On the interpretation of peak metamorphic temperatures in light of garnet diffusion during cooling

Abstract Finite difference models of Fe-Mg diffusion in garnet undergoing cooling from metamorphic peak conditions are used to infer the significance of temperatures calculated using garnet-biotite Fe-Mg exchange thermometry. For rocks cooled from high grades where the garnet was initially homogeneous, the calculated temperature (T_calc) using garnet core and matrix biotite depends on the size of the garnet, the ratio of garnet to biotite in the rock (V_garnet/V_biotite) and the cooling rate. For garnets with radii of 1 mm and V_garnet/V_biotite<1, T_calc is 633, 700 and 777°C for cooling rates of 1, 10 and 100°C/Ma. For V_garnet/V_biotite= 1 and 4 and a cooling rate of 10° C/Ma, T_calc is approximately 660 and 610° C, respectively. Smaller and larger garnets have lower and higher T_calc, respectively. These results suggest that peak metamorphic temperatures may be reliably attained from rocks crystallized at conditions below T_calc of the garnet core, provided that V_garnet/V_biotite is sufficiently small (<0.1) and that the composition of the biotite at the metamorphic peak has not been altered during cooling. Numerical experiments on amphibolite facies garnets with nominal peak temperatures of 550–600° C generate a ‘well’in Fe/(Fe + Mg) near the rim during cooling. Maximum calculated temperatures for the assemblage garnet + chlorite + biotite + muscovite + plagioclase + quartz using the Fe/(Fe + Mg) at the bottom of the ‘well’with matrix biotite range from 23–43° C to 5–12° C below the peak metamorphic temperature for cooling rates of 1 and 100° C/Ma, respectively. Maximum calculated temperatures for the assemblage garnet + staurolite + biotite + muscovite + plagioclase + quartz are approximately 70° C below the peak metamorphic temperature and are not strongly dependent on cooling rate. The results of this study indicate that it may be very difficult to calculate peak metamorphic temperatures using garnet-biotite Fe-Mg exchange thermometry on amphibolite facies rocks (T_max > 550° C) because the rim composition of the garnet, which is required to calculate the peak temperature, is that most easily destroyed by diffusion.     

Interpreting granulite facies events through rare earth element partitioning arrays

The use of rare earth element (REE) partition coefficients is an increasingly common tool in metamorphic studies, linking the growth or modification of accessory mineral geochronometers to the bulk silicate mineral assemblage. The most commonly used mineral pair for the study of high‐grade metamorphic rocks is zircon and garnet. The link from U–Pb ages provided by zircon to the P–T information recorded by garnet can be interpreted in relation to experimental data. The simplistic approach of taking the average REE abundances for zircon and garnet and comparing them directly to experimentally derived partition coefficients is imperfect, in that it cannot represent the complexity of a natural rock system. This study describes a method that uses all the zircon analyses from a sample, and compares them to different garnet compositions in the same rock. Using the most important REE values, it is possible to define zircon–garnet equilibrium using an array rather than an average. The array plot describes partitioning between zircon and garnet using D_Yb and D_Yb/D_Gd as the defining features of the relationship. This approach provides far more sensitivity to mineral reactions and diffusional processes, enabling a more detailed interpretation of metamorphic history of the sample.     

