Surface alteration of arsenopyrite (FeAsS) by Thiobacillus ferrooxidans

The surface of arsenopyrite was characterized after acidic, oxidative leaching in the presence of the bacterial species Thiobacillus ferrooxidans. Polished single-crystal grains of arsenopyrite were reacted for 1, 2, and 3 weeks with T. ferrooxidans suspended in a solution (pH 2.3) of essential salts (MgSO₄·7H₂O, [NH₄]₂SO₄, KH₂PO₄, and KCl). Abiotic control experiments were conducted in identical solutions. Reaction between arsenopyrite and T. ferrooxidans in the essential salts solution produced a uniform solid FePO₄ overlayer (∼0.2 μm thick) on the arsenopyrite surface within 1 week. The overlayer was detected visually by scanning electron microscopy (SEM) and chemically by X-ray photoelectron spectroscopy (XPS). It could not be distinguished by energy-dispersive X-ray analyses. No overlayer formed in the abiotic control. The uniform thickness and lateral continuity of the overlayer suggest an inorganic origin promoted by bacterial production of Fe³⁺. Iron released from arsenopyrite was oxidized by bacteria and subsequently precipitated with PO₄³⁻ (from the essential salts), forming ferric phosphate. After 2 and 3 weeks, SEM images revealed a roughened arsenopyrite surface, and XPS depth profiles indicated a progressively thicker phosphate overlayer and continued oxidation, diffusion, and dissolution of arsenopyrite beneath the overlayer. After only 1 week, the cells were isolated from the arsenopyrite surface by the uniform overlayer. Therefore, bacteria need not be attached to arsenopyrite to promote rapid reaction, and the mechanism of alteration at the arsenopyrite surface must have been inorganic. Because the delicate overlayer did not prevent continued alteration of arsenopyrite, FePO₄ may not be an effective barrier to oxidation in the tailings environment. The FePO₄ coating has likely formed in other experiments using these bacteria but was not detected because analytical techniques were not sufficiently surface sensitive to identify a separate, compositionally distinct overlayer. Some previous experimental results thus may be misleading or inapplicable to the tailings environment.     

Dissolution of arsenopyrite (FeAsS) and galena (PbS) in the presence of desferrioxamine-B at pH 5

Microorganisms and higher plants produce biogenic ligands, such as siderophores, to mobilize Fe that otherwise would be unavailable. In this paper, we study the stability of arsenopyrite (FeAsS), one of the most important natural sources of arsenic on Earth, in the presence of desferrioxamine (DFO-B), a common siderophore ligand, at pH 5. Arsenopyrite specimens from mines in Panasqueira, Portugal (100-149 μm) that contained incrustations of Pb, corresponding to elemental Pb as determined by scanning electron microscopy-electron diffraction spectroscopy (SEM-EDX), were used for this study. Batch dissolution experiments of arsenopyrite (1 g L⁻¹) in the presence of 200 μM DFO-B at initial pH (pH₀) 5 were conducted for 110 h. In the presence of DFO-B, release of Fe, As, and Pb showed positive trends with time; less dependency was observed for the release of Fe, As, and Pb in the presence of only water under similar experimental conditions. Detected concentrations of soluble Fe, As, and Pb in suspensions containing only water were found to be ca. 0.09 ± 0.004, 0.15 ± 0.003, and 0.01 ± 0.01 ppm, respectively. In contrast, concentrations of soluble Fe, As, and Pb in suspensions containing DFO-B were found to be 0.4 ± 0.006, 0.27 ± 0.009, and 0.14 ± 0.005 ppm, respectively. Notably, the effectiveness of DFO-B for releasing Pb was ca. 10 times higher than that for releasing Fe. These results cannot be accounted for by thermodynamic considerations, namely, by size-to-charge ratio considerations of metal complexation by DFO-B. As determined by SEM-EDX, elemental sample enrichment analysis supports the idea that the Fe-S subunit bond energy is limiting for Fe release. Likely, the mechanism(s) of dissolution for Pb incrustations is independent and occurs concurrently to that for Fe and As. Our results show that dissolution of arsenopyrite leads to precipitation of elemental sulfur, and is consistent with a non-enzymatic mineral dissolution pathway. Finally, speciation analyses for As indicate variability in the As(III)/As(V) ratio with time, regardless of the presence of DFO-B or water. At reaction times <30 h, As(V) concentrations were found to be 50-70%, regardless of the presence of DFO-B. These results are interpreted to indicate that transformations of As are not imposed by ligand-mediated mechanisms. Experiments were also conducted to study the dissolution behavior of galena (PbS) in the presence of 200 μM at pH₀ 5. Results show that, unlike arsenopyrite, the dissolution behavior of galena shows coupled increases in pH with decreases in metal solubility at t > 80 h. Oxidative dissolution mechanisms conveying sulfur oxidation bring about the production of {H⁺}. However, dissolution data trends for arsenopyrite and galena indicate {H⁺} consumption. It is plausible that the formation of Pb species is dependent on {H⁺} and {OH⁻}, namely, stable surface hydroxyl complexes of the form (pH₅₀ 5.8) and for pH values 5.8 or above.     

