A new view on gold speciation in sulfur-bearing hydrothermal fluids from in situ X-ray absorption spectroscopy and quantum-chemical modeling

Despite the common belief that Au^I complexes with hydrogen sulfide ligands (H₂S/HS⁻) are the major carriers of gold in natural hydrothermal fluids, their identity, structure and stability are still subjects of debate. Here we present the first in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of the stability and structure of aqueous Au^I–S complexes at temperatures and pressures (T–P) typical of natural sulfur-rich ore-forming fluids. The solubility of native gold and the local atomic structure around the dissolved metal in S–NaOH–Na₂SO₄–H₂SO₄ aqueous solutions were characterized at temperatures 200–450 °C and pressures 300–600 bar using an X-ray cell that allows simultaneous measurement of the absolute concentration of the absorbing atom (Au) and its local atomic environment in the fluid phase. Structural and solubility data obtained from XAFS spectra, combined with quantum-chemical calculations of species geometries, show that gold bis(hydrogensulfide) Au(HS)₂⁻ is the dominant Au species in neutral-to-basic solutions (5.5  pH  8.5; H₂O–S–NaOH) over a wide range of sulfur concentrations (0.2 < ΣS < 3.6 mol/kg), in agreement with previous solubility studies. Our results provide the first direct determination of this species structure, in which two sulfur atoms are in a linear geometry around Au^I at an average distance of 2.29 ± 0.01 Å. At acidic conditions (1.5  pH  5.0; H₂O–S–Na₂SO₄–H₂SO₄), the Au atomic environment determined by XAFS is similar to that in neutral solutions. These findings, together with measured high Au solubilities, are inconsistent with the predominance of the gold hydrogensulfide Au(HS)⁰ complex suggested by recent solubility studies. Our spectroscopic data and quantum-chemical calculations imply the formation of species composed of linear S–Au–S moieties, like the neutral [H₂S–Au–SH] complex. This species may account for the elevated Au solubilities in acidic fluids and vapors with H₂S concentrations higher than 0.1–0.2 mol/kg. However, because of the complex sulfur speciation in acidic solutions that involves sulfite, thiosulfate and polysulfide species, the formation of Au^I complexes with these ligands (e.g., AuHS(SO₂)⁰, Au(HS₂O₃)₂⁻, Au(HS_n)₂⁻) cannot be ruled out. The existence of such species may significantly enhance Au transport by high T–P acidic ore-forming fluids and vapors, responsible for the formation of a major part of the gold resources on Earth.     

Plio-Quaternary reactivation of the Neogene margin off NW Algiers, Algeria: The Khayr al Din bank

The Algiers region, northern Algeria, is known to be seismically active, with recurrent large (M>6) earthquakes. Because of the lack of high-resolution bathymetry, the offshore structures remained for a long time poorly known. Thanks to a new marine data base (MARADJA 2003 cruise), the offshore part of the margin is accurately mapped, and new active and recent structures are described. West of the bay of Algiers, the margin enlarges, forming the Khayr al Din bank, interpreted as a tilted block of the passive margin born during the opening of the Algero-Provençal basin. At the slope break, a 80 km-long fault-tip Quaternary fold, namely the Khayr al Din fault, extends at the foot of the margin off NW Algiers and represents the largest active structure of the coastal area, together with the Sahel anticline. We also map for the first time a set of overlapping, en echelon active folds in the upper part of the Khayr al Din bank, located off previously known active structures on land. Most of these faults represent actually a threat for the Algiers region in terms of seismic hazard but also geological hazards, such as tsunamis, as most of them depicts significant dimensions and slip rates. The highest long-term horizontal shortening rate is found on the Khayr al Din fault and is estimated at 0.5 ± 0.1 mm/yr, with a maximal magnitude of 7.3, which provides one of the highest seismogenic potential in the region.A new tectonic framework for the Algiers region is proposed, in which the main south-dipping offshore structure, of opposite vergence relative to most thrusts on land, appears to be nowadays the main driving fault system, as also found further east in the Boumerdès (M 6.8) 2003 rupture zone. The overall apparent pop-up structure of the recent and active faults may result from a progressive migration of the plate limit from the Late Miocene, north-dipping suture zone on land, to the Quaternary, south-dipping main Khayr al Din fault at sea, suggesting a process of subduction inception.     