Disequilibrium for Ca during growth of pelitic garnet

Compositional zoning in hundreds of almandine-rich garnets in amphibolite by facies micaceous quartzites from the Picuris Range, north-central New Mexico USA, indicates that although Mn, Mg and Fe achieve chemical equilibrium at hand-sample scale during garnet growth, Ca does not. Instead, Ca concentrations at the surface of growing garnets appear to depend strongly on kinetic factors that govern the local chemical environment, yielding disequilibrium for Ca at scales larger than the region immediately surrounding an individual porphyroblast. Detailed zoning profiles were obtained for 371 garnet crystals in a small volume of a single sample of garnetiferous quartzite, and core analyses were made of 97 additional crystals. Each analysis was made on a section that passed precisely through the morphological centre of the crystal, located by means of 3-D imagery from computed X-ray tomography. The data reveal strong correlations between crystal size and concentrations of Mn, Mg and Fe (but not Ca) in garnet cores; a relationship between crystal size and isolation; rigorous cross-correlations among concentrations of Mn, Mg and Fe (but not Ca); and systematic variations in Ca concentrations as a function of crystal size and core composition that are anomalous in comparison to the behaviour of the other divalent cations. We interpret these observations as the result of thermally accelerated diffusion-controlled garnet growth, in circumstances that promoted rapid intergranular diffusion and thus rock-wide equilibration of Mn, Mg and Fe, but that prevented equilibration at similar scale for Ca because of its more sluggish intergranular diffusion. The anomalous behaviour of Ca is made evident in these garnets by the presence of sharp spikes in Ca concentration, which are demonstrably not a consequence of any simultaneous rock-wide event, such as a change in pressure, temperature, or some other intensive parameter. Instead, Ca concentrations probably reflect the local extent of reaction in the immediate vicinity of each porphyroblast. To the degree that such kinetic factors introduce departures from chemical equilibrium for Ca, thermobarometric estimates that involve grossular contents of pelitic garnet will be in error.     

Controls on metamorphic equilibration: the importance of intergranular solubilities mediated by fluid composition

A dramatic demonstration of the role of intergranular solubility in promoting chemical equilibration during metamorphism is found in the unusual zoning of garnet in pelitic schist exposed at Harpswell Neck, Maine, USA. Many garnet crystals have irregular, patchy distributions of Mn, Cr, Fe and Mg in their inclusion‐rich interiors, transitioning to smooth, concentric zoning in their inclusion‐poor outer rims; in contrast, zoning of Ca and Y is comparatively smooth and concentric throughout. We re‐assess the disputed origin of these zoning features by examining garnet growth in the context of the thermal and structural history of the rocks, and by evaluating the record of fluid–rock interaction revealed in outcrop‐scale veining and fluid‐inclusion assemblages. The transition in the character of garnet zoning correlates with the onset of a synkinematic, simple‐shear‐dominated phase of garnet growth and with a shift in the composition of the intergranular fluid from CO₂‐rich to H₂O‐rich. Compositional variations in garnet are therefore best explained by a two‐stage growth history in which intergranular diffusive fluxes reflect differences in the concentration of dissolved species in these two contrasting fluids. Interiors of garnet crystals grew in the presence of a CO₂‐rich fluid, in which limited solubility for Mn and Cr (and perhaps Fe and Mg) produced patchy disequilibrium overprint zoning, while appreciable solubility for Ca and Y permitted their rock‐wide equilibration. Rims grew in the presence of an H₂O‐rich fluid, in which high intergranular concentrations for all elements except Cr enabled diffusion over length scales sufficient for rock‐wide equilibration. This striking example of partial chemical equilibrium during reaction and porphyroblast growth implies that thermal effects may commonly be subsidiary in importance to solubilities in the intergranular medium as determinants of length scales for metamorphic equilibration.     

Intergranular diffusion rates from the analysis of garnet surfaces: Implications for metamorphic equilibration

Novel approaches to garnet analysis have been used to assess rates of intergranular diffusion between different matrix phases and garnet porphyroblasts in a regionally metamorphosed staurolite‐mica‐schist from the Barrovian‐type area in Scotland. X‐ray maps and chemical traverses of planar porphyroblast surfaces reveal chemical heterogeneity of the garnet grain boundary linked to the nature of the adjacent matrix phase. The garnet preserves evidence of low temperature retrograde exchange with matrix minerals and diffusion profiles documenting cation movement along the garnet boundaries. Garnet–quartz and garnet–plagioclase boundaries preserve evidence of sluggish Mg, Mn and Fe diffusion at comparable rates to volume diffusion in garnet, whereas diffusion along garnet–biotite interfaces is much more effective. Evidence of particularly slow Al transport, probably coupled to Fe³⁺ exchange, is locally preserved on garnet surfaces adjacent to Fe‐oxide phases. The Ca distribution on the garnet surface shows the most complex behaviour, with long‐wavelength heterogeneities apparently unrelated to the matrix grain boundaries. This implies that the Ca content of garnet is controlled by local availability and is thought likely to reflect disequilibrium established during garnet growth. Geochemical anomalies on the garnet surfaces are also linked to the location of triple junctions between the porphyroblasts and the matrix phases, and imply enhanced transport along these channels. The slow rates of intergranular diffusion and the characteristics of different boundary types may explain many features associated with the prograde growth of garnet porphyroblasts. Thus, minerals such as quartz, Fe‐oxides and plagioclase whose boundaries with garnet are characterized by slow intergranular diffusion rates appear to be preferentially trapped as inclusions within porphyroblasts. As such grain boundary diffusion rates may be a significant kinetic impediment to metamorphic equilibrium and garnet may struggle to maintain chemical and textural equilibrium during growth in pelites.     

