Formation and sorption behavior of the palladium thiosulfate complexes under natural conditions (model experiments)

The formation of significant amounts of thiosulfate ion (up to 42 mg/L) was established in experiments on the interaction of sulfide-bearing rocks with water. The possibility of the formation of palladium compounds with thiosulfate ion [Pd(S₂O₃)₂]^2– was demonstrated. The stability constant of the complex is 3.7 × 10⁹, which may provide intense migration of this palladium species in ecosystem. The study of the behavior of palladium thiosulfates during interaction with inorganic and organic components of geochemical barriers showed that around 50–55% of thiosulfate-bound palladium is extracted by humic acid in the pH range typical of natural waters. Under these conditions, ferrihydrite sorbes palladium quantitatively, and may serve as efficient barrier to the interaction of palladium compounds with particulate matters of waters and bottom sediments.     

分光光度最小二乘法同时测定金钯铊

在ｐＨ３．３的ＨＡＣ－ＮａＡＣ缓冲介质中，金、钯、铊分别与硫代米Ｃｈｉ酮（ＴＭＫ）形成有色配合物，在吐温－８０存在下，不但实现水相显色，而且提高了灵敏度。利用分光光度法多波长测定和反推最小二乘法，建立了金、钯、铊三组分同时测定的方法。检出限为：１０ｎｇＡｕ／ｍＬ；４ｎｇＰｄ／ｍＬ，３０ｎｇＴｌ／ｍＬ。     

阴离子交换树脂-活性炭动态吸附无火焰原子吸收法测定矿石中的微量金铂钯

采用717阴离子交换树脂-活性炭分离富集矿石中的微量Au、Pt、Pd。40μg待测元素富集结果表明,Au、Pt、Pd的回收率分别为100%、95.3%和96.3%。以HC l为介质在无火焰原子吸收仪上测定。方法经对国家一级标准物质GBW 07291、GBW 07292分析检验,结果与标准值相符。对GBW 07291国家一级标准物质测定7次,其精密度(RSD)分别为:Au 9.4%、Pt 11.2%、Pd 3.0%。方法适用于矿石中10-6~10-9量级Au、Pt、Pd的测定。     

Migration of platinum,palladium, and gold in the water systems of platinum deposits

In order to explore the behavior of platinum group elements in the ecosystems of mineral deposits, the migration characteristics of platinum and palladium were determined in the pH range typical of surface waters. Model sorption experiments on the precipitation of platinum and palladium on iron oxyhydroxide in the presence of major natural inorganic and organic ligands showed that platinum interacts most actively with an iron oxyhydroxide (ferrihydrite) precipitate within the whole pH range, both in the absence and presence of natural organic substances, whereas palladium is preferentially bound to dissolved, suspended, and sedimentary humic substances. The thermodynamic calculation of coexisting platinum and palladium species is qualitatively consistent with experimental data on the character of accumulation and migration of these elements. The obtained data suggest that the migration of platinum and palladium into highly colored waters in the zones of platinum group element deposits results in their extensive deposition on natural geochemical barriers.     

我国W区超镁铁-镁铁杂岩体钯、铂元素地球化学研究

我国W区岩体产在上古生代凹陷西北边缘与中间隆起交接处,北东向深大断裂带东侧。区内地层主要由石炭纪砂板岩、片理化酸性火山碎屑岩;二迭纪砂页岩、中酸性火山岩、火山碎屑岩及第四纪松散沉积物所组成。本区侵入岩异常发育,属海西年代,包括两     

新显色剂5-(5-氟-2-吡啶偶氮)-2,4-二氨基甲苯的合成及其与钯的显色反应

合成并用红外光谱和元素分析鉴定了氟代吡啶偶氮氨类新试剂5-(5-氟-2-吡啶偶氮)-2,4-二氨基甲苯(5-F-PADAT),并研究了该试剂与钯显色的反应。结果表明,在0.32~3.84 mol/L高氯酸溶液中,试剂与钯形成1∶1的紫红色络合物,其最大吸收峰位于566 nm,表观摩尔吸光系数为4.84×104L.mol-1.cm-1,钯的浓度在0~2000μg/L符合比耳定律。方法选择性好,大量常见金属离子不干扰钯的测定,操作简单,应用于矿样和催化剂中微量钯的测定,结果与原子吸收光谱法相符。     

