The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite

Density functional theory calculations have been used to study the pressure-induced changes of the hydrogen bond of Fe-free orthozoisite and clinozoisite and the concomitant shifts of the OH-stretching frequencies. Two independent parameter-free lattice dynamical calculations have been employed. One was based on a plane-wave basis set in conjunction with norm-conserving pseudopotentials and a density functional perturbation theory approach, while the other used a localised basis set and a finite displacement algorithm for the lattice dynamical calculations. Both models confirm the unusually large pressure-induced red-shift found experimentally (−33.89 cm⁻¹/GPa) in orthozoisite, while the pressure-induced shifts in clinozoisite are much smaller (−5 to −9 cm⁻¹/GPa). The atomistic model calculations show that in orthozoisite the nearly linear O–H⋯O arrangement is compressed by about 8% on a pressure increase to 10 GPa, while concomitantly the O–H distance is significantly elongated (by 2.5% at 10 GPa). In clinozoisite, the O–H⋯O arrangement is kinked at ambient conditions and remains kinked at high pressures, while the O-H distance is elongated by only 0.5% at 10 GPa. The current calculations confirm that correlations between the distances and dynamics of hydrogen bonds, which have been established at ambient conditions, cannot be used to infer hydrogen positions at high pressures.     

Draa Sfar, Morocco: A Visean (331 Ma) pyrrhotite-rich, polymetallic volcanogenic massive sulphide deposit in a Hercynian sediment-dominant terrane

Draa Sfar is a Visean, stratabound, volcanogenic massive sulphide ore deposit hosted by a Hercynian carbonaceous, black shale-rich succession of the Jebilet terrane, Morocco. The ore deposit contains 10 Mt grading 5.3 wt.% Zn, 2 wt.% Pb, and 0.3 wt.% Cu within two main massive sulphides orebodies, Tazakourt (Zn-rich) and Sidi M'Barek (Zn–Cu rich). Pyrrhotite is by far the dominant sulphide (70 to 95% of total sulphides), sphalerite is fairly abundant, chalcopyrite and galena are accessory, pyrite, arsenopyrite and bismuth minerals are rare. Pyrrhotite is monoclinic and mineralogical criteria indicate that it is of primary origin and not formed during metamorphism. Its composition is very homogeneous, close to Fe₇S₈, and its absolute magnetic susceptibility is 2.10^− 3 SI/g. Ar–Ar dating of hydrothermal sericites from a coherent rhyolite flow or dome within the immediate deposit footwall indicates an age of 331.7 ± 7.9 Ma for the Draa Sfar deposit and rhyolite volcanism.The Draa Sfar deposit has undergone a low-grade regional metamorphic event that caused pervasive recrystallization, followed by a ductile–brittle deformation event that has locally imparted a mylonitic texture to the sulphides and, in part, is responsible for the elongated and sheet-like morphology of the sulphide orebodies. Lead isotope data fall into two compositional end-members. The least radiogenic end-member, (²⁰⁶Pb/²⁰⁴Pb = 18.28), is characteristic of the Tazakourt orebody, whereas the more radiogenic end-member (²⁰⁶Pb/²⁰⁴Pb  18.80) is associated with the Sidi M'Barek orebody, giving a mixing trend between the two end-members. Lead isotope compositions at Draa Sfar testify to a significant continental crust source for the base metals, but are different than those of the Hajar and South Iberian Pyrite Belt VMS deposits.The abundance of pyrrhotite versus pyrite in the orebodies is attributed to low fO₂ conditions and neither a high temperature nor a low aH₂S (below 10^− 3) is required. The highly anoxic conditions required to stabilize pyrrhotite over pyrite are consistent with formation of the deposit within a restricted, sediment-starved, anoxic basin characterized by the deposition of carbonaceous, pelagic sediments along the flank of a rhyolitic flow-dome complex that was buried by pelitic sediments. Deposition of sulphides likely occurred at and below the seafloor within anoxic and carbonaceous muds.Draa Sfar and other Moroccan volcanogenic massive sulphide deposits occur in an epicontinental volcanic domain within the outer zone of the Hercynian belt and formed within a sedimentary environment that has a high pelagic component. In spite of the diachronous emplacement between the IPB deposits (late Devonian to Visean) and Moroccan deposits (Dinantian), all were formed around 340 ± 10 Ma following a major phase of the Devonian compression.     

