Thermodynamic behaviour of the high-temperature P\bar 1{\text{-}}I\bar 1 phase transition along the CaAl2Si2O8–SrAl2Si2O8 join

In situ high-temperature synchrotron radiation powder diffraction patterns were taken from room temperature to T = 740°C from synthetic feldspars along the join CaAl₂Si₂O₈–SrAl₂Si₂O₈ (An–SrF). Three samples of composition An₉₅SrF₅, An₉₀SrF₁₀ and An₈₅SrF₁₅ were investigated, and the evolution of cell parameters with T was determined by Rietveld analysis of powder X-ray diffraction patterns. The high-temperature $P\bar 1{\text{-}}I\bar 1$ phase transition, previously observed with T _c = 241°C in anorthite, was found in An₉₅SrF₅, An₉₀SrF₁₀ and An₈₅SrF₁₅ feldspars at T _c = 233(5)°, 195(2)° and 174(2)°C respectively. The transition was revealed by the disappearance of critical reflections and variations in the rate of change of cell parameters with temperature. A significant, although small (between 0.0025 and 0.0012 at room temperature), spontaneous strain could be measured, allowing the thermodynamic behaviour of the transition to be modelled. A second-order trend for An₉₀SrF₁₀ and An₈₅SrF₁₅ [β = 0.504(7) and 0.505(7) respectively] or nearly second-order for An₉₅SrF₅[β = 0.458(4)] was observed in contrast with tricritical behaviour of end member anorthite. An extrapolation of the T _c versus composition to room temperature indicates that the critical composition for the $P\bar 1$ phase is An₆₀SrF₄₀.     

The high-temperature P2/c<Subscript>1</Subscript>–C2/c phase transition in Fe-free Ca-rich P2<Subscript>1</Subscript>/c clinopyroxenes

An in situ, high-temperature, powder diffraction investigation was performed for iron-free clinopyroxenes with compositions Ca_0.40Mg_1.60Si₂O₆, Ca_0.52Mg_1.46Al_0.05Si_1.98O₆, Ca_0.59Mg_1.41Si₂O₆ and Ca_0.70Mg_1.30Si₂O₆, up to 850 °C using synchrotron radiation (ESRF, Grenoble). In samples with compositions Ca_0.52Mg_1.46Al_0.05Si_1.98O₆ and Ca_0.59Mg_1.41Si₂O₆, evidence of for the P2₁/c-C2/c displacive phase transition was seen in changes in lattice parameters at T 550 and 300 °C respectively. Landau modelling of the phase transition behaviour for the sample with composition Ca_0.52Mg_1.46Al_0.05Si_1.98O₆ shows a tricritical behaviour [T _c =547(16)]. Comparison with the transition behaviour in other samples with lower Ca contents along the join diopside–enstatite indicates that a decrease in T _{c ,} and a switch from first-order to tricritical behavior occurs with increasing Ca content. The change in the transition behaviour was related to an interaction with the antiphase domains at the nanoscale.     

Analysis of the Marmara flood in Turkey, 7–10 September 2009: an assessment from hydrometeorological perspective

