Petrology and geothermometry of retrograded Hercynian charnockites and host gneisses, Agly Massif, French Pyrenees

Abstract A Hercynian charnockite occurs within high-grade gneisses in the Agly Massif, French Pyrenees. Its thermal history has been evaluated using the Fe-Mg distribution coefticient ( K _D) between garnet and biotite. These minerals have different origins but similar compositions in the charnockites and host gneisses. In the charnockite, the Bi–Ga pairs are the retrograde products of Opx alteration. This Opx reaction with feldspar can be written. Opx + PI + Fluid 1(H₂O + Al + K + Fe + Ti) = Bi + Ga + Q + Fluid 2(H₂O + Na). The garnets are relatively Ca poor (4–2.5% grossular); they are automorphic and zoned in the gneisses and poikiloblastic in the charnockites. Both types show a retrograde rim (of few hundred microns'width) across which Fe and Mn increase as Mg decreases. The biotites show a good correlation between the octahedral cations (Ti⁴⁺+ Fe²⁺) and (Mg²⁺+ Al³⁺_VI); Ti and Fe both increase, whereas Mg and Al_VI decrease. There is an inverse linear correlation between Fe²⁺ and Mg²⁺ and the Fe/Mg ratio increases as Ti increases. The relation between Ti and K ^Ga-Bi_DFe-Mg is less clear: it seems that K _D slightly decreases as Ti increases. The equilibration temperatures of Ga–Bi pairs are discussed: the charnockite Ga-Bi pairs have equilibrated between 550°C and 600°C; whereas those of the gneisses have equilibrated between 550°C and 650°C. Two main thermal steps appear: one in the gneisses between 600-650°C and a second one in both the gneisses and the charnockites between 550°C and 600°C.     

TEM observations of several spinel-garnet assemblies: toward the rheology of the transition zone

In order to better identify the mineral phase which controls the rheology of the transition zone (between 410 and 660 km depth) transmission electron microscopy observations were made on several coexisting spinel-garnet assemblies: alkremite xenolith; pyrope-rich – MgO:1.1Al₂O₃ spinel assembly deformed at 1173K, 800 MPa in a Griggs apparatus; (Mg,Fe)₃(Al,Mg,Si)₂Si₃O₁₂ majorite – (Mg,Fe)₂SiO₄ spinel assembly synthesized in a laser heated diamond anvil cell. It was found that garnet crystals systematically remain undeformed while spinel crystals are plastically deformed. These results are in accord with the assumption that the rheology of majorite is stronger than the rheology of spinel, in the conditions of the transition zone.     

Cation Leaching from the Basalt JB–1a by 2M NaCl Hydrothermal Solutions

Abstract: The basalt JB–1a was reacted with 2M NaCl solutions, and the leaching behavior of the cations Na, K, Ca, Mg, Fe, Mn, Zn and Co was monitored. The experiments were carried out using standard cold-seal pressure vessels in the temperature range from 300 to 800C under the constant pressure of 1000 bars and also in the pressure range from 500 to 1000 bars at 600°C.
The concentrations of Fe, Mn, Zn and Co in the hydrothermal solutions increased significantly with increasing temperature and with decreasing pressure. The thermodynamic analysis of the experimental results suggests that this is due to the formation of trichloro-complexes and also partly due to the temperature dependence of ion exchange between augite and aqueous chloride solution. The Na concentration in the aqueous solution decreases with increasing temperature and with decreasing pressure. On the other hand, the behavior of K, Ca and Mg is complex and their concentrations seem to be controlled by the coexisting minerals.
Judging from the experimental results, it is concluded that the transition elements are effectively leached from the basalt under higher temperatures and lower pressures. This means that higher temperature and lower pressure conditions are preferable for the production of ore-forming hydrothermal solutions.     

