Determination of Platinum and Palladium in Geological Samples by Inductively Coupled Plasma-Atomic Emission Spectrometry after Preconcentration with Immobilised Nanometric Titanium Dioxide

A new method has been developed for the determination of platinum and palladium based on separation and preconcentration with a microcolumn packed with nanometric TiO₂ immobilised on silica gel (immobilised nanometric TiO₂) prior to their determination by inductively coupled plasma-atomic emission spectrometry. The optimum experimental parameters for the preconcentration of Pt and Pd, such as the pH of the sample solution, its flow rate and volume, the type and concentration of eluent and interfering ions, have been investigated. Platinum and Pd could be quantitatively retained by immobilised nanometric TiO₂ in the pH range 6–8, then eluted completely with 2.0 ml of 3% m/v thiourea in 1.0 mol l⁻¹ HNO₃. The detection limits of this method for Pt and Pd were 12 and 7. 6 ng l⁻¹ with an enrichment factor of 100, and the relative standard deviations were 4.7% and 3.3% at the 10 ng ml⁻¹ level. The method has been applied for the determination of Pt and Pd in geological samples with satisfactory results.     

Dynamic sea-level change during the last deglaciation of northern Iceland

Rundgren, M., Ingólfsson, Ó., Björck, S., Jiang, H. & Haflioason, H. 1997 (September): Dynamic sea-level change during the last deglaciation of northern Iceland. Boreas , Vol. 26, pp. 201–215. Oslo. ISSN 0300–9483.
A detailed reconstruction of deglacial relative sea-level changes at the northern coast of Iceland, based on the litho- and biostratigraphy of lake basins, indicates an overall fall in relative sea level of about 45 m between 11300 and 9100 BP, corresponding to an isostatic rebound of 77 m. The overall regression was interrupted by two minor transgressions during the late Younger Dryas and in early Preboreal, and these were probably caused by a combination of expansions of local ice caps and readvances of the Icelandic inland ice-sheet margin. Maximum absolute uplift rates are recorded during the regressional phase between the two transgressions (10000–9850 BP), with a mean value of c . 15 cm ¹⁴C yr^-1 or 11–12 cm cal. yr^-1. Mean absolute uplift during the regressional phase following the second transgression (9700–9100 BP) was around 6 cm ¹⁴C yr^-1, corresponding to c . 3 cm cal. yr^-1, and relative sea level dropped below present-day sea level at 9000 BP.     

40Ar/39Ar Constraints on the tectonic history and architecture of the ultrahigh-pressure Sulu orogen

New ⁴⁰Ar/³⁹Ar ages are presented from the giant Sulu ultrahigh-pressure (UHP) terrane and surrounding areas. Combined with U-Pb ages, Sm-Nd ages, Rb-Sr ages, inclusion relationships, and geological relationships, they help define the orogenic events before, during and after the Triassic collision between the Sino–Korean and Yangtze Cratons. In the Qinling microcontinent, tectonism occurred between 2.0 and 1.4 Ga. The UHP metamorphism occurred in the Yangtze Craton between 240 and 222 Ma; its thermal effect on the Qinling microcontinent was limited to partial resetting of K-feldspar ⁴⁰Ar/³⁹Ar ages. Subsequent unroofing at rates of 5–25 km Myr⁻¹ brought the UHP terrane to crustal levels where it underwent a relatively short amphibolite facies metamorphism. The end of that metamorphism is marked by ⁴⁰Ar/³⁹Ar ages in the 219–210 Ma range, implying cooling at crustal depths at rates of 50–200 °C Myr⁻¹. Ages in the 210–170 Ma range may reflect protracted cooling or partial resetting by Jurassic or Cretaceous magmatism. Jurassic 166–149 Ma plutonism was followed by cooling at rates of c. 15 °C Myr⁻¹, suggesting relatively deep crustal conditions, whereas Cretaceous 129–118 Ma plutonism was succeeded by cooling at rates of c. 50 C Myr⁻¹, suggesting relatively shallow crustal depths.     

