Explore the vast range of titles available.

Although REE (lanthanides+Sc+Y) mineralization in alkaline silicate systems is commonly accompanied with Zr mineralization worldwide, our understanding of the relationship between Zr and REE mineralization is still incomplete. The Baerzhe deposit in Northeastern China is a reservoir of REE, Nb, Zr, and Be linked to the formation of an Early Cretaceous, silica-saturated, alkaline intrusive complex. In this study, we use in situ laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analyses of zircon and monazite crystals to constrain the relationship between Zr and REE mineralization at Baerzhe. Three groups of zircon are identified and are differentiated based upon textural observations and compositional characteristics. Type Ia zircons display well-developed oscillatory zoning. Type Ib zircons are darker in cathodoluminescence images and have more irregular zoning and resorption features than type Ia zircons. In addition, type Ib zircons can locally occur as overgrowths on type Ia zircons. Type II zircons contain irregular but translucent cores and rims with oscillatory zoning that are murky brown in color and occur in aggregates. Textural features and compositional data suggest that types Ia and Ib zircon crystallized at the magmatic stage, with type Ia being least-altered and type Ib being strongly altered. Type II zircons, on the other hand, precipitated during the magmatic to magmatic-hydrothermal transition. Whereas the magnitude of the Eu anomaly is moderate in the barren alkaline granite, both magmatic and deuteric zircon exhibit pronounced negative anomalies. Such features are difficult to explain exclusively by feldspar fractionation and could indicate the presence of fluid induced modification of the rocks. Monazite crystals occur mostly through replacement of zircon and sodic amphibole; monazite clusters are also present. Textural and compositional evidence suggests that monazite at Baerzhe is hydrothermal. Types Ia and Ib magmatic zircon yield 207Pb-corrected 206Pb/238U ages of 127.2±1.3 and 125.4±0.7 Ma, respectively. Type II deuteric zircon precipitated at 124.9±0.6 Ma. The chronological data suggest that the magmatic stage of the highly evolved Baerzhe alkaline granite lasted less than two million years. Hydrothermal monazite records a REE mineralization event at 122.8±0.6 Ma, approximately 1 or 2 million years after Zr mineralization. We therefore propose a model in which parental magmas of the Baerzhe pluton underwent extensive magmatic differentiation while residual melts interacted with aqueous hydrothermal fluids. Deuteric zircon precipitated from a hydrosilicate liquid, and subsequent REE mineralization, exemplified by hydrothermal monazite, correlates with hydrothermal metasomatic alteration that postdated the hydrosilicate liquid event. Such interplay between magmatic and hydrothermal processes resulted in the formation of discrete Zr and REE mineralization at Baerzhe.

In this study, we use micro-X-ray absorption near-edge structures (µ-XANES) spectroscopy at the S K-edge to investigate the oxidation state of S in natural magmatic-hydrothermal apatite (Durango, Mexico, and Mina Carmen, Chile) and experimental apatites crystallized from volatile-saturated lamproitic melts at 1000 °C and 300 MPa over a broad range of oxygen fugacities [log(fO2)=FMQ, FMQ+1.2, FMQ+3; FMQ = fayalite-magnetite-quartz solid buffer]. The data are used to test the hypothesis that S oxidation states other than S6+ may substitute into the apatite structure. Peak energies corresponding to sulfate S6+ (∼2482 eV), sulfite S4+ (∼2478 eV), and sulfide S2- (∼2470 eV) were observed in apatite, and the integrated areas of the different sulfur peaks correspond to changes in fO2 and bulk S content. Here, multiple tests confirmed that the S oxidation state in apatite remains constant when exposed to the synchrotron beam, at least for up to 1 h exposure (i.e., no irradiation damages). To our knowledge, this observation makes apatite the first mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions as a function of the prevailing fO2 of the system. Apatites crystallized under oxidizing conditions (FMQ+1.2 and FMQ+3), where the S6+/STotal peak area ratio in the coexisting glass (i.e., quenched melt) is ∼1, are dominated by S6+ with a small contribution of S4+, whereas apatites crystallizing at reduced conditions (FMQ) contain predominantly S2-, lesser amounts of S6+, and possibly traces of S4+. A sulfur oxidation state vs. S concentration analytical line transect across hydrothermally altered apatite from the Mina Carmen iron oxide-apatite (IOA) deposit (Chile) demonstrates that apatite can become enriched in S4+ relative to S6+, indicating metasomatic overprinting via a SO2-bearing fluid or vapor phase. This XANES study demonstrates that as the fO2 increases from FQM to FMQ+1.2 to FMQ+3 the oxidation state of S in igneous apatite changes from S2- dominant to S6+ > S4+ to S6+ >> S4+ Furthermore, these results suggest that spectroscopic studies of igneous apatite have potential to trace the oxidation state of S in magmas. The presence of three S oxidations states in apatite may in part explain the non-Henrian partitioning of S between apatite and melt. Our study reveals the potential to use the S signature of apatite to elucidate both oxygen and sulfur fugacity in magmatic and hydrothermal systems.

