Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

History of crustal growth and recycling at the Pacific convergent margin of South America at latitudes 29°–36° S revealed by a U–Pb and Lu–Hf isotope study of detrital zircon from late Paleozoic accretionary systems

Detrital zircon provides a powerful archive of continental growth and recycling processes. We have tested this by a combined laser ablation ICP-MS U–Pb and Lu–Hf analysis of homogeneous growth domains in detrital zircon from late Paleozoic coastal accretionary systems in central Chile and the collisional Guarguaráz Complex in W Argentina. Because detritus from a large part of W Gondwana is present here, the data delineate the crustal evolution of southern South America at its Paleopacific margin, consistent with known data in the source regions.Zircon in the Guarguaráz Complex mainly displays an U–Pb age cluster at 0.93–1.46 Ga, similar to zircon in sediments of the adjacent allochthonous Cuyania Terrane. By contrast, zircon from the coastal accretionary systems shows a mixed provenance: Age clusters at 363–722 Ma are typical for zircon grown during the Braziliano, Pampean, Famatinian and post-Famatinian orogenic episodes east of Cuyania. An age spectrum at 1.00–1.39 Ga is interpreted as a mixture of zircon from Cuyania and several sources further east. Minor age clusters between 1.46 and 3.20 Ga suggest recycling of material from cratons within W Gondwana.The youngest age cluster (294–346 Ma) in the coastal accretionary prisms reflects a so far unknown local magmatic event, also represented by rhyolite and leucogranite pebbles. It sets time marks for the accretion history: Maximum depositional ages of most accreted metasediments are Middle to Upper Carboniferous. A change of the accretion mode occurred before 308 Ma, when also a concomitant retrowedge basin formed.Initial Hf-isotope compositions reveal at least three juvenile crust-forming periods in southern South America characterised by three major periods of juvenile magma production at 2.7–3.4 Ga, 1.9–2.3 Ga and 0.8–1.5 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf of Mesoproterozoic zircon from the coastal accretionary systems is consistent with extensive crustal recycling and addition of some juvenile, mantle-derived magma, while that of zircon from the Guarguaráz Complex has a largely juvenile crustal signature. Zircon with Pampean, Famatinian and Braziliano ages (< 660 Ma) originated from recycled crust of variable age, which is, however, mainly Mesoproterozoic. By contrast, the Carboniferous magmatic event shows less variable and more radiogenic ¹⁷⁶Hf/¹⁷⁷Hf, pointing to a mean early Neoproterozoic crustal residence. This zircon is unlikely to have crystallized from melts of metasediments of the accretionary systems, but probably derived from a more juvenile crust in their backstop system.     

Geophysical evidence of mud diapirism on the Mediterranean Ridge accretionary complex

Mud volcanoes, mud cones, and mud ridges have been identified on the inner portion of the crestal area, and possibly on the inner escarpment, of the Mediterranean Ridge accretionary complex. Four areas containing one or more mud diapirs have been investigated through bathymetric profiling, single channel seismic reflection profiling, heat flow measurements, and coring. A sequence of events is identified in the evolution of the mud diapirs: initially the expulsion on the seafloor of gasrich mud produces a seafloor depression outlined in the seismic record by downward dip of the host sediment reflectors towards the mud conduit; subsequent eruptions of fluid mud may create a flat topped mud volcano with step-like profile; finally, the intrusion of viscous mud produces a mud cone.The origin of the diapirs is deep within the Mediterranean Ridge. Although a minimum depth of about 400 m below the seafloor has been computed from the hydrostatic balance between the diapiric sediments and the host sediments, a maximum depth, suggested by geometric considerations, ranges between 5.3 and 7 km. The presence of thermogenic gas in the diapiric sediments suggests a better constrained origin depth of at least 2.2 km.The heat flow measured within the Olimpi mud diapir field and along a transect orthogonal to the diapiric field is low, ranging between 16 ± 5 and 41 ± 6 mW m^–2. Due to the presence of gas, the thermal conductivity of the diapiric sediments is lower than that of the host hemipelagic oozes (0.6–0.9 and 1.0–1.15 W m^–1 K^–1 respectively).We consider the distribution of mud diapirs to be controlled by the presence of tectonic features such as reverse faults or thrusts (inner escarpment) that develop where the thickness of the Late Miocene evaporites appears to be minimum. An upward migration through time of the position of the décollement within the stratigraphic column from the Upper Oligocene (diapiric sediments) to the Upper Miocene (present position) is identified.     

