Journal articles on the topic 'Trace element thermometry'

Trace element distribution and Zr-in-rutile temperature have been investigated in accessory rutile from stratiform (UG2, Merensky Reef, Jacurici), podiform (Loma Peguera), and metamorphic chromitites in cratonic shields (Cedrolina, Nuasahi). Rutile from chromitite has typical finger-print of Cr-V-Nb-W-Zr, whose relative abundance distinguishes magmatic from metamorphic chromitite. In magmatic deposits, rutile precipitates as an intercumulus phase, or forms by exsolution from chromite, between 870 °C and 540 °C. The Cr-V in rutile reflects the composition of chromite, both Nb and Zr are moderately enriched, and W is depleted, except for in Jacurici, where moderate W excess was a result of crustal contamination of the mafic magma. In metamorphic deposits, rutile forms by removal of Ti-Cr-V from chromite during metamorphism between 650 °C and 400 °C, consistent with greenschist-amphibolite facies, and displays variable Cr-Nb, low V-Zr, and anomalous enrichment in W caused by reaction with felsic fluids emanating from granitoid intrusions. All deposits, except Cedrolina, contain Rutile+PGM composite grains (<10 µm) locked in chromite, possibly representing relics of orthomagmatic assemblages. The high Cr-V content and the distinctive W-Nb-Zr signature that typifies accessory rutile in chromitite provide a new pathfinder to trace the provenance of detrital rutile in placer deposits.

AbstractThis paper presents the first major and trace element compositions of mantle-derived garnet xenocrysts from the diamondiferous No. 30 kimberlite pipe in the Wafangdian region, and these are used to constrain the nature and evolution of mantle metasomatism beneath the North China Craton (NCC). The major element data were acquired using an electron probe micro-analyzer and the trace element data were obtained using laser ablation inductively coupled plasma-mass spectrometry. Based on Ni-in-garnet thermometry, equilibrium temperatures of 1107–1365 °C were estimated for peridotitic garnets xenocrysts from the No. 30 kimberlite, with an average temperature of 1258 °C, and pressures calculated to be between 5.0 and 7.4 GPa. In a CaO versus Cr2O3 diagram, 52% of the garnets fall in the lherzolite field and 28% in the harzburgite field; a few of the garnets are eclogitic. Based on rare earth element patterns, the lherzolitic garnets are further divided into three groups. The compositional variations in garnet xenocrysts reflect two stages of metasomatism: early carbonatite melt/fluid metasomatism and late kimberlite metasomatism. The carbonatite melt/fluids are effective at introducing Sr and the light rare earth elements, but ineffective at transporting much Zr, Ti, Y, or heavy rare earth elements. The kimberlite metasomatic agent is highly effective at element transport, introducing, e.g., Ti, Zr, Y, and the rare earth elements. Combined with compositional data for garnet inclusions in diamonds and megacrysts from the Mengyin and Wafangdian kimberlites, we suggest that these signatures reflect a two-stage evolution of the sub-continental lithospheric mantle (SCLM) beneath the NCC: (1) early-stage carbonatite melt/fluid metasomatism resulting in metasomatic modification of the SCLM and likely associated with diamond crystallization; (2) late-stage kimberlite metasomatism related to the eruption of the 465 Ma kimberlite.

Abstract. In order to assess the potential of the honeycomb oyster Pycnodonte vesicularis for the reconstruction of palaeoseasonality, several specimens recovered from late Maastrichtian strata in the Neuquén Basin (Argentina) were subject to a multi-proxy investigation, involving scanning techniques and trace element and isotopic analysis. Combined CT scanning and light microscopy reveals two calcite microstructures in P. vesicularis shells (vesicular and foliated calcite). Micro-XRF analysis and cathodoluminescence microscopy show that reducing pore fluids were able to migrate through the vesicular portions of the shells (aided by bore holes) and cause recrystallization of the vesicular calcite. This renders the vesicular portions not suitable for palaeoenvironmental reconstruction. In contrast, stable isotope and trace element compositions show that the original chemical composition of the foliated calcite is well-preserved and can be used for the reconstruction of palaeoenvironmental conditions. Stable oxygen and clumped isotope thermometry on carbonate from the dense hinge of the shell yield sea water temperatures of 11°C, while previous TEX86H palaeothermometry yielded much higher temperatures. The difference is ascribed to seasonal bias in the growth of P. vesicularis, causing warm seasons to be underrepresented from the record, while TEX86H palaeothermometry seems to be biased towards warmer surface water temperatures. The multi-proxy approach employed here enables us to differentiate between well-preserved and diagenetically altered portions of the shells and provides an improved methodology for reconstructing palaeoenvironmental conditions in deep time. While establishing a chronology for these shells was complicated by growth cessations and diagenesis, cyclicity in trace elements and stable isotopes allowed for a tentative interpretation of the seasonal cycle in late Maastrichtian palaeoenvironment of the Neuquén Basin. Attempts to independently verify the seasonality in sea water temperature by Mg ∕ Ca ratios of shell calcite are hampered by significant uncertainty due to the lack of proper transfer functions for pycnodontein oysters. Future studies of fossil ostreid bivalves should target dense, foliated calcite rather than sampling bulk or vesicular calcite. Successful application of clumped isotope thermometry on fossil bivalve calcite in this study indicates that temperature seasonality in fossil ostreid bivalves may be constrained by the sequential analysis of well-preserved foliated calcite samples using this method.

This paper reports the results of a study of naturally and experimentally quenched melt inclusions in magnesian olivine (Fo77–89) from a basalt sample from the Karymsky volcanic center, which is located in the middle segment of the Eastern Volcanic Front of Kamchatka. The conditions of parental magma formation were estimated using modern methods of trace-element thermometry. Based on direct H2O measurements in inclusions and thermometry of coexisting olivine and spinel, it was shown that the parent melts contained at least 4.5 wt % H2O and crystallized at a temperature of 1114 ± 27°C and an oxygen fugacity of DQFM = 1.5 ± 0.4. The obtained estimates of H2O content and crystallization temperature are among the first and currently most reliable data for the Eastern Volcanic Front of Kamchatka. The primary melt of the Karymsky volcanic center was derived from peridotitic material and could be produced by ~12–17% melting of an enriched MORB source (E-DMM) at ~1230–1250°C and ~1.5 GPa. Our estimates of mantle melting temperature beneath Kamchatka are slightly lower than values reported previously and up to 50°C lower than the dry peridotite solidus, which indicates the influence of a slab-derived hydrous melt. The combined approach to the estimation of the initial H2O content of melt employed in this study can provide a more reliable data in future investigations, and its application will probably to decrease the existing temperature estimates for the mantle wedge above subduction zones.

Zircon macrocrysts in (sub)volcanic silica-undersaturated rocks are an important source of information about mantle processes and their relative timing with respect to magmatism. The present work describes variations in trace element (Sc, Ti, Y, Nb, lanthanides, Hf, Ta, Pb, Th, and U) and isotopic (U-Pb) composition of zircon from the Drybones Bay kimberlite, Northwest Territories, Canada. These data were acquired at a spatial resolution of ≤100 µm and correlated to the internal characteristics of macrocrysts (imaged using cathodoluminescence, CL). Six types of zircon were distinguished on the basis of its luminescence characteristics, with the majority of grains exhibiting more than one type of CL response. The oscillatory-zoned core and growth sectors of Drybones Bay zircon show consistent variations in rare-earth elements (REE), Hf, Th, and U. Their chondrite-normalized REE patterns are typical of macrocrystic zircon and exhibit extreme enrichment in heavy lanthanides and a positive Ce anomaly. Their Ti content decreases slightly from the core into growth sectors, but the Ti-in-zircon thermometry gives overlapping average crystallization temperatures (820 ± 26 °C to 781 ± 19 °C, respectively). There is no trace element or CL evidence for Pb loss or other forms of chemical re-equilibration. All distinct zircon types are concordant and give a U-Pb age of 445.6 ± 0.8 Ma. We interpret the examined macrocrysts as products of interaction between a shallow (<100 km) mantle source and transient kimberlitic melt.

