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1.
The concentrations of numerous constituents must be evaluated in rock samples if they are to be used as reference materials. Because of varying degrees of specialized skills in earth-science laboratories, the collaboration of many institutions is required in order to establish reliable values. Analytical data reported in such operations are highly variable. The number of constituents reported per sample varies from one laboratory to another. The number of values reported varies from one constituent to another. The reported values for each constituent are generally incoherent, often displaying skewed distributions. The problem is then how to deduce the most probably “true’ concentration for each constituent. Various computation schemes, based on medians, means and related measures, are discussed. A new scheme, involving a combination of modes, is proposed.  相似文献   

2.
The International Association of Geoanalysts (IAG) has certified a slate sample, OU-6, for twelve major and minor constituents, as well as thirty-five trace elements through an interlaboratory programme conducted in close compliance with the International Organization for Standardization (ISO) Guide 35 (1989). Laboratories were qualified for participation in the certification programme, based on their performance in the prior analysis of OU-6 as a proficiency test material. Thirty laboratories provided data for the certification, though not for each constituent that was certified. Certification criteria included a means of establishing traceability for the certification data, generally through concurrent analysis of the existing Geological Survey of Japan reference material JSl-1, agreement of results between laboratories and methods, and a minimum of data rejection (4% rejection rate for OU-6 data and 6% for JSl-1 data), preferably for well-understood technical reasons only. Information values are provided for an additional eight constituents where certification criteria were not met. Uncertainties developed in accordance with the "Guide on Uncertainty in Measurement" (Eurachem 2000) and representing the 95% confidence interval of the certified and information values are reported for all fifty five constituents. The material is currently available in 40 g units for distribution by the IAG. Supply is anticipated to last about ten years.  相似文献   

3.

Background

Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach??the pilot ion method??has not been documented in detail.

Results

A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15???M Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(?II) varied by almost 20% from one Hg/Au electrode to another, and S(?II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(?II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(?II).

Conclusions

Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O2, S(?II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle??the independence of slope ratios??is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction.  相似文献   

4.
The results presented in this paper on uranium in bottled and tap water were determined within the scope of the project “European Groundwater Geochemistry: Bottled Water” of the Geochemistry Expert Group of EuroGeoSurveys. The analyses of bottled water provide an inexpensive approach to obtain information about European groundwater geochemistry. For this study, the uranium concentrations in 1785 European mineral water samples were analyzed by ICP–QMS in the BGR laboratories. The dataset is used to obtain a first impression about natural concentration levels and variation of uranium in groundwater (and bottled water) at the German and European scale.  相似文献   

5.
Five Belgian sedimentary rock reference materials have been prepared and distributed by the Geology, Petrology and Geochemistry Laboratory (Liège University, Belgium). Thirty-six laboratories participated in the international co-operative study. The individual data received from the participating laboratories are listed. Tables of compiled results are presented for major, minor and trace elements. These updated values are summarized into means, associated standard deviations, medians, and concentration ranges. "Recommended" (or proposed) values are presented.  相似文献   

6.
Total sulfur is an analyte for which there are few determinations published, despite the fact that it is a very important element (e.g., a major element in most ores, an important gas constituent in global warming, an active participant in acid drainage). Most geological reference materials have very poor quality sulfur results, that is with relative standard deviations (RSD) in the range of 30–50%, even for concentrations over 100 μg g−1 S, which compromises their use as calibrators. In order to provide modern results with low RSD, sulfur was determined in twenty-nine geological reference materials with a state-of-the-art elemental S/C analyser using metal chips (certified reference materials with a traceability link) and analytical grade sulfur for high concentration samples. Analytical parameters (sample mass, crucible degassing, calibration strategy, etc.) were optimised by testing. Our results agreed with reference material values provided by issuing bodies. Results for CCRMP SY-2 (129 ± 13 μg g−1 S), which has been proposed as a sulfur reference material, were in agreement with the proposed modern value of 122 ± 3.7 μg g−1 S.  相似文献   

