A molecular orbital study of bonding in sulfate molecules: Implications for sulfate crystal structures

Molecular orbital calculations have been completed on sulfate monomers and a dimer in a determination of minimum-energy geometries and electron density distributions. SO bond lengths calculated for the monomer and dimer correlate linearly with the fractional s-characters of the bonds, as observed for sulfate groups in crystals. With increasing coordination number of S, the bonded radii of S and O, as determined from electron density maps, increase at the same rate. This is at variance with the assumption that the radius of the oxide ion is nearly constant and that bond length variations arise primarily from changes in cation radii. The dimer shows a relatively large change in energy as its SOS angle is deformed from its minimum-energy value (125.6°) to 180°, in conformity with the small variation among observed angles. This is in contrast to the wide variation of bridging angles observed for silicate and phosphate dimers in crystals and molecules, and may imply that significant differences should be expected in the behavior of sulfates with respect to polymorphism and glass formation. The reaction energy of SO₃ + H₂O → H₂SO₄, calculated with second-order Møller-Plesset perturbation theory, agrees with the experimental value. Other properties of H₂SO₄ are also calculated and compared with experimental observations and previous calculations.     

Muscovite surface structure imaged by fluid contact mode AFM

The surface structure of muscovite was imaged using an atomic force microscope (AFM) in contact mode in water. The following three types of AFM images were observed: (1) those showing clearly the arrangement of hexagonal rings of SiO₄ tetrahedra; (2) those showing a hexagonal array of bright spots separated by a distance of about 5.3 Å; and (3) those changing gradually from image (2) to image (1). Image (1) successfully provides information on the tetrahedral tilt and basal surface corrugation that are particularly characteristic of dioctahedral micas. The mean unit cell dimensions for the muscovite surface measured from Image (1) were slightly longer than those of the bulk structure, due to the rehydration of the tetrahedral sheet and/or surface relaxation. Image (2) was made by varying the scan angles, even on the same surface in which Image (1) was obtained. Image (3) has information on a single plane rather than on two or more planes involving steps, kinks and so on. Therefore, what is depicted in Images (2) and (3) is not the arrangement of interlayer K ions but the basal plane of the tetrahedral sheet. Some structural relaxation of the tetrahedral sheet surface was also observed. Gradual expansion and contraction of hexagonal rings were randomly found on the muscovite surface. The surface relaxation results from a tetrahedral rotation and/or tilting after cleaving, since significant variations of both distances and bond angles between adjacent SiO₄ tetrahedra on the surface were found.     

铁尖晶橄榄石的穆斯堡尔谱研究

本文使用穆斯堡尔效应研究了在高温高压下合成的铁橄榄石和铁尖晶橄榄石。２９８Ｋ温度下铁橄榄石的穆斯堡尔谱由一组双峰组成，它被指派给Ｆｅ＾２＋（Ｍ１，Ｍ２）离子。２９８Ｋ温度下铁尖晶橄榄石的穆斯堡尔谱由三组双峰组成，其中两组双峰指派给八面体位置Ｂ上的Ｆｅ＾２＋，另一组双峰归为四面体位置Ａ上的Ｆｅ＾３＋，两组Ｆｅ＾２＋双峰的同质异能迁移近似相等而四极分裂不同，Ｓｉ原子在八面体位置上的占有率为６％～１０％     

A method for calculating fractional s-character for bonds of tetrahedral oxyanions in crystals

A method for calculating fractional s-character, f _s , for TO bonds has been devised to apply to TO₄ tetrahedral oxyanions in crystals. These f _s -values rank bond lengths with the better correlations obtained for T atoms associated with larger bond strengths and larger electronegativities. As a simple formula, it is found that 2cot²〈?〉₃ does a good job of estimating f _s where 〈?〉₃ is the triple angle average of the three angles common to a given bond.     

