Empirical tests of carbon isotope thermometry in granulites from southern California

Abstract ‘Peak’metamorphic carbon isotope fractionations between calcite and graphite (Δ_Cal–Gr) in marbles and calc-silicates from the Cucamonga granulite terrane (San Gabriel Mountains, California) range from 3.48 to 2.90%. The data are used to test three previously published calibrations of the calcite–graphite carbon isotope thermometer. An empirical calibration of the calcite–graphite carbon isotope thermometer gives temperatures of 700–750°C; a theoretical–experimental calibration of the system gives temperatures of 760°–870°C; an experimental calibration gives temperatures of 870–1300°C. Temperatures calculated using the empirical calibration are in agreement with those calculated from garnet-based cation exchange thermometry when uncertainty is considered. Temperatures calculated using the theoretical–experimental calibration overlap the upper range of cation exchange thermometry temperatures and range to 50°C higher. The experimental calibration yields temperatures from 50 to 480°C higher than those from cation exchange thermometry. Moreover, temperatures from the experimental calibration are also inconsistent with mineral and melt equilibria in the granulite phase assemblage. Despite the better agreement between cation exchange thermometry and the empirical calibration of the calcite–graphite system, temperatures calculated using the theoretical–experimental calibration may be real peak metamorphic temperatures. If retrograde diffusion partially reset garnet-based cation exchange thermometers by c. 50°C, then the cation exchange temperatures are consistent with those from the theoretical–empirical calibration. Thermometric evidence from biotite dehydration melting equilibria is consistent with either the empirical calibration if melting was fluid-present, or the theoretical–experimental calibration if melting was fluid-absent.     

Empirical garnet–muscovite geothermometry in low-grade metapelites, Selwyn Range (Canadian Rockies)

Abstract Partitioning of Fe and Mg between garnet and phengitic muscovite was calibrated as a geothermometer by Green & Hellman (1982) using experimental data at 25–30 kbar. When the thermometer is applied to pelites regionally metamorphosed at pressures of between 3 and 7 kbar it yields temperatures much higher than those from the garnet–biotite thermometer. A new empirical calibration is proposed for use with such rocks, with particular application where garnet occurs at lower grades than biotite. The new calibration is where K is given by: In K = In K _d and X _ii are mole fractions in the garnets.
The calibration was derived from comparison with the garnet–biotite thermometer of Ferry & Spear (1978), assuming no pressure-dependence for the partitioning between garnet and muscovite, no ferric iron partitioning, ideal mixing in muscovite, and the garnet mixing model of Ganguly & Saxena (1984) modified for a non-linear Ca effect. This latter garnet mixing model was selected because it gave the geologically most reasonable results. It has not proved possible to distinguish a pressure effect from a ferric-iron effect.
Despite the simplifying assumptions used to derive the calibration, it yields temperatures generally within 15°C of those given by the garnet–biotite thermometer, and has been used to supply thermometric data in a low-grade region of the Canadian Rockies.     

Oxygen Isotope Fractionation in TiO2 Polymorphs and Application to Geothermometry of Eclogites

Oxygen isotope fractionation in TiO2 polymorphs has been calculated by the modi-fied increment method .The results that rutile is enriched in ^18O relative to brookite but depleted in ^18O relative to anatase.Due to the same crystal structure ,oxygen isotope partitioning in the TiO2 polymorphs is determined by the cation-oxygen inter-atomic distances.The theoretical calibrations involving rutile are in fair agreement with known experimental measurements and empirical estimates.Application of the theoretic-cal quartz-rutile calibration to geothermometry of natural eclogite assemblages indicates the preservation of isotopic equilibrium at high temperatures.The isotopic temperatures calculated are only slightly lower than the non-isotopic temperatures,indicating the slow rates of exchange for oxygen diffusion in rutile.The kinetics of exchange for oxygen diffu-sion in rutile is accordingly estimated by reconciling the differences between the isotopic and the non-isotopic temperatures.The rates of exchange for oxygen diffusion in rutile should be smaller than those for hornblende,but may be equal to or greater than those for diopside.     

