Hydrothermal jarosite and hematite in a pyroxene-hosted melt inclusion in martian meteorite Miller Range (MIL) 03346: Implications for magmatic-hydrothermal fluids on Mars

Low-temperature aqueous processes have been implicated in the generation of jarosite and hematite on the martian surface, but little is known regarding the role that high-temperature magmatic fluids may have played in producing similar assemblages on Mars. We have identified jarosite and hematite in a clinopyroxene-hosted melt inclusion in martian meteorite MIL 03346 that shows evidence of having been hydrothermally precipitated. In addition to jarosite and hematite, the melt inclusion contains titanomagnetite, pyrrhotite, potassic-chlorohastingsite, an iron-rich silicate glass and possibly goethite. These phases were identified and characterized using scanning electron microscopy (SEM), con-focal Raman-spectroscopy and electron probe microanalysis (EPMA).Based on observed textural relationships and the compositions of the hosted phases, we report that the jarosite-bearing melt inclusion in MIL 03346 has recorded a fluid-rich history that began in the magmatic stage and continued to low-temperatures. This history begins at entrapment of a volatile-rich silicate melt that likely reached fluid-saturation after only minor crystallization within the melt inclusion. This fluid, rich in chlorine, reacted with surrounding silicate material to produce the potassic-chlorohastingsite. As cooling proceeded, the liquid phase eventually became more oxidized and reacted with the pyrrhotite. Sulfide oxidation resulted in SO₄²⁻ formation and concomitant acid production, setting the stage for jarosite formation once the fluid cooled beyond the upper thermal stability of jarosite (∼200 °C). As the fluid cooled below 200 °C, jarosite continued to precipitate with hematite and/or goethite until equilibrium was established or reactions became kinetically unfavorable.This work suggests an additional jarosite-hematite formation pathway on Mars; one that may be important wherever magmatic-hydrothermal fluids come into contact with primary sulfide grains at the martian surface or subsurface. Moreover, hydrothermal fluids rich in chlorine, sulfur, and iron are important for ore-forming processes on Earth, and their indirect identification on Mars may have important implications for ore-formation on Mars.     

Iron weathering products in a CO2 + (H2O or H2O2) atmosphere: Implications for weathering processes on the surface of Mars

Various iron-bearing primary phases and rocks have been weathered experimentally to simulate possible present and past weathering processes occurring on Mars. We used magnetite, monoclinic and hexagonal pyrrhotites, and metallic iron as it is suggested that meteoritic input to the martian surface may account for an important source of reduced iron. The phases were weathered in two different atmospheres: one composed of CO₂ + H₂O, to model the present and primary martian atmosphere, and a CO₂ + H₂O + H₂O₂ atmosphere to simulate the effect of strong oxidizing agents. Experiments were conducted at room temperature and a pressure of 0.75 atm. Magnetite is the only stable phase in the experiments and is thus likely to be released on the surface of Mars from primary rocks during weathering processes. Siderite, elemental sulfur, ferrous sulfates and ferric (oxy)hydroxides (goethite and lepidocrocite) are the main products in a water-bearing atmosphere, depending on the substrate. In the peroxide atmosphere, weathering products are dominated by ferric sulfates and goethite. A kinetic model was then developed for iron weathering in a water atmosphere, using the shrinking core model (SCM). This model includes competition between chemical reaction and diffusion of reactants through porous layers of secondary products. The results indicate that for short time scales, the mechanism is dominated by a chemical reaction with second order kinetics (k = 7.75 × 10⁻⁵ g⁻¹/h), whereas for longer time scales, the mechanism is diffusion-controlled (De_A = 2.71 × 10⁻¹⁰ m²/h). The results indicate that a primary CO₂- and H₂O-rich atmosphere should favour sulfur, ferrous phases such as siderite or Fe²⁺-sulfates, associated with ferric (oxy)hydroxides (goethite and lepidocrocite). Further evolution to more oxidizing conditions may have forced these precursors to evolve into ferric sulfates and goethite/hematite.     

