bluuebunny/crossref_metadata_2025 huggingface dataset:
MEASURING CHANGES IN JUVENILE GRAY SEAL BODY COMPOSITION
Authors: Hall Ailsa J. , McConnell Bernie J.
Published: May 2007

Abstract

Determining body composition in gray seals (Halichoerus grypus) is important when studying their physiology and life history. In this study we investigated the predictability of total body fat (TBF) and protein (TBP) in postweaned gray seal pups from morphometric measurements, blubber thickness using ultrasonographs and bioelectrical impedance analysis (BIA). In postweaned pups, TBF (kg) could be estimated from girth measurements and sex (n= 45, r2= 0.878) using hydrogen isotope dilution methods as the reference. However, TBP could not be reliably estimated from morphometric data. TBF (kg) in yearlings was best predicted from mass (n= 6, r2= 0.776) and TBP (kg) from mass/length (r2= 0.949). Dorsal blubber thickness using B‐mode ultrasound was also a significant predictor of TBF (kg) in postweaned pups (r2= 0.725) but BIA was not. Marked pups were recaptured during their first few months of life (n= 48) and body composition changes investigated. Animals lost mass and TBF after leaving the breeding beach, largely during the first 5–6 mo of life. Postweaned pups were ∼40% TBF and ∼13% TBP whereas yearlings were ∼12% TBF and ∼20% TBP. Pups that survived beyond 6 mo of age then regained mass as protein. Morphometric measurements are a useful field indication of body condition when isotope dilution is impractical.
SIMULATED VESSEL APPROACHES ELICIT DIFFERENTIAL RESPONSES FROM MANATEES
Authors: Miksis‐Olds Jennifer L. , Donaghay Percy L. , Miller James H. , Tyack Peter L. , Reynolds John E.
Published: May 2007

Abstract

One of the most pressing concerns associated with conservation of the endangered Florida manatee is mortality and serious injury due to collisions with watercraft. Watercraft collisions are the leading identified cause of manatee mortality, averaging 25% and reaching 31% of deaths each year. The successful establishment and management of protected areas depend upon the acquisition of data assessing how manatees use different habitats, and identification of environmental characteristics influencing manatee behavior and habitat selection. Acoustic playback experiments were conducted to assess the behavioral responses of manatees to watercraft approaches. Playback stimuli made from prerecorded watercraft approaches were constructed to simulate a vessel approach to approximately 10 m in sea grass habitats. Stimulus categories were (1) silent control, (2) approach with outboard at idle speed, (3) vessel approach at planning speed, and (4) fast personal watercraft approach. Analyses of swim speed, changes in behavioral state, and respiration rate indicate that the animals responded differentially to the playback categories. The most pronounced responses, relative to the controls, were elicited by personal watercraft. Quantitative documentation of response during playbacks provides data that may be used as the basis for future models to predict the impact of specific human activities on manatees and other marine mammal populations.
ONTOGENY OF MOVEMENTS AND FORAGING RANGES IN THE AUSTRALIAN SEA LION
Authors: Fowler Shannon L. , Costa Daniel P. , Arnould John P. Y.
Published: May 2007

Abstract

This study tracked the movements of Australian sea lion (Neophoca cinerea) pups, juveniles, and adult females to identify home ranges and determine if young sea lions accompanied their mothers at sea. Satellite tags were deployed on nine 15‐mo‐old pups, nine 23‐mo‐old juveniles, and twenty‐nine adult female Australian sea lions at Seal Bay Conservation Park, Kangaroo Island, South Australia. Females did not travel with their offspring at sea, suggesting young Australian sea lions learn foraging behaviors independently. Although home ranges increased with age, 23‐mo‐old juveniles had not developed adult movement capacity and their range was only 40.6% of the adult range. Juveniles traveled shorter distances (34.8 ± 5.5 km) at slower speeds (2.0 ± 0.3 km/h) than adults (67.9 ± 3.5 km and 3.9 ± 0.3 km/h). Young sea lions also stayed in shallower waters; sea floor depths of mean locations were 48 ± 7 m for juveniles and 74 ± 2 m for females. Restricted to shallow coastal waters, pups and juveniles are more likely to be disproportionately impacted by human activities. With limited available foraging habitat, young Australian sea lions appear particularly vulnerable to environmental alterations resulting from fisheries or climate change.
Analytical Procedures for the Measurement of Boron Isotope Compositions by Ion Microprobe in Meteorites and Mantle Rocks
Authors: Chaussidon Marc , Robert François , Mangin Denis , Hanon Pascal , Rose Estelle F.
Published: May 2007

An analytical procedure has been developed to measure in situ the 11 B/10 B ratio in terrestrial basaltic rocks and meteoritic chondrules having B concentration of less than 1 μg g−1 using a small radius ims3f ion microprobe. The central difficulties for these measurements are (i) the removal of the trace amount of B contamination introduced in the sample during polishing, (ii) the precise calibration of instrumental mass fractionation of B isotopes and (iii) the low count rates of 10 B and 11 B. Contamination experiments conducted with isotopically labelled B enriched in 10 B showed that ultrasonic cleaning in bi‐distilled water (< 1 ng g−1 B) and pre‐sputtering of the analysed area decrease B contamination to the level of 0.01 μg g−1. Analyses of isotope standards spanning a range of 11 B/10 B between 3.93 and 4.20 showed that instrumental mass fractionation was constant within? during one session of analyses. Repeated analyses of a standard glass showed a reproducibility of instrumental mass fractionation between February 1991 and October 1996 of 1.3. Taking into account all sources of error, boron isotope measurements are accurate to within 5 for meteoritic samples having B contents in the range 0.1 to 1 μg g−1. A slightly better accuracy of 1.5 can be achieved for basaltic glasses which can be sputtered with very intense primary beams.
Re‐Os Isotopic Measurements at the Femtomole Level in Natural Samples
Authors: Birck Jean Louis , Barman Matthieu Roy , Capmas Françoise
Published: May 2007