7.
Using the compiled analytical data for the constituents of four Canadian iron-formation reference samples, a comparison is made among nine different "robust" estimators of "true" value, including the median, median, Gastwirth median, trimean, quarter-trimmed and sixthtrimmed means and the three Hampel estimators. Individual estimators and combinations of them are compared by means of the summation and "iron-oxide compatibility" tests. Comparisons are also made with values derived by the "select laboratories" method.  相似文献   

8.
A comparison is made between various measures proposed thus far for deducing the "best values" from discordant data received in the course of collaborative analysis of proposed reference rocks. Using the raw data on three Canadian samples and the summation and "iron-oxide compatibility" tests, it is claimed that the "select laboratories" method produces the best results.  相似文献   

9.
Results are presented for round one of a new international proficiency testing programme designed for microprobe laboratories involved in the routine analysis of silicate minerals. The sample used for this round was TB-1, a basaltic glass fused and prepared by the USGS. Thirty nine laboratories contributed data to this round, the majority of major element results being undertaken by EPMA and the majority of trace elements by LA-ICP-MS. Assigned values were derived from the median of results produced by nine selected laboratories that analysed powdered material by conventional ICP-MS, INAA and XRF techniques using bulk powders of the sample. Submitted microprobe results were evaluated using a target precision calculated using the Horwitz function, adopting the same criteria as those used for "applied" geochemistry laboratories in the companion GeoPT proficiency testing programme for laboratories involved in the routine bulk analysis of silicate rocks. An evaluation of results from participating microprobe laboratories indicated that overall, data were compatible with this precision function. A comparison between the performance of bulk and microprobe techniques used in the analysis of the basaltic glass showed remarkably good agreement, with significant bias only observed for the major oxide MgO.  相似文献   

10.
The Institute of Geophysical and Geochemical Exploration in China recently prepared ten biogeochemical certified reference samples GSB1‐10 (CRMs). The samples are primary agricultural products such as rice, wheat, corn, soybean, cabbage, spinach, tea, powder, chicken and apple. Lyophilisation technology and a high‐alumina ball mill were used to process the samples. Fourteen laboratories and hundreds analysts in China participated in the certification analysis. Over ten reliable analytical methods, predominately ICP‐MS, ICP‐AES and INAA, were used for analysing the samples for fifty‐nine elements. A total of 22477 determinations led to 5136 average data sets. Certified values of fifty‐four elements were assigned.  相似文献   

11.
在皖北矿区采取了2 2个深层地下水水样,测试Ag、Al、As、Ba等2 0种微量元素,建立了主成分分析模型。根据元素相关性、特征值与累计方差贡献率,进行了地下水的微量元素主成分分析和地下水主成分解释。在此基础上建立了皖北矿区主要突水水源4个主成分的判别表达式,从而得出结论:矿区地下水,特别是四含、太灰与奥灰3个突水含水层微量元素的质量浓度与4个主成分息息相关,可以简单地把第一、二、三、四主成分概括为地下水的溶滤作用、越流作用、河流补给作用、构造裂隙补给作用。   相似文献   

12.
The "Five-Mode Method" for evaluation of compiled data has been applied to three well-established GIT-IWG rock reference samples: Anorthosite AN-G, Basalt BE-N and Granite MA-N. Results are compared to the accepted values, and where the two values are not in accord, a new procedure, the Graphical Moving Mode, is introduced. It is used to provide a clearer picture of the nature of the distribution of the raw data for each constituent, and, possibly to demonstrate the advantages of using the modal approach.  相似文献   