Hydrogen isotope fractionation factors between hydrous minerals and ore fluids at low temperatures: evidence from the Granny Smith gold deposit,Western Australia

There are no reported experimental data on hydrogen isotope fractionation between muscovite and water at low temperatures (< 400 °C). A fractionation curve derived from extrapolation of the high temperature calibration of Suzuoki and Epstein (1976) yields 20 to 40%. higher D values than the empirical graphical calibration of Bowers and Taylor (1985) at temperatures of about 300 °C. Data from natural hydrothermal systems formed at approximately 300 °C, where D analyses are available both from fluid inclusions and alteration muscovite/sericite, support the Bowers and Taylor (1985) calibration, thus indicating smaller fractionation factors at these temperatures than suggested by extrapolations from high-temperature experimental results.     

A precise olivine-augite Mg-Fe-exchange geothermometer

 Olivine and augite that were experimentally equilibrated in the temperature interval 1175–1080°C at 1 bar in natural basaltic and andesitic bulk compositions are used to calibrate an Mg-Fe²⁺ cation-exchange geothermometer. Within its temperature interval of experimental calibration, and over a broad range in olivine Mg/Fe ratio, the geothermometer has a standard error of ±6°C. In compositionally simpler synthetic systems, the same calibration retrieves appropriate experimental temperatures up to at least 1250°C. In application to intermediate and felsic volcanic rocks erupted at ∼1080 –800°C (below the range of experimental calibration), calculated olivine-augite temperatures are in good agreement with Fe-Ti oxide thermometry in the same samples. These results encourage confidence in the olivine-augite geothermometer over at least the 800–1250°C interval at low pressures. Sparse experimental data up to 1250°C at higher pressures for olivine + augite in the assemblage olivine + plagioclase + augite ± pigeonite or orthopyroxene suggest that the low-pressure calibration recovers experimental temperatures without systematic bias to pressures of 10 kbar. Examples illustrate applications to determining igneous equilibration temperatures in holocrystalline extrusive and intrusive rocks, and to estimating intratelluric H₂O content dissolved in magmas. Received: 24 February 1995 / Accepted: 1 March 1996     

Spinel-olivine geothermometry in peridotites from ultramafic complexes

An empirical calibration of the spinel-olivine geothermometer (Evans and Frost, 1975) is attempted and applied to parageneses of lherzolitic rocks. In ultramafic complexes, most of the derived temperature estimates range between 700 ° and 850 °C, and appear generally lower than those given by other geothermometers, based upon Ca or Al contents of coexisting pyroxenes. A comparison of the different thermometric data in two well studied occurrences, the Ronda ultramafic complex and the San Carlos xenolith field, suggests that differential rates of diffusion and recrystalization may account for the large range of temperatures (between 700 ° and 1200 °C) determined by various mineral geothermometers in peridotites. The equilibrium exchange of Mg and Fe between spinel and olivine would be the fastest one and would continue effectively during the cooling down to relatively low temperatures, while other exchange reactions used as geothermometers in peridotites, like partitioning of Ca and Al in coexisting pyroxenes, are blocked at higher temperatures.     

Assessment of the garnet–clinopyroxene Fe–Mg exchange thermometer using new experimental data

A detailed high-pressure experimental study of two mafic xenoliths, in which coexisting garnet and clinopyroxene (± plagioclase, spinel and olivine) were crystallized over a P–T range of 10–30 kbar and 950–1200°C, has revealed significant differences in temperatures from those estimated for coexisting garnets and clinopyroxenes using the Ellis & Green Fe–Mg exchange thermometer. The results show perfect matching at 30 kbar, 1150–1200°C, but increasing deviation at lower pressure and lower temperature, with the Ellis & Green calibration reaching a Δ T (overestimate) of c. 145°C at 10–12 kbar and 950°C. The grossular content of the garnet increases from c. 21 mol.% at 10 kbar to 26–31 mol.% at 30 kbar. These results confirm other recent experimental studies that show that the pressure correction, and possibly to a lesser extent the correction for grossular content, applied by Ellis & Green, are not appropriate for lower pressure conditions, and give estimated temperatures that are significantly high when applied to granulitic terranes formed at c. 10 kbar. The new reconnaissance results allow a graphical interpolation of a garnet–clinopyroxene geothermometer based on the Fe–Mg exchange reaction which should be applicable to assemblages formed under lower crustal conditions.     

