Lead Removal from Aqueous Solution by Natural and Pretreated Zeolites

Hazardous metal cations enter water through the natural geochemical route or from the industrial wastes. Their separation and removal can be achieved by adsorptive accumulation of the cations on a suitable adsorbent. In the present work, toxic Pb(II) ions are removed from water by accumulating it on the surface of natural zeolite in three different forms; one untreated and two treated samples, one sample treated with 2 M HCI solution and other is treated with 3 M NaOH solution. Natural zeolite is mainly composed of clinoptilolite, and mordenite, with amount of non-zeolite phase (smectite and illite) and C and CT opal. The adsorption experiments are carried out using a batch process in environments of different pH, initial Pb(II) concentration, interaction time and amount of zeolites. Treated zeolite samples show high exchange capacity for Pb(II) compared to untreated sample, however, acid-treated sample shows an exceedingly good exchange capacity. Equilibrium data fitted well with the Langmuir isotherm model with maximum adsorption capacity of 115, 126, and 132 mg g⁻¹ of untreated natural zeolites, alkali-treated zeolites and acid-treated zeolites respectively. The rates of adsorption were found to confirm to pseudo-first order kinetic with good correlation and the overall rate of lead ions uptake.     

天然硅酸岩铷锶同位素稀释测定小交换柱化学制备方法研究

本篇报道用于铷锶同位素年代测量的小柱分析流程。方法是在我们1972年草酸淋洗流程的基础上建立的。同时参考W.康普斯敦教授1977年介绍的小交换柱铷锶化学流程。样品提取方式、交换柱分离条件和操作步骤,是根据自己的实验确定的。流程有自身的特点。     

暴露测年样品中26Al和10Be分离及其加速器质谱测定

在已有实验流程基础上,建立并优化了石英样品中Be和Al提取、纯化等实验流程,设计的流程条件实验包括实验试剂、器皿和离子交换柱选择、离子交换树脂分离Be和Al时酸浓度选择等。结果表明,选择钢铁研究总院研制的⁹Be标准溶液作为¹⁰Be样品制备的载体;使用一次性实验器皿;选用4 cm规格的离子交换柱;用0.05 mol/L草酸和0.75 mol/L盐酸混合溶液洗脱吸附于阴离子树脂上的Al,可有效提取、纯化样品中的Be和Al。加速器质谱(AMS)测量结果显示,13组化学空白的¹⁰Be/⁹Be和²⁶Al/²⁷Al比值平均值分别为7.48×10^-15和1.96×10^-15,与国内已有宇宙成因核素实验室的结果(5×10^-15~8×10^-15)具有可比性。电感耦合等离子体发射光谱(ICP-AES)的测量结果表明,Be、Al回收率分别达90%和60%。基于新建立的实验流程分析了祁连山北侧金佛寺的一个岩石样品,获得了¹⁰Be和²⁶Al的暴露年代分别为(10.7±1.0) ka和(10.0±1.2) ka,与前人研究结果一致。     

Sample preparation for isotopic determination of boron in clay sediments

The procedures of sample preparation for isotopic determination of boron in clay sediments is very cumbersome, by far, there haven’t been relevant reports on that. In order to establish an effective method for sample preparation, a series of experiments were carried out. In this paper, boron in clay sediments was extracted with HCl solution and purified by two-step ion exchange method. Extracted HCl solution should be adjusted to alkalescency before passing through the Amberlite IRA 743 resin column due to the fact that Amberlite IRA 743 resin absorbs boron only from alkalescent solution. However, a mass of hydroxides of Al and Fe will be precipitated when the extracted HCl solution becomes alkalescent. Hydroxides of Al and Fe have a strong adsorption capacity for boron, which can cause boron isotope fractionation. To treat precipitated hydroxides of Al and Fe, four procedures, namely direct ion exchange (DRIE), decationizing ion exchange (DCIE), once sedimentation ion exchange (OSIE) and repeated sedimentation ion exchange (RSIE) were used and assessed. The influences of the four procedures on separation and extraction and isotopic composition of boron in experimental solutions and clay sediments were also discussed. According to the results, the DRIE, DCIE and OSIE are improper. The result of sample determination indicates that when extracting boron via RSIE, with the increase of precipitation times, there’s an obvious decrease in boron content in the precipitated hydroxides while a sharp increase in recovery of boron and it is favorable for weakening the influence of boron isotope fractionation. But the process of RSIE is time consuming and it may introduce boron. It needs further research to establish a more effective sample preparation method for isotopic deter- mination of boron in clay sediments.     