Turkey often suffers from flood-related damages and causalities as a result of intense and prolonged storms that are usually convective or cyclonic in origin. The impact is more distinctive in Aegean and Mediterranean coasts of the country where quantity and distribution of rainfall is influenced by Mediterranean cyclones, especially in late autumn and early winter. The floods sometimes became very hazardous when combined with urbanization effects, especially in the densely populated coastal communities and major cities. Severe weather was marked in the early parts of September 2009 that produced record-setting rainfall amounts across the Marmara region of Turkey and led a series of flash floods which affected ?stanbul and Tekirda? provinces especially. The overall flooding was the result of successive and persistent intense rainfall episodes over a 3-day period which produced more than 250-mm rainfall over portions of the region. The floods resulted in death of 32 people and caused extensive environmental and infrastructural damage in the region. This study provides in-depth analysis of hydrometeorological conditions that led to the occurrence of flash floods in Marmara region during 7–10 September 2009 period and also discusses non-meteorological factors that exacerbated the flooding conditions. Main meteorological settings that led to intense storms were presence of cold air in the upper atmosphere, a slow-moving quasi-stationary trough, and continuous resupply of moisture to the surface low from the warm Aegean Sea. Radar images showed the development of clusters of convective cells that remained quasi-stationary over portions of the region. The 24-h rainfall amounts varied between 100 and 253 mm in most parts of the region during the flooding period with diverse spatial patterns. The southern locations received the highest amount of the rainfall as compared to stations located in northern slopes of the region. Typical effects of orography that enhance rainfall in the coastal areas, however, were not observed during the Marmara flood. Some features of the synoptic pattern observed prior and during the flooding period, supported the back door cold front concept. This is characterized with easterly to northeasterly surface flows forced by an anticyclone, advection of cold continental air over the warm Black Sea which provided anomalous moisture to trigger cyclogenesis over the Marmara region, and falling of core of the intense rainfall over the Marmara Sea. The study concluded that although the meteorological settings were favorable for the convective rainfalls, urbanization factors, such as land use changes and occupation of flood plains, played major role in aggravating the worst flood observed in the region in recent decades.     

The Microarea Composition of Garnet and Biotite from the Ji‘an Group in Tonghua District and Its Significance as an Indicator of Metamorphic P—T—t Path

The garnet(Grt)and biotite(Bt) from gneisses of the Ji‘an Group are characterized by diffusion zoning at the rim,but equilibrium composition of metamorphic peak is usually remained in extensive interior area.Garnet with growth zoning is also found in the kyanite zone.In the light of microarea compositional variation of Grt and Bt,the temperature and pressure at the progressive,peak and post-peak metamorphic stages are determined by correctly using Grt Bt thermometer and GASP barometer.On this basis,a counterclockwise P-T-t path can be constructed,which reflects the closing process of an ensialic rift belt in this region during the Early Proterozoic.     

The Cu-Mo Mineralization of the Late Jurassic Porphyry in the Northern Great Xing’an Range: Constraints from Zircon U-Pb Ages of the Ore-Causative Granites

The Great Xing’an Range(GXAR)is one of the most important metallogenic belts in China.Previous study has shown that porphyry Cu-Mo deposit distributed in the northern Great Xing’an Range formed mainly in two stages:(1)Early Ordovician,such as Duobaoshan and Tongshan deposits(Liu et al.,2017);2)Triassic-Early Jurassic,including Wunugetushan,Taipingchuan and Badaguan deposits(Tang et al.,2016).In recent years,two potential porphyry Cu-Mo deposits,Huoluotai and Xiaokele,were discovered in the Erguna Block,northern GXAR(Figs.1a–b).However,the ore formation ages and regional metallogenic regularity are ambiguous due to the lack of isotopic ages.Two zircon U-Pb ages from the ore-causative granites were reported in this paper,with the aims to constrain the metallogenic ages and provide evidence for study of the regional metallogenic regularity and ore prospect prediction.     

Spatial distribution and contamination assessment of heavy metals in urban topsoil from inside the Xi’an second ringroad, NW China

The paper reports the spatial distribution and contamination level of heavy metals (Co, Cr, Cu, Mn, Ni, Pb, Zn and V) in urban topsoil from the interior area of the second ringroad of Xi’an city, China, based on X-ray fluorescence spectroscopy measurements. Geostatistical analysis shows that Co, Cu, and Pb have similar spatial distribution patterns. Heavy traffic density mainly contributed to the high concentrations of Co, Cu and Pb. The spatial distribution of Cr coincides with the industrial activity, whereas the spatial distribution of Zn differs from other heavy metals. The high concentrations of Zn coincide with heavy traffic and high population density. For Mn, Ni and V, natural factors are important in controlling their distribution. The calculated geoaccumulation indices indicate that urban topsoil inside the Xi’an second ringroad was uncontaminated by Cr, V, Mn and Ni, while Pb, Cu, Co and Zn are classified as uncontaminated to moderately contaminated with means of 0.64, 0.46, 0.26 and 0.21, respectively. The Nemero synthesis pollution index of these heavy metals revealed that the topsoil inside Xi’an second ringroad has been heavily contaminated due to anthropogenic activity.     

