沉积地球科学若干理论问题的演革与启示——献给业治铮教授八十华诞

沉积地球科学中若干理论概念经过百余年的争论与探索，已经成为建立在地质现象有序性的基础上，以渐进演化和突变事件为指导思想，以活动论作为世界观，以模拟对比作为主要方法手段，以三维空间作为探索方向的成熟的地球科学分支学科。仅以崇敬的心情献上此文，庆祝业治铮教授八十年诞。     

Regional variability in dust‐on‐snow processes and impacts in the Upper Colorado River Basin

Dust deposition onto mountain snow cover in the Upper Colorado River Basin frequently occurs in the spring when wind speeds and dust emission peaks on the nearby Colorado Plateau. Dust loading has increased since the intensive settlement in the western USA in the mid 1880s. The effects of dust‐on‐snow have been well studied at Senator Beck Basin Study Area (SBBSA) in the San Juan Mountains, CO, the first high‐altitude area of contact for predominantly southwesterly winds transporting dust from the southern Colorado Plateau. To capture variability in dust transport from the broader Colorado Plateau and dust deposition across a larger area of the Colorado River water sources, an additional study plot was established in 2009 on Grand Mesa, 150 km to the north of SBBSA in west central, CO. Here, we compare the 4‐year (2010–2013) dust source, deposition, and radiative forcing records at Grand Mesa Study Plot (GMSP) and Swamp Angel Study Plot (SASP), SBBSA's subalpine study plot. The study plots have similar site elevations/environments and differ mainly in the amount of dust deposited and ensuing impacts. At SASP, end of year dust concentrations ranged from 0.83 mg g^?1 to 4.80 mg g^?1, and daily mean spring dust radiative forcing ranged from 50–65 W m^?2, advancing melt by 24–49 days. At GMSP, which received 1.0 mg g^?1 less dust per season on average, spring radiative forcings of 32–50 W m^?2 advanced melt by 15–30 days. Remote sensing imagery showed that observed dust events were frequently associated with dust emission from the southern Colorado Plateau. Dust from these sources generally passed south of GMSP, and back trajectory footprints modelled for observed dust events were commonly more westerly and northerly for GMSP relative to SASP. These factors suggest that although the southern Colorado Plateau contains important dust sources, dust contributions from other dust sources contribute to dust loading in this region, and likely account for the majority of dust loading at GMSP. Copyright © 2015 John Wiley & Sons, Ltd.     

Coordination and valent state of nickel ions in beryl and chrysoberyl crystals

We have studied the polarized optical absorption and the EPR spectra of Ni-doped beryls grown by hydrothermal, flux and gas-transport methods, and chrysoberyl grown by the Czochralski and flux methods. In beryls, three groups of bands belonging to three various Ni centres were distinguished by analysis of the absorption band intensities. The first group, bands with maximums at 21740 (E ⊥ c), 17240 (E || c) and 9260 (E ⊥ + || c), 7140 (E || + ⊥ c) cm⁻¹, are due to Ni³⁺ in octahedral Al³⁺ site. The second group is bands at 25640 (E ⊥ c), 22220 (E || c) and 13520 (E || + ⊥ c), 13160 (E ⊥+ || c) cm⁻¹ and 8930 (E ⊥ + || c), 7460 (E || c) cm⁻¹, which are caused by Ni²⁺ in octahedral Al³⁺ site. Weak wide bands at 17540 (E ⊥ c), 15500 (E || c) cm⁻¹ and 6580 (E || + ⊥ c), 5950 (E || c) cm⁻¹ are related to Ni²⁺ in tetrahedral Be²⁺ site. The occurrence of Ni ions in Be²⁺ site is proved by the EPR spectra of ^1VNi⁺ in γ-irradiated samples. According to the spectra of optical absorption of Ni-doped chrysoberyl, two types of Ni centres have been established: Ni³⁺ and Ni²⁺ ions in octahedral Al³⁺ sites. From the EPR spectra of the X-ray irradiated crystals BeAl₂O₄: Ni, it follows that 68% of Ni⁺ ions occupy octahedral Al³⁺ sites with mirror symmetry and 32% are in Al³⁺ sites with inversion symmetry. In the approximation of trigonal field with regard to Trees correction, the energy levels of Ni³⁺ and Ni²⁺ have been calculated in octahedral and tetrahedral coordination. There is good agreement between the obtained experimental and calculated data. The polarization dependence of the optical absorption bands is well explained in terms of the spin–orbit interaction.     