On the mechanism of resorption zoning in metamorphic garnet

Abstract An analytical electron microscope study of almandine garnet from a metamorphosed Al–Fe‐rich rock revealed detailed composition profiles and defect microstructures of resorption zoning along fluid‐infiltrated veins and even into the garnet/ilmenite (inclusion) interface. This indicates a limited volume diffusion for the cations in substitution (mainly Ca and Fe) and an interface‐controlled partition for the extension of a composition‐invariant margin. A corrugated interface between the Ca‐rich margin/zone and the almandine garnet core is characterized by dislocation arrays and recovery texture further suggesting a resorption process facilitated by diffusion‐induced recrystallization, diffusion‐induced dislocation migration and diffusion–induced grain boundary migration. Integrated microstructural and chemical studies are essential for understanding the underlying mechanisms of processes such as garnet zoning and its modification. Without this understanding, it will not be possible to reliably use garnet compositions for thermobarometry and other applications that rely on garnet chemical information.     

The duration of near‐peak metamorphism from diffusion modelling of garnet zoning

Garnet in a staurolite–kyanite zone sample from central Vermont displays a bell‐shaped Mn growth zoning with diffusional modification over the outer 100 μm. The diffusion is driven by the prograde net transfer reaction garnet + chlorite = kyanite + biotite as is evidenced by a well‐defined resorption zone on the rim. Analysis of the reaction history and resorbed garnet composition suggests that the peak temperature attained was 620–660 °C. Diffusional modelling of the rim diffusion provides an estimate of the duration of the metamorphic episode over which significant garnet diffusion occurs. The duration is a function of the assumed peak temperature and garnet diffusivities and range from a few hundred thousand years to a few million years. Such short durations require rapid tectonic burial and exhumation of relatively thin tectonic slices.     

非洲稀土资源研究进展

稀土是现代高科技产业发展的关键金属,被世界主要经济体列为关键矿产资源。虽然中国稀土资源丰富,但2017年以来中国稀土资源进口量呈现出明显的上升趋势。总结中国稀土资源的进口数据,以及非洲稀土项目分布、储量及资源量、矿床类型、成矿时代、典型矿床特征及勘查投资等情况,以提升对非洲稀土资源的认识。研究表明,非洲稀土资源丰富,稀土氧化物的高级资源量超过1000×104 t,近年来勘探及开发进度提升迅速。稀土储量及资源量主要集中于坦桑尼亚等12个国家,成矿类型可划分为火成碳酸岩型及离子吸附型等8种（成矿时代跨度大）,其中火成碳酸岩型和离子吸附型稀土矿床是目前勘探及开发的重点。非洲稀土矿床勘查投资规模2012年达到顶峰,之后持续下降,2017年降至低谷,2018年开始迅速反弹。未来,随着国际上稀土矿项目逐步投产,由中国主导全球稀土市场价格的局面将面临挑战。非洲稀土矿成矿条件优越,中资企业可利用地-采-选-冶的技术优势,积极引导并推动非洲稀土生产进入中国产业链。     

华北地区稀土矿床特征及找矿方向

在系统收集华北地区稀土矿床资料基础上,分析了华北地区稀土资源现状及稀土矿床的时间、空间分布规律.分析认为,华北地区稀土矿床成矿类型主要包括沉积变质型、火成碳酸岩浆型、岩浆热液型、伟晶岩型和离子吸附型.根据华北地区稀土矿床构造位置及控矿特征,认为华北地区古老变质基底、太古宙—古元古代陆块边缘裂谷带、中元古代陆缘裂谷带、燕...     

