Platinum group element (PGE) geochemistry to understand the chemical evolution of the Earth’s mantle

Platinum group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd) are important geochemical and cosmochemical tracers. Depending on physical and chemical behaviour the PGEs are divided into two subgroups: IPGE (Ir, Os, Ru) and PPGE (Pd, Pt, Rh). Platinum group elements show strong siderophile and chalcophile affinity. Base metal sulfides control the PGE budget of the Earth’s mantle. Mantle xenoliths contain two types of sulfide populations: (1) enclosed within silicate minerals, and (2) interstitial to the silicate minerals. In terms of PGE characters the included variety shows IPGE enriched patterns — similar to the melt-depleted mantle harzburgite, whereas the interstitial variety shows PPGE enriched patterns — resembling the fractionated PGE patterns of the basalt. These PGE characters of the mantle sulfides have been interpreted to be representative of multi-stages melting process of the mantle that helped to shape the chemical evolution of the Earth.     

Rare earth element (REE) geochemistry and genetic implications of the Morta? bauxite deposit (Seydi?ehir/Konya - Southern Turkey)

The Mediterranean-type karst-bauxite deposit of Morta?, south Turkey, placed unconformably between Cenomanian and Senonian shallow marine limestones is built of massive (MB), oolithic (OB), breccia-bearing (BB) and earthy (EB) bauxite horizons, from top to bottom. The MB layer is enriched in Al and REE (except Ce) due to loss of Si, Na, K, Mg and P. REE are accumulated in the BB but depleted in the EB layers. The ferruginous OB lost LREE and gained in HREE probable due to scavenging by authigenic heavy minerals like rutile, anatase and titanite. Total REE contents in the bauxite profile display an increasing trend from bottom to top, while negative and maximum positive Ce anomalies characterize the upper and the lower parts of the profile, respectively. This unusual REE behavior is explicable by assuming mobilization of Ce(IV) either under reducing condition or chemical complexation under alkaline conditions in the top layer and scavenging of Ce by Al-Mg hydrosilicates and Ti-oxides and/or precipitation with authigenic REE minerals, especially of the bastnäsite group near the bedrock limestones. Similarity in chondrite normalized-REE patterns of the Seydi?ehir phyllites, bauxite and terra rossa samples and the presence of tridymite (?) in bauxites makes a felsic source rock most likely and reveal a close genetic relationship between the Seydi?ehir phyllites and the recent terra rossa occurrences. The REE patterns of the bauxites resemble those of the Katrangedi?i limestone despite variations in ΣREE. Field observations and geochemical data together with mass-balance calculations suggest that the Morta? deposit was derived from the Seydi?ehir phyllites and argillic phase within the Katrangedi?i limestone which in turn have Precambrian (?) felsic, probably granitic precursors.     

Leaching experiments on trace element release from the arsenic-bearing tailings of Khovu–Aksy (Tuva Republic,Russia)

The study of inactive As-bearing tailings impoundments at the Khovu-Aksy mine-site (Russia) revealed high concentrations of As in the porewater of tailings solids and in their aqueous extracts, as well as in adjacent soils. In these investigations, experimental leaching of As-containing tailings was performed in the laboratory. The three types of solutions which were used in the leach experiments to model natural waters and waters of anthropogenic origin were H₂O, HNO₃ and NH₄HCO₃, and during leaching with these solutions As concentrations were maintained at 10±2, 16±1 and ∼20 mg/l. No low-pH waters were observed at the end of the leach experiments, where pH varied between 8.3 and 9.1. These alkaline pH conditions are attributed to the effect of acid consuming carbonate mineral dissolution reactions, which are also indicated by increased concentrations of Mg and Ca. Also, the solution of certain heavy metals (Co, Ni, Fe) was negligible compared to that of As, and these metals were assumed to have been conserved in the solid phase. Analysis of the leach solutions, and modeling of the results showed that As could be removed from the surface of different particles where it had been adsorbed, and also its concentration could increase with time from the breakdown of Ca(Mg)- and Ni(Co)-arsenate phases. In the absence of an effective remediation program, As release will continue to be an environmental problem.     