应用离子交换剂分解磷块岩的分析方法

氟是磷灰石的重要化学组成之一^[1]。磷块岩和磷灰石中氟的测定,对磷灰石类型的鉴定和磷块岩的成因研究有重要意义。目前,氟的测定方法广泛地采用酸、碱溶(融)样,用蒸馏法进行元素分离^[2,3,4]。近十几年来,由于离子选择电极法操作方便,被广泛地应用于各种类型物质中氟的测定^[5]。离子交换剂可以用来分解某些难溶性的天然和合成材料,但是至今这个方法还未得到广泛地应用。     

利用多接收器电感耦合等离子体质谱仪(MC-ICPMS)测定镁铁-超镁铁质岩石中的铼-锇同位素组成

报道了用多接收器电感耦合等离子体质谱仪(MC-ICPMS)测定Re-Os同位素组成的质谱方法和化学分离方法,并应用该方法测定了天然镁铁-超镁铁质岩石样品中的Os同位素组成及Re、Os含量.Re同位素组成的MC-ICPMS测定利用膜除溶雾化器(Aridus)和静态法拉第杯接收的方式完成,采用Ir标准溶液在线校正仪器的质量分馏.Os同位素组成的MC-ICPMS测定采用常规雾化器和离子计数器静态接收的方式完成,并用10%的HCl-EtOH和10%的HCl溶液交替清洗进样系统来消除Os的"记忆效应".岩石样品的Re和Os化学分离采用Carius管溶样法,结合CCl4萃取以及微蒸馏的方法分离纯化Os,利用阴离子交换树脂的方法分离纯化Re.运用上述方法,对6个镁铁-超镁铁质岩石样品中的Re、Os含量和187Os/188Os同位素比值进行了测定,获得了理想的分析结果.     

环境水样中铬形态分析方法研究

研究了水体中几种形态铬的存在状态,分离条件。提出离子交换为主的铬形态分离流程。结合二苯碳酰二肼光度法可测定水样中总铬,溶解态铬,颗粒态铬,六价态铬,无机态和有机态三价铬。已用所拟流程于水样及药物中铬的形态分析,水样加标回收率在９２％－９７％,药物分析结果与标量相符。     

Chemical Separation of Tungsten and Other Trace Elements for TIMS Isotope Ratio Measurements Using Organic Acids

One requirement for isotope ratio measurement results with small measurement uncertainties is that the element of interest is effectively separated from the sample matrix. Efficient chemical separation of W from matrix components, especially Ti, can be challenging, particularly for large test portion masses (> 1 g). We present a new W separation procedure that takes advantage of the distinct complexation behaviour of Ti and W with citrate ligand in a moderately low pH, oxidising solution. This preparation procedure can reduce the Ti/W ratio of large (4–10 g) basaltic (i.e., high‐matrix) test portions by a factor of 10⁵, relative to their original compositions, in a two‐step separation procedure. The procedure additionally provides a separate, well‐purified Mo fraction. We show that optimal separation requires precise selection of reagent concentrations and sample load. The procedure was employed to determine the μ¹⁸²W composition of BHVO‐2 as ?6.7 ± 4.2 (2 standard deviation, 2s). The principles derived from this method may prove useful for chemical separation of other elements used for geochemical and cosmochemical applications given an appropriate selection of organic acid. Future successful applications of this method may reveal that the use of organic acids as procedural reagents is a currently under‐utilised tool for efficient chemical separation protocols.     

