Re-evaluation of Reference Materials, IGS 21-39

The 20 ore and concentrate reference materials originally issued by the Institute of Geological Sciences (as it then was) in 1977 have been reevaluated using robust as opposed to classical statistical techniques. The opportunity has also been taken to correct minor errors and to incorporate any new data. One material, the nickel concentrate, IGS 20, has been withdrawn due to incipient oxidation. A total of 24 elemental concentrations in the remaining 19 samples have received revised values.     

Usable Values of Nickel Ore and Nickel Concentrate Certified Reference Materials

The preparation and characterisation of three nickel ores and two nickel concentrate certified reference materials are described in this paper. The samples of nickel ore and nickel concentrate were collected from the Hongqiling nickel deposit in Jilin province. The raw materials were crushed and passed through a 2.0‐mm sieve. The rough samples were then ground for 48 hr in a high‐alumina ball mill to a final size of < 0.074 mm. Homogeneity of the samples was tested by X‐ray fluorescence spectrometry (WD‐XRF) and inductively coupled plasma‐atomic emission spectrometry (ICP‐AES). The relative standard deviations (RSD) of results on mass fraction measurements by WD‐XRF were < 1.0% m/m for eighteen components. F‐tests showed that all five samples were homogeneous. Nineteen laboratories contributed with measurement results (2127 in total) for the certification of mass fractions for twenty‐three elements and compounds. Twenty‐three components in the nickel ores and twenty components in the nickel concentrates were characterised as certified values, while the Ni mass fractions ranges from 0.1 to 9.02% m/m in these certified reference materials. These five samples were approved as national certified reference materials by the National Organisation of Reference Materials of China in 2012.     

磷矿石化学成分分析标准物质研制

磷矿的开发与综合利用不仅需要分析磷等主要元素,也需要准确地测定稀土元素和微量元素。分析测试过程需要含量适中、定值组分全的磷矿石标准物质进行质量监控,国内外现有的磷矿石标准物质无论是从定值指标还是含量梯度范围等方面均无法满足此需求。本文研制了4个不同类型磷矿石成分分析标准物质。样品采集自河北张家口钒山磷矿、贵州织金新华磷矿、云南昆阳磷矿、湖北神农架火炼坡磷矿4个典型矿区,其中张家口钒山磷矿和织金新华磷矿为含稀土的磷矿。检验结果表明样品的均匀性、稳定性良好;通过11家实验室协作定值,定值元素包括造岩主量元素、稀土元素和痕量元素共37项,其中3个组分为参考值,其余均给出标准值和不确定度。4个磷矿石标准物质形成了一个从边界品位、工业品位到磷精矿较为完整的含量系列,P_2O_5的含量分别为10.57%、18.91%、27.78%、39.40%,稀土元素总量分别为0.16%、0.11%、0.032%、0.0083%,可满足磷矿勘查、评价和综合利用开发中对标准物质的需求。     

喷流沉积型多金属矿床中镍钼的赋存特征

喷流沉积型矿床是矿床地质学研究的前沿课题,查明矿石中重要组分(镍和钼)的赋存状态是该类矿床地质学研究的重要内容。湘黔地区天鹅山-黄家湾、大坪-大浒镍钼矿带是典型的海底喷流沉积矿床,本文采集该矿区的样品,应用化学和光谱定量分析、偏光显微镜和X射线衍射、扫描电镜、电子探针等大型现代仪器相结合的分析手段,研究了矿石中镍和钼的赋存状态。化学和光谱分析确定矿石中镍含量为3.76％,钼含量为4.99％;偏光显微镜下观察发现金属矿物零星分布,颗粒细小,结晶程度差,光学特征极不明显,晶体形貌特征难以观察,初步推断矿石矿物以胶状形式存在,但在光学显微镜下很难为这些矿物定名和描述;X射线衍射分析验证了偏光显微镜鉴定结果,印证了样品中存在很多非晶质矿物,仅有钨钼钙矿和镍黄铁矿两种矿物含有镍钼,且矿物含量很低(分别为0.4%和0.8%),对比化学分析结果,可推断样品还存在其他富含镍钼元素的矿物。进一步对富集镍钼元素的区域进行电子探针分析,最终确定了镍除了赋存于辉砷镍矿、方硫镍矿中,在胶状黄铁矿和磁黄铁矿边缘呈蠕虫状花边的镍黄铁矿中也有富集;钼主要赋存于碳硫钼矿中。矿石中的镍钼主要赋存于由胶态向结晶态过渡的金属矿物中,研究成果为该类矿床的矿石矿物学研究、选矿、冶炼及矿石综合利用提供重要的信息和依据。     