华南早更新世巨猿动物群的ESR/U-系年代

华南的第四纪喀斯特洞穴堆积含有丰富的哺乳动物群化石,其中以步氏巨猿（Gigantopithecus blacki）为代表的巨猿动物群化石一直备受学术界关注。为建立巨猿动物群演化的绝对年代框架,本文采用牙化石ESR/U-系结合测年法测定重庆龙骨坡、广西田东吹风洞和么会洞以及广西崇左三合大洞动物群的地质年代。牙化石ESR/U-系结合测年法是将牙化石样品的ESR分析（古剂量和年剂量）与U-系分析（U-Th同位素）相结合用来模拟牙齿各个组织在地质时期的U-吸附过程,以计算牙组织中的U对古剂量的贡献,因此ESR/U-系年代比常规ESR年代更准确。本文测定了28个大型哺乳动物牙化石的ESR/U-系年代,结果表明龙骨坡动物群的地质年代为上新世晚期至早更新世早期,可限定为2.86~1.95Ma;吹风洞和么会洞动物群的地质年代在误差范围内一致,为1.97~1.38Ma;三合大洞动物群的地质年代为早更新世晚期至中更新世之初,约910~600ka。     

科克苏-穹库什太古生代构造-岩浆作用及其对西南天山造山时代的约束

天山造山带是古生代多期碰撞增生作用的产物,其确切的造山时代是当前争议较多的热点问题.分布在西南天山的科克苏-穹库什太剖面经历了复杂的构造变形,最明显的两期变形事件分别为朝北的推覆作用和NE-SW韧性走滑作用.本剖面可分为伊犁岩浆岛弧、伊犁结晶基底、高压变质杂岩三个岩石-构造单元.野外可见黑云母花岗闪长岩侵入到绿片岩相变质岩中,岩脉切穿绿片岩中面理构造.通过锆石U-Pb LA-ICPMS测年,科克苏剖面钾长花岗岩的年龄为341±6Ma和338±8Ma,穹库什太黑云母花岗闪长岩的年龄为313±4Ma.其中,花岗闪长岩发生了黑云母定向排列,通过对黑云母进行^40 Ar/^39 Ar测年,获得坪年龄为263.4士0.6Ma,表明该花岗闪长岩受过后期热事件的干扰.地球化学分析表明,黑云母花岗闪长岩属于钙碱性系列,Nb和Ta含量低而Rb,Ba和TH含量很高,与俯冲作用有关的岛弧岩浆岩地球化学组成非常相似.结合前人对该地区高压变质岩、花岗岩和火山岩的研究成果,本文提出,西南天山俯冲-碰撞造山作用发生在晚石炭世之前,研究区后碰撞区域走滑作用标志着西南天山碰撞造山作用在二叠纪之前全部结束.     

Crystal chemistry of suspended matter in a tropical hydrosystem, Nyong basin (Cameroon, Africa)

Suspended matter (SM) from the Nyong basin (Cameroon, Africa), a tropical watershed, was collected by tangential flow ultrafiltration to separate particulate (>0.45 μm) and colloidal (<0.45 μm; >20 kDa) fractions. In this basin, two distinctive systems in a selected small catchment (Nsimi–Zoétélé) of the Nyong river basin have been considered: (i) colourless water (groundwater and spring) with a low suspended load (<3 mg/l) and a low total organic carbon content (TOC<1 mg/l) and (ii) coloured water (Mengong brook and Nyong river), which is organic rich (TOC>10 mg/l) and contains higher amounts of SM (10–20 mg/l) than the colourless water. Freeze-dried samples of SM have been analysed by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), electron paramagnetic resonance spectroscopy (EPR), and visible diffuse reflectance spectroscopy (DRS).

Colourless water mainly contains mineral phases, such as poorly ordered kaolinite, plus quartz and goethite in the particulate fraction, and euhedral kaolinite plus amorphous iron oxyhydroxides in the colloidal fraction. In contrast, the SM in coloured water is mainly organic in nature. The mineral phases in the particulate fraction are similar to those from clear water, but with additional phytoliths and diatom frustules composed of biogenic opal. In the colloidal fraction, complexation of Fe³⁺ and Mn²⁺ with organic matter is evidenced by EPR, together with significant occurrence of Fe oxyhydroxides associated with organic matter.

The sites of Al, Si, Fe, Mn in colloidal fractions derived from spectroscopic analyses are discussed with reference to chemical analyses performed by inductively coupled plasma mass spectrometry. Most of the observed solid phases or species correspond to those expected from published thermodynamic calculations for the same hydrosystem, except the colloidal iron oxyhydroxides in the coloured water. The presence of such iron phases is emphasised since they are expected to have large sorption capacities for numerous trace elements.

The crystal chemistry of SM is used to discuss the origin of the mineral particles transported from the soil to the main rivers in terms of mechanical and chemical erosion processes.     

Surinamite analogs in the MgO-Ga2O3-GeO2 and MgO-Al2O3-GeO2 systems

New germanate analogs of the mineral surinamite, Mg₃Al₄BeSi₃O₁₆, have been synthesized with composition Mg₄A₄Ge₃O₁₆ (A=Al, Ga) and have been characterized by powder X-ray diffraction and transmission electron microscopy. The Al surinamite phase crystallizes with a primitive unit-cell (P2/n, a=10.153(1), b=11.708(2), c=9.920(1) Å, β=110.18 (2)° and Z=4) similar to that of the silicate mineral. The Ga surinamite-like phase crystallizes with a larger unit-cell (C2/c, a=10.308(2), b=23.690(5), c=10.057(l) Å, β=110.23 (2)° and Z=8). High-resolution electron microscopy has shown the common formation of intergrowths between the surinamite and sapphirine structures, illustrating the polysomatic structural relationship between them. Observations of disordered microstructures in the Al surinamite suggest the occurrence of a P2/n?C2/c transformation.     