Abstract There is still debate whether Large Igneous Provinces (LIPs) are caused by high mantle temperatures induced by thermal plumes or by other factors that enhance melt production from the mantle. A prerequisite for assessing the thermal plume model is a reliable estimate of liquidus temperatures of the magmas produced, preferably based on more than one method of geothermometry. The study reported here compares multiple geothermometers for the Etendeka LIP, which is among the largest Phanerozoic examples and one that shows several features suggestive of a plume origin (continental flood basalt province linked via an age-progressive volcanic ridge to an active hotspot). Magnesium (Mg)-rich magmas emplaced as dikes in NW Namibia are the most primitive rocks known from this province and are thus best suited to determine the composition and melting conditions of their mantle source. Earlier studies of the Etendeka Mg-rich dikes reported high liquidus temperatures based on olivine-melt Mg–Fe equilibria. We extend that work to a larger set of samples and compare the results of olivine-melt Mg–Fe thermometry with other methods based on spinel-melt and spinel–olivine equilibria (Al-in-olivine thermometry), as well as olivine-melt trace-element exchange (Sc/Y thermometry and V oxybarometry). All methods used the same starting assumptions of nominally anhydrous melts and a crystallization pressure of 0·5 GPa. Only mineral-melt or mineral-mineral pairs consistent with compositional equilibrium were used for calculating temperatures. The trace-element compositions of olivine are also used to discuss the relative proportion of peridotite and pyroxenite in the mantle source for these magmas. Twelve dike samples were studied, with whole-rock MgO concentrations ranging from 8·4 to 19·4 wt %. Diagnostic element ratios of transition metals in olivine (e.g., Mn/Fe, Mn/Zn, Zn/Fe) indicate a peridotite-dominated mantle source for the magmas, which is consistent with the other indicators based on whole-rock data e.g., 10 000×Zn/Fe, CaO–MgO trend, FeO/MnO and FC3MS (FeO/CaO–3×MgO/SiO2). The temperature variations show a positive correlation with the Fo-content of host olivines, and values from high-Fo olivine agree well with olivine and spinel liquidus temperatures calculated from thermodynamic models of bulk-rock composition. All methods and most samples yielded a temperature range between 1300 °C and 1400 °C. An exceptional few samples returned temperatures below 1300 °C, the minimum being 1193 °C, whereas several samples yielded temperatures above 1400 °C, the upper range being 1420–1440°C, which we consider to be a robust estimate of the maximum liquidus temperatures for the high-Mg magmas studied. The conversion to mantle potential temperatures is complicated by uncertain depth and degree of melting, but the functional relationship between Tp and primary melt MgO contents, using melt inclusions from olivine phenocrysts with of Fo &gt; 90, indicate a Tp range from 1414 to 1525 °C ( 42 °C), which is 100–150°C higher than estimates of ambient upper mantle Tp in the South Atlantic today.

Abstract The Appalachian orogen has long been enigmatic because, compared to other parts of the Paleozoic orogens that formed following the subduction of the Iapetus Ocean, direct evidence for ultrahigh-pressure (UHP) metamorphism has never been found. We report the first discovery of coesite in the Appalachian orogen in a metapelite from the mid-Ordovician (Taconic orogeny) Tillotson Peak Complex in Vermont (USA). Relict coesite occurs within a bimineralic SiO2 inclusion in garnet. In situ elastic barometry and trace-element thermometry allow reconstruction of the garnet growth history during prograde metamorphism. The data are interpreted to indicate garnet nucleation and crystallization during blueschist- to eclogite-facies subduction zone metamorphism, followed by garnet rim growth at UHP conditions of &gt; 28 kbar and &gt; 530 ° C. Results provide the first direct evidence that rocks of the Appalachian orogen underwent UHP metamorphism to depths of &gt; 75 km and warrant future studies that constrain the extent of UHP metamorphism.

This study presents major and trace element data for 243 mantle garnet xenocrysts from six kimberlites in parts of western North America. The geochemical data for the garnet xenocrysts are used to infer the composition, thickness, and tectonothermal affinity of the mantle lithosphere beneath western Laurentia at the time of kimberlite eruption. The garnets record temperatures between 800 and 1450°C using Ni-in-garnet thermometry and represent mainly lherzolitic mantle lithosphere sampled over an interval from about 110–260 km depth. Garnets with sinuous rare-earth element patterns, high Sr, and high Sc/V occur mainly at shallow depths and occur almost exclusively in kimberlites interpreted to have sampled Archean mantle lithosphere beneath the Wyoming Province in Laurentia, and are notably absent in garnets from kimberlites erupting through the Proterozoic Yavapai Mazatzal and Trans-Hudson provinces. The similarities in depths of equilibration, but differing geochemical patterns in garnets from the Cross kimberlite (southeastern British Columbia) compared to kimberlites in the Wyoming Province argue for post-Archean replacement and (or) modification of mantle beneath the Archean Hearne Province. Convective removal of mantle lithosphere beneath the Archean Hearne Province in a "tectonic vise" during the Proterozoic terminal collisions that formed Laurentia either did not occur, or was followed by replacement of thick mantle lithosphere that was sampled by kimberlite in the Triassic, and is still observed there seismically today.

Abstract Amphibole fractionation during the early evolution of arc magmas has been widely inferred on the basis of distinctive geochemical fingerprints of the evolved melts, although amphibole is rarely found as a major mineral phase in arc volcanic rocks, so-called cryptic amphibole fractionation. Here, we present a detailed case study of xenoliths of amphibole-rich cumulate from the Zhazhalong intrusive suite, Gangdese arc, which enables an investigation of this differentiation process using a combination of petrological observations and in situ geochemical constraints. Evidence that the xenoliths represent fragments of igneous cumulates includes: (1) the presence of an amphibole-dominated crystal framework; (2) mineral and whole-rock Fe–Mg exchange coefficients; (3) rare-earth element patterns that are similar in the amphiboles and the xenoliths; (4) the compositions of basaltic to andesitic liquids in equilibrium with amphiboles; and (5) enrichment of the xenoliths in compatible elements and depletion in incompatible elements. The amount of trapped liquid based on La, Ce, and Dy abundances varies from ~12 to ~20%. Actinolitic cores within amphibole grains likely represent reaction between olivine precursor and hydrous melt, as evidenced by their high Cr and Ni contents. Amphibole thermometry and oxybarometry calculations indicate that crystal accumulation occurred over temperatures of 857–1014 °C, at mid-crustal pressures of 312 to 692 MPa and oxygen fugacity between 0.4 and 1.9 log units above the nickel–nickel oxide buffer. Quantification of the major-element compositions of the parent liquids indicates that the Zhazhalong amphibole cumulates crystallized from basaltic to andesitic magmas, probably with a shoshonitic affinity, and with SiO2 contents of 46.4–66.4 wt%. Appropriate partition coefficients, calculated using a parameterized lattice strain model and an empirical partitioning scheme, were employed to calculate the trace-element compositions of the liquids in equilibrium with amphibole. Our results confirm that Dy/Yb and Dy/Dy* ratios, which decrease with increasing degrees of differentiation, can be used as robust signatures of amphibole fractionation. This work presents a direct snapshot of the process of amphibole fractionation and provides a natural example of the hidden amphibole “sponge” in arc crust. In particular, this study also suggests that some appinites likely represent amphibole-rich cumulates, which may help to explain the genesis of other unusual but petrologically significant rocks.

AbstractPegmatites and associated granitoids are integral parts of the Alvand plutonic complex in the Sanandaj–Sirjan zone, Iran. Whole rock major- and trace-element lithogeochemistry together with zircon U–Pb geochronology and zircon geochemistry are examined to evaluate the petrogenesis of sapphire-bearing pegmatites and other peraluminous pegmatites in the region. Pegmatites vary in their chemical compositions from mostly peraluminous, high-K calc-alkaline to shoshonitic signatures. A rare variety of extremely peraluminous sapphire-bearing syenitoid pegmatite (Al2O3 > 30 wt %; A/CNK > 2) exists. This silica-undersaturated pegmatite and its sapphire crystals have a primary igneous origin. U–Pb zircon geochronology of three separate samples from this pegmatite indicates the following ages: 168 ± 1 Ma, 166 ± 1 Ma and 164 ± 1 Ma. The zircon grains have notable amounts of Hf (up to 17 200 ppm), U (up to 13 580 ppm), Th (up to 5148 ppm), Y (up to 4764 ppm) and ∑REE (up to 2534 ppm). There is a positive correlation between Hf and Th, Nb and Ta, U and Th, and Y and HREE and a negative correlation between Hf and Y values in the zircons. These zircons exhibit pronounced positive Ce anomalies (Ce/Ce* = 1.15–68.06) and negative Eu anomalies (Eu/Eu* = 0.001–0.56), indicative of the relatively oxidized conditions of the parent magma. Ti-in-zircon thermometry reveals temperatures from as low as ~683 °C up to ~828 °C (average = 755° ± 73 °C). Zircon and monazite saturation equilibria are also consistent with these temperatures. Zircon grains are magmatic (average La < 1.5, (Sm/La)N > 100 and Th/U > 0.7), with chemical characteristics similar to zircons from continental crust.

