Methane-Derived Carbonates in a Native Sulfur Deposit: Stable Isotope and Trace Element Discriminations Related to the Transformation of Aragonite to Calcite

Abstract

Stable isotope (¹³C, ¹⁸O, ³⁴S) and trace element (Sr²⁺, Mg²⁺, Mn²⁺, Ba²⁺, Na⁺) investigations of elemental sulfur, primary calcites and mixtures of aragonite with secondary, post-aragonitic calcite from sulfur-bearing limestones have provided new insights into the geochemistry of the mineral forming environment of the native sulfur deposit at Machów (SE-Poland). The carbon isotopic composition of carbonates (δ¹³C = ?41 to ?47‰ vs. PDB) associated with native sulfur (δ³⁴S = + 10 to + 15‰ vs. V-CDT) relates their formation to the microbiological anaerobic oxidation of methane and the reduction of sulfate derived from Miocene gypsum. From a comparison with experimentally derived fractionation factors the element ratios of the aqueous fluids responsible for carbonate formation are estimated. In agreement with field and laboratory observations, ratios near seawater composition are obtained for primary aragonite, whereas the fluids were relatively enriched in dissolved calcium during the formation of primary and secondary calcites. Based on the oxygen isotope composition of the carbonates (δ¹⁸O = ?3.9 to ?5.9‰ vs. PDB) and a secondary SrSO₄ (δ¹⁸O = + 20‰ vs. SMOW; δ³⁴S = + 59‰ vs. V-CDT), maximum formation temperatures of 35°C (carbonates) and 47°C (celestite) are obtained, in agreement with estimates for West Ukraine sulfur ores. The sulfur isotopic composition of elemental sulfur associated with carbonates points to intense microbial reduction of sulfate derived from Miocene gypsum (δ³⁴S ≈ + 23‰) prior to the re-oxidation of dissolved reduced sulfur species.     

Coherent Raman and Infrared Studies of Sulfur Trioxide

High-resolution (0.001 cm⁻¹) coherent anti-Stokes Raman scattering (CARS) was used to observe the Q-branch structure of the IR-inactive ν₁ symmetric stretching mode of ³²S¹⁶O₃ and its various ¹⁸O isotopomers. The ν₁ spectrum of ³²S¹⁶O₃ reveals two intense Q-branches in the region 1065–1067 cm⁻¹, with surprisingly complex vibrational–rotational structure not resolved in earlier studies. Efforts to simulate this with a simple Fermi-resonance model involving ν₁ and 2ν₄ states do not reproduce the spectral detail, nor do they yield reasonable spectroscopic parameters. A more subtle combination of Fermi resonance and indirect Coriolis interactions with nearby states, 2ν₄(1=0, ±2), ν₂+ν₄(1=±1), 2ν₂(1=0), is suspected and a determination of the location of these coupled states by high-resolution infrared measurements is under way. At medium resolution (0.125 cm⁻¹), the infrared spectra reveal Q-branch features from which approximate band origins are estimated for the ν₂, ν₃, and ν₄ fundamental modes of ³²S¹⁸O₃, ³²S¹⁸O₂¹⁶O, and ³²S¹⁸O¹⁶O₂. These and literature data for ³²S¹⁶O₃ are used to calculate force constants for SO₃ and a comparison is made with similar values for SO₂ and SO. The frequencies and force constants are in excellent agreement with those obtained by Martin in a recent ab initio calculation.     

S2激光器的发展

本文回顾硫双原子分子激光器的发展历史,通过借鉴已有激光器件在设计上积累的成功经验和存在的不足之处,提出一种新型可拆卸式横向脉冲快放电S₂激光管的设计方案,并给出此激光管设计的截面图和立体图。     

Sulfur removal from bauxite water slurry (BWS) electrolysis intensified by ultrasonic

Effects of ultrasonic on desulfurization ratio from bauxite water slurry (BWS) electrolysis in NaOH solution were examined under constant current. The results indicated that ultrasonic improved the desulfurization ratio at high temperatures because of the diffusion and transfer of oxygen gas in electrolyte. However, due to the increase in oxygen gas emission, ultrasonic could not improve the desulfurization ratio obviously at low temperatures. Additionally, the particle size of bauxite became fine in the presence of ultrasonic, indicating that the mass transfer of FeS₂ phase was improved. According to the polarization curves, the current density increased in the presence of ultrasonic, indicating that the mass transfer of liquid phase was improved. The apparent activation energy (AAE) of electrode reaction revealed that ultrasonic did not change the pathway of water electrolysis. However, ultrasonic changed the pathway of BWS electrolysis, converting indirect oxidation into direct oxidation. The AAE of BWS electrolysis in the presence of ultrasonic was higher than that in the absence of ultrasonic. And the low AAEs (less than 20 kJ/mol) clearly indicated the diffusion control during BWS electrolysis reaction.     