Experimental Study on Formation Conditions of Ammoniojarosite and Its Environmental Significance

Formation conditions of ammoniojarosite in system Fe2（SO4）3-（NH4）2SO4-H2O are investigated in this paper. The results show that ammoniojarosite can be formed rapidly under normal temperature and pressure by controlling suitable pH value and Fe2（SO4）3 and （NH4）2SO4 concentrations. The pH value, temperature and concentration of Fe2（SO4）3 medium are key factors influencing the formation of ammoniojarosite. Under normal temperature, precipitation of ammoniojarosite can be seen within 24 hours at pH values between 2.6-3.1, and a great quantity of ammoniojarosite is formed within 48 hours. At about 90℃, the pH value range forming ammoniojarosite extends to 1.2-3.1, and within this range the rise of pH value is advantageous to the formation of ammoniojarosite and high Fe2（SO4）3 concentration is also advantageous. Relative pure ammoniojarosite is synthesized under high Fe2（SO4）3 concentration （≥0.05 M） and ammoniojarosite containing melanterite and colloid amorphous hydroxide vitriol iron is formed at low Fe2（SO4）3 concentration. The deposition process of ammoniojarosite can be used to harness wastewater from mines and other industries and remove S, Fe and other toxic and harmful elements, such as As, Cr, Hg, Pb in water. Rapid formation of ammoniojarosite and other jarosite analogs under normal temperature and pressure has a good potential prospect for harnessing acid wastewater by means of precipitation of jarosite and its analogs.     

K-H3OFe3(SO4)2(OH)6铁矾的XRD研究

根据X射线衍射(XRD)分析发现: A Fe₃(SO₄)₂(OH)₆(A=K⁺、H₃O⁺)系列铁钒的XRD数据十分相近,难以用XRD区别,需通过能谱(EDS)辅助分析,才能区分此类铁矾。另外,此类铁矾的003和107面网间距d随K⁺含量增大而增大,且呈一元三次方程的关系;而033和220面网间距d随K⁺含量增大而减小,呈一元二次方程的关系。对该现象从铁矾晶体结构方面进行解释:K⁺、H₃O⁺离子位于较大空隙中,且沿着Z轴方向排列,当K⁺、H₃O⁺离子之间相互替换时,会导致该铁矾晶体结构在Z轴方向有较明显的变化。     

The aqueous oxidation of complex sulfide concentrates in hydrochloric acid

Complex sulfides containing sphalerite, galena, chalcopyrite, and small amounts of silver in a matrix of pyrite can be decomposed at 120°C and oxygen pressure of 1000 kPa in 1–2 N HCl for 90 min to yield > 97% of the zinc and > 95% of the copper in solution while about 83% of the lead remains in the residue as PbCl₂ and PbSO₄ and 85% of the silver, together with most of the pyrite. The recovery of elemental sulfur is nearly 100% with respect to ZnS, PbS, and CuFeS₂. Leaching in HCl is faster than in H₂SO₄ at the same acid normality, and the process is diffusion-controlled (strongly dependant on agitation speed and having an activation energy of 3.6 kcal/mole). Lead jarosite, Pb_0.5Fe₃ (SO₄)₂?(OH)₆, is mainly formed when H₂SO₄ is used as a leaching agent.     

Single-crystal X-ray diffraction study of synthetic sodium–hydronium jarosite

Na–H₃O jarosite was synthesized hydrothermally at 413 K for 8 days and investigated using single-crystal X-ray diffraction (XRD) and electron microprobe analysis (EMPA). The chemical composition of the studied crystal is [Na_0.57(3) (H₃O)_0.36 (H₂O)_0.07]^A Fe_2.93(3) (SO₄)₂ (OH)_5.70 (H₂O)_0.30, and Fe deficiency was confirmed by both EMPA and XRD analysis. The single-crystal XRD data were collected at 298 and 102 K, and crystal structures were refined in space group \( R\overline{3}m\). The room-temperature data match structural trends of the jarosite group, which vary linearly with the c axis. The low-temperature structure at 102 K shows an anisotropic decrease in the unit cell parameters, with c and a decreasing by 0.45 and 0.03 %, respectively. Structural changes are mainly confined to the A site environment. Only minor changes occur in FeO₆ and SO₄ polyhedra. The structure responds upon cooling by increasing bond length distortion and by decreasing quadratic elongation of the large AO₁₂ polyhedra. The structural parameters at low temperature follow very similar patterns to structural changes that correspond to compositional variation in the jarosite group, which is characterised by the flexibility of AO₁₂ polyhedra and rigidity of Fe(OH)₄O₂–SO₄ layers. The most flexible areas in the jarosite structure are localized at AO₁₂ edges that are not shared with neighbouring FeO₆ octahedra. Importantly, for the application of XRD in planetary settings, the temperature-related changes in jarosite can mimic compositional change.     

