A Comprehensive Method for Precise Determination of Re,Os, Ir,Ru, Pt,Pd Concentrations and Os Isotopic Compositions in Geological Samples

A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl₄ method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO₃‐H₂SO₄ as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.     

Spectrophotometric Determination of Gold (III) after Liquid–Liquid Extraction and Selective Pre‐concentration with a Novel Dibenzo‐18‐Crown‐6 Derivative

A selective and sensitive method for the extraction and spectrophotometric determination of gold with N,N′‐6,7,9,10,17,18,20,21‐octahydrodibenzo[b,k][1,4,7,10,13,16] hexaoxacyclo‐octadecine‐2,13–diylbis(2‐chloroacetamide) (ODBOCA) is described. The ODBOCA–Au(III) complex was extracted from a slightly acidic aqueous solution (pH 5) into a chloroform layer and then the absorbance of the extract was measured using a UV–Vis spectrophotometer with 1.0 cm quartz cells at 540 nm. An enrichment factor of 200 was achieved. In the chloroform medium at 540 nm, the molar absorptivity and Sandell’s sensitivity were 4.12 × 10³ l mol^?1 cm^?1 and 0.048 μg cm^?2, respectively. Beer’s law was obeyed in the range of 0.5–15 μg ml^?1 in the measured solution. The relative standard deviation for ten replicate samples at the 1.0 μg ml^?1 level was 3.0%. The limit of detection, based on 3s, was 0.5 μg l^?1 in the original sample. The effects of pH, ligand concentration and shaking time were studied. The ratio of the metal ion to ligand molecules in the complex was found to be 1:2 according to the Job Method. The effects of interference by a number of metal ions were investigated. The method was verified with certified reference materials and spiked tests, and quantitative recovery values were obtained. The method was fast, accurate, selective and precise, and was applied to the determination of gold in water and ore with good results.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.     

Determination of Trace Silver in Polymetallic Ore Samples by Flame Atomic Absorption Spectrometry after Solid‐Phase Extraction Using a Microcolumn Comprising Eggshell Membrane

A rapid and inexpensive method was developed for the determination of trace silver in polymetallic ore samples by use of eggshell membrane (ESM), a natural biomaterial, as the solid‐phase extraction (SPE) adsorbent coupled with flame atomic absorption spectrometry (FAAS). The ESM was used for the separation/pre‐concentration of silver, and the parameters affecting sensitivity, such as pH, sample flow rate, eluent volume and eluent flow rate, were carefully investigated. ESM was found to be an effective solid phase extractant for the adsorption of trace silver over a wide range of acidity from 0.02 to 0.50 mol l^?1 HNO₃. The sample solution in 0.4 mol l^?1 HNO₃ was pumped through an ESM microcolumn at the rate of 1.0 ml min^?1. Silver was absorbed, and then eluted with a solution of 1.0% m/v thiourea–0.5% v/v HCl. Under these optimal conditions, ESM exhibited a good enrichment efficiency for silver with a dynamic adsorption capacity of 1.7 mg g^?1. The proposed method was applied to the FAAS determination of trace silver in polymetallic ores and geological reference materials, GSO‐2, 3 and 5, and GSD‐11, GSD‐12, and the determined values were in good agreement with certified values.     

Determination of the Concentration of Carbonic Species in Natural Waters: Results from a World‐Wide Proficiency Test

The results of an international interlaboratory proficiency test for the determination of carbonic species are presented. Eight laboratories analysed twelve water samples (four synthetic waters, one lake water, four geothermal waters, one seawater and two petroleum waters) by two methods: (a) individual laboratory analytical procedure and (b) acid–base titration curves in tabular form following a standardised protocol. In case (b), the concentrations of carbonic species were calculated by the organiser using the (1) Hydrologists' method, (2) Geochemists' method and/or (3) initial pH and total alkalinity method. For synthetic waters, the averaged % trueness and precision of measurement of the two methods were (trueness = 7.6, precision = 9.4) and (9.0, 3.4) for total alkalinity, and (6.6, 31.0) and (7.8, 6.1) for carbonic alkalinity, respectively. This indicates that the total alkalinity calculation procedure is in general correct in the individual laboratory method, but the carbonic alkalinity calculation procedure has serious problems. The measurements of total alkalinity for lake and seawaters were in agreement in both the methods; however, the individual laboratory measurement method for geothermal and petroleum waters was conceptually incorrect. Thus, the analytical procedures for the determination of carbonic species were reviewed. To apply the Hydrologists' and/or Geochemists' methods, the location of NaHCO₃EP and H₂CO₃EP is necessary, even for samples with pH lower than that of NaHCO₃EP, and a backward titration curve after complete removal of CO₂ must be performed. The initial pH and total alkalinity method is appropriate where a complete analysis of species that contribute to the alkalinity is known.     