Fifty-five-million-year history of oceanic subduction and exhumation at the northern edge of the Caribbean plate (Sierra del Convento mélange, Cuba)

Petrological and geochronological data of six representative samples of exotic blocks of amphibolite and associated tonalite-trondhjemite from the serpentinitic mélange of the Sierra del Convento (eastern Cuba) indicate counterclockwise P–T paths typical of material subducted in hot and young subduction zones. Peak conditions attained were ∼750 °C and 15 kbar, consistent with the generation of tonalitic partial melts observed in amphibolite. A tonalite boulder provides a U-Pb zircon crystallization age of 112.8 ± 1.1 Ma, and Ar/Ar amphibole dating yielded two groups of cooling ages of 106–97 Ma (interpreted as cooling of metamorphic/magmatic pargasite) and 87–83 Ma (interpreted as growth/cooling of retrograde overprints). These geochronological data, in combination with other published data, allow the following history of subduction and exhumation to be established in the region: (i) a stage of hot subduction 120–115 Ma, developed upon onset of subduction; (ii) relatively fast near-isobaric cooling (25 °C Myr⁻¹) 115–107 Ma, after accretion of the blocks to the upper plate lithospheric mantle; (iii) slow syn-subduction cooling (4 °C Myr⁻¹) and exhumation (0.7 km Myr⁻¹) in the subduction channel 107–70 Ma; and (iv) fast syn-collision cooling (74 °C Myr⁻¹) and exhumation (5 km Myr⁻¹) 70–60 Ma.     

Determination of Selenium in Fifty Two Geochemical Reference Materials by Hydride Generation Atomic Absorption Spectrometry

The selenium content of fifty two geochemical reference samples, issued by several reference material producers (ANRT, GIT-IWG, USGS, NIST and GSJ) has been determined by continuous hydride generation and atomic absorption spectrometry. Selenium(VI) in the digested solutions was pre-reduced to selenium(IV) by heating in 6 mol l⁻¹ HCl solution. The limit of detection was 3 ng g⁻¹ selenium in common geological samples. Some samples which contain a large amount of heavy metals were analysed by the standard addition technique. The agreement between the reported results and published data is satisfactory.     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

High Precision Hf-W Isotopic Measurements in Meteoritic Material Using Negative Thermal Ionisation Mass Spectrometry (NTIMS)

This paper presents a two-stage anion-exchange procedure for tungsten extraction, an improved mass spectrometric procedure for tungsten analysis and a simplified chemical separation and TIMS procedure for the determination of Hf concentrations. The chemical separation of tungsten is based on its complexing properties with HF and H₂O₂. The blank level for a sample size of 300 mg is about 80 pg for tungsten. The procedure is designed for the high sensitivity of negative thermal ionisation mass spectrometry (NTIMS) provided by the use of Mg oxide as an emitter on Ir filaments. Tungsten can be readily measured with a high precision in various meteoritical material and especially in small W-poor silicate fractions. Samples containing as little as a few ng g^-1 tungsten can be analysed reliably with this method.     

Pressure–temperature conditions and retrograde paths of eclogites, garnet–glaucophane rocks and schists from South Sulawesi, Indonesia

High-pressure metamorphic rocks exposed in the Bantimala area, c . 40  km north-east of Ujung Pandang, were formed as a Cretaceous subduction complex with fault-bounded slices of melange, chert, basalt, turbidite, shallow-marine sedimentary rocks and ultrabasic rocks. Eclogites, garnet–glaucophane rocks and schists of the Bantimala complex have estimated peak temperatures of T  =580–630 °C at 18  kbar and T  =590–640 °C at 24  kbar, using the garnet–clinopyroxene geothermometer. The garnet–omphacite–phengite equilibrium is used to estimate pressures. The distribution coefficient K _D1=[( X _pyr)³( X _grs)⁶/( X _di)⁶]/[(Al/Mg)_M2,wm (Al/Si)_T2,wm]³ among omphacite, garnet and phengite is a good index for metamorphic pressures. The K _D1values of the Bantimala eclogites were compared with those of eclogites with reliable P–T  estimates. This comparison suggests that peak pressures of the Bantimala eclogites were P =18–24  kbar at T  =580–640 °C. These results are consistent with the P–T  range calculated using garnet–rutile–epidote–quartz and lawsonite–omphacite–glaucophane–epidote equilibria.     