Chloritoid-bearing rocks associated with blueschists and eclogites, northern New Caledonia

Abstract Chloritoid-bearing metasedimentary rocks occur in close proximity to blueschists and eclogites in the Tertiary high-pressure metamorphic belt of northern New Caledonia. The typical assemblage of chloritoid-bearing rocks in the epidote zone is quartzchlorite-muscovite-garnet-chloritoid. In the omphacite zone, epidote is an additional member of the chloritoid-bearing assemblage. Paragonite is rare, plagioclase was not detected, and rutile and ilmenite are the Fe-Ti oxide phases. Chloritoid-glaucophane is not a common assemblage. Chloritoid-bearing rocks have relatively low (Ca+K+Na)/Al ratios and the chloritoids are relatively Mg-rich with Mg/ (Mg+Fe) up to about 0.4. A comparison of the mineral assemblages and mineral chemistry with experimental and computed phase equilibria suggest an upper temperature limit near 560° C in the omphacite zone and a minimum temperature limit near 450° C at 10 kbar. An empirical garnet-chlorite Fe-Mg exchange thermometer does not yield consistent results for the higher-grade rocks, suggesting T s ranging from 390 to 535° C in the omphacite zone and 420–465° C in the epidote zone. The distribution coefficient K _D = (Fe/Mg)_ctd/(Fe/Mg)_chl for chloritoid and chlorite ranges from 3.9 to 6.4, values which are lower than those (=10) from lower greenschist facies rocks, but are near those of upper greenschist facies and albite-epidote amphibolite facies.     

大洋磷酸盐化作用对富钴结壳元素富集的影响

中国首次对与大洋富钴结壳密切相关的磷酸盐化作用进行了研究。对取自西太平洋麦哲伦海山区一厚度为 10cm的富钴结壳样品 ,自顶至底以 5mm间距采取了 2 0个分层样品进行了成矿元素和稀土元素分析。结果表明 ,未被磷酸盐化的新结壳和磷酸盐化的老结壳间主要成矿元素的含量相差显著。老结壳中Fe、Mn、Si、Al、Zn、Mg、Co、Ni、Cu元素亏损 ,亏损次序为Co >Ni>Mg >Al>Mn >Si>Cu >Zn >Fe;而Ca、P、Sr、Ba、Pb元素含量增加 ,富集次序为P >Ca >Ba >Pb >Sr。研究认为 ,结壳中磷酸盐化作用的强弱制约着富钴结壳成矿元素含量的变化 ,磷酸盐化作用是造成老结壳中主要成矿元素Co、Ni等贫化流失的根本原因。研究还表明 ,磷酸盐化作用对富钴结壳的稀土元素丰度也产生一定影响 ,使老结壳的稀土总量和Ce含量高于新结壳 ,但未显著改变其稀土配分模式和分馏特征。研究证实 ,老结壳的Y正异常与磷酸盐化作用无关。磷酸盐化作用的研究为富钴结壳矿产资源的评价和综合利用提供了有用信息。     

东营凹陷古近系中深层湖盆演化中的无机元素响应

为查明无机元素分布与水深、盐度等沉积环境以及湖盆演化过程的关系,采用电感耦合等离子体发射光谱仪分析对东营凹陷郝科1科探井古近系深层微量元素含量进行了测试、分析,所涉及的研究层位是该凹陷的主要烃源岩层段（沙河街组三亚段、沙河街组四亚段、孔店组）,分析结果表明:在水体浅、蒸发作用强烈的孔店组—沙四下亚段强氧化性滨浅湖环境里,钙、锶含量和Ca/Mg、Sr/Ba、Sr/Ca参数值具低值响应,铁、铝、钡、钒含量和（Fe+Al）/(Ca+Mg)参数值具高值响应;在沙四中亚段膏岩、盐岩等普遍发育的盐湖环境中,钠、锶含量和Sr/Ba、Fe/Mn、Sr/Ca均出现高值响应,锰、钡、钒含量和V/Ni、(Fe+Al)/(Ca+Mg)出现低值响应;在还原性的沙四上亚段半咸化深湖环境中,钾、钠、铁含量和Fe/Mn值具低值响应,钙、锰含量具高值响应;在沙四中亚段膏盐与泥岩共生体系中元素分布离散性明显,呈现波动性特征;Sr/Ba、Sr/Ca在盐湖环境中出现显著的高值响应,被证实可以作为良好的水体盐度指标参数,Fe/Mn、(Fe+Al)/(Ca+Mg)随水体加深逐渐增大,是良好的水体深浅指标参数。元素分布受沉积环境、岩性特征等多种地质因素的影响,在利用元素含量分布及特征元素比值来判断某单个地质因素的变化时,应该应用多种参数,进行综合判断。     

Determination of Rare Earth Elements and Y in Ultramafic Rocks by ICP-MS After Preconcentration Using Fe(OH)3 and Mg(OH)2 Coprecipitation