Iron mineralisation in Mio-Pliocene sediments of the Tamra iron mine (Nefza mining district, Tunisia): Mixed influence of pedogenesis and hydrothermal alteration

The Tamra iron mine (Nefza mining district, N. Tunisia) has been exploited for about one century. There are, however, very few publications modelling the mineralisation within this 50 m-thick Messinian–Zanclean sedimentary series. We present the result of a detailed sedimentological, mineralogical and geochemical study on the siliciclastic sediments heavily mineralised in iron. In their present state of preservation, these are rather unusual sediments, wherein most of sedimentological information is obliterated by iron impregnation. The whole series consists of a succession of fining-upward sequences (a few meters in thickness) that are capped by clay-bearing variegated and mottled horizons, each sequence being interpreted as a shallowing-upward sequence topped by an emersive horizon corresponding to a paleosoil. We propose that alteration and/or pedogenesis by the downward percolation of meteoric fluids accounts for most of the initial iron concentration, while a hydrothermal overprint, linked to the neighbouring Miocene magmatic rocks and associated mineral deposits (Sidi Driss Fe–Pb–Zn mine), accounts for the existing extreme iron enrichment. The proposed model is likely to apply to several other iron mines linked to the Miocene magmatic activity in the whole Maghreb area, and especially along the Apenninic thrust front (locally known as Tell-Rif front).     

锍镍试金富集-等离子体质谱法测定煌斑岩中铂族元素

试金配料中适量加入铁粉,控制硫化铁在锍扣中的含量在20%~40%,获得的锍扣直接用水浸泡粉化后加盐酸分解,分解结束后趁热过滤,沉淀用1mL王水溶解,定容后上机测定,Cs作内标。改进后的方法空白水平进一步降低,检出限得到显著改善,分析流程简化。采用改进后的锍镍试金富集-等离子体质谱法测定了云南哀牢山金矿带煌斑岩和国家一级标准物质GBW 07288(GPt-1)、GBW 07290(GPt-3)中的铂族元素(PGEs)含量,方法检出限为0.001~0.01ng/g,精密度(RSD,n=5)为7.49%~16.6%。     

Hydrogen partitioning between melt,clinopyroxene, and garnet at 3 GPa in a hydrous MORB with 6 wt.% H<Subscript>2</Subscript>O

To understand partitioning of hydrogen between hydrous basaltic and andesitic liquids and coexisting clinopyroxene and garnet, experiments using a mid-ocean ridge basalt (MORB) + 6 wt.% H₂O were conducted at 3 GPa and 1,150–1,325°C. These included both isothermal and controlled cooling rate crystallization experiments, as crystals from the former were too small for ion microprobe (SIMS) analyses. Three runs at lower bulk water content are also reported. H₂O was measured in minerals by SIMS and in glasses by SIMS, Fourier Transform infrared spectroscopy (FTIR), and from oxide totals of electron microprobe (EMP) analyses. At 3 GPa, the liquidus for MORB with 6 wt.% H₂O is between 1,300 and 1,325°C. In the temperature interval investigated, the melt proportion varies from 100 to 45% and the modes of garnet and clinopyroxene are nearly equal. Liquid composition varies from basaltic to andesitic. The crystallization experiments starting from above the liquidus failed to nucleate garnets, but those starting from below the liquidus crystallized both garnet and clinopyroxene. SIMS analyses of glasses with >7 wt.% H₂O yield spuriously low concentrations, perhaps owing to hydrogen degassing in the ultra-high vacuum of the ion microprobe sample chamber. FTIR and EMP analyses show that the glasses have 3.4 to 11.9 wt.% water, whilst SIMS analyses indicate that clinopyroxenes have 1,340–2,330 ppm and garnets have 98–209 ppm H₂O. D _H ^cpx−gt is 11 ± 3, D _H ^cpx−melt is 0.023 ± 0.005 and D _H ^gt−melt is 0.0018 ± 0.0006. Most garnet/melt pairs have low values of D _H ^gt−melt, but D _H ^gt−melt increases with TiO₂ in the garnet. As also found by previous studies, values of D _H ^cpx−melt increase with Al₂O₃ of the crystal. For garnet pyroxenite, estimated values of D _H ^{pyroxenite−melt} decrease from 0.015 at 2.5 GPa to 0.0089 at 5 GPa. Hydration will increase the depth interval between pyroxenite and peridotite solidi for mantle upwelling beneath ridges or oceanic islands. This is partly because the greater pyroxene/olivine ratio in pyroxenite will tend to enhance the H₂O concentration of pyroxenite, assuming that neighboring pyroxenite and peridotite bodies have similar H₂O in their pyroxenes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Monitoring of the integrated column of hydrogen fluoride above the Jungfraujoch Station since 1977 — the HF/HCl column ratio