Here we describe a new chemical separation method for Os and an improved mass spectrometric procedure for Re and Os. This technique is based on the selective extraction of OsO4 from aqueous solution in liquid bromine. Among other advantages, this procedure avoids the cumbersome distillation procedure for Os and uses only commercial “off the shelf” PFA teflon labware. Blank levels for 0.5 g sample sizes are: 0.06 pg and 0.5 pg for Os and Re respectively. Samples containing as little as 1 pg g−1 Os can be analysed reliably with this method. Adaptation to other dissolution methods is also discussed.
ISO Guides for Reference Material Certification and Use: Application to Geochemical Reference Materials
Authors: Kane Jean S. , Potts Philip J.
Published: May 2007

The International Organisation for Standardisation (ISO) is a federation of national standards bodies that has developed a number of international agreements concerning the standardisation of various commercial and scientific activities which have been published as technical standards and guides. Several of the documents describe the way in which measurements should be made to ensure that all laboratories measuring the same quantity in the same material will produce results that are in harmony with one another. Others describe universally accepted practices for the production and use of reference materials. A summary of the ISO guides most relevant to the production of geochemical reference materials is presented; producers of these materials are encouraged to accept these guides in the interest of increasing the credibility and status of reference materials available to the geoanalytical community.
1Determination of As, Bi, Sb, Se and Te in Fifty Five Reference Materials by Hydride Generation ICP‐MS
Authors: Hall Gwendy E.M. , Pelchat Jean‐Claude
Published: May 2007

Analytical data are reported for As, Bi, Sb, Se and Te in fifty five geological reference materials (RM). The method used is based on hydride generation inductively coupled plasma‐mass spectrometry (HG‐ICP‐MS) following digestion of the samples in the mixed acid attack of HF‐HClO4‐HNO3‐HCl. Analytes were separated from potential interferences by coprecipitation with La(OH)3. This scheme results in method detections limits of: 1 ng g−1 for Bi and Te; 6 ng g−1 for Sb and Se; and 10 ng g−1 for As. The average relative standard deviation (RSD) for three 0.5 g subsamples of each RM analysed by this method are: 3.7% for As in the range 0.35‐187 μg g−1; 5.6% for Sb in the range 0.03‐22 μg g−1; 6.8% for Bi in the range 0.002‐48 μg g−1; 7.2% for Se in the range 6‐3610 ng g−1; and 9.0% for Te in the range 2‐445 ng g−1.
A Compilation of New and Published Major and Trace Element Data for NIST SRM 610 and NIST SRM 612 Glass Reference Materials
Authors: Pearce Nicholas J.G. , Perkins William T. , Westgate John A. , Gorton Michael P. , Jackson Simon E. , Neal Clive R. , Chenery Simon P.
Published: May 2007

Microanalytical trace element techniques (such as ion probe or laser ablation ICP‐MS) are hampered by a lack of well characterized, homogeneous standards. Two silicate glass reference materials produced by National Institute of Standards and Technology (NIST), NIST SRM 610 and NIST SRM 612, have been shown to be homogeneous and are spiked with up to sixty one trace elements at nominal concentrations of 500 μg g‐1 and 50 μg g‐1 respectively. These samples (supplied as 3 mm wafers) are equivalent to NIST SRM 611 and NIST SRM 613 respectively (which are supplied as 1 mm wafers) and are becoming more widely used as potential microanalytical reference materials. NIST however, only certifies up to eight elements in these glasses. Here we have compiled concentration data from approximately sixty published works for both glasses, and have produced new analyses from our laboratories. Compilations are presented for the matrix composition of these glasses and for fifty eight trace elements. The trace element data includes all available new and published data, and summaries present the overall average and standard deviation, the range, median, geometric mean and a preferred average (which excludes all data outside ± one standard deviation of the overall average). For the elements which have been certified, there is a good agreement between the compiled averages and the NIST data. This compilation is designed to provide useful new working values for these reference materials.
Ultraviolet Laser Sampling and High Resolution Inductively Coupled Plasma‐Mass Spectrometry of NIST and BCR‐2G Glass Reference Materials
Authors: Lahaye Yann , Lambert David , Walters Steve
Published: May 2007