四川杨柳坪低品位镍矿工艺矿物学特征

四川杨柳坪镍矿石属于低品位镍矿资源,其矿石中镍的品位为0.45%,主要以硫化物形式存在(磁黄铁矿、镍黄铁矿)。镍黄铁矿和磁黄铁矿中镍的占有率在90%以上。主要矿物的工艺嵌布粒度统计分析表明,在较细粒级0.040 mm以下粒级及0.020 mm以下级分别有10%~15%及3.5%~5.5%的含量分布,因此选矿分选过程中,将有部分嵌布粒度较细的硫化物矿物难于解离,由于硫化物的磨矿解离度不高,且主要的硫化物彼此间的连体较多,选矿采用以磁黄铁矿为主的硫化物集合体作为回收单位较为适宜。此外,研究区硫化物矿物的物性较脆,磨矿过程中应防止其过粉碎。     

钼矿石与钼精矿成分分析标准物质研制

钼矿勘查开发与综合利用评价等工作需对其化学成分进行准确测试,标准物质可为分析测试提供基础标准和技术支撑。我国已有的钼矿石和钼精矿标准物质系列性不足,且余量不多,多数样品已耗尽。本文为满足钼矿资源勘查、开发与贸易的总体需求,研制了3个钼矿石和1个钼精矿成分分析标准物质。根据设计的钼含量的梯度范围和钼矿的矿床成因,在钼矿资源储量最多的河南省采集了1个钼尾矿(Mo含量0.02%)、1个钼矿石(Mo含量0.09%)和1个钼精矿(Mo含量50.0%)。3个钼矿石采用重量法组合制备的方式加工,1个钼精矿为原样粉碎加工,钼精矿在加工制备过程向球磨机内充氩气保护,防止硫化物氧化。按照一级标准物质研制规范,采用13家实验室使用多种准确可靠的方法共同定值,定值元素包括成矿元素(Mo),可综合利用元素(W、S、Cu、Pb、Zn、Fe、Bi),具找矿和矿产评价意义的微量元素(Ag、As、Cd、Mn、P、Pb、Sb)及构成脉石的主成分(SiO₂、Al₂O₃、Fe₂O₃、CaO、MgO、Na₂O、K₂O)共计26种。3个钼矿石标准物质Mo的含量分别为0.066%、0.15%、0.54%,1个钼精矿标准物质Mo的含量为50.08%,是已有标准物质的良好补充和完善。标准物质经均匀性和稳定性统计检验具有良好的均匀性和稳定性;标准值计算方法正确,不确定度评定合理,经国家质量监督检验检疫总局批准为国家一级标准物质(编号为GBW 07141~GBW 07144),可用于钼矿的勘查、开发、选冶及贸易中化学成分测试的量值标准与分析质量监控。     

电感耦合等离子体发射光谱法同时测定铜铅锌矿石中铜铅锌钴镍等元素方法确认

文章在修订GB/T 14353—1993《铜矿石、铅矿石和锌矿石化学分析方法》研究工作中,建立了电感耦合等离子体发射光谱同时测定铜铅锌矿石中铜铅锌钴镍等元素的标准分析方法。通过控制试样量和制备试样溶液的体积,可实现主量元素铜、铅、锌与次量元素钴、镍的同时测定。测定范围为铜0.002%~8.5%,铅0.01%~5%,锌0.005%~3%,钴0.001 5%~0.5%,镍0.003%~0.5%。按照相关国家标准对测量方法与结果的准确度进行8个实验室协同参加的准确度试验,统计参数结果表明在限定水平范围内方法偏倚不显著;利用方法重复性限参数,计算可能产生的最大相对偏差。分析方法精密度满足《地质矿产实验室测试质量管理规范》的要求。     

New Progress on Certified Reference Materials for Platinum-Group Elements: IGGE GPt-8, GPt-9 and GPt-10

Three new certified reference materials (CRM), certified for the platinum-group elements (PGE), GPt-8, GPt-9 and GPt-10 were developed based on the previous CRMs IGGE GPt-1 to GPt-7. The PGE concentration of GPt-8 is about 1 ng g^-1. GPt-9 and GPt-10 are ore samples with PGE concentrations of more than 1 μg g^-1. A multi-laboratory collaborative analysis scheme was adopted in the certification procedure, in which nine highly-experienced institutes and laboratories participated. The samples were analysed for the six platinum-group elements by nickel sulfide mini fire assay, with Te coprecipitation, and were determined by ICP-MS. Osmium was determined by isotope dilution.     