An experimental study of the partitioning of a rare earth element (Gd) in the system diopside—aqueous vapour

The partitioning of Gd in the experimental system diopside-aqueous vapor as a function of temperature, pressure, composition of the phases, time, grain size, solid-liquid ratio and Gd concentration has been investigated. A radioactive tracer measurement was used to determine Gd concentration in the separated phases. Diposides were reacted with aqueous vapor containing tracer Gd and reversibility was tested by reacting Gd-doped diopsides with pure aqueous vapor. Equilibration of Gd between the bulk of the diopside and the liquid was found to be limited by the slow rate of Gd diffusion in diopside, maximum value of D = 2 × 10^?15cm²sec^?1 at 800°C and 1 kb. Depending on whether the diopside was previously synthesized or synthesized from an oxide mix during the experiment, Gd concentrations were zoned in the crystal such that higher concentrations existed at the edges or center, respectively. Equilibrium is difficult to achieve in these experiments, but at the optimum experimental conditions for equilibration, the Gd diopside-aqueous vapor distribution coefficient is 20 ± 6 (800°C, 1 kb) in approximate agreement with previous results of 55 ± 23. Changing the composition of the aqueous vapor indicated that possible mechanisms for Gd substitution included coupling of Gd³⁺ with H⁺ or Na⁺ replacing 2Ca²⁺, or substitution of 2Gd³⁺ for 3Ca²⁺ with formation of a cation vacancy.     

Clinopyroxene/liquid trace element partitioning in natural trachyte–trachyphonolite systems: insights from Campi Flegrei (southern Italy)

Trace element partition coefficients between clinopyroxenes and associated glassy matrix (^Cpx/L D) have been determined for 13 REE, HFSE^4+,5+, U, Th, Sr, Pb, Sc and V from combined LA-ICP-MS/EMP analyses in selected trachytes and trachyphonolites from Campi Flegrei. Composition of clinopyroxene and glass is pretty homogeneous in the trachyphonolites, pointing to an overall attainment of the equilibrium conditions. In trachytes, conversely, phases show some compositional heterogeneity (due to the presence of clinopyroxene xenocrysts) that requested a more careful petrographic and geochemical inspection of the samples to assess the equilibrium clinopyroxene composition. In the trachyte clinopyroxenes, REE are compatible from Nd to Lu (^Cpx/L D up to 2.9), like Y, Ti, Sc and V. The ^Cpx/L D for Eu is lower than those of the adjacent REE, highlighting Eu²⁺ contribution. High D values are also shown by U, Th, Pb, Zr, Hf, Nb and Ta relatively to basaltic and andesitic systems, whereas the D _Sr is roughly similar to that found for less evolved magmas. Trachyphonolites are characterized by an overall decrease of the ^Cpx/L D for highly-charged cations (with the exception of V), and by a slight increase of D _Sr. REE are still compatible from Nd to Lu (^Cpx/L D up to 2.1), like Ti, Y, Sc and V. This variation is also predicted for REE and Y by models based on the elastic strain theory, being consistent with the slightly lower polymerization degree estimated for the trachyphonolites. However, the observed ^Cpx/L D _(REE,Y) are matched by the modelled ones only considering very low T (≤825°C), which are believed unlikely. This mismatch cannot be attributed to effects induced by the water-rich composition of the trachyte–trachyphonolite suite, since they would lower the observed ^Cpx/L D _(REE,Y). Moreover, the anomalous inflections of measured ^Cpx/L D for HREE suggests some crystal-chemical control, such as the entrance of these elements in a site distinct from M2. It is concluded that the large ^Cpx/L D determined for trachytes and trachyphonolites are likely induced by hitherto unconstrained changes of the Z³⁺ activities related to the composition of melt and/or solid. All these considerations strongly highlight the importance of a direct characterization of trace element partitioning in natural samples from magmatic systems poorly characterized by experimental studies. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

REE and HFS element behaviour in the alteration facies of the Erenler Dağı Volcanics (Konya,Turkey) and kaolinite occurrence