Oxygen isotope paleotemperature studies of the Mesozoic and Paleozoic are based mainly on conodonts, belemnite guards, and brachiopod shells—material resistant to diagenesis and generally precipitated in oxygen isotope equilibrium with ambient water. The greatest obstacle to accurate oxygen isotope paleothermometry in deep time is uncertainty in the oxygen isotopic composition of the ambient seawater. The second greatest obstacle is fossil diagenesis. Useful application of the oxygen isotope method to brachiopod shells requires extreme care in sample screening and analyses, and is best done with scanning-electron microscopy, and petrographic and cathodoluminescence microscopy, and trace-element analysis. Correct interpretation of oxygen isotope data is greatly aided by thorough understanding of the paleolatitude, paleoecology, and depositional environment of the samples. The oxygen isotope record for the Triassic, based on brachiopod shells, is too sparse to show any distinct isotopic features. Jurassic and Early Cretaceous δ18O records, based on belemnites, show a Toarcian (Jurassic) decline (warming), a Callovian-Oxfordian acme, and an Early Cretaceous increase (cooling) to a Valanginian-Hauterivian maximum, followed by a decline (warming) to a middle Barremian minimum. Deep-time applications to oxygen isotope thermometry provide evidence for cooling and glaciation in the Ordovician, Carboniferous, and Permian. The δ18O values from Silurian and Devonian brachiopod shells and conodonts average lower than those of the remaining Phanerozoic because of the absence of continental glaciers and possibly higher temperatures (~37°?), although slightly lower (≤2%o) seawater δ18O cannot be ruled out. The hypothesis of high temperatures in the early Paleozoic implies a relatively constant hydrospheric δ18O, which is supported by clumped isotope paleotemperatures. However, more research is needed to develop methods for evaluating clumped isotope reordering in fossils. Ongoing and future research in oxygen isotope and clumped isotope thermometry hold the promise of resolving deep-time temperatures, seawater δ18O, and salinity with heretofore unavailable accuracy (±2°, ±0.4%o, and ±2 psu), providing the environmental setting for the evolution of metazoan life on Earth.

Calc-alkaline andesitic rocks are a major product of subduction-related magmatism at convergent margins. Where these melts are originated, how long they are stored in the magma chambers, and how they evolved is still a matter of debate. In this study, we present new data of whole-rock elemental and Sr-Nd-Pb isotope compositions, and zircon U-Pb-Th isotopes and trace element contents of Nageng (basaltic-)andesites in the East Kunlun Orogen (NW China). The similar age and whole-rock elemental and Sr-Nd-Pb isotope contents suggest that the Nageng andesite and basaltic andesite are co-magmatic. Their low initial 87Sr/86Sr (0.7084–0.7086) but negative εNd(t) values (−10.61 to −9.49) are consistent with a magma source from the juvenile mafic lower crust, possibly related to the mantle wedge with recycled sediment input. The U-Pb age gap between the zircon core (ca. 248 Ma) and rim (ca. 240 Ma) reveals a protracted magma storage (~8 Myr) prior to the volcanic eruption. When compared to the zircon rims, the zircon cores have higher Ti content and Zr/Hf and Nb/Ta ratios, but lower Hf content and light/heavy rare earth element ratios, which suggests that the parental magma was hotter and less evolved than the basaltic andesite. The plagioclase accumulation likely resulted in Al2O3-enrichment and Fe-depletion, forming the calc-alkaline signature of the Nageng (basaltic-)andesites. The magma temperature, as indicated by the zircon saturation and Ti-in-zircon thermometry, remained low (725–828 °C), and allowed for the magma chamber to survive over ~8 Myr. The decreasing εHf(t) values from zircon core (avg. 0.21, range: −1.28 to 1.32) to rim (avg. −3.68, range: −7.30 to −1.13), together with the presence of some very old xenocrystic zircons (268–856 Ma), suggest that the magma chamber had undergone extensive crustal contamination.

Abstract Arc magmatism was widespread in the Cordillera of North America during Middle Jurassic time. The predominant representative of this arc magmatism in the Klamath Mountain province is the western Hayfork terrane (WHT). This terrane is primarily metasedimentary, consisting mainly of crystal-lithic arenite, argillitic sediments and lahar deposits, rare lavas, and sparse quartz-rich arenite. Because lavas are rare, petrologic study using bulk-rock compositions is restricted to analysis of cobbles in lahar deposits. Moreover, the WHT underwent greenschist-facies regional metamorphism with consequent modification of bulk-rock compositions. However, many of the sandstones preserve igneous clinopyroxene and calcic amphibole, which were phenocrysts in the original volcanic rocks. Major- and trace-element compositions of the magmatic pyroxene and amphibole permit reconstruction of the range of rock types eroded from the arc, specifically scant basalt, volumetrically dominant basaltic andesite and andesite, and smaller but significant amounts of dacite and rhyodacite. Eruptive temperatures reached ∼1180 °C and may have been as low as ∼800 °C on the basis of pyroxene and amphibole thermometry, with most eruptive temperatures &gt;1000 °C. On the basis of augite compositions, WHT magmatism is divided into two suites. One features high-Mg augite with high abundances of Cr and Sr, high Sr/Y and Nd/Yb values, and low Y and heavy rare-earth elements (REE). These compositions are typical of high-Mg andesite and dacite suites in which garnet is a residual mineral, most probably in a metasomatized upper mantle setting. The other suite contains augite with lower Sr, Sr/Y, and Nd/Yb; these features are typical of normal calc-alkaline magmas. Augite from a coeval pluton emplaced inboard of the western Hayfork outcrop belt is similar to augite from the low-Sr group of WHT samples. In contrast, augite from the Ironside Mountain pluton, previously considered the plutonic equivalent of WHT sediments, is Fe-rich, with low Cr and Sr and relatively high Zr and REE. Previous suggestions that the Ironside Mountain pluton is correlative with the WHT are not supported by these data. The magmatic diversity of the WHT is typical of the modern Aleutian and Cascade arcs, among others, and could reflect subduction of relatively young oceanic lithosphere or fragmentation of the subduction slab. Although we favor the former setting, present data cannot rule out the latter. The presence of scant quartz-rich sedimentary rocks within the predominantly volcanogenic WHT is consistent with deposition as a sedimentary apron associated with a west-facing magmatic arc with late-stage input from cratonal sources. The results of this study indicate that detailed petrographic study of arc-derived sedimentary rocks, including major- and trace-element analysis of preserved magmatic phases, yields information about magmatic affinities, processes, and temperatures.

Magmatic and hydrothermal systems are intimately linked, significantly overlapping through time but persisting in different parts of a system. New preliminary U-Pb and trace element petrochronology from zircon and titanite demonstrate the protracted and episodic record of magmatic and hydrothermal processes in the Alta stock–Little Cottonwood stock plutonic and volcanic system. This system spans the upper ~11.5 km of the crust and includes a large composite pluton (e.g., Little Cottonwood stock), dike-like conduit (e.g., Alta stock), and surficial volcanic edifices (East Traverse and Park City volcanic units). A temperature–time path for the system was constructed using U-Pb and tetravalent cation thermometry to establish a record of >10 Myr of pluton emplacement, magma transport, volcanic eruption, and coeval hydrothermal circulation. Zircons from the Alta and Little Cottonwood stocks recorded a single population of apparent temperatures of ~625 ± 35 °C, while titanite apparent temperatures formed two distinct populations interpreted as magmatic (~725 ± 50 °C) and hydrothermal (~575 ± 50 °C). The spatial and temporal variations required episodic magma input, which overlapped in time with hydrothermal fluid flow in the structurally higher portions of the system. The hydrothermal system was itself episodic and migrated within the margin of the Alta stock and its aureole through time, and eventually focused at the contact of the Alta stock. First-order estimates of magma flux in this system suggest that the volcanic flux was 2–5× higher than the intrusive magma accumulation rate throughout its lifespan, consistent with intrusive volcanic systems around the world.

AbstractWe review the causes, mechanisms and consequences of crustal anatexis during the exhumation of metamorphic terranes, from a petrological perspective. During both prograde and retrograde metamorphism, limited influx of free hydrous fluids may result in small volumes of very hydrous melts, which cannot ascend far (if at all) before reaching their solidus. If thermal conditions for dehydration melting are attained in fertile micaceous crustal layers, much larger volumes of water-undersaturated granitic magmas may result, especially where limited external fluid influx raises water activities above those that may be buffered by dehydrating hydrous phases. Magmas have specific trace element characteristics depending on the reaction which formed them which, combined with accessory phase thermometry, may enable the (P-T) conditions of melting to be ascertained. Small volume-fraction magmas will typically remain as in situ migmatites unless their extraction is assisted by deformation. In turn, deformation will be focused in weaker partially molten zones, so that water-undersaturated magmas may often be mobilized. Once segregated, their ascent is limited by the rate of dyke propagation, and they may reach shallow levels (<2 kbar) before crystallizing. The complex interplay between deformation and melting is exemplified by the Miocene evolution of the central Himalaya, where thrust and normal faulting, melting and exhumation were all simultaneously active processes which were linked by feedback relations. In the Nanga Parbat Massif of the western Himalaya, rapid post-Miocene denudation and vigorous fluid flux enabled rocks to experience more than one episode of melting simultaneously, at different levels of the same exhuming crustal section.