Deformation Patterns of an Accretionary Wedge in the Transition Zone from Subduction to Collision Offshore Southwestern Taiwan

Swath bathymetry data and seismic reflection profiles have been used to investigate details of the deformation pattern in the area offshore southwestern Taiwan where the Luzon subduction complex encroaches on the passive Chinese continental margin. Distinctive fold-and-thrust structures of the convergent zone and horst-and-graben structures of the passive margin are separated by a deformation front that extends NNW-ward from the eastern edge of the Manila Trench to the foot of the continental slope. This deformation front gradually turns into a NNE–SSW trending direction across the continental slope and the Kaoping Shelf, and connects to the frontal thrusts of the mountain belt on land Taiwan. However, the complex Penghu submarine canyon system blurs the exact location of the deformation front and nature of many morphotectonic features offshore SW Taiwan. We suggest that the deformation front offshore SW Taiwan does not appear as a simple structural line, but is characterized by a series of N–S trending folds and thrusts that terminate sequentially in an en-echelon pattern across the passive Chinese continental slope. A number of NE–SW trending lineaments cut across the fold-and-thrust structures of the frontal accretionary wedge and exhibit prominent dextral displacement indicative of the lateral expulsion of SW Taiwan. One of the prominent lineaments, named the Yung-An lineament, forms the southeastern boundary of the upper part of the Penghu submarine canyon, and has conspicuous influence over the drainage pattern of the canyon     

砷酸根的液—固界面交换吸附研究——pH和Ca(Ⅱ)的影响

研究ｐＨ和Ｃａ（Ⅱ）对砷酸根在海水与ＮａＣｌ介质中对水合氧化物和粘土矿物上交换吸附的影响：（１）在酸性条件下和海水及ＮａＣｌ介质中，砷酸根在针铁矿上的交换率Ｅ（％）—ｐＨ曲线呈平顶峰型、在δ－ＭｎＯ呈峰型、在粘土上分别呈双峰型和肩峰型。这是砷酸根存在多种形式与固体表面发生离子／配位子交换以及介质中阴离子竞争交换吸附共同作用的结果。（２）在碱性条件下的海水介质中，砷酸根与水合氧化物和粘土矿物的Ｅ（％）—ｐＨ曲线都呈Ｖ型，这是因为生成了具有一定结构的液—固界面三元络合物之故。（３）在ＮａＣｌ介质中，Ｃａ加入起促进作用，再次证明液—固界面三元络合物生成机理与Ｖ型曲线的内在关系     

康定杂岩Rb-Sr、Sm-Nd同位素系统及其意义

通过对康定—冕宁地区出露的英云闪长岩、黑云角闪斜长片麻岩、角闪变粒岩全岩及其中所分离出的角闪石、黑云母、斜长石、钾长石的Rb-Sr、Sm-Nd同位素的系统测定,结合岩石的锆石U-Pb年龄结果,确定这些变质杂岩由于经历了复杂的形成过程与变质历史,Rb-Sr、Sm-Nd同位素体系难以确定其结晶年龄。由单矿物与全岩Rb-Sr、Sm-Nd体系拟合的~700 M a的等时线年龄反映了角闪岩相-高角闪岩相的变质作用年龄。Sm-Nd同位素体系由于在变质作用过程中的部分开放性,很容易给出无意义的较老的混合年龄。康定杂岩结晶后并没有经历麻粒岩相变质作用,区域上所含的麻粒岩透镜体可能是新元古代(773~721 M a)期间由Rod in ia超大陆裂解产生的新生洋壳向扬子克拉通陆块俯冲消减过程的变质产物。俯冲到一定深度后,由于板片被拉断,软流圈上涌导致变质洋壳板片岩石、先前底侵变质的镁铁质岩石及扬子陆块长英质基底岩石发生部分熔融,以镁铁质岩石熔融产生的熔浆为主(>70%),与长英质基底岩石熔融产生的熔浆混合形成w(Na2O)/w(K2O)>1的TTG组合。     