Initial Processes of Sulfur Adsorption on Si(100) Surface

The adsorption of one monolayer S atoms on ideal Si(100) surface is studied by using the self-consistent tight binding linear muffin-tin orbital method. Energies of adsorption systems of S atoms on different sites are calculated.It is found that the adsorbed S atoms are more favorable on B1 site (bridge site) with a distance 0.131 nm above the Si surface. The S, Si mixed layer might exist at S/Si(100) interface. The layer projected density of states are calculated and compared with that of the clean surface. The charge transfers are also investigated.     

燃煤循环流化床燃烧脱硫的模型预测

燃煤循环流化床燃烧脱硫的模型预测池涌，岑可法，倪明江Ｐ·Ｂａｓｕ（浙江大学能源系杭州３１００２７）关键词：循环流化床，燃烧，脱硫，模型预测一、引言循环流化床锅炉在过去十几年中得到了广泛的应用，但与此同时由于循环流化床内流体动力特性的高度复杂使得数学模...     

煤质硫含量紫外差分吸收测量方法研究

快速准确地测定煤质硫含量,可为企业、环境监督部门提供重要的技术依据。国内外已有多种煤质硫含量分析仪器,但或多或少存在令操作人员不满意的地方。提出一种基于紫外(UV)差分吸收光谱(DOAS)的煤质硫含量测量方法。针对分子数分数测量范围宽、光程短等问题,在传统算法的基础上,提出基于有限脉冲响应(FIR)滤波和四阶多项式非线性补偿的改进DOAS算法。搭建了实验测量系统,对5种标准煤样进行了实验研究。结果表明,测量系统的下限为0.014%,能够去除烟尘和背景气体的影响,降低系统的维护量,单次测量时间在4min左右,测量系统的重复性满足国家标准的要求。     

Initial Processes of Sulfur Adsorption on Si（100） Surface

The adsorption of one monolayer S atoms on ideal Si（100） surface is studied by using the self-consistent tight binding linear muffon-tin orbital method. Energies of adsorption systems ors atoms on different sites are calculated. It is found that the adsorbed S atoms are more favorable on B1 site （bridge site） with a distance 0.131 nm above the Si surface. The .S, Si mixed layer might exist at S/Si（100） interface. The layer projected density of states are calculated and compared with that of the clean surface. The charge transfers are also investigated.     

Initiation of petroleum formation and antioxidant function – a DFT study of sulfur?sulfur bond dissociation enthalpies

Experimental studies showed that sulfur radicals play the vital role in petroleum formation. 1 Sulfur‐ centered radicals also exhibit activities in antioxidant functions. Here we conduct a theoretical investigation of their precursor‐disulfides. By investigation into substituent effect on sulfur? sulfur bond dissociation enthalpies (S? S BDEs), we would like to find the most effective provider for sulfur radicals. In the present work, 50 alpha‐substituted disulfides and 16 para‐substituted aryl disulfides are studied systematically, with the general formula XS‐SX or HS‐SX. The substituent effect on S? S BDEs is found to be very eminent, ranging from 33.2 to 75.0 kcal/mol for alpha‐substituted disulfide, and from 43.7 to 59.7 kcal/mol for para‐substituted phenyl disulfides. We also evaluate the performance of 44 density functional methods to get an accurate prediction. A further study indicates that substituents play a major role in radical energies, instead of molecule energies, which is substantiated by the good linearity between XS‐SX bond dissociation enthalpy (BDE) and HS‐SX BDE. Copyright © 2007 John Wiley & Sons, Ltd.     

Modellrechnungen zur Isotopentrennung durch Multiphotonen-Photodissoziation von Molekülen

Für stoßfreie SF₆-Moleküle werden Mulltiphotonen-Photofragmentierungswahrscheinlichkeiten im intensiven IR-LASER-Feld berechnet einschließlich der Isotopenselektivität derartiger Prozesse in Abhängigkeit von der eingestrahlten LASER-Linie, der Leistungsdichte, dem Impulsprofil und der Temperatur. Über ein quantenmechanisches Modell werden die Rotationsschtwingungsniveaus des SF₆-Moleküls, die Verstimmung zwischen LASER- und Molekülschwin-gungsfrequenz und die intramolekulare Schwingungsrelaxation berücksichtigt.