皖西霞石正长岩合成沸石分子筛及提钾的实验研究

合成沸石因具有优异的吸附及离子交换性能而备受关注。本实验以皖西地区霞石正长岩为主要原料 ,成功地合成了 13 X型沸石分子筛 ,母液经蒸发、分离 ,制得了白炭黑及碳酸钾 ,表明霞石正长岩具有巨大的潜在综合利用价值。合成沸石、白炭黑和碳酸钾的成分、结构及性能分析表明 ,3种产品均达到了国家或化工行业标准。基于此 ,对工艺技术可行性作了分析评价     

A Triple‐Stack Column Procedure for Rapid Separation of Cu and Zn from Geological Samples

We present a new procedure for the separation and purification of Cu and Zn from geological samples. Our procedure employed a single pass, triple‐stack column set‐up. The first column, filled with TRU resin (TrisKem International), quantitatively removed Fe and Ti from sample matrices. A second column, filled with pre‐filter resin (TrisKem International), removed organic compounds. Finally, a third column, filled with anion exchange resin (AG1‐X8, 200–400 mesh, Bio‐Rad), was used to separate Cu and Zn from the remaining matrix. Our procedure required about 50% less acid volume than previously reported methods for Cu and Zn separation, thereby minimising analytical blanks and column running times. Copper and Zn stable isotope ratios were determined by a Thermo Neptune Plus MC‐ICP‐MS using Zn and Cu external normalisation, respectively, in addition to sample‐standard bracketing to correct for instrumental mass bias. We explore the inter‐calibration of Cu and Zn isotope fractionation coefficients during analysis by measuring mixed Cu–Zn solutions with enhanced mass bias variation generated by varying sample gas flow rates. Our results demonstrate that this procedure is useful when variation in instrumental mass bias throughout analytical sequences is insufficient to inter‐calibrate Cu and Zn fractionation coefficients.     

一次溶样分离地质样品中Pb-Sr-Nd方法的可行性研究

现有的地质样品中Pb、Sr、Nd分离分析方法是对Pb和Sr - Nd分别采用两份样品进行分离,多消耗一份样品量,因而制约了样品量少的研究.本文提出了基于HNO3 - HF - HClO4混合酸熔融样品,采用AG1 - X8、AG50W - X8和HDEHP组合离子交换柱,对同一份地质样品一次溶样,连续分离Pb、Sr、Nd.用该方法对国际标准样品AGV -2、BHVO-2中的Pb、Sr、Nd进行分离,回收率均优于95％,全流程空白分别为Pb＜ 0.2 ng,Sr＜1.5 ng,Nd＜1.1 ng.用多接收器-电感耦合等离子体质谱(MC -ICP - MS)进行同位素比值测定,结果表明本研究提出的一份样品连续分离后的同位素测定结果与传统方法利用两份样品分别进行分离的结果在误差范围内完全一致.本文的研究可实现微量岩石样品的Pb、Sr、Nd同位素准确分析,对于珍贵样品的同位素组成研究具有重要意义.     

Multivariate statistical techniques applied to pisolitic laterite geochemistry at Golden Grove, Western Australia

Multivariate statistical procedures are applied to pisolitic laterite geochemistry in a study of the Golden Grove massive sulphide district. The objective is to optimize identification of geochemical anomalies caused by base metal mineral deposits.The statistical approach used in this paper depends upon geochemical data for appropriate reference groups (or training sets) being available. The target group consists of orientation data from pisolitic laterite about the Gossan Hill Cu-Zn massive sulphide deposit. A group representing background sequence was selected by combining three subareas in a geochemically quiet part of the prospective acid volcano-sedimentary sequence.A multi-element allocation procedure was set up using data from the reference groups. The exploration samples are then allocated, one sample at a time, to either one of the reference group categories, using the probability of group membership. A map showing the relative probability values for each sample site is the final product for interpretation, aided by ancillary use of an index of typicality.The allocation procedures were carried out using different element combinations, these being based on a procedure for subset selection to give maximum separation of reference groups, and on geochemical insight. Whilst many versions of the allocation procedure gave positive identification of the anomaly related to the blind Scuddles Cu-Zn deposit, allocation using only Cu, Pb, Zn and Ag did not. The results emphasize the importance of pathfinder elements in geochemical studies in weathered terrain.The allocation procedure using the most appropriate element combinations provided more positive identification of the main areas of known mineralization than had the previously used empirically derived methods of Smith and Perdrix (1983). The formal allocation procedure has the following additional advantages: results are not markedly affected by a very high value for any single element since robust procedures are incorporated into the analysis; better discrimination appears to be possible for weaker anomalies; separation of target from background can be optimized by formal calculations instead of by trial and error; and better suppression of background variation results.     