A Merchantek LUV266TM petrographic ultraviolet (UV) laser microprobe has been used in conjunction with a Finnigan MAT ELEMENTTM high resolution ICP double‐focusing mass spectrometer (HR‐ICP‐MS) for solid microsampling and geochemical analysis. This new configuration for laser ablation has the advantage of coupling the high sensitivity and fast scanning technology applied in the ELEMENT with the ablation efficiency of a UV laser. Optimisation of the configuration on the synthetic NIST SRM 612 glass standard reference material using Q‐switched UV laser energy of 2 mJ and a 5 Hz repetition rate demonstrates: (1) a linear element response factor throughout the mass spectrum, suggesting limited fractionation during laser ablation; (2) a high sensitivity and very low background noise for most elements of interest; (3) limits of detection ranging from 3 ng g‐1 for Sc to 300 pg g‐1 for U; (4) a flat topped peak shape suitable for precise isotopic measurements; and (5) a flat bottomed crater geometry which permits progressive ablation for the analysis of thin sections. Average precision and accuracy estimates based on replicate analyses of synthetic NIST standard reference material and USGS BCR‐2G glasses are below 10% for most elements.
Analysis of Re, Au, Pd, Pt and Rh in NIST Glass Certified Reference Materials and Natural Basalt Glasses by Laser Ablation ICP‐MS
Authors: Sylvester Paul J. , Eggins Stephen M.
Published: May 2007

A new technique for the in situ analysis of Re, Au, Pd, Pt and Rh in natural basalt glass by laser ablation (LA)‐ICP‐MS is described. The method involves external calibration against NIST SRM 612/613 or 614/615 glass certified reference materials, internal standardisation using Ca, and ablation with a 200 μm wide beam spot and a pulsed laser repetition rate of 50 Hz. Under these conditions, sensitivities for Re, Au, Pd, Pt and Rh analyte ions are ˜ 5000 to 100,000 cps/μg g‐1. This is sufficient to make measurements precise to ˜ 10% at the 2‐10 μg g‐1 level, which is well within the range of concentrations expected in many basalts. For LA‐ICP‐MS calibration and a demonstration of the accuracy of the technique, concentrations of Re, Au, Pd, Pt and Rh in the NIST SRM 610/611 (˜ 1 to 50 μg g‐1), 612/613 (˜ 1 to 7 μg g‐1), 614/615 (˜ 0.2 to 2 μg g‐1) and 616/617 (˜ 0.004 to 2 μg g‐1) glasses were determined by solution‐nebulisation (SN)‐ICP‐MS. Using the 612/613 or 614/615 glasses as calibration standards, LA‐ICP‐MS measurements of these elements in the other NIST glasses fell within ˜ 15% of those determined by SN‐ICP‐MS. Replicate LA‐ICP‐MS analyses of the 612/613 and 614/615 glasses indicate that, apart from certain anomalous domains, the glasses are homogeneous for Re, Au, Pd, Pt and Rh to better than 3.5%. Two LA‐ICP‐MS analyses of natural, island‐arc basalt glasses exhibit large fractionations of Re, Au and Pd relative to Pt and Rh, compared to the relative abundances in the primitive mantle.
Characterisation of Memory Effects and Development of an Effective Wash Protocol for the Measurement of Petrogenetically Critical Trace Elements in Geological Samples by ICP‐MS
Authors: McGinnis Cathleen E. , Jain Jinesh C. , Neal Clive R.
Published: May 2007

High sensitivity and low detection limits would seem to make inductively coupled plasma‐mass spectrometry (ICP‐MS) an ideal analytical tool for determining low (sub‐μg g‐1) concentrations of the rare earth elements (REE), Y, Zr, Nb, Hf, Ta, Sn, W, Mo, Th, and U in most mafic materials (e.g. Hall and Plant 1992). However, the generally “sticky” nature exhibited by most of the high field strength elements (HFSEs: Zr, Nb, Hf, Ta, Th and U) as well as Sn, W and Mo can result in spurious results due to memory effects transmitted between unknowns and calibration samples. This, in turn, can seriously compromise the sensitivity, accuracy, and precision of ICP‐MS analyses for these elements in geological materials. Data resulting from analyses with poor accuracy and precision can lead to erroneous interpretation and misleading petrogenetic modelling. To resolve this problem, we propose an effective wash protocol for these critical trace elements.
Major and Trace Element Composition and Homogeneity of Microbeam Reference Material: Basalt Glass USGS BCR‐2G
Authors: Rocholl Alexander
Published: May 2007

Major and trace element abundances in two different fragments of reference material basalt glass BCR‐2G are reported. The data were obtained by ion and electron microprobe and represent both random point and profile analyses. Major and trace element abundances are constant within a few per mil and a few percent, respectively. This overall homogeneity is valid for scales of a few tens of micrometres to a few tens of centimetres. It is shown that the difference in the scatter of apparent element abundances is not due to chemical heterogeneity but reflects analytical uncertainty. Within error, the concentrations of both the major and lithophile trace elements in BCR‐2G appear to be identical to the bulk dry weight abundances in BCR‐1. Possible exceptions are the alkali metals.
The Preparation of Marine Geological Certified Reference Materials ‐ Polymetallic Nodule GSPN‐1 and Marine Sediment GSMS‐1 from the Central Pacific Ocean*
Authors: Chen Guofang , Wang Jiwu
Published: May 2007