Rutile solubility and mobility in supercritical aqueous fluids

Experimental and thermodynamic data and the apparent immobility of Ti under metamorphic conditions suggest that rutile is very insoluble in aqueous fluids at upper crustal conditions. New solubility measurements at 1.0–2.93 GPa and 800–1200°C show, however, that under certain pressure and temperature conditions rutile is quite soluble in H₂O. Solubilities were estimated from the measured weight loss of a single crystal equilibrated with a known mass of fluid in a piston cylinder apparatus. Measured solubilities in H₂O range from 0.15 wt% (wt loss crystal/wt fluid) at 2.93 GPa and 1000°C to 1.9% at 1.0 GPa and 1100°C. Solubility increases with increasing temperature and with decreasing pressure in a manner given by the following fit to the experimental data:

Calcite solubility and speciation in supercritical NaCl-HCl aqueous fluids

The solubility of calcite in NaCl-H₂O and in HCl-H₂O fluids was measured using an extraction-quench hydrothermal apparatus. Experiments were conducted at 2 kbar, between 400° C and 600° C. Measurements in NaCl-H₂O were conducted in two ways: 1) at constant pressure and NaCl concentration, as a function of temperature; and 2) at constant pressure and temperature, as a function of NaCl concentration. In both the NaCl-H₂O and the HCl-H₂O systems, the solubility of calcite increases with increasing chlorine concentrations. For example, the log calcium molality in equilibrium with calcite increases from –3.75 at 2 kbar and 500° C, in pure H₂O to –3.10 at 2 kbar and 500° C at log NaCl molality=–1.67. At fixed pressure and NaCl molality, the solubility of calcite is almost constant from 400° C to 550° C, but increases somewhat at higher temperatures. The results can be used to determine the dominant calcium species in the experimental solutions as a function of NaCl concentration and to obtain values for the second dissociation constant of CaCl_2(aq). At 2 kbar, 400° C, 500° C, and 600° C, we calculate values for the log of the dissociation constant of CaCl⁺ of –2.1, –3.2, and –4.3, respectively. The 400° C and 500° C values are consistent with those obtained by Frantz and Marshall (1982) using electrical conductance techniques. However, our 600° C value is 0.8 log units higher than that reported by Frantz and Marshall. The calcite solubilities in the NaCl-H₂O and HCl-H₂O systems are inconsistent with the solubilities of calcite in pure H₂O reported by Walther and Long (1986). They are, however, consistent with the measurements of calcite solubilities in pure H₂O presented in this study. These results allow for the calculation of the solubilities of calcium silicates and carbonates in fluids that contain CO₂ and NaCl.     

