Coexisting pyroxenes — a multivariate statistical approach

A population of 117 coexisting nonalkaline pyroxene pairs has been studied statistically to evaluate compositional and thermal effects on the element distribution. K_DMg^opx-cpx is influenced by the Fe/Mg-ratio, by the Ca content—especially of clinopyroxene—and by the content of tetrahedral Al. Fe and tetrahedral Al are found to be negatively correlated. A principal component analysis based on the variation of Si, Al^IV, Al^VI, Fe, Mg, Mn, Ca is performed. Dropping of highly correlated variables does not affect the result significantly. The first principal component reflects the major chemical variation in Fe and Mg. When using ferrous and ferric iron as separate entries of the analysis, either the second or the third component demonstrates a temperature dependence. It is, however, not possible to obtain pure temperature and chemical components due to the composition not being uncorrelated to temperature of formation. From these components a graph reflecting temperature of formation has been constructed.     

Silicate solid solutions and geothermometry

Principal component analysis, using eigenvalues and eigenvectors, of the encountered variation in the chemistry of 153 garnets indicates the following: (1) In low grade metamorphic rocks, spessertite and almandine are distinctly isomorphous. The variability of pyrope content does not influence the binary Fe-Mn relationship. However there may be some influence of the grossularite content. (2) In high grade metamorphic rocks, pyrope and almandine are distinctly isomorphous. Variability of grossularite content does not affect the binary Mg-Fe relationship. However, variability in spessertite content may influence the linearity particularly when there is little pyrope.Similar statistical analysis of the chemical data on 119 samples of clinopyroxenes indicates that only significant changes in the concentrations of Al in octahedral and/or of Al in tetrahedral sites and Ti could cause some change in the FeMg ratio in the mineral.Principal component analysis of the data on coexisting garnet and clinopyroxene could be used to classify rocks into their petrogenetic types.Distribution coefficient calculated by assuming ideal binary solution of Mg and Fe members in pyroxene and garnet is useful to indicate the P-T of the formation of the rocks.     

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.     

甘肃庄浪全新世黄土-古土壤序列元素分布特征及意义

通过对渭河上游XJN全新世剖面的Fe、Al、Si、K、Ca、Mg、Na、Ti和Sr元素含量的分析,发现这些元素的分布与气候密切相关。在剖面中表现为:迁移序列是Ca>Sr>Na>Mg,Fe、Al、Si、K和Ti则相对富集;Ca-Sr关系呈两段式分布,指示全新世早期的一次环境变化;Ki残积系数增大,Ca/Mg比值减小,指示化学风化作用增强。     

Amphibolitization of metagabbros in the Scottish Highlands

Abstract Compositions of actinolite, hornblende and cummingtonite, together with pyroxene and plagioclase, are studied in basic intrusions in the Dalradian of north-east Scotland, and the Glen Scaddle complex in the West Moine. Amphibolitization is due to influx of water from the country rocks. Pyroxene compositions are found to have adjusted to the regional metamorphic environment. Owing to the difficulty of diffusion of Al and Si, calcic amphiboles are zoned and commonly contain quartz blebs. Discontinuities in zoning give rise to actinolite-hornblende pairs. Compared with north-east Scotland, disequilibrium is less strong in the Glen Scaddle area: in the latter, plagioclase compositions have been greatly changed, Na partition between hornblende and plagioclase is close to equilibrium, the maximum Al content of hornblende is lower and zoning patterns are more consistent. The Fe/Mg ratio in calcic amphiboles varies with Al content, while approaching equilibrium partition with other minerals. Both zoning patterns and Fe/Mg partition with cummingtonite suggest that Fe/Mg of the calcic amphiboles increases more strongly with increasing (Al^vi+Fe³⁺) than can be explained simply by substitution of Al,Fe³⁺ for Mg on M2. Model reactions for amphibole formation are constructed. Cummingtonite formed at lower chemical potential of CaO than actinolite: Ca was exchanged for Mg,Fe between orthopyroxene-derived and clinopyroxene-derived local systems. Both cummingtonite and actinolite were formed because of kinetic constraints, as intermediate reaction products: actinolite-hornblende pairs represent disequilibrium. This work suggests that many occurrences of actinolite with hornblende, where the minerals are zoned, may also be due to diffusion kinetics.     

