Evaluation of a Quality Control Monitor Material for the Routine Electron Probe Microanalysis of Kimberlite Exploration Garnets

Election probe microanalysis of indicator minerals is extensively used in the exploration for kimberlite deposits, the evaluation of specific kimberlite occurrences for their diamond bearing potential and to classify grains into different chemical and lithological mantle associations. Kimberlite exploration programmes can involve several tens of thousands of indicator mineral analyses. Procedures for monitoring data quality and consistency of analyses across large data sets are commonly absent. Suitable monitor minerals should be used to verify the data quality of kimberlite exploration and evaluation data sets. This material should have a suitable composition, be homogenous, be available in sufficient quantities and have a similar appearance to the unknown samples. Garnet P1, a megacryst garnet from the Premier kimberlite, was found to have a suitable composition as a monitor for kimberlite garnet analyses. Data were collected on the monitor material at regular intervals during routine analyses, over an extended period, both as a fixed grain mounted on the sample holder and as separate grains set within batches of routine samples. The data were evaluated to assess the quality and consistency in the analyses of large data sets over time. The monitor material was also analysed at independent laboratories using their routine analytical set-up and calibration procedures for comparative purposes. Values are given for the mean ± 2s range, which can serve as guide values for acceptable analyses for all elements.     

Accurate and Precise Elemental Abundance of Zinc in Reference Materials by an Isotope Dilution Mass Spectrometry TIMS Technique

A thermal ionisation mass spectrometric technique enabled the abundance of Zn in geological and biological reference materials and water samples to be measured by double spiking isotope dilution mass spectrometry enriched in the ⁶⁷Zn and ⁷⁰Zn isotopes. In the past, thermal ionisation mass spectrometry proved to be difficult for low-level zinc isotopic measurements. The size of Zn samples used for isotopic determination, in particular the biological RMs, represents an important breakthrough. These results represent the most accurate and precise concentrations measured for Zn in these samples. The maximum fractional uncertainty was that for TILL-3 (2%), while the minimum fractional uncertainty was 0.7% for both BCR-1 and W-2. The inhomogeneity of Zn in HISS-1 was revealed while other reference materials appeared homogeneous at the 95% confidence uncertainty. The certified concentration of Zn in HISS-1 and IMEP-19 by their producers are 28% and 3.8% higher than the values measured in this work. These are the first Zn concentration measurements in these materials by the isotope dilution-TIMS technique, except for BCR-1, NIES N^o 9 and IMEP-19. Reducing the blank enabled accurate measurement in water at the ng g^-1 level demonstrating the applicability of the technique for low-level Zn samples.     

Calcium,Na, K and Mg Concentrations in Seawater by Inductively Coupled Plasma‐Atomic Emission Spectrometry: Applications to IAPSO Seawater Reference Material,Hydrothermal Fluids and Synthetic Seawater Solutions

We report a measurement procedure to determine simultaneously the major cation concentrations (Na, Ca, K and Mg) of seawater‐derived solutions by inductively coupled plasma‐atomic emission spectrometry. The best results were obtained when the IAPSO (‘standard’) seawater reference material was diluted by thirty times with Milli‐Q^® water. We obtained an average reference value r_K (the ratio of the mass fraction of potassium to that of chlorine, i.e., (g kg^?1)/(g kg^?1)) for IAPSO seawater of 0.0205 ± 0.0006 (2.9% RSD), not significantly different from 0.0206 ± 0.0005 (2.4% RSD) for seawater composition reported in the literature. The measured Na, Ca and Mg concentrations correspond to r_Na, r_Ca and r_Mg values of 0.5406 ± 0.0026 (0.5% RSD), 0.02192 ± 0.00048 (2.2% RSD) and 0.06830 ± 0.00047 (0.7% RSD), respectively, in line with previous values measured by wet‐chemistry and atomic absorption spectrophotometry or wet‐chemical titration. Our measurement procedure was used successfully on synthetic seawater solutions and high‐temperature hydrothermal fluids.     

Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.     

Precise and Accurate In Situ Determination of Lead Isotope Ratios in NIST,USGS, MPI‐DING and CGSG Glass Reference Materials using Femtosecond Laser Ablation MC‐ICP‐MS

Lead isotope ratio data were obtained with good precision and accuracy using a 266 nm femtosecond laser ablation (fLA) system connected to a multi‐collector ICP‐MS (MC‐ICP‐MS) and through careful control of analytical procedures. The mass fractionation coefficient induced by 266 nm femtosecond laser ablation was approximately 28% lower than that by 193 nm excimer laser ablation (eLA) with helium carrier gas. The exponential law correction method for Tl normalisation with optimum adjusted Tl ratio was utilised to obtain Pb isotopic data with good precision and accuracy. The Pb isotopic ratios of the glass reference materials NIST SRM 610, 612, 614; USGS BHVO‐2G, BCR‐2G, GSD‐1G, BIR‐1G; and MPI‐DING GOR132‐G, KL2‐G, T1‐G, StHs60/80‐G, ATHO‐G and ML3B‐G were determined using fLA‐MC‐ICP‐MS. The measured Pb isotopic ratios were in good agreement with the reference or published values within 2s measurement uncertainties. We also present the first high‐precision Pb isotopic data for GSE‐1G, GSC‐1G, GSA‐1G and CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 glass reference materials obtained using the femtosecond laser ablation MC‐ICP‐MS analysis technique.     