Mantle potential temperatures (Tp) provide insights into mantle circulation and tests of whether Earth is the only planet to exhibit thermally bi-modal volcanism-a distinctive signature of modern plate tectonics. Planets that have a stagnant lid, for example, should exhibit volcanism that is uni-modal with Tp, since mantle plumes would have a monopoly on the genesis of volcanism. But new studies of magmatic ferric-ferrous ratios (XliqFe2O3/XliqFeO) (Cottrell and Kelley 2011) and the olivine-liquid Fe-Mg exchange coefficient, KD(Fe-Mg)Ol-liq (or KD) (Matzen et al. 2011) indicate that re-evaluations of Tp are needed. New tests and calibrations are thus presented for oxygen fugacity (fO2), XliqFe2O3/XliqFeO, potential temperature (Tp), melt fraction (F), KD, and peridotite enthalpies of fusion (ΔHfus) and heat capacities (CP). The new models for XliqFe2O3/XliqFeO and fO2 reduce error by 25-30%, and residual error for all models appears random; this last observation supports the common, but mostly untested, assumption that equilibrium is the most probable of states obtained by experiment, and perhaps in nature as well. Aggregate 1σ error on Tp is as high as ∼±77 °C, and estimates of F, and mantle olivine composition, are the greatest sources of error. Pressure and ΔHfus account for smaller, but systematic uncertainties (a constant ΔHfus can under-predict Texcess = Tpplume - Tpambient; assumptions of 1 atm can under-predict Tp). However, assumptions about whether parental magmas are incremental, accumulated, or isobaric batch melts induces no additional systematic error. The new models show that maximum Tp estimates on the oldest samples from Earth, Mars, Moon, and Vesta, decrease as planet size decreases. This may be expected since Tp should scale with accretion energy and reflect the Clausius-Clapeyron slope for the melting of silicates and Fe-Ni alloys. This outcome, however, occurs only if shergottites (from Mars) are 4.3 Ga (e.g., Bouvier et al. 2009; Werner et al. 2014), and the highest MgO komatiites from Earth's Archean era (27-30% MgO; Green et al. 1975) are used to estimate Tp. With these assumptions, Earth and Mars exhibit monotonic cooling, and support for Stevenson's (2003) idea that smaller planets cool at similar rates (∼90 - 135 °C/Ga), but at lower absolute temperatures. Tp estimates for Mars and Earth are also important in two other ways: Mars exhibits non-linear cooling, with rates as high as 275-550 °C/Ga in its first 0.5 Ga, and Archean volcanism on Earth was thermally bi-modal. Several hundred Archean volcanic compositions are in equilibrium with Fo92-94 olivine, and yield Tp modes at 1940 and 1720 °C, possibly representing plume and ambient mantle, respectively. These estimates compare to modern Tp values of 1560-1670 °C at Mauna Loa (plume) and 1330-1450 °C at MORB (ambient). We conclude that plate tectonics was active in some manner in the Archean, and that assertions of an Archean \"thermal catastrophe\" are exaggerated. Our new models also show that the modern Hawaiian source, when compared at the same T, has a lower fO2 compared to MORB, which would discount a Hawaiian source rich in recycled pyroxenite.

