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.     

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。     

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.     

Preservation/exhumation of ultrahigh-pressure subduction complexes

Ultrahigh-pressure (UHP) metamorphic terranes reflect subduction of continental crust to depths of 90–140 km in Phanerozoic contractional orogens. Rocks are intensely overprinted by lower pressure mineral assemblages; traces of relict UHP phases are preserved only under kinetically inhibiting circumstances. Most UHP complexes present in the upper crust are thin, imbricate sheets consisting chiefly of felsic units ± serpentinites; dense mafic and peridotitic rocks make up less than  10% of each exhumed subduction complex. Roundtrip prograde–retrograde P–T paths are completed in 10–20 Myr, and rates of ascent to mid-crustal levels approximate descent velocities. Late-stage domical uplifts typify many UHP complexes.

Sialic crust may be deeply subducted, reflecting profound underflow of an oceanic plate prior to collisional suturing. Exhumation involves decompression through the P–T stability fields of lower pressure metamorphic facies. Scattered UHP relics are retained in strong, refractory, watertight host minerals (e.g., zircon, pyroxene, garnet) typified by low rates of intracrystalline diffusion. Isolation of such inclusions from the recrystallizing rock matrix impedes back reaction. Thin-aspect ratio, ductile-deformed nappes are formed in the subduction zone; heat is conducted away from UHP complexes as they rise along the subduction channel. The low aggregate density of continental crust is much less than that of the mantle it displaces during underflow; its rapid ascent to mid-crustal levels is driven by buoyancy. Return to shallow levels does not require removal of the overlying mantle wedge. Late-stage underplating, structural contraction, tectonic aneurysms and/or plate shallowing convey mid-crustal UHP décollements surfaceward in domical uplifts where they are exposed by erosion. Unless these situations are mutually satisfied, UHP complexes are completely transformed to low-pressure assemblages, obliterating all evidence of profound subduction.     

新疆东昆仑木孜塔格蛇绿混杂岩中发现富Nb玄武岩

富Nb 玄武岩以相对高的TiO2 含量、低的LILE/HFSE和LREE/HFSE比值以及(La/Nb)MN＜2为特征,是岛弧环境的典型产物。首次报道发现于新疆东昆仑木孜塔格蛇绿混杂岩中的富Nb玄武岩,并分析了它们的典型地球化学特征和构造环境,表明了它们形成在岛弧环境。     

Crustal structure of the Ruby Mountains and southern Carlin Trend region, Nevada, from magnetotelluric data

We have collected about 150 magnetotelluric (MT) soundings in northeastern Nevada in the region of the Ruby Mountains metamorphic core complex uplift and southern Carlin mineral trend, in an effort to illuminate controls on core complex evolution and deposition of world-class gold deposits. The region has experienced a broad range of tectonic events including several periods of compressional and extensional deformation, which have contributed to the total expression of electrical resistivity. Most of the soundings reside in three east–west profiles across increasing degrees of core uplift to the north (Bald Mountain, Harrison Pass, and Secret Pass latitudes). One short cross-line was also taken to assess an east–west structure to the north of the northern profile. Model resistivity cross-sections were derived from the MT data using a 2-D inversion algorithm, which damps departures of model parameters from an a priori structure. Geological interpretation of the resistivity combines previous seismic, potential field and isotope models, structural and petrological models for regional compression and extension, and detailed structural/stratigraphic interpretations incorporating drilling for petroleum and mineral exploration. To first order, the resistivity structure is one of a moderately conductive, Phanerozoic sedimentary section fundamentally disrupted by intrusion and uplift of resistive crystalline rocks. Late Devonian and early Mississippian shales of the Pilot and Chainman Formations together form an important conductive marker sequence in the stratigraphy and show pronounced increases in conductance (conductivity–thickness product) from east to west. These increases are attributed to graphitization caused by Elko–Sevier era compressional shear deformation and possibly by intrusive heating. The resistive crystalline central massifs adjoin the host stratigraphy across crustal-scale, steeply dipping fault zones. The zones provide pathways to the lower crust for heterogeneous, upper crustal induced, electric current flow. Resistive core complex crust appears steeply bounded under the middle of the neighboring grabens and not to deepen at a shallow angle to arbitrary distances to the west. The numerous crustal breaks imaged with MT may contribute to the low effective elastic thickness (T_e) estimated regionally for the Great Basin and exemplify the mid-crustal, steeply dipping slip zones in which major earthquakes nucleate. An east–west oriented conductor in the crystalline upper crust spans the East Humboldt Range and northern Ruby Mountains. The conductor may be related to nearby graphitic metasediments, with possible alteration by middle Tertiary magmatism. Lower crustal resistivity everywhere under the profiles is low and appears quasi one-dimensional. It is consistent with a low rock porosity (<1 vol.%) containing hypersaline brines and possible water-undersaturated crustal melts, residual to the mostly Miocene regional extension. The resistivity expression of the southern Carlin Trend (CT) in the Pinon Range is not a simple lineament but rather a family of structures attributed to Eocene intrusion, stratal deformation, and alteration/graphitization. Substantial reactivation or overprinting by core complex uplift or Basin–Range extensional events seems likely. We concur with others that the Carlin Trend may result in part from overlap of the large Eocene Northeast Nevada Volcanic Field with Precambrian–Paleozoic deep-water clastic source rocks thickening abruptly to the west of the Pinon Range, and projecting to the north–northwest.     

由膨润土提铝残渣直接合成五配位体有机硅化合物

研究了以膨润土提铝残渣为原料，采用低温加热法直接合成有机硅化合物新方法。由实验确定了最佳的合成条件。用红外光谱法和X射线衍射法分析了合成产物的结构。结果表明，当以碱金属氢氧化物为介质时，合成的产物为五配位体有机硅化合物；在最佳合成条件下，钠盐和锂盐的收率分别为63．0％和44．9％。     

略阳─石泉边界地质体特征

略阳─石泉构造带是一板块缝合带，经历了长期复杂的演化历史。现由不同时期、不同构造体制下的断裂构造系统，裹挟不同构造演化阶段的各类建造─蛇绿混杂岩、陆缘楔状体，岛孤岩浆岩及外来岩块等，共同组成了分隔秦岭、扬子地块的一个特殊边界地质体。     

滇西北金沙江带蛇绿岩,蛇绿混杂岩形成环境及时代

本文对滇西北金沙江带蛇绿岩及其混杂岩的产状、规模，岩石学及岩石化学特征等进行系统的综合研究，并根据大量的化石资料，将该区蛇绿岩的形成时代厘定为晚石炭世至二叠纪，蛇绿要岩的形成时代厘定为早、中三叠世，论证了本区蛇绿岩产于规模较小的洋盆环境之中，由于金沙江洋盆发育阶段较短暂，不具有隔离冈瓦纳及扬子两大古生物地理区系的作用，因此，金沙江缝合带不能构成古特提斯域的主缝合带。