The Determination of Major Oxide and Trace Element Concentrations in Eighteen Chinese Standard Reference Samples by X-ray Fluorescence Spectrometry

Eighteen Chinese geologic reference samples (stream sediments GSD 9–12, soils GSS 1–8, and rocks GSR 1–6) were analyzed by wavelength-dispersive X-ray fluorescence spectrometry (XRFS) for major elements Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P, and by energy-dispersive XRFS for trace elements Ba, Ce, Cr, Cu, La, Nb, Ni, Rb, Sr, Y, Zn, and Zr. Major element analysis followed gravimetric determination of loss on ignition, and samples were prepared by fusion with Li₂B₄O₇. A loose-powder sample preparation was used for trace element analysis. The results reported in this study are, generally, in good agreement with concentrations compiled by X. Xie of the Geochemical Standard Reference Group and the Institute of Geophysical and Geochemical Exploration (People's Republic of China).     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

U-Pb Zircon Geochronology with an Integrated LA-ICP-MS Microanalytical Workstation: Achievements in Precision and Accuracy

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a microanalytical tool especially suitable for providing fast and precise U-Pb geochronological results on zircon grains. A new 193 nm excimer laser adapted to a micromachining workstation, equipped with a newly designed two-volume ablation cell and coupled with a quadrupole ICP-MS, is presented here. The system was tuned routinely to achieve sensitivities in the range of 3000 cps/μg g⁻¹ for ²³⁸U (< 2% RSD), with a 34 μm spot size, at 5 Hz and ∼ 8 J cm⁻², while ablating the NIST SRM 612 glass reference material. The system was capable of providing fast (< 1.5 minutes each analysis) and precise (generally < 1.5% 1s errors) ²⁰⁶Pb/²³⁸U zircon ages. The ages of widely used reference material zircons (Plesovice, 337 Ma; Temora, 416 Ma; R33, 418 Ma; Sri Lanka, 564 Ma; 91500, 1065 Ma) could be precisely matched, with an accuracy on isotopic ratios that ranged from ∼ 2 to ∼ 6%, depending on the homogeneity of the natural reference materials.     

Quantitative temperature-time information from retrograde diffusion zoning in garnet: constraints for the P–T–t history of the Central Black Forest, Germany

Garnet from a kinzigite, a high-grade gneiss from the central Black Forest (Germany), displays a prominent and regular retrograde diffusion zoning in Fe, Mn and particularly Mg. The Mg diffusion profiles are suitable to derive cooling rates using recent datasets for cation diffusion in garnet. This information, together with textural relationships, thermobarometry and thermochronology, is used to constrain the pressure–temperature–time history of the high-grade gneisses. The garnet–biotite thermometer indicates peak metamorphic temperatures for the garnet cores of 730–810  °C. The temperatures for the outer rims are 600–650  °C. Garnet–Al₂SiO₅–plagioclase–quartz (GASP) barometry, garnet–rutile–Al₂SiO₅–ilmenite (GRAIL) and garnet–rutile–ilmenite–plagioclase–quartz (GRIPS) barometry yield pressures from 6–9  kbar. U–Pb ages of monazite of 341±2  Ma date the low- P high- T metamorphism in the central Black Forest. A Rb/Sr biotite–whole rock pair defines a cooling age of 321±2  Ma. The two mineral ages yield a cooling rate of about 15±2  °C Ma⁻¹. The petrologic cooling rates, with particular consideration of the f O₂ conditions for modelling retrograde diffusion profiles, agree with the geochronological cooling rate. The oldest sediments overlying the crystalline basement indicate a minimum cooling rate of 10  °C Ma⁻¹.     