Mainly high-K, calc-alkaline, Late Miocene to Pliocene volcanic rocks cropped out of the Konya area in Central Anatolia, Turkey. The volcanic rocks are predominantly andesitic to dacitic in composition and rarely basalt, basaltic andesite, basaltic trachyandesite and pyroclastics. Kaolinite, illite, Ca-montmorillonite, alunite, jarosite, minamiite and silica polymorphs were formed by widespread and intense hydrothermal alteration in or around the volcanic products. To investigate the effects of hydrothermal alteration on the chemistry of volcanic rocks, the whole rock chemical composition (major and trace elements, including rare-earth elements (REE) was analysed. The results of the study demonstrate notable differences in the REE behaviour in the different sample groups. REE trends of fresh parent rocks to weakly-, moderately-altered, kaolinitic and alunitic rocks are characterised by strong LREE enrichment ((La/Lu)_cn = 14.57, 11,8 to 15.20, 4.54 to 13.30, 12.5 to 24.2 and 34.6 to 47.26, respectively). Most of the samples have pronounced negative and/or weakly-negative Eu anomalies ranging from 0.75 to 0.98 while three samples have weakly-positive Eu anomalies. LRE element contents are higher than those of HREE in the samples. The LRE elements were strongly enriched in the kaolinitic and alunitic alteration; in weakly- and moderately-altered rocks. LREE are nearly immobile whereas HRE elements show different behaviour in different rock groups. The HFS and TRT elements are slightly mobilised in weakly-altered rocks, but enriched in other alteration types. Elements commonly assumed to be immobile (e.g. Y, Zr, Nb, Hf, TiO₂, Al₂O₃, REE) show variation in mass calculation. LIL elements showed enrichment over LREE and MREE, and similar behaviour, in contrast with HFSE. A clear increment of trans-transition elements (TRTE) was found mainly in alunitic and partly in kaolinitic samples.     

Thermodynamics of element partitioning: (1) Systematics of transition metals in crystalline and molten silicates and (2) Defect chemistry and “the Henry's law problem”

The distribution of Mg, Mn, Fe, Co and Ni among olivine, orthopyroxene, calcic clinopyroxene and liquid can be described by exchange reactions of the form: M (phase A) + Mg (phase B) = M (phase B) + Mg (phase A). The thermochemical data predict the observed partitioning within the limits of error of both sets of data when assumptions of ideal solid solution are used, except for Mn-Mg exchange. Because ΔS and ΔV for these exchange reactions are generally small, K_D varies relatively little with temperature and pressure, although individual ion distribution coefficients (D values) are more sensitive to these variables and to changing liquid composition.Trace elements present at the ppm level can enter crystals in normal lattice sites, can participate in point defect equilibria and can enter various defect sites present metastably in the crystal as a result of its P,T history. Metastable defect equilibria, in which the number of sites (grain boundaries, surfaces, intergrowths, etc.) is fixed, can lead to enhanced trace element solubility in the crystal at very low concentrations and thus to apparent deviations from Henry's law.     

Meshless numerical modeling of brittle–viscous deformation: first results on boudinage and hydrofracturing using a coupling of discrete element method (DEM) and smoothed particle hydrodynamics (SPH)

We have developed a new approach for the numerical modeling of deformation processes combining brittle fracture and viscous flow. The new approach is based on the combination of two meshless particle-based methods: the discrete element method (DEM) for the brittle part of the model and smooth particle hydrodynamics (SPH) for the viscous part. Both methods are well established in their respective application domains. The two methods are coupled at the particle scale, with two different coupling mechanisms explored: one is where DEM particles act as virtual SPH particles and one where SPH particles are treated like DEM particles when interacting with other DEM particles. The suitability of the combined approach is demonstrated by applying it to two geological processes, boudinage, and hydrofracturing, which involve the coupled deformation of a brittle solid and a viscous fluid. Initial results for those applications show that the new approach has strong potential for the numerical modeling of coupled brittle–viscous deformation processes.     

