Selective flocculation of synthetic mineral mixtures using modified polymers

The role of the presence of active groups in polymers and operating variables such as conditioning time in producing flocculation in single and mixed mineral slimes made of hematite, quartz and chalcopyrite is examined at different conditions of pH. Selective flocculation was achieved on the basis of results obtained for single mineral systems as, for example, in the case of hematite—quartz mixtures using sulfonated polymer. Flocculation was found to go through a maximum as the mineral was conditioned with the polymer solution. Interestingly, the times of maximum flocculation for various minerals were sufficiently different from each other so that it could be considered as a potential factor for achieving selectivity. Also, cleaning of the selectively flocculated product by simple redispersion in water improved the separation. Electrokinetic studies conducted to study the mechanisms involved provided indication for the shift of shear plane.     

Selective flocculation of hematite in the hematite-quartz-ferric ion-polyacrylic acid system. Part 1, activation and deactivation of quartz

This investigation has shown that quartz can be activated for polyacrylic acid adsorption by hydrolyzing metal cations, similar to activation in flotation. Detailed experiments on activation phenomena with ferric ions have been performed. The flocculation of activated quartz can be prevented by suitable additions of disodium EDTA, sodium hexametaphosphate or potassium fluoride. Selective flocculation of hematite with polyacrylic acid from a hematite/quartz mixture can be achieved in the pH range 3 to 9, but the process is not selective in the presence of ferric ions. Suitable additions of EDTA or KF are particularly successful in preventing quartz activation by ferric ions and the facilitating selective flocculation of hematite in artificial mixtures of quartz and hematite.     

Geochemistry of cassiterite and wolframite from tin and tungsten quartz veins in Portugal

Cassiterite and wolframite compositions from Sn > W- and W > Sn-bearing quartz veins in Northern and Central Portugal are compared to provide evidence on fluid compositions. In Sn > W-bearing quartz veins, euhedral cassiterite shows sequences of alternating parallel darker and lighter zones. The darker zones are pleochroic, oscillatory zoned, exhibit exsolutions of columbite and ixiolite and are richer in Nb, Ta and Fe than the lighter zones which consist of nearly pure SnO₂. Cassiterite from W > Sn-bearing quartz veins is usually zoned, with homogeneous and slightly pleochroic darker zones, which are chemically similar to lighter zones. Both zones have inclusions of rutile and rare ilmenite. The darker zones of cassiterite from the former veins are richer in Nb, Ta and Fe contents and poorer in Ti than the darker and lighter zones of cassiterite from the latter veins. This is attributed to differences in the composition of magmatic hydrothermal fluids.Wolframite compositions from Sn > W- and W > Sn-bearing quartz veins do not show any significant distinction, because they precipitate from relatively similar magmatic hydrothermal fluids. In some deposits, most wolframite crystals are homogeneous, but others are heterogeneous. Inner patches, rich in a hübnerite component, rarely occur in crystals from the Filharoso and Panasqueira deposits. Zoned crystals, showing an increase in Fe and a decrease in Mn from core to rim, were found in the Vale das Gatas deposit. Complex oscillatory zoned crystals occur. In the Carris deposit, later wolframite contains inclusions of scheelite, partially replaces it and is richer in Fe and poorer in Mn than earlier wolframite. Wolframite from Sn > W-bearing quartz veins in the Argozelo deposit and W > Sn-bearing quartz veins from Vale das Gatas and Panasqueira deposits has significant Nb content. This does not depend on the Fe and Mn content of the wolframite, but W content is negatively correlated with Nb content. Only very rare single crystals of wolframite show an increase in W and a decrease in Nb from core to rim. Sn > W-bearing quartz veins contain wolframite poorer in Nb than the darker zones of cassiterite, which exsolved columbite and ixiolite. In W > Sn-bearing quartz veins from Panasqueira and Vale das Gatas, the wolframite has a higher Nb content than the cassiterite, which contains rutile inclusions enriched in Nb, because cassiterite and wolframite are derived from two distinct magmatic hydrothermal fluids of different age. The fluid responsible for wolframite precipitation will have a similar composition to that resulting from the evolution of the fluid responsible for cassiterite precipitation in the Sn > W-bearing quartz veins.     