The amount of hydrogen fluoride (HF) above the International Scientific Station of the Jungfraujoch (Switzerland) has been monitored during the last 8 years. The results deduced spectro-scopically from solar IR absorption measurements near 2.48 m indicate a cumulative trend equivalent to (8.5±1)% increase per year, as well as short-term variability which appears to be strongly correlated with meridional circulation patterns during the February–April months. Based on intensified measurements made over the last three years, it is found that the integrated content of HF undergoes a seasonal change with a minimum occurring in the fall. The HF/HCl ratio derived from simultaneous HF and HCl measurements was found equal to 0.15 during the period 1977–79, and 0.24 for the 1983–85 timespan.     

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol

The reactions of OH radicals with SO₂, H₂S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH₃ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO₂, H₂S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10^-12, (5.5±0.8)×10^-12 and (1.1±0.2)×10^-11 cm³ s^-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O₂ and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H₂O₂ at wavelengths greater than 260 nm as the OH source in 1 atm N₂, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10^-11 cm³ s^-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.     

Contributions of H2S to the atmospheric sulfur cycle

H₂S is a most important biogenic sulfur compound with regard to the atmospheric sulfur cycle. Our present knowledge of the spatial and temporal distribution of this trace gas is rather incomplete owing to unreliable analytical methods. Therefore, a new method for the analysis of H₂S in the g-range was applied. This paper deals with the results of ground- and aircraft measurements of H₂S in unpolluted air over swamps and tidal flats. Based on the measured vertical distributions a removal coefficient of 2.3×10^–5 sec^–1 and an average lifetime of 12 hours were calculated. Some conclusions of the contribution of H₂S to the atmospheric sulfur budget are added.     

新疆铜镍硫化物矿床地质-地球物理模式及找矿标志

在应用地质地球物理方法普查找矿时,从设计到野外工作,以及对所取得成果资料的解释推断都需要了解研究有关调查地区及探测目标的地质-地球物理条件及其主要特性,以便确定有效的普查找矿方法和提出切合实际的解释推断意见.建立和应用探测目标的地质-地球物理模式,对解决上述问题具有重要意义.我们总结建立了新疆铜镍硫化物矿床地质-地球物理模式,指出了普查寻找这类矿床的主要标志和基本方法.     

Gas phase measurements of hydrogen peroxide in Greenland and their meaning for the interpretation of H2O2 records in ice cores

The gas phase concentration of hydrogen peroxide at Summit, Central Greenland, has been measured continuously during June/July 1990 using a coil scrubber technique combined with liquid phase fluorometry. The concentrations ranged between 0.3 ppbv and 3.5 ppbv, which is considerably higher than expected from model calculations and can be explained by low deposition rates. The record shows pronounced diurnal variations with minimum concentrations during night and maximum concentrations in the afternoon. The nocturnal minima can be explained by scavenging of H₂O₂ by hoarfrost. The scavenging mechanisms of H₂O₂ by snow and the redistribution of H₂O₂ during firnification are discussed. There is indirect evidence, that H₂O₂ is uniformly distributed in the ice lattice and that the fractionation between H₂O₂ and H₂O is small during diffusional crystal growth from the vapor phase (co-condensation).