水镁石—水体系氧同位素分馏系数的低温实验研究

在15—120℃的低温范围内分别应用氮化镁法、氯化镁法和氧化镁法3种化学合成方法,对水镁石-水体系氧同位素分馏系数进行了实验测定。所有合成样品的晶体结构均由XRD测定,其形貌特征则由SEM确定。应用3种不同合成方法得到了一致的水镁石—水体系氧同位素分馏系数,证明同位素平衡分馏已经达到。在实验温度范围内,水镁石—水体系氧同位素分馏系数主要决定于温度,而溶液的酸碱度、化学组分和陈化时间的影响不明显。由实验数据得到的氧同位素分馏曲线方程为:10~3Inα=1.59×10~6/T~2-14.10(r=0.9921)。结合前人对三水铝石—水体系和针铁矿—水体系氧同位素分馏系数的低温实验测定,可以得到氢氧化物中金属M—OH键的~(18)O富集顺序:Al~(3+)-OH>Fe~(3+)-OH>Mg~(2+)-OH。应用化学合成方法实验测定低温条件下水镁石—水体系氧同位素分馏系数,不仅克服了同位素交换反应实验的一些缺陷(如交换速率缓慢、仪器设备复杂昂贵等),而且可以应用不同的化学合成反应机理来检验同位素平衡是否达到,这为研究低温地球化学过程作用提供了有价值的基本参数。     

Ultrahigh-pressure metamorphic rocks and the thermal evolution of continent collision belts

Abstract Coesite-bearing eclogites exposed in the Alpine, Qinling-Dabie (China), Caledonian, and Ural orogenic belts provide insight into the time-dependent thermal structure of continent collision belts. Coesite-bearing eclogites record peak metamorphic temperatures of 550-900°C at pressures ≥ 2.5 GPa reflecting anomalously cool conditions at depths of 90 km or more. The low temperatures recorded by coesite-bearing eclogites strongly suggest formation in a convergent plate margin where the downward advection of cool lithosphere depresses isotherms on a regional scale. Subduction zone pressure-temperature (P-T) paths calculated using a two-dimensional finite-difference model predict steady-state temperatures of 450-650°C at 100 km depth at the slab-mantle interface for convergence rates of 10 to 100 mm/yr. Coesite-bearing eclogites record peak temperatures ~100-250°C higher, possibly reflecting (i) formation during the early stages of convergence prior to the achievement of thermal steady state; (ii) attainment of peak metamorphic temperatures during decompression (exhumation); (iii) formation during slow, <10 mm/yr, convergence; or (iv) uncertainties in the modeling parameters. Retrograde P-T paths determined for coesite-bearing eclogites from the western Alps and China indicate cooling during decompression from depths of ~100 km. Cooling of eclogite terrains during exhumation requires loss of heat downward into lithosphere that continues to subduct beneath the eclogites, loss of heat upward into the cooler hanging wall of a large-scale normal fault/shear zone, or a combination of the two scenarios.     

Partially retrograded eclogites of the Münchberg Massif, Germany: records of a multi-stage Variscan uplift history in the Bohemian Massif

Abstract Eclogites with a wide range in bulk composition are present in the Münchberg Massif, part of the Variscan basement of the Bohemian Massif in north-east Bavaria. New analyses of the primary phases garnet, omphacite, phengite and amphibole, as well as the secondary phases clinopyroxene II, various amphiboles, biotite/phlogopite, plagioclase, margarite, paragonite, prehnite and pumpellyite, reveal a complex uplift history. New discoveries were made of samples with very jadeite-rich primary omphacite as well as a secondary omphacite in a symplectite with albite. Various geothermobarometric techniques, together with thermodynamic databases (incorporating separately determined activity–composition values) and experimental data have clustered the minimum conditions for the primary assemblages to the P–T range 650 ± 60° C, 14.3 ± 1 kbar. However, jadeite (in omphacite)–kyanite–paragonite (in phengite) and zoisite–grossular (in garnet)–kyanite–quartz relationships suggests pressures of 25–28 kbar at the same temperatures. The fact that the secondary omphacite–plagioclase assemblage yields pressures within a few hundred bars of the minimum pressures for the plagioclase-free assemblages strongly suggests that the minimum values are serious underestimates.
Zoning, inclusion suites and breakdown reactions of primary phases, in addition to new minerals formed during uplift, define a polyphase metamorphic evolution which, from geochronological evidence, occurred solely within the Variscan cycle. The complex breakdown in other Bohemian Massif eclogites and the distinct variation in their temperatures during uplift suggest a multi-stage thrusting model for the regional evolution of the eclogites. Such an evolution has significance with respect to incorporation of mantle slices into crustal sequences and fluid derivation from successively subducted units, possibly driving the breakdown reactions.     