Statistical and geostatistical investigations into the effects of the Gabcikovo hydropower plant on the groundwater resources of northwest Hungary / Analyses statistiques et géostatistiques des effets de la centrale hydroélectrique de Gabcikovo sur les ressources en eaux souterraines du Nord-Ouest de la Hongrie

Abstract

Abstract The construction of the Gabcikovo hydropower plant and the diversion of the Danube River over 25 km into an artificial channel in 1992 influenced the groundwater regime of the region considerably. Statistical and geostatistical methods are used to quantify changes of different groundwater characteristics on the Hungarian side of the river based on observations in the time period 1960–2000. External drift kriging was used to interpolate groundwater levels and the other related variables. While mean groundwater levels did not change appreciably, there are significant changes in the variability. Standard deviations of the groundwater levels and the amplitude of the annual cycle decreased near the old river bed of the Danube. The water-level fluctuations of the Danube have a decreased influence on the groundwater dynamics. Interrelationships between water levels in wells have also changed.     

Educating the compassionate water engineer–a remedy to avoid future water management failures? / Former des spécialistes de l’eau citoyens–une solution pour éviter de futurs échecs en gestion de l’eau?

Abstract

Abstract The number of local and regional-scale water management failures appears steadily to increase despite an apparently higher level of engineering solutions at hand. The objective of this paper is to examine the challenges the existing education system needs to meet in order to produce water engineers capable of responding to the complexity of contemporary and future water problems in relation to societal needs. The next generation of water engineers may stay in their professional functions until 2040 or 2050. It is likely that in this period more critical water management and environmental problems will be experienced than have been encountered so far. The question then arises whether the present water engineers have the proper background education to understand environmental, hydrological, ecological and socio-economic problems to resolve related water management problems. Future water engineers must, to a greater extent, include socio-economic consequences in planned and/or designed water management systems and convey greater transparency regarding risks and societal effects.     

Fuzzy logic model approaches to daily pan evaporation estimation in western Turkey / Estimation de l’évaporation journalière du bac dans l’Ouest de la Turquie par des modèles à base de logique floue

Abstract

Abstract Evaporation is one of the fundamental elements in the hydrological cycle, which affects the yield of river basins, the capacity of reservoirs, the consumptive use of water by crops and the yield of underground supplies. In general, there are two approaches in the evaporation estimation, namely, direct and indirect. The indirect methods such as the Penman and Priestley-Taylor methods are based on meteorological variables, whereas the direct methods include the class A pan evaporation measurement as well as others such as class GGI-3000 pan and class U pan. The major difficulty in using a class A pan for the direct measurements arises because of the subsequent application of coefficients based on the measurements from a small tank to large bodies of open water. Such difficulties can be accommodated by fuzzy logic reasoning and models as alternative approaches to classical evaporation estimation formulations were applied to Lake Egirdir in the western part of Turkey. This study has three objectives: to develop fuzzy models for daily pan evaporation estimation from measured meteorological data, to compare the fuzzy models with the widely-used Penman method, and finally to evaluate the potential of fuzzy models in such applications. Among the measured meteorological variables used to implement the models of daily pan evaporation prediction are the daily observations of air and water temperatures, sunshine hours, solar radiation, air pressure, relative humidity and wind speed. Comparison of the classical and fuzzy logic models shows a better agreement between the fuzzy model estimations and measurements of daily pan evaporation than the Penman method.     

Analysis of flood propagation changes in the Kienstock—Bratislava reach of the Danube River/Analyse des changements de propagation des crues dans le tronçon Kienstock—Bratislava du Fleuve Danube

Abstract

In the first part of this study, a flood wave transformation analysis for the largest historical floods in the Danube River reach Kienstock–Bratislava was carried out. For the simulation of the historical (1899 and 1954) flood propagation, the nonlinear river model NLN-Danube (calibrated on the recent river reach conditions) was used. It was shown that the simulated peak discharges were not changed significantly when compared to their historical counterparts. However, the simulated hydrographs exhibit a significant acceleration of the flood wave movement at discharges of between 5000 and 9000 m³ s^-1. In the second part, the travel time-water level relationships between Kienstock and Bratislava were analysed on a dataset of the flood peak water levels for the period 1991–2002. An empirical regression routing scheme for the Danube short-term water level forecast at Bratislava station was derived. This is based on the measured water level at Kienstock gauging station.