Measurement of the Isotopic Composition of Molybdenum in Geological Samples by MC‐ICP‐MS using a Novel Chromatographic Extraction Technique

A novel preconcentration method is presented for the determination of Mo isotope ratios by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N‐benzoyl‐N‐phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG‐71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A ¹⁰⁰Mo‐⁹⁷Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass‐dependent isotopic fractionation to be determined with a measurement reproducibility of  < 0.09‰ (δ^98/95Mo, 2s) by MC‐ICP‐MS. The mean δ^98/95Mo_{SRM 3134} (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples.     

Measurement of 34S/32S Ratios of NBS 120c and BCR 32 Phosphorites Using Purge and Trap EA‐IRMS Technology

Measurements of sulfur stable isotope ratios (³⁴S/³²S) have suffered from technical difficulties in analysing low‐S materials reducing their use despite their undeniable scientific interest. The measurement of ³⁴S/³²S ratios is a powerful tool for deciphering problems such as determining the sources of environmental pollutants, to detect adulteration, tracking the evolution of the redox state of the oceans and quantifying the role of the bacterial activity in sulfide minerals genesis. We have used a high‐precision method of sulfur isotope determination using a new type of elemental analyser based on ‘purge and trap’ technology. This new technique demonstrates the high quality of ³⁴S/³²S measurements for samples with S concentrations lower than 1% m/m. International calibrated references of diverse sulfur‐bearing materials were used to calibrate two low (< 1%) S‐bearing phosphorites used as compositional reference material for future use as isotopic references: BCR 32 and NBS 120c. δ³⁴S_CDT values of, respectively, 18.2‰ (1s = 0.3; n = 23) and 18.3‰ (1s = 0.4; n = 20) are proposed for these. Calibration of both phosphorites with international reference materials led to calculation of a mean standard error close to 0.4‰. The demonstration of a capability to reliably measure S isotope ratios in low‐S phosphate minerals or rocks opens up new fields of palaeoenvironmental reconstructions.     

Discrimination between primary magmatic biotites, reequilibrated biotites and neoformed biotites

The ternary diagram TiO₂–FeO*–MgO (FeO* = FeO + MnO) is proposed as a quantitative objective tool for distinguishing between primary magmatic biotites and those that are more or less reequilibrated, or possibly neoformed, by or within a hydrothermal fluid. The limit of the domains of the primary magmatic biotites, the reequilibrated biotites and the neoformed biotites were determined on the basis of optical, paragenetic and chemical criteria. To cite this article: H. Nachit et al., C. R. Geoscience 337 (2005).     

金云母-蛭石间层矿物阳离子交换容量的影响因素研究

采用氯化铵交换-原子吸收光谱法和CaCl2-甲醛缩合法测定3个金云母-蛭石间层矿物样品的各阳离子交换分量和阳离子交换总量,通过分析样品粒度和溶液pH值对阳离子交换容量的影响及晶层端面水解使表面荷电的特点,确定样品的等电点.结果表明,随着粒度的增大,样品的阳离子交换容量逐渐减小;随着pH值的增大,样品的阳离子交换容量先急剧减小(pH=2～5),后趋于平缓(pH=5～9),而后再急剧减小(pH=9～11.5),这些变化主要与晶层端面的水解作用和八面体片阳离子的溶出作用有关;样品的等电点为pH值≈9.研究结果对于排除端面水解作用对阳离子交换容量的影响和进一步确定蛭石晶层的层电荷具有重要的意义.     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.     