离子吸附型稀土矿床形成的矿物表/界面反应机制

华南离子吸附型稀土矿床提供了全球超过90%的重稀土,是我国优势的战略性关键金属矿产资源。掌握这类矿床的成矿机制和禀赋特征,可为增加稀土资源储量和高效利用稀土资源提供理论支撑。离子吸附型稀土矿床主要发育在富稀土花岗岩、浅变质岩及火山岩的风化壳中。基岩中的(含)稀土矿物是风化壳中离子态稀土的主要来源,其矿物组合很大程度上决定了稀土矿床的禀赋和分异特征。在物理-化学风化和微生物作用下,造岩矿物、含稀土矿物和稀土独立矿物逐渐溶解,使稀土元素活化和再富集。一方面,母岩风化形成的黏土矿物和铁锰氧化物具有较大的比表面积和一定的表面电荷密度,是稀土离子的主要载体;另一方面,稀土离子通过离子交换、表面吸附与络合、共沉淀,以及形成次生稀土矿物等途径富集在次生矿物表面,其富集-分异特征和赋存状态受矿物类型、pH、微生物活动等因素所控制。利用高分辨透射电镜结合选区电子衍射和电子能量损失谱,以及同步辐射X射线吸收精细结构谱,有望在原子级尺度查明稀土的微观赋存状态。未来研究需更多关注基岩中(含)稀土矿物组合及其演化路径的制约因素、微生物风化对离子吸附型稀土矿床成矿作用的约束,以及稀土元素的微观赋存状态等问题。     

Rare earth element and gallium diffusion in yttrium aluminum garnet

Diffusion of four rare-earth elements and gallium has been measured in yttrium aluminum garnet (YAG). Sources of diffusant were mixtures of alumina and rare-earth element oxides for REE diffusion, and mixtures of gallium and yttrium oxides for Ga diffusion. Diffusion profiles were measured with Rutherford backscattering spectrometry (RBS). For the rare-earth elements investigated, the following Arrhenius relations were obtained: D_La=6.87×10^–1 exp (–582±21 kJ mol^–1 /RT) m²s^–1 D_Nd=1.63×10^–1 exp (–567±15 kJ mol^–1 /RT) m²s^–1 D_Dy=2.70×10⁰ exp (–603±35 kJ mol^–1 /RT) m²s^–1 D_Yb=1.50×10^–2 exp (–540±26 kJ mol^–1 /RT) m²s^–1 Diffusion rates for the rare earths are quite similar, in contrast with trends noted for zircon. It is likely that these differences are a consequence of the relative ionic radii of the REE and the cations for which they substitute in the mineral lattice. For gallium, the following Arrhenius relation was determined: D_Ga=9.96×10^–6 exp (–404±19 kJ mol^–1 /RT) m²s^–1 Gallium diffuses faster than the REE in YAG and has a smaller activation energy for diffusion. These data mirror relative trends in diffusion rates for YIG, in which trivalent cations occupying tetrahedral and octahedral sites (i.e., Al, Ga, Fe) diffuse faster than trivalent cations occupying dodecahedral sites (i.e., Y and the REE), and suggest that the rate-limiting process in the diffusion-controlled regime of solid-state creep of YAG is the diffusion of yttrium. Received: 10 November 1997 / Revised; accepted: 13 March 1998     

Peak metamorphic temperatures from cation diffusion zoning in garnet

A model that relates the characteristic diffusion length and average cooling rate to peak temperature was developed for chemical diffusion in spherical geometries on the basis of geospeedometry principles and diffusion theory. The model is quantitatively evaluated for cation diffusion profiles in garnet. Important model parameters were calibrated empirically using diffusion zoning of Ca in garnet from the Pikwitonei Granulite Domain, a terrane for which the thermal history has been well characterized. The results are used: (i) to empirically test diffusion parameters for Mg and Fe(II) and (ii) to develop a tool that uses the diffusion zoning of these cations in garnet to constrain peak temperature conditions for garnet‐bearing rocks. The thermometric approach was externally tested by applying it to garnet crystals from various metamorphic terranes worldwide and comparing the results to published peak temperature estimates. The results overlap within uncertainties in all cases, but result that are based on Fe(II) and Mg chemical‐diffusion profiles are up to three times more precise than those acquired by conventional methods. The remarkable consistency of the results implies that the model is robust and provides a reliable means of estimating peak temperatures for different types of high‐grade metamorphic rock. The tool could be of particular advantage in rocks where critical assemblages for conventional thermometry do not occur or have been replaced during retrogression.     