湘东桐木山云英岩型锡矿床锡石及共生石英中流体包裹体研究

桐木山云英岩型锡矿床是湘东锡田锡多金属矿田中一个典型矿床,在详尽的野外考察、矿石结构观察以及流体包裹体岩相学研究的基础上,采用流体包裹体组合的研究方法,利用冷热台、激光拉曼等测试手段,对矿床中锡石中流体包裹体进行直接测定,同时开展与锡石共生的石英及切割矿体的后期石英脉石英中流体包裹体对比研究。结果显示,锡石中流体包裹体的组分、均一温度、盐度与共生的石英存在明显差异,表明锡石与石英形成的P-T-X条件不同。切割矿体的石英脉为成岩成矿后流体作用的产物。与锡石形成相关的流体为中高温、中低盐度的NaCl-H₂O流体体系,与石英形成相关的流体为复杂的含碳流体。流体体系的冷却作用及流体与围岩的反应可能是导致锡石沉淀的主要因素,与石英形成相关的流体在演化过程中则经历了明显的流体不混溶作用。

     

Two modified smoky quartz centers in natural citrine

Electron paramagnetic resonance (EPR) measurements on natural citrine and greenish-yellow quartz revealed the presence of several localized hole centers adjacent to an aluminium impurity. The g tensors and their principal axes directions were determined for the two most prominent centers. The g-tensor variations and ²⁷Al hyperfine splittings are roughly half as large as for the well-known smoky quartz centers. Optical and infrared absorption, thermal stability and thermoluminescence were also studied. In these citrine centers an additional defect must be present in the immediate neighborhood of the hole, but the exact nature of this defect is still unknown.     

Elimination of hydraulic effects for cassiterite in a Malaysian Stream

Geochemical patterns for elements, such as Sn, W and Au, present in drainage sediments as resistate heavy minerals are often erratic and difficult to interpret. To investigate the source of these problems and develop methods of eliminating them we have compared the behavior of Sn, present as cassiterite, and associated pathfinder elements downstream from a small primary Sn deposit in Perak, Peninsular Malaysia.Dispersion trains for the pathfinder elements are characterized by smooth decay patterns and differences in concentrations between high- and low-energy environments, characterized by coarse-and medium-grained sands respectively, are not significant. In contrast, Sn (and magnetite) concentrations are extremely erratic with significantly higher concentrations in high- compared to low-energy environments. As a result the dispersion train for Sn exhibits no regular decay pattern away from its source. These findings suggest that the action of the stream is analogous to that of sluice box, with light minerals being winnowed away and cassiterite, together with magnetite, accumulating. For all but the finest sizes this process, which is most efficient in high-energy environments, causes considerable local variability in Sn content of the sediments. However, because the hydraulic behavior of cassiterite and magnetite is similar, but magnetite is not associated with the primary mineralization, the Sn/magnetite ratio can be used to eliminate Sn anomalies resulting from local variations in hydraulic conditions.The concept of hydraulic equivalence of cassiterite and magnetite was extended to examining the relationship between Sn and different size fractions of the light minerals that constitute the bulk of most sediments. Greatest contrast is obtained when the Sn content of the −270 mesh (−53 μm) fraction is re-expressed as its hydraulic equivalent concentration in −65 + 100 mesh (−212 + 150 μm) material.For exploration purposes it is concluded that: (1) providing cassiterite is present in the fine size fractions, sampling of this material will reduce hydraulic effects, thereby reducing data variability, and can also increase the length of the anomalous dispersion train; and (2) hydraulic effects can also be reduced by re-expressing Sn concentrations as ratios to magnetite (provided this is not associated with the primary Sn mineralization) or a hydraulically equivalent size fraction of the light minerals that constitute the bulk of the sediment. Similar principles probably apply to the interpretation of geochemical data for other elements dispersed in drainage sediments as heavy minerals; this warrants further investigation.     