Multi-technique monitoring of ocean tide loading in northern France

We have organised afield study of ocean tide loading in the northwestern part of France, where tidal amplitudes are known to be among the highest in the world. GPS and gravimetric techniques have already proved their capability to measure such weak and high-frequency signals. In this study, these classical observations are complemented with less usual techniques, such as tiltmeter and Satellite Laser Ranging (SLR) measurements. We present here the preliminary results for a common period of observations spanning from 12–19 May 2004. Additional measurements from the French Transportable Laser Ranging Station (FTLRS) were available during September and October 2004. Observation residuals are computed as the difference between the observed and the predicted time signals. We obtain small RMS residuals for GPS measurements (2.5/3.1/4.5 mm for the eastward, northward and upward components), for absolute and relative gravimetry (9 nm/s² and 13 nm/s²) and for tiltmeters (0.05 μrad for EW component). We also fit the amplitude of the main M2 tidal constituent to FTLRS observations and we find a value of 3.731 cm, which is comparable to the theoretical value.     

Evaluation of In Situ Heterogeneity of Elements in Solids: Implications for Analytical Geochemistry

A general method for the evaluation of in situ heterogeneity of geochemical materials is described and the significance of the results discussed, by using three case studies and earlier data sets. The heterogeneity of Pb in soil (expressed as RSD due to sampling, RSD_samp) varies from < 5 to > 100% between different sites, in a way that relates to the mode of deposition of the element. The heterogeneity of an element also varies systematically as a function of the distance scale at some sites. This variation can be modelled using linear regression, accounting for over 90% of the experimental variance, at seven scales over three orders of magnitude. Variation in heterogeneity between elements at the same site, seems to be somewhat diagnostic of the origin of the element, lithogenic being less than anthropogenic, although the later is also being modified by the mode of deposition. Where the heterogeneity is large (RSD > 30%), it is proposed that it can be expressed more accurately as a heterogeneity factor (10^GSDsamp), to reflect its frequency distribution, which is positively skewed towards higher concentration values.     

Eclogite and pyroxenite xenoliths from off-craton kimberlites near the Kaapvaal Craton, South Africa

Mantle xenoliths brought to the surface by kimberlite magmas along the south-western margin of the Kaapvaal craton in South Africa can be subdivided into eclogites sensu stricto, kyanite eclogites and orthopyroxene eclogites, all containing omphacite, and garnet clinopyroxenites and garnet websterites characterised by diopside. Texturally, chemically (major elements) and thermally, we observe an evolution from garnet websterites (T_EG = 742–781 °C) towards garnet clinopyroxenites (T_EG = 715–830 °C) and to eclogites (T_EG = 707–1056 °C, mean value of 913 °C). Pressures calculated for orthopyroxene-bearing samples suggest upper mantle conditions of equilibration (P = 16–33 kb for the garnet websterites, 18 kb for a garnet clinopyroxenite and 23 kb for an opx-bearing eclogite). The overall geochemical similarity between the two groups of xenoliths (omphacite-bearing and diopside-bearing) as well as the similar trace element patterns of clinopyroxenes and garnet suggest a common origin for these rocks. Recently acquired oxygen isotope data on garnet (δ¹⁸O_gnt = 5.25–6.78 ‰ for eclogites, δ¹⁸O_gnt = 5.24–7.03 ‰ for garnet clinopyroxenites) yield values ranging from typical mantle values to other interpreted as resulting from low-temperature alteration or precursors sea-floor basalts and associated rocks. These rocks could then represent former magmatic oceanic rocks that crystallised from a same parental magma as plagioclase free diopside-bearing and plagioclase-bearing crustal rocks. During subduction, these oceanic rock protoliths equilibrated at mantle depth, with the plagioclase-bearing rocks converting to omphacite and garnet-bearing lithologies (eclogites sensu largo), whereas the plagioclase-free diopside-bearing rocks converted to diopside and garnet-bearing lithologies (garnet websterites and garnet clinopyroxenites).     

