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     

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.     

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.     

矿产开发与环境保护

通过国内多个矿区实例，较系统地叙述了矿产资源开发导致的生态环境破坏和污染状况。表明矿产开发中对环境污染的途径包括河流、土壤、等。最后简要介绍了国内、国外几种对采矿污染比较有效的防治措施。     

Mise au point d'un milieu de culture pour l'étude de l'altération de silicates en présence de Pseudomonas aeruginosa

The influence of microorganisms on mineral alteration is not easy to determine in environmental conditions, because of the difficulty to raise for comparison purposes an identical but abiotic system. Another problem in this context is the choice of reliable tracers to evaluate the alteration rate of materials during in vitro experiments. To face such difficulties, we elaborated a defined medium allowing both the growth of Pseudomonas aeruginosa and a precise measurement of the elements solubilized from the minerals. Thanks to this medium, we were able to quantitatively determine the amounts of major elements solubilized from the materials in the presence of bacterial growth, compared to a sterile system. Moreover, the analysis by ICP-MS of trace elements was possible after a chromatographic treatment, which selectively eliminated 99% of the sodium content of the medium. To cite this article: G. Aouad et al., C. R. Geoscience 337 (2005).     

Three dimensional seismic studies of deep-water hazard-related features on the northern slope of South China Sea

Mass transport deposits and geological features related to fluid flow such as gas chimneys, mud diapirs and volcanos, pockmarks and gas hydrates are pervasive on the canyon dominated northern slope of the Pearl River Mouth basin of the South China Sea. These deposits and structures are linked to serious geohazards and are considered risk factors for seabed installations. Based on high resolution three dimensional seismic surveys, seismic characteristics, distributions and origins of these features are analyzed. A distribution map is presented and geometrical parameters and spatial distribution patterns are summarized. Results show that various groups of the mapped features are closely tied to local or regional tectonism and sedimentary processes. Mass transport complexes are classified as slides near the shelf break, initially deformed slumps on the flanks of canyons and highly deformed slumps on the lower slope downslope of the mouth of canyons. We propose them to be preconditioned by pore pressure changes related to sea level fluctuations, steep topography, and fluid and fault activities. Gas chimneys are mainly located in the vicinity of gas reservoirs, while bottom-simulating reflectors are observed within the gas chimney regions, suggesting gas chimneys serve as conduits for thermogenic gas. Mud diapirs/volcanos and pockmarks are observed in small numbers and the formation of pockmarks is related to underlying gas chimneys and faults. This study aims at reducing risks for deep-water engineering on the northern slope of South China Sea.     

Stratigraphic evolution of Eocene clinoforms from northern Santos Basin,offshore Brazil: Evaluating controlling factors on shelf-margin growth and deep-water sedimentation

In order to assess the controlling factors on the evolution of a shelf margin and the timing of sediment transfer to deep waters, a seismic stratigraphic investigation was carried out in the Eocene interval of northern Santos Basin, offshore Brazil. The studied succession configures a complex of prograding slope clinoforms formed in a passive margin and encompasses five seismic facies and their respective depositional settings: shelf-margin deltas/shorefaces, oblique slope clinoforms, sigmoidal slope clinoforms, continental to shelfal deposits and mass-transport deposits. These are stratigraphically arranged as seven depositional sequences recording a total shelf-edge progradation of about 35 km and a progradation rate of 1,75 km/My. Two main types of sequences can be recognized, the first one (type A) being dominated by oblique slope clinoforms and shelf-margin deltas/shorefaces in which shelf-edge trajectories were essentially flat to descending and extensive sandy turbidites were deposited on the foreset to bottomset zones. Sequences of this type are dominated by forced-regressive units deposited during extensive periods of relative sea-level fall. Type B comprises an upper part represented by aggradational shelfal deposits and a lower part composed of mass-transport deposits and high-relief sigmoidal clinoforms with descending shelf-edge trajectory. Steep slump scars deeply cut the shelfal strata and constitutes the boundary between the two intervals observed in type B sequences. Sandy turbidites occur at the same frequency in both forced- and normal-regressive units but are more voluminous within forced-regressive clinoforms associated with shelf-margin deltas/shorefaces. Major slope failures and mass-transport deposits, by the other hand, occurred exclusively in type B sequences during the onset of sea-level fall and their volume are directly related to the thickness of the shelfal sediments formed during the pre-failure normal regressions.     

壳聚糖硫酸酯金属配合物的抗氧化活性

以吩嗪硫酸甲酯-NADH为超氧阴离子自由基(O_2~(·-))产生、检测体系和EDTANa_2-Fe(Ⅱ)-H_2O_2为羟自由基(~·OH)产生、检测体系,对壳聚糖硫酸酯铜、锌配合物和不同分子质量壳聚糖进行了抗O_2~(·-)和~·OH自由基的活性研究.结果表明,壳聚糖硫酸酯金属配合物对于O_2~(·-)自由基的清除能力明显高于壳聚糖,在质量浓度为0.025 g/L时,壳聚糖硫酸酯铜配合物对O_2~(·-)自由基的清除能力达到94.18%,壳聚糖硫酸酯锌配合物达到93.19%;壳聚糖硫酸酯铜、锌配合物对~·OH自由基的清除能力(67.39%、60.46%)低于相同分子质量的壳聚糖(88.06%),而高于高分子质量壳聚糖761 ku(18.71%);壳聚糖分子质量大小对O_2~(·-)和~·OH自由基的清除能力有较大影响,质量浓度为1.6 g/L壳聚糖分子质量为20 ku时,对O_2~(·-)清除率达54.69%,而分子质量在761 ku时,对O_2~(·-)清除率仅为35.50%;各样品对O_2~(·-)和~·OH自由基的清除能力均随着质量浓度的增加而上升,壳聚糖硫酸酯铜、锌配合物在相当低的浓度下(0.025 g/L)就可以达到明显清除O_2~(·-)自由基的效果(≥90%).