This report describes the location, collection, preparation, homogeneity testing, analysis, data‐processing and assignment of certified values of a polymetallic nodule (GSPN‐1) and marine sediment (GSMS‐1). Materials used in the preparation of these reference materials were collected in 1986 and 1987 from the central Pacific Ocean, by the Chinese Ministry of Geology and Mineral Resources (MGMR). A total of fifty one recommended element concentrations and five proposed concentrations are reported for GSPN‐1. For GSMS‐1, a total of fifty recommended and seven proposed values are presented.
Precise Determination of Cadmium, Indium and Tellurium Using Multiple Collector ICP‐MS
Authors: Yi Wen , Halliday Alex N. , Lee Der‐Chuen , Rehkämper Mark
Published: May 2007

New sample preparation and ion‐exchange separation methods as well as instrumental measurement protocols were established for the determination of trace‐level Cd, In, and Te concentrations in geological materials by isotope‐dilution mass spectrometry. High precision isotope ratio measurements were performed with a multiple collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS). The mass biases incurred for In and Te were corrected by adding and monitoring Pd and Sb standard solutions, respectively. Mass fractionation of Cd was corrected by using the mass fractionation factor calculated from the measurement of a standard solution. The measurement precision was better than 1 % for Cd, In and Te. Detection limits were < 1 ng g‐1 for Cd, < 0.02 ng g‐1 for In and Te. Using these new analytical techniques, the concentrations of Cd, In and Te were determined in six international geological reference materials. Concentrations could be reproduced within 3% for Cd, 4% for In and 10% for Te. Sample heterogeneity and volatility problems might have been the reason for the relatively large differences between Te replicates. Our results displayed excellent reproducibility compared with those of other techniques and agree well with data from previously published recommended values.
Determination of Iodine in Thirty Two International Geochemical Reference Materials
Authors: Rae Joy E. , Malik Salim A.
Published: May 2007

Thirty two geochemical reference samples have been analysed for their iodine contents by a pyrohydrolysis extraction technique, followed by colourimetry. In spite of the existence of few reported values for iodine, limiting comparison with results from this study, the four available “reference” values show good agreement with the work reported here.
Platinum‐Group Element Geochemical Certified Reference Materials (GPt1‐7)
Authors: Yan Mingcai , Wang Chunshu , Gu Tiexin , Chi Qinghua , Zhang Zhong
Published: May 2007

Unlike the situation for other elements, few reference materials certified for the platinum‐group elements are currently available. Therefore, the GPt1‐7 series of PGE geochemical CRMs, prepared by the IGGE, represent an important addition and comprise a range of matrix types, including a soil, stream sediment, Mg‐rich ultramafic rock, Fe‐rich ultramafic rock, platinoid ore depleted in Cu, Ni and Fe, and a chromitite. The concentration of PGE in these samples ranges over 4‐5 orders of magnitude and the samples were shown to have good homogeneity as assessed by a variance test. Analytical methods based on different principles were used in sample certification, including several fire assay and wet chemical procedures used for decomposition and preconcentration. Certified values for the elements Pt, Pd, Os, Ru, Ir, Rh and Au were determined by AAS, catalytic colourimetry (COL), catalytic polarography (POL), atomic emission spectrometry (AES), ICP‐MS and NAA. Recently, the GPt1‐7 samples were approved as national primary CRMs by the State Bureau of Technical Supervision of China.
Determination of Scandium, Yttrium and Rare Earth Elements in Rocks by High Resolution Inductively Coupled Plasma‐Mass Spectrometry
Authors: Robinson Philip , Townsend Ashley T. , Yu Zongshou , Münker Carsten
Published: May 2007

The high sensitivity, minimal oxide formation and single internal standard capability of high resolution inductively coupled plasma‐mass spectrometry (HR‐ICP‐MS) is demonstrated in the direct determination of Sc, Y and REE in the international reference materials: basalts (BCR‐1, BHVO‐1, BIR‐1, DNC‐1), andesite (AGV‐1) andultramafics (UB‐N, PCC‐1 and DTS‐1). Time consuming ion exchange separation or preconcentration were found to be unnecessary. Smooth chondrite normalized plots of the REE in PCC‐1 and DTS‐1 were obtained in the range 0.8‐50 ng g‐1 (0.01‐0.1x chondrite). Method precision was found to be digestion dependent with an average external repeatability of 2‐4% for the basalts, AGV‐1 and UB‐N, and 10% for PCC‐1 and DTS‐1. The mass peak due to 45Sc was completely resolved from 29Si16O and 28Si16O1H spectral interferences using medium resolution, which casts doubt on the accuracy of Sc determinations using quadrupole ICP‐MS. Literature values for Y in rock reference materials were found to be approximately 9% high after HR‐ICP‐MS and XRF analysis.
Determination of Incompatible Trace Elements in Mantle Clinopyroxenes by LA‐ICP‐MS: A Comparison of Analytical Performance with Established Techniques
Authors: Mason Paul R.D. , Jarvis Kym E. , Downes Hilary , Vannucci Riccardo
Published: May 2007