The influence of impurities on the dissolution of Ca- and Sr-bearing barite at room temperature

1INTRODUCTION BARITE(BASO4)ISANEXTREMELYINSOLUBLESALT;THISAROUSESPROBLEMSINPETROLEUMINDUSTRYBECAUSE BASO4ISAPARTICULARLYINTRACTABLESCALINGAGENT.BARITE PRECIPITATIONINTHEWELLBOREENVIRONMENTGENERALLYRE QUIRESMECHANICALREMOVAL,WITHCONSIDERABLEASSOCIAT EDEXPE…     

冰雪层中记录气候与环境变化的痕量含碳杂质

冰雪层是记录全球变化的主要信息载体之一,其中由生源要素碳形成的杂质种类最多。总结了这些含碳杂质记录古气候和古环境变化方面的研究进展,涉及温室气体、低分子可溶性有机酸、人为有机污染物以及孢粉和高碳数有机质。讨论了今后这些研究的重点所在。     

Ab initio Hartree–Fock study and charge density analysis of beryl (Al4Be6Si12O36)

 An ab initio Hartree–Fock calculation on beryl structure has been performed and the wave function has been used for an analysis of the electron density. The equilibrium geometry, determined by minimizing the energy with respect to cell parameters and fractional coordinates, is in good agreement with structural experimental measurements; small differences in length between the various Si–O bonds of the structure are well reproduced by the calculation. The two non-equivalent oxygen atoms (O1 and O2) of beryl show different electron distributions. In particular, the valence shell charge concentration (VSCC) of O1 (the bridge between two Si ions) has a torus-like shape, showing a bulge on the external side of the Si–O–Si angle and a thinning on the internal side of it; by contrast O2 has two lone pairs which are approximately located on the line for O2, normal to the plane passing, on average, through the atoms O2, Si, Be and Al. The electron density of each oxygen is strongly polarized toward the Si ions and much less polarized towards the other cations. Such features of the VSCC of the oxygens can be recast in terms of the valence bond theory, to explain the observed differences in bond lengths. By calculating the potential inside the channels of the beryl structure, predictions could be made about the positions occupied by alkali cations, which are often found in natural minerals belonging to the beryl group: results agree in general with experimental findings, but foresee a shift of such cations off the central positions located on the six fold symmetry axis. Additionally, calculations of position and orientation of H₂O inside the channel, in the alkali-free beryl, locate the molecule close to the basal plane, with the H⋯H axis parallel to [001] or oriented at 40^∘ from it. Received: 12 December 2001 / Accepted: 6 April 2002     

The single-crystal,polarized-light,FTIR spectrum of stoppaniite,the Fe analogue of beryl

We report here a single-crystal polarized-light study of stoppaniite, ideally (Fe,Al,Mg)₄(Be₆Si₁₂O₃₆)(H₂O)₂(Na,□), from Capranica (Viterbo). Polarized-light FTIR spectra were collected on an oriented (hk0) section, doubly polished to 15 μm. The spectrum shows two main bands at 3,660 and 3,595 cm⁻¹; the former is strongly polarized for E ⊥c, while the latter is polarized for E //c. A sharp and very intense band at 1,620 cm⁻¹, plus minor features at 4,000 and 3,228 cm⁻¹ are also polarized for E //c. On the basis of literature data and considering the pleochroic behavior of the absorptions, the 3,660 cm⁻¹ band is assigned to the ν₃ stretching mode and the 1,620 cm⁻¹ (associated with an overtone 2*ν₂ at 3,230 cm⁻¹) band to the ν₂ bending mode of “type II” water molecules within the structural channels of the studied beryl. The sharp band at 3,595 cm⁻¹ is not associated with a corresponding ν₂ bending mode; thus it is assigned to the stretching vibration of O–H groups in the sample. The minor 4,000 cm⁻¹ feature can be assigned to the combination of the O–H bond parallel to c with a low-frequency metal-oxygen mode such as the Na–O stretching mode. The present results suggest that the interpretation of the FTIR spectrum of Na-rich beryl needs to be carefully reconsidered.     