Experimental constraints on the evaporation of partially oxidized acid-sulfate waters at the martian surface

Isothermal evaporation experiments were carried out on an acidic (pH 2), partially oxidized (Fe²⁺/Fe_T ∼0.5) brine with a cation composition consistent with derivation from the chemical weathering of martian basalt. During evaporation, the brine composition evolved to a highly acidic (un-scaled pH −1.3) Mg-Fe-SO₄-Cl brine depleted in Ca, Al and K. Evaporite minerals identified throughout the course of the experiment include (in order of crystallization): gypsum, Mg-rich voltaite, (Mg_0.7, )SO₄·7H₂O and rhomboclase. The solid solution compositions of voltaite and (Mg_0.7, )SO₄·7H₂O, although uncommon in analogous environments on Earth, result from the distinct chemistry of evaporating martian surface fluids. Analysis of brine compositions with available thermodynamic models indicates that, although gypsum and rhomboclase precipitate at equilibrium saturation, kinetic controls on the precipitation of copiapite-group minerals affect the subsequent sulfate mineralogy and evolving chemistry of the entire system. In addition, geochemical simulations of the experimental evaporation process suggest that the appearance of voltaite and rhomboclase indicate a “metastable” evaporation pathway for martian fluids whereby bilinite and copiapite-group minerals did not form despite thermodynamic saturation. Comparison of the experimentally-produced assemblage to available observations of saline minerals at the martian surface represents a step toward systematically characterizing evaporite mineralogy as a function of Fe-oxidation in the initially dilute fluid. Deconvolving the complexity of Fe-sulfate formation in martian environments ultimately will help to exploit the sensitivity of these minerals to pH and redox conditions present at the ancient martian surface.     

Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO₄²⁻-CH₄ transition where H₂S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H₂S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe²⁺ diffusing up from below. The H₂S-Fe²⁺ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO₄²⁻ and 10 yr for H₂S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO₄²⁻-CH₄ and H₂S-Fe²⁺ cause the trapping of isotopically heavy iron sulfide with δ³⁴S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO₄²⁻ diffusing downward into the SO₄²⁻-CH₄ transition has an isotopic composition of +19‰, close to the +23‰ of H₂S diffusing upward. These isotopic compositions are, however, very different from the porewater SO₄²⁻ (+43‰) and H₂S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H₂S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.     

膏盐层在Ni-Cu-PGE硫化物矿床成矿中的作用 ——以俄罗斯诺里尔斯克矿床为例

与基性-超基性侵入体有关的Ni-Cu-PGE硫化物矿床是镍-铜-铂族元素矿床的最重要类型。传统观点认为,Ni-Cu-PGE硫化物矿床是由成矿岩浆分异演化、熔离形成的,与围岩性质关系不大。实际上,大部分基性-超基性岩浆是硫化物不饱和的,在岩浆自身演化过程中难以聚集大量硫化物而形成有经济价值的大型高品位NiCu-PGE硫化物矿床。因此,壳源硫的加入是基性-超基性岩浆中硫化物浓度达到过饱和,熔离形成Ni-Cu-PGE硫化物矿床的关键。膏盐层是富含石膏等硫酸盐(SO24-)的蒸发沉积建造,除SO24-外,还富含Cl-、CO23-、Na+、K+等盐类物质,在自然界分布广、面积大,是地壳中重要的硫源层和氧化障。但膏盐层在Ni-Cu-PGE硫化物矿床中的作用长期被忽视,制约了Ni-Cu-PGE硫化物矿床成矿找矿理论的发展。文章以世界最大的俄罗斯诺里尔斯克Ni-CuPGE硫化物矿床为例,介绍了膏盐层与矿床分布的空间关系、石膏等硫酸盐矿物在矿床和蚀变围岩中的分布、成矿元素和硫同位素组成特征及变化规律,阐明了膏盐层在成矿中的作用和控矿机理。膏盐(SO24-)的加入,可以大幅度提高成矿系统的氧逸度,将成矿岩浆中Fe2+氧化成Fe3+,形成铁氧化物,SO24-自身被还原,向成矿系统提供还原硫S2-,与Cu2+、Ni2+等结合,形成铜镍硫化物等,使基性-超基性成矿岩浆由硫化物不饱和变为过饱和,形成硫化物小液滴,在岩浆房经聚集-熔离-富集,形成岩浆型Ni-Cu-PGE硫化物矿床。除膏盐层外,富含硫化物的地层也是形成Ni-Cu-PGE硫化物矿床的重要硫源层。     