A simple and reliable method to separate rare earth elements (REE) from Mg, Fe, K, Na, Ca and Ba in ultramafic rocks has been developed, thereby concentrating their abundances. The sample (0.3 g) was digested with HF and HNO₃ in a PTFE bomb, placed in a stainless steel container and, after drying, the insoluble residue was dissolved in 6 ml of 10% v/v HNO₃. Following the addition of 50% triethanolamine and 30% m/v NaOH solution, the REE were precipitated along with Mg(OH)₂, such that the majority of Fe, K and Na in the solution could be separated by centrifuging. The precipitate was dissolved in 1 ml HNO₃ and a buffer solution of NH₄Cl/NH₄OH at pH = 9.0 was added to precipitate the REE along with any remaining Fe as Fe(OH)₃, and so achieve separation from Mg, Ca and Ba, which remained in the solution. In this way, REE could be separated from major elements and were concentrated by a factor of about 60. The recovery of REE was more than 95% using this method. Four ultramafic rock reference materials, PCC-1 (USGS), JP-1 (GSJ), DZE-1, DZE-2 (IGGE) and one new proficiency testing sample GeoPT12 (GAS Serpentinite) were analysed by ICP-MS using indium as an internal standard. The quantitation limits were about 0.02–0.2 ng g⁻¹. Smooth chondrite-normalised REE patterns were obtained with a precision for REE determination of about 2–9%.     

杭州湾及其邻近海域沉积物中Fe、Mn、Ca、Mg的地球化学研究

本文通过对杭州湾及其邻近海域29个站位的表层沉积物化学、粘土矿物及碎屑矿物资料的分析,详细研究了开放型海湾沉积物中Fe、Mn、Ca、Mg元素地球化学特征。研究表明,1)与同类型海湾相比,杭州湾显示高Fe、Mn、Mg低Ca的特点。表明物质来源丰富,而生物作用较弱;2)Fe、Mn主要来自长江和钱塘江径流搬运,受粘土控制。Mg主要来自粘土对海水中Mg2+的吸附,同时受上覆水盐度的影响;3)北区元素间关系明显的比南区强烈,表明南区物质来源较北区复杂;4)主断面沉积物中Mg/Ca由河口向海洋增加,并与有机碳呈明显的正相关,显示杭州湾及邻近陆架区可能发生着原始碳酸盐（钙）白云岩化的反应。     

Cu–Fe Bearing Zinc Sulfide from Laloki Stratabound Massive Sulfide Deposit, Papua New Guinea: Chemical Characterization

Abstract: A strange, unidentified, Cu-Fe bearing zinc sulfide occurs in the Laloki massive sulfide deposit, Papua New Guinea. The mineral is optically uniform in texture but is chemically variable and zoned even within a single grain. Copper contents vary from 0.1 up to 8.85 wt%. Iron reaches 18.31 wt% at maximum and decreases as Cu increases. It is remarkable, however, that the total Fe+Cu remains essentially unchanged between roughly 18 and 20 wt%. Zn and S are least variable, giving 45.85–47.84 wt% and 33.48–34.58 wt%, respectively. Other trace elements such as Cd and Mn are in general less than 0.2 wt%. It is strongly suggested that the mineral in question constitutes a unique Fe-Cu substitutional solid solution series belonging essentially to the Zn–Fe–Cu–S system.
The ideal chemical formula of the solid solution series can well be presented as Zn₁₀(Fe, Cu)₅S₁₅ or Zn₂(Fe, Cu)S₃, where Fe is always greater than Cu. It is intriguing that chalcopyrite blebs are recognizable restrictively only in nearby portions of the Cu-rich end member with the ideal composition close to Zn₁₀Fe₃Cu₂S_15. It has been confirmed by vacuum-sealed heating experiments that this mineral is decomposed to produce chalcopyrite and Fe-bearing normal sphalerite at temperatures below 200C. This would provide another evidence for the existence of such distinct phase as suggested here.     

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

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

The Determination of Major Oxide and Trace Element Concentrations in Eighteen Chinese Standard Reference Samples by X-ray Fluorescence Spectrometry

Eighteen Chinese geologic reference samples (stream sediments GSD 9–12, soils GSS 1–8, and rocks GSR 1–6) were analyzed by wavelength-dispersive X-ray fluorescence spectrometry (XRFS) for major elements Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P, and by energy-dispersive XRFS for trace elements Ba, Ce, Cr, Cu, La, Nb, Ni, Rb, Sr, Y, Zn, and Zr. Major element analysis followed gravimetric determination of loss on ignition, and samples were prepared by fusion with Li₂B₄O₇. A loose-powder sample preparation was used for trace element analysis. The results reported in this study are, generally, in good agreement with concentrations compiled by X. Xie of the Geochemical Standard Reference Group and the Institute of Geophysical and Geochemical Exploration (People's Republic of China).     