This paper documents the data on high-Mg porphyrite dykes (PDs) from the mafic to felsic (~2.09 Ma) plutons of Elan complex (EC). The low-thickness (first centimeters) synplutonic dykes are characterized by sharp straight contacts without visible chilling zones, in contrast to the larger (up to 119 m) dykes that have gradual transitions. The dykes are fresh, porphyritic (bronzite, Al-enstatite, labradorite) and has fine-grained mainly quartzo-feldspathic (+biotite, sulfides, accessories, ±hypersthene) matrix. Based on geochemistry data the PDs are intermediate rocks (SiO2 = 58.9–60.3 wt. %) and plot into calc-alkaline series with high magnesian of whole rock (Mg# ~0.7) and felsic (68.9–70.2 wt. %) matrix (Mg# ~0.5). The PDs show differentiated rare-earth element patterns with negligible Eu anomalies. The bronzite phenocrysts varying sizes are characterized by block zoning and contain irregular inclusions of olivine (Mg# ~0.85), clinopyroxene (Mg# ~0.88), phlogopite (Mg# up to 0.94), labradorite, chrome spinel, graphite and sulfides. The Al-enstatite phenocrysts are practically sterile with respect to trace elements and mineral inclusions. The geochemical features as well as diffusion zones, reaction rims, and resorbed faces of the phenocrysts such as orthopyroxene and plagioclase indicate processes of recrystallization and/or partial dissolution of nonequilibrium crystals in the melt and indicate intratelluric nature of the dyke phenocrysts that cores are inherited from the EC derivatives/cumulate. The mineral thermometry estimates are: (1) the parent magma starting temperatures of 1200–1400 °С and (2) the EC crystallization temperatures 1080–1155 °С, (3) the PD emplacement temperatures 910–1070 °С. The petrogenetic model supposes the generation of EC high-temperature magmas similar to boninites from an upper metasomatized mantle. The melt is contaminated with continental crust lithologies. It implies the half-way evolved magma chamber in the crust. The PD melt, as a result of ending of the half-way magma chamber evolution, was emplaced into the still unheated EC plutons.

Abstract Iron oxide copper-gold (IOCG) and iron oxide-apatite (IOA) deposits are major sources of Fe, Cu, and Au. Magnetite is the modally dominant and commodity mineral in IOA deposits, whereas magnetite and hematite are predominant in IOCG deposits, with copper sulfides being the primary commodity minerals. It is generally accepted that IOCG deposits formed by hydrothermal processes, but there is a lack of consensus for the source of the ore fluid(s). There are multiple competing hypotheses for the formation of IOA deposits, with models that range from purely magmatic to purely hydrothermal. In the Chilean iron belt, the spatial and temporal association of IOCG and IOA deposits has led to the hypothesis that IOA and IOCG deposits are genetically connected, where S-Cu-Au–poor magnetite-dominated IOA deposits represent the stratigraphically deeper levels of S-Cu-Au–rich magnetite- and hematite-dominated IOCG deposits. Here we report minor element and Fe and O stable isotope abundances for magnetite and H stable isotope abundances for actinolite from the Candelaria IOCG deposit and Quince IOA prospect in the Chilean iron belt. Backscattered electron imaging reveals textures of igneous and magmatic-hydrothermal affinities and the exsolution of Mn-rich ilmenite from magnetite in Quince and deep levels of Candelaria (&gt;500 m below the bottom of the open pit). Trace element concentrations in magnetite systematically increase with depth in both deposits and decrease from core to rim within magnetite grains in shallow samples from Candelaria. These results are consistent with a cooling trend for magnetite growth from deep to shallow levels in both systems. Iron isotope compositions of magnetite range from δ56Fe values of 0.11 ± 0.07 to 0.16 ± 0.05‰ for Quince and between 0.16 ± 0.03 and 0.42 ± 0.04‰ for Candelaria. Oxygen isotope compositions of magnetite range from δ18O values of 2.65 ± 0.07 to 3.33 ± 0.07‰ for Quince and between 1.16 ± 0.07 and 7.80 ± 0.07‰ for Candelaria. For cogenetic actinolite, δD values range from –41.7 ± 2.10 to –39.0 ± 2.10‰ for Quince and from –93.9 ± 2.10 to –54.0 ± 2.10‰ for Candelaria, and δ18O values range between 5.89 ± 0.23 and 6.02 ± 0.23‰ for Quince and between 7.50 ± 0.23 and 7.69 ± 0.23‰ for Candelaria. The paired Fe and O isotope compositions of magnetite and the H isotope signature of actinolite fingerprint a magmatic source reservoir for ore fluids at Candelaria and Quince. Temperature estimates from O isotope thermometry and Fe# of actinolite (Fe# = [molar Fe]/([molar Fe] + [molar Mg])) are consistent with high-temperature mineralization (600°–860°C). The reintegrated composition of primary Ti-rich magnetite is consistent with igneous magnetite and supports magmatic conditions for the formation of magnetite in the Quince prospect and the deep portion of the Candelaria deposit. The trace element variations and zonation in magnetite from shallower levels of Candelaria are consistent with magnetite growth from a cooling magmatic-hydrothermal fluid. The combined chemical and textural data are consistent with a combined igneous and magmatic-hydrothermal origin for Quince and Candelaria, where the deeper portion of Candelaria corresponds to a transitional phase between the shallower IOCG deposit and a deeper IOA system analogous to the Quince IOA prospect, providing evidence for a continuum between both deposit types.

Abstract Cumulate processes in granitic magma systems are thought by some to be negligible and by others to be common and widespread. Because most granitic rocks lack obvious evidence of accumulation, such as modal layering, other means of identifying cumulate rocks and estimating proportions of melt lost must be developed. The approach presented here utilizes major and trace element compositions of hornblende to estimate melt compositions necessary for zircon saturation. It then compares these estimates with bulk-rock compositions to estimate proportions of extracted melt. Data from three arc-related magmatic systems were used (English Peak pluton, Wooley Creek batholith, and Tuolumne Intrusive Complex). In all three systems, magmatic hornblende displays core-to-rim decreases in Zr, Hf, and Zr/Hf. This zoning indicates that zircon must have fractionated during crystallization of hornblende, at temperatures greater than 800 °C. This T estimate is in agreement with Ti-in-zircon thermometry, which yields a maximum T estimate of 855 °C. On the basis of this evidence, concentrations of Zr in melts from which hornblende and zircon crystallized were calculated by (1) applying saturation equations to bulk-rock compositions, (2) applying saturation equations to calculated melt compositions, and (3) using hornblende/melt partition coefficients for Zr. The results indicate that melt was lost during crystallization of the granitic magmas, conservatively at least as much as 40 %. These results are in agreement with published estimates of melt loss from other plutonic systems and suggest that bulk-rock compositions of many granitic rocks reflect crystal accumulation and are therefore inappropriate for use in thermodynamic calculations and in direct comparison of potentially consanguineous volcanic and plutonic suites.