Geochemical models of the impact of acidic groundwater and evaporative sulfate salts on Boulder Creek at Iron Mountain,California

During dry season baseflow conditions approximately 20% of the flow in Boulder Creek is comprised of acidic metals-bearing groundwater. Significant amounts of efflorescent salts accumulate around intermittent seeps and surface streams as a result of evaporation of acid rock drainage. Those salts include the Fe-sulfates — rhomboclase ((H₃O)Fe³⁺(SO₄)₂·3H₂O), ferricopiapite (Fe³⁺₅(SO₄)₆O(OH)·20H₂O), and bilinite (Fe²⁺Fe₂³⁺(SO₄)₄·22H₂O); Al-sulfates — alunogen (Al₂(SO₄)₃·17H₂O) and kalinite (KAl(SO₄)₂·11H₂O); and Ca- and Mg-sulfates — gypsum (CaSO₄·2H₂O), and hexahydrite (MgSO₄·6H₂O). The dissolution of evaporative sulfate salt accumulations during the first major storm of the wet season at Iron Mountain produces a characteristic hydrogeochemical response (so-called “rinse-out”) in surface waters that is subdued in later storms. Geochemical modeling shows that the solutes from relatively minor amounts of dissolved sulfate salts will maintain the pH of surface streams near 3.0 during a rainstorm. On a weight basis, Fe-sulfate salts are capable of producing more acidity than Al- or Mg-sulfate salts. The primary mechanism for the production of acidity from salts involves the hydrolysis of the dissolved dissolved metals, especially Fe³⁺. In addition to the lowering of pH values and providing dissolved Fe and Al to surface streams, the soluble salts appear to be a significant source of dissolved Cu, Zn, and other metals during the first significant storm of the season.     

The composition and evolution of primordial solutions on Mars, with application to other planetary bodies

We examine a model for Mars involving bulk primordial solutions (oceans and lakes) that were relatively Mg-rich and SO₄/(SO₄ + Cl)-rich. Such solutions could be produced when (1) volatiles leached a planet (or portions of a planet) with an ultramafic-mafic composition in a process called “planetary leaching”; and/or by (2) “impactor leaching” where meteoritic and/or cometary impactor fragments were leached. When Mg-SO₄/(SO₄ + Cl)-rich solutions are concentrated, we predict that the following sequence of salts precipitates: phosphates; carbonates; gypsum; epsomite; bloedite; halite; hexahydrite; and, finally bischofite. This sequence is modified slightly if appreciable Fe-, Mg- or Na-carbonates, Fe-sulfates, Mg-phosphate, or other halide salts crystallized before the Mg-Na-sulfate salts, or if HCO₃+CO₃ concentrations vary due to other effects (e.g., atmosphere CO₂ levels change).On Mars, the initial primordial solutions would have been relatively salt-rich and water-poor; therefore, the surface solutions formed Mg-Na-SO₄-Cl salts (cements, veneers, and dust) and subsurface solutions or ice (solid H₂O). This model is supported by the compositions of cements in the regolith on Mars (high Mg, Na, S, and Cl) and geochemical and petrographic evidence that the salts precipitated in the predicted sequence. We suggest that the partial pressure of oxygen was above the hematite-magnetite buffer where Fe³⁺-(hydrous)-oxides are stable and SO₄^2- or HSO₄^- are solutes in any solution. Such a partial pressure of oxygen may have been attained via H₂-loss.In contrast, on the Galilean satellites (Europa, Ganymede, and Callisto) surface solutions were relatively water-rich and formed ice, Mg-SO₄-rich salts, and solutions, thereby producing surface features dependent on the initial water content and the crystallization path. Unlike the Na-Cl-rich oceans on Earth, the solutions of these planetary bodies likely did not change greatly from their bulk primordial Mg-rich, SO₄/(SO₄ + Cl)-rich compositions; hence they did not attain compositions similar to modern seawater.     