The role of tectonic shear strain on the illitization mechanism of mixed-layers illite–smectite. A case study from a fault zone in the Northern Apennines,Italy

The influence of tectonic strain on the diagenetic degree and illitization process of mixed-layers illite–smectite at shallow crustal conditions was studied. For this purpose, the modal composition of clay fraction and illite FWHM parameters of argillites deformed by a regional-scale fault zone were studied in detail by XRD, chemical analyses and by SEM observations. Analyses were performed on deformed samples of the fault rock and compared with the non-deformed rocks off the fault zone. In addition, this paper reports a detailed comparative analysis of deformed (shear surfaces and cleavage domains) and non-deformed domains (lithon cores) of a scaly fabric in the fault rock. A systematic increase in illite concentration, a decrease of Kübler index and FWHM₍₀₀₂₎ values, and an enrichment of K⁺ ions were observed in cleavage domains with respect to the non-deformed sediments off the fault zone and the lithon cores within the fault rock. Migration of K⁺-rich fluids along scaly cleavage domains causes progressive conversion of smectite-rich I–S to illite-rich I–S and thickening of illite crystallites along the c-direction. Changes in mineralogical and crystallographic parameters, therefore, seem to be strongly controlled by shear plane development in highly sheared rocks.     

Inferred phase relations in part of the system Au–Ag–Te: an integrated analytical study of gold ore from the Golden Mile, Kalgoorlie, Australia

Summary Integrated X-ray powder diffraction, scanning electron microscopy, electron probe, and transmission electron microscopy studies have identified the rare contact assemblage calaverite–sylvanite–hessite in a sample of gold ore from the Golden Mile deposit, Kalgoorlie, Australia. The presence of coexisting calaverite–hessite at Kalgoorlie is a non-equilibrium assemblage whereby the stable hessite-bearing assemblage is hessite–sylvanite, which formed from the breakdown of the -phase or -phase below 120°C, stützite+-phase, or sylvanite+stützite+-phase, as predicted by Cabri (1965).     

The 6-methyl branched tetraethers significantly affect the performance of the methylation index (MBT′) in soils from an altitudinal transect at Mount Shennongjia

The methylation index (MBT or MBT′) of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils along altitudinal transects of some mountains, e.g. Mount (Mt.) Shennongjia and Mt. Gongga, exhibited no correlation with altitude or mean annual air temperature (MAT) alone. However, a significant correlation between MBT′, cyclization ratio (CBT) of brGDGTs and MAT for each transect could still be found. To investigate the reason, we reanalyzed the brGDGTs in soils from Mt. Shennongjia using an improved liquid chromatography method and examined whether the newly described 6-methyl brGDGTs were the main cause of the large scatter in the correlation between MBT′ and MAT. In contrast to MBT′, the MBT′_5ME, based on 5-methyl brGDGTs alone, correlated significantly with MAT (R² 0.89, p < 0.001) but had no relationship with soil pH. However, MBT′_6ME, based only on 6-methyl brGDGTs, was strongly dependent on soil pH. This suggests that pH dependent 6-methyl brGDGTs introduce large scatter in the correlation between MBT′ and MAT, which is likely to mechanistically explain the poor relationship between MBT′ and MAT, yet good correlation between MBT′, pH and MAT. A series of indices derived from 6-methyl brGDGTs, including IR_IIIa′ and IR_IIa′ (isomer ratio of structures IIIa′ and IIa′, respectively), correlated with soil pH and can be used as new paleo pH indicators to supplement the classic CBT proxy. The tetramethylated brGDGTs with 0–1 cyclopentyl rings (Ia and Ib) were found to comprise unknown isomers, whose abundances also appear to increase with soil pH. A further optimized liquid chromatography method is needed to quantify these new isomers more accurately and to determine the environmental controls on them.     