The oxidative dissolution of arsenopyrite (FeAsS) and enargite (Cu3AsS4) by Leptospirillum ferrooxidans

Arsenopyrite (FeAsS) and enargite (Cu₃AsS₄) fractured in a nitrogen atmosphere were characterised after acidic (pH 1.8), oxidative dissolution in both the presence and absence of the acidophilic microorganism Leptospirillum ferrooxidans. Dissolution was monitored through analysis of the coexisting aqueous solution using inductively coupled plasma atomic emission spectroscopy and coupled ion chromatography-inductively coupled plasma mass spectrometry, and chemical changes at the mineral surface observed using X-ray photoelectron spectroscopy and environmental scanning electron microscopy (ESEM). Biologically mediated oxidation of arsenopyrite and enargite (2.5 g in 25 ml) was seen to proceed to a greater extent than abiotic oxidation, although arsenopyrite oxidation was significantly greater than enargite oxidation. These dissolution reactions were associated with the release of ∼917 and ∼180 ppm of arsenic into solution. The formation of Fe(III)-oxyhydroxides, ferric sulphate and arsenate was observed for arsenopyrite, thiosulphate and an unknown arsenic oxide for enargite. ESEM revealed an extensive coating of an extracellular polymeric substance associated with the L. ferrooxidans cells on the arsenopyrite surface and bacterial leach pits suggest a direct biological oxidation mechanism, although a combination of indirect and direct bioleaching cannot be ruled out. Although the relative oxidation rates of enargite were greater in the presence of L. ferrooxidans, cells were not in contact with the surface suggesting an indirect biological oxidation mechanism. Cells of L. ferrooxidans appear able to withstand several hundreds of ppm of As(III) and As(V).     

Distribution of crustal fluids in Northeast Japan as inferred from resistivity surveys

We carried out magnetotelluric (MT) surveys in central northeastern Japan. Two-dimensional resistivity profiles along three survey lines show similar features each other. By comparing the resistivity distribution to the distribution of seismic velocities, we inferred the distribution and flow of crustal fluids. Three fluid flow paths were detected based on the distribution of regions of low resistivity. The first path ascends from the top of the upper mantle, passes through the lower crust, and reaches the surface, forming a fluid chamber within the lower or middle crust. This path is related to the volcanic activity in the backbone range. The second path rises from the first fluid chamber and has produced small fluid reservoirs on both sides of the backbone range. These small reservoirs are considered to be related to the seismicity of the region. The third path is located to the east of the volcanic front and represents another fluid flow path from the uppermost mantle to the lower crust that may have formed a small fluid reservoir to the east of the volcanic front.     

Distribution of crustal fluids in Northeast Japan as inferred from resistivity surveys

We carried out magnetotelluric (MT) surveys in central northeastern Japan. Two-dimensional resistivity profiles along three survey lines show similar features each other. By comparing the resistivity distribution to the distribution of seismic velocities, we inferred the distribution and flow of crustal fluids. Three fluid flow paths were detected based on the distribution of regions of low resistivity. The first path ascends from the top of the upper mantle, passes through the lower crust, and reaches the surface, forming a fluid chamber within the lower or middle crust. This path is related to the volcanic activity in the backbone range. The second path rises from the first fluid chamber and has produced small fluid reservoirs on both sides of the backbone range. These small reservoirs are considered to be related to the seismicity of the region. The third path is located to the east of the volcanic front and represents another fluid flow path from the uppermost mantle to the lower crust that may have formed a small fluid reservoir to the east of the volcanic front.     

不同酸液条件下叙利亚灰岩溶蚀能力的实验研究

文章根据SY/T 6526-2002《盐酸与碳酸盐岩动态反应速率测定方法》,利用高温高压酸岩反应仪进行了普通盐酸、有机盐酸、胶凝酸、乳化酸和地面交联酸与叙利亚灰岩粉末在两个目的层温度95 ℃和150 ℃下2.0 h的溶蚀实验。结果显示,五种酸液2.0 h的酸溶解率都在90%以上,普通盐酸、有机盐酸的溶蚀能力高于胶凝酸、乳化酸和地面交联酸三种缓速酸;95 ℃下乳化酸和地面交联酸溶解慢、溶解率低,而150 ℃下是地面交联酸和胶凝酸;适当条件下,“多相隔离”对H+抑制作用要比高粘度溶液强,而且随着酸液内部高分子之间链接复杂程度的提高,H+被束缚的程度也增大;温度提高增大了酸溶解率,对乳化酸、地面交联酸和胶凝酸影响比较显著,对普通盐酸和有机盐酸不明显。      