Tectonic overpressure in competent mafic layers and the development of isolated eclogites

Abstract Variation in the state of stress during heterogeneous deformation should be reflected in variation in the effective pressure of metamorphic reactions, whether this is mean stress or the normal stress acting across the reacting interface. The magnitude of this pressure variation will determine whether it is discernible in the preserved metamorphic mineral assemblages of heterogeneously deformed rocks. The magnitude of the mean stress difference across a non-slipping interface between two materials with viscosity ratio >c. 20:1 is effectively equal to the maximum shear stress for flow in the more viscous material. Progressive shortening of the interface results in a higher mean stress in the more competent material, whereas extension results in a lower mean stress. For high-P/low-T eclogite facies conditions, current experimental data indicate that clinopyroxene- and garnet-rich layers of eclogite should be very strong and that pressure differences of up to 800 MPa (8 kbar) between competent layer and weaker matrix may be possible. Such high values can be obtained in widely separated competent layers for values of bulk stress in the overall multilayer that are much lower (by a factor approaching the viscosity ratio). Extrusion of material between more rigid plates, which has been proposed as a regional mechanism of lateral ‘continental escape’for both the Alps and the Himalayas, should also be accompanied by a lateral gradient in effective pressure; otherwise extrusion could not occur. Maximum mean stresses with magnitudes that are many times the maximum shear stress required for plastic flow should develop for deformation zones that are long relative to their width (e.g. around 20 times for a width-to-thickness ratio of 10). Tectonic overpressure in progressively shortened competent layers, particularly in regions of extrusion between more rigid plates, might help explain the occurrence of isolated layers and pods of low-T eclogite (<550°C) with estimated peak pressures markedly in excess of those in the surrounding matrix. It cannot explain the occurrence of isolated high-T eclogites, because at temperatures >c. 550°C, the dramatic weakening of clinopyroxene in the power-law creep field precludes the development of significant overpressures in eclogite layers.     

Sm-Nd isotopic evidence on the age of eclogitization in the Zermatt-Saas ophiolite

Rocks within the Zermatt-Saas ophiolite of the western Alps have undergone eclogite facies metamorphism during subduction prior to the Alpine collision. The metamorphic history of these rocks is well defined, with eclogitic assemblages being followed by the limited growth of blueschist assemblages of glaucophane and paragonite. Subsequent greenschist alteration occurs adjacent to faults, veins and metasediments. Away from such sources of water, retrogression is very limited. Sm-Nd isotopic analyses of an essentially unretrogressed eclogitic metabasalt suggest that eclogite facies metamorphism occurred at 52 ± 18 Ma. The large uncertainty is due to the presence of very small amounts of Nd-rich epidote present as inclusions within garnet. As the closure temperature of garnet to Sm & Nd is thought to be >600C, resetting due to post-high-pressure diffusion is thought to be insignificant. Given the fine-grained protolith to the sample analysed, and its extensive deformation under eclogite facies conditions, incomplete homogenization of pre-metamorphic isotopic variations is also considered unlikely to be responsible for the young age. A Tertiary age of eclogitization means that models of early Alpine evolution based on the cessation of high-pressure metamorphism in the Cretaceous need to be revised.     

Low-temperature, polysulfide reactions of conjugated ene carbonyls: A reaction model for the geologic origin of S-heterocycles

The theoretical basis for a type of reaction of sulfur-acceptor carbon molecules with donor catenated forms of sulfur is presented. The reactions between conjugated ene carbonyls as sulfur-acceptors and polysulfide as a sulfur donor are described. The scope of this reaction is broadened by demonstrating that the room-temperature action of polysulfide on dienones produces thiophenes. Evidence is given for the structure of 2-benzoyl-5-phenylthiophene, resulting from 1,5-diphenyl-2,4-pentadien-1-one, and 2-acetyl-5-phenylthiophene, resulting from 6-phenyl-3,5-hexadien-2-one. Evidence is also presented for the structure of 2,4-dibenzoyl-3,5-diphenylthiolane, the product resulting from the action of polysulfide on the mixture of benzaldehyde and acetophenone. The same thiolane is shown to result as the minor thiolane component when chalcone reacts with polysulfide in 80% water/20% ethanol. The major component is a known rearranged thiolane identified by its physical properties. The reactiol of chalcone and polysulfide in ethanol at 0 or 25°C results in thiolane formation as evidenced by the isolation of 2,4-dibenzoyl-3,5-diphenylthiolane. However, the reaction of the same two compounds in boiling methanol (65°C) results in a competitive hydrogenation of chalcone giving dihydrochalcone in addition to the formation of thiolane. The demonstration of the low-temperature reaction of polysulfide with conjugated ene carbonyls in the present work adds an additional pathway for possible formation of S-heterocycles in the geosphere.