Incompatible trace element abundances have been determined in mantle‐derived clinopyroxenes by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) in a comparative study with established microanalytical and bulk techniques. Individual clinopyroxene grains were sampled for the laser ablation study from sieved mineral separate fractions, from which similar mineral grains had been previously extracted for microprobe (SIMS) and bulk (INAA and ID‐TIMS) analysis. Mineral grains were ablated with variable degrees of surface spatial resolution (50‐200 μm) in order to maximise ICP‐MS analyte count rates and to improve detection limits. A comparison of results from the different techniques reveals that for the most homogeneous samples LA‐ICP‐MS can achieve excellent levels of agreement with other techniques (10%) and good precision for most of the studied elements (1‐5% RSD). Variations in calculated concentrations by LA‐ICP‐MS confirm inter‐ and intra‐mineral heterogeneity determined by SIMS, reflecting changes in sample composition and texture. The long‐term reproducibility of the technique is shown by the consistency of results for one sample analysed on thirteen occasions over a period of nine months.
1998 Compilation of Analytical Data for Five GSJ Geochemical Reference Samples: The “Instrumental Analysis Series”
Authors: Imai Noboru , Terashima Shigeru , Itoh Shiro , Ando Atsushi
Published: May 2007

Analytical data for five GSJ (Geological Survey of Japan) reference samples, the “Instrumental analysis series” received by October 1998, are compiled. The data reported in publications and personal communications were evaluated statistically, taking into account the analytical method and sample preparation. Based on the selected available data, recommended and preferred values for fourteen major and fifty one minor and trace elements are proposed.
Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP‐MS after HF/HClO4 High Pressure Digestion
Authors: Yu Zongshou , Robinson Philip , Townsend Ashley T. , Mnker Carsten , Crawford Anthony J.
Published: May 2007

Six low abundance rock reference materials (basalt BIR‐1, dunite DTS‐1, dolerite DNC‐1, peridotite PCC‐1, serpentine UB‐N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 levels (in rock) by magnetic sector inductively coupled plasma‐mass spectrometry after HF/HClO4 high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml−1 in solution (equivalent to 0.08 to 16.2 ng g−1 in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS‐1 and PCC‐1 (1.3 and 0.5 ng g−1) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR‐1, DTS‐1 and PCC‐1 (2, 0.4 and 0.8 ng g−1). Compared with quadrupole ICP‐MS studies, the proposed magnetic sector ICP‐MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 levels can be achieved without pre‐concentration, ion exchange separation or other specialised techniques.
Determination of Selenium in Fifty Two Geochemical Reference Materials by Hydride Generation Atomic Absorption Spectrometry
Authors: Terashima Shigeru , Imai Noboru
Published: May 2007

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.
GeoPT4. An International Proficiency Test for Analytical Geochemistry Laboratories ‐ Report on Round 4 (March 1999)
Authors: Thompson Michael , Potts Philip J. , Kane Jean S. , Webb Peter C. , Watson John S.
Published: May 2007

Results are presented from the seventy five laboratories participating in GeoPT4, round four of the international proficiency testing programme for analytical geochemistry laboratories. Laboratories were required to analyse the sample OU‐2 (Belford dolerite) using routine methods of analysis. The sample was distributed during September 1998 with a deadline for the submission of results of 15th January 1999. In this report, contributed data are analysed and z‐scores calculated. Z‐score values provide participating laboratories with information concerning the quality of their results and indicate data that may be subject to unsuspected analytical bias. Laboratories are invited to examine these data and take the appropriate action.
Gold and Platinum‐Group Element Analysis of Geochemical and Platinum Reference Materials Using Fluoroxidation Decomposition
Authors: Mitkin Valentin N.
Published: May 2007

A novel method is described for the rapid dissolution of various geological, geochemical and related reference samples for the determination of Au and the platinum‐group elements. The decomposition procedure is based on reaction with the fluoroxidants, liquid bromine trifluoride or molten potassium tetrafluorobromate. Results by this novel procedure are compared with data obtained by traditional methods of sample decomposition, including fire assay, autoclave techniques and an aqua regia leach. The oxidative fluorination procedure with the subsequent conversion of fluorocomplexes into the chloride form was found to be an effective and rapid method for the quantification of all the precious metals in a range of sample types.
Techniques for the Determination of Cyanide in a Process Environment: A Review
Authors: Barnes Deon E. , Wright Peter J. , Graham Sandra M. , Jones‐Watson Elaine A.
Published: May 2007

The determination of cyanide in various forms is important for industrial processes as well as for environmental investigations and monitoring associated with these processes. The accurate determination of cyanide is difficult for various reasons. Depending on the pH of the solution, cyanide is present both in molecular form (HCN) and ionic form (CN). Furthermore, cyanide is a good complexing reagent and reacts with almost all cations resulting in complexes with widely varying properties, such as stabilities, solubilities and rates of reaction. Cyanide also breaks down in sunlight and air, so that sampling and sample treatment become very important aspects to consider in the methodologies. During the last fifty years the determination of cyanide has been approached from various angles and a myriad of methods has been developed for its determination. This study represents a survey of methods commonly used in industrial laboratories for the analysis of cyanide‐containing solutions. An overview of the nomenclature often used for the various forms of cyanides is discussed and the values resulting from a particular analysis will be interpreted. Most common interferences in samples originating from gold processing plants will be discussed.
Y/Ho Ratios in the Late Cenozoic Basalts from the Eastern Tuva, Russia: An ICP‐MS Study with Enhanced Data Quality
Authors: Ivanov Alexei V. , Rasskazov Sergei V. , Chebykin Evgeny P. , Markova Margarita E. , Saranina Elena V.
Published: May 2007