An Optimised 1,10‐Phenanthroline Method for the Determination of Ferrous and Ferric Oxides in Silicate Rocks,Soils and Minerals

A precise, accurate and rapid method for the sequential determination of FeO and Fe₂O₃ in rocks, soils and some non‐refractory minerals by 1,10‐phenanthroline spectrophotometry is described. Fe(II) and Fe(III) were leached from the sample (?200 mesh) using a mixture of NH₄HF₂ and H₂SO₄ at 40–80 °C for 10 min on a hot plate. Both Fe(II) and Fe(III) could be conveniently estimated sequentially from the same reaction mixture at the μg g^?1 to percentage level. The method is better than the existing wet chemical methods, including the commonly used Pratt's titrimetric redox method, for Fe(II) and Fe(III) determinations in rock and soil samples in terms of precision, accuracy and rapidity. The throughput of the method was very high; at least forty to fifty samples could be estimated easily in a day. The results obtained compare favourably with those obtained by Pratt's method, as well as for certified/recommended values of a set of eleven certified reference materials having FeO and Fe₂O₃ contents in the range 0.21–14.63% and 0.58–8.48%, respectively. The optimised 1,10 phenanthroline method was found to be accurate to within 0.21% m/m FeO and 0.30% m/m Fe₂O₃ compared with the literature values of the certified reference materials studied.     

Sorption and precipitation of Co(II) in Hanford sediments and alkaline aluminate solutions

Sorption and precipitation of Co(II) in simplified model systems related to the Hanford site high-level nuclear waste tank leakage were investigated through solution studies, geochemical modeling, and X-ray absorption fine structure (XAFS) spectroscopy. Studies of Co(II) sorption to pristine Hanford sediments (ERDF and Sub), which consist predominantly of quartz, plagioclase, and alkali feldspar, show an adsorption edge centered at pH ≈ 8.0 for both sediments studied, with sorption >99% above pH ≈ 9.0. Aqueous SiO₂ resulting from dissolution of the sediments increased in concentration with increasing pH, though the systems remained undersaturated with respect to quartz. XAFS studies of Co(II) sorption to both sediment samples reveal the oxidation of Co(II) to Co(III), likely by dissolved O₂, although this oxidation was incomplete in the Sub sediment samples. The authors propose that Fe(II) species, either in aqueous solution or at mineral surfaces, partially inhibited Co(II) oxidation in the Sub sediment samples, as these sediments contain significantly higher quantities of Fe(II)-bearing minerals which likely partially dissolved under the high-pH solution conditions. In alkaline solutions, Al precipitated as bayerite, gibbsite, or a mixture of the two at pH > 7; an amorphous gel formed at pH values less than 7. Aqueous Co concentrations were well below the solubility of known Co-bearing phases at low pH, suggesting that Co was removed from solution through an adsorption mechanism. At higher pH values, Co concentrations closely matched the solubility of a Co-bearing hydrotalcite-like solid. XAFS spectra of Co(II) sorbed to Al-hydroxide precipitates are similar to previously reported spectra for such hydrotalcite-like phases. The precipitation processes observed in this study can significantly reduce the environmental hazard posed by ⁶⁰Co in the environment.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

水体中主要阴离子及pH值对双氯芬酸液相色谱定量的影响

双氯芬酸(DCF)是一种常用的非甾体消炎药,随着生产量和使用量的不断增大,其在环境中被频繁检出。DCF能在生物体内富集,对生物具有潜在毒性,已经引起了广大学者的关注。DCF的准确定量是开展其相关研究的基础,在应用液相色谱测试DCF的过程中,通常通过前处理消除样品基质干扰,但关于基质如何干扰DCF测量并没有详细研究。为了满足野外及实验室测试需要,本文针对高效液相色谱-紫外检测DCF过程中,水体中常见的阴离子SO_4~(2-)、Cl~-和NO_3~-,液相色谱流动相组成和水样pH对DCF准确定量的影响展开研究。结果表明:(1)SO_4~(2-)和Cl~-对DCF的最大吸收波长(277 nm)没有影响,但是NO_3~-的存在会使DCF的最大吸收峰发生偏移,产生红移现象,并且使吸光度略微增大;(2)同等条件下,在酸性介质(pH5)中DCF的定量结果比在碱性介质中的低。与碱性介质(pH=7.26)中DCF的峰面积相比,样品在pH=2.01的酸性介质中测得的峰面积减少73.14%,因此在碱性条件下DCF定量更为准确。     