苏北平原2.58Ma以来的海陆环境演变历史* ——宝应钻孔沉积物的常量元素记录

苏北盆地是一个以箕状断陷为特点的复合型沉积盆地。文章根据2004年夏采集的苏北盆地宝应钻孔(BY1)97m沉积物的124个样品11种常量元素SiO₂,Al₂O₃,TiO₂,Fe₂O₃,MgO,MnO,CaO,K₂O,Na₂O,P₂O₅和SO₂的地球化学特征分析,探讨了海相沉积环境与陆相沉积环境的元素分布特点、成因、相互之间的联系和物质来源。根据沉积物常量元素含量的垂向变化,结合沉积相、岩性特征、有孔虫分析、古地磁及¹⁴ C定年,分析了苏北盆地2.58Ma以来不同阶段海陆交互作用下的常量元素变化特点,反映了苏北平原在第四纪曾经历了4次海水淹覆, 海-陆交互堆积作用明显, 经滨浅海→泻湖→湖泊→洼地,最后由河流冲积物覆盖成陆。     

Fe---Mg partitioning between coexisting garnet and phengite at high pressure, and comments on a garnet-phengite geothermometer

The Fe---Mg exchange reaction between coexisting garnet and phengite has been studied by reacting a natural phengite (mg = 67) in the presence of quartz and water at pressures of 20–35 kb and temperatures of 800–1000°C. Compositions of coexisting garnet and mica indicate a linear relation between both the InK_D((Fe/Mg) garnet/(Fe/Mg) phengite) and temperature, and InK_D and pressure in the above P.T range. This Fe---Mg exchange reaction between garnet and phengite is shown to be dependent on the Ca-content of the garnet, and on the mg number of the bulk composition. These two composition effects have been studied by usin phengitic mica mixes with mg numbers of 23 and 46, and by using a synthetic basaltic composition. The overall results allow broad empirical calibration of separate geothermometers for pelitic and basaltic systems, respectively. However, because of non-ideality in the exchange reaction, this geothermometer should not be used in any practical application outside the composition ranges studied. Also, careful consideration of the presence of Fe³⁺ in phengite must be made. If the Fe³⁺ content of the natural phengite is unknown, then the temperatures obtained will be maximum temperatures only.     

Oxygen isotope geothermometers for metamorphic rocks

The Chicago mineral-carbonate oxygen isotope fractionation curves have been combined with mineral-water fractionation data for jadeite, zoisite and rutile and new data for grossular-water to provide a set of self-consistent mineral-pair calibrations. The A coefficients in the equation 1000 In α= A × 10⁶T^-2 of the new mineral-pair fractionations are
Jadeite Zoisite Grossular Rutile
Quartz 1.69 2.00 3.03 5.02
Jadeite 0.31 1.34 3.33
Zoisite 1.03 3.02
Grossular 1.99
The isotopic fractionation properties of natural pyralspite garnet [(Ca, Fe, Mg, Mn)₃Al₂Si₃O₁₂] can be approximated by those of the grossular end-member. Appropriate substitutions also yield coefficients for the solid-solution minerals: sodic pyroxene and epidote, e.g.
A _{quartz-sodic pyroxene}= 2.75 - 1.06X_jd,
A _{quartz-epidote}= 2.00 + 0.75X_ps
where X _Jd and X _Ps are the mole fractions of the jadeite and pistacite components, respectively.
The new data set is particularly suitable for the geothermometry of metamorphic rocks. δ¹⁸O data from minerals of the high-pressure metamorphic rocks of the Sesia Zone of Italy and Cyclades Complex of Greece yield well-constrained mean temperatures of 572 and 478 C, respectively. Type III blueschist metabasalts of the Franciscan Formation of California give mean quartz-garnet temperatures of 354 C.     

