Geochemical behaviours of chemical elements during subduction-zone metamorphism and geodynamic significance

ABSTRACT

Seafloor subduction and subduction-zone metamorphism (SZM) are understood to be the very cause of both subduction-zone magmatism and mantle compositional heterogeneity. In this article, we compile geochemical data for blueschist and eclogite facies rocks from global palaeo-subduction-zones in the literature, including those from the Chinese Western Tianshan ultrahigh pressure (UHP) metamorphic belt. We synthesize our up-to-date understanding on how chemical elements behave and their controls during subduction-zone metamorphism. Although the compositional heterogeneity of metamorphic minerals from subducted rocks has been recently reported, we emphasize that the mineral compositional heterogeneity is controlled by elemental availability during mineral growth, which is affected by the protolith composition, the inherited composition of precursor minerals, and the competition with neighbouring growing minerals. In addition, given the likely effects of varying protolith compositions and metamorphic conditions on elemental behaviours, we classify meta-mafic rocks from global palaeo-subduction-zones with varying metamorphic conditions into groups in terms of their protolith compositions (i.e. ocean island basalt (OIB)-like, enriched mid-ocean ridge basalt (MORB)-like, normal [N]-MORB-like), and discuss geochemical behaviours of chemical elements within these co-genetic groups rather than simply accepting the conclusions in the literature. We also discuss the geochemical consequences of SZM with implications for chemical geodynamics, and propose with emphasis that: (1) the traditionally accepted ‘fluid flux induced-melting’ model for arc magmatism requires revision; and (2) the residual subducted ocean crust cannot be the major source material for OIB, although it can contribute to the deep mantle compositional heterogeneity. We also highlight some important questions and problems that need further investigations, e.g. complex subduction-zone geochemical processes, different contributions of seafloor subduction and resultant subduction of continental materials, and the representativeness of studied HP–UHP metamorphic rocks.     

Zr-in-rutile thermometry of eclogite in the Dabie orogen: Constraints on rutile growth during continental subduction-zone metamorphism

The Zr content of rutile was analysed by both EMP and LA-ICPMS for low-T/UHP eclogite and enclosed kyanite–quartz veins in the Dabie orogen, China. Zr-in-rutile temperatures were calculated at different pressures and then compared with temperatures derived from Ti-in-zircon, mineral-reaction, quartz–mineral O-isotope and garnet–clinopyroxene Fe–Mg exchange thermometers. All thermometric data are interpreted within the framework of petrologically and geochronologically constrained P–T–t path. As a consequence, variable Zr-in-rutile temperatures for different occurrences of rutiles are used to indicate their growth in different stages during continental subduction-zone metamorphism. Thus, some rutiles would grow at the peak pressure, whereas other rutiles would either grow before the peak pressure during the subduction or grow at or after the peak temperature during exhumation. The mineral O-isotope and Fe–Mg exchange thermometers also yield variably lower temperatures for the eclogite. The similar results were obtained for mid-T/UHP eclogites in the Dabie-Sulu orogenic belt. This is ascribed to the characteristic P–T–t path of UHP metamorphic rocks, in which metamorphic temperatures at peak pressures are lower than the peak temperatures at decreased pressures during exhumation. Thus, there is a contest between thermodynamics and kinetics during metamorphic reactions in response to P–T changes. Therefore, the reasonable interpretation of thermometric data requires comprehensive understanding of thermometric methodology from physicochemical principles to geological applicabilities.     

A simple relationship between isothermal bulk modulus and thermal pressure for geophysical minerals

The variations in isothermal bulk modulus with an increase in temperature are found to be related linearly with the change in thermal pressure for geophysical minerals, such as MgO, CaO, Al₂O₃, MgAl₂O₄ and Mg₂SiO₄. Analysis of the relationship yields a value of the Anderson–Gruneisen parameter for each mineral in close agreement with known values. An important finding of the present study is the derivation of an isobaric equation of state representing the relationship between volume and temperature at ambient pressure. This equation for isobaric volume expansion looks like the Birch equation for isothermal compression. The calculated values of volume expansion for the minerals at high temperatures present close agreement with the available experimental data. The formulation developed in the present study has also been used to predict the volumes at simultaneously elevated temperatures and pressures for CaSiO₃ perovskite and NaCl minerals, in good agreement with the experimental values.     