The Sr,Nd, and Hf isotopic geochemistry of rocks of the gabbro–diorite–tonalite association from the Eastern Segment of the Middle Urals as an indicator of the age of the continental crust in this area

According to isotopic analysis of rocks of the Reft gabbro–diorite–tonalite complex (Middle Urals), gabbro and related diorite and dikes and vein-shaped bodies of plagiogranitoids, crosscutting gabbro, are similar to the depleted mantle substance in ε_Nd(T) = 8.6–9.7 and ε_Hf(T) = 15.9–17.9. Their model Hf ages are correlated with the time of crystallization. Here, the tonalites and quartz diorites constituting most of the Reft massif are characterized by lower values: ε_Nd(T) = 3.7–6.0, ε_Hf(T) = 11.1–12.7, and T _DM values significantly exceeding the age datings. This is evidence that Neoproterozoic crustal rocks were a source of parental magma for these rocks. The primary ⁸⁷Sr/⁸⁶Sr ratio in rocks of both groups is highly variable (0.70348–0.70495). The data obtained allow us to reach the conclusion that the Reft gabbro–diorite–tonalite complex was formed as a result of nearly synchronous processes occurring in the crust and the mantle within a limited area.     

The rapidly shrinking cryopshere in the past decade：an interpretation of cryospheric changes from IPCC WGI Sixth Assessment Report北大核心CSCD

The Working Group I report of the Sixth Assessment Report（AR6）of the Intergovernmental Panel on Climate Change（IPCC）was released in August 2021. Base on updated and expanding data, AR6 presented the improved assessment of past changes and processes of cryosphere. AR6 also predicted the future changes us⁃ ing the models in CMIP6. The components of cryosphere were rapid shrinking under climate warming in the last decade. There were decreasing trends in Arctic sea-ice area and thickness. Sea-ice loss was significant. The Greenland Ice Sheet, the Antarctic Ice Sheet and all glaciers lost more mass than in any other decade. Global warming over the last decades had led to widespread permafrost warming, active layer thickness increasing and subsea permafrost extent reducing. Snow cover extent in the Northern Hemisphere also decreased significantly. However, the variations of snow depth and snow water equivalent showed great spatial heterogeneity. The rapid shrinking of the cryosphere accelerated the global mean sea level rise. The impact of human activities on cryo⁃ sphere will become more significant in the future. The Arctic sea-ice area will decrease, and the Arctic Ocean will likely become practically sea ice-free. The Greenland Ice Sheet, the Antarctic Ice Sheet and glaciers will continue to lose mass throughout this century. Permafrost and Northern Hemisphere snow cover extent will con⁃ tinue to decrease as global climate continues to warm. In addition, there are still uncertainties in the prediction of cryosphere due to the absence of observations, the poor sensitivity of models to the components and processes of cryosphere, and the inexplicit represent of the mechanism of light-absorbing impurities. More attentions should be paid on these issues in the future. © 2022 Science Press (China). All rights reserved.     

Contribution of {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} and 13CTDIC Evaluation to the Identification of CO2 Sources in Volcanic Groundwater Systems: Influence of Hydrometeorological Conditions and Lava Flow Morphologies—Application to the Argnat Basin (Chaîne des Puys, Massif Central, France)

Mineralization of groundwater in volcanic aquifers is partly acquired through silicates weathering. This alteration depends on the dissolution of atmospheric, biogenic, or mantellic gaseous CO₂ whose contributions may depend on substratum geology, surface features, and lava flow hydrological functionings. Investigations of $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC (total dissolved inorganic carbon) on various spatiotemporal scales in the unsaturated and saturated zones of volcanic flows of the Argnat basin (French Massif Central) have been carried out to identify the carbon sources in the system. Mantellic sources are related to faults promoting CO₂ uplift from the mantle to the saturated zone. The contribution of this source is counterbalanced by infiltration of water through the unsaturated zone, accompanied by dissolution of soil CO₂ or even atmospheric CO₂ during cold periods. Monitoring and modeling of δ¹³C_TDIC in the unsaturated zone shows that both $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC are controlled by air temperature which influences soil respiration and soil-atmosphere CO₂ exchanges. The internal geometry of volcanic lava flows controls water patterns from the unsaturated zone to saturated zone and thus may explain δ¹³C heterogeneity in the saturated zone at the basin scale.     