新疆北部古生代大陆增生构造

古生代亚洲中部是一幅两陆夹一洋、洋中多地体的构造图案，大地构造框架与现代西南太平洋格局十分相似。中亚造山带是晚古生代复杂地体的拼贴带。新疆北部古生代存在4类成因的8个地体构造。它们以裂解陆块地层块体、海山和火山弧的形式散布在中蒙大洋中，诸地体间是一系列的小洋盆。晚古生代，这些地体开始彼此拼贴并导致强烈推覆作用。石炭纪末－二叠纪初，中蒙大洋闭合，散布其中的诸地体分别增生到塔里木大陆北缘和西伯利亚大陆南缘。北天山－准噶尔地区6条蛇绿岩带记录了诸地体间碰撞事件。     

Determination of cirrus radiative parameters from combination between active and passive remote sensing measurements during FRENCH/DIRAC 2001

In the context of the next AQUA Train satellite experiment, airborne measurements were carried out to simulate satellite measurements. They were conducted between September 25 and October 12, 2001, off the coast of southern France over the Atlantic Ocean and over the Mediterranean Sea, respectively. During the intensive Field Radiation Experiment on Natural Cirrus and High-level clouds (FRENCH/DIRAC 2001), natural ice clouds were sampled from in situ and remote sensing measurements. On October 5 and 7, 2001, cirrus cloud decks were described by a complete data set acquired by: (i) in situ microphysical instruments onboard the TBM-700 aircraft: PMS probe, and Polar Nephelometer (ii) and downward-looking radiative instruments onboard the Mystère 20 aircraft: an infrared radiometer, a lidar, a visible imager with polarisation capabilities, and a middle infrared radiometer. Moreover, classical thermodynamical measurements were carried out onboard the Mystère 20. Mean microphysical characteristics of cirrus deck are derived from interpretation of remote sensing measurements. These properties are compared with those derived from in situ microphysical measurements in order to evaluate the radiative impact of natural cirrus clouds.     

Incipient charnockites from southern India:The role of brines

Southern India and Sri-Lanka are the places where "incipient charnockites",i.e.the local transformation of amphibolite-facies gneisses into orthopyroxene-bearing,igneous looking charnockites,have been discovered in the early sixties.The fact that some incipient charnockites occur along a network of brittle fractures,together with CO_2 remnants preserved in mineral inclusions,had called for the role of fluids during charnockite alteration.The present work presents new observations on fluid inclusions and microtextures of incipient charnockites from type localities in southern India.In addition to CO_2-rich fluid inclusions in quartz and feldspar,all of the occurrences have disrupted remnants of concentrated aqueous alkali chloride solutions.CO_2 inclusions are more abundant in paragneiss(Kerala)than in orthogneiss(Karnataka/Tamil Nadu).The finding of disrupted brine inclusions in the Kabbal charnockite is a key link between closely associated massive charnockites and Closepet Granite,both of which also share the brine remnants.All of the occurrences studied here have feldspar or feldspar-quartz microvein networks along grain boundaries of recrystallized quartz,feldspar and orthopyroxene.These metasomatic veins again indicate the action of alkali-exchanging fluids(i.e.,saline solutions).Feldspar microveins,which have been found in most "massive" charnockites,along with the CO_2-rich fluid inclusions,suggest a commonality of incipient charnockite and massive charnockite,both types differing in intensity of interaction with metasomatizing pore fluids.     

SORTAN: An Analytical Method to Determine Fault Slip as Induced by Stress

We propose an analytical method, namely the SORTAN method, to determine the sense of slip on faults as induced by stresses. This method is useful to infer the sense of motion along faults whose surface cannot be directly accessed, such as faults imaged in the subsurface. Because the SORTAN method is based on the Wallace–Bott hypothesis, we assume that the shear stress vector applied to a given fault is parallel to the slip vector on this fault. The assumptions allow for simplification of the method that in turn implies very short calculation times. A concise formalism is adopted. We introduce the stress ratio ' that accounts for (1) the type of stress regime (i.e., strike-slip, reverse or normal) and (2) the degree of anisotropy of the stress state. The formalism of the SORTAN method permits an easy exploration and imaging of the complete collection of slip motions that may theoretically occur on fault planes. The input parameters are the fault plane orientation, the type and anisotropy of the stress regime, and the azimuth of the horizontal stress axes.