Oxygen isotope thermometry using quartz inclusions in garnet

Oxygen isotope ratios of quartz inclusions (QI) within garnet from granulite and amphibolite facies gneisses in the Adirondack Mountains, NY were analysed and used to determine metamorphic temperatures. Primary QI for eight of 12 samples have δ¹⁸O values significantly lower than matrix quartz (MQ). The primary QI retain δ¹⁸O values representative of thermal conditions during garnet crystallization, whereas the δ¹⁸O values of MQ were raised by diffusive exchange with other matrix minerals (e.g. mica and feldspar) during cooling. The δ¹⁸O differences between QI and MQ show that garnet (a mineral with slow diffusion of oxygen) can armour QI from isotopic exchange with surrounding matrix, even during slow cooling. These differences between δ¹⁸O in MQ and QI can further be used to test cooling rates by Fast Grain Boundary diffusion modelling. Criteria for identifying QI that preserve primary compositions and are suitable for thermometry were developed based on comparative tests. Relations between δ¹⁸O and inclusion size, distance of inclusion to host–garnet rim, core–rim zonation of individual inclusions, and presence or absence of petrological features (healed cracks in QI, inclusions in contact with garnet cracks lined by secondary minerals, and secondary minerals along the inclusion grain boundary) were investigated. In this study, 61% of QI preserve primary δ¹⁸O and 39% were associated with features that were linked to reset δ¹⁸O values. If δ¹⁸O in garnet is homogeneous and inclusions are removed, laser‐fluorination δ¹⁸O values of bulk garnet are more precise, more accurate, and best for thermometry. Intragrain δ¹⁸O(Grt) profiles measured in situ by ion microprobe show no δ¹⁸O zonation. Almandine–rich garnet (Alm_60–75) from each sample was measured by laser‐fluorination mass‐spectrometry (LF‐MS) for δ¹⁸O and compared with ion microprobe measurements of δ¹⁸O in QI for thermometry. The Δ¹⁸O(Qz–Grt) values for Adirondack samples range from 2.66 to 3.24‰, corresponding to temperatures of 640–740 °C (A[Qz–Alm] = 2.71). Out of 12 samples that were used for thermometry, nine are consistent with previous estimates of peak temperature (625–800 °C) based on petrological and carbon–isotope thermometry for regional granulite and upper amphibolite facies metamorphism. The three samples that disagree with independent thermometry for peak metamorphism are from the anorthosite–mangerite–charnockite–granite suite in the central Adirondacks and yield temperatures of 640–665 °C, ~100 °C lower than previous estimates. These low temperatures could be interpreted as thermal conditions during late (post‐peak) crystallization of garnet on the retrograde path.     

Energy associated with dislocations: A calorimetric study using synthetic quartz

High temperature oxide melt solution calorimetry was used to study the energy associated with dislocations in quartz by comparing undeformed and deformed single crystals of synthetic quartz. Samples were deformed at 698 K, 1000–1500 MPa at a strain rate of 10^–5 sec^–1. Two sets of calorimetric measurements were made: (i) using a Pt capsule as a container for powdered sample, and (ii) using pellets made from sample powder without any container. For the first set of measurements, the undeformed sample with a dislocation density of enthalpy is sum of heat content H ₉₇₃-H ₂₉₅ and enthalpy of solution in molten lead borate at 973 K of 39.22 ± 1.00 kJ mol^–1, while the sample deformed in the dislocation creep regime with a dislocation density of 6 × 10¹⁰ to 1 × 10¹¹ cm^–2 gave an enthalpy of 38.59 ± 0.78 kJ mol^–1. For the second set of measurements the measured enthalpy of the undeformed sample was 38.87 ± 0.31 kJ mol^–1, and that of a deformed sample with a dislocation density of 3 × 10¹⁰ to 1 × 10¹¹ cm^–2 was 38.24 ± 0.58 kJ mol^–1.The present study and previous theoretical calculations and estimates are consistent and suggest that the energy associated with dislocations in quartz is 0.6 ± 0.6 kJ mol^–1 for a dislocation density of 10¹¹ cm^–2; a precise value is difficult to determine because of the overlapping errors. These results indicate that for geologically realistic dislocation densities, the maximum excess energy due to dislocations would be 0.5 kJ mol^–1 for most minerals; the exact value would depend on the Burgers vector as well as the shear modulus.     