铜精矿化学成分分析实验室间比对结果评价和离群值原因分析

铜精矿成分分析是判定其品质的重要手段,尤其是主元素铜的分析.目前,测定铜精矿中铜含量的主要分析方法有碘量法、电感耦合等离子体发射光谱法(ICP-OES)、火焰原子吸收光谱法(FAAS)、X射线荧光光谱法(XRF)、电解重量法等.为确保检测标准量值统一、准确、可靠,本文组织开展了铜精矿中铜镁铅锌的测定实验室间比对活动.通...     

内蒙古阿右旗低品位镍矿石可选性试验研究

该试验对低品位镍矿进行了选矿试验研究。结果表明：采用一段磨矿、细度-0．074mm 85％、先反浮选脱泥、脱泥后的尾矿进行粗选,两次粗扫选、三次精选流程;浮选药剂采用碳酸钠、2^#油、CMC、硫酸铜、丁基黄药、J-622;试验指标为：原矿镍品位0．18％、浮选精矿镍品位3．15％、浮选尾矿品位0．11％、反浮选产品镍品位0．19％、精矿镍回收率39．17％。该研究结果为该矿石的可选性评价提供了技术依据。     

X射线荧光光谱法同时测定钛精矿中主次量组分

采用铁矿标准样品和高纯二氧化钛混合配制钛精矿的校准样品,X射线荧光光谱法同时测定钛精矿中氧化镁、三氧化二铝、二氧化硅、磷、硫、氧化钙、二氧化钛、五氧化二钒、锰、铁等主次量成分,并对熔剂选择、熔融条件、钒Kα峰位确定及基体效应校正等进行了探讨。测定结果与标准样品标称值吻合,相对标准偏差(RSD,n=7)除低含量的磷、硫外均在5%以下,能满足钛精矿的检测需要。     

高频燃烧-红外吸收光谱法测定钼矿石和镍矿石中的高含量硫

高频燃烧-红外吸收法用于分析矿石中低含量硫的测定结果较为准确,但对于高含量的硫,分析结果的准确度不高。本文采用高频燃烧-红外碳硫分析仪测定钼矿石和镍矿石中的高含量硫,选择纯铁屑和钨粒作助熔剂,高温燃烧分解样品,通过实验优化了样品称样量、助熔剂用量、仪器分析时间等测定条件。用国家标准物质进行验证,方法精密度(RSD,n=9)小于1%,加标回收率为96.0%～101.9%;与传统的硫酸钡重量法进行比对试验,测定值的相对误差小于2%。针对不同的矿石样品,研究了实际样品与标准物质的基体匹配问题,消除了基体效应的影响,对于钼矿石和镍矿石样品中含量在1%～35%范围内的硫,均能够准确测定,解决了钼矿石和镍矿石中高含量硫的快速、准确测定问题。     

Composition and origin of lateritic nickel ore at Tagaung Taung,Burma

The recently discovered lateritic nickel ore deposit on the summit area of the Tagaung Taung contains about 40 million DMT nickel-saprolite ore with approximately 2% Ni. The serpentinite massif is covered with a thick weathering mantle consisting of saprolite, limonite, and an allochthonous lateritic surface layer. The thickness, nickel content, and physical properties of the ore are very variable. The main minerals in the nickel saprolite ore are nickeliferous serpentine and smectite. Microprobe analyses show a strong depletion of Mg with increasing nickel content in the serpentine minerals; smectite generally contains less nickel than serpentine. Chemical analyses of samples from more than 100 drill holes are used to calculate the mean chemical compositions, mean accumulation factors, and gain and loss of major and trace elements for the various layers. This permits a quantitative approach to be made to the genetic history of the weathering mantle. Gain and loss determinations on the basis of constant chromium content and of constant volume give nearly identical results for the saprolite layer. Calculations on the basis of Ni/Cr ratios indicate that three-quarters of a former 20-m-thick limonite layer has been eroded away. Only the lower part of the original limonite layer with a relatively high SiO₂ content is preserved. The kaolinite- and illite-rich surface layer is a mixture of limonite and weathered clayey material, which was probably derived from adjacent rocks. Part of the autochthonous weathering section is contaminated with infiltrated allochthonous surface material. It is not possible that colluvial-alluvial deposition of clayey material from nonultramafic rocks could have taken place under the present geomorphic regime. Thus, lateritization of the serpentinite and deposition of siallitic material must have occurred before exposure of the Tagaung Taung in its present form.     