A set of forty seven Late Cenozoic basaltic rocks from the Eastern Tuva (southern Siberia, Russia) have been studied by ICP‐MS using In as an internal standard. Yttrium and Ho concentrations, determined along with other trace elements, varied systematically from one analytical run to another and covered the entire charge‐and‐radius‐controlled field within the range 24 < Y/Ho < 34, so obscuring any geochemical interpretation. A correction procedure was therefore developed in which the Y/Ho ratios were recalculated using concentrations of these elements determined in international and in‐house reference materials (BHVO‐1, AGV‐1, BIR‐1 and U‐94‐5). Statistical analysis of the recalculated data set revealed two groups of samples not related by their genesis but rather by their respective analytical runs. Fourteen samples originally analysed in five different runs were then re‐measured by the same instrument in peak‐hopping mode using only specific mass peaks (m/z = 89, 115 and 165). All of these samples yielded Y/Ho ratios in a narrow range between 29 and 31, thus illustrating how analytical problems in the determination of Y and Ho by routine ICP‐MS procedures can be overcome. Finally, a mean value of Y/Ho = 30.3 ± 1.1 (1s) was derived for the basaltic rocks of the Eastern Tuva. This is close to the value of 28.8 accepted for chondrites and for ocean island basalts. Despite the uniform Y/Ho ratio, the element concentrations in basaltic rocks from the Eastern Tuva show systematic enrichment in heavy rare earth elements and yttrium from the Miocene to the Quaternary.
Arsenic Speciation in a Contaminated Gold Processing Tailings Dam
Authors: Shuvaeva Olga V. , Bortnikova Svetlana B. , Korda Tamara M. , Lazareva Elena V.
Published: May 2007

Gold recovery in ores containing arsenopyrite releases significant amounts of arsenic into the environment due to mineral processing and oxidation during storage. The extent of arsenic weathering in a tailings dam has been investigated. Speciation of As in surface and pore waters and pond sediments showed that for gold tailings in the dam, As enrichment took place in the pore water relative to the surface water. In pond sediments As was predominantly present as residual arsenopyrite and partly as a substance co‐precipitated with iron hydroxide. The arsenic release from the sediment results from a reductive dissolution of the arsenopyrite and Fe oxides. In the surface water, arsenate and arsenite are the main arsenic species (arsenate is dominant), but in the pore waters methylation processes play a significant role. Arsenic transport is accompanied by the transformation of As into the less toxic compounds (methylated species) co‐existing with the most toxic species (arsenite).
CO2‐Laser Extraction‐Static Mass Spectrometry Analysis of Ultra‐Low Concentrations of Nitrogen in Silicates
Authors: Humbert Franck , Libourel Guy , France‐Lanord Christian , Zimmermann Laurent , Marty Bernard
Published: May 2007

A new installation for the analysis of picomole quantities of nitrogen has been designed and constructed. It permits the simultaneous analysis of N and rare gases extracted from silicates by heating. The extraction procedure involves the use of a CO2 laser as a heater, and the analysis is made by static mass spectrometry using a high sensitivity, high resolution mass spectrometer. Procedural blanks of 2 picomoles N2 (60 picogram N) allow us to analyse routinely N in mg‐sized samples such as mantle‐derived and meteoritic minerals, and Lunar soil grains.
Routine Analyses of Trace Elements in Geological Samples using Flow Injection and Low Pressure On‐Line Liquid Chromatography Coupled to ICP‐MS: A Study of Geochemical Reference Materials BR, DR‐N, UB‐N, AN‐G and GH
Authors: Carignan Jean , Hild Pascal , Mevelle Guy , Morel Jacques , Yeghicheyan Delphine
Published: May 2007

We describe analytical procedures for trace element determinations developed at the CNRS Service d'Analyse des Roches et des Minéraux (SARM) and report results obtained for five geochemical reference materials: basalt BR, diorite DR‐N, serpentinite UB‐N, anorthosite AN‐G and granite GH. Results for rare earth elements, U and Th are also reported for other reference materials including dunite DTS‐1, peridotite PCC‐1 and basalt BIR‐1. All rocks were decomposed using alkali fusion. Analyses were done by flow injection ICP‐MS and by on‐line low pressure liquid chromatography (LC)‐ICP‐MS for samples containing very low REE, U and Th concentrations. This latter method yielded limits of determination much lower than data by direct introduction and eliminated possible isobaric interference on these elements. Although results agree with most of the working values, when available, results for some elements differed slightly from the recommended concentrations. In these cases, we propose new values for Co, Y and Zn in basalt BR, Zr in diorite DR‐N, Sr and U in granite GH, and Ga and Y in anorthosite AN‐G. Furthermore, although the Sb concentration measured in AN‐G was very close to our limit of determination, our value (0.3 ± 0.1 μg g−1) is much lower than the reported working value of 1.4 ± 0.2 μg g−1. These new values would need to be confirmed by a new inter‐laboratory programme to further characterise these reference materials.