Trace Element Data for Gold, Iridium and Silver in Seventy Geochemical Reference Materials

New concentrations for Au, Ir and Ag obtained by instrumental neutron activation analysis are presented for seventy geochemical reference materials. Results in agreement with literature values for Au and Ir down to concentrations of a few ng g⁻¹ were obtained. For Au and Ir concentrations above 10 ng g⁻¹, the repeatability of replicate analyses of reference materials was mostly better than 10%. For concentrations between 1 and 10 ng g⁻¹ the RSD for Ir was 10–30%, whereas for Au it was higher and more variable (20–50%). In addition, concentrations for Cd and Hg are presented for some of the same reference materials. The high RSD at relatively high concentrations seen in gold for some RMs (e.g., WMG-1, WMS-1) did not exist for Ir and suggests homogeneity for this platinum-group element at the sub-sample size used in this study. For the following eight RMs, mostly ultramafic rocks (CHR-Pt+, OREAS-13P, OREAS-14P, PCC-1, UMT-1, WMG-1, WMS-1, WPR-1), Ir measurements agreed within ± 10% of mostly certified or recommended concentrations, which ranged from 2 ng g⁻¹ to 6 μg g⁻¹. For the reference material UB-N, iridium concentration compared favourably to published results obtained by isotope dilution ICP-MS methods and a previously unrecognised heterogeneity is inferred for Au, Hg and Sb, but not for the other measured elements.     

Interpretation of porphyroblast inclusion trails: limitations imposed by growth kinetics and strain rates

Porphyroblast inclusion trails provide important information about the tectonometamorphic evolution of a metamorphic rock. However, there remains considerable controversy over whether porphyroblasts rotate during bulk non-coaxial deformation.
With reference to an area of the Scandinavian Caledonides and utilizing existing data from theoretical and experimental modelling, this study demonstrates that both 'straight' and 'S-shaped' inclusion trails are consistent with an interpretation in terms of syndeformational porphyroblast growth in a regime approximating to Newtonian simple shear. At crustal strain rates of 10^-14 s^-1 and porphyroblast growth times of 0.1–1.0 Ma, it is shown that a maximum of 5-9 angular rotation would occur during growth. At faster strain rates of 10^-12 s^-1 (e.g. those in a shear zone) porphyroblast angular rotations of 90 are shown to occur in 0.1–0.25 Ma (i.e. times comparable with or faster than porphyroblastesis). In view of this, 'S-shaped' inclusion trails are to be expected in porphyroblasts growing in active shear zones or other situations of high shear strain, whereas 'straight' inclusion trails can be interpreted as static overgrowth of an existing fabric or as syndeformational porphyroblastesis at low strain rates.     

Oxygen bulk diffusion measurements and TEM characterization of a natural ultramylonite: implications for fluid transport in mica-bearing rocks

Oxygen bulk diffusion rates were experimentally determined in a natural ultramylonite sample ( c . 5   μ m grain size; 15–20% biotite, 20% quartz, 60–65% feldspars, and minor Fe-oxides) from the Gerrish Island shear zone, SE Maine, USA. The diffusion experiments were performed at 250–550  °C and 100  MPa water pressure. Oxygen bulk diffusion rates were determined both parallel and perpendicular to the strong foliation of the sample. The Arrhenius parameters for transport parallel to the foliation are: D _bulk0=2.0×10⁻¹¹ m² s⁻¹ and Q =30±6 kJ mol⁻¹. The bulk diffusivity perpendicular to the foliation is about a factor of 3.5 less than that parallel to the foliation with the same activation energy. The values of bulk diffusivity and activation energy obtained are consistent with ionic diffusion through a static aqueous fluid, suggesting that an interconnected fluid exists in the ultramylonite even under hydrostatic conditions. The microstructure of the ultramylonite was characterized using transmission electron microscopy (TEM). The nature and distribution of the interconnected fluid cannot be completely resolved from the TEM analysis; however, the low percentage of three-grain channels and open grain/interphase boundaries suggests that the fluid resides as a thin film on the grain surfaces. The results of this study have direct applications in many important geological settings and provide valuable insights into the observed rapid diffusion rates, strong lithological control and pervasive nature of fluid transport in mica-bearing rocks.     