Field tracer test for denitrification in a pyrite-bearing schist aquifer

A small-scale artificial tracer test performed on a schist aquifer in Brittany has helped clarify mechanisms and kinetics of in situ autotrophic denitrification. NO₃ was injected as a pulse simultaneously with a conservative tracer -Br⁻. During the test, which lasted 210 h, 73% of the injected Br⁻ was recovered, as against only 47% of the NO₃. The 26% difference in the recovery of the two injected species is interpreted as being the result of denitrification, in part due to the direct oxidation of pyrite present in the solid aquifer according to the reaction: 5FeS₂+14NO₃⁻+4H⁺→7N₂+10SO₄²⁻+5Fe²⁺+2H₂O, and in part due to subsequent iron oxidation according to the reaction: NO₃⁻+5Fe²⁺+6H⁺→1/2N₂+5Fe³⁺+3H₂O. Despite the potential increase in SO₄ and Fe resulting from denitrification through pyrite oxidation, the concentrations of these elements in the groundwater remain moderate due to the precipitation of minerals such as jarosite and/or natroalunite. Tracer transfer takes place in a heterogeneous medium which, according to the breakthrough curves, can be simplified to a dual-porosity aquifer comprising a high-permeability (fractures or large fissures) medium of low porosity from which only minor denitrification of circulating NO₃-bearing water was observed and a low-permeability (small fissures) medium of high porosity which induces a higher denitrification rate in the circulating NO₃-bearing water. The kinetics of the denitrification reaction are high compared with results obtained for other environments and can be described by a first-order model with a half life of 7.9 days for the low-porosity medium and only 2.1 days for the high-porosity medium.     

A theoretical model of the stable sulfur isotope distribution in marine sediments

A diffusion-diagenesis model of the sulfur cycle is developed to calculate theoretical distributions of stable sulfur isotopes in marine sediments. The model describes the depth variation in δ³⁴S of dissolved sulfate and H₂S. and of pyrite. The effects of sulfate reduction, sulfate and H₂S diffusion. and of sedimentation are considered as well as the bacterial isotope fractionation and the degree of pyrite formation. Under open system conditions of sulfur diagenesis the isotopic difference, ΔSO^2?₄ — H₂S, tends to increase with depth being smaller than the bacterial fractionation factor near the sediment surface and larger in deeper layers. The two isotopes in SO^2?₄ or in H₂S do not diffuse in the same proportion as they occur in the porewater. This explains why sulfur, which is incorporated from seawater sulfate by diffusion and precipitation as pyrite, can be enriched in ³²S relative to the seawater sulfate. The model calculations demonstrate the importance of taking the whole dynamic sulfur cycle into account before drawing conclusions about sulfur diagenesis from the stable isotope distribution.     

Computer simulations of the interactions of the (0 1 2) and (0 0 1) surfaces of jarosite with Al, Cd, Cu and Zn

Jarosite is an important mineral on Earth, and possibly on Mars, where it controls the mobility of iron, sulfate and potentially toxic metals. Atomistic simulations have been used to study the incorporation of Al³⁺, and the M²⁺ impurities Cd, Cu and Zn, in the (0 1 2) and (0 0 1) surfaces of jarosite. The calculations show that the incorporation of Al on an Fe site is favorable on all surfaces in which terminal Fe ions are exposed, and especially on the (0 0 1) [Fe₃(OH)₃]⁶⁺ surface. Incorporation of Cd, Cu or Zn on a K site balanced by a K vacancy is predicted to stabilize the surfaces, but calculated endothermic solution energies and the high degree of distortion of the surfaces following incorporation suggest that these substitutions will be limited. The calculations also suggest that incorporation of Cd, Cu and Zn on an Fe site balanced by an OH vacancy, or by coupled substitution on both K and Fe sites, is unfavorable, although this might be compensated for by growth of a new layer of jarosite or goethite, as predicted for bulk jarosite. The results of the simulations show that surface structure will exert an influence on uptake of impurities in the order Cu > Cd > Zn, with the most favorable surfaces for incorporation being (0 1 2) [KFe(OH)₄]⁰ and (0 0 1) [Fe₃(OH)₃]⁶⁺.     