峨嵋玄武岩铂钯赋存状态分析

以黔西峨嵋玄武岩和辉长岩为测试对象，在矿物鉴定基础上，建立了Pt、Pd在硫化物、金属互化物、吸附态和硅酸盐类质同象不同赋存状态查定的流程，查明了峨嵋玄武岩中Pt、Pd是以硫化物态和金属互化物态为主，少量呈吸附态和硅酸盐类质同象态存在，讨论了峨嵋玄武岩铂钯状态丰度与铂族元素可能成矿的关系。     

Migration behavior of platinum group elements in natural and technogeneous systems

Data were summarized on the speciation of the main platinum group elements (PGE) platinum, palladium, and rhodium in aqueous media, forms of their input into the environment, and mechanisms of accumulation by natural sorptive phases. In some cases, the results obtained for PGE were compared with those for gold. Data on PGE speciation in a number of natural environments were analyzed. It was found that the main factor controlling the migration ability of PGE (Pd > Pt»Rh) is the formation of stable compounds with dissolved organic matter, hydroxyl, and thiosulfate ions and nanometer-sized particles. The transport of dissolved PGE species by marine, riverine, and technogeneous suspended materials was evaluated as an alternative way of an increase in PGE mobility. Significant differences were revealed in the migration behavior of platinum, palladium, and rhodium indicating the dominance of palladium dissipation in a dissolved state. The possibility of the prediction of PGE accumulation and dissipation in technogeneous systems was demonstrated.     

扫描电镜-X射线能谱仪在丹巴地区铂族矿物物相特征分析中的应用

丹巴地区铜镍硫化物铂族矿床品位低、铂族矿物颗粒细、铂族元素间的类质同象普遍,此类铂族资源的赋存状态研究及矿石的选冶长期以来都是较为棘手的问题。本文采用扫描电镜-X射线能谱仪器组合,对丹巴铜镍硫化物铂族矿床中含量达到1‰的元素进行快速的定性/定量分析,研究了铂族矿物原位的赋存状态和形貌特征。通过扫描电镜观察到该矿床的铂族矿物主要为砷铂矿、锑钯矿、碲锑钯矿,其次以自然铂、硫砷铑矿、硫砷铱矿,呈椭圆状、纺锤状等形式赋存于黄铁矿、磁黄铁矿及蛇纹石中,部分以类质同象的形式存在,极少量的铂与钯元素呈固溶体形式存在。X射线能谱分析表明该矿床中主要的铂族元素为Pt、Pd,其次为Ru、Rh、Ir、Os; 点分析表明砷铂矿中Pt的含量为52.84%,锑钯矿中Pd的含量为45.15%; 线扫描和面扫描分析表明铂族元素主要分布在含铁的硫化物中,Pt、Pd等铂族元素的含量与铁、镍的含量成正相关关系,反映了丹巴地区铂族元素亲铁、亲镍、亲硫的地球化学特征。     

Strong metal–support interaction as activity requirement of palladium-supported tin oxide sol–gel catalyst for water denitration

Two nanocrystalline palladium-supported tin oxide catalysts for water denitration were synthesized by a modified sol?Cgel technique using appropriate chloride precursors for both support and active phases, and citric acid to tune the rate of hydrolysis and condensation. The difference among sample preparation procedures refers to the moment of the noble metal loading to the support, as well as to the calcination temperature altitude followed. Thus, mesoporous tin oxide was synthesized by a sol?Cgel method following calcination at 700°C. The palladium active phase was introduced afterwards by means of palladium chloride solution impregnation, followed by calcination at 400°C (sample 1). Alternatively, simultaneous complexation of both metal and support precursors followed by single calcination at 700°C was applied for preparation of sample 2. The former sample showed higher activity and selectivity in hydro-denitration of water model system initially containing 100?ppm of nitrates. This was explained by preferential textural, morphological and structural properties accomplished by early contact of metal and support nanoparticles, while achieved by calcination at high single temperature forcing diffusion of palladium ions into the tin oxide matrix. The outcome is very well distribution of palladium and strong metal?Csupport interaction leading to multivalent tin. This indicates partly reduced tin oxide formation in the course of its reduction in hydrogen, which may act as active site in denitration reaction.     