Molecular orbital studies of geometries and spectra of minerals and inorganic compounds

Extended Hückel molecular orbital theory (EHT) and simple, approximate Self-Consistent-Field MO methods are employed to explain the geometries of nontransition metal bearing minerals and inorganic compounds. The spectra of such minerals and the electronic structure of transition metal oxidic minerals are explained using the Self-Consistent-Field X α MO method. EHT provides an objective algorithm for rationalizing and correlating bond length and angle data for insular and polymerized TO ₄ ^?n tetrahedral oxyanions where T=Be, B, Al, Si, P, S, Ge, As and Se. Calculated bond overlap populations n(T-O), correlate linearly with the observed T-O bond lengths with shorter bonds tending to involve larger n(T-O) values. Such calculations show that n(T-O) is strongly dependent upon the average of the three O-T-O angles associated with a common bond, larger n(T-O) values involving wider angles. Calculations of n(T-O) as a function of the T-O-T angles in T ₂O ₇ ^?n ions, indicate that the n(T-O) values for the bonds to the bridging oxygen atoms increase nonlinearly with increasing T-O-T angle whereas those the nonbridging oxygens decrease slightly as the angle widens. In agreement with the experimental data, these results predict that shorter T-O bonds should involve wider O-T-O and T-O-T angles. The SCF-X α MO cluster model is then applied to silica and FeO. The calculations yield a satisfactory interpretation of the visible, UV and X-ray emission and X-ray photoelectron spectra of these materials. Theoretical and empirical MO diagrams are constructed and the electronic structures of the materials are discussed.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—I. Electronic structure of H6Si2O7, H6AlSiO71−, and H6Al2O72−

As part of a study of the effect of geologically common network modifiers on polymerization in silicate melts, glasses, and silica-rich aqueous solutions, we have studied the energies, electronic structures, and inferred chemical properties of ^IVT-O-^IVT linkages in the tetrahedral dimers H₆,Si₂O₇, H₆AlSiO₇^1?, and H₆Al₂O₇^2? using semi-empirical molecular orbital theory (CNDO/2). Our results indicate that the electron donating character of the bridging oxygen, O(br), linking two tetrahedra increases with increasing T-O(br) bond length but decreases with decreasing T-O(br)-T angles and increasing O-T-O(br) angles. This increase or decrease of the donor character of O(br) coincides with an increase or decrease of the affinity of O(br) for hard acceptors. The calculated electronic structure for the H₆Si₂O₇ molecule is compared with the observed X-ray emission, absorption, and photoelectron spectra of quartz and vitreous silica; the reasonable match between calculated and observed oxygen Kα emission spectra of vitreous silica supports our assertion that non-bonded O(br) electron density energetically at the top of the valence band controls the chemical reactivity of ^IVT-O-^IVT linkages in polymerized tetrahedral environments.     

The Possible Topologic structure Types of Orthopyroxene with Space Group P21ca

The possible topologic structure types of orthopyroxene with space group P21ca comprise four kinds of tetrahedral chains and four kinds of octahedral sites.all of which are non-equivalent in symmetry,In these structure types,the skew of the octahedral layers has a sequence of --,There are sixteen possible combination forms for the rotation type of tetradral chain.Twelve of them violate Thompson ‘s sparity rule and the remainder constitutes two pairs.In each pair,the two polar forms show a relationship of anti-orientation for their polar a-axes.Thus,there are only two possible different topologic structure types for P21ca-orthopyroxene.The ratios of O-rotated and S-rotated tetrahedral chains for these two structure types are 3:1 and 1:3,respectively,In the view S-rotated tetrahedral chains for these two structure types are 3:1 and 1:3,respectively,In the view of crystallochemical principle,the most likely form is the one with a ratio of 3:1,and its constitutions of two stacks of I-beam,which are non-equivalent both in symmetry and in topology,are and the configurations of the two types of M2 sites are P.P and P.N,respectively,A complementary twinning on(100) would be formed between the anti-oriented structure pairs,and their twin boundary is exactly equivalent to the inversion boundary,Moreover,it is possible that the ordered structure would appear when the atom ratio of Mg:Fe is equal to 3:1 as well as to 1：1。     