The high PT stability of apatite and Cl partitioning between apatite and hydrous potassic phases in peridotite: an experimental study to 19 GPa with implications for the transport of P,Cl and K in the upper mantle

High PT experiments were performed in the range 2.5–19 GPa and 800–1,500°C using a synthetic peridotite doped with trace elements and OH-apatite or with Cl-apatite + phlogopite. The aim of the study was (1) to investigate the stability and phase relations of apatite and its high PT breakdown products, (2) to study the compositional evolution with P and T of phosphate and coexisting silicate phases and (3) to measure the Cl-OH partitioning between apatite and coexisting calcic amphibole, phlogopite and K-richterite. Apatite is stable in a garnet-lherzolite assemblage in the range 2.5–8.7 GPa and 800–1,100°C. The high-P breakdown product of apatite is tuite γ-Ca₃ (PO₄)₂, which is stable in the range 8–15 GPa and 1,100–1,300°C. Coexisting apatite and tuite were observed at 8 GPa/1,050°C and 8.7 GPa/1,000°C. MgO in apatite increases with P from 0.8 wt% at 2.5 GPa to 3.2 wt% at 8.7 GPa. Both apatite and tuite may contain significant Na, Sr and REE with a correlation indicating 2 Ca²⁺=Na⁺ + REE³⁺. Tuite has always higher Sr and REE and lower Fe and Mg than apatite. Phosphorus in the peridotite phases decreases in the order P_melt ≫ P_grt ≫ P_Mg2SiO4 > P_cpx > P_opx. The phosphate-saturated P₂O₅ content of garnet increases from 0.07 wt% at 2.5 GPa to 1.5 wt% at 12.8 GPa. Due to the low bulk Na content of the peridotite, ^[8]Na^[4]P^[8]M²⁺ ₋₁ ^[4]Si₋₁ only plays a minor role in controlling the phosphorus content of garnet. Instead, element correlations indicate a major contribution of ^[6]M^2+[4]P^[6]M³⁺ ₋₁ ^[4]Si₋₁. Pyroxenes contain ~200–500 ppm P and olivine has 0.14–0.23 wt% P₂O₅ in the P range 4–8.7 GPa without correlation with P, T or X_Mg. At ≥12.7 GPa, all Mg₂SiO₄ polymorphs have <200 ppm P. Coexisting olivine and wadsleyite show an equal preference for phosphorus. In case of coexisting wadsleyite and ringwoodite, the latter fractionates phosphorus. Although garnet shows by far the highest phosphorus concentrations of any peridotite silicate phase, olivine is no less important as phosphorus carrier and could store the entire bulk phosphorus budget of primitive mantle. In the Cl-apatite + phlogopite-doped peridotite, apatite contains 0.65–1.35 wt% Cl in the PT range 2.5–8.7 GPa/800–1,000°C. Apatite coexists with calcic amphibole at 2.5 GPa, phlogopite at 2.5–5 GPa and K-richterite at 7 GPa, and all silicates contain between 0.2 and 0.6 wt% Cl. No solid potassic phase is stable between 5 and 8.7 GPa. Cl strongly increases the solubility of K in hydrous fluids. This may lead to the breakdown of phlogopite and give rise to the local presence in the mantle of fluids strongly enriched in K, Cl, P and incompatible trace elements. Such fluids may get trapped as micro-inclusions in diamonds and provide bulk compositions suitable for the formation of unusual phases such as KCl or hypersilicic Cl-rich mica.     

