Thermodynamic properties of tooeleite,Fe63+(As3+O3)4(SO4)(OH)4·4H2O     

《Chemie der Erde / Geochemistry》2016,76(3):419-428

Tooeleite, nominally Fe₆³⁺(As³⁺O₃)₄(SO₄)(OH)₄·4H₂O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol⁻¹. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol⁻¹ K⁻¹. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol⁻¹. The log K_sp value, calculated for the reaction Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O + 16H⁺ = 6Fe³⁺ + 4H₃AsO₃ + SO₄²⁻ + 8H₂O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe³⁺ and As³⁺ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe²⁺ to Fe³⁺ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.  相似文献   

Stabilisation/solidification and bioaugmentation treatment of petroleum drill cuttings     

《Applied Geochemistry》2016

Petroleum drill cuttings are usually treated by techniques suitable for particular contaminant groups. The significance of this study consists in the development of a treatment technology that can simultaneously handle the hydrocarbon and metal constituents of drill cuttings. Bioaugmentation is combined with stabilisation/solidification (S/S), within S/S monoliths and in granulated S/S monoliths. Portland cement was used for S/S treatment at 30% binder dosage. Bioaugmentation treatment involved two bacterial densities of a mixed culture bio-preparation. The effects of inclusion of compost, fertiliser and activated carbon were also evaluated. After 28 days, the combined S/S and bioaugmentation treatments recorded up to 15% higher total petroleum hydrocarbon (TPH) loss than control S/S treatment without bioaugmentation. Embedding fertiliser, activated carbon and higher bacterial density within S/S monoliths resulted in the highest (99%) TPH reduction but higher concentrations of metals. The addition of compost and lower bacterial density to granulated S/S monoliths led to similar (98%) TPH degradation and lower amounts of metals. The results suggest that with better mixture optimisation, combining S/S and bioaugmentation could engender more sustainable treatment of drill cuttings.  相似文献   

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions     

《Applied Geochemistry》2016

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.  相似文献   

Investigation of moment-rotation relation in different joint types and evaluation of their effects on segmental tunnel lining     

Abbas?Majdi  Hamed?Ajamzadeh  Siavash?NadimiEmail author 《Arabian Journal of Geosciences》2016,9(7):512

This paper presents the results of a numerical study that has been performed to investigate the different joint types that affect the moment-rotation relation and ultimate bending moment capacity of a joint. A 3D finite element method was adapted to establish elaborate numerical models of segments. To evaluate the possible differences in moment-rotation behavior between different joint types, 10 different joint types were simulated. Additionally, the effect of different joint types on behavior of a lining ring was investigated. The validity of the peridynamic simulation was tested by comparing results obtained in this paper against the results obtained in a study performed by Hordijk and Gijsbers. Observations of the results demonstrate that in a flat joint, the expanding of joint height increased the rotation stiffness of the joint in the linear branch, and accordingly, the ultimate bending moment of the joint increased. In the ring model, it was observed that the expanding of joint height led to the decreased of ring displacement and stress concentration in the joint. Whenever there were full surface contacts (contact two segment in total cross section) in the joints, the rotation stiffness of the joints in the linear branch became equal, and, as a result, the displacement in the ring model was the same in all joint types. In addition, it was observed that using a convex joint in the ring model increases the displacement of the ring. The ultimate bending moment of bolted joints was higher than that of joints without bolts, especially in the case of a negative moment.  相似文献   

A novel method to estimate mineral compositions of mudrocks: A case study for the Canadian unconventional petroleum systems     