Multicomponent diffusion in aluminosilicate garnet: coupling effects due to charge compensation

ABSTRACT

Three kinds of multicomponent diffusion effects, arising from three distinct physical mechanisms, are evident in stranded diffusion profiles at the rims of partially resorbed garnets from the contact aureole of the Makhavinekh Lake Pluton, northern Labrador. Profiles that display a subtle maximum in Ca concentration are explained by the prevailing ideal mean-field theory of multicomponent diffusion, but models implementing that theory cannot replicate inverted profiles for Li and internal maxima for Nd, Sm, and Eu. The anomalous profiles are quantitatively reproduced, however, by numerical simulations employing a model based on coupled movement of charge-compensating groups during diffusional transport of yttrium and the rare-earth elements (Y+REEs). An alkali-type charge-compensation mechanism for the heterovalent substitution of Y+REEs on dodecahedral sites in garnet produces direct charge coupling between Li⁺ and (Y+REE)³⁺ and leads to co-diffusion of Li⁺-(Y+REE)³⁺ pairs, with the result that Li profiles closely mimic those for Y+REEs. A menzerite-type charge-compensation mechanism produces indirect charge coupling among all Y+REE components, with the result that the fluxes of low-abundance REEs become partly dependent on the fluxes of Y+REEs present in higher abundance. These findings have implications for the robustness of Li profiles in garnet as monitors of fluid–rock interaction, for geochronology based on the Sm–Nd and Lu–Hf systems, and for future experimental attempts to quantify rates of diffusion in garnet.     

Experimental determination of REE partition coefficients between zircon,garnet and melt: a key to understanding high‐T crustal processes

The partitioning of rare earth elements (REE) between zircon, garnet and silicate melt was determined using synthetic compositions designed to represent partial melts formed in the lower crust during anatexis. The experiments, performed using internally heated gas pressure vessels at 7 kbar and 900–1000 °C, represent equilibrium partitioning of the middle to heavy REE between zircon and garnet during high‐grade metamorphism in the mid to lower crust. The D_REE (zircon/garnet) values show a clear partitioning signature close to unity from Gd to Lu. Because the light REE have low concentrations in both minerals, values are calculated from strain modelling of the middle to heavy REE experimental data; these results show that zircon is favoured over garnet by up to two orders of magnitude. The resulting general concave‐up shape to the partitioning pattern across the REE reflects the preferential incorporation of middle REE into garnet, with D_Gd (zircon/garnet) ranging from 0.7 to 1.1, D_Ho (zircon/garnet) from 0.4 to 0.7 and D_Lu (zircon/garnet) from 0.6 to 1.3. There is no significant temperature dependence in the zircon–garnet REE partitioning at 7 kbar and 900–1000 °C, suggesting that these values can be applied to the interpretation of zircon–garnet equilibrium and timing relationships in the ultrahigh‐T metamorphism of low‐Ca pelitic and aluminous granulites.     

Petrological significance of prograde homogenization of growth zoning in garnet: an example from the Llano Uplift'pa

In the Llano Uplift of central Texas (USA), prograde homogenization of garnet growth zoning took place during moderate- to high-pressure dynamothermal metamorphism over a narrow temperature range near the transition from the amphibolite to the granulite facies. This subtle record of early dynamothermal metamorphism survived subsequent static metamorphism at low pressures in the middle-amphibolite facies, despite the destruction of most high-pressure mineral assemblages that originated in the early metamorphic episode. Geographically systematic variations in the degree of homogenization indicate that the uplift as a whole underwent high-pressure metamorphism, in accord with emerging tectonic models for the mid-Proterozoic evolution of the southern margin of the North American continent.     