The results of experimental studies of sensitive elements of temperature transducers based on semiconductor thermometric material Lu1-xScxNiSb, x=0.01–0.10, are presented. Thermometric materials Lu1-xScxNiSb were made by fusing a mixture of components in an electric arc furnace with a tungsten electrode (cathode) in an atmosphere of purified argon under a pressure of 0.1 kPa on a copper water-cooled hearth (anode). Heat treatment of alloys consisted of homogenizing annealing for 720 h in vacuumed to 1.0 PA at a temperature of 1073 K. Arrays of diffraction data of X-ray diffraction studies were obtained on a powder diffractometer STOE STADI-P, and using the program Fullprof calculated structural characteristics. The chemical and phase compositions of the samples were monitored by metallographic analysis (scanning electron microscope Tescan Vega 3 LMU). The basis of the sensitive element of the resistance thermometer on Lu1-xScxNiSb materials is polycrystalline samples in the form of rectangular parallelepipeds with a size of 0.5 × 0.5 × 5 (mm3 ), to which the contacts are made of copper and/or platinum wire. Experimental measurements of electrical resistance values were performed using the four-contact method, and the values of the thermopower coefficient by the potentiometric method concerning copper and/or platinum. The thermoelectric pair platinumthermometric material was the basis of the thermoelectric converter. Modeling of thermometric characteristics of sensitive elements of the thermometer of resistance of the thermoelectric converter is carried out by a full potential method of linearized plane waves (Full Potential Linearized Augmented Plane Waves, Elk software package). The results of experimental measurements served as reference currents in modeling the characteristics. X-ray phase analysis showed the homogeneity of the studied samples of thermometric materials Lu1-xScxNiSb, as evidenced by the absence of traces of extraneous phases on the diffractograms. The dependences of the period of the unit cell a(x) Lu1-xScxNiSb are not linear, which indicates more complex structural changes than the one-act substitution of the Lu atom by Sc. Measurements of the values of the specific magnetic susceptibility χ (T, x) were performed by the relative Faraday method at T=273 K using a thermogravimetric installation with an electronic microbalance EM-5-ZMP in magnetic fields up to 10 kGs. Experimental studies of the specific magnetic susceptibility of χ(x) sensitive elements have shown that the samples at all concentrations are Pauli paramagnetics, and the value of χ(x) is determined by the electron gas. In this case, the values of the magnetic susceptibility χ(x) are proportional to the density of electronic states at the Fermi level g(εF). In the area of concentrations x=0–0.02, the values of magnetic susceptibility χ(x) undergo insignificant changes, which indicates small changes in the concentration of current carriers. At a concentration x>0.02 there is a rapid increase in the density of electronic states at the Fermi level g(εF), indicating an increase in the concentration of free current carriers. The presence of high-temperature activation sites on the temperature dependences of the resistivity ln(ρ(1/T)) for all Lu1-xScxNiSb samples indicates the location of the Fermi level εF in the band gap εg of the semiconductor, and positive values of the thermopower coefficient α(T) specify its position - near the valence band εV. The main carriers of electric current are holes. The nature of the behavior of the resistivity ρ (x, T) Lu1-xScxNiSb at all temperatures also corresponds to the results of modeling the kinetic properties. The fact that in the range of concentrations x=0–0.04 the values of the resistivity ρ (x, T) Lu1-xScxNiSb change slightly at all temperatures indicates a significant advantage of the concentration of holes over electrons. This is indicated by positive values of the thermopower coefficient α (x, T). At concentrations x≥0.04, the resistivity increases rapidly, which is due to the appearance of donors, which partially compensate for the acceptors, which reduces the concentration of free holes, and, as a result, we have an increase in the resistance. The behavior of the thermopower coefficient α (x, T) Lu1-xScxNiSb is adequate. The appearance and increase in the electron concentration are accompanied by an increase in the thermopower coefficient α (x, T). At a concentration of x≈0.07, the dependence of the thermopower coefficient contains an extremum, and then the values of the thermopower coefficient rapidly decrease at a temperature of T=80 K and concentrations at x≈0.1. Electrons are already the main current carriers. This is indicated by the negative values of the thermopower coefficient. It was experimentally established that at the concentration range x= 0–0.07 the Fermi level velocity εF from the valence band εV is ΔεF/Δx=4.9 meV /% Sc, and at the concentration, x≥0.07 – ΔεF/Δx=11.2 meV /% Sc. The presence of a difference in the velocities of the Fermi level εF indicates different rates of generation of acceptors and donors: at a concentration of x≥0.07, the concentration of donors increases ~2 times faster than at the site x=0–0.07. The functions of conversion of sensitive elements of resistance thermometer and thermoelectric transducers in the temperature range 4.2–1000 K are modeled. The ratio of the change in the values of the thermopower coefficient to the range of temperature measurements in thermocouples is greater than all known industrial thermocouples. In addition, the temperature coefficient of resistance (TCR) of the obtained resistance thermometers is higher than the TCR of metals but is inferior to the value of TCR of sensitive elements made of traditional semiconductors. At the same time, none of the known resistance thermometers based on traditional semiconductors provides stable characteristics at temperatures of 4.2÷1000 K.

Study of petrological and geochemical characteristics of mantle peridotite xenoliths in Pliocene alkaline basalt in Nghia Dan (West Nghe An) was carried out. Rock-forming clinopyroxenes, the major trace element containers, were separated from the xenoliths to analyze for major, trace element and Sr-Nd isotopic compositions. The data were interpreted for source geochemical characteristics and geodynamic processes of the lithospheric mantle beneath the region. The peridotite xenoliths being mostly spinel-lherzolites in composition, are residual entities having been produced following partial melting events of ultramafic rocks in the asthenosphere. They are depleted in trace element abundance and Sr-Nd isotopic composition. Some are even more depleted as compared to mid-ocean ridge mantle xenoliths. Modelled calculation based on trace element abundances and their corresponding solid/liquid distribution coefficients showed that the Nghia Dan mantle xenoliths may be produced of melting degrees from 8 to 12%. Applying various methods for two-pyroxene temperature- pressure estimates, the Nghia Dan mantle xenoliths show ranges of crystallization temperature and pressure, respectively, of 1010-1044°C and 13-14.2 kbar, roughly about 43km. A geotherm constructed for the mantle xenoliths showed a higher geothermal gradient as compared to that of in the western Highlands (Vietnam) and a conductive model, implying a thermal perturbation under the region. The calculated Sm-Nd model ages for the clinopyroxenes yielded 127 and 122 Ma. 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1) ZINC: In 1963, Prasad found that dwarfism in Egypt was caused by zinc deficiency. Since then, many clinical pictures involving zinc deficiency have been reported on, such as alopecia (baldness), intestinal acrodermatitis (dermatitis of the extremities), alcohol-induced anencephalic children, and depressed immune response. 2) COPPER: Wilson’s disease is characterized by hepato-cerebral degeneration, which is caused by the deposition of copper in the liver and the cerebrum. Chelete therapy has been applied to remove the copper from the organs in order to treat Wilson’s disease. However, during the last several years zinc or manganese has also been applied to remove copper. The therapy mechanism is based on the interaction of copper to zinc and manganese. Zinc and copper deficiency is also an important topic in medical elementology. 3) MERCURY: Sir Isaac Newton was well known to be distrustful of others in his last years. The clinical picture was characterized by severe neuropathy, which was caused by heavy exposure to mercury during his long scholarly life. Children sometimes break thermometer in their mouth. Does metallic mercury in the thermometer induce mercury intoxication ? The answer is no. Intestinal absorption of metallic mercury is quite low, and thus ingested mercury rarely induces intoxication. The mercury is simply excreted through the feces within a day or two. One should attempt to wash the mercury out from the stomach with water. However, do not treat the child with laxatives, as they can increase the intestinal absorption of mercury, resulting in intoxication. 4) METHYLMERCURY: Severe neuropathy was endemic among fishermen and their families in a particular area of Kyushu Island, Japan. They were found to have eaten a great amount of fish, which were contaminated with organic mercury emitted from a fertilizer producing plant. The disease was later named as Minamata disease. The total number of recognized patients has amounted to 3,000 people, to date. 5) CADMIUM: Cadmium deficiency was recently found to depress the development of baby animals by Anke. This finding suggests that cadmium is not only a harmful element but also an essential element. Itai-Itai disease is characterized as osteomalacia, which is followed by severe renal tubular damage. Patients were comprised largely of elderly women who lived in the Jintsu river basin over a long period, and ingested excess cadmium emitted from a mine, which contaminated the local rice and drinking water. Long-term monkey experiments could not demonstrate osteomalacia by cadmium, however, epidemiological and experimental studies showed that an age-related increase in blood pressure is accelerated by cadmium at low doses, but depressed by cadmium at high doses. 6) LEAD: Lead is a very useful element, but a very harmful element as well. Lead has a potent hematopoietic effect on adults, and also negative psycho-neurological effects on babies. Soil pollution from lead has been discussed in relation to depressed intelligence among children living in U. S. slums. Sometimes residents in rural areas are shot with lead slugs by mistake. Do does lead slugs cause lead intoxication? Usually not. Medication is necessary only when lead slugs injure blood vessels or neurons. Most lead slugs do not induce lead intoxication because the lead slugs are soon covered with granular tissues. 7) CHROMIUM: Chromium is one of the essential trace elements, and is related to glucose tolerance and transmission velocity of peripheral nerves. Adverse effects of excessive chromium are chromium ulcers, perforation of the nasal septum, and lung cancer. 8) ARSENIC: Neutron activation analysis revealed excess amounts of arsenic in the hair of Napoleon. It was then suspected that he was killed with arsenic. Concerning the cause of his death, it was shown that grapes were disinfected with arsenic in those days, and that Napoleon might have consumed excess arsenic from drinking wine. However, the cause of his death remains unsolved. On the other hand, arsenic was used to promote health in Austria. Huge doses of arsenic, lethal for ordinary people, were administered to Austrian youths to assist them in Alpinc hiking. Japanese, especially residents in seashore areas, eat sizable amounts of sea weeds, which contain a huge amount of arsenic. Do they suffer from arsenic intoxication? The answer is no. The chemical form of arsenic in sea weeds is methyl-arsenic, the detoxicated chemical form, which does not revert to the active chemical form of arsenic.