Color removal from industrial wastewater with a novel coagulant flocculant formulation

Chemically enhanced wastewater treatment is attracting substantial interest among the currently employed chemical unit processes in wastewater treatment. Coagulation-flocculation has received considerable attention for yielding high pollutant removal, especially color removal. This investigation presents a novel formulation of coagulation-flocculation for color removal from industrial wastewater and illustrates its efficiency, with aid of measurement of solid sludge content, suspended solid content, percentage of solid recovery, UV absorption in wastewater effluent from two automotive factories. The results show that the novel formulation can remove color content from wastewater efficiently. The treated wastewater had UV absorption close to distillated water and color was removed up to 96% by flocculation / coagulation treatment.     

Influence of frothers on floatability. II. Flotation of chalcocite and quartz mixtures

Influence of frothers (α-terpineol or n-amyl alcohol) on the floatability of chalcocite and quartz mixtures, with potassium ethyl xanthate as a collector at pH 5.5–6, was investigated with a Hallimond tube.Activation of quartz by the presence of chalcocite was observed and interpreted as due to copper ionic species originating from chalcocite oxidation products. Best selectivity of separation between chalcocite and quartz was obtained when the frother concentration was kept sufficiently low. Collector—frother interactions during formation of three-phase mineral grain/solution/gas bubble contacts were observed.     

絮凝−电渗法联合治理淤泥质土试验研究

针对传统电渗法治理淤泥质土过程中排水效率低且治理后土体不均匀等问题,从改变软黏土颗粒自身持水特性角度出发,提出采用新型有机高分子材料阴离子型聚丙烯酰胺（APAM）联合电渗法治理淤泥质土的思路。利用自制的一维电渗固结试验装置,探究絮凝−电渗法联合作用机制以及不同絮凝剂掺入比对电渗排水加固效果的影响规律。试验结果表明：与传统电渗法相比较,絮凝剂 APAM 的掺入减少了软黏土颗粒表面的结合水膜厚度,使得淤泥质土的前期电渗排水速率和累计排水量显著提升,从而降低了电渗法的平均能耗系数;同时,絮凝剂高分子长链的“吸附架桥”作用增强了土颗粒的黏结力和絮凝沉积效果,有效缓解了电渗过程中细小黏粒迁移集聚而造成的阴极淤堵问题;治理后淤泥质土的抗剪强度大幅增高,土体的均匀性也得到了明显改善,且当絮凝剂 APAM 掺入比为 0.30% 时,土体的电渗排水固结效果最佳。     

Measuring quartz solubility by in situ weight-loss determination using a hydrothermal diamond cell

The solubility of quartz was determined using a hydrothermal diamond anvil cell (HDAC) within the temperature and pressure ranges of 126 to 490°C and up to 8.9 kbar, respectively. A novel approach has been used to measure the amount of dissolved silica. The quartz was abraded into spheres which have a diameter of ∼40 μm. The spheres were then placed in pure water inside the diamond anvil cell and heated externally. Because the transparency of the diamonds allows direct observation of the sample chamber during the experiment, we were able to estimate the amount of quartz dissolved in the water at various stages of the dissolution process by measuring the decrease in the sphere’s diameter over time. Experiments were performed along isochores between 0.92 and 0.99 g/cm³. The maximum solubility measured was 0.165 molal. The experimental solubility data were limited to 370°C because of overestimation of solubilities above this temperature. Reprecipitation of silica inside the HDAC sample chamber and the refaceting of the spheres to trigonal form at temperatures above 350°C are major contributors to the overestimation.     