Environmental mineralogy – Understanding element behavior in ecosystems

Environmental Mineralogy has developed over the past decade in response to the recognition that minerals are linked in many important ways with the global ecosystem. Minerals are the main repositories of the chemical elements in Earth's crust and thus are the main sources of elements needed for the development of civilization, contaminant and pollutant elements that impact global and local ecosystems, and elements that are essential plant nutrients. These elements are released from minerals through natural processes, such as chemical weathering, and anthropogenic activities, such as mining and energy production, agriculture and industrial activities, and careless waste disposal. Minerals also play key roles in the biogeochemical cycling of the elements, sequestering elements and releasing them as the primary minerals in crustal rocks undergo various structural and compositional transformations in response to physical, chemical, and biological processes that produce secondary minerals and soils. These processes have resulted in the release of toxic elements such as arsenic in groundwater aquifers, which is having a major impact on the health of millions of people in South and Southeast Asia. The interfaces between mineral surfaces and aqueous solutions are the locations of most chemical reactions that control the composition of the natural environment, including the composition of natural waters. The nuclear fuel cycle, from uranium mining to the disposition of high-level nuclear waste, is also intimately related to minerals. A fundamental understanding of these processes requires molecular-scale information about minerals, their bulk structures and properties such as solubility, their surfaces, and their interactions with aqueous solutions, atmospheric and soil gases, natural organic matter, and biological organisms. Gaining this understanding is further complicated by the presence of natural, incidental, and manufactured nanoparticles in the environment, which are becoming increasingly important due to the rapidly developing field of nanotechnology. As a result of this complexity, Environmental Mineralogy requires the use of the most modern molecular-scale analytical and theoretical methods and overlaps substantially with closely related fields such as Environmental Sciences, low-temperature Geochemistry, and Geomicrobiology. This paper provides brief overviews of the above topics and discusses the complexity of minerals, natural vs. anthropogenic inputs of elements and pollutants into the biosphere, the role of minerals in the biogeochemical cycling of elements, natural nanoparticles, and the Environmental Mineralogy of three major potential pollutant elements (Hg, As and U).     

Oxygen isotope and trace element evidence for three-stage petrogenesis of the youngest episode (260–79 ka) of Yellowstone rhyolitic volcanism

We report the first high-precision δ¹⁸O analyses of glass, δ¹⁸O of minerals, and trace element concentrations in glass and minerals for the 260–79 ka Central Plateau Member (CPM) rhyolites of Yellowstone, a >350 km³ cumulative volume of lavas erupted inside of 630 ka Lava Creek Tuff (LCT) caldera. The glass analyses of these crystal-poor rhyolites provide direct characterization of the melt and its evolution through time. The δ¹⁸O_glass values are low and mostly homogeneous (4.5 ± 0.14 ‰) within and in between lavas that erupted in four different temporal episodes during 200 ka of CPM volcanism with a slight shift to lower δ¹⁸O in the youngest episode (Pitchstone Plateau). These values are lower than Yellowstone basalts (5.7–6 ‰), LCT (5.5 ‰), pre-, and extracaldera rhyolites (~7–8 ‰), but higher than the earliest 550–450 ka post-LCT rhyolites (1–2 ‰). The glass δ¹⁸O value is coupled with new clinopyroxene analyses and previously reported zircon analyses to calculate oxygen isotope equilibration temperatures. Clinopyroxene records >900 °C near-liquidus temperatures, while zircon records temperatures <850 °C similar to zircon saturation temperature estimates. Trace element concentrations in the same glass analyzed for oxygen isotopes show evidence for temporal decreases in Ti, Sr, Ba, and Eu—related to Fe–Ti oxide and sanidine (±quartz) crystallization control, while other trace elements remain similar or are enriched through time. The slight temporal increase in glass Zr concentrations may reflect similar or higher temperature magmas (via zircon saturation) through time, while previosuly reported temperature decreases (e.g., Ti-in-quartz) might reflect changing Ti concentrations with progressive melt evolution. Multiple analyses of glass across single samples and in profiles across lava flow surfaces document trace element heterogeneity with compatible behavior of all analyzed elements except Rb, Nb, and U. These new data provide evidence for a three-stage geochemical evolution of these most recent Yellowstone rhyolites: (1) repeated batch melting events at the base of a homogenized low-δ¹⁸O intracaldera fill resulting in liquidus rhyolite melt and a refractory residue that sequesters feldspar-compatible elements over time. This melting may be triggered by conductive "hot plate" heating by basaltic magma intruding beneath the Yellowstone caldera resulting in contact rhyolitic melt that crystallizes early clinopyroxene and/or sanidine at high temperature. (2) Heterogeneity within individual samples and across flows reflects crystallization of these melts during preeruptive storage of magma at at lower, zircon-saturated temperatures. Compatible behavior and variations of most trace elements within individual lava flows are the result of sanidine, quartz, Fe–Ti oxide, zircon, and chevkinite crystallization at this stage. (3) Internal mixing immediately prior to and/or during eruption disrupts, these compositional gradients in each parental magma body that are preserved as melt domains distributed throughout the lava flows. These results based on the most recent and best-preserved volcanic products from the Yellowstone volcanic system provide new insight into the multiple stages required to generate highly fractionated hot spot and rift-related rhyolites. Our proposed model differs from previous interpretations that extreme Sr and Ba depletion result from long-term crystallization of a single magma body—instead we suggest that punctuated batch melting events generated a sanidine-rich refractory residue and a melt source region progressively depleted in Sr and Ba.     