13.
Two international inter-comparison exercises devoted to dissolved gases and isotope analyses in groundwater, used as tools for groundwater dating were organized in 2012 in France (IDES – Université Paris Sud – CNRS and OSUR – Université Rennes 1 – CNRS). The goal was to compare sampling and analytical protocols through results obtained by the community of groundwater dating laboratories. The two exercises were: GDAT1 on three supply boreholes in a homogeneous sand-aquifer of Fontainebleau (Paris Basin, France) and GDAT2 on two supply boreholes (shallow and deep) in a fractured rock aquifer in French Brittany. This two-step exercise is the first exercise which included a large number of gases and isotopes usually used in groundwater as dating tools and also permit to discuss the uncertainties related to sampling protocols issuing from each laboratory methods. The two tests allowed 31 laboratories from 14 countries to compare their protocols for both sampling and analyses. This paper presents the participants and parameters measured, and focuses on the validation of the sampling strategy. Two laboratories analyzed CFC and SF6 samples collected at regular intervals during the sampling operations in order to verify water homogeneity. The results obtained by the two “reference” laboratories along with monitoring of field parameters showed no clear trend of gas concentration or physic-chemical properties. It can be concluded that the pumped groundwater composition remained constant during sampling. This study also shows the potential for relatively constant pumped groundwater composition from a specific well despite the complexity and/or mixing processes that may occur at a larger scale in the aquifer.  相似文献   

14.
All data reported by 200 analysts (106 laboratories) are presented for the four ANRT samples: Diorite DR-N, Serpentine UB-N, Bauxite BX-N and Disthène DT-N. Recommended values are given for the major and minor elements. As far as the as trace elements are concerned, DR-N has been characterized for 35 elements whereas the other three samples have been for only 20 elements. Wherever possible, brief comments have been inserted so as to explain our way of assigning recommended or proposed values.
After more than a decade of existence the total number of data reported for all the four samples reach only 3200 units which are not sufficient enough for a valid evaluation of compiled data. It is also pointed out that these samples are most likely to be available even during the next century as they have been prepared in large quantities of the order of one ton. A plea is therefore made for contribution of more data particularly for trace elements and for major elements which are present as trace elements in UB-N, BX-N and DT-N.  相似文献   

15.
Five samples from Suriname have been analysed for their chemical composition by 18 laboratories. The proposed reference samples are four soil samples and one lateritic bauxite. The samples were analyzed for major and minor elements as well as for 36 trace elements. More data are needed for better characterization of these samples, particularly for trace elements.  相似文献   

16.
The original certification protocol, published by the International Association of Geoanalysts in 2003, specified that the competence of laboratories selected as competent to contribute certification measurements should be evaluated from their performance in the GeoPT proficiency testing programme. Round 39 of the IAG GeoPT proficiency testing programme provided an opportunity to examine four methods of evaluating laboratory competence based largely on the use of proficiency testing z‐scores as performance indicators. This opportunity arose because two test materials were co‐analysed by participating laboratories in this round: a syenite, SyMP‐1, supplied by the USGS, and an established CRM, the nepheline syenite, CGL 006. The performance of laboratories was assessed in four ways; in each case, consensus values and their uncertainties as derived from selective data sets of competent laboratories were compared with results derived from the routine GeoPT data assessment, involving all submitted measurements. An overall comparison of results showed no significant statistical differences in either consensus values or uncertainties between these data sets. This conclusion was unexpected and calls into question the widely held assumption that ‘better’ consensus data would be obtained from a subset of laboratories judged to be competent on the basis of proficiency testing performance indicators.  相似文献   

