Structure of the αFexAl1:xOOH solid solution

The three-dimensional local organisation around Fe atoms in a natural diaspore (Al_0.9955Fe_0.0045OOH) has been investigated by angular measurements of X-ray absorption spectra. It is demonstrated that in a single crystal of diaspore, the absorption cross-section exhibits the special case of trichroism where three independent measurements are needed to determine the absorption cross-section for any direction of polarization. Extended X-ray absorption fine structure (EXAFS) spectra were thus recorded at the following orientations of the polarization vector: , , and . The incoming white beam was monochromatized using two Si(331) crystals, which deliver at the Fe K-edge a completely linearly polarized X-ray beam. The reliability of our measurements was checked by comparing the isotropic EXAFS spectrum calculated from the three orthogonal measurements to the one of the diaspore powder recorded at the magic angle. It is shown that Fe³⁺ ions are not randomly distributed within the diaspore framework. Furthermore, only part of the Fe³⁺ ions substitutes Al, the others being located in the channels of the structure. The 3D local structure of the Fe domains has been modeled assuming hematite-like clusters of three Fe octahedra topotactically grafted to aluminous chains. These Fe clusters are thought to represent ancient multinuclear Fe surface complexes having formed at the time of the diaspore growth, and being sealed in its bulk structure. The whole crystal of diaspore is then thought to have kept the memory of the heterogeneous nucleation mechanism of these hematite nuclei. In addition to the well-known examples of atom segregations, ion vacancies, and intergrowths of discrete phases, this new type of crystal defect represents another evidence of non-equilibrium crystallization process under the thermodynamic and kinetic conditions that prevail at the earth's surface.     

An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.     

Iron (III)-silica interactions in aqueous solution: insights from X-ray absorption fine structure spectroscopy

The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (m_Fe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H₂O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (N_edge = 1-2; N_corner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Fe_edge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe₂Si_1-2 and Fe₃Si_2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO₆-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (R_Fe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters.     

华北克拉通南缘中条山-嵩山地区1.78Ga基性岩墙群的地球化学特征及构造环境

幔源岩浆侵位产生的基性岩墙群是地壳伸展裂解的重要标志。华北克拉通南缘中条山-嵩山地区出露有大量的中元古代基性岩墙群,对其研究将有助于深入了解华北克拉通中元古代构造演化特征。其岩石类型以辉绿岩为主,少量辉长辉绿岩和辉绿玢岩;主要造岩矿物为斜长石和单斜辉石,其它矿物包括角闪石、Fe-Ti氧化物、磷灰石、黑云母、碱性长石和石英。锆石SHRIMPU-Pb年龄为1785±18Ma,代表岩墙的结晶年龄。岩石K2O+Na2O含量为3.63%～6.18%,K2O/Na2O比值为0.73～1.38,FeOT含量较高(10.03%～13.59%),属于拉斑玄武岩系列。岩石的稀土元素含量高(142×10-6～381×10-6),亏损Nb、Ta、Zr、Hf等高场强元素,富集Rb、Ba、La等大离子亲石元素,全岩εNd(t)值为-6.2～-8.1。岩墙的固结指数(SI)和MgO含量呈明显的正相关关系,说明幔源岩浆发生过明显的结晶分异作用。地球化学分析表明,研究区基性岩墙属于板内拉斑玄武岩系列,与熊耳群火山岩有相似的地球化学特征;基于两者紧密的产出关系,我们认为该区岩墙可能是熊耳群火山岩的通道岩墙,共同代表了华北克拉通东、西陆块碰撞后伸展事件。     

Stable isotope analysis of consumer food webs indicates ecosystem recovery following prolonged drought in a subtropical estuarine lake

Assessing changes in food-web structure provides a useful monitoring tool for gauging the resilience of ecosystems in the face of climatic impacts. We consider the ecological resilience of a large estuarine lake (St Lucia Estuary, South Africa) in the wake of an extreme climatic event (prolonged drought). Using carbon and nitrogen stable isotopes, food-web structure was assessed at five sites across the estuary during the winter and spring of 2013. Sampling occurred approximately three years after heavy rains flooded the system and returned it to a relatively diluted state following an almost decade-long drought that decimated food webs in the upper parts of the estuary due to hypersalinity effects. Comparisons of niche width and variance of consumer food webs among sites revealed a general homogenisation of food webs across the entire system, contrasting with the spatial differentiation of food webs documented during the drought phase. Our results indicate that the estuary is able to maintain ecological resilience at the whole-system level in the face of an extreme drought. This is likely facilitated by source pools of species residing in the relatively stable lower estuary, which are able to rapidly recolonise areas denuded by drought in the upper estuary.     