(八) 河床演变(一)

沿长江顺流而下,可以看到千山万谷,汹涌澎湃的三峡,也可以看到九曲回肠的荆江和潮平岸阔的江苏江段。在宜昌南津关,“山随平野尽,江入大荒流”(李白《渡荆门送别诗》)。长江就在这里由山区进入平原。一般说来,天然河流都可象长江一样,分为山区和平原两段。山区河流是水流改造山谷的产物。地壳运动,增加了河床演变的复杂性。山区河流具有下列特点:(1)河床纵比降大;(2)水流湍急紊乱;(3)山谷沿程宽窄不一,河道在平面上具有藕节状外形;     

(2)PALEOBOTANY (3)PALEOZOOLOGY

971349 Che;19 Jie(China Universityseienees,Beijing)The MammaljanShowjng ClimatieF盆uetuat应on—ExamPle of the Early Pleistoceneof Ge。FaunaS AS anMam-malian Faunas from Zhoukoudian,Beijing,China(ESI矛,ISSN 1 005一2321,CN 11一3370/P,4(2),1997,p·275一279,1 graph,1 table,10 ref) By analyses of the four local marnmalianfaunas from Zhoukoudian,Beijing,the EarlyPleistoeene elimatie and eeologieal environ-CN 11一1 905/Q1 53,1 graph,1735(2).1997,P.145一mental ehangespaper.One of1 .90M…     

Major element geochemistry of recent sediments from the Fláje basin (Krus̆né hory–Erzgebirge,Czech Republic)

The weathering products of the granitic rocks (which are poor in base cations) and their sediments in the Fláje basin, in an environment that is strongly influenced by SO₂ and NO_x emissions have been studied. High deposition of SO₂ and consequent acidification of the environment causes further depletion of base cations, mobilisation of Al and modification of the weathering reactions resulting in changes of the geochemical features of recent sediments. Depletion of the bottom sediments of the Fláje basin in base cations and Al and their enrichment in Si, compared to the fresh stream sediments and eluvium, suggests a mineralogical modification of the weathering product due to prolonged contact with basin water. Depletion of the non-silicate phase of the sediment in base cations which are replaced with Al on the other hand appears to be more effective in eluvium and those sediments which are exposed directly to the effect of acid deposition, i.e. which are not below water level for the major part of the year. The water of the basin appears to be the main factor influencing the composition of the recent sediments of the basin in the acidified catchment.     

(九)河床演变(二)

自然河流或者处于单向演变状态,或者处于准平衡状态。这是按平均概念而言。实际河床演变就是围绕这种均衡状态或正或负地交替进行。河流一旦受到外力干扰,均衡状态被破坏之后,河床演变过程也将随之改变。有的干扰、改变甚至破坏会很强烈。这种演变开始时都比较急剧,然后逐渐衰减,最终达到新的均衡状态。干扰河床演变均衡状态的途径有二:(1)改变河道的来水来沙条件。如河段以上的水土保持工程、拦沙工程、水库枢纽工程、分流堵汊工程和引水工程等的作用。它们增减水量、沙量,改变水流过程和输沙过程以及水沙搭配关系等。(2)改变河段河床形     

Trace element modelling of the origin and evolution of the Oyaca‐Boyalik volcanic rocks (NE of Haymana,Ankara, Turkey)