汝箕沟晚中生代玄武岩的确定与煤变质作用关系简论

汝箕沟矿区无烟煤产于侏罗纪地层中,在宁夏地区中生代煤中变质程度最高。本文简述了汝箕沟矿区变质煤系的基本特征,首次论证了该区早白垩世晚期玄武岩的发育是引起煤层变质的最直接和主要原因,并简述了该玄武岩的特征、发育构造背景及其区域意义。     

A note on the relationship between dip-slip fault parameters and plate parameters in the two-dimensional modelling of preseismic deformation

Preseismic lithospheric deformation at a subduction zone can be modelled as dip-slip dislocation on an inclined fault or as flexure of a thin plate. Both these models predict a region of positive topography known as forebulge or outer rise. By matching the location and the magnitude of the forebulge, we derive useful relations between the dip-slip fault parameters and the plate parameters. In particular, we determine the width of a long dip-slip fault of given dip corresponding to a semi-infinite plate of given thickness. The displacement profiles of the two models are also compared.     

Chemical geodynamics of continental subduction-zone metamorphism: Insights from studies of the Chinese Continental Scientific Drilling (CCSD) core samples

The Dabie–Sulu orogenic belt of east-central China has long been a type location for the study of geodynamic processes associated with ultrahigh-pressure (UHP) tectonics. Much of our understanding of the world's most enigmatic processes in continental deep-subduction zones has been deduced from various records in this belt. By taking advantage of having depth profiles from core samples of the Chinese Continental Scientific Drilling (CCSD) project in the Sulu orogen, a series of combined studies were carried out for UHP metamorphic rocks from the main hole (MH) at continuous depths of 100 to 5000 m. The results provide new insights into the chemical geodynamics of continental subduction-zone metamorphism, especially on the issues that are not able to be resolved from the surface outcrops. Available results from our geochemical studies of CCSD-MH core samples can be outlined as follows. (1) An O isotope profile of 100 to 5000 m is established for the UHP metamorphic minerals, with finding of ¹⁸O depletion as deep as 3300 m. Along with areal ¹⁸O depletion of over 30,000 km² along the Dabie–Sulu orogenic belt, three-dimensional ¹⁸O depletion of over 100,000 km³ occurs along the northern margin of the South China Block. (2) Changes in mineral O isotope, H isotope and water content occur in eclogite-gneiss transitions, concordant with petrographic changes. The contact between different lithologies is thus the most favorable place for fluid action; fluid for retrogression of the eclogites away from the eclogite-gneiss boundary was derived from the decompression exsolution. For the eclogites adjacent to gneiss, in contrast, the retrograde metamorphism was principally caused by aqueous fluid from the gneiss that is relatively rich in water. Inspection of the relationship between the distance, petrography and δ¹⁸O values of adjacent samples shows O isotope heterogeneities between the different and same lithologies on scales of 20 to 50 cm, corresponding to the maximum scales of fluid mobility during the continental collision. (3) Studies of major and trace elements in the two continuous core segments indicate high mobility of LILE and LREE but immobility of HFSE and HREE. Some eclogites have andesitic compositions with high SiO₂, alkalis, LREE and LILE but low CaO, MgO and FeO contents. These features likely result from chemical exchange with gneisses, possibly due to the metasomatism of felsic melt produced by partial melting of the associated gneisses during the exhumation. On the other hand, some eclogites appear to have geochemical affinity to refractory rocks formed by melt extraction as evidence by strong LREE and LILE depletion and the absence of hydrous minerals. These results provide evidence for melt-induced element mobility in the UHP metamorphic rocks, and thus the possible presence of supercritical fluid during exhumation. In particular, large variations in the abundance of such elements as SiO₂, LREE and LILE occur at the contact between eclogite and gneiss. This indicates their mobility between different slab components, although it only occurs on small scales and is thus limited in local open-systems. (4) Despite the widespread retrogression, retrograde fluid was internally buffered in stable isotope compositions, and the retrograde fluid was of deuteric origin and thus was derived from the decompression exsolution of structural hydroxyl and molecular water in nominally anhydrous minerals. (5) A combined study of petrography and geochronology reveals the episode of HP eclogite-facies recrystallization at 216 ± 3 Ma, with timescale of 1.9 to 9.3 Myr or less. Collectively, the Dabie–Sulu UHP terrenes underwent the protracted exhumation (2–3 mm/yr) in the HP-UHP regime. (6) Zircon U–Pb ages and Hf isotopes indicate that mid-Neoproterozoic protoliths of bimodal UHP metaigneous rocks formed during supercontinental rifting along preexisting arc-continent collision orogen, corresponding to dual bimodal magmatism in response to the attempted breakup of the supercontinent Rodinia at about 780 Ma. The first type of bimodal magmatism was formed by reworking of juvenile Late Mesoproterozoic crust, whereas the second type of bimodal magmatism was principally generated by rifting anatexis of ancient Middle Paleoproterozoic crust. In conclusion, the geochemical studies of CCSD-MH core samples have placed important constraints on the nature and scale of fluid action and element mobility during the continental subduction and UHP metamorphism.     