The Late Triassic I–Type Granites from the Longmu Co–Shuanghu Suture Zone in the interior of Tibetan Plateau, China: Petrogenesis and Implication for Slab Break–Off

The Jiangaidarina granitic mass(JM) is an important part of the magmatic belt in Longmu CoShuanghu Suture Zone(LSSZ) in the central Tibetan Plateau. An integrated research involving wholerock geochemistry, zircon LA-ICP-MS U-Pb ages and Hf isotopic compositions was carried out to define the timing, genesis and tectonic setting of the JM. Zircon LA-ICP-MS U-Pb ages have been obtained ranging from 210 to 215 Ma, rather than the Early Jurassic as previously thought. Fifteen granite samples contain hornblendes and show a negative correlation between P_2 O_5 and SiO_2, indicating that the JM is an I-type granite. All the granites are enriched in LREE relative to HREE, with negative Eu anomalies(Eu/Eu*=0.56-0.81), and have similar trace elements patterns, with depletion of Ba, Nb, Sr and P. These suggest that the JM was fractionated, and this is also proved by the characteristic of negative correlations between oxide elements(TiO_2, MgO, FeOt, MnO, CaO) and SiO_2. Almost all ε_(Hf)(t) values of the granites are between-10.3 and-5.8, implying that the JM has a crustal source intimately related with the South Qiangtang Block(SQB), except for one(+10.2), showing a minor contribution from mantle source.Moreover, relatively low Na_2 O/K_2 O ratios(0.42-0.93) and high A/CNK values(0.91-1.50) reflect that the JM was predominately derived from the medium-high potassium basaltic crust, interacted with greywacke. Our new geochemical data and geochronological results imply that the Late Triassic magmas were generated in a post-collisional tectonic setting, probably caused by slab break-off of the Longmu Co-Shuanghu Tethyan Ocean(LSTO). This mechanism caused the asthenosphere upwelling, formed extension setting, offered an enormous amount of heat, and provided favorable conditions for emplacement of voluminous felsic magmas. Furthermore, the LSTO could be completely closed during the Middle Triassic, succeed by continental collision and later the slab broke off in the Late Triassic.     

The role of trace element partitioning between garnet,zircon and orthopyroxene on the interpretation of zircon U–Pb ages: an example from high-grade basement in Calabria (Southern Italy)

The recognition of the coeval growth of zircon, orthopyroxene and garnet domains formed during the same metamorphic cycle has been attempted with detailed microanalyses coupled with textural analyses. A coronitic garnet-bearing granulite from the lower crust of Calabria has been considered. U–Pb zircon data and zircon, garnet and orthopyroxene chemistries, at different textural sites, on a thin section of the considered granulite have been used to test possible equilibrium and better constrain the geological significance of the U–Pb ages related to zircon separates from other rocks of the same structural level. The garnet is very rich in REE and is characterised by a decrease in HREE from core to outer core and an increase in the margin. Zircons show core–overgrowth structures showing different chemistries, likely reflecting episodic metamorphic new growth. Zircon grains in matrix, corona around garnet and within the inner rim of garnet, are decidedly poorer in HREE up to Ho than garnet interior. Orthopyroxene in matrix and corona is homogeneously poor in REE. Thus, the outer core of garnet and the analysed zircon grains grew or equilibrated in a REE depleted system due to the former growth of garnet core. Zircon ages ranging from 357 to 333 Ma have been determined in the matrix, whereas ages 327–320 Ma and around 300 Ma have been determined, respectively, on cores and overgrowths of zircons from matrix, corona and inner rim of garnet. The calculated DREE_zrn/grt and DREE_opx/grt are largely different from the equilibrium values of literature due to strong depletion up to Ho in zircon and orthopyroxene with respect to garnet. On the other hand, the literature data show large variability. In the case study, (1) the D _zrn/grt values define positive and linear trends from Gd to Lu as many examples from literature do and the values from Er to Lu approach the experimental results at about 900 °C in the combination zircon dated from 339 to 305 Ma with garnet outer core, and (2) D _opx/grt values define positive trends reaching values considered as suggestive of equilibrium from Er to Lu only with respect to the outer core of garnet. The presence of a zircon core dated 320 Ma in the inner rim of garnet suggests that it, as well as those dated at 325–320 Ma in the other textural sites and, probably, those dated at 339–336 Ma showing depletion of HREE, grew after the garnet core, which sequestered a lot of HREE and earlier than the HREE rich margin of garnet. The quite uniform REE contents in orthopyroxene from matrix and corona and the low and uniform contents of HREE in the zircon overgrowths dated at about 300 Ma allow to think that homogenisation occurred during or after the corona formation around this age. The domains dated around 325–320 Ma would approximate the stages of decompression, whereas the metamorphic peak probably occurred earlier than 339 Ma.     