Lower Miocene Boyalik volcanic rocks, situated approximately 80 km south of Ankara, exhibit both alkaline and calc‐alkaline characteristics. Alkaline products are trachybasaltic and trachyandesitic, whereas calc‐alkaline products are dacitic. The phenocrysts in the dacites consist primarily of plagioclase and hornblende, with lesser amounts of biotite. The groundmass contains plagioclase and quartz microcrysts. Trachyandesites are mainly composed of plagioclase and biotite phenocrysts with a groundmass of alkali feldspar microlites and minor clinopyroxene microcrysts. Trachybasalts are mainly composed of olivine and plagioclase phenocrysts, with minor clinopyroxene phenocrysts associated with alkali feldspar, plagioclase and clinopyroxene microlites and microcrysts in the groundmass. Oxides are common accessory phases in all products. Boyalik volcanic rocks have essentially homogeneous incompatible trace element patterns with variable Nb and Th anomalies, enrichment in Rb, Ba, K, La, Ce and Nd, and positive Sr anomalies. Some trace element ratios (e.g. Ba/Ta, Ba/Nb, Th/U and Ce/Pb) are variable among the series. For instance, dacites and trachyandesites have higher Ba/Ta (724–2509), Ba/Nb (45–173) and Th/U (3.5–8.7) and lower Ce/Pb (7.1–3.9) values than the trachybasalts. Trace element data indicate that the series are chemically distinct but probably were derived from a common lithospheric mantle source via variable degrees of partial melting. The magmas then underwent a process of evolution involving assimilation and fractional crystallization (AFC) during ascent to the surface. Although trachyandesites and dacites were generated from a lithospheric mantle source via ～1% and ～1.5% to ～5% degrees of partial melting, respectively, trachybasalts were derived from the same source via higher degrees of partial melting (～20%) with neglegible crustal contamination. Boyalik volcanism is linked to an intracontinental transpressional setting. However, the overall geochemical features are consistent with derivation from a mantle source that records earlier Eocene subduction between the Sakarya continental fragment and the K?r?ehir block during time.     

Seawater-like trace element signatures (REE + Y) of Eoarchaean chemical sedimentary rocks from southern West Greenland,and their corruption during high-grade metamorphism

Modern chemical sediments display a distinctive rare earth element + yttrium (REE + Y) pattern involving depleted LREE, positive La/La*_SN, Eu/Eu*_SN, and Y_SN anomalies (SN = shale normalised) that is related to precipitation from circumneutral to high pH waters with solution complexation of the REEs dominated by carbonate ions. This is often interpreted as reflecting precipitation from surface waters (usually marine). The oldest broadly accepted chemical sediments are c. 3,700 Ma amphibolite facies banded iron-formation (BIF) units in the Isua supracrustal belt, Greenland. Isua BIFs, including the BIF international reference material IF-G are generally considered to be seawater precipitates, and display these REE + Y patterns (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004). Greenland Eoarchaean BIF metamorphosed up to granulite facies from several localities in the vicinity of Akilia (island), display REE + Y patterns identical to Isua BIF, consistent with an origin by chemical sedimentation from seawater and a paucity of clastic input. Furthermore, the much-debated magnetite-bearing siliceous unit of “earliest life” rocks (sample G91/26) from Akilia has the same REE + Y pattern. This suggests that sample G91/26 is also a chemical sediment, contrary to previous assertions (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004), and including suggestions that the Akilia unit containing G91/26 consists entirely of silica-penetrated, metasomatised, mafic rock (Fedo and Whitehouse 2002a). Integration of our trace element data with those of Bolhar et al. (Earth Planet Sci Lett 222:43–60, 2004) demonstrates that Eoarchaean siliceous rocks in Greenland, with ages from 3.6 to 3.85 Ga, have diverse trace element signatures. There are now geographically-dispersed, widespread examples with Isua BIF-like REE + Y signatures, that are interpreted as chemically unaltered, albeit metamorphosed, chemical sediments. Other samples retain remnants of LREE depletion but are beginning to lose the distinct La, Eu and Y positive anomalies and are interpreted as metasomatised chemical sediments. Finally there are some siliceous samples with completely different trace element patterns that are interpreted as rocks of non-sedimentary origin, and include metasomatised mafic rocks. The positive La/La*_SN, Eu/Eu*_SN and Y_SN anomalies found in Isua BIFs and other Eoarchaean Greenland samples, such as G91/26 from Akilia, suggests that the processes of carbonate ion complexation controlling the REE − Y patterns were already established in the hydrosphere at the start of the sedimentary record 3,600–3,850 Ma ago. This is in accord with the presence of Eoarchaean siderite-bearing marbles of sedimentary origin, and suggests that CO₂ may have been a significant greenhouse gas at that time.     