A chlorite solid solution geothermometer the Los Azufres (Mexico) geothermal system

Chlorite constitutes a major hydrothermal alteration product of metamorphism of andesites, in the active geothermal system of Los Azufres (Mexico). Electron microprobe analyses performed on a set of crystals from each sample show wide variations in composition. Correlation coefficients among chemical constituents were calculated. It is shown that the tetrahedral charge is positively correlated with the octahedral vacancy and negatively with the iron content, and there is almost no correlation with the octahedral aluminium and magnesium content. A procedure is proposed to select end-members and substitution vectors, and to give a general formula for these chlorites.Their formation temperatures are estimated with great accuracy, combining results of microthermometric data on fluid inclusions from gangue minerals of chlorites (quartz, calcite), direct measurements in wells (Kuster equipment), and chemical geothermometers. Correlations between chlorite compositions, range and nature of site occupancy, and temperature are good. Formation temperatures of chlorites range from 130° C to 300° C. As no other thermodynamic parameter varies significantly in the studied field (composition of the host rocks, nature of the geothermal fluids, pressure, ...), these variations of site occupancy (mainly Al(IV) and the octahedral occupancy (6-Al(VI)-(Mg+Fe(2+)) = VAC) are considered mainly as temperature dependent.Molar fractions of each end-member show very different variations with increasing temperature: X-kaolinite decreases, and X-chamosite increases, while X-talc-3 brucite does not show significant change. From these data, activity coefficients and standard state chemical potential of major components, and molar free energy formation of chlorite have been calculated for each temperature of crystallisation.     

Minor and trace element incorporation into branching coral Acropora nobilis skeleton

Chemical and isotopic compositions of the Acropora nobilis skeleton were analyzed at various spatial resolutions to investigate the mechanism by which elements are incorporated into the skeleton. Chemical and isotopic profiles along growth axes of axial and radial corallites did not show seasonal variation, with the exception of the δ¹⁸O profile of the axial corallite. Detailed observations of the skeletal structure revealed that the skeletal density increased with distance from the tip because secondarily precipitated aragonite (here called the “infilling” skeleton) filled pore spaces in the “framework” skeleton. Microscale element analyses revealed that main part of the infilling skeleton had lower Mg/Ca and higher Sr/Ca and U/Ca than the framework skeleton. At microscale, Sr/Ca and U/Ca were positively correlated with each other, and negatively correlated with Mg/Ca but only weakly. The results showed that the infilling skeleton differed significantly from the adjacent framework skeleton in terms of not only formation chronology but also chemical composition, and that the bulk composition was influenced by the infilling/framework skeletal ratio. In order to use the Acropora skeleton as a paleoclimate archive, the relationship between environmental factors and the chemical composition of each skeletal component needs to be established.     

青藏铁路沱沱河取土场草本植物固土力学强度与化学元素含量特征

以青藏铁路沱沱河取土场草本植物种植区为例, 在野外和室内分别对生长期为5 a的6种草本做了原位拉拔试验、 室内拉伸试验和剪切试验, 分别得到了试验区梭罗草、 碱茅、 冷地早熟禾、 赖草、 垂穗披碱草、 星星草等6种草本根系抗拔力为187.34~57.89 N、 抗拉力为4.44~2.99 N, 抗剪力为4.33~3.85 N. 同时, 对取土场试验区6种草本地上茎叶、 地下根系15种化学元素进行了分析. 结果表明, 地上茎叶和地下根系主要含有Al、 Ca、 Mg、 K、 Fe、 Sr、 Zn、 Mn等8种元素, 其中Al、 Ca、 Mg、 K等4种元素较其余元素含量显著; 此外, 6种草本其根系所含Ca、 Fe、 Zn、 Sr、 Ni、 Cu等6种元素含量均显著大于相应草本种的茎叶部分. 试验区6种草本抗拔力由大至小依次为梭罗草、 赖草、 冷地早熟禾、 垂穗披碱草、 碱茅、 星星草, 6种草本其根系所含的其中前8种主要化学元素依次为Al、 Ca、 Mg、 K、 Fe 、 Zn、 Mn、 Sr等元素, 这说明了取土场试验区6种草本根系固土力学强度与根系所含化学元素具有一定的关系.     