A note on the weather and rice yield relationship at some stations in India

A study was conducted with four traditional photosensitive and one high yielding rice varieties grown during the kharif season under rainfed conditions. The curvilinear technique was used to examine the influence of meteorological parameters on the yield of rice. Rice varieties grown in different agroclimatic regions performed differently to climatic parameters. The maximum yield was observed when rainfall ranged between 100 and 115 cm. Maximum and minimum temperature ranges of 29–32°C and 23–25°C respectively appear ideal for optimum yield. Photoinsensitive high yielding variety performed well even at low light intensity (250-350 hours of bright sunshine).     

Trace elements in zircon and coexisting minerals from low-T/UHP metagranite in the Dabie orogen: Implications for action of supercritical fluid during continental subduction-zone metamorphism

Simultaneously in-situ analyses of U–Pb isotopes and trace elements were carried out for zircons, in combination with the in-situ analyses of trace elements in coexisting minerals, from low-T/UHP metagranite in the Dabie orogen. The results provide geochemical evidence for the existence of supercritical fluid during continental subduction-zone metamorphism. The zircons are categorized into three types based on their patterns of REE distribution. Type I zircons show increasing enrichment from La to Lu, with prominent positive Ce anomalies and negative Eu anomalies, which are typical of magmatic zircon. Some of them display regular or blurred oscillatory-zoned texture and apparent ²⁰⁶Pb/²³⁸U ages of 341 to 780 Ma, suggesting metamorphic modification by solid-state recrystallization with no significant involvement of metamorphic fluid. Type II zircons share similar Th, U and HFSE contents and REE patterns to Type I zircons. However, they exhibit blurred oscillatory-zoned texture or are unzoned, have apparent ²⁰⁶Pb/²³⁸U ages of 348 to 709 Ma, and are LREE-enriched relative to Type I zircons. This suggests that they underwent metamorphic reworking by replacement recrystallization in the presence of metamorphic fluid. The LREE enrichment is due to the presence of microscale LREE-bearing mineral inclusions (such as apatite, monazite or epidote) in the zircons. Type III zircons, representing the majority of the present analyses, are characterized by spongy texture and consistent enrichment of LREE, HREE, Th, U and HFSE relative to Type I zircons. They yield nearly concordant U–Pb ages close to the discordia lower-intercept. The consistent enrichment of trace elements relative to the magmatic zircon indicates involvement of a special UHP metamorphic fluid that has a strong capacity to extract significant amounts of LREE, HREE, Th, U and HFSE from such accessory minerals as allanite, garnet, rutile and zircon. Because these minerals are stable in the field of hydrous melt in granite–water systems, they are not able to be decomposed during the exhumation of deeply subducted continental crust. Thus, a supercritical fluid is suggested to transport the LREE, HREE, Th, U and HFSE in the accessory minerals to recrystallized zircons. The mechanism of dissolution recrystallization is responsible for the spongy texture and the very high concentration of trace elements in this type of metamorphic zircons. Therefore, the action of supercritical fluid is evident under the low-T/UHP metamorphic conditions.     