新疆阿尔泰萨热阔布-铁木尔特地区两类矿化及成因

新疆阿尔泰南缘萨热阔布-铁木尔特一带的矿床均赋存于下泥盆统康布铁堡组的变质岩系中。早泥盆世的海相火山形成了Zn--Pb ( Cu) 矿化,晚泥盆世--早石炭世的碰撞造山相应形成了Cu--Au 石英脉矿化; 前者以铁木尔特VMS 型Zn--Pb ( Cu) 矿床为代表,后者以造山型萨热阔布金矿为代表,与造山有关的脉状矿化还叠加在铁木尔特等VMS 矿床中。通过对比两类矿化的稳定同位素特征,结合矿化的变形变质和流体包裹体特征,研究了成矿物质、成矿流体来源和矿床成因。萨热阔布金矿主成矿阶段硫化物石英脉和铁木尔特Zn--Pb ( Cu) 矿床中晚期发育的含黄铜矿石英脉中均富含碳质 ( CO2--CH4--N2 ) 流体包裹体,可能与碰撞造山的热液流体作用有关。铁木尔特Zn--Pb ( Cu) 矿床中代表VMS 期的浸染状矿石中硫化物δ34S 为－26. 46 × 10-3 ～ －19. 72 × 10 -3,硫主要来源于海水硫酸盐的无机还原和细菌还原作用; 而代表后期叠加改造的脉状矿化硫化物值与萨热阔布金矿床硫化物石英脉中δ34S 值接近,硫主要来源于造山过程中的深源流体。萨热阔布金矿床硫化物石英脉和铁木尔特Zn-- Pb ( Cu) 矿床晚期含黄铜矿石英脉的δDH2O 值和δ18OH2O 值,均反映了碰撞造山期热液与岩浆活动和变质作用有关。萨热阔布金矿硫化物石英脉中碳质流体包裹体CO2 体系中δ13 C 为－ 21. 15 × 10-3 ～ －7. 51 × 10 -3,CH4 体系的δ13C 为－34. 11 × 10 -3 ～ －28. 38 × 10-3 ; 铁木尔特Zn--Pb ( Cu) 矿床含黄铜矿石英脉中碳质包裹体测得的δ13C 为－8. 02 × 10 -3 ～ －6. 99 × 10 -3,δ13 C 特征与海相火山沉积无关,具岩浆源或深部源的特点。     

Sulfur and oxygen isotope study of sulfate reduction in experiments with natural populations from Fællestrand, Denmark

This study investigates the sulfur and oxygen isotope fractionations of dissimilatory sulfate reduction and works to reconcile the relationships between the oxygen and sulfur isotopic and elemental systems. We report results of experiments with natural populations of sulfate-reducing bacteria using sediment and seawater from a marine lagoon at Fællestrand on the northern shore of the island of Fyn, Denmark. The experiments yielded relatively large magnitude sulfur isotope fractionations for dissimilatory sulfate reduction (up to approximately 45‰ for ³⁴S/³²S) with higher δ¹⁸O accompanying higher δ³⁴S, similar to that observed in previous studies. The seawater used in the experiments was spiked by addition of ¹⁷O-labeled water and the ¹⁷O content of residual sulfate was found to depend on the fraction of sulfate reduced in the experiments. The ¹⁷O data provides evidence for recycling of sulfur from metabolic intermediates and for an ¹⁸O/¹⁶O fractionation of ∼25-30‰ for dissimilatory sulfate reduction. The close correlation between the ¹⁷O data and the sulfur isotope data suggests that isotopic exchange between cell water and external water (reactor water) was rapid under experimental conditions. The molar ratio of oxygen exchange to sulfate reduction was found to be about 2.5. This value is slightly lower than observed in studies of natural ecosystems [e.g., Wortmann U. G., Chernyavsky B., Bernasconi S. M., Brunner B., Böttcher M. E. and Swart P. K. (2007) Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130). Geochim. Cosmochim. Acta71, 4221-4232]. Using recent models of sulfur isotope fractionations we find that our combined sulfur and oxygen isotopic data places constraints on the proportion of sulfate recycled to the medium (78-96%), the proportion of sulfur intermediate sulfite that was recycled by way of APS to sulfate and released back to the external sulfate pool (∼70%), and also that a fraction of the sulfur intermediates between sulfite and sulfide were recycled to sulfate. These parameters can be constrained because of the independent information provided by δ¹⁸O, δ³⁴S, δ¹⁷O labels, and Δ³³S.     