K-Ar Radiometric Age Determinations of White Micas from the Piemont Zone,French-Italian Western Alps

The olivine-clinopyroxene (Fe-Mg partition) geothermometer of Powell and Powell (1974) was derived on the basis of clinopyroxene mixing parameters which imply a large miscibility gap in CaFeSi₂O₆-CaMgSi₂O₆-CaAl₂SiO₆ clinopyroxenes at 950° C. Application of the Powell and Powell thermometer in an empirical way (ignoring likely errors in mixing parameters) is limited by the fact that almost all natural clinopyroxene-olivine pairs are constrained by the form of the equation to have 1-bar temperatures within the narrow (915–1,060° C) limits of their calibration points.Temperatures obtained from the Powell and Powell thermometer have been compared with those obtained from clinopyroxene-orthopyroxene (miscibility gap) thermometers; agreement with the latter is poor. There are discrepancies between calculated and observed (experimental) temperatures for iron-rich clinopyroxene-olivine pairs. It is concluded that application of the thermometer in its present form is unlikely to produce reliable results.     

Benthic foraminiferal Mg/Ca-paleothermometry: a revised core-top calibration

Core-top samples from different ocean basins have been analyzed to refine our current understanding of the sensitivity of benthic foraminiferal calcite magnesium/calcium (Mg/Ca) to bottom water temperatures (BWT). Benthic foraminifera collected from Hawaii, Little Bahama Bank, Sea of Okhotsk, Gulf of California, NE Atlantic, Ceara Rise, Sierra Leone Rise, the Ontong Java Plateau, and the Southern Ocean covering a temperature range of 0.8 to 18°C were used to revise the Cibicidoides Mg/Ca-temperature calibration. The Mg/Ca-BWT relationship of three common Cibicidoides species is described by an exponential equation: Mg/Ca = 0.867 ± 0.049 exp (0.109 ± 0.007 × BWT) (stated errors are 95% CI). The temperature sensitivity is very similar to a previously published calibration. However, the revised calibration has a significantly different preexponential constant, resulting in different predicted absolute temperatures. We attribute this difference in the preexponential constant to an analytical issue of accuracy. Some genera, notably Uvigerina, show apparently lower temperature sensitivity than others, suggesting that the use of constant offsets to account for vital effects in Mg/Ca may not be appropriate. Downcore Mg/Ca reproducibility, as determined on replicate foraminiferal samples, is typically better than 0.1 mmol mol⁻¹ (2 S.E.). Thus, considering the errors associated with the Cibicidoides calibration and the downcore reproducibility, BWT may be estimated to within ±1°C. Application of the revised core-top Mg/Ca-BWT data to Cenozoic foraminiferal Mg/Ca suggests that seawater Mg/Ca was not more than 35% lower than today in the ice-free ocean at 50 Ma.     

Olivine-melt and orthopyroxene-melt equilibria

The use of non-regular solution models for silicate melts allows saturation temperatures to be calculated with an accuracy of±10 K for Mg and Fe, olivine or orthopyroxene components; and±20 K for Mn, Co and Ni components. This accuracy is comparable to that of the temperature measurement in the experiments with which the models are calibrated. The errors in the temperature calculation are less than a third of those associated with a regular solution model of mineral-melt equilibria. The values of thermodynamic properties predicted by these empirical solution models are larger than those found calorimetrically, but provide a better fit to the existing experimental data. The calculation of thermochemical properties of olivine and orthopyroxene species in both the crystalline and melt phases allows the calculation of mineral-melt s; the values calculated are within one standard error of those reported in the literature. Eruption temperatures calculated from the composition of Hawaiian tholeiite glasses range from 1135 to 1185°C, and are comparable to measured lava temperatures. These temperatures are lower than those calculated for Atlantic MORB confirming that extensive fractional crystallisation has occurred.     