Results obtained for REE, Th and U concentrations using the on‐line low pressure LC‐ICP‐MS yielded good limits of determination (ng g−1to sub‐ng g−1for rocks and ng l−1to sub‐ng l−1for natural waters) and accurate results. The efficiency of the matrix separation allowed accurate measurements of Eu without the need to correct the BaO isobaric interference for samples having Ba/Eu ratios as high as 27700. For REE concentrations in PCC‐1 and DTS‐1, differences with values reported in the literature are interpreted as resulting from possible heterogeneity of the reference materials. Thorium and U values are proposed for these two samples, as well as for AN‐G and UB‐N.
An Evaluation of Methods for the Chemical Decomposition of Geological Materials for Trace Element Determination using ICP‐MS
Authors: Yu Zongshou , Robinson Philip , McGoldrick Peter
Published: May 2007

Complete dissolution is essential to obtain accurate analytical results using ICP‐MS. In this study, decomposition techniques (i.e. acid digestions using Savillex Teflon vials, a high pressure digestion system and microwave oven, a combined lithium tetraborate fusion ‐ HF/HNO3 acid decomposition and sodium peroxide sinter) for the total dissolution of different types of geological reference materials have been investigated. Savillex Teflon vial HF/HNO3 digestion is effective for basaltic samples. The high pressure HF/HClO4 digestion (PicoTrace TC‐805 digestion system, Bovenden, Germany) allows dissolution of basalts and ironstones. Granites and magnetite‐rich samples can be dissolved using a high pressure HF/H2SO4 method. Geological samples cannot be effectively attacked by microwave acid digestion. A combined lithium tetraborate fusion ‐ HF/HNO3 acid digestion method allows complete dissolution of many different types of geological materials; however, this method precludes the determination of volatile elements due to the high fusion temperature (1000 °C). A sodium peroxide sinter method at 480 °C has the potential for the rapid determination of Y, Sc and REE in different types of geological materials. However, the lack of ultra‐pure reagents precludes the use of lithium tetraborate fusion and sodium peroxide sinter methods for the measurement of geological samples with low trace element abundances.
Problems Associated with the Determination of Rare Earth Elements of a “Gem” Quality Zircon by Inductively Coupled Plasma‐Mass Spectrometry
Authors: Jain Jinesh C. , Neal Clive R. , Hanchar John M.
Published: May 2007

A gem quality zircon crystal from the Mud Tank Carbonatite, Australia, was carefully crushed, sieved, acid leached and hand‐picked to produce three different zircon fractions: 1) clear and apparently free of inclusions; 2) with inclusions; 3) with inclusions and adhering alteration/matrix material. Each separate and the bulk sample was dissolved by 1) lithium metaborate fusion and 2) Parr bomb digestion utilizing 29 mol l−1 hydrofluoric (HF) and 16 mol l−1 nitric (HNO3) acids. In situ analyses were performed using laser ablation ICP‐MS and demonstrate that, on the basis of REE, two types of inclusions are present: 1) those with a positive Ce anomaly and 2) those with no Ce anomaly. The former type of inclusion appears to be smaller than the latter. Analysis of the digested samples for the rare earth elements (REE) was then performed using a quadrupole ICP‐MS. Comparison of the chondrite‐normalized REE patterns for the different fractions gave apparent positive anomalies at Sm and Eu in the acid digestions but not in the fused samples. Zirconium has five isotopes (90Zr, 91Zr, 92Zr, 94Zr and 96Zr) and there is a strong tendency for Zr to combine with fluorine (19 F). Based on calculations and experiments, the increased levels of Sm and Eu in the acid digested samples were due to interferences of 90Zr19 F3 on 147 Sm and of 94Zr19 F3 on 151 Eu. Decreasing the ratio of HF:HNO3 did not remove these interferences, nor did post‐treatment with perchloric acid. A mathematical method was developed to correct for these polyatomic interferences.
The Calcium Isotope Composition of Modern Seawater Determined by Thermal Ionisation Mass Spectrometry
Authors: Schmitt Anne‐Désirée , Bracke Guido , Stille Peter , Kiefel Bernard
Published: May 2007

The Ca isotopic composition of modern seawater has been determined using a 43Ca‐48Ca double spike, which was calibrated using a 42Ca/44Ca seawater ratio of 0.30587 ± 0.00026. This ratio was determined from a total evaporation experiment in which the ion beam was measured from the beginning to the end of the emission. With integration of the peak intensities, the fractionation effects can be minimised, since total evaporation of the reservoir cancels out the effect of vapour enrichment in the light isotopes. This experiment avoids the gravimetric uncertainty inherent in the double spike calibration. This calibration allows the precise redetermination of the seawater isotopic composition of Ca. A mean 40Ca/44Ca ratio for two Atlantic water samples of 45.143 (2smean= 0.003) was found. The good reproducibility of the Ca isotope ratios in present seawater and the very strong isotopic homogeneity of Ca in the oceans illustrate the advantage of using seawater as the common standard, with the advantage of decreasing interlaboratory bias.
Routine Control of Accuracy in Silicate Rock Analysis by X‐Ray Fluorescence Spectrometry
Authors: Vendemiatto Maria Aparecida , Enzweiler Jacinta
Published: May 2007