Quantitative Separation of Molybdenum and Rhenium from Geological Materials for Isotopic Determination by MC-ICP-MS

We have developed a new chemical procedure for the quantitative separation of molybdenum (Mo) and rhenium (Re) from a wide variety of geological samples. A single pass anion exchange separation provided complete recovery of pure Mo and Re in a form that was ideal for subsequent isotope and abundance determination by multi-collector inductively coupled plasma-mass spectroscopy (MC-ICP-MS). An enriched ¹⁰⁰Mo-⁹⁷Mo solution, mixed with the sample before digestion, enabled natural mass-dependant isotopic fractionation of Mo to be determined with an external reproducibility of < 0.12‰ (δ⁹⁸Mo/⁹⁵Mo, 2 s ). Determination of the concentration of Mo and Re in the same sample was achieved by isotope dilution, with instrumental mass-fractionation of Re being corrected by the simultaneous measurement of the ¹⁹¹Ir/¹⁹³Ir ratio. We have applied the new procedure to a variety of samples, including seawater, basalt and organic-rich mudrock. The procedure is ideally suited to palaeoredox studies requiring the precise determination of the Mo isotope composition and the Re/Mo ratio from the same sample.     

艾斯卡试剂熔矿、动态树脂交换——等离子体质谱法测定土壤样品中的痕量碘

研究了电感耦合等离子体质谱法（ICP—MS）测定土壤样品中微量碘的可行性,对测定碘的条件作了部分改进及进一步优化。样品经艾斯卡试剂分解,热水提取,阳离子交换树脂动态分离溶液中大量的钠、铁、锌等阳离子,干过滤部分溶液,采用电感耦合等离体子质谱法（ICP—MS）直接测定溶液中的碘。本方法用国家标准物质进行验证,测定结果和标准值吻合。并用该法顺利完成了陕西省宝鸡地区多目标区域地球化学调查样品中碘的测定。     

Accurate Determination of Nickel in South African Primary and Secondary Geochemical Reference Materials by Cation Exchange Chromatography and Atomic Absorption Spectrometry

Nickel in the six SA primary (NIMROCS) and fourteen secondary reference materials as well as in a phosphate rock has been determined accurately by means of atomic absorption spectrometry. A selective and quantitative twocolumn ion exchange separation procedure, using AG50W-X4 cation exchange resin, is employed for the separation of nickel from all other elements. The accuracy and precision of the described method are demonstrated by the analysis of synthetic rock solutions containing various amounts of nickel.     

Separation of concentrated acid and salt solutions in nanoporous media as the basis for a new technology of processing of phosphorus-containing raw materials

The physical and mathematical models were used to study the method of acid retardation for separating acids from their salts in concentrated multicomponent solutions using nanoporous sorption materials. A combined mechanism of separation relies on the fact that in the sorption phase having a low dielectric permittivity, smaller-sized acid particles, namely, the molecules or strongly bound and weakly hydrated ion pairs, can penetrate the nanopores and are retained within these pores due to molecular sorption or competitive solvation forces. The dissolved salts presented by highly hydrated ions or weakly bound ion pairs can easily pass through the porous medium with a flow of concentrated solution, which is pumped through the column packed with the granulated bed of gel-type ion exchange resins or hypercrosslinked polymers. In conventional cyclic AR processes, purified acid is desorbed by water according to the mechanism of competitive solvation. However, such processes can be successfully used only when the salts separated from acids are highly soluble, as is the case with chloride and nitrate solutions free of components that may form compounds insoluble in neutral medium. At the separation in real sulfate and phosphate media, which normally contain alkaline earth metals and other components, conventional AR- based technologies proved to be unsuccessful. The new modified version of acid retardation is based on the previously discovered effect of stabilization of colloidal systems and supersaturated solutions in porous ion exchange media. A distinctive feature of the proposed technique is the use of weakly acidic aqueous solutions, instead of water, at the stages of acid displace in the cyclic AR processes. The proposed technique of WPA purification using strong-base gel-type ion exchangers in the phosphate form opens up the possibility of stable and feasible processes of acid separation and purification with simultaneous extraction of valuable components, e.g., REE concentrate.     