The origin of accretionary lapilli

Experimental investigations in a recirculating wind tunnel of the mechanisms of formation of accretionary lapilli have demonstrated that growth is controlled by collision of liquid-coated particles, due to differences in fall velocities, and binding as a result of surface tension forces and secondary mineral growth. The liquids present on particle surfaces in eruption plumes are acid solutions stable at 100% relative humidity, from which secondary minerals, e.g. calcium sulphate and sodium chloride, precipitate prior to impact of accretionary lapilli with the ground. Concentric grain-size zones within accretionary lapilli build up due to differences in the supply of particular particle sizes during aggregate growth. Accretionary lapilli do not evolve by scavenging of particles by liquid drops followed by evaporation — a process which, in wind tunnel experiments, generates horizontally layered hemispherical aggregates. Size analysis of particles in the wind tunnel air stream and particles adhering to growing aggregates demonstrate that the aggregation coefficient is highly grain-size dependent. Theoretical simulation of accretionary lapilli growth in eruption plumes predicts maximum sizes in the range 0.7–20 mm for ash cloud thicknesses of 0.5–10 km respectively.     

On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

塔里木克拉通东北缘二叠纪镁铁质岩浆氧化物与硫化物成矿条件对比

塔里木克拉通东北缘坡北、磁海等地二叠纪幔源岩浆活动形成了镍钴硫化物矿床和铁钴氧化物矿床，两者赋矿镁铁 超镁铁岩体的年龄相近(290~260 Ma)，主、微量元素和Sr Nd Hf同位素组成相似，分配系数接近的微量元素比值分布于相同趋势线，揭示两者岩浆源区相同，可能为俯冲板片流体交代的亏损地幔或软流圈地幔。两类矿床镁铁 超镁铁质岩中Co与Ni含量正相关，Co主要富集在基性程度高的岩石中；块状硫化物与磁铁矿矿石中Co与Ni相关性差，Co和Ni具有不同的富集机制，Co热液富集作用明显。北山镁铁 超镁铁杂岩体是地幔柱相关软流圈上涌，诱发俯冲板片交代的亏损岩石圈地幔发生部分熔融，形成的高镁母岩浆演化过程中经历壳源混染、硫化物饱和富集镍钴形成铜镍钴硫化物矿床，富铁母岩浆氧逸度高、富水，岩浆分离结晶磁铁矿、叠加热液作用富集钴，形成铁钴氧化物矿床。     

Lermontovskoe Tungsten Skarn Deposit: the Oldest Mineralization in the Sikhote-Alin Orogen, Far East Russia

Abstract. Lermontovskoe tungsten skarn deposit in central Sikhote-Alin is concluded to have formed at 132 Ma in the Early Cretaceous, based on K-Ar age data for muscovite concentrates from high-grade scheelite ore and greisenized granite. Late Paleozoic limestone in Jurassic - early Early Cretaceous accretionary complexes was replaced during hydrothermal activity related to the Lermontovskoe granodiorite stock of reduced type. The ores, characterized by Mo-poor scheelite and Fe^3+- poor mineral assemblages, indicate that this deposit is a reduced-type tungsten skarn (Sato, 1980, 1982), in accordance with the reduced nature of the granodiorite stock.
The Lermontovskoe deposit, the oldest mineralization so far known in the Sikhote-Alin orogen, formed in the initial stage of Early Cretaceous felsic magmatism. The magmatism began shortly after the accretionary tectonics ceased, suggesting an abrupt change of subduction system. Style of the Early Cretaceous magmatism and mineralization is significantly different between central Sikhote-Alin and Northeast Japan; reduced-type and oxidized-type, respectively. The different styles may reflect different tectonic environments; compressional and extensional, respectively. These two areas, which were closer together before the opening of the Japan Sea in the Miocene, may have been juxtaposed under a transpressional tectonic regime after the magmatism.