Framework silica structures generated using simulated annealing with a potential energy function based on an H6Si2O7 molecule

A simulated annealing technique was used to search for global and local minimum energy structures of a potential energy model for silica. The model is based on ab initio SCF MO calculations on the disilicic acid molecule, H₆Si₂O₇. Starting with 4 SiO₂ units, with the atoms randomly distributed in the unit cell, 23 distinct silica tetrahedral framework structures were found, with a variety of space group symmetries and cell dimensions. Despite the assumption of P 1 space group symmetry for the starting structure, only 7 of the local minimum energy structures were found to possess triclinic symmetry with the remainder exhibiting symmetries ranging from P c to to within 0.001 Å. Although the interaction potential for the disilicic acid molecule has a single minimum energy SiO bond length and SiOSi angle, the local minimum energy structures exhibit angles that range between 105° and 180° and bond lengths that range between 1.55 and 1.68 Å. The correlation observed for coesite and the other silica polymorphs between SiO bond length and f_s(O) is reproduced. The generated structures show a wide variety of coordination sequences, ring sizes and framework densities, the later ranging from 19.8 to 35.5 Si/1000 ų. The energies of these structures correlate with their framework densities, particularly for higher energy structures.     

Mineral species control of aluminum solubility in sulfate-rich acidic waters

The identification of the mineral species controlling the solubility of Al in acidic waters rich in sulfate has presented researchers with several challenges. One of the particular challenges is that the mineral species may be amorphous by X-ray diffraction. The difficulty in discerning between adsorbed or structural sulfate is a further complication. Numerous studies have employed theoretical calculations to determine the Al mineral species forming in acid sulfate soil environments. The vast majority of these studies indicate the formation of a mineral species matching the stoichiometry of jurbanite, Al(OH)SO₄·5H₂O. Much debate, however, exists as to the reality of jurbanite forming in natural environments, particularly in view of its apparent rare occurrence. In this work the use of Al, S and O K-edge XANES spectroscopy, in combination with elemental composition analyses of groundwater precipitates and a theoretical analysis of soluble Al concentrations ranging from pH 3.5 to 7, were employed to determine the mineral species controlling the solubility of Al draining from acid sulfate soils into Blacks Drain in north-eastern New South Wales, Australia. The results indicate that a mixture of amorphous Al hydroxide (Al(OH)₃) and basaluminite (Al₄(SO₄)(OH)₁₀·5H₂O) was forming. The use of XANES spectroscopy is particularly useful as it provides insight into the nature of the bond between sulfate and Al, and confirms the presence of basaluminite. This counters the possibility that an Al hydroxide species, with appreciable amounts of adsorbed sulfate, is forming within these groundwaters.Below approximately pH 4.5, prior to precipitation of this amorphous Al(OH)₃/basaluminite mixture, our studies indicate that the Al³⁺ activity of these acidic sulfate-rich waters is limited by the availability of dissolved Al from exchangeable and amorphous/poorly crystalline mineral species within adjacent soils. Further evidence suggests the Al³⁺ activity below pH 4.5 is then further controlled by dilution with either rainwater or pH 6-8 buffered estuarine water, and not a notional Al(OH)SO₄ mineral species.     

The tetrahedral framework in glasses and melts — inferences from molecular orbital calculations and implications for structure,thermodynamics, and physical properties

Results of ab initio molecular orbital (MO) calculations provide a basis for the interpretation of structural and thermodynamic properties of crystals, glasses, and melts containing tetrahedrally coordinated Si, Al, and B. Calculated and experimental tetrahedral atom-oxygen (TO) bond lengths are in good agreement and the observed average SiO and AlO bond lengths remain relatively constant in crystalline, glassy, and molten materials. The TOT framework geometry, which determines the major structural features, is governed largely by the local constraints of the strong TO bonds and its major features are modeled well by ab initio calculations on small clusters. Observed bond lengths for non-framework cations are not always in agreement with calculated values, and reasons for this are discussed in the text. The flexibility of SiOSi, SiOAl, and AlOAl angles is in accord with easy glass formation in silicates and aluminosilicates. The stronger constraints on tetrahedral BOB and BOSi angles, as evidenced by much deeper and steeper calculated potential energy versus angle curves, suggest much greater difficulty in substituting tetrahedral B than Al for Si. This is supported by the pattern of immiscibility in borosilicate glasses, although the occurrence of boron in trigonal coordination is an added complication. The limitations on glass formation in oxysulfide and oxynitride systems may be related to the angular requirements of SiSSi and Si(NH)Si groups. Although the SiO and AlO bonds are the strongest ones in silicates and aluminosilicates, they are perturbed by other cations. Increasing perturbation and weakening of the framework occurs with increasing ability of the other atom to compete with Si or Al for bonding to oxygen, that is, with increasing cation field strength. The perturbation of TOT groups, as evidenced by TO bond lengthening predicted by MO calculations and observed in ordered crystalline aluminosilicates, increases in the series Ca, Mg and K, Na, Li. This perturbation correlates strongly with thermochemical mixing properties of glasses in the systems SiO₂-M ₁ ^n/n+ AlO₂ and SiO₂-M ⁿ⁺O _n/2 (M=Li, Na, K, Rb, Cs, and Mg, Ca, Sr, Ba, Pb), with tendencies toward immiscibility in these systems, and with systematics in vibrational spectra. Trends in physical properties, including viscosity at atmospheric and high pressure, can also be correlated.     