17.
Interlaboratory comparisons have been widely used in applied radiocarbon science. These are an important part of ongoing quality assurance (QA) programmes, which are vital to the appropriate interpretation of the evidence provided by the 14C record in Quaternary applications (including climate change and environmental reconstruction). International comparisons of laboratory performance are an essential component of the quality assurance process in radiocarbon dating. If the user community is to have confidence in radiocarbon results, it needs to be assured that laboratories world wide are producing measurements that are reliable and in accordance with ‘good practice’. The findings from the most recent (completed in 2001) and extensive (more than 90 participating laboratories) radiocarbon intercomparison (FIRI) are reported here. This study was designed (i) to assess comparability, or otherwise, of the results from different laboratories and (ii) to quantify the extent and possible causes of any interlaboratory variation. The results demonstrate that there are no significant differences amongst the main measurement techniques (gas proportional counting, liquid scintillation counting and accelerator mass spectrometry (AMS)) but there is evidence of small laboratory offsets relative to known age samples for some laboratories. There is also evidence in some cases of underestimation of measurement precision. Approximately 10% of all results were classified as extreme (outliers) and these results were generated by 14% of the laboratories. Overall, the evidence supports the fact that radiocarbon laboratories are generally accurate and precise but that, notwithstanding internal QA procedures, some problems still occur, which can best be detected by participation in independent intercomparisons such as FIRI, where the results allow individual laboratories to assess their performance and to take remedial measures where necessary. The results from FIRI are significant in that they show a broad measure of agreement between measurements made in different laboratories on a wide range of materials and they also demonstrate no statistically significant difference between measurements made by radiometric or AMS techniques. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

18.
Mixing plots, in which a dissolved constituent is plotted against salinity or chlorinity, are commonly used to interpret conservative and non-conservative processes in estuarine systems. A bend in the resulting curve is generally interpreted as indicative of the reactive or non-conservative nature of the constituent or the presence of multiple sources or sinks within the estuary. This paper demonstrates analytically that bends in mixing curves may also result from temporal variations in end-member (river or ocean) constituent concentrations even for conservative constituents. A one-dimensional dispersion equation is used to calculate the distribution of salinity and a conservative constituent in a model estuary. Both straight and bent mixing curves are shown resulting simply from changing the variability of the river constituent concentration. For no variability the curve is straight. For variability with a period much less than the flushing time, the average curve for a general data set straight, whereas the curve for a synoptic data set is bent. For variability with a period greater than the flushing time a bent curve results. Since bent mixing curves can occur for conservative properties, the use of these curves for interpretation of estuarine processes must be undertaken with an understanding of the temporal variability of the river and ocean constituents and their relationship to the estuary mixing properties and flushing time.  相似文献   

19.
Geochemical Reference Samples, Drainage Sediment GSD 1 - 8 from China   总被引：4，自引：0，他引：4  
A set of eight geochemical standard reference samples of stream sediments was prepared. The original purpose was to use these samples as primary standards for the data quality monitoring of a nation-wide regional geochemical survey program in China. But their use has been soon extended to other fields. Forty-one laboratories in China have joined in a collaborative venture to analyse these samples, using a variety of analytical procedures. Recommended values for over 50 trace and minor elements were derived by a method of repetitive elimination of outliers and calculation of central "tendency" from several central values.  相似文献   

20.
秦岭南麓汉江流域上游地区分布着厚达二、三十米的黄土堆积,与秦岭以北地区黄土相比差异明显。汉江流域黄土中的钙结核分布十分广泛,钙结核内壁附着纯净致密的碳酸盐晶体,而秦岭以北黄土钙结核中却少有碳酸盐晶体析出。铀系不平衡测年是一门发展成熟、测年精度高、测年范围相对较广的第四纪重要测年方法,本文尝试利用铀系测年法对汉江流域上游柳陂黄土剖面钙结核样品内的碳酸盐晶体进行了铀系测年分析。柳陂剖面厚约17 m,可辨认出多层古土壤与黄土地层。自柳陂剖面中下部获取的4件钙结核样品测年结果分别为距今115.57±0.66 ka、130.15±0.65 ka、303.97±14.47 ka和356.40±11.60 ka,随着地层深度增加,^230Th年代增长,且与磁化率揭示的土壤地层序列基本一致。所以初步推断柳陂黄土剖面的地层序列为S1、L2、S2-I、S2-II、L3和S3。研究表明,秦岭南麓钙结核的^230Th年龄可为黄土地层的独立定年提供重要参考。根据碳酸盐钙结核形成机制,认为钙结核中碳酸盐晶体的^230Th年代能够指示相应黄土地层的最小年龄。  相似文献   

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