Viscosity ratio estimates from natural Rayleigh-Taylor instabilities

The geometry of natural gravity-driven overturns potentially contains information on viscosity ratios of the material involved. Irregularities at the interface between two superposed horizontal fluid layers tend to amplify and grow with time with a regular wavelength if the top iayer is more dense, Published formulas (Woidt), for such Rayleigh-Taylor (R-T) instabilities have been used to construct graphs which can constrain the effective viscosity ratio at the onset of the overturn. Only the initial thicknesses of the two layers and the final wavelength of the structures need be known. The theory is based on an infinite two-layer system of Newtonian fluids between rigid boundaries with no slip or free slip at contacts.
Geological examples included are; soft-sediment dewatering on the scale of decimetres in northern Norway, an unusual instability between basalt and sand in Australia of hundreds of metres, salt diapirism of kilometres in Germany and the Persian Gulf, and granitic diapirism from northern Sweden of tens of kilometres. Viscosity ratios in the order of 1–10 are found for soft sediments with the top layer as the more viscous. Ratios inferred from patterns of salt diapirs are very large, with the overburden approximately 10³-⁻10⁵ times more viscous than the salt. The viscosities of granites are indicated as lower than their overburden and with ratios of 10³.     

Ultra-Trace Element Analysis of NIST SRM 616 and 614 using Laser Ablation Microprobe-Inductively Coupled Plasma-Mass Spectrometry (LAM-ICP-MS): a Comparison with Secondary Ion Mass Spectrometry (SIMS)

The microanalytical capability of laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to determine ultra trace elemental concentrations has been demonstrated by the analysis of two low concentration glass standard reference materials, NIST SRM 614 and 616. Results for fifty two elements at concentrations in the low ng g^-1 range are compared with those determined using secondary ion mass spectrometry (SIMS). Both techniques provide results at these concentrations that generally agree within 95% confidence limits, demonstrating the accuracy for ultra-trace level of in situ determinations by the two techniques. At concentrations of less than 20 ng g^-1 in NIST SRM 616, an accuracy and precision of better than 10% has been obtained for most mono-isotopic rare earth elements, when a spot size of 50 μm is used. Limits of detection for selected elements were as low as 0.5 ng g^-1.     

Mo-related Adakitic Granitoids from Non-island-arc Setting: Jecheon Pluton of South Korea

Abstract. The Jecheon granitoids, having an elongated shape of NE-SW 27 km and NW-SE 13 km (190 km²), are composed mostly of magnetite-series hornblende-biotite granodiorite and biotite granite, which intrude into the Neoproterozoic metamor-phic and Paleozoic sedimentary rocks of the Ogcheon Belt. The granitoids have Triassic-Jurassic age of 202.7 ±1.9 Ma with very high ⁸⁷Sr/⁸⁶Sr initial ratio of 0.7140. The granodiorite has 63–69 % SiO₂, 15.1–17.3 % Al₂O₃, <1.6 % MgO, 6–15 ppm Y and Sr/Y ratios of 24–76, and is depleted in HREE. Biotite granite together, the Jecheon pluton has adakitic characteristics, which are unique in a continental tectonic setting. The granitoids may have been generated by partial melting of an older adakitic granitoid of I-type basement, or by separation of early crystallized garnet and hornblende from an anatectic melt.