Selective nickel and cobalt uptake from pressure sulfuric acid leach solutions using column resin sorption

Selective removal of Ni and Co, from a high pressure acid leach (HPAL) solution of a Brazilian laterite nickel ore that contains relatively high concentration of impurities, was carried out with an ion exchange chelating resin possessing iminodiacetic acid group (Amberlite IRC 748®). The resin was tested in column experiments. The experimental results showed that higher pH values improved the ion exchanger performance and higher nickel load capacities were achieved. Besides, increasing nickel concentration in solution, nickel uptake and selectivity were substantially improved. The breakthrough experimental curves also showed that many metals were immediately brokenthrough just after the initiation of the feed, while the breakthrough of Ni began later. These results suggested that it is feasible to purify HPAL solution recovering nickel selectively using the chelating resin Amberlite IRC748® if some specific conditions related to pH, flow rate and nickel concentration are applied. Removal of metals from the resin was successfully performed with HCl and H₂SO₄ solutions. Nickel was eluted concentrated more than 20 times its initial concentration in the feed solution, while only a trace amount of impurities was eluted.     

铌钽精矿标准物质研制

铌钽精矿标准物质在监控选冶样品分析的过程起到重要作用,在选厂及冶金系统有很大的需求,国内外的文献检索均未发现铌钽精矿标准物质的报道;而铌钽矿物的性质决定了铌钽精矿的粉碎粒度及均匀性对铌钽精矿标准物质的研制提出了更高的要求。本文阐述了4个铌钽精矿标准物质的研制过程,铌钽精矿采集于宜春及尼日利亚铌钽选厂,样品经气流粉碎和高铝球磨两次细碎及机械混匀后,随机抽取包装好的样品进行均匀性和稳定性检验及定值。采用电感耦合等离子体发射光谱法与质谱法(ICP-OES/MS)进行均匀性和稳定性检验,结果表明样品的均匀性和稳定性良好。采用多个实验室协同测试的定值方式,利用不同原理的分析方法对此样品的铌钽等12个元素进行定值,给出了各定值元素的认定值和不确定度。4个铌钽精矿标准物质Ta(Nb)_2O_5的含量为9. 89%、20. 55%、40. 79%、53. 69%,形成一个从粗精矿到精矿较为完整的含量体系,可以满足选冶试验各阶段流程样品分析对标准物质的需求。     

Preparation and Certification of High-Grade Gold Ore Reference Materials (GAu 19-22)

Two types of gold deposit with both good homogeneity and a high-grade of gold were selected to prepare four gold ore reference materials (GAu-19,GAu-20,GAu-21 and GAu-22) by the Institute of Geophysical and Geochemical Exploration (IGGE),China.Seven laboratories participated in the certification programme. Volumetric methods for GAu19-21 and atomic absorption spectrometry for GAu-22 were used for the homogeneity testing,the coefficient of variation being found to be less than 3%.After sample digestion and preconcentration,the samples were analysed by flame atomic absorption spectrometry (AAS),colorimetry,neutron activation analysis (NAA)and volumetric analysis. The certified values for the gold concentration in GAu19-22 are 18.3 μg g -1, 32.3 μg g -1, 53.0 μg g -1 and 5.72 μg g -1,respectively.     