Anomalous alkaline rocks of Soustov, Kola: evidence of mantle-derived metasomatic fluids affecting crustal materials

The intrusive complexes of Gremiakha-Vyrmes and Soustov represent the two extremes of the Early Proterozoic alkaline plutons of Kola, predominantly composed of feldespathoidal syenites. Gremiakha-Vyrmes rocks (zircon age: 1,884Lj Ma) have trace-element and isotope signatures (⁸⁷Sr/⁸⁶Sr_tƸ.704, )Nd_t,-3-1.3) compatible with an ultimate mantle origin. Soustov syenites (zircon age: 1,872NJ Ma) are totally different and show an acute crustal imprint. They have sodaline and analcite instead of nepheline, contain a plethora of REE-HFSE-rich accessories, and are characterised by elevated contents of F, Cl, REE, Y, Th, U, Zr, Hf, Nb, Ta, Sn, Be, Li, Rb, Tl, Pb and Cs, negative Eu anomalies, K/Rb겞-160, Nd/Thƻ, and Nb/Taᄼ, with extremely high ⁸⁷Sr/⁸⁶Sr_t (>0.720) and, at the same time, relatively high )Nd_t (,-1.6-1.7). In this paper, we explore the idea that the anomalous features of Soustov syenites can be explained if we assume they are derived from a metasomatic agent, initially an H₂O-CO₂ supercritical fluid released by alkaline mafic magmas, that was profoundly contaminated during percolation through crustal materials. As percolation advanced, the bulk composition of the fluid solute changed from alkali halides and carbonates to a silica-undersaturated alkaline melt. When the fluid cooled to a temperature of ~550-600 °C, it reached the point at which vapor and melt were no longer miscible and split into two components, a vapour phase and a Cl- and F-rich silica-undersaturated silicate melt that crystallised to produce Soustov syenites. To study this process, we have developed a numerical method for modelling the solute composition of the fluid during the infiltration metasomatism. Our results, using the LREE abundances and the Sr and Nd isotope composition of a Gremiakha-Vyrmes pegmatite as the starting solute composition of the fluid, and the mode and mineral trace-element and isotope composition of a common Kola gneiss as representative of percolated materials, indicate that the fluid would have acquired a signature closely matching Soustov's, even in the case of Nd isotopes, if the gneiss age is 2.9 Ga, near its real age. This model is still a mere working hypothesis that needs further refinements, but may represent a reasonable explanation of the genesis of anomalous alkaline rocks with high ⁸⁷Sr/⁸⁶Sr_t and )Nd_t̾, either saturated or undersaturated, which are difficult to understand in terms of magmatic fractionation/contamination.     

福建泉州市区域稳定性的探讨

本文对泉州市区域地壳结构、地质构造、构造应力场和地震活动性进行了综合分析.结果表明,泉州市在第四纪中更新世之前位于环太平洋中、新生代构造-岩浆活动带中,地壳运动频繁而又强烈,地质构造复杂;现代处于菲律宾海板块对欧亚板块挤压形成的"台湾动力触角"影响区,但区内的断裂不具全新世活动性,新构造运动不强烈,有史以来未见≥5.0级地震记载,属于地壳相对稳定区,未来遭遇6.0级地震的危险性不大,其地震破坏性影响主要来自周边孕震区,特别是东部海域,与"台湾动力触角"的作用和滨海断裂带的活动有关.     