陈家山矿煤中微量元素和稀土元素地球化学特征

通过对陈家山煤矿中下侏罗统延安组4^#主采煤层中微量元素和稀土元素的测试分析,发现煤中富集亲花岗岩的钨钼族元素W、Mo、Bi、Sn、Ba、Sr和Li,说明该区煤系形成期间的陆源碎屑主要来自花岗岩和花岗片麻岩等中、酸性岩石。4^#煤中ΣREE平均值为98.2×10^-6,稀土元素分布模式十分相似,呈左高右低的宽缓“V”型曲线,Eu负异常明显,反映出稀土元素与陆源碎屑岩关系密切,成煤期间稀土元素来源一致,陆源物质的供应相对稳定。     

Trace and rare earth element geochemistry of the Upper Triassic mudstones in the southern Ordos Basin,Central China

Oil‐source correlation studies have demonstrated that the crude oils in the Ordos Basin were mainly derived from organic‐rich lacustrine mudstones of the Yanchang Formation. The sedimentology, petrology and organic geochemistry of these mudstones have been studied intensively, but their trace and rare earth element (REE) characteristics have received little attention. In this paper, we present trace and rare earth element data of the Upper Triassic Yanchang Formation mudstones in the southern Ordos Basin to constrain the palaeoenvironment, provenance and depositional setting. Our results show that the REE and trace element concentrations of the Yanchang Formation mudstones are higher than those of the upper continental crust (UCC). The Sr contents and Sr/Ba and Y/Ho ratios of these mudstones indicate the absence of a marine transgression during the sedimentation of the Upper Triassic mudstones. The depositional environment of the Upper Triassic mudstones was slightly oxic as evidenced by the values of Eu/Eu*, Ce/Ce*, Ce_anom, δU, U/Th, V/Cr and Ni/Co. The UCC‐normalized distribution pattern of REEs, spider diagrams, the ratios of related elements, the bivariate diagrams of Th/Sc–Zr/Sc and La/Th–Hf and the ternary plots of La–Th–Sc and Th–Sc–Zr/10 signify that the provenances of the Chang9–7 mudstones were mainly derived from a continental island arc, whereas the provenances of the Chang6–3 mudstones were mainly derived from a mixture of continental island arc and active continental margin, and the latter contain less recycled materials. Combined with the previous studies of detrital zircon dating and petrography of the Yanchang Formation sandstones in the southern Ordos basin, we propose that the Qinling orogenic belt served as one of the primary source regions occurring between the Chang7 and Chang6 periods, corresponding to the initial uplift of the west Qinling Mountains due to the collision between the Yangtze and North China blocks. Copyright © 2014 John Wiley & Sons, Ltd.     

云南大平掌铜多金属矿床稀土元素地球化学特征

滇西大平掌铜多金属矿床具典型的“双层结构”。对上部盆地相的块状硫化物和下部通道相的细脉浸染状硫化物的稀土元素分析表明,前者具正Eu异常的球粒陨石标准化配分模式,后者具负Eu异常的配分模式。这种变化与成矿流体演化有关。通过与大西洋中脊TAG热液活动区表层沉积硫化物和黑烟囱流体等的稀土元素配分模式对比,可以认为成矿是火山喷流沉积作用的结果。     

REE partitioning between monazite and garnet: Implications for petrochronology

Rare‐earth element and Y partitioning between garnet and monazite was measured in metamorphic rocks from western Norway to provide more confidence in tying monazite U/Th–Pb dates to P–T conditions recorded in garnet. A subset of samples has low‐Y garnet mantles and low‐Y monazite cores that gave Y‐partitioning temperatures similar to independently determined metamorphic temperatures. In combination with previously published data, these monazite–garnet pairs have temperature‐dependent partitioning of the HREE from Dy to Lu, and nonsystematic partitioning of the LREE from La–Gd. The temperature‐dependent partitioning must be considered when using HREE to assess which portions of garnet and monazite might have coexisted, but experiments are needed to place the dependence on a firm footing.