《Marine and Petroleum Geology》2016

The mineral composition of mudrocks is an essential attribute in controlling the reservoir quality of unconventional petroleum systems. The present study introduces a semi-quantitative method to estimate mineral phases of mudrocks in various Canadian unconventional hydrocarbon systems using total elemental analysis (inductively coupled plasma-mass spectrometry (ICP-MS)) and Rock-Eval data (total organic carbon (TOC) and mineral carbon (MinC)).This method involves statistical analysis based on a sound knowledge of hydrocarbon source rock inorganic geochemistry. The workflow can be divided into four steps: (i) converting major elements (Si, Al, Fe, K, Na, Ca, Mg, Ti, and P) to their oxides, (ii) inferring modes of occurrence of elements using statistical analysis of geochemical data (major elements, TOC, and MinC), (iii) identifying the mineral types (oxide, aluminosilicates, carbonates, sulfide, and phosphate) according to elemental occurrences and calculating mineral phase concentrations, and (iv) verifying the results by comparing to XRD data on selected samples. The results, especially for brittle minerals such as quartz, carbonates (e.g. calcite, dolomite, and ankerite), and pyrite, show that the estimated mineral compositions correspond closely and consistently with measured mineralogy obtained from XRD. This method takes advantage of bulk geochemical data already available for hydrocarbon potential and chemostratigraphic studies, without devoting additional samples and cost for XRD analysis.  相似文献   

锂光卤石X-ray衍射标准图谱          下载免费PDF全文

阳海棠  曾德文  唐垂云  李凯明  韩海军 《盐湖研究》2016,24(4):32-36

盐湖卤水提锂过程中需了解与掌握锂元素结晶析出与赋存状态,锂光卤石(LiCl·MgCl_2·7H_2O)作为重要的中间产物,其结构与种类均需鉴别,但由于缺乏锂光卤石的X-ray衍射标准图谱,使得常见的Xray衍射方法无法应用。利用相图原理,通过湿固相法制备高纯锂光卤石,然后对其进行X-ray衍射分析,从而提供锂光卤石X-ray衍射的标准图谱,为高镁锂比盐湖卤水提锂过程分析提供可靠的理论支撑。  相似文献   

Spatial Modeling of Geometallurgical Properties: Techniques and a Case Study     

Jared L. Deutsch  Kevin Palmer  Clayton V. Deutsch  Jozef Szymanski  Thomas H. Etsell 《Natural Resources Research》2016,25(2):161-181

High-resolution spatial numerical models of metallurgical properties constrained by geological controls and more extensively by measured grade and geomechanical properties constitute an important part of geometallurgy. Geostatistical and other numerical techniques are adapted and developed to construct these high-resolution models accounting for all available data. Important issues that must be addressed include unequal sampling of the metallurgical properties versus grade assays, measurements at different scale, and complex nonlinear averaging of many metallurgical parameters. This paper establishes techniques to address each of these issues with the required implementation details and also demonstrates geometallurgical mineral deposit characterization for a copper–molybdenum deposit in South America. High-resolution models of grades and comminution indices are constructed, checked, and are rigorously validated. The workflow demonstrated in this case study is applicable to many other deposit types.  相似文献   

Application of a square wave potentiometry technique for electroreductive sulfur removal from a thiophenic model fuel     

A. Behrouzifar  S. Rowshanzamir  Z. Alipoor  M. Bazmi 《International Journal of Environmental Science and Technology》2016,13(12):2883-2892

Thiophene-containing solutions were electroreductively desulfurized by a dynamic method. Initially, cyclic voltammetry was utilized to study thiophene electroadsorption from aqueous solution onto a platinum electrode surface and also to investigate the thiophene electroreductive behavior. Then, the solution was desulfurized via a square wave potentiometry method. The objective of this study was to find the optimal conditions. In this regard, the best adsorption potential, electroreduction potential, and square wave frequency were found to be ?0.54 V, ?0.95 V, and 1 Hz, respectively. Finally, a model fuel (containing 294 part per millions thiophene) was desulfurized by the square wave potentiometry method. Gas chromatography and Fourier transform infrared spectroscopy were used to examine the feed and product solutions. Gas chromatographic measurements revealed that sulfur content decreased to 55 part per millions. Based on the acquired results, electroreductive desulfurization could be designated as an efficient superseded for the commercial hydrodesulfurization process. However, more studies must perform to overcome technical limitations of electroreductive desulfurization technique and to guarantee its reliability.  相似文献   