Abstract. The influence of salinity in the incorporation of trace elements in the skeleton of calcareous organisms is still poorly known. Studies on foraminiferal Mg/Ca thermometry have suggested a bias due to Sea Surface Salinity (SSS) variations, leading to potential erroneous estimation of Mg/Ca-based Sea Surface Temperature (SST). Culture experiments seem to indicate that in three coral species (not including the widely used Porites genus), salinity does not influence the Sr/Ca thermometer. In this study, we test the salinity effect on coral Sr/Ca-based SST reconstructions at monthly and interannual timescales in open-ocean environmental conditions, using a large spatial compilation of published coral data (mainly based on the Porites genus) originating from the Western Pacific Ocean, the Atlantic Ocean, the Indian Ocean, the China Sea and the Red Sea and adding a new Eastern Pacific coral Sr/Ca record from the Clipperton atoll. We use simple and multiple regressions between Sr/Ca on one hand and SST and SSS on the other hand at the various sites. We find no evidence for a salinity bias on the Sr/Ca SST proxy for the two studied timescales. This study reinforces the use of coral Sr/Ca as a reliable paleothermometer.

Abstract Archaean zircons from the Kaapvaal Craton, South Africa, were analyzed by Laser Ablation (LA)-ICP-MS to obtain a coupled record of U-Th-Pb isotope ratios and selected trace elements with the aim to develop insights into physico-chemical conditions during igneous zircon crystallization and subsequent compositional alteration. Four rock samples previously dated by SIMS U-Pb using zircon were selected: 3.56 Ga Ngwane Gneiss, 3.55 Ga Theespruit felsic metavolcanic, 3.50 Ga Steynsdorp Gneiss and 2.98 Ga Nhlangano Gneiss. LA-ICP-MS U-Pb zircon ages agree with published SIMS U-Pb ages within analytical uncertainty. Assessment of the magmatic crystallization histories was based on near-concordant grains, and discordant grains were used to examine post-igneous element mobilization and alteration. Time-resolved laser drilling experiments allowed distinction of concordant and discordant zircon domains, but also revealed systematic changes in REE + Ti geochemistry, U + Th content, discordance and metamictization. Th/U and Zr/Hf, coupled with REE patterns, effectively distinguish compositional zircon types that reflect variable degrees of igneous differentiation and melt compositions. Eu/Eu* values indicate significant feldspar fractionation in some magmas. Averaged crystallization temperatures of magmatic zircons, as derived from the Ti-in-zircon thermometer, define a narrow range of 650 to 750°C for (near-)concordant grains, consistent with general constraints on temperatures at zircon saturation for felsic magmas, and testifying to a closed-system behavior of Ti (and other trace elements). Systematic deviations from primary igneous trace element signatures are strongly correlated with radiation damage. Specifically, Th/U and, to some extent, Zr/Hf decrease, and Ti increases with increasing U (+Th) content and isotopic disturbance (discordance).

Abstract An estimate of TiO2 activity (aTiO2melt-sat) is necessary for the application of trace-element thermobarometry of magmatic systems where melts are typically undersaturated with respect to rutile/anatase. Experiments were performed in the system SiO2-Na2O-TiO2 to develop two independent methods of estimating aTiO2melt-sat—one based on the commonly applied rutile-saturation technique and another utilizing a novel Ti-in-tridymite thermometer. It is demonstrated that the rutile-saturation model can lead to an overestimate of aTiO2melt-sat relative to TiO2 activity calculated using the solubility of Ti in tridymite (SiO2) coexisting with rutile. Overestimation via the rutile-saturation technique is due to variations in the solubility mechanisms of Ti in the melt phase as a function of Ti content. In natural systems, overestimates of aTiO2melt-sat will lead to an underestimation of crystallization temperatures by Ti-based trace-element thermobarometers. Although this study is not directly applicable to natural systems, it lays the groundwork for future research on natural composition magmas to constrain TiO2 activity in melts.

Abstract The petrography and mineral chemistry of the coarse-grained, weakly porphyritic (muscovite-) biotite Říčany granite (Variscan Central Bohemian Plutonic Complex, Bohemian Massif) were studied in order to assess the distribution of major and trace elements among its minerals, with consequences for granite petrogenesis and availability of geochemical species during supergene processes. It is demonstrated that chemistry-based approaches are the best suited for modal analyses of granites, especially methods taking into account compositions of whole-rock samples as well as their mineral constituents, such as constrained least-squares algorithm. They smooth out any local variations (mineral zoning, presence of phenocrysts, schlieren…) and are robust in respect to the presence of phenocrysts or fabrics. The study confirms the notion that the accessory phases play a key role in incorporation of many elements during crystallization of granitic magmas. Especially the REE seem of little value in petrogenetic modelling, unless the role of accessories is properly assessed and saturation models for apatite, zircon, monazite±rutile carefully considered. At the same time, the presence of several P-, Zr- and LREE-bearing phases may have some important consequences for saturation thermometry of apatite, zircon and monazite.

The hard tissues of cephalopod, namely statoliths were analyzed with PIXE for the Japanese common squid Todarodes pacificus of the Sea of Japan origin in order to examine the relationship between the amount of trace elements in statoliths and environmental temperature of the squid habitat. Calcium, iron, zinc. copper and strontium were detected in the statoliths. Negative relationship was observed between Sr concentration in statoliths and environmental temperature. On the contrary to Sr, Fe and Zn concentration in statoliths related positively with environmental temperature. These observations revealed that the statoliths would be a useful thermometer for reconstructing the environmental temperature of cephalopod habitat as seen in the hard tissues of other marine organisms.

The results of experimental research of perspective thermometric material Lu1-xZrxNiSbwhich can be used for the production of sensitive elements of thermoelectric and electroresistive thermometers are presented. Thermometric materials Lu1-xZrxNiSb, x=0.01–0.10, were made by fusing a charge of components in an electric arc furnace with a tungsten electrode (cathode) in an atmosphere of purified argon under a pressure of 0.1 kPa on a copper water-cooled hearth (anode). Heat treatment of alloys consisted of homogenizing annealing at a temperature of 1073 K. Annealing of samples was carried out for 720 h in vacuumed up to 1.0 Pa ampoules of quartz glass in muffle electric furnaces with temperature control with an accuracy of ±10 K. Diffraction arrays were obtained on a diffractometer DRON-4.0 (FeKα radiation), and the structural characteristics of Lu1-xZrxNiSbwere calculated using the Fullprof program. The chemical and phase compositions of the samples were monitored using a scanning electron microscope (Tescan Vega 3 LMU). The study of the temperature dependences of the resistivity ρ(T,x) and the thermopower coefficientα(T,x) Lu1-xZrxNiSb was performed in the temperature range of 80÷400 K on samples in the form of rectangular parallelepipeds measuring ~1.0×1.0×5.0 mm3 . Measurements of the values of the specific magnetic susceptibility χ(x) of Lu1-xZrxNiSb samples were performed by the relative Faraday method at a temperature of 273 K using a thermogravimetric installation with an electronic microbalance EM-5-ZMP in magnetic fields up to 10 kGs. Microprobe analysis of the concentration of atoms on the surface of Lu1-xZrxNiSb samples, x=0.01–0.10, established their correspondence to the initial compositions of the charge, and X-ray phase analysis showed no traces of extraneous phases on the sample diffractograms, except for the main phase. The nonmonotonic nature of the change in the values of the unit cell period of the thermometric material an (x) Lu1-xZrxNiSb, x=0.01–0.10, which differs from the results of modeling structural characteristics using software packages AkaiKKR and Elk. The nonmonotonic change in the values of the period of the unit cell a(x) Lu1-xZrxNiSband the presence of the extremum dependence suggests that the impurity Zr atoms introduced into the matrix of the LuNiSb basic semiconductor can simultaneously occupy partially different crystallographic positions in different ratios. The temperature resistivities ρ and the thermopower coefficientα of the LuNiSb base semiconductor contain high- and lowtemperature activation regions, which is characteristic of doped and compensated semiconductors. The introduction into the LuNiSb structure of the lowest concentration of impurity Zr atoms in the experiment (x=0.01) radically changes both the behavior of the temperature dependences of the resistivity ρ and the thermopower coefficientα and the type of the main electric current carriers. The values of the resistivity ρ(T,x) Lu1-xZrxNiSbonly increase with increasing temperature, which is characteristic of the metallic type of electrical conductivity and is due to the mechanisms of scattering of current carriers. This nature of the change in electrical resistance ρ(T,x) is evidence that the Fermi level εF has left the bandgap εg and is in the conduction band εC. This is indicated by the negative values of thermopower coefficientα(T,x) at all concentrations and temperatures. Studies of the magnetic susceptibility χ(x) showed that the samples as a basic semiconductor LuNiSb, as well as the thermometric material Lu1-xZrxNiSb, at all concentrations of impurities Zr, are Pauli paramagnetic. There is a synchronicity of the behavior of χ(x) with the dependences of the resistivity ρ(x, T) and the thermopower coefficient α(x, T), which is due to the change in the density of states at the Fermi level g(εF). The results of experimental studies of the Lu1-xZrxNiSbthermometric material completely coincide with the results of modeling its kinetic characteristics under the presence of vacancies in the crystallographic positions 4a and 4c of the Lu and Ni atoms, respectively. Such studies allow making adjustments in the structural studies of thermometric material with an accuracy that significantly exceeds the accuracy of X-ray research methods. The obtained results will allow us to clarify the spatial arrangement of atoms in the nodes of the unit cell, as well as to identify the mechanisms of electrical conductivity to determine the conditions for the synthesis of thermosensitive materials with maximum efficiency of thermal energy conversion into electricity.