Experimental evaluation of garnet–clinopyroxene geothermometry as applied to eclogites

This study performed equilibrium experiments in order to evaluate previously proposed formulations of the garnet (Grt)–clinopyroxene (Cpx) thermometer as applied to eclogites. The starting material is fine-grained powder of natural eclogite (<10 μm), whose main constituents are Grt (Fe:Mg:Ca∼44:28:28), Cpx (Na pfu∼0.55–0.60), phengite, quartz and rutile. Experimental conditions are 1,100–1,250°C at 2.5 GPa, and the run duration is 193–334 h. The experimental run products mainly consist of Grt, Cpx, and glass. In a preliminary experiment at 1,000°C for 144 h, Cpx grains are clearly zoned and most Grt grains maintain primary compositions. In the higher T (≥1,100°C) and longer run (≥193 h) experiments, Cpx in the run products becomes poorer in Na and higher in Fe/Mg compared with the starting material, and each grain does not show clear chemical zoning. Garnet compositions become poorer in Ca [Ca/(Fe+Mn+Mg+Ca)∼0.2–0.25] and lower in Fe/Mg compared with the starting material. The average composition of Cpx and the average of Ca-poor Grt compositions in each run product were used to evaluate previously proposed formulations of the Grt–Cpx thermometer. Temperatures calculated with formulations by Pattison and Newton (1989) and Berman et al. (1995) are much lower than the experimental temperatures, even though these formulations are based on the compositional bracketing-type experiment. One of the reasons for this discrepancy might be uncertainty of solid-solution properties of Al in Cpx, because the value of the excess interaction parameter for Al in the generally low-Al Cpx modeled by Berman et al. (1995) is much higher than those proposed by independent experiments, resulting in the estimated temperatures being significantly lower than the experimental temperatures.     

负温条件下激光位移传感器的标定

在使用激光位移传感器测试冻土位移中,由于测试现场环境条件恶劣,厂家给出的传感器线性度会降低,因此,需要对所有传感器在使用前应模拟使用时的环境条件重新进行标定。为验证激光位移传感器在冻土测试中的适用性,依据德国森萨帕特FT-50RLA220型激光位移传感器的结构、使用特点、技术指标,设计了由控温箱、标定支架、激光位移传感器、量块及数据采集装置组成的标定的装置,进行了不同负温条件下对激光位移传感器标定,并依据标定试验结果进行拟合参数修正,得到不同环境温度下的试验结果的线性度和迟滞特性。试验结果表明：不同的环境温度下,两个激光位移传感器与标准厂家测试曲线存在差异,不同负温条件下标定的两个激光位移传感器的拟合优度R²分别为0.999和1;线性度最大值分别为0.88%FS和0.32%FS。     

Experimental hydrogen isotope studies III: Diffusion of hydrogen in hydrous minerals,and stable isotope exchange in metamorphic rocks

Diffusion parameters for hydrogen diffusion in epidote-group minerals and micas have been measured under hydrothermal conditions, or calculated from existing experimental data, for bulk hydrogen isotope exchange experiments between hydrous minerals and water. Activation energies in the range 14 to 31 kcals/g-atom H are comparable to those derived by application of kinetic theory to experimental hydrogen isotope exchange data, and to those for oxygen diffusion in minerals under hydrothermal conditions. Diffusion of hydrogen in epidote is about four orders of magnitude faster than in muscovite, and about two orders of magnitude faster than in zoisite. Hydrogen diffusion in micas is about five orders of magnitude faster than oxygen diffusion, and hydrogen transport occurs dominantly parallel to the layers rather than parallel to the c-axis as for oxygen.Rapid hydrogen transport in minerals may proceed by hydrolysis of Si-O and Al-O bonds, followed by exchange of hydrolyzed oxygens with slower-diffusing (OH) or H₂O. Water appears to be essential for stable isotope exchange between minerals in slowly cooling metamorphic rocks.Stable isotope data for regional metamorphic mineral assemblages suggests that water is usually present in small amounts during cooling of prograde regional metamorphic systems, and estimated closure temperatures for cessation of stable isotope exchange are often more comparable to those calculated from diffusion data than to likely temperatures of metamorphism.Alpine deformation of the Hercynian Monte Rose Granite (Frey et al. 1976) permitted access of water and initiated stable isotope exchange amongst coexisting minerals. The diffusional behaviour of species in relict Hercynian muscovites is consistent with available experimental diffusion data.     