利用同一化学流程分析地质样品中的铂族元素含量和铼-锇同位素组成

报道了利用一次溶样和同一化学流程分离富集地质样品中铂族元素(Pt、Pd、Os、Ir和Ru)和Re的方法.该化学流程包括以下几个步骤:(1) Carius管溶样法分解岩石样品中富集铂族元素的矿物;(2)四氯化碳萃取法分离出Os;(3)微蒸馏法进一步纯化Os;(4)阳离子交换树脂法将铂族元素(Pt、Pd、Ir和Ru)以及R...     

Identification and evolution of hydrogeochemical processes in the groundwater environment in an area of the Palar and Cheyyar River Basins,Southern India

The Palar and Cheyyar River Basins in Tamil Nadu state of Southern India are characterised by different geological formations, and groundwater is the major source for domestic, agricultural and other water-related activities. Hydrogeochemical studies were carried out in this area with the objective of identifying the geochemical processes and their relation to groundwater quality. Groundwater samples were collected once a month from 43 groundwater wells in this area from January 1998 to July 1999. Sampling procedures and chemical analysis were carried out as per the standard methods. Chemical data are used for mathematical calculations and graphical plots to understand the chemical process and its relation to the groundwater quality. The chemical composition of groundwater in the central part of the study area mainly depends on the recharge from lakes and the river, which is explained by a mixing mechanism. In addition, weathering of silicate minerals controls the concentration of major ions such as sodium, calcium, magnesium and potassium in the groundwater of this area. Further, the activity ratios indicate that the groundwater is in equilibrium with kaolinite, smectite and montmorrillonite. The reverse ion exchange process controls the concentration of calcium, magnesium and sodium in hard rock formations, and dissolution of carbonate minerals and accessory minerals is the source of Ca and Mg, in addition to cation exchange in the sedimentary formations. In general, the chemical composition of the groundwater in this area is influenced by rock–water interaction, dissolution and deposition of carbonate and silicate minerals, ion exchange, and surface water interactions.     

Determination of the platinum-group elements and gold in ferromanganese nodule reference material NOD-A-1

The concentrations of Ru, Pd, Ir, Pt, and Au were determined in a ferromanganese nodule reference sample NOD-A-1 by inductively coupled plasma mass-spectrometry. Sample preparation procedures include acid digestion and anion exchange preconcentration. Standard addition method was used to eliminate losses of the analyte during the chromatographic separation. The results are in agreement with previously published data. The low level of intermediate precision for Au between different subsamples of the same sample probably originates from the heterogeneous distribution of Au in ferromanganese nodules. The accumulation of PGE in ferromanganese nodules was studied using international reference samples.     

Groundwater flow,nutrient, and stable isotope dynamics in the parafluvial-hyporheic zone of the regulated Lower Colorado River (Texas,USA) over the course of a small flood

Periodic releases from an upstream dam cause rapid stage fluctuations in the Lower Colorado River near Austin, Texas, USA. These daily pulses modulate fluid exchange and residence times in the hyporheic zone where biogeochemical reactions are typically pronounced. The effects of a small flood pulse under low-flow conditions on surface-water/groundwater exchange and biogeochemical processes were studied by monitoring and sampling from two dense transects of wells perpendicular to the river. The first transect recorded water levels and the second transect was used for water sample collection at three depths. Samples were collected from 12 wells every 2 h over a 24-h period which had a 16-cm flood pulse. Analyses included nutrients, carbon, major ions, and stable isotopes of water. The relatively small flood pulse did not cause significant mixing in the parafluvial zone. Under these conditions, the river and groundwater were decoupled, showed potentially minimal mixing at the interface, and did not exhibit any discernible denitrification of river-borne nitrate. The chemical patterns observed in the parafluvial zone can be explained by evaporation of groundwater with little mixing with river water. Thus, large pulses may be necessary in order for substantial hyporheic mixing and exchange to occur. The large regulated river under a low-flow and small flood pulse regime functioned mainly as a gaining river with little hydrologic connectivity beyond a narrow hyporheic zone.