Context. Barium stars are s-process enriched giants. They owe their chemical peculiarities to a past mass transfer phase. During this phase they were polluted by their binary companion, which at the time was an asymptotic giant branch (AGB) star, but is now an extinct white dwarf. Barium stars are thus ideal targets for understanding and constraining the s-process in low- and intermediate-mass AGB stars. Aims. We derive the abundances of a large number of heavy elements in order to shed light on the conditions of operation of the neutron source responsible for the production of s-elements in the former companions of the barium stars. Methods. Adopting a recently used methodology, we analyse a sample of eighteen highly enriched barium stars observed with the high-resolution HERMES spectrograph mounted on the Mercator telescope (La Palma). We determine the stellar parameters and abundances using MARCS model atmospheres. In particular, we derive the Nb–Zr ratio which was previously shown to be a sensitive thermometer for the s-process nucleosynthesis. Indeed, in barium stars, 93Zr has fully decayed into mono-isotopic 93Nb, so Nb/Zr is a measure of the temperature-sensitive 93Zr/Zr isotopic ratio. Results. HD 28159, previously classified as K5III and initially selected to serve as a reference cool K star for our abundance analysis, turns out to be enriched in s-process elements, and as such is a new barium star. Four stars are characterised by high nitrogen abundances, and among those three have high [Nb/Zr] and [hs/ls] ratios. The derived Zr and Nb abundances provide more accurate constraints on the s-process neutron source, identified to be 13C(α, n)16O for barium stars. The comparison with stellar evolution and nucleosynthesis models shows that the investigated barium stars were polluted by a low-mass (M ∼ 2 − 3 M⊙) AGB star. HD 100503 is potentially identified as a high metallicity analogue of carbon-enhanced metal-poor star enriched in both r- and s-process elements (CEMP-rs).

Kyshtymites are the unique corundum-blue sapphire-bearing variety of anorthosites of debatable geological origin found in the Ilmenogorsky-Vishnevogorsky complex (IVC) in the South Urals, Russia. Their mineral association includes corundum-sapphire, plagioclase (An61–93), muscovite, clinochlore, and clinozoisite. Zircon, churchite-(Y), monazite-(Ce), and apatite group minerals are found as accessory phases. Besides, churchite-(Y) and zircon are also identified as syngenetic solid inclusions within the sapphires. In situ Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) U-Pb zircon geochronology showed the ages at about 290–330 Ma linked to the Hercynian orogeny in IVC. These ages are close to those of the syenitic and carbonatitic magmas of the IVC, pointing to their syngenetic origin, which is in agreement with the trace element geochemistry of the zircons demonstrating clear magmatic signature. However, the trace element composition of sapphires shows mostly metamorphic signature with metasomatic overprints in contrast to the geochemistry of zircons. The reason for this discrepancy can be the fact that the discrimination diagrams for sapphires are not as universal as assumed. Hence, they cannot provide an unambiguous determination of sapphire origin. If it is true and zircons can be used as traces of anorthosite genesis, then it can be suggested that kyshtymites are formed in a magmatic process at 440–420 Ma ago, most probably as plagioclase cumulates in a magma chamber. This cumulate rock was affected by a second magmatic event at 290–330 Ma as recorded in zircon and sapphire zoning. On the other hand, Ti-in-zircon thermometer indicates that processes operated at relatively lower temperature (<900 °C), which is not enough to re-melt the anorthosites. Hence, zircons in kyshtymites can be magmatic but inherited from another rock, which was re-worked during metamorphism. The most probable candidate for the anorthosite protolith is carbonatites assuming that metamorphic fluids could likely leave Al- and Si-rich residue, but removed Ca and CO2. Further, Si is consumed by the silicification of ultramafic host rocks. However, kyshtymites do not show clear evidence of pronounced metasomatic zonation and evidence for large volume changes due to metamorphic alteration of carbonatites. Thus, the obtained data still do not allow for univocal reconstruction of the kyshtymite origin and further investigations are required.

The W–Sn Panasqueira ore deposit is a magmatic-hydrothermal system, which includes a high-grade quartz-vein type mineralization and a disseminated greisen-type mineralization occurring in the upper part of the Panasqueira two-mica granite. We investigated the genetic and chronological relationships between the greisenization of the Panasqueira granite and the formation of ore-bearing quartz veins by monitoring major and trace elements variations in quartz-white mica assemblages composing the two-mica granite, greisen and W–Sn-bearing quartz veins. The greisen is characterized by an overall depletion in Mg, Ti, Ca, Na, Ba, Sr, REE and enrichment in Fe, Li, Rb, Cs, Sn, W which reflect the breakdown of feldspars and fluid-rock interactions with W–Sn-bearing fluids. White-mica from greisen and mineralized quartz veins are enriched in granophile elements (F, Rb, Cs, Li, Sn, W and Zn) compared to magmatic muscovite from the two-mica granite. Trace elements contents in quartz depict trends which show the progressive enrichment in Ge and B and depletion in Al, Ti and Li from magmatic to hydrothermal quartz that emphasize the progressive evolution and cooling of the magmatic-hydrothermal system of Panasqueira. Geochemical similarities between quartz-white mica assemblages from greisen and wolframite-bearing veins suggest that greisenization and the formation of mineralized veins result from the same hydrothermal event and derived from the same source of hydrothermal fluids. Apatite from greisen and quartz vein yielded U–Pb ages of 292 ± 10 Ma and 295 ± 5 Ma respectively confirming that greisenization and the formation of mineralized veins occurred roughly at the same time. These ages also overlap with the emplacement age of the Panasqueira granite (296 ± 4 Ma), indicating a temporal link between greisenization, W–Sn mineralization and granite crystallization. Temperatures of the magmatic-hydrothermal system constrained by Ti-in quartz thermometry depicts a cooling trend from magmatic quartz of granite (700–600 °C) to hydrothermal quartz of greisen (500–400 °C) and veins (450–350 °C). These results suggest that greisenization and the formation of W–Sn bearing quartz veins occurred at the magmatic-hydrothermal transition, during which orthomagmatic fluids rich in volatils, incompatible elements and W–Sn were exsolved during the final solidification stage of the Panasqueira two-mica granite.

Transformation of the oceanic crust into the continental one in orogenic belts is an important problem in petrological studies. In the paleocontinental sector of the Urals, a key object for tracing the stages of metamorphism and investigating the origin of anatectic granites is the Murzinka-Adui metamorphic complex. We have analyzed trace elements in zircons and established their genesis, sources, crystallization conditions, and stages of metamorphic events and granite generation in this complex. Zircons compositions were determined by the LA-ICP-MS method. Temperatures were calculated from Ti contents in the zircons. We distinguish three geochemical types of zircons, which differ in the ratios of light and heavy REE, U, Th, Ti, Y and show different values of Ce- and Eu-anomalies and Zr/Hf ratios, which are indicative of different crystallization conditions, as follows. Type I: minimal total LREE content; clear negative Eu- and Ce- anomalies; features of magmatic genesis; crystallization temperatures from 629 to 782 °C. Type II: higher contents of Ti, La, and LREE; low Ce-anomaly; assumed crystallization from highly fluidized melts or solutions. Type III: low positive Eu-anomaly; high REE content; low Th/U-ratio; zircons are assumed to originate from a specific fluidized melt with a high Eu-concentration. Ancient relict zircons (2300–330 Ma) in gneisses and granites show features of magma genesis and belong to types I and II. Such grains were possibly inherited from granitoid sources with different SiO2 contents and different degrees of metamorphism. Based on the geological and petrogeochemical features and zircon geochemistry of the Murzinka-Adui complex, there are grounds to conclude that the material composing this complex was generated from the sialic crust. The main stages of metamorphism and/or granite generation, which are traceable from the changes in types and compositions of the zircons, are dated at 1639, 380–370, 330, and 276–246 Ma. Thus, transformation of the oceanic crust into the continental one was a long-term and complicated process, and, as a result, the thickness of the sialic crust is increased in the study area.