The five stable isotope compositions of Fig Tree barites: Implications on sulfur cycle in ca. 3.2 Ga oceans

The discovery of ³³S anomalies in Archean sedimentary rocks has established that the early Earth before ∼2.2 Ga (billion years ago) had a very different sulfur cycle than today. The origin of the anomalies and the nature of early sulfur cycle are, however, poorly known and debated. In this study, we analyzed the total sulfur and oxygen isotope compositions, the δ¹⁸O, Δ¹⁷O, δ³⁴S, Δ³³S, and Δ³⁶S, for the >3.2 Ga Fig Tree barite deposits from the Barberton Greenstone Belt, South Africa. The goal is to address two questions: (1) was Archean barite sulfate a mixture of ³³S-anomalous sulfate of photolysis origin and ³³S-normal sulfate of other origins? (2) did the underlying photochemical reactions that generated the observed ³³S anomalies for sulfide and sulfate also generate ¹⁷O anomalies for sulfate?We developed a new method in which pure barite sulfate is extracted for oxygen and sulfur isotope measurements from a mixture of barite sands, cherts, and other oxygen-bearing silicates. The isotope data reveal that (1) there is no distinct ¹⁷O anomaly for Fig Tree barite, with an average Δ¹⁷O value the same as that of the bulk Earth (−0.02 ± 0.07‰, N = 49); and (2) the average δ¹⁸O value is +10.6 ± 1.1‰, close to that of the modern seawater sulfate value (+9.3‰). Evidence from petrography and from the δ¹⁸O of barites and co-existing cherts suggest minimum overprinting of later metamorphism on the sulfate’s oxygen isotope composition. Assuming no other processes (e.g., biological) independently induced oxygen isotope exchange between sulfate and water, the lack of reasonable correlation between the δ¹⁸O and Δ³³S or between the δ³⁴S and Δ³³S suggests two mutually exclusive scenarios: (1) An overwhelming majority of the sulfate in the Archean ocean was of photolysis origin, or (2) The early Archean sulfate was a mixture of ³³S-normal sulfates and a small portion (<5%?) of ³³S-anomalous sulfate of photolysis origin from the atmosphere. Scenario 1 requires that sulfate of photolysis origin must have had only small ³³S or ³⁶S anomalies and no ¹⁷O anomaly. Scenario 2 requires that the photolysis sulfate have had highly negative δ³⁴S and Δ³³S values, recommending future theoretical and experimental work to look into photochemical processes that generate sulfate in Quadrant I and sulfide in Quadrant III in a δ³⁴S (X)-Δ³³S (Y) Cartesian plane. A total sulfur and oxygen isotope analysis has provided constraints on the underlying chemical reactions that produced the observed sulfate isotope signature as well as the accompanying atmospheric, oceanic, and biological conditions.     

几种锡矿物的穆斯堡尔谱研究

本文对我国一些地区的锡石、黄锡矿、辉锑锡铅矿等锡矿物样品进行了化学成分分析、穆斯堡尔谱测试,并利用穆斯堡尔谱方法区分了这些锡矿物中锡的价态。实测结果表明,锡石中的锡全是Sn~(4+)(六配位),黄锡矿中的锡是Sn~(4+)(四配位),辉锑锡铅矿中的锡有Sn~(4+)及少量 的Sn~(2+)。钙铁榴石中的锡是Sn~(4+),它是以类质同像替换方式进入[Y]位替换Fe~(3+)。同时,讨论了同质异能位移值与价态的关系,I.S值的增大顺序为:Sn~(4+)→Sn~0→Sn~(2+)。根据经验公式,估算了一些锡矿物中氧和硫配位基的电负性,     