Determination of Platinum‐Group Elements in Geological Samples by Isotope Dilution‐Inductively Coupled Plasma‐Mass Spectrometry Combined with Sulfide Fire Assay Preconcentration

A method was developed for the determination of platinum‐group elements (PGE) in geological samples by isotope dilution‐inductively coupled plasma‐mass spectrometry combined with sulfide fire assay preconcentration. Samples were fused and PGE analytes were concentrated in sulfide buttons. The buttons were dissolved using HCl leaving PGE analytes in insoluble residues, which were digested in HNO₃ and simultaneously processed for the distillation of Os. The remaining solutions were further prepared for the purification of Ru, Rh, Pd, Ir and Pt using a tandem assembly of cation and Ln resin columns. The eluents were directly analysed by membrane desolvation‐ICP‐MS. Ruthenium, Pd, Os, Ir and Pt were determined by isotope dilution, whereas Rh was determined by conventional reference material calibration combined with ¹⁹³Ir as the internal standard element. The method was validated using a series of PGE reference materials, and the measurement data were consistent with the recommended and the literature values. The measurement precision was better than 10% RSD. The procedural blanks were 0.121 ng for Ru, 0.204 for Rh, 0.960 ng for Pd, 0.111 ng for Os, 0.045 ng for Ir and 0.661 ng for Pt, and the limits of detection (3s) were 0.011 ng g^?1 for Ru, 0.008 ng g^?1 for Rh, 0.045 ng g^?1 for Pd, 0.009 ng g^?1 for Os, 0.006 ng g^?1 for Ir and 0.016 ng g^?1 for Pt when a test portion mass of 10 g was used. This indicates that the proposed method can be used for the determination of trace amounts of PGE in geological samples.     

Cation exchange capacity of loess and overlying soil in the non-carbonate loess sections, North-Western Croatia

The adsorption properties in terms of cation exchange capacity and their relation to the soil and sediment constituents (clay minerals, Fe-, Mn-, and Al-oxyhydroxides, organic matter) were investigated in loess, soil-loess transition zone, and soil at four loess-soil sections in North-Western Croatia. Cation exchange capacity of the bulk samples, the samples after oxalate extraction of Fe, Mn and Al, and after removal of organic matter, as well as of the separated clay fraction, was determined using copper ethylenediamine. Cation exchange capacity (pH～7) of the bulk samples ranges from 5 to 12 cmol _c /kg in soil, from 7 to 15 cmol _c /kg in the soil-loess transition zone, and from 12 to 20 cmol _c /kg in loess. Generally, CEC values increase with depth. Oxalate extraction of Fe, Mn, and Al, and removal of organic matter cause a CEC decrease of 3–38% and 8–55%, respectively, proving a considerable influence of these constituents to the bulk CEC values. In the separated clay fraction (<2 μm) CEC values are up to several times higher relative to those in the bulk samples. The measured CEC values of the bulk samples generally correspond to the clay mineral content identified. Also, a slight increase in muscovite/illite content with depth and the vermiculite occurrence in the loess horizon are concomitant with the CEC increase in deeper horizons, irrespective of the sample pretreatment.     

Development of a New Method of Extraction of Interstitial Water from Low‐Porosity Consolidated Sediments Recovered During Super‐Deep Drilling Projects

During the Integrated Ocean Drilling Program (IODP) Expedition 338, several methods were tested for the extraction of interstitial water in consolidated, low‐porosity deep‐sea sediments from Site C0002 in the Kumano Basin. On the basis of those tests, we propose a modified ground rock interstitial normative determination (GRIND) method of extraction of interstitial water. In separate runs of the new method, sediment samples were ground in a ball mill with either ultrapure water or a solution of HNO₃. The interstitial water was then extracted with a conventional squeezer. Sufficient solution was extracted by this method to analyse most major and a few minor components of interstitial water that were comparable to those previously reported for samples extracted by the conventional squeezing method. The new method requires much smaller amounts of sediment than that of the conventional method and will be useful for analysis of samples recovered during super‐deep drilling programmes.