Apatite is an excellent tracer of petrogenetic processes as it can incorporate a large range of elements that are sensitive to melt evolution (LREE-MREE, Sr, Pb, Mn, halogens, Nd isotopes). Recent advances in the understanding of trace element concentrations and isotope ratios in apatite provide a novel tool to investigate magmatic petrogenesis and sediment provenance. Recent experimental work has better characterized trace element partition coefficients for apatite, which are sensitive to changes in magma composition (e.g., SiO2 and the aluminum saturation index value). The chemistry of apatites from granitoids has been suggested to reflect the composition of the host magma and yield information about petrogenetic processes that are invisible at the whole-rock scale (mixing, in situ crystal fractionation, metasomatism). Nd isotopes in apatite can now be analyzed by LA-MC-ICP-MS to constrain mantle and crustal contributions to the source(s) of the studied magma. These recent advances highlight exciting new horizons to understand igneous processes using accessory minerals. In this contribution, we use a compilation of recent data to show that apatite in the matrix and as inclusions within zircon and titanite is useful for providing insights into the nature and petrogenesis of the parental magma. Trace element modeling from in situ analyses of apatite and titanite can reliably estimate the original magma composition, using appropriate partition coefficients and careful imaging. This provides a new way to look at magmatic petrogenesis that have been overprinted by metamorphic processes. It also provides the rationale for new investigations of sedimentary provenance using detrital accessory minerals, and could provide a powerful new window into early Earth processes if applied to Archean or Hadean samples.

We present a statistical approach to data mining and quantitatively evaluating detrital age spectra for sedimentary provenance analyses and palaeogeographic reconstructions. Multidimensional scaling coupled with density-based clustering allows the objective identification of provenance end-member populations and sedimentary mixing processes for a composite crust. We compiled 58 601 detrital zircon U–Pb ages from 770 Precambrian to Lower Palaeozoic shelf sedimentary rocks from 160 publications and applied statistical provenance analysis for the Peri-Gondwanan crust north of Africa and the adjacent areas. We have filtered the dataset to reduce the age spectra to the provenance signal, and compared the signal with age patterns of potential source regions. In terms of provenance, our results reveal three distinct areas, namely the Avalonian, West African and East African–Arabian zircon provinces. Except for the Rheic Ocean separating the Avalonian Zircon Province from Gondwana, the statistical analysis provides no evidence for the existence of additional oceanic lithosphere. This implies a vast and contiguous Peri-Gondwanan shelf south of the Rheic Ocean that is supplied by two contrasting super-fan systems, reflected in the zircon provinces of West Africa and East Africa–Arabia.

Elastic geobarometry for host-inclusion systems can provide new constraints to assess the pressure and temperature conditions attained during metamorphism. Current experimental approaches and theory are developed only for crystals immersed in a hydrostatic stress field, whereas inclusions experience deviatoric stress. We have developed a method to determine the strains in quartz inclusions from Raman spectroscopy using the concept of the phonon-mode Gruneisen tensor. We used ab initio Hartree-Fock/Density Functional Theory to calculate the wavenumbers of the Raman-active modes as a function of different strain conditions. Least-squares fits of the phonon-wavenumber shifts against strains have been used to obtain the components of the mode Gruneisen tensor of quartz (γ1m and γ3m) that can be used to calculate the strains in inclusions directly from the measured Raman shifts. The concept is demonstrated with the example of a natural quartz inclusion in eclogitic garnet from Mir kimberlite and has been validated against direct X-ray diffraction measurement of the strains in the same inclusion.

The continental crust is the archive of the geological history of the Earth. Only 7% of the crust is older than 2.5 Ga, and yet significantly more crust was generated before 2.5 Ga than subsequently. Zircons offer robust records of the magmatic and crust-forming events preserved in the continental crust. They yield marked peaks of ages of crystallization and of crust formation. The latter might reflect periods of high rates of crust generation, and as such be due to magmatism associated with deep-seated mantle plumes. Alternatively the peaks are artefacts of preservation, they mark the times of supercontinent formation, and magmas generated in some tectonic settings may be preferentially preserved. There is increasing evidence that depletion of the upper mantle was in response to early planetary differentiation events. Arguments in favour of large volumes of continental crust before the end of the Archaean, and the thickness of felsic and mafic crust, therefore rely on thermal models for the progressively cooling Earth. They are consistent with recent estimates that the rates of crust generation and destruction along modern subduction zones are strikingly similar. The implication is that the present volume of continental crust was established 2-3 Ga ago.