Spectroscopic and bond-topological investigation of interstitial volatiles in beryl from Slovakia

Nine beryl samples from Western Carpathians, Slovakia, were investigated by infrared and Raman spectroscopy and differential thermal analysis. Two types of water H₂O I and H₂O II were detected. Infrared spectroscopy proved the presence of water type I and II in the presence of alkali cations with several bands: (1) symmetric stretching vibration—ν₁; (2) antisymmetric stretching mode—ν₃; (3) bending vibration—ν₂. The presence of singly and doubly coordinated type II water (IIs and IId) was confirmed by single-crystal IR spectroscopy. From Raman spectra a band at 3606 cm^?1 was assigned to ν₁ of water type I and the range of 3597–3600 cm^?1 to water type II. The presence of doubly coordinating water indicates a relatively highly hydrated environment with the presence of alkali ions including Na as the dominant cation coordinated by H₂O II. CO₂ bands were detected only by single-crystal IR spectroscopy. Thermal analysis proved total water loss in the range of 1.4–2.0 wt% and three main dehydration events. Based on the study of bond-topological arrangements two molecules of H₂O IId are each bound with two H···O1 bonds and one Na–O_W bond with an angular distortion, and by releasing one H₂O molecule more stable H₂O IIs is produced. The H₂O I molecule is bound only by two equivalent hydrogen bonds. The H₂O IIs molecule with a Na–O_W bond strength of 0.28 vu and two H···O1 bonds of 0.14 vu without any forced angular distortion is the most stable of all.     

拉曼光谱方法测量流体包裹体的内压及其应用

通过金刚石压腔和显微激光拉曼光谱方法,获得了流体包裹体中H2O-NaCl体系的O—H、碳酸根的C—O、硫酸根的S—O和正庚烷-环己烷的C—H振动拉曼位移与温度和压力关系的表达式。该研究结果可以用于实测流体包裹体在不同温度下的内压,并可由此获得流体包裹体的p-t线或等容线。这不仅有助于精确获得流体包裹体的形成温度和形成压力,也可为研究和确定流体包裹体中流体的组成和性质提供依据。     

Isotope geochemistry of waters affected by mining activities in Sierra Minera and Portman Bay (SE,Spain)

The objective of this work was to evaluate processes affecting waters from Portman Bay by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. In addition, surface waters from Sierra Minera were examined for the purpose of determining if these waters are affected by similar processes. The results obtained indicate that Portman Bay waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe³⁺ was predominant in the surface, and controlled by Acidithiobacillus ferrooxidans, while at depth, sulfate reduction occurred.     

Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a δ³⁴S versus δ¹⁸O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The δ³⁴S versus δ¹⁸O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H₂O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.     

元素分析仪-气体同位素质谱法分析硫酸钙样品的硫同位素组成

硫酸盐硫同位素的常规分析方法是将硫酸盐转化为硫酸钡后搭配双路进样SO2法,该法易于操作、数据稳定,但样品用量大、费时费力,需要繁杂的前处理,无法满足微量分析发展方向的需求。本文以石膏为例,以元素分析仪-气体同位素质谱法(EA-IRMS)直接测定硫酸钙样品硫同位素比值,对同一样品分别采用:①硫酸钙与V2O5混合后包裹于锡杯中密封,直接进行元素分析仪-气体同位素质谱分析;②硫酸钙充分溶于去离子水中,向溶有硫酸钙样品的液体中加入沉淀试剂BaCl2,将生成的硫酸钡沉淀滤出后,用去离子水清洗2~3遍,烘干后与V2O5混合包裹于锡杯中密封再进行质谱测定。实验选取了13件δ34S值变化范围介于-20‰^+30‰之间的天然石膏样品,将获得的硫同位素比值进行对比,二者δ34SV-CDT绝对差值在0.00‰~0.24‰,表明同一样品的硫同位素比值结果在误差范围内基本一致。与常规分析方法相比,本文建立的直接在线分析时无需任何化学前处理,只需直接加入适量的V2O5,V2O5和氧气中的外部氧在瞬间燃烧的过程中替代了硫酸钙本身的氧,生成的SO2气体的氧是均一的,其硫同位素比值能代表样品的硫同位素组成,无需进行氧同位素的校正。经过验证表明,硫酸钙样品的直接在线分析是完全可行的。