Petrological and age relationship between emplacement of magmatic breccia, alkaline magmatism, and static metamorphism in the North Pyrenean Zone

A magmatic breccia showing peculiar structural and geochemical features has been found in the North Pyrenean Zone (Lherz area). The features (concentric zoning, “fluidal” structure, reaction rim at the matrix-clast interface, high Co, Sc and REE contents) indicate a genetic relationship between the breccia and fluids of deep origin which have infiltrated the Mesozoic series. These fluids, probably related to the alkaline magmatism commonly observed in the Pyrenees, could be locally responsible for the static Pyrenean metamorphism.³⁹Ar/⁴⁰Ar age determinations have been made in order to compare (a) the age of the neoblastesis in the magmatic breccia matrix (95 ± 2 Ma), (b) the age of the unoriented metamorphic minerals in the surrounding marbles (98.5 ± 2.2 Ma) and (c) the age of the alkaline magmatism in the Corbières and Lherz areas (95.4 ± 2.3 Ma and 101.2 ± 2.5 Ma, respectively).     

A note on the stratigraphic relationship of the leven schist and monadhliath schist in the central highlands of Scotland

The Monadhliath and Leven Schists are separated north of Glen Roy by some 500m of psammitic rock. Junctions are gradational and conformable, and evidence from sedimentary structures indicates that all three face upwards. The two schists should not be equated, nor should the Monadhliath Schist be included in the Dalradian Supergroup unless the entire Grampian Division is also included.     

A Study on the Relationship between the Color and paramagnetic Impurities in Dolomite—Marble

Dolomite-marble is widely used as a high-grade building material.The color caused by impurities and its stability are important criteria to judge the quality of dolomite-marble and its value in the market.Therefore,the study of the relation between the color and the impurities is of important commercial significance.Up to now,no detailed study on dolomite-marble color has been reported.In this work the relation beween the color of dolomite-marble and the trace paramagnetic ions is studied in detail using electron paramagnetic resonance(EPR),X-ray diffraction,polished section identification and chemical analysis.     

Geological note: New field evidence resolving the relationship between the Grampians group and the Rocklands Rhyolite,western Victoria

The Rocklands Rhyolite is a latest Silurian to Early Devonian sequence of silicic ignimbrite, lava, volcanic sedimentary rocks and dykes in western Victoria. These volcanic rocks lie west of the Grampians Ranges, which consist of a thick succession of quartz sandstone of presumed Silurian age called the Grampians Group. The previously unresolved stratigraphic relationship between these two sequences of rocks is clarified by an exposed contact between steeply dipping Grampians Group cut by quartz veins, and overlying undeformed rhyolite. The implications of this relationship are that the Grampians Group is older than the Rocklands Rhyolite and that parts of the sandstone succession were locally deformed prior to volcanism. Furthermore, other outlying areas of sandstone and rhyolite, previously correlated with the Grampians Group and Rocklands Rhyolite, respectively, display different timing relationships and are proposed to be significantly younger.     

A note on the Goodman Jack

SummaryA Note on the Goodman Jack Reconnaissance experiments, performed to evaluate the practical utility of the hard-rock variety of the Goodman Jack, reveal that the Hustrulid-T^* correction adequately reconciles the discrepancy between the measured and true deformation modulus of the rock mass in the range of 30 to 50 gigapascals.With 3 Figures     

基于三维模型的西峪金伯利岩管与断裂构造关系探讨

山东蒙阴金刚石矿床是中国著名的金伯利岩型金刚石矿床,西峪金伯利岩管是山东蒙阴地区的典型代表。三维建模技术于近些年来被广泛应用于地学研究领域。本文选择山东蒙阴地区西峪金伯利岩管为研究对象,借助于三维建模技术构建金伯利岩管和断裂构造的三维实体模型,在岩管成矿地质背景分析基础上,开展断裂构造三维空间特征定量分析和三维模型叠合讨论,探讨西峪金伯利岩管与断裂构造特征的关系。结果表明:金伯利岩管呈现出连续的上大下小"放射状"空间形态特征,岩管赋存部位往往断裂构造密集;金伯利岩岩浆上涌的通道可能为F1、F2、F10等深大断裂,岩管分布于断裂交点旁侧,岩管形态与构造交点形态相似。     