Temperature dependence of strontium/calcium (Sr/Ca) ratios in foraminiferal calcite and coral aragonite is well established; however, factors controlling Sr/Ca ratios in fish otoliths remain obscure. To assess temperature dependence of Sr/Ca in marine fish otoliths, we reared spot (Leiostomus xanthurus) larvae under controlled temperature (17–26 °C) and salinity (15‰ and 25‰). We found a significant linear relationship between temperature and Sr/Ca ratios, with a sensitivity of approximately 5%·°C–1. Otolith Sr/Ca values were also significantly higher at a salinity of 25‰ vs. 15‰, after accounting for differences in dissolved Sr/Ca ratios in the ambient water, with a sensitivity of approximately 1%/salinity (‰). These observations complicate the use of Sr/Ca ratios to determine temperature histories of spot larvae, because accurate temperature reconstructions are possible only with a priori knowledge of both ambient salinity and dissolved Sr/Ca ratios. Fully marine species residing in oceanic waters will not experience significant salinity variations; therefore, otolith Sr/Ca ratios may be useful recorders of temperature exposure. Otolith Sr/Ca thermometry in coastal fish species that make regular excursions into estuarine waters will be more problematic. Multiple geochemical tracers, including oxygen stable isotopes and other trace elements, may be necessary to accurately reconstruct temperature and salinity histories in these species.

Abstract The Permian carbonate-hosted Farsesh barite deposit is located southeast of the City of Aligudarz in the province of Lorestan, Iran. Structurally, this deposit lies in the Zagros metallogenic belt and the Sanandaj-Sirjan Zone. Barite mineralisations occur as open-space flling veins, and as massive and replacement ores along fractures, faults and shear zones of the Permian carbonate host rocks. In order to determine the structure, in addition to pe-trographic and fuid-inclusions studies, an ICP-MS analysis was carried out in order to measure the major as well as the trace and rare earth elements. The Farsesh barite deposit has a simple mineralogy, of which barite is the main mineral, followed by calcite, dolomite, quartz, and opaque minerals such as Fe-oxides. Replacement of bar-ite by calcite is common and is more frequent than space-flling mineralisation. Sulphide minerals are minor and mainly consist of chalcopyrite and pyrite, which are altered by weathering to covellite, malachite and azurite. Petrographic analysis and micro-thermometry were carried out on the two-phase liquid/vapour inclusions in ellipsoidal or irregularly shaped minerals ranging in size from 5–10 µm. The measurements were conducted on fuid inclusions during the heating and subsequent homogenisation in the liquid phase. The low homogenisation temperatures (200–125°C) and low to moderate salinity (4.2–20 eq wt% NaCl) indicate that the barite had precipitated from hydrothermal basinal water with low to moderate salinity. It appears from the major and trace elements that geochemical features such as Ba and Sr enrichment in the barite samples was accompanied by depletion of Pb, Zn, Hg, Cu and Sb. The geochemistry of the rare earth elements, such as low σREE concentrations, LREE-enrichment chondrite-normalised REE patterns, the negative Ce and positive Eu anomalies, the low Ce/La ratio and the positive La and Gd anomalies, suggest that the Farsesh barite was deposited from hydrothermally infuenced sea water. The Farsesh deposit contains low-temperature hydrothermal barite. The scatter plots of the barite (close to sea water) in different areas on the CeN/SmN versus CeN/YbN diagram support the possibility that the barite was formed from seawater-bearing hydrothermal fuids.

AbstractThe major- and trace-element chemistry of pyrite and arsenopyrite from the mesothermal Roudný gold deposits was studied by electron microprobe and laser ablation ICP-MS techniques. In total, four generations of pyrite and two of arsenopyrite were distinguished. The pyrite is enriched in As through an Fe (AsxS1–x)2 substitution mechanism. The As-rich zones of pyrite-2 (up to 4.5 wt.% As) are also enriched in gold (up to 20 ppm), lead (commonly up to 220 ppm, exceptionally up to 1500 ppm) and antimony (commonly <600 ppm, rarely up to 1350 ppm). Positive correlation of As and Au in the studied pyrites is not coupled with an Fe deficiency, in contrast to Au-rich As-bearing pyrites in Carlintype gold deposits. The As-rich pyrite-2 coprecipitated with the Sb-rich (1 –4.2 wt.%) and Au-rich (40 –150 ppm) arsenopyrite-1. The younger arsenopyrite-2 is significantly less enriched in these elements (0 –70 ppm of Au).The chemical zonality of pyrites in the Roudný gold deposits reflects the chemical evolution of orebearing fluids that are not observed in any other mineral phases. The data available suggest relatively high activity of sulphur and low activities of arsenic and gold during crystallization of the older pyrite generation (pyrite-1). Later, after particular dissolution of pyrite-1, Au-rich As-bearing pyrite-2 and arsenopyrite precipitated. These facts suggest a marked increase in the arsenic and gold activities in ore-bearing fluids. The As-content of pyrite-2 decreases in an oscillatory manner from the core to the rim, reflecting changes in the As activity or/and in the P-T conditions. The As-bearing pyrites were formed at temperatures of at least 320–330°C, based on arsenopyrite thermometers and fluid inclusion data.

An abundance of the trace elements has been determined in olivine of the Archean spinel-bearing phlogopite harzburgite enclave (sample UR17/2) from the Bug granulite complex of the Ukrainian Shield by SIMS analysis. Major elements were analyzed in the olivine by SEM-EDS and EPMA analysis. The olivine shows a homogeneous chemical composition: MgO — 45.20—45.64 wt.%, FeO — 13.66—14.23 wt.%, with Fo85—86 and Fe/Mn ratio of 68.3—68.6 which corresponds to the ratio of 60—70 in olivine of peridotites. Ni content in the UR17/2 olivine ranges from 4730 to 5612 ppm, which is higher than in olivine from mantle peridotites, high magnesium OIB and Hawaiian picrites. The olivine has average content of Ti — 20.6 ppm, Nb — 0.03 ppm, Zr — 0.32—0.60 ppm, the low total REE (0.1—0.5 ppm). The olivine crystallization temperature, calculated using an Al-in-olivine thermometer, corresponds to ~ 900°C. Enrichment in Fe and Ni is the main feature that distinguishes the UR17/2 olivine from other mantle-derived olivine. Сomposition of the UR17/2 olivine and host harzburgite indicates an influence of T, P, the oxygen fugacity and composition of parent magma on the partition coefficients of Fe and Ni. Сomposition and structure (degree of polymerization) of magma are the main factors responsible for the olivine enrichment by iron and nickel.

This study documents the compositional variations of phenocrysts from a basaltic trachyandesitic sill emplaced in the Valle del Bove at Mt. Etna volcano (Sicily, Italy). The physicochemical conditions driving the crystallization and emplacement of the sill magma have been reconstructed by barometers, oxygen barometers, thermometers and hygrometers based on clinopyroxene, feldspar (plagioclase + K-feldspar) and titanomagnetite. Clinopyroxene is the liquidus phase, recording decompression and cooling paths decreasing from 200 to 0.1 MPa and from 1050 to 940 °C, respectively. Plagioclase and K-feldspar cosaturate the melt in a lower temperature interval of ~1000–870 °C. Cation exchanges in clinopyroxene (Mg-Fe) and feldspar (Ca-Na) indicate that magma ascent is accompanied by progressive H2O exsolution (up to ~2.2 wt. %) under more oxidizing conditions (up to ΔNNO + 0.5). Geospeedometric constraints provided by Ti–Al–Mg cation redistributions in titanomagnetite indicate that the travel time (up to 23 h) and ascent velocity of magma (up to 0.78 m/s) are consistent with those inferred for other eruptions at Mt. Etna. These kinetic effects are ascribed to a degassing-induced undercooling path caused principally by H2O loss at shallow crustal conditions. Rare earth element (REE) modeling based on the lattice strain theory supports the hypothesis that the sill magma formed from primitive basaltic compositions after clinopyroxene (≤41%) and plagioclase (≤12%) fractionation. Early formation of clinopyroxene at depth is the main controlling factor for the REE signature, whereas subsequent degassing at low pressure conditions enlarges the stability field of plagioclase causing trace element enrichments during eruption towards the surface.

Abstract. Porites coral-based sea surface temperature (SST) reconstructions are obtained from the measurement of skeleton Sr/Ca ratio. However, the influence of salinity in the incorporation of these trace elements in the Porites aragonitic skeleton is still poorly documented. Laboratory experiments indicate that in three different coral species (not including the widely used Porites genus), salinity does not influence the Sr/Ca thermometer. In this study, we test the salinity effect on Porites Sr/Ca-based SST reconstructions at monthly and interannual timescales in open-ocean environmental conditions. We use a large spatial compilation of published Porites data from the Red Sea and Pacific and Indian oceans. Additionally to those published records, we add a new eastern Pacific coral Sr/Ca record from Clipperton Atoll. Using two different salinity products (Simple Ocean Data Assimilation (SODA) SSS reanalyses version 2.2.4, Carton and Giese, 2008; and instrumental SSS from the Institut de Recherche pour le Développement, France (IRD) Delcroix et al., 2011), we find no evidence of salinity bias on the Sr/Ca SST proxy at monthly and interannual timescales. We conclude that Porites Sr/Ca is a reliable palaeothermometer that is not influenced by salinity variability.