Antimony speciation in saline hydrothermal fluids: A combined X-ray absorption fine structure spectroscopy and solubility study

Solubility of senarmontite (Sb₂O₃, cubic) in pure water and NaCl-HCl aqueous solutions, and local atomic structure around antimony in these fluids were characterized using in situ X-ray absorption fine structure (XAFS) spectroscopy at temperatures to 450 °C and pressures to 600 bars. These experiments were performed using a new X-ray cell which allows simultaneous measurement of the absolute concentration of the absorbing element in the fluid, and atomic environment around the absorber. Results show that aqueous Sb(III) speciation is dominated by the complex in pure water, mixed Sb-hydroxide-chloride complexes in acidic NaCl-HCl solutions (2 m NaCl-0.1 m HCl), and by Sb-chloride species in concentrated HCl solutions (3.5 m HCl). Interatomic Sb-O and Sb-Cl distances in these complexes range from 1.96 to 1.97 Å and from 2.37 to 2.47 Å, respectively. These structural data, together with senarmontite solubility determined from XAFS spectra, were complemented by batch-reactor measurements of senarmontite and stibnite (Sb₂S₃, rhombic) solubilities over a wide range of HCl and NaCl concentrations from 300 to 400 °C. Analysis of the whole dataset shows that Sb(III) speciation in high-temperature moderately acid (pH > 2-3) Cl-rich fluids is dominated by mixed hydroxy-chloride species like Sb(OH)₂Cl° and Sb(OH)₃Cl⁻, but other species containing two or three Cl atoms appear at higher acidities and moderate temperatures (?300 °C). Calculations using stability constants retrieved in this study indicate that mixed hydroxy-chloride complexes control antimony transport in saline high-temperature ore fluids at acidic conditions. Such species allow for a more effective Sb partitioning into the vapor phase during boiling and vapor-brine separation processes occurring in magmatic-hydrothermal systems. Antimony hydroxy-chloride complexes are however minor in the neutral low- to moderate-temperature solutions (?250-300 °C) typical of Sb deposits formation; the antimony speciation in these systems is dominated by Sb(OH)₃ and potentially Sb-sulfide species.     

铜陵狮子山地区中酸性侵入岩锆石SHRIMP U-Pb定年及岩浆作用的深部过程

铜陵狮子山地区中酸性侵入岩锆石SHRIMP U-Pb定年结果表明,白茫山辉石二长闪长岩、鸡冠山和大团山石英二长闪长岩以及胡村花岗闪长岩的年龄分别为:138.21 ±0.82Ma、139.9 ±1.1Ma、139.3 ±1.2Ma和140.9 ±1.2Ma.岩浆侵位顺序为花岗闪长岩→石英二长闪长岩→辉石二长闪长岩.根据锆石SHRIMP U-Pb年龄变化范围,推测该区岩浆活动持续的时间约为15Ma,且岩浆属脉动式多次侵位,后期岩浆侵位的热使早期岩体中已结晶的锆石发生熔解、重结晶,形成新的锆石.地下深部岩浆活动频繁,形成了多级岩浆房,使得本区的莫霍面界线不明显.     

The solubility of nantokite (CuCl(s)) and Cu speciation in low-density fluids near the critical isochore: An in-situ XAS study

The solubility of nantokite (CuCl_(s)) and the structure of the predominant copper species in supercritical water (290-400 bar at 420 °C; 350-450 °C at 290 bar; 500 °C at 350 bar; density = 0.14-0.65 g/cm³) were investigated concurrently using synchrotron X-ray absorption spectroscopy (XAS) techniques. These conditions were chosen as they represent single phase solutions near the critical isochore, where the fluid density is intermediate of typical values for vapour and brine and is highly sensitive to even small changes in pressure. X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption spectroscopy (EXAFS) analyses show that aqueous copper occurs in a slightly distorted linear coordination in the solutions studied, with an average of 1.35(±0.3) Cl and 0.65(±0.3) O neighbours. The solubility of CuCl_(s) decreases exponentially with decreasing water density (i.e., decreasing pressure at constant temperature), in a manner similar to the solubility behaviour of salts such as NaCl in water vapour. Based on this similarity, an apparent equilibrium constant for the dissolution reaction of 0.5 ± 0.4 was calculated from a regression of the data at 420 °C, and it was determined that each Cu atom is solvated by approximately three water molecules. This indicates that under these conditions, copper solubility is controlled mainly by the structure of the second-shell hydration, which is essentially invisible to the XAS techniques used in this study.These results demonstrate that for a supercritical fluid near the critical isochore, decreasing pressure may initiate precipitation of copper even before boiling or phase separation. Such a process could be responsible for near-surface ore deposition in seafloor hydrothermal systems, where supercritical fluids experience rapid pressure changes during the transition between lithostatic and hydrostatic domains.