CO<Subscript>2</Subscript>-assisted removal of nutrients from municipal wastewater by microalgae <Emphasis Type="Italic">Chlorella vulgaris</Emphasis> and <Emphasis Type="Italic">Scenedesmus obliquus</Emphasis>     

R. Chaudhary  Y. W. Tong  A. K. Dikshit 《International Journal of Environmental Science and Technology》2018,15(10):2183-2192

Axenic culture of microalgae Chlorella vulgaris ATCC^® 13482 and Scenedesmus obliquus FACHB 417 was used for phycoremediation of primary municipal wastewater. The main aim of this study was to measure the effects of normal air and CO₂-augmented air on the removal efficacy of nutrients (ammonia N and phosphate P) from municipal wastewater by the two microalgae. Batch experiments were carried out in cylindrical glass bottles of 1 L working volume at 25 °C and cool fluorescent light of 6500 lux maintaining 14/10 h of light/dark cycle with normal air supplied at 0.2 L min^?1 per liter of the liquid for both algal strains for the experimental period. In the next set of experiments, the treatment process was enhanced by using 1, 2 and 5% CO₂/air (vol./vol.) supply into microalgal cultures. The enrichment of inlet air with CO₂ was found to be beneficial. The maximum removal of 76.3 and 76% COD, 94.2 and 92.6% ammonia, and 94.8 and 93.1% phosphate after a period of 10 days was reported for C. vulgaris and S. obliquus, respectively, with 5% CO₂/air supply. Comparing the two microalgae, maximum removal rates of ammonia and phosphate by C. vulgaris were 4.12 and 1.75 mg L^?1 day^?1, respectively, at 5% CO₂/air supply. From kinetic study data, it was found that the specific rates of phosphate utilization (q _phsophate) by C. vulgaris and S. obliquus at 5% CO₂/air supply were 1.98 and 2.11 day^?1, respectively. Scale-up estimation of a reactor removing phosphate (the criteria pollutant) from 50 MLD wastewater influent was also done.  相似文献   

High-performing antifouling bacterial consortium for submerged membrane bioreactor treating synthetic wastewater     

H. Waheed  S. Pervez  I. Hashmi  S. J. Khan  S.-R. Kim 《International Journal of Environmental Science and Technology》2018,15(2):395-404

Biofouling, associated with membranes, is considered as a major operational challenge in membrane bioreactor (MBR) technology. Interrupting the process for the formation of biofilm by the action of interspecies quorum quenching (QQ) has received a significant attention since recent years. An antifouling bacterial consortium was identified to improve biofouling inhibition performance during MBR operation. For this purpose, various QQ bacteria were isolated from laboratory-scale MBR using enrichment culture method and identified via 16S rRNA. Potential quenching strains including Enterobacter cloaca, Delftia sp., and Pseudomonas sp. were utilized to control biofouling in the MBR operated in the continuous mode for 38 days. Three laboratory-scale MBRs, including two MBRs with different anti fouling consortium and a control, were operated in parallel under similar operating conditions. Biofouling control by QQ bacteria was compared based on the membrane permeability and EPS secretion from biofilm on the membrane. Both MBRs with antifouling consortium (AC-MBRs) experienced around three times less biofouling as compared to conventional MBR leading to significant decrease in acyl homoserine lactones (AHLs) concentration in the biocake. More than 90, 45, and 49% of COD, NH₄–N, and PO₄ ^3?–P removal efficiencies elucidate that QQ bacterial consortium could effectively reduce membrane biofouling without compromising the MBR efficiency. Comparatively lower concentration of bound EPS in AC-MBRs restricted the bacterial adhesion to membrane resulting in enhanced membrane permeability depicting that a broader range of signal molecules could be hydrolyzed using antifouling consortium than single or no QQ strain in the submerged MBR.  相似文献