Interrelationship between geochemical elements of sediment and groundwater at Samrak Park Delta of Nakdong River Basin in Korea: multivariate statistical analyses and artificial neural network approaches

This research was conducted at Samrak Park Delta of Nakdong River Basin in Busan Metropolitan City, Korea. The main objective of this study was to evaluate the interrelationship of geochemical elements in sediments and groundwater through multivariate statistical analyses and a multilayer perceptron artificial neural network model. The mean concentrations of chemical elements were Si (46%), Fe (16.9%), Al (15.7%), K (7.5%) and Ca (4.5%) in sediments, and Na (8650 mg/L), Mg (999 mg/L), Ca (432 mg/L), K (293 mg/L) and Cl (17,640 mg/L) in groundwater, respectively. The principal component analysis produced 3 kinds of factors with the variances of 63.37, 27.02 and 9.62%, respectively. It is suggested that the chemical components of sediments and groundwater were mainly originated from source rocks and seawater intrusion, with the minor impacts of irrigation and industry. Cluster analysis also showed that chemical elements were mainly controlled by the natural geogenic sources and seawater intrusion. Multilayer perceptron of artificial neural network (ANN) presented the good interrelationship between sediment and groundwater. The determination coefficients (R ²) between ANN predicted values and observed values in groundwater showed the high values of 0.61–0.97 except Mg, Mn and Sr. It is revealed that the chemical components of sediment and groundwater were derived from local geological origin and from the minor impact of anthropogenic sources. Multivariate analyses and ANN contributed to the identification of the mutual relationship between the geochemical elements of sediment and those of groundwater.     

Chemical anomalies of lunar plagioclase,described by substitution vectors and their relation to optical and structural properties

Lunar plagioclase posed an enigma because optical properties indicate slow cooling while structural properties suggest rapid quenching when compared directly to terrestrial plagioclase. If, however, the An-content is inferred from the Al/Si ratio rather than from the Ca/Na ratio, lunar plagioclase corresponds more closely to normal volcanic plagioclase. The differences between An=4(Al/(Al+Si))-1 and An=Ca/(Ca+Na+K) is caused by substitutions which appear so far to be unique to lunar feldspars. A vector representation of chemical composition makes it possible to single out several substitutions which account for the chemical peculiarities of lunar plagioclase. It permits to assign sites in the structure to various minor elements simply from the chemical analysis without having to rely on sophisticated spectroscopic techniques or an X-ray structure determination. 1. The deficiency in Al+Si (up to 0.06 per formula unit) is compensated for by Fe, Mg, and small amounts of Na or Ca occupying tetrahedral sites. The Ca/Na ratio is increased accordingly to balance the electric charge. This substitution accounts for most of the differences. 2. The vacancycoupled substitution Ca+□ → 2 Na (Weill et al., 1970) is another cause for the increased Ca/Na ratio. 3. The amount of alkali evaporation from plagioclase, if it occurred, is probably small. These unusual substitutions are an expression of special conditions on the moon during the crystallization of plagioclase. Crystallization at high temperatures, rapid cooling, and peculiar magma composition seem to be important factors, but experimental work and detailed study of terrestrial volcanic plagioclase are necessary to interpret the chemical composition quantitatively.     

Phase relations of pumpellyite-actinolite facies metabasites in the Sanbagawa metamorphic belt in central Shikoku, Japan