北秦岭构造带与华北板块关系探讨: 来自宽坪杂岩变碎屑岩锆石U-Pb年代学与变质作用证据

宽坪杂岩是连接北秦岭构造带和华北板块的重要岩石-构造单元之一,其物质组成和变质变形特征可为探讨北秦岭构造带与华北板块构造关系及演化提供重要证据。本文在已有研究基础上,对宝鸡-眉县-洛南一带宽坪变碎屑岩进行了系统的岩石学、矿物学和碎屑锆石U-Pb年代学研究。结果表明,宽坪碎屑岩最年轻碎屑锆石年龄峰值为~550Ma,最主要碎屑锆石年龄集中区为~2.5Ga和1.0~0.9Ga,次要年龄集中区为1.3~1.0Ga和850~750Ma。通过与周缘可能物源区的年代学特征对比揭示,宽坪碎屑岩物源主要来自北秦岭新元古代花岗岩与秦岭岩群副片麻岩,部分来自南秦岭和扬子板块北缘新元古代花岗岩以及太古宙基底岩系,缺乏华北板块物质;宽坪碎屑岩的碎屑锆石年龄谱特征与南侧的二郎坪碎屑岩近乎一致,暗示两者可能形成于同一沉积盆地。相平衡模拟结果显示,洛南红土岭宽坪杂岩含石榴子石石英片岩记录了顺时针P-T演化轨迹,峰期变质条件为P=7.17~7.92kbar,T=557~563℃,形成于大陆碰撞过程。结合前人报道宽坪杂岩~440Ma的变质年龄,我们认为在早志留世时期宽坪和二郎坪沉积盆地闭合,北秦岭构造带与华北板块碰撞形成现今的构造格局,在此之前北秦岭构造带与华北板块不具有亲缘性。

     

Relations between metamorphism and orogeny in a typical section of the Indian Himalayas

Summary A comprehensive geological and petrological investigation has been undertaken in an area of about 10 000 km² in the Indian Himalaya (S-Lahul, Himachal Pradesh). The development of mineral assemblages in metamorphic rocks of medium grade is considered to be a dominant Alpine event, although almost exclusively Paleozoic and Precambrian rocks have been involved. The Barrowian type of this metamorphism, ranging from the anchi- to the sillimanite zone, took place under the elavated T-gradient of about 4°C/100 m. It is suggested that normal geothermal conditions prevailed only in the outermost zone of this orogenic belt. In the Late Tertiary this metamorphic series has been moved as a huge nappe upon the Lower Himalaya. During this process a unique feature of reverse metamorphism has been formed. It can be shown that this feature was caused by a combination of metamorphism and very rapid tectonic movements.

---

Beziehungen zwischen Metamorphose und Orogenese in einem typischen Querschnitt des Indischen Himalaya

Zusammenfassung Ein etwa 10 000 km² großes Gebiet des Indischen Himalaya (S-Lahul, Himachal Pradesh) wurde einer umfassenden geologischen und petrographischen Bearbeitung unterzogen. Die Ausbildung der in den mittelgradig metamorphen Gesteinen vorliegenden Mineralparagenesen wird als ein dominant alpines Ereignis betrachtet, obwohl fast nur paläozoische und präkambrische Gesteine einbezogen wurden. Die Metamorphose selbst ist von Barrow-Typus und reicht von der Anchi- bis zur Sillimanitzone. Sie fand unter einem erhöhten Temperaturgradienten von etwa 4°C/100 m statt. Nur in der äußersten Zone des Orogens entsprach der Gradient etwa normalen geothermischen Verhältnissen. Im Spättertiär wurde diese alpin-metamorphe Serie in Form einer mächtigen Kristallindecke dem Niedrigen Himalaya aufgeschoben. Dabei wurde eine einzigartige Zone inverser Metamorphose ausgebildet. Es konnte gezeigt werden, daß diese inverse Metamorphose durch das Zusammenwirken von Metamorphose und sehr rasch ablaufender Tektonik entstand.