Indium in cassiterite and ores of tin deposits

The results obtained with LA-ICP-MS by less abundant lighter ¹¹³In isotope and EPMA show that in cassiterite of cassiterite–quartz veins the indium contents do not exceed 160 ppm, while cassiterite from Sn–sulfide veins is characterized by higher indium contents from 40 to 485 ppm; sulfides of Sn–sulfide veins unlike sulfides of cassiterite–quartz veins also have the highest indium contents: Fe-sphalerite (100–25,000 ppm), chalcopyrite (up to 1000 ppm), and stannite (up to 60,000 ppm). Indium contents in the Sn–sulfide ore of the Tigrinoe and Pravourmiiskoe deposits obtained using SR-XRF, ICP-MS and atomic absorption methods range from 10 to 433 ppm with average values of 56–65 ppm. Indium-rich Sn–sulfide mineralization in five large Sn–Ag ore districts of the Far East Russia (Khingansky, Badzhalsky, Komsomolsky, Arminsky, Kavalerovsky) provides the impetus for further exploration of deposits with Sn–sulfide mineralization as the most promising indium resources in Russia. Empirical observations from geology and geochronology of cassiterite–quartz and Sn–sulfide mineralization show that the combined contribution from granite and alkaline–subalkaline mafic sources and multistage ore-forming processes doubled indium resources of deposits being the main factors in the formation of high grade indium mineralization.     

非基体匹配分馏校正的LA-ICP-MS锡石微区U-Pb定年方法研究

锡石原位微区U-Pb同位素测年,样品制备简单,具有高空间分辨率、高性价比、高效率等显著优势,是锡多金属矿床直接定年的有效手段.然而,基体效应的影响和标样的缺乏是制约该方法发展的关键.本次研究在He做载气以及加入不同辅助气(N2、水蒸气)条件下使用锆石作为外部标准物质对锡石标准和样品进行元素、同位素分馏校准,并采用Ter...     

Aluminum in quartz as a geothermometer

Quartz forming in aluminum-saturated environments has a trace aluminum content which varies linearly and directly with its temperature of crystallization. The aluminum content varies at a rate of approximately 1 ppm Al per 3.6° C change in temperature. Use of this geothermometer gives temperatures which are consistent with those expected by geologic reasoning or through the use of other geothermometers.     

Strain-rate estimation using fractal analysis of quartz grains in naturally deformed rocks

The area-perimeter fractal dimension (D) of quartz grains has earlier been proposed as a strain-rate gauge based on experimental deformation of quartz aggregates. To test the application in naturally deformed rocks, D is calculated in (a) three quartzites belonging to the Lunavada Group of rocks (Aravalli Mountain Belt, NW India) that developed textures between 420–600°C and (b) one quartz reef sample from the Malanjkhand Granite (Central India), which underwent dynamic recrystallization between 250–400°C. Using the above T ranges and calculated D values, strain-rates are calculated for the two sets of samples. A 10^−12.7 s⁻¹ strain rate at 250°C is calculated for the quartz reef sample. However, at higher temperatures the calculated strain-rate is >10⁻¹⁰ s⁻¹ for the quartz reef and the quartzite samples. The quartzites show evidence of dynamic recrystallization by grain boundary migration (GBM) and subgrain rotation (SGR), while the quartz reef is replete with evidence of bulging (BLG) recrystallization. T and calculated strainrates are plotted on available recrystallization map of quartz. It is demonstrated that whilst the T/strain-rate of the quartzites does not fall in the region of GBM and SGR, the T/strain-rate of the quartz reef falls in the BLG region. The problems with strain-rate calculations using area perimeter fractal dimension are discussed. It is concluded that the method of strain-rate calculation can be used only for lower T.     