Trace element and Pb–B–Li isotope systematics of olivine-hosted melt inclusions: insights into source metasomatism beneath Stromboli (southern Italy)

We studied the elemental and isotopic (Pb, B and Li isotopes) composition of melt inclusions hosted in highly forsteritic (Fo_83–91) olivines that were collected from San Bartolo lava and pumice (ST79p, ST82p and ST531p) samples erupted by Stromboli in historical times. The studied melt inclusions have primitive calcalkaline to shoshonitic basaltic compositions. They cover a compositional range far wider than that exhibited by the whole-rocks and differ in key trace element ratios. San Bartolo melt inclusions are characterized by lower incompatible trace element abundances, higher ratios between fluid-mobile (B, Pb, U and LILE) and less fluid-mobile (REE, Th, HFSE) elements and lower La/Yb ratios relative to the pumice-hosted melt inclusions and pumiceous melts erupted during paroxysmal events. Trace elements, along with different Pb, B and Li isotopic signatures, attest to source heterogeneity on the small scale and provide new insights into subducted components beneath Stromboli. Results of a mixing model suggest that metasomatism of the mantle source of pumice-hosted melt inclusions was driven by solute-rich high-pressure fluids (<20%) expelled from the deep portion of the slab. Heterogeneous Pb isotopic composition together with light δ¹¹B (−8.6 to −13.7‰) and δ⁷Li (+2.3 to −1.7‰) indicates that high-pressure liquids were released in variable proportions from highly dehydrated metabasalts and metasediments. On the other hand, the elemental and isotopic (δ¹¹B ~ −1.9 to −5.9‰) composition of San Bartolo melt inclusions is better explained by the addition of a prevalent aqueous component (~2 to 4%) escaped at shallower depths from sediments and altered basaltic crust in almost equivalent proportions, with a smaller contribution by high-pressure fluids. Owing to the high-angle dip of the subducted cold Ionian slab, aqueous fluids and high-pressure fluids would rise through the mantle wedge and locally superimpose on each other, thus giving origin to variously metasomatized mantle domains.     

Volatile (sulphur and chlorine), major,and trace element geochemistry of mafic to intermediate tephras from the Chilean Southern Volcanic Zone (33–43°S)

Here we present the first systematic investigation of volatile geochemistry along the Southern Volcanic Zone (SVZ) of Chile. Holocene olivine-hosted melt inclusions in the most mafic tephras sampled from 16 volcanoes along the volcanic front of the SVZ between 33°S and 43°S were analysed for pre-eruptive sulphur, chlorine, and major element contents. These results are combined with trace element compositions of the host whole rocks. The highest fractionation-corrected gas contents occur in the least-degassed melt inclusions from small monogenetic cones of Los Hornitos, Cabeza de Vaca, and Apagado from both the transitional and the southern-central SVZ, reaching ~3,000 μg/g S and 1,400 μg/g Cl, while the lowest abundances of ~1,100 μg/g S and ~600 μg/g Cl were found in the central SVZ at Volcán Lonquimay, Volcán Llaima, and Volcán Villarrica. Chlorine co-varies with trace element indicators for the degree of melting and/or source enrichment, such that the lowest Cl contents are found in high-degree melts from the most depleted mantle sources. The size of the volcanic edifices correlates inversely with Cl abundances in the melt. This could reflect more extensive degassing during ascent through the complex magma plumbing systems beneath the stratovolcanoes or greater dilution during larger degrees of melting of more depleted sources, or a combination of these factors. Compared to other subduction zones, the SVZ melt inclusions exhibit Cl and S abundances in the same range as most of those from the Central American and those from the Marianas arcs.