---

---

With 13 Figures

---

Dedicated to Prof. Dr. Dr. h. c.B. Sander on the occasion of his 90th birthday.     

A note on fault reactivation

Reactivation of existing faults whose normal lies in the σ₁^′σ₃^′ plane of a stress field with effective principal compressive stresses σ₁^′ >σ₂^′ >σ₃^′ is considered for the simplest frictional failure criterion, τ = μσ_n^′ = μ(σ_n − P), where τ and σ_n are respectively the shear and normal stresses to the existing fault, P is the fluid pressure and μ is the static friction. For a plane oriented at θ to σ₁^′, the stress ratio for reactivation is (σ₁^′/σ₃^′) = (1 + μ cot θ)/(1 − μ tan θ). This ratio has a minimum positive value at the optimum angle for reactivation given by (1/μ) but reaches infinity when θ = 2θ^*, beyond which σ₃^′ < 0 is a necessary condition for reactivation. An important consequence is that for typical rock friction coefficients, it is unlikely that normal faults will be reactivated as high-angle reverse faults or thrusts as low-angle normal faults, unless the effective least principal stress is tensile.     

A note on stilpnomelane mineralogy

Stilpnomelane analyses are classified into two separate groups of ferro- and ferristilpnomelanes on the H₂O(+)-Fe₂O₃/(Fe₂O₃+FeO) diagram. The relation is not comparable with that of oxyhornblende.     

Dykes,sulphide deposits,and regional metamorphism: Criteria for determining their time relationship

Relation of orebodies to adjacent dykes, often obscured by their mutual interpenetration along the contact, may be further masked due to the effects of intervening or subsequent regional metamorphism. The actual chronological sequence of the three episodes (Viz. mineralization intrusion, and dregional metamorphism) — an information often crucial from stratigraphic an oregenetic viewpoints — can be deciphered only through analyses of changes in the fabric, mineralogy, and chemistry of the contact zone and through consideration of heat and mass transfer phenomena across the interface. An attempt is made to establish objective criteria for recognition of the actual sequence of events, after examining numerous cases representing almost all possible time-sequence combinations.

---

Zusammenfassung Die Wechselbeziehungen zwischen Ganggefolgen und Erzkörpern sind oft verborgen durch die widersprechenden Beweise für die gegenseitigen Durchdringungen; sie können weiter kompliziert werden durch die dazwischenkommenden oder späteren Regionalmetamorphosen. Die eigentliche Zeitfolge der drei Vorgänge, nämlich Mineralisation, Eindringen des Ganges und die Regionalmetamorphose — eine aus stratigraphischen und erzgenetischen Gesichtspunkten oft sehr wichtige Angabe — kann nur entziffert werden durch eine sorgfältige Analyse der Gefügenänderungen, der Mineralogie und die chemische Zusammensetzung und Vorgänge in der Kontaktzone, sowie durch eine Betrachtung der Wärme- und Massenübertragungserscheinungen. Die vorliegende Arbeit versucht, Kriterien zur Bestimmung der eigentlichen Altersfolge aufzustellen. Dabei werden mehrere Fälle zitiert, die fast alle möglichen Zeitfolgekombinationen aufweisen.

     

A note on the history and literature of geochemical exploration

The widespread belief that 20th-century geochemical prospecting ‘originated’ in the old world and spread to the United States after 1945 is, at best, highly debatable. A largescale groundwater hydrogeochemical exploration survey was undertaken in Texas and Louisiana in the early 1920's. Boltman (1904) and Lester (1918) described early studies of spring waters associated with uranium ores in the United States. These can perhaps be regarded as forms of orientation surveys. There are now about 2000–3000 literature items dealing with groundwater hydrogeochemical exploration, and the total number of articles from all branches of geochemical prospecting is probably approaching 30,000.