An evaluation of garnet-clinopyroxene geothermometry in granulites

Four new formulations of the garnet-clinopyroxene geothermometer (Ellis and Green 1979; Ganguly 1979; Saxena 1979; Dahl 1980) have been evaluated in the Adirondacks and five other granulite terranes using results from 94 mineral pairs. The Saxena and Ganguly formulations give temperatures that are generally 100–150° C above those constrained by phase equilibria and other independent thermometry while the empirical calibration of Dahl gives widely scattered, erratic results. Despite some scatter in the data, the Ellis and Green calibration appears to be more accurate and precise than the others and is the most useful garnet-clinopyroxene thermometer currently available for quantitative thermometry in granulites. All four formulations are sensitive to large variations (>70–80° C) in temperature suggesting that problems with accuracy and precision can be improved with further refinement of model-based aspects of the thermometers.     

离心模型试验中微型土压力盒土压力测定

土压力作为离心模型试验中重要的测试参数,受土压力盒的性能、离心机数据采集系统稳定性及外部环境等诸多因素的影响,准确地测量土压力较为困难。土压力盒作为土压力测试元件,其性能对土压力测量准确性有直接影响。为获得较为准确的土压力测试数据,结合离心机数据采集系统,选择两种常见的电阻应变式土压力盒。通过标定试验得出两种土压力盒砂标系数均小于出厂标定系数,Ⅰ型偏小64.75%,Ⅱ型偏小18.77%,Ⅱ型土压力盒与出厂数据的重合度比Ⅰ型好;在研究墙高10～30 m类扶壁式挡墙侧向土压力分布的离心模型试验中,与Ⅱ型土压力盒相比,Ⅰ型存在按出厂系数测得数据失真、灵敏度低和稳定性差的缺点。标定试验和离心试验结果表明,接入自行组建的数据采集系统的Ⅱ型土压力盒比接入静态应变数据采集系统的Ⅰ型土压力盒性能更佳。     

用于低温测量的SKLFSE-TS热敏电阻温度传感器长期稳定性论证

介绍了用于低温测量的单点热敏电阻温度传感器及多点测温电缆的结构和使用特点.将2003年埋设在青藏高原冻土区某测温孔的一根测温电缆于2010年取出, 在实验室重新进行温度标定试验.为了保证2003年和2010年标定时的条件完全相同, 并将2010年标定时的温度点设置成与2003年标定时的完全一致.利用2003年的标定系数和2010年标定时得到的电阻值反算温度值、 并与标定温度值对比, 发现8个温度传感器的温度漂移均为正漂移, 最大值为0.032 ℃, 年漂移最大值为0.0046 ℃, 低于热敏电阻温度传感器本身的测温精度值0.05 ℃, 从而验证了SKLFSE-TS型热敏电阻温度传感器以及用其制作而成多点测温电缆的长期稳定性.     