Crystal chemical algorithms were used to estimate the chemical composition of selected mineral phases observed with the CheMin X-ray diffractometer onboard the NASA Curiosity rover in Gale crater, Mars. The sampled materials include two wind-blown soils, Rocknest and Gobabeb, six mudstones in the Yellowknife Bay formation (John Klein and Cumberland) and the Murray formation (Confidence Hills, Mojave2, and Telegraph Peak), as well as five sandstones, Windjana and the samples of the unaltered Stimson formation (Big Sky and Okoruso) and the altered Stimson formation (Greenhorn and Lubango). The major mineral phases observed with the CheMin instrument in the Gale crater include plagioclase, sanidine, P21/c and C2/c clinopyroxene, orthopyroxene, olivine, spinel, and alunite-jarosite group minerals. The plagioclase analyzed with CheMin has an overall estimated average of An40(11) with a range of An30(8) to An63(6). The soil samples, Rocknest and Gobabeb, have an average of An56(8) while the Murray, Yellowknife Bay, unaltered Stimson, and altered Stimson formations have averages of An38(2), An37(5), An45(7), and An35(6), respectively. Alkali feldspar, specifically sanidine, average composition is Or74(17) with fully disordered Al/Si. Sanidine is most abundant in the Wind-jana sample (∼26 wt% of the crystalline material) and is fully disordered with a composition of Or87(5). The P21/c clinopyroxene pigeonite observed in Gale crater has a broad compositional range {[Mg0.95(12)-1.54(17)Fe0.18(17)-1.03(9)Ca0.00-0.28(6)]Σ2Si2O6} with an overall average of Mg1.18(19)Fe0.72(7)Ca0.10(9)Si2O6. The soils have the lowest Mg and highest Fe compositions [Mg0.95(5)Fe1.02(7)Ca0.03(4)Si2O6] of all of the Gale samples. Of the remaining samples, those of the Stimson formation exhibit the highest Mg and lowest Fe [average = Mg1.45(7)Fe0.35(13)Ca0.19(6)Si2O6]. Augite, C2/c clinopyroxene, is detected in just three samples, the soil samples [average = Mg0.92(5)Ca0.72(2)Fe0.36(5)Si2O6] and Windjana (Mg1.03(7)Ca0.75(4)Fe0.21(9)Si2O6). Orthopyroxene was not detected in the soil samples and has an overall average composition of Mg0.79(6)Fe1.20(6)Ca0.01(2)Si2O6 and a range of [Mg0.69(7)-0.86(20)Fe1.14(20)-1.31(7)Ca0.00-0.04(4)]Σ2Si2O6, with Big Sky exhibiting the lowest Mg content [Mg0.69(7)Fe1.31(7)Si2O6] and Okoruso exhibiting the highest [Mg0.86(20)Fe1.14(20)Si2O6]. Appreciable olivine was observed in only three of the Gale crater samples, the soils and Windjana. Assuming no Mn or Ca, the olivine has an average composition of Mg1.19(12)Fe0.81(12)SiO4 with a range of 1.08(3) to 1.45(7) Mg apfu. The soil samples [average = Mg1.11(4)Fe0.89SiO4] are significantly less magnesian than Windjana [Mg1.35(7)Fe0.65(7)SiO4]. We assume magnetite (Fe3O4) is cation-deficient (Fe3-x∎xO4) in Gale crater samples [average = Fe2.83(5)∎0.14O4; range 2.75(5) to 2.90(5) Fe apfu], but we also report other plausible cation substitutions such as Al, Mg, and Cr that would yield equivalent unit-cell parameters. Assuming cation-deficient magnetite, the Murray formation [average = Fe2.77(2)∎0.23O4] is noticeably more cation-deficient than the other Gale samples analyzed by CheMin. Note that despite the presence of Ti-rich magnetite in martian meteorites, the unit-cell parameters of Gale magnetite do not permit significant Ti substitution. Abundant jarosite is found in only one sample, Mojave2; its estimated composition is (K0.51(12)Na0.49)(Fe2.68(7)Al0.32)(SO4)2(OH)6. In addition to providing composition and abundances of the crystalline phases, we calculate the lower limit of the abundance of X-ray amorphous material and the composition thereof for each of the samples analyzed with CheMin. Each of the CheMin samples had a significant proportion of amorphous SiO2, except Windjana that has 3.6 wt% SiO2. Excluding Windjana, the amorphous materials have an SiO2 range of 24.1 to 75.9 wt% and an average of 47.6 wt%. Windjana has the highest FeOT (total Fe content calculated as FeO) at 43.1 wt%, but most of the CheMin samples also contain appreciable Fe, with an average of 16.8 wt%. With the exception of the altered Stimson formation samples, Greenhorn and Lubango, the majority of the observed SO3 is concentrated in the amorphous component (average = 11.6 wt%). Furthermore, we provide average amorphous-component compositions for the soils and the Mount Sharp group formations, as well as the limiting element for each CheMin sample.