电感耦合等离子体质谱法测定硫时不同形态硫的影响

电感耦合等离子体质谱(ICP-MS)常常被应用于矿石、蛋白质和化石燃料等材料中硫含量的测定。文章综合研究比较了四极杆电感耦合等离子体质谱(Q-ICP-MS)和扇形磁场电感耦合等离子体质谱(SF-ICP-MS)测定硫的灵敏度、检出限及空白干扰。重点考察了两种不同的样品介质(水和2% HNO₃)中不同形态的硫对SF-ICP-MS测定硫信号的影响,并且深入研究了影响的原因。结果表明,硫含量相同但形态不同的含硫阴离子(S^2-、S₂O₃^2-、SO₃^2-、SO₄^2-)在2%的HNO₃介质中的信号比在水介质中的信号稳定,2%的HNO₃更适合于作为ICP-MS测定硫的介质。在2%的HNO₃介质中,S^2-、SO₃^2-中S的ICP-MS测量灵敏度(即标准曲线的斜率)分别为7828 cps/(μg·L^-1)、5528 cps/(μg·L^-1),SO₄^2-和S₂O₃^2-的测量灵敏度分别是为1321 cps/(μg·L^-1)、1299 cps/(μg·L^-1)。S^2-和SO₃^2-的灵敏度分别约为SO₄^2-的6倍和4倍;而S₂O₃^2-的灵敏度与SO₄^2-基本一致。主要原因在于S^2-、SO₃^2-形态的硫在HNO₃介质中形成了气态的H₂S和SO₂,相当于提高了雾化效率,从而使这两种形态硫的灵敏度大幅度提高。     

The Use of Stable Sulfur, Oxygen and Hydrogen Isotope Ratios as Geochemical Tracers of Sulfates in the Podwiśniówka Acid Drainage Area (South-Central Poland)

The paper presents the results of determinations of stable S and O isotopes of dissolved sulfates and O and H stable isotopes of waters from three ponds, that is, Marczakowe Do?y acid pond, Marczakowe Do?y fish pond and Podwi?niówka acid pit pond, located in the Holy Cross Mountains (south-central Poland). The δ³⁴S_V-CDT and δ¹⁸O_V-SMOW of SO₄ ^2? in waters of three ponds (n = 14) varied from ?16.2 to ?9.5 ‰ (mean of ?13.6 ‰) and from ?8.1 to ?3.2 ‰ (mean of ?4.8 ‰), respectively. The mean δ³⁴S–SO₄ ^2? values were closer to those of pyrite (mean of ?25.4 ‰) and efflorescent sulfate salts (mean of ?25.6 ‰), recorded previously in the Podwi?niówka quarry, than to sulfates derived from other anthropogenic or soil and bedrock sources. The SO₄ ^2? ions formed by bacterially induced pyrite oxidation combined with bacterial (dissimilatory) dissolved sulfate reduction, and presumably with subordinate mineralization of carbon-bonded sulfur compounds, especially in both Marczakowe Do?y ponds. In addition, the comparison of δ¹⁸O–SO₄ ^2? and δ¹⁸O–H₂O values indicated that 75–100 % of sulfate oxygen was derived from water. Due to the largest size, the Podwi?niówka acid pit pond revealed distinct seasonal variations in both δ¹⁸O–H₂O (?9.2 to ?1.6) and δD–H₂O (?29.7 to ?71.3) values. The strong correlation coefficient (r ² = 0.99) was noted between δ¹⁸O–H₂O and δD–H₂O values, which points to atmospheric precipitation as the only source of water. The sediments of both acid ponds display different mineral inventory: the Marczakowe Do?y acid pond sediment consists of schwertmannite and goethite, whereas Podwi?niówka acid pit pond sediment is composed of quartz, illite, chlorite and kaolinite with some admixture of jarosite reflecting a more acidic environment. Geochemical modeling of two acid ponds indicated that the saturation indices of schwertmannite and nanosized ε-Fe₂O₃ (Fe³⁺ oxide polymorph) were closest to thermodynamic equilibrium state with water, varying from ?1.44 to 3.05 and from ?3.42 to 6.04, respectively. This evidence matches well with the obtained mineralogical results.     