Sanbagawa metabasites metamorphosed at conditions near the upper limit of the pumpellytic-actinolite facies were examined in terms of phase equilibria in the five component system Al₂O₃---Fe₂O₃---CaO---MgO---FeO. The Fe³⁺ content of epidote measured as X^Ep_Fe (=Fe/(Fe + Al) of epidote) in the assemblage epidote-chlorite-actinolite-pumpellyite decreases gradually towards the higher-grade, pumpellyite-free areas. The progressive change in X_Fe^Ep can be detected within one metabasite bed 200 meters thick near the upper limit of the pumpellyite-actinolite facies. The Mg---Fe²⁺ substitution, as expressed by variation of Fe/(Fe + Mg) in chlorite (0.40–0.55) has little effect on the Fe³⁺ + Al) ratios of epidote and pumpellyite in the above-mentioned assemblage. The lowet X_Fe^Ep in the pumpellite-bearing assemblage is 0.15 and hence the upper limit of the pumpellyite-actinolite facies is defined by the appearance of an epidote-chlorite-actinolite assemblage with X^Ep_Fc = C.15     

Chemical composition and origin of the earth's primitive mantle

An attempt has been made to estimate the chemical composition of the earth's primitive mantle by a critical evaluation of data derived from ultramafic mantle samples and partial melting model calculations for mafic and ultramafic magmas of various ages.Compatible (Al, Ca, Si, Mg, Fe) and moderately incompatible (Ti, Zr, heavy and middle rare earth) elements in basaltic magma sources have not changed significantly since the early Archaean (~3.5 Byr). Estimated abundances for refractory lithophile elements (such as Al, Ca, Ti, Zr, Y, Se, REE etc.) in the primitive mantle are about 2.0 times ordinary chondrites (~ 1.1 times Cl chondrites relative to Mg). Highly incompatible volatile elements (K, Rb, Cs, Tl, Pb etc.) are depleted in the mantle throughout geological time. Abundances of Fe, Ni and Co are obtained on the basis of values for ultramafic nodules and model calculations using komatiites of various ages. The results show little (? 20%?) dispersion and there is no obvious secular variation since 3.5 Byr. Noble metals show similar effects. These data permit constraints to be placed on the timing of core formation.The estimated elemental abundances for the primitive mantle are normalized to Cl chondrites relative to Mg and plotted against the solar condensation temperature at 10^?4 atm. Above 700 K there are two parallel trends which are defined by lithophile elements (Al, Ca, REE, Ti, Mg, Si, Cr, Mn, Na, K, Rb, F, Zn etc.) and siderophile elements (W, Ni, Co, P, As, Ag, Sb and Ge) respectively. The depletion factor for the siderophile trend relative to the lithophile trend is about 0.085. Within each trend there is a continuous depletion towards lower temperature. A third trend is defined by noble metals (Ir, Os, Re, Pd, Pt and Au) with a depletion factor of about 0.003 relative to Cl chondrites. These trends are interpreted in terms of core-mantle differentiation and volatility-controlled processes operating before and during earth accretion.     

利用矿质元素的测定数据判别茶叶的产地和品种

应用微渡消解处理样品，电感耦舍等离子体质谱法测定，考察了不同产地、不同种类的29种茶叶中的Mg、Al、P、Ca、Cr、Mn、Fe、Co、Ni、Cu、Zn、Sr和Ph共13种元素的含量。原始数据经过标准化处理后，结合聚类分析和主成分分析，对来自江西、云南、广东和福建四个地区的茶叶进行了产地判别。对不同种类的茶叶（红茶、绿茶、鸟龙茶、黑茶）也进行了区分，结果令人满意。茶叶中矿质元素的含量可做为茶叶产地判别的测量指标之一。     

Inorganic synthesis of Fe–Ca–Mg carbonates at low temperature

A set of free-drift experiments was undertaken to synthesize carbonates of mixed cation content (Fe, Ca, Mg) from solution at 25 and 70 °C to better understand the relationship between the mineralogy and composition of these phases and the solutions from which they precipitate. Metastable solid solutions formed at 25 °C which are not predicted from the extrapolation of higher temperature equilibrium assemblages; instead, solids formed that were intermediary in chemical composition to known magnesite–siderite and dolomite solid solutions. A calcite–siderite solid solution precipitated at 25 °C, with the percentage of CaCO₃ in the solid being proportional to the aqueous Ca/Fe ratio of the solution, while Mg was excluded from the crystal structure except at relatively high aqueous Mg/Ca and Mg/Fe ratios and a low Ca content. Alternatively, at 70 °C Mg was the predominant cation of the solid solutions. These results are compatible with the hypothesis that the relative dehydration energies of Fe, Ca and Mg play an important role in the formation of mixed cation carbonates in nature.     