汉江上游庹家湾剖面化学风化特征及其意义

通过对庹家湾黄土剖面元素的分析,揭示汉江上游地区黄土中常量元素的地球化学行为及对气候变化的响应。用X-Ray荧光光谱仪、MS-2型磁化率仪分别测量了庹家湾剖面元素含量及磁化率值,实验结果显示:庹家湾剖面的风成黄土化学成分以SiO₂、Al₂O₃和Fe₂O₃为主,三者含量分别为355.83 g/kg、79.62 g/kg、62.64 g/kg;以Ti为参比,Na、Ca、Mg、Si、K表现为迁移淋失,Fe、Al元素相对富集,元素的活动性及其迁移序列为Na > Ca > Mg > Si > K > Al > Fe;Fe和Al元素含量曲线及CIA曲线在228~260 cm（L₁~S₁）和294~370 cm（L₁~S₂）深度处出现明显的峰值,并与磁化率曲线呈现出高度一致性,指示该层化学风化程度明显高于典型黄土,接近于古土壤（S₀）,OSL年龄在27.5~21.5 ka B.P.之间。庹家湾剖面常量元素在剖面的变化,表明在汉江上游地区晚更新世末期的气候并非是持续干燥寒冷,而是存在一定的气候波动,在27.5~21.5 ka B.P.期间风化成壤作用较为明显,气候相对温暖湿润。     

Titanian clinohumite–garnet–pyroxene rock from the Su-Lu UHP metamorphic terrane, China: chemical evolution and tectonic implications

A garnet–pyroxene rock containing abundant Ti-clinohumite (ca. 40 vol.%) occurs along with eclogites as small blocks in quartzo-feldsparthic gneiss in the southern end of the Chinese Su-Lu ultrahigh-pressure (UHP) metamorphic terrane. It consists of three aggregates: (1) Ti-clinohumite-dominated aggregate with interstitial garnet and pyroxene, (2) garnet+pyroxene aggregate with Ti-clinohumite inclusions, and (3) Ti-clinohumite-free aggregate dominated by garnet. Apatite, phlogopite, zircon, hematite, pentlandite, and an unknown Ni-Fe-volatile-Si (NFVS) mineral, which is replaced by Ni-greenalite, occur as accessories. Serpentine is the major secondary mineral. Garnet (Prp_63.9–64.6Alm_25.8–26.9Grs_1.4–7.9Uva_0.5–7.6Sps_1.0) in all three aggregates is pyrope-rich with very low grossular component, with that in the aggregate (2) most enriched in Cr (Cr₂O₃=2.55 wt.%). Orthopyroxene is depleted in Al (Al₂O₃=0.16 wt.% in the cores) and Ca (CaO=0.06–0.09 wt.% in the cores), with X_Mg (Mg/(Mg+Fe)) values at ca. 0.900. Clinopyroxene is chromian diopside with Fe³⁺≥Fe²⁺. Matrix clinopyroxene has a lower X_Mg (0.862) than that (0.887) included in Ti-clinohumite. The rock contains modest amount of heavy rare earth elements (HREE) (10 to 12×C1 chondrite), with significant enrichment in Cr, Co, Ni, V, Sr, and light rare earth elements (LREE) (22 to 33×C1 chondrite). The clinopyroxene is very enriched in Cr (Cr₂O₃ is up to 2.09 wt.% in the cores) and Sr (ca. 350 ppm) and LREE (Ce_N/Yb_N=157.7). Ti-clinohumite is enriched in Ni (1981 ppm), Co (123 ppm), and Nb (85 ppm).

While it is possible to enrich ultramafites in incompatible elements in a subducted slab, the high Al, Fe, Ti, and low Si, Ca, and Na contents in the Ti-clinohumite rock are difficult to account for by crustal metasomatism of an ultramafite. On the other hand, the similarity in major and trace element compositions and their systematic variations between the Ti-clinohumite-garnet-pyroxene rock of this study and those of Mg-metasomatised Fe–Ti gabbros reported in the literature suggest that crustal metasomatism occurred in a gabbroic protolith, which resulted in addition of Cr, Co, Ni, and Mg and removal of Si, Ca, Na, Al, and Fe. This implies that the rock was in contact with an ultramafite at low pressure. During subsequent subduction, the metagabbro was thrust into the country gneiss, where gneiss-derived hydrous fluids caused enrichment of Sr and LREE in recrystallised clinopyroxene. P–T estimates for the high-pressure assemblage are ca. 4.2 GPa and ca. 760 °C, compatible with those for the eclogites and gneisses in this terrane. It is possible that the Ti-clinohumite-garnet-pyroxene rock and associated eclogites represent remnants of former oceanic crust that was subducted to a great depth.     