土壤样品中贵金属活动态提取技术

介绍了土壤样品中贵金属铂、钯、金的水提取态、黏土吸附态与可交换态、有机质结合态以及铁锰氧化物结合态等不同相态的提取方法与测定方法。方法检出限为铂0.03 ng/g,钯和金0.01 ng/g。实验了铂、钯、金活动态金属各种提取液介质中痕量贵金属的稳定性、固-液分离方法、提取温度的影响及提取液的处理方法。通过在南非隐伏铂钯矿或矿化区的试验,结果表明所圈定的异常与实际矿(化)体相符,为识别隐伏贵金属铂钯矿床提供了有效信息,对寻找隐伏矿床具有一定的指导意义。     

河北红石砬铂矿床铂、钯地球化学异常特征

红石砬铂矿地球化学异常组分简单,仅发育Ｐｔ和Ｐｄ的强异常,部分伴生Ａｕ异常,不伴生Ｃｒ、Ｃｏ、Ｃｕ、Ｎｉ、Ｖ、Ａｓ、Ｓｂ、Ａｇ、Ｐｂ等元素异常。岩石、土壤、水系沉积物中Ｐｔ、Ｐｄ的分布和异常模式与铂族矿化特征、矿体剥蚀程度及其表生地球化学行为等有关。矿体出露地表时,Ｐｔ、Ｐｄ呈强异常分布,异常的ｗ（Ｐｔ）／ｗ（Ｐｄ）比值与矿石中ｗ（Ｐｔ）／ｗ（Ｐｄ）比率基本一致;隐伏矿体上方,Ｐｄ有明显的浓集,ｗ（Ｐｔ）／ｗ（Ｐｄ）比值小于地表矿体。表生环境中,Ｐｔ、Ｐｄ可以呈矿物碎屑、可溶态等多种形式迁移,在疏松沉积物中形成异常。因此,以Ｐｔ、Ｐｄ作为直接指示元素,进行地球化学勘查,可以发现这种类型的铂族矿床。     

5—（偶氮苯）—8—（4—硝基—1—重氮苯）—氨基喹啉与钯的显色反应及应用

在弱碱性介质中,乳化剂－ＯＰ存在下,５－（偶氮苯）－８－（４－硝基－１－重氮苯）－氨基喹啉（ＰＡＮＰＡＱ）与钯发生显色反应,生成ｎＰＡＮＰＡＱ∶ｎＰｄ（Ⅱ）＝２∶１的蓝色络合物,最大吸收峰位于６４０ｎｍ,摩尔吸光系数为１．０８×１０５Ｌ·ｍｏｌ－１·ｃｍ－１,钯的质量浓度在０～６００μｇ／Ｌ符合比尔定律。所考查的５４种共存离子,对测定Ｐｄ（Ⅱ）基本无影响。方法已用于钯催化剂中Ｐｄ（Ⅱ）的测定,结果与原子吸收法相符,５次测定的ＲＳＤ在１．３％～１．５％。     

Mass Spectrometric Isotope Dilution Determination Of Palladium in Geochemical Reference Samples

Fifteen geochemical reference samples have been analysed for palladium using the stable isotope dilution technique. These include seven USGS, five CRPG and three CCRMP samples. Our results ape in reasonable agreement with the presently accepted values for the USGS samples, but are significantly lower than the present CCRMP values. Our data for the CRPG samples are the first to be published. This is the first reported study of the determination of palladium in silicate samples using the isctope dilution technique.     

REGULARITIES IN THE DISTRIBUTION OF NONFERROUS AND PRECIOUS METALS IN PRINCIPAL ORE MINERALS AND SILICATES OF THE NORIL'SK DEPOSITS

The results of a study of copper, nickel, cobalt, platinum, palladium, gold, and rhodium distribution in basic ore-forming sulfide minerals (chalcopyrite and pyrrhotites) as well as in the silicate portion of the host rocks of the Noril'sk deposit, are given. Interrelations between metals in different sulfide minerals and silicates are characterized. It has been established that palladium, platinum, and gold are concentrated in chalcopyrite while cobalt and rhodium are concentrated in pyrrhotite. The cobalt and precious metal content in sulfides grows with the increase of their nickel content. The relative content, however, of all these elements estimated for 1% of nickel is different in chalcopyrites and pyrrhotites. The former show a high platinum, palladium, and gold content and the latter--cobalt and rhodium. Ratios of these elements in sulfides and silicates are different. The relative platinum content increases in silicates due to a considerably greater content of mineralized platinum. Both nickel and cobalt form silicate compounds the latter to a much greater extent than the former. The relative cobalt content is therefore higher in silicates than in sulfides. In descending order, the element concentrations in sulfides range as follows: copper, nickel, palladium, gold, cobalt, platinum. — Auth. English Summ.     

