Cation distribution in amphiboles synthesized along the Ga analogue of the tremolite–aluminotschermakite join

 Amphiboles were synthesized from bulk compositions prepared along the join Ca_1.8Mg_5.2Si₈O₂₂(OH)₂–Ca_1.8Mg₃Ga₄Si₆O₂₂(OH)₂ hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca₂Mg₅Si₈O₂₂F₂–Ca₂Mg₃Ga₄Si₆O₂₂F₂, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: ^[6]Ga³⁺+2^[4]Ga³⁺+1/2^[A] Ca²⁺ = ^[6]Mg²⁺+2^[4]Si⁴⁺+1/2^[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001     

一种水不溶灰树花菌丝体多糖(GF4A)硫酸酯化研究

以灰树花发酵菌丝体水不溶性多糖GF4A为原料,以三氧化硫三甲胺盐(SO3·Me3N)为酯化试剂,探讨了GF4A的硫酸酯化工艺.实验结果表明,当三氧化硫与GF4A中单糖摩尔比为5.8∶1、反应温度为80 ℃、反应时间6 h时,所得酯化产物(SGF4A)水溶性好、产率高.该产物硫酸酯取代度为1.6, 相对分子质量为88 kD.通过红外光谱及核磁共振碳谱分析表明,糖残基中所有C-6羟基以及部分C-4和C-2位羟基被酯化.体外实验表明,SGF4A具有较好的抗凝活性.     

Leaching behavior of Li and Ga from granitic rocks and sorption on kaolinite: Implications for their enrichment in the Jungar Coalfield,Ordos Basin

The granite collected from the Yinshan Mountain and kaolinite has been selected for the leaching and adsorption experiment,respectively,aiming to clarify the enrichment processes of Li and Ga during the deposition.Results suggest both Li and Ga could be leached out from granite by using different acid solutions of different p H and kaolinite can adsorb Li and Ga with varying degrees.Lithium and Ga had the highest leaching ratio when p H=1.Special geological events(e.g.volcanic eruptions and wildfires),which could result in very low p H values of water in peatland,may have accelerated the release of Li and Ga from the source rocks.Kaolinite has the highest adsorption fraction was obtained at p H=8.The different characteristics of Li and Ga displayed in the leaching and adsorption experiments probably result from the different occurrences and enrichment processes of Li and Ga in the coals.Lithium was probably enriched before the Li carriers(e.g.kaolinite)had been transported into paleomires because of its high leaching ratio and high adsorption fraction under neutral and alkaline conditions,whereas Ga was more likely concentrated by kaolinite and other carriers after it had been transported into the peat mires.     

熔融制样X射线荧光光谱法测定碳化钨及其废料中的钨

碳化钨被广泛应用于硬质合金生产材料,其钨的含量关系碳化钨的性能及货物结算,生产过程中因配比错误、打磨等原因还会产生大量的含钨废料,从废料中回收钨能弥补钨资源的不足,因此测定碳化钨及其废料中的钨具有重要意义。目前碳化钨中钨含量的测定通常参照国家标准采用辛可宁重量法,准确度较高,但只适用于检测三氧化钨含量大于50%的样品,且过程繁琐,工作量大。本文根据碳化钨在高温下易氧化的特点,借鉴国际标准ASTM B890-07,提出将碳化钨转化为三氧化钨,采用熔融制样-X射线荧光光谱(XRF)测定钨含量的方法。即碳化钨先在马弗炉中灼烧至钨完全转化为三氧化钨,再加入五氧化二钽作内标,四硼酸钠-四硼酸锂为混合熔剂,在1150℃下熔融制成试样片,用XRF法测定钨的含量。结果表明,最佳的灼烧温度为800℃,在此温度下碳化钨完全转化成三氧化钨,有效地解决了碳化钨熔融制样的难点;方法精密度(RSD)为0.2%,实际样品的测定值与国家标准方法(辛可宁重量法)一致,可测量三氧化钨含量的范围为30%~100%,且分析时间大大缩短,可满足大量实际样品检测的需要。     

A New Method for Low‐Temperature Decomposition of Chromites and Dichromium Trioxide using Bromic Acid Evaluated by Chromium Isotope Measurements

In recent years, routine application of the stable isotope determination of chromium (Cr) in environmental and health protection research has led to the search for simpler chromite decomposition techniques. As the range of Cr isotope abundance ratios in nature is very narrow, conventional chromite decomposition techniques are no longer suitable, due to the relatively high risk of contamination during laboratory procedures. We have developed a protocol for the decomposition of chromites based on oxidation by bromic acid at room temperature. The procedure takes 15 d and requires two doses of bromic acid during the reaction period (day 1 and 8), due to the limited stability of the reagent. Chromium extracted by alkaline oxidative fusion and by bromic acid decomposition yielded statistically indistinguishable δ⁵³Cr values, measured by multi‐collector inductively coupled plasma‐mass spectrometry following addition of a ⁵⁰Cr‐⁵⁴Cr double‐spike.     