High-pressure yield strength of rocksalt structures using quartz Raman piezometry

The Raman frequencies of quartz are used to evaluate deviatoric stresses in rocksalt-structure media in diamond-anvil cell experiments to pressures up to 20 GPa. The piezospectroscopic effect in quartz is modeled by first-principles calculations. Non-hydrostatic stresses measured in halogen salts give yield strength estimates of 3 GPa in the B1 structure (NaCl), and 4.5 GPa for the B2 structure (KCl and KBr). Raman measurements in MgO show that the yield strength is reached at around 6 ± 1 GPa. Measurements on quartz alone indicate similar yield strength. The estimated yield strength in MgO is thus likely a lower bound, in consistency with former radial X-ray diffraction measurements that gave a yield strength of 8 ± 1 GPa, and lower-pressure large-volume press experiments indicating a yield strength of 6 GPa at 5 GPa. Former values of the yield strength below 2 GPa determined by pressure gradient measurements were underestimated due to unverified assumptions in boundary conditions. The yield strength increases with increasing coordination of ionic solids, likely contributing to increase viscosity at phase transitions near the upper–lower mantle boundary.     

Radiation-induced defects in quartz. II. Single-crystal W-band EPR study of a natural citrine quartz

Single-crystal electron paramagnetic resonance (EPR) spectra of a natural citrine quartz without any artificial irradiation, measured at W-band frequencies (∼94 GHz) and temperatures of 77, 110 and 298 K, allow better characterization of three previously-reported Centers (#6, #7 and B) and discovery of three new defects (B′, C′ and G′). The W-band EPR spectra reveal that Centers #6 and #7 do not reside on twofold symmetry axes, contrary to results from a previous X-band EPR study. The W-band spectra also show that the previously reported Center B is a mixture of two defects (B and B′) with similar g matrices but different-sized ²⁷Al hyperfine structures. Center C′ has similar principal g values to the previously reported Center C but is distinct from the latter by a larger ²⁷Al hyperfine structure with splittings from 0.10 to 0.22 mT. Also, Center G′ has a similar g matrix to the previously reported Center G but a different ²⁷Al hyperfine structure with splittings from 0.41 to 0.53 mT. These spin-Hamiltonian parameters, together with observed thermal properties and microwave-power dependence, suggest that Centers #6 and #7 probably represent O₂³⁻ type defects. Centers B and B′ are probably superoxide radicals (O₂⁻) with the unpaired spin localized on the same pair of oxygen atoms around a missing Si atom but linked to a substitutional Al³⁺ ion each at different neighboring tetrahedral sites. Similarly, Centers G and G′ are most likely superoxide radicals with the unpaired spin localized on another pair of oxygen atoms around a missing Si atom and linked to a substitutional Al³⁺ ion each at different neighboring tetrahedral sites. Center C′ is probably an ozonide radical associated with a missing Si atom and linked to a substitutional Al³⁺ ion at the neighboring tetrahedral site. This study exemplifies the value of  high-frequency EPR for discrimination of  similar defect centers and determination of  small local structural distortions that are often difficult to resolve in conventional  X- and Q-band EPR studies.     

Development of a selective flocculation process for a complex copper ore

Problems encountered in developing a selective flocculation process for a complex copper ore and ways of overcoming these difficulties are reported. To obtain a useful enrichment ratio, multiple stages of flocculation and redispersion were found necessary in order to release entrapped, unwanted particles. Particular attention was given to the dispersion process of the ore suspensions, and the importance of mechanical and chemical factors were established. The effects of solids content and quality of water on the performance of selective flocculation have been investigated. The possibility of developing new, selective or more powerful dispersants was confirmed and one such reagent was tested.