Jarosite and akaganéite from White Island volcano,New Zealand: An X-ray and Mössbauer study

Computer-based Mössbauer spectroscopic and X-ray diffraction procedures have been used to study the yellow/brown surface deposits, occurring on andesite boulders and rock fragments near gently steaming areas, fumarole vents, boiling pools and streams on White Island, New Zealand. These deposits result from alteration of the rock, and consist chiefly of a potassium-sodium-hydronium jarosite, (K_0.56Na_0.39H⁺₃O_0.05) (Al_0.16Fe_0.84)₃ (SO₄)₂(OH)₆ and akaganéite, β-FeOOH, with lesser amounts of goethite, α-FeOOH, in some cases.     

Sideronatrite: A mineral with a {Fe2(SO4)4(OH)2} guildite type chain?

Summary Recently several natural and artificial ferric iron sulphate crystal structures have been solved. Sideronatrite, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, does not provide good crystals for structural purposes. However if we examine crystallographic, chemical and physical data some useful information about the ...Fe–O–S... structural topology can be inferred. In fact this analysis strengthens the hypothesis that there is a {Fe ₂ ³⁺ (SO₄)₄(OH)₂} chain in sideronatrite like that found in guildite, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O.

---

Sideronatrit: Ein Mineral mit einer {Fe₂(SO₄)₄(OH)₂}-Kette vom Typ Guildit?

Zusammenfassung Kürzlich wurden die Kristallstrukturen mehrerer natürlicher und künstlicher Ferrisulfate gelöst. Sideronatrit, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, liefert keine für die Strukturuntersuchung gut geeigneten Kristalle. Dennoch erhält man aus der Untersuchung der kristallographischen, chemischen und physikalischen Daten nützliche Information über die ...Fe–O–S...-Topologie der Struktur. Eine solche Analyse spricht für die Hypothese, daß der Sideronatrit eine {Fe ₂ ³⁺ (SO₄)₄(OH₂)}-Kette enthält, wie sie im Guildit, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O, gefunden wurde.

---

---

With 1 Figure

---

Paper presented at the Sixth European Crystallographic Meeting. Barcelona, Spain 1980.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

Thermochemistry of yavapaiite KFe(SO4)2: Formation and decomposition

Yavapaiite, KFe(SO₄)₂, is a rare mineral in nature, but its structure is considered as a reference for many synthetic compounds in the alum supergroup. Several authors mention the formation of yavapaiite by heating potassium jarosite above ca. 400°C. To understand the thermal decomposition of jarosite, thermodynamic data for phases in the K-Fe-S-O-(H) system, including yavapaiite, are needed. A synthetic sample of yavapaiite was characterized in this work by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermal analysis. Based on X-ray diffraction pattern refinement, the unit cell dimensions for this sample were found to be a = 8.152 ± 0.001 Å, b = 5.151 ± 0.001 Å, c = 7.875 ± 0.001 Å, and β = 94.80°. Thermal decomposition indicates that the final breakdown of the yavapaiite structure takes place at 700°C (first major endothermic peak), but the decomposition starts earlier, around 500°C. The enthalpy of formation from the elements of yavapaiite, KFe(SO₄)₂, ΔH°_f = −2042.8 ± 6.2 kJ/mol, was determined by high-temperature oxide melt solution calorimetry. Using literature data for hematite, corundum, and Fe/Al sulfates, the standard entropy and Gibbs free energy of formation of yavapaiite at 25°C (298 K) were calculated as S°(yavapaiite) = 224.7 ± 2.0 J.mol⁻¹.K⁻¹ and ΔG°_f = −1818.8 ± 6.4 kJ/mol. The equilibrium decomposition curve for the reaction jarosite = yavapaiite + Fe₂O₃ + H₂O has been calculated, at pH₂O = 1 atm, the phase boundary lies at 219 ± 2°C.