黑云母的红外光谱研究

关于云母族矿物的红外光谱研究,国内外一些学者曾做过不少工作。笔者就近年来所收集到的一些产自宁芜地区、南岭地区花岗岩类岩石中27个黑云母样品,进行了红外光谱测定,确定了某些特征吸收峰的偏移及其与化学组分之间的关系,并探讨了黑云母矿物中主要金属阳离子的相互置换和     

古代陶范原料配方含有草木灰的化学判断方法

通过模拟试验,烧制一批添加不同含量草木灰的陶范,应用其特征元素指标Ca/Al、K/Al、Mg/Al、P/Al、Mn/Al等5对元素含量比值分析古代陶范原料中草木灰的添加情况。模拟陶范成分分析表明,草木灰添加量越多,Ca/Al、K/Al、Mg/Al、P/Al、Mn/Al等5对元素含量比值增加。陶器烧制不需要添加草木灰,其成分可视为古代陶范的黏土原料成分,通过统计分析古代陶器和陶范,可以判断古代陶范含有较多的草木灰。对比不同遗址不同时代的陶器和陶范中5对元素含量比值,可以认为草木灰是古代陶范原料配方的重要组成部分。     

阜平杂岩中低品位磁铁矿的形成与深熔作用的关系

在中-高级变质的阜平杂岩中可以形成低品位磁铁矿.除碎屑岩中继承的磁铁矿外,新生变质磁铁矿多呈斑晶,可出现于多种岩石类型,如变基性岩、中性岩、酸性岩和变沉积岩中,表明新生磁铁矿的形成不受层位控制.磁铁矿可由物理重结晶和化学反应2种形式形成,重结晶过程主要为矿物颗粒的加粗,但没有明显的脱水反应.变质化学反应形成的磁铁矿与各单元所经受的后期变质事件改造有关,这类磁铁矿的出现与岩石中TFe的含量没有必然的联系,关键在于变质反应中是否有适量的铁组分的迁移和富集.变质反应过程中,初期黑云母变质转化形成角闪石,即变质反应不全是脱水或吸水过程,表明阜平杂岩主要的变质过程发生在含水体系中.在进一步的变质改造中,黑云母、角闪石可深熔转化形成磁铁矿.在片麻岩的含水熔融过程中,Mg、Ca优先迁移,而Fe(Ti,Al)迁移微弱,造成Fe(Ti,Al)与Mg组分的分离,残留的相对富铁组分形成磁铁矿、钛铁矿.磁铁矿结晶时没有明显的挤压或剪切,张应力可能占主导地位,相应的深熔作用主要发生在构造静应力期或体系略微抬升的过程中.     

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。     

广西桂林石灰土元素迁移特征及影响因素 ——以会仙峰丛谷地石灰土为例

碳酸盐岩的化学风化是岩溶关键带各圈层相互作用的主要形式,风化壳中蕴含重要气候环境和物质循环信息.通过对广西桂林会仙峰丛谷地石灰土的化学风化强度及元素迁移特征的研究,并与滇黔湘和青藏高原的岩溶风化壳的对比分析,结果表明:(1)会仙石灰土化学蚀变指数(CIA)均值为92.14,与贵州兴义岩溶风化壳相当,反映炎热潮湿气候下的...     

吉林省白山地区新厂期上斜正笔石式树形笔石体壁的化学成分

应用扫描电子显微镜对白山地区新厂期上斜正笔石式树形笔石的体壁进行了能谱分析，测出了笔石体壁中的Ｍｇ、Ｃａ、Ａｌ、Ｆｅ、Ｓｉ、Ｓ、Ｋ７种元素的含量，其中Ｍｇ、Ａｌ、Ｆｅ、Ｓｉ、Ｓ、Ｋ６种元素含量稳定，含量从高到低依次为Ｆｅ，Ｓｉ、Ａｌ、Ｓ、Ｍｇ、Ｋ。这６种元素可能是构成笔石体壁原始化学成分中的重要元素。