湖南产于前寒武系中金矿床毒砂的标型特征

湖南产于前寒武系中的金矿床尤其是砷金矿床 ,毒砂分布甚广 ,毒砂中 Au含量一般 12 0×10 -6～ 2 50× 10 -6,金的分布率达 64.3%～ 93.1% ,是金的主要载体矿物。毒砂的形成有早、晚两期 ,化学成分为 S富 As亏型 ,并以富含微量元素 Sb、 ( Se)、 Ni、 Co而贫 Mn以及晶胞参数 a0 值增大等为标型特征。绝大部分含 Au毒砂的光片没有显微金存在 ,即使利用电子探针也难以发现金。由此产生了毒砂中的金以超微细颗粒存在或以晶格金形式存在的分歧。经有关金矿床多项实验研究结果 ,初步认为毒砂中的“不可见金”大多数是以纳米级微细粒状存在。     

Water solubility in haplogranitic melts coexisting with H2O-H2 fluids

The water solubility in haplogranitic melts (normative composition Ab₃₉Or₃₂Qz₂₉) coexisting with H₂O-H₂ fluids at 800 and 950 °C and 1, 2 and 3 kbar vapour pressure has been determined using IR spectroscopy. The experiments were performed in internally heated pressure vessels and the hydrogen fugacity (f _H2) was controlled using the double capsule technique and oxygen buffer assemblages (WM and IW). Due to the limited lifetimes of these oxygen buffers the water solubility was determined from diffusion profiles (concentration-distance profiles) measured with IR spectroscopy in the quenched glasses. The reliability of the experimental strategy was demonstrated by comparing the results of short- and long-duration experiments performed with pure H₂O fluids. The water solubility in Ab₃₉Or₃₂Qz₂₉ melts equilibrated with H₂O-H₂ fluids decreases progressively with decreasing f _H2O, as f _H2 (or X _H2) increases in the fluid phase. The effect of H₂ on the evolution of the water solubility is similar to that of CO₂ or another volatile with a low solubility in the melt and can be calculated in a first approximation with the Burnham water solubility model. Recalculation of high temperature water speciation for AOQ melts coexisting with H₂O-H₂ fluids at 800 °C, 2 kbar suggests that the concentrations of molecular H₂O are proportional to f _H2O (calculated using available mixing models), indicating Henrian behaviour for the solubility of molecular H₂O in haplogranitic melts. Received: 29 June 1998 / Accepted: 10 March 1999     

Geochemistry of loess,continental crustal composition and crustal model ages

Isotopic, major and trace element studies of loess deposits from America, China, Europe and New Zealand show general uniformity of composition. Silica, Zr and Hf are enriched relative to estimates of bulk composition of the upper continental crust. The REE data are indistinguishable from those of average shales, confirming the concept that these REE patterns ($\text{La}{}_{\mathrm{N}}\text{/}\text{Yb}{}_{\mathrm{N}}\text{= 9.5}\text{Eu}\text{/}\text{Eu}{}^1\text{= 0.66}$) represent the upper crustal average. Sm-Nd model ages are variable but <1700 m.y. They reflect derivation from younger elevated erogenic areas subject to Pleistocene glaciation. Although Sm-Nd model ages vary by a factor of two, the REE patterns remain constant. This indicates that processes responsible for formation of the upper crust have produced no secular change in composition since the mid-Proterozoic.     

Pyrite,marcasite, and arsenopyrite type minerals: Crystal chemical and structural principles

Quantitative molecular orbital (MO) calculations and qualitative perturbational MO arguments are used to interpret the spectra and structure of transition metal dichalcogenides and related compounds. Competition between pyrite (FeS₂), marcasite (FeS₂) and loellingite (FeAs₂) structure types is explained in terms of the number of electrons occupying a set of MO's obtained from the mixing of dianion (A ₂) orbitals and metal (M) dσ orbitals. Direct metal-metal d orbital interaction is argued to be small. Attention is focused upon the M - A - M angles which differ substantially among the three structure types as a consequence of varying numbers of electrons in orbitals which closely resemble the pπ* orbitals of the dianions. Variations in M - A and A - A distances can also be understood in terms of the occupations of this set of MO's. Disulfide valence region photo-emission spectra are interpreted in terms of calculations on MS₆ and S₆ molecular clusters. M3d orbitals are found to progressively approach the S3p orbitals with increasing atomic number of M from Fe to Ni. For CuS₂ comparison of calculation and experiment supports an approximate electron configuration of Cu⁺¹ S ₂ ^?1 .     