Recovery of Gallium and Arsenic from Gallium Arsenide Waste in the Electronics Industry

Gallium arsenide (GaAs) has both high saturated electron velocity and high electron mobility, making it useful as a semiconductor material in a variety of applications, including light‐emitting diodes (LEDs), integrated circuits (ICs), and microwave appliances. A side effect of the use of gallium (Ga) is the production of a relatively large amount of hazardous waste. This study aimed at the recovery of Ga and arsenic (As) from GaAs waste using hydrometallurgical methods involving leaching and coagulation and a dry annealing process that involves annealing, vacuum separation, and sublimation by heating. Our research has shown that GaAs can be leached using nitric acid (HNO₃) to obtain 100% Ga and As with a leaching solution at pH 0.1, with subsequent adjustment of the leaching solution to pH 3 with sodium hydroxide (NaOH). Another method used a leaching solution at pH 2, then adjusting to pH 11 using NaOH. Ferric hydroxide (FeO(OH)) was added at 90°C after NaOH was added to the leaching solution. At pH 2 and 11, 55.5 and 21.9% of the As could be removed from the hazardous waste, respectively. The Ga could also be precipitated. When GaAs powder was heated to 1000°C over 3 h, 100% As removal was achieved, and 92.6% of the Ga was removed by formation of 99.9% gallium trioxide (Ga₂O₃). Arsenic was vaporized when the temperature was elevated to 1000°C, allowing arsenic trioxide (As₂O₃) to condense with 99.2% purity. The Ga₂O₃ powder produced was then dissolved and electrolyzed, allowing for 95.9% recovery of Ga with a purity of 99.9%.     

Digital GaAs Autocorrelator Developed for Space Borne Submillimeter Astronomy

We present the development of a correlator module intended for space borne high resolution heterodyne spectroscopy. Our attention has been focused on power consumption reduction (few mW per channel needed), while looking for a high clock frequency (few hundreds of MHz) to cover wide bandwidths. The module proposed, which may be the base of an hybrid analog/digital spectrometer, is composed of two full custom Very Low Scale Integration (VLSI) circuits using two different technologies: a high speed MEtal Semiconductor Field Effect Transistor (MESFET) on Gallium Arsenide substrate (GaAs) and a low power Complementary Metal Oxide Semiconductor (CMOS) on Silicon substrate (Si). A 0.8 m GaAs prototype circuit has been built and tested. It shows a correct global operation up to 242 MHz – and for marginal functions up to 611 MHz –, and a power consumption as expected by the simulations (less than 2 W). Expected improvements of the technology, together with some modifications developed here, demonstrate that a high frequency correlator module, meeting spatial requirements (many hundreds of channels and few mW per resolution point), should be feasible.     

电感耦合等离子体发射光谱法测定石膏矿样品中的三氧化硫

样品用稀盐酸处理,在酸性条件下石膏样品中的三氧化硫以硫酸根状态存在于待测溶液中,过滤除去酸不溶物。处理好的待测溶液可直接上等离子体发射光谱仪ICAP-6300(美国热电制造)上测定。方法的检出限为0.01%,采用本法测定国家标准物质GBW03109,GBW03109a,GBW03110,GBW03111a,结果表明标准样品测定的相对误差为-0.411%~0.274%,相对误差允许限为1.07%,能够满足分析质量要求。     

氢化物发生-原子荧光光谱法测定三氧化二锑中锡

500℃时在锌粉、氯化铵存在下,锑以三氯化锑形式被挥发除去,锡与锌形成锌-锡合金留在残渣中,从而消除锑对锡的干扰。在10%(体积分数)的盐酸介质中,硼氢化钾将锡(Ⅱ)还原成四氢化锡,用氢化物发生-原子荧光光谱法测定锡的荧光强度。方法检出限为0.20 mg/kg,精密度(RSD,n=7)为3.73%,回收率为91.0%~104.5%。     

Quantifying the potential for recoverable resources of gallium,germanium and antimony as companion metals in Australia

Although critical to newly evolving and increasingly essential technologies, antimony (Sb), gallium (Ga), and germanium (Ge) are generally recovered as byproducts or ‘companion metals’ of other metal ores. The stage at which companion metals are extracted depends on metallurgical processes by which the host ore mineral is extracted and processed; many companion metals are recovered late during this processing. Therefore, the current and future supply of companion metals relies not only on production of major commodities, but also on the efficient recovery of these metals during processing that recovers the primary commodity.National geological surveys, particularly the USGS, publish annual estimates of global reserves for a variety of primary metals, but generally not for companion metals. This study provides estimates for the geogenic stocks (in waste rock piles, tailings, smelting, and refining) of Ga, Ge, and Sb as companion metals. These elements are mined in Australia but may be recovered outside of Australia, but their life cycles have not yet been well understood.Based on the methodology adapted, this paper estimates a minimum of 970–1230 kt of Ga, 30–10,000 kt of Ge and 70–1000 kt of Sb in current Australian lead-zinc-silver, gold, copper, iron ore, coal, bauxite, and bauxite residue (red mud) resources. The large range of estimated stocks stems from the variable range of ore grades reported by companies and the considerable uncertainty that exists among the grade estimates presented. However, these estimates are reflective of best practice in mineral resource estimation of Ga, Ge, and Sb, and provide a basis for determining similar recoverable resource estimates of other companion metals, such as indium, rhenium, and selenium, all of which are of increasing importance in modern-day life.