The hydrolysis and precipitation of Pd(II) in 0.6 mol kg NaCl: A potentiometric, spectrophotometric, and EXAFS study

The soluble and insoluble hydrolysis products of palladium were investigated in aqueous solutions of 0.6 mol kg⁻¹ NaCl at 298.2 K. Potentiometric titrations of millimolal palladium(II) solutions were used to monitor hydrolysis reactions of the mononuclear PdCl₃OH²⁻ and species. Spectrophotometric titrations were also used to corroborate the speciation change and to extract the correlative molar absorption coefficients for the PdCl₃OH²⁻ species in the 210-320 nm range. Longer-term potentiometric titrations systematically yielded precipitates which matured over a period of 6 weeks and resulted in a more extensive release of protons to the solution. Precipitation experiments in the 3-11 pH range showed the dominant precipitating phase to be Pd(OH)_1.72Cl_0.28. EXAFS measurements yielded an average of 3.50 O and 0.50 Cl atoms per Pd atom with a Pd-O distance of 2.012 Å and a Pd-Cl distance of 2.185 Å. Speciation modeling of proton and palladium mass balance data of experiments for palladium concentrations ranging from 0.047 to 10.0  mmol kg⁻¹ required the presence of polynuclear complexes containing 3-9 palladium atoms. The existence of such complexes is moreover supported by previous investigations of palladium hydroxide chains of the type [Pd(OH)_1.72Cl_0.28]_n, that are coiled and/or aggregated into nanometer-sized (15-40 Å) spheroids.     

氮配位的磁性高分子复合微球P（GMA—MMA—AA）／Fe3O4负载钯催化水相Suzuki反应的研究

以可控自由基聚合技术制备的磁性高分子复合微球P（GMA—MMA．AA）／Fe3O4为载体,三乙烯四胺为配体制备了一种新型的负载型钯催化剂。采用透射电镜、振动样品磁强计、x射线光电子能谱仪和x射线衍射分析仪等手段对催化剂进行了表征,并评价了催化剂对水相Suzuki反应的催化活性。结果表明,催化剂的平均粒径为800nm左右,钯在载体表面呈高度分散状态,整个催化剂呈超顺磁性。该催化剂在空气氛围中就能较好的催化水相中芳基卤代物与苯硼酸的Suzuki反应,较高产率且立体选择性地生成取代的联苯产物,反应过程中催化剂可稳定分散于反应体系中,并可在外磁场作用下快速与从体系分离。催化剂重复使用5次后,仍具有较高的活性。     

催化光度法测定化探样品中的痕量钯

本文对催化（Ce^＋4～Hg2^＋2体系）光度法测定钯的测定条件进行了实验和探讨。实验发现,在文献的基础上,改变试剂的加入顺序（先加Ce^＋4、后加Hg2^＋2）,延长催化反应时间到60min,可使该体系的检测下限降到0．18ng／g,因此,本文制定的分析方法可满足新地球化学研究对钯的测定要求（要求测定下限为0．2ng／g）用本文所制定的方法对含钯为：0．26、2．3、4．6、60．0ng／g的标样分别进行9次测定、其测定结果与标准值相符,相对标准偏差分别为：11．7％、10．4％、7．8％、4．8％。     

Determination of Ruthenium,Palladium and Iridium in 27 In ternational Reference Silicate and I Ron-Formation Rocks,Ores and Related Materials By Isotope Dilution Inductively-Coupled Plasma Mass Spectrometry*

Ruthenium, palladium and iridium have been determined in 27 international reference rocks, ores and related materials by inductively-coupled plasma mass spectrometry using isotope dilution and sample introduction by solution nebulization and electrothermal vaporization, after chemical separation by co-precipitation with tellurium. The accuracy of the procedure is discussed by comparison of the results obtained with synthetic solutions and standard samples.