Epigenetic tourmalinite and arsenopyrite in the aureole of the Leinster batholith,SE Ireland

Metasomatic tourmaline-quartz-hydromuscovite/phengite-fluorite rocks which locally contain in excess of 40% disseminated arsenopyrite and lesser amounts of pyrrhotite, chalcopyrite, pyrite, molybdenite, rutile, ilmenite and Fe-rich chlorite, occur near the village of Inistioge in SE Ireland. They are developed within Lower Palaeozoic phyllites close to the northwest margin of the southern termination of the Leinster batholith. The mineralization occurs within a belt of anomalously high (Caledonian) strain which was active during batholith-intrusion and which is essentially a product of heterogeneous shortening. Tourmaline constitutes up to 60% of the volume of the metasomatic material and although the lithology exhibits bed-parallel lamination, both detailed field and textural relationships demonstrate its origin to be epigenetic. The mineralization is spatially related to pegmatitic (K-feldspar, fluorite and muscovite-bearing) quartz veins with greisen alteration envelopes composed of coarse-grained muscovite, fluorite, apatite and tourmaline. The mineralized rocks were produced during alteration of aluminous metasediments by magmatic and/or meteoric fluids which were channelled through the high strain zone during cooling of the batholith.     

氧化亚铁硫杆菌与毒砂相互作用的阶段性及其机理研究

设计了毒砂的生物氧化和化学氧化两组对比实验,并对反应35d的溶液化学、固相产物成分和矿物表面元素化合态变化进行了分析,以说明氧化亚铁硫杆菌（A．ferrooxidans）与毒砂的相互作用机理。研究发现,毒砂的生物氧化过程随A．ferrooxidans菌生长规律分为三个阶段：（1）反应前7d,生物氧化作用还很弱,以自然氧化反应为主;（2）反应8～21d,生物氧化反应开始发生,细菌进入迟缓生长期;（3）反应22～35d,细菌处于对数生长期,生物氧化作用强烈。由离子浓度变化规律反映,前两个阶段生物氧化速率低于化学氧化,第三阶段起生物氧化速率高于化学氧化。细菌生长受溶液累积的As抑制,A．ferrooxidans菌能促进As和Fe形成砷酸铁沉淀,以降低As的抑制作用。毒砂表面高价态元素的比例随细菌生长和溶液Fe离子浓度的升高而增大,生物氧化第三阶段毒砂表面高价态元素的比例高于化学氧化。氧化过程中毒砂表面覆盖中间氧化产物S^0和As2S3沉积层,对比化学氧化,Aferrooxidans菌能不断把Fe^2＋氧化成Fe^3＋,促进毒砂表面中间产物氧化,并间接氧化毒砂。     

Kinetics of arsenopyrite oxidative dissolution by oxygen

We used a mixed flow reactor system to determine the rate and infer a mechanism for arsenopyrite (FeAsS) oxidation by dissolved oxygen (DO) at 25 °C and circumneutral pH. Results indicate that under circumneutral pH (6.3-6.7), the rate of arsenopyrite oxidation, 10^{−10.14±0.03} mol m⁻² s⁻¹, is essentially independent of DO over the geologically significant range of 0.3-17 mg L⁻¹. Arsenic and sulfur are released from arsenopyrite in an approximate 1:1 molar ratio, suggesting that oxidative dissolution by oxygen under circumneutral pH is congruent. Slower rates of iron release from the reactor indicate that some of the iron is lost from the effluent by oxidation to Fe(III) which subsequently hydrolyzes and precipitates. Using the electrochemical cell model for understanding sulfide oxidation, our results suggest that the rate-determining step in arsenopyrite oxidation is the reduction of water at the anodic site rather than the transfer of electrons from the cathodic site to oxygen as has been suggested for other sulfide minerals such as pyrite.