In situ X-ray diffraction measurements of the <Emphasis Type="Italic">fcc</Emphasis>–<Emphasis Type="Italic">hcp</Emphasis> phase transition boundary of an Fe–Ni alloy in an internally heated diamond anvil cell

The phase transition boundary between the face-centered cubic (fcc) structure and hexagonal close-packed (hcp) structure in an Fe–Ni alloy was determined at pressures from 25 to 107 GPa by using an internally resistive-heated diamond anvil cell (DAC), combined with in situ synchrotron X-ray diffraction measurements. The fcc–hcp phase transition boundary in Fe–9.7 wt% Ni is located at slightly lower temperatures than that in pure Fe, confirming the previous understanding that the addition of Ni expands the stability field of the fcc phase. The dP/dT slope of the boundary was determined to be 0.0426 GPa/K, which is slightly larger than that of pure Fe. The pressure interval of the two-phase region is about 6 GPa at a constant temperature, implying that the previous estimates by laser-heated DAC experiments of 10–20 GPa were overestimated. The two-phase region of fcc + hcp would be limited to a pressure of about 120 GPa even in Fe–15 wt%Ni, excluding the possibility of the existence of the fcc phase in the inner core if the simple linear extrapolation of the two-phase region is applied. The pressure and temperature dependences of the c/a axial ratio of the hcp phase in Fe–9.7 wt% Ni are generally consistent with those in pure Fe, suggesting that Ni has minor effects on the c/a ratio.     

HTP21/c–C2/c phase transition and kinetics of Fe2+–Mg order–disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

A natural Ca-poor pigeonite (Wo₆En₇₆Fs₁₈) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2₁/c, was annealed up to 1,093°C to induce a phase transition from P2₁/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P2₁/c phase) showed a displacive phase transition P2₁/c to C2/c at a transition temperature T _Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k _D versus 1/T yielded the following equation: ln k_\textD = - 3717( ±416)/T(K) + 1.290( ±0.378);    (R² = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T _c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve the disordering rate constants C ₀ K _dis⁺ for all three temperatures yielding the following Arrhenius relation: ln( C₀ K_\textdis ⁺ ) = ln K₀ - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K);    (R² = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X _Fe (in the range of X _Fe = 0.20–0.50): ln( C₀ K_\textdis ⁺ ) = (21.185 - 1.47X_\textFe ) - \frac(27267 - 4170X_\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10⁻¹ K⁻¹ year⁻¹ calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.     

Comment on: “Enriched mantle – Dupal signature in the genesis of the Jurassic Ferrar tholeiites from Prince Albert Mountains (Victoria Land, Antarctica)” by Antonini P. et al. (Contributions to Mineralogy and Petrology 136, 1–19; 1999)

18 O values, the magmas retain initial ⁸⁷Sr/⁸⁶Sr Compositions of greater than 0.709 (e.g. Hoefs et al. 1980). Consistent with this is the lack of a radiogenic Os isotope signature in these rocks (e.g. Molzahn et al. 1996) as would be expected with assimilation of continental crust. Comments here are not concerned with the AFC calculations employed to describe the variations within the suite of samples from the Prince Albert mountains studied by Antonini et al., but rather, the extrapolation of these to more primitive compositions. Antonini et al. have revived the possibility that the unusual chemical features of the least evolved low Ti continental flood basalts of the Ferrar Province reflect a crustal-level interplay between mantle-derived magmas and the continental crust. It is argued here that they have not demonstrated their claim. Received: 7 October 1999 / Accepted: 25 January 2000