光谱研究了方解石、白云石和菱镁矿的光谱学特征,探究了影响三种矿物红外辐射性能的因素。三种矿物的拉曼光谱(Raman)、中红外吸收光谱(MIR)、远红外吸收光谱(FIR)显示随着矿物中镁含量的增大将会影响CO₃^2-的面外弯曲振动(ν₂)、反对称伸缩振动(ν₃)和平面内弯曲振动(ν₄),使各光谱特征峰均向高频端迁移。基于黑体辐射定律以及在80 ℃、400~2 000 cm^-1矿物的辐射能量谱,结果显示方解石、白云石、菱镁矿的发射率依次减少(0.951,0.938,0.895)。三种矿物的红外吸收光谱和发射光谱中的振动位置均受CO₃^2-基频的显著影响,在1 300~1 650 cm^-1均产生宽的低吸收带,该吸收带与CO₃^2-的反对称伸缩振动相关,且吸收带范围(202,236,272 cm^-1)与发射率之间呈负相关关系。因此,当最强化学键的振动出现在发射光谱窄的吸收带范围内会产生相对较高的辐射能和发射率。此外,矿物的晶体结构也会影响发射率,大的离子半径、键长和晶胞体积将降低辐射过程中能量的吸收,增强辐射特性。综上研究结果,方解石、白云石和菱镁矿的拉曼光谱和红外光谱揭示了金属原子的相对质量对光谱学特征的显著影响,其发射率可能受到C—O键的反伸缩振动范围、最强吸收带控制的最低发射率以及矿物晶体结构的共同影响。这项研究呈现了必要的光谱信息和热发射率数据以识别特定的碳酸盐矿物,为类似矿物的光谱特征研究奠定了基础;同时为进一步认识地壳中大量的碳酸盐矿物提供了研究方法,也为地外勘探的深入研究给予相关的理论基础。     

Ga/Mg ratio as a new geochemical tool to differentiate magmatic from metamorphic blue sapphires

Using ICP-MS–LA analyses, we demonstrate that the use of the Ga/Mg ratio, in conjunction with the Fe concentration, is an efficient tool in discriminating between “metamorphic” and “magmatic” blue sapphires. Magmatic blue sapphires found in alkali basalts (e.g. southeastern Asia, China, Africa) are commonly medium-rich to rich in Fe (with average contents between 2000 and 11000 ppm), high in Ga (> 140 ppm), and low in Mg (generally < 20 ppm) with high Ga/Mg ratios (> 10). Conversely, metamorphic blue sapphires found in basalts (e.g. Pailin pastel) and in metamorphic terrains (e.g. Mogok, Sri Lanka, Ilakaka) are characterized by low average iron contents (< 3000 ppm), low Ga contents (< 75 ppm), and high Mg values (> 60 ppm) with low average Ga/Mg ratios (< 10). Basaltic magmatic sapphires have Fe, Ga and Mg contents similar to those obtained for primary magmatic sapphires found in the Garba Tula syenite. This suggests that these both sets of sapphires have a possible common “syenitic” origin, as previously proposed from other criteria. In addition, plumasite-related sapphires and metamorphic sapphires also exhibit similar composition in trace elements. Based on results from the present study, we suggest that fluid circulations during a metamorphic stage produced metasomatic exchanges between mafic and acidic rocks (plumasite model), thus explaining the high Mg contents and converging Ga/Mg ratios observed in metamorphic sapphires.