In this study, we used the modified Horwitz expression (Hc= 0.01c0.8495, which gives the precision as a function of concentration) to evaluate and control the accuracy of results of silicate rock analysis obtained by X‐ray fluorescence spectrometry. This expression is currently used by the organisers of the GeoPT international proficiency tests, to assign the precision limits of each analyte and subsequently to evaluate the data provided by laboratories whose main application is geochemistry. Results for major and trace elements, determined in glass disk and pressed pellets, respectively, were evaluated. Nine international silicate rock reference materials were analysed and results were compared to the recommended values plus and minus the limits given by the above expression. Those limits are easily attained for most major elements, but not for trace elements. Sample preparation and sub‐sampling contributions to precision were evaluated by analysis of an in‐house reference sample. In our results, precision does not follow the Horwitz expression relationship with concentration. It is known that the final accuracy in XRF analysis depends strongly on instrumental settings and on the uncertainties associated with the certified or recommended values of the reference materials used to calibrate the spectrometer, but our results indicate that the precision expression can be useful, especially to inspect and correct calibration curves and to check routine instrumental accuracy.
Spectral Interference in the Determination of Molybdenum in Geological Samples by ICP‐AES: A Reassessment
Authors: Agnihotri Rajesh , Sarin Manmohan
Published: May 2007

Molybdenum concentrations in USGS reference materials and marine sediments have been measured using ICP‐AES following dissolution of samples in HF‐HNO3‐HCl with final aliquots made in 1 mol l−1 HCl. The concentrations determined at one of the recommended wavelengths, 281.615 nm, are found to be severely affected by a spectral interference from Al, leading to inaccurate analytical results. At an alternative wavelength, 202.030 nm, the Mo emission signal is attenuated in the window size 0.094 nm due to the presence of an Fe line (202.074 nm), thus affecting the analytical sensitivity of measurements. The attenuation of the emission signal at 202.030 nm could severely limit the determination of Mo in geological samples.
Neutron Activation Analysis Applied to the Determination of Heavy Metals and Other Trace Elements in Sediments from Sepetiba Bay (RJ), Brazil
Authors: Pellegatti Fàbio , Figueiredo Ana M.G. , Wasserman Julio C.
Published: May 2007

In this work, instrumental neutron activation analysis (INAA) was applied to the determination of the elements As, Ba, Br, Ce, Co, Cr, Cs, Eu, Fe, Hf, La, Lu, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb, Zn in twenty eight bottom sediment samples from Sepetiba Bay, Rio de Janeiro, Brazil. With the concentration data obtained, contour maps were prepared, by using Kriging method, to show the spatial distribution of the studied elements in the Bay. The elements Co, Cr, Cs, Fe, Sc, Ta and Zn showed similar behaviour in the sediments, with higher concentrations along the northern coast of the bay, where the fluvial water inputs are concentrated. The distribution of U, rare earth elements and Ba in the Bay indicates that these elements are not deposited as contaminants.
Determination of Selenium Concentration in Sixty Five Reference Materials for Geochemical Analysis by GFAAS after Separation with Thiol Cotton
Authors: Marin Luc , Lhomme Jitka , Carignan Jean
Published: May 2007

Selenium has been determined in sixty five geological reference materials of different origins by graphite furnace atomic absorption spectrometry. Samples were decomposed with a mixture of nitric and hydrofluoric acids. Selenium was reduced to SeIV with hydrochloric acid, and then fixed and separated from the matrix on thiol cotton. After digestion of the thiol cotton in hot nitric acid, the Se concentration was measured using palladium and magnesium nitrates as a matrix modifier. The limit of determination was 0.02 μg g−1, the precision of the results (relative standard deviation of 3 to 8 replicates) varied from 2.6 to 17.7% with an average of 7.9% in the range 0.02‐42.7 μg g−1 and was similar to the value obtained for synthetic samples. Our results are in good agreement with available literature values.
Electron Probe Microanalysis of Environmental Samples: Preparation of Reference Materials, Correction for Particle Size Effects and Representative Results on Sediments Recovered from Snow, Power Station Fly Ash and Bone Samples
Authors: Pavlova Ludmila A. , Paradina Ludmila Ph. , Belozerova Olga Yu.
Published: May 2007

In this paper we report the results of electron probe X‐ray microanalysis (EPMA) that was used to study environmental materials. The mode of preparation and certification of reference samples based on a basaltic glass matrix for environmental applications of EPMA is described. These samples were prepared containing scandium, strontium and barium (from 0.03 up to 7% m/m) and an evaluation was made of homogeneity, their stability to local heating, followed by analysis by independent methods for certification of composition. Matrix correction procedures for the EPMA technique have been developed for particles having a size commensurable with the volume of X‐ray generation. An analytical equation for the size factor is proposed and two techniques for selecting optimum conditions for the analysis of environmental samples by EPMA are reported. These procedures provided satisfactory results when utilized in analysing sediments recovered from snow, coal fly ash and the bones of animals and fish, results from which can be used as indicators for evaluating the pollution level of the lower atmosphere, surface and ground water, as well as revealing pollution mechanisms.
Determination of Platinum‐Group Elements and Forty Two Other Elements in Two Candidate Danish Cretaceous‐Tertiary Boundary Clay Reference Materials by INAA, ENAA and RNAA
Authors: Mao Xueying , Hou Xiaolin , Li Chungsheng , Ouyang Hong , Chai Zhifang
Published: May 2007

Ruthenium, rhodium, palladium, osmium, iridium and platinum (PGEs) and forty two other elements in two candidate geological Cretaceous‐Tertiary boundary clay reference materials taken from the Fish Clay, Stevns Klint, Denmark, were determined by a combination of neutron activation analysis (NAA) consisting of instrumental, epithermal and radiochemical NAA with or without nickel sulfide fire assay preconcentration. The accuracy of the experimental values was assessed by the comparative analysis of the certified reference materials.