Quantitative estimates of temperature changes over the last 2700 years in Michigan based on pollen data

Temperatures for the past 2700 yr are estimated using well-dated pollen data from northwestern lower Michigan. The pollen data were sampled from sediment cores of four lakes along a 75-km transect, with fine-grained morainic soils around the two western lakes and sandy outwash soils around the lakes to the east. Climatic reconstructions based on the pollen data from the sandy sites show less temperature change than the reconstructions from the other sites, because variations in the composition of the vegetation at the sandy sites are edaphically restricted. One of the cores studied was dated by counting visible annual laminations (varves). The cores from the other lakes were dated based on three radiocarbon dates per core as well as the historically determined age of the settlement horizons. All the time scales were cross-checked using pollen-stratigraphic correlation between the four sites. A calibration function was developed using a network of modern pollen and climate data covering all of lower Michigan. Based on this calibration function, the 2700-yr reconstruction for Marion Lake indicates an estimated growing-season temperature range of 1.3°C between extreme 30-yr means. Mild conditions persisted prior to ca. A.D. 400, but a cold interval occurred between ca. A.D. 500 and 800. The well-marked warm period evident from ca. A.D. 1000 to 1200 was the last time when temperatures were about equal to the 1931–1960 mean. A prolonged longed cooling occurred after A.D. 1200 and reached 1°C below the 1931–1960 mean by the 1700s. A warming of 0.5°C is indicated from ca. A.D. 1750 to 1850. The estimated temperatures for the 1830s at Marion Lake agree with the instrumental data for that period and this provides some validation of the calibration-function results.     

地质流体状态方程

几乎所有的地球化学过程都有地质流体参加, 定量地了解地质流体的物理化学性质是定量研究地球化学过程的基础.100多年以来, 广大化学和实验地球化学工作者做了大量的实验测定工作, 可是所有这些工作之和, 仅仅覆盖地球范围内一个不大的温压空间, 远远不能满足地球化学研究的需要.近年来, 我们试图通过分子水平上的研究, 结合热力学和统计力学方面的知识, 在重现前人实验结果的基础上, 研究实验工作者没有或不能研究的温压和成分空间, 得到了一系列能够精确预测地质流体在广阔的温压范围内的物理化学性质的状态方程.这些状态方程不仅能够重现实验数据, 而且具有良好的外延能力, 可以应用于地球化学领域诸多方面的研究.重点讨论了几个状态方程(包括纯流体状态方程含水溶液状态方程和含盐-水-气的状态方程) 在预测流体的溶解度、相平衡、化学位和PVT性质方面的应用.简要介绍了近年来笔者应用分子动力学和蒙特卡罗模拟在地质流体研究方面所取得的成果      

The high pressure experimental crystallization of staurolite in hydrous mafic compositions

The experimental crystallization of staurolite in two mafic compositions at high pressures (24–26 kb) and temperatures (740 °–760 ° C) is reported. This, together with a recent report of staurolite from metamorphosed basic igneous rocks from Fiordland, New Zealand, leads to the conclusion that Staurolite may be an important subordinate phase in the subducted lithosphere. The synthesized staurolites are more magnesian than those occuring in natural metapelitic assemblages and are characterized by relatively high Si, Ti, Mg, Ca, and low Al, Fe.     

Effect of Temperature upon Fe-Mg Composition of Garnet in Pelitic System

Garnet is an essential phase in a wide range of metamorphic grades. Ratios of Fe and Mg concentrations in garnet have been widely used as a geothermometer for the crystallization, cooling rate and tectonic uplift rate because garnets in natural rocks always show a variety of Fe-Mg compositional partition. Normally, Fe-Mg concentrations of natural garnets vary widely and the Fe-Mg exchange reactions usually occur in a complex chemical system. Effect of pressure and temperature on Fe-Mg compositions of garnet in natural pelitic system was studied experimentally at temperatures of 700 to 780 ℃ and pressures from 21 to 29.4 kbar. The concentrations of FeO and MgO of garnet in the run products showed a linear relation with experimental temperatures. The result provided experimental evidence of Fe-Mg partition trend with temperature in a complex natural rock and therefore improved our understanding in the determinations of metamorphic temperature calculated by garnet geothermometer. Although the accurate geological application of our results requires the knowledge of the effects of other components upon [D(Mg)] and [D(Fe)] which is largely unknown currently, the data provided in this study are useful to build the relation between FeO-MgO contents and temperature, which is useful in the metamorphic temperatures determine of rocks with pelitic composition.