Total uncertainty budget as method evaluation criterion for the determination of tracer (111Cd) cadmium and indigenous cadmium in soil column effluents with ICP-MS

2001 ◽  
Vol 16 (4) ◽  
pp. 307-314 ◽  
Author(s):  
Kristof Tirez ◽  
Michael Berglund ◽  
Piet Seuntjens ◽  
Nicole De Brucker
2020 ◽  
Author(s):  
Emiliya Vassileva ◽  
Anna Maria Orani ◽  
Sergey Assonov

<p><span><span>Lead is a non-essential toxic element that at high levels of human exposure causes damage to many organs of the human body. This element naturally occurs in the Earth crust, but its biogeochemical cycle has been altered by anthropogenic activities, which have introduced high amount of this element from different sources. Among inorganic contaminants, Pb is perhaps the most studied, but the determination of its total concentration only is not sufficient for a proper evaluation of contamination sources. Discrimination of anthropogenic and geogenic lead sources requires both precise and accurate isotope ratio determination as well as high versatility due to the complexity of environmental matrices, such as sediments, biota and seawater. This element has a partially radiogenic isotopic composition with 208Pb, 206Pb and 207Pb originating from the radioactive decay of 238U, 235U and 232Th respectively and 204Pb representing the only natural stable isotope. This characteristic isotopic composition represents a powerful analytical tool as it allows to trace the sources, fate and effects of possible Pb contamination. The most common way to express the Pb isotopic composition is using the ratio 206Pb/207Pb, because of the easy interference-free determination and isotopes’ abundance. The determination of 204Pb by ICP-MS is quite challenging as this is also the least abundant among Pb isotopes (about 1.4%) and it is also affected by isobaric interference from 204Hg. The latter derives from both sample matrices and from plasma/sweep gas supplies and it represents a big analytical challenge, especially for marine biota samples, where the amount of Hg can be up to 100 times higher than Pb. </span></span></p><p><span><span>In this work we present the development and the application of analytical methodology for the accurate and precise determination of Pb isotope ratios by HR-ICP-MS in different marine environmental matrices (sediments, seawater and biota). Analytical procedures are involving a separation of Pb from the sample matrix and mercury, present in the sample. For seawater samples, the use of the SeaFAST automated system allowed simultaneous matrix separation and analyte pre-concentration before ICP-MS analysis. A comparison of results for lead isotope ratios obtained with MC-ICP-MS and HR ICP-MS in the same samples, in all cases, showed very good agreement . The total uncertainty associated to each result was estimated and all major contributions to the combined uncertainty of the obtained results were identified. As all such studies involve companions of different datasets, the uncertainty estimation is critical to ensure correct companions.  The developed methodology was applied to different marine samples, namely sediments from Caribbean, Baltic and Namibian coasts, biota samples from French Polynesia, seawater samples from Mediterranean and Arctic seas.</span></span><span><span> </span></span></p>


Metrologia ◽  
2021 ◽  
Author(s):  
Ellie Molloy ◽  
Peter Saunders ◽  
Annette Koo

Abstract Goniometric measurements are essential for the determination of many optical quantities, and quantifying the effects of errors in the rotation axes on these quantities is a complex task. In this paper, we show how a measurement model for a four-axis goniometric system can be developed to allow the effects of alignment and rotation errors to be included in the uncertainty of the measurement. We use three different computational methods to propagate the uncertainties due to several error sources through the model to the rotation angles and then to the measurement of bidirectional reflectance and integrated diffuse reflectance, a task that would otherwise be intractable. While all three methods give the same result, the GTC Python package is the simplest and intrinsically provides a full uncertainty budget, including all correlations between measurement parameters. We then demonstrate how the development of a measurement model and the use of GTC has improved our understanding of the system. As a consequence, taking advantage of negative correlations between measurements in different geometries allows us to minimise the total uncertainty in integrated diffuse reflectance, lowering the standard uncertainty from 0.0029 to 0.0015.


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