高REE-Nb-Fe-Mn样品Mg同位素测定的化学分离方法

利用多接收电感耦合等离子体质谱仪测定Mg同位素比值时,样品溶液中的基质元素可影响Mg同位素比值的准确测定。根据白云鄂博样品富含REE、Nb、Fe(REE质量分数可达10%、Nb质量分数可达0.1%)等元素的特性,本研究在评估测试溶液中Nd(REE)、Mn元素质量比对Mg同位素比值影响的基础上,建立了适用于富含REE、Nb、Fe等元素的特殊样品中Mg同位素的化学纯化方法。研究表明,当m（Nd）/m（Mg）>0.2、m（Mn）/m（Mg）>0.2时,REE和Mn的存在明显影响Mg同位素测定值的准确性,应予以去除。所建纯化方法首先是利用AG MP-1阴离子交换树脂,以10 mol/L HCl+0.001% H₂O₂溶液为上样介质和淋洗液,接取前2.5 mL淋洗液,去除样品中 Fe、Mn等杂质元素;然后利用AG50W-X12阳离子交换树脂,以2 mol/L HCl为上样介质和淋洗液,去除REE、Nb等杂质元素。所建方法满足多接收器等离子体质谱进行高REE-Nb-Fe-Mn样品中Mg同位素测定的要求。     

Well-preserved garnet growth zoning in granulite from the Dabie Mountains, central China

Ultra-high pressure eclogites and granulites both occur in the Dabie Mountains, central China. A garnet porphyroblast from felsic granulite in the Dabie Mountains has been analysed for compositional zoning by electron microprobe. Two segments of the porphyroblast have opposite compositional variations. Segment I (from centre outward 9  mm to analytical point 18) has decreasing X_Sps and increasing X_Pyr, while Segment II (from analytical point 18, 1  mm outward to the rim) has increasing X_Sps and X_Alm and decreasing X_Pyr and X_Grs. The compositional zoning in segment I is considered as growth zoning and that in Segment II as diffusive retrograde zoning. Garnet growth zoning records a P–T  path prior to the peak granulite metamorphism. The minimum P – T  conditions are estimated to be 1.35  GPa and 850  °C for peak metamorphism, based on the highest Mg/(Fe+Mg) composition in the garnet (analytical point 18) and matrix hypersthene, biotite and plagioclase. A symplectitic corona surrounds the porphyroblast and appears to have formed at 0.6  GPa and 700  °C. The well-preserved growth zoning in garnet suggests a short residence time for the granulite at peak metamorphism and thus rapid tectonic uplift history. The P–T  path is consistent with that of ultra-high-pressure eclogite in the area. Tectonic movements during a collisional event could have brought both the granulite and the eclogite to their present positions.     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

Quantitative temperature-time information from retrograde diffusion zoning in garnet: constraints for the P–T–t history of the Central Black Forest, Germany

Garnet from a kinzigite, a high-grade gneiss from the central Black Forest (Germany), displays a prominent and regular retrograde diffusion zoning in Fe, Mn and particularly Mg. The Mg diffusion profiles are suitable to derive cooling rates using recent datasets for cation diffusion in garnet. This information, together with textural relationships, thermobarometry and thermochronology, is used to constrain the pressure–temperature–time history of the high-grade gneisses. The garnet–biotite thermometer indicates peak metamorphic temperatures for the garnet cores of 730–810  °C. The temperatures for the outer rims are 600–650  °C. Garnet–Al₂SiO₅–plagioclase–quartz (GASP) barometry, garnet–rutile–Al₂SiO₅–ilmenite (GRAIL) and garnet–rutile–ilmenite–plagioclase–quartz (GRIPS) barometry yield pressures from 6–9  kbar. U–Pb ages of monazite of 341±2  Ma date the low- P high- T metamorphism in the central Black Forest. A Rb/Sr biotite–whole rock pair defines a cooling age of 321±2  Ma. The two mineral ages yield a cooling rate of about 15±2  °C Ma⁻¹. The petrologic cooling rates, with particular consideration of the f O₂ conditions for modelling retrograde diffusion profiles, agree with the geochronological cooling rate. The oldest sediments overlying the crystalline basement indicate a minimum cooling rate of 10  °C Ma⁻¹.