Minerals at high pressure. Mechanics of compression from quantum mechanical calculations in a case study: the beryl (Al<Subscript>4</Subscript>Be<Subscript>6</Subscript>Si<Subscript>12</Subscript>O<Subscript>36</Subscript>)

The Bader topological analysis has been applied to ab initio computed electron densities of beryl, in order to clarify its mechanism of compression. Full structural optimization and total energy (E) calculations were performed at different cell volumes (V _c). The pressure at each volume and the equation of state were estimated from the first and second derivatives of the resultant E(V _c) curve. The total (negative) potential energy of the crystal, sum of both attractive and repulsive electrostatic terms, was found to systematically decrease (i.e., it moved to more negative values) up to the highest pressure considered (28.4 GPa), indicating that interelectronic and internuclear repulsions are not the only terms controlling the compressibility, at least in the pressure range investigated. Electronic kinetic energy increases as the cell volume is reduced, leading to a parallel increase of the total energy. Both structure at equilibrium and compressibility are therefore due to the balance between the opposing kinetic and potential energy terms. The Bader theory has been used to identify the topological atoms within the structure and to calculate their properties, with particular attention to the forces driving the structural relaxation at high pressure. On a qualitative basis, the obtained results are expected to be transferable to the discussion of compressibility of other mineral phases.     

Modes of trace element occurrence in galena from the Partizansky base metal-skarn deposit, Primorye

The localization and chemical composition of the galena from the Partizansky base metal-skarn deposit have been studied in the Second Contact ore body and Bol’nichnaya ore lode. The Partizansky deposit was formed during two stages: base metal-skarn and silver-sulfosalt. Much of the galena was deposited with the productive galena-sphalerite assemblage at the first stage. The galena of the productive stage of the Second Contact body shows wide variations in trace element composition. The galena from the root zone of the ore-bodies (the level of ?135 m) is characterized by steady high contents of economically important isomorphic and mechanical admixtures of bismuth and silver. The galena from the middle levels is almost devoid of isomorphic admixtures and occasionally contains fine inclusions of Ag-tetrahedrite. The high silver (and stibium) contents in the galena from the uppermost horizon (the level of +285 m) are mainly related to mineral inclusions of diverse silver minerals of the late silver-bearing assemblage. The galena from the Bol’nichnaya lode over a large depth interval has elevated contents of isomorphic silver and bismuth, with abundant inclusions of native bismuth.     

Quantum-mechanical modeling of minerals at high pressures. The role of the Hamiltonian in a case study: the beryl (Al4Be6Si12O36)

Ab initio calculations of the beryl structure at room and higher pressures, and of its equation of state, have been performed both at the Hartree–Fock (HF) and density functional (DFT) level. In the latter case, three different hybrid HF/DFT Hamiltonians have been employed, in which the exact non-local exchange contribution increases from 20% (B3LYP Hamiltonian, indicated with the symbol F20) to 50% (F50) and 60% (F60). Within the DFT series, the equilibrium volume (V ₀) increases as the HF exchange contribution decreases; with respect to the experimental datum, F20 overestimates V ₀ by 2.9%, whereas F60 underestimates it by 0.9%; F50 (and HF) volume is very close to the experimental datum (error less than −0.1%). All four Hamiltonians overestimate the bulk modulus (K ₀); with respect to the experimental datum (obtained in the present work) [K ₀=179(1) GPa], the F20 Hamiltonian leads to the smallest error (+2.7%); the corresponding errors for the F50, F60 and HF Hamiltonians are +13.2, +16.2 and +16.3%, respectively. In the case of F20, in spite of the small error in K ₀, the relatively large error in V ₀ leads to an incorrect P(V) equation of state, which significantly overestimates the pressure at a given volume, compared to the experimental one at the same volume; the maximum error in the pressure range investigated is at the largest pressure (P _max=26.4 GPa) and amounts to +34.8%. The corresponding errors for the F50, F60 and HF Hamiltonians are +12.9, +5.7 and +15.5%.