Lateritic nickel deposits of Brazil

Many nickel deposits are known in Brazil, accounting for about 350 · 10⁶ tons of ore with an average of 1.5% Ni. All are of the lateritic type. These deposits are scattered throughout the country, being rarer in the Northeastern Region and in the South, below 25 °S latitude. They are mainly associated with mafic-ultramafic massifs of large dimensions and ultramafic alkaline complexes, and occur in climatic regions of contrasting seasons. The weathering profile developed over the fresh rock consists, from bottom to top, of the following horizons: altered rock, coarse saprolite, argillaceous saprolite, ferruginous saprolite and lateritic overburden. The thickness of each horizon varies from one deposit to another, the whole profile generally exceeding 20 m. The saprolitic horizons with inherited minerals (serpentine, chlorite) or neoformed minerals (smectites) constitute the silicated nickel ore and are thicker were climatic conditions are drier; the ferruginous upper horizons made up of iron oxide-hydroxides are more developed in more humid regions. In Brazil, the silicated ore generally prevails over the oxidized ore. The main Ni-bearing minerals are serpentine, smectite, garnierite and goethite. The lateritic nickel deposits of Brazil may be correlated with two erosion surfaces, corresponding to the Sul Americano (Lower Tertiary) and Velhas (Upper Tertiary) levelling cycles. The degree of dismantling of the higher and more ancient surface and the consequent development of the Velhas Surface control the position of the nickel accumulation in the landscape. Thus, the deposits may be found either in the lowlands or in the highlands, where they are always covered by a silcrete layer. The alteration profiles in the Brazilian lateritic nickel deposits are broadly similar to those described elsewhere in the world. However, they present two characteristic features: the silicated ore prevails over the oxidized ore, and a silicified layer covers the profies developed on the highlands.     

Bias in the analysis of geological materials for gold using current methods

A consistent pattern has been observed in the results obtained for Au in three soil and two porphyry copper ore samples serving as control reference standards in geochemical analyses. The mean reported by wet chemical methods (regardless of the measurement technique) was less than the mean by fire assay-based methods which, in turn, was less than the mean reported by laboratories using direct instrumental neutron activation analysis (INAA). These data have been obtained from 16 laboratories, some employing more than one method. Compared to INAA, values obtained for Au (at the 30–300 ppb level) using aqua regia (AR) dissolution were low by 24–42%, while those reported by fire assay-based methods were low by 14–26%.Studies of these samples and 32 rocks of widely varying composition revealed that the amount of Au remaining in the residue after AR attack ranged from 4% to 59% of the total. Gold dissolved by AR was determined by graphite furnace atomic absorption spectrometry (GFAAS) after extraction into MIBK (methyl isobutyl ketone), whereas Au remaining in the residue was determined by INAA. The slope of the line obtained by plotting Au by INAA vs. the sum of Au by AR/GFAAS and Au in the residue was not significantly different from 1.0.Modifications to the AR procedure such as prior attack by HCl or HF did not improve the recovery of Au in the three reference soils. However, reduction of sample size from 10 g to 1 g while maintaining the volume of AR at about 30 ml did increase results for Au. Furthermore, addition of HF in the attack on 1-g samples yielded results virtually identical to those obtained by INAA. It is thought that the poor extraction efficiency by AR is due to non-wetting of the larger sized sample, a lack of intimate, prolonged contact between the grains of the sample and the acid mixture and the presence of insoluble gangue surrounding Au particles. Constant agitation of the sample during evaporation with AR is desirable.The mean values obtained for Au in the soils by fire assay methods were not significantly different from the results by INAA (low by 14–19%); this was not the case for the two copper ore samples (low by 26%). This probably reflects the difficulties encountered in fire assay by high concentrations of Cu which hinder effective collection and separation of Au into the Pb button. However, the accuracy of the INAA method has not been established and is dependent upon measurement procedures and the degree of certainty associated with the Au values assumed for the reference materials employed for calibration. While estimation of precision does not present a problem, accuracy is difficult to assess in the absence of certified reference materials for Au at concentrations in the 10–300 ppb range. However, it is concluded that methods based upon AR dissolution can lead to low results, the magnitude being dependent upon the sample matrix and the mineralogical association of the Au present.     

The Preparation and Certification of Two Samples of Chromium Ore

The preparation of two chromium ores as reference materials is described and the procedures used in the measurement of the homogeneity of the samples are outlined. Statistical analysis of the data submitted by 32 laboratories that resulted in the certification of the samples is presented. Certified values have been assigned for 11 constituents in the one sample and for 10 in the other sample. Provisional values have been assigned for FeO in both samples and CaO in one of the samples.