Laboratory for Geotechnical and Geoenvironmental Engineering, École de Technologie Supérieure (ETS). 1100 Notre-Dame Ouest, Montreal, H2L 3M4, Canada.
KHE Consulting(1), Copenhagen, Denmark; Visiting professor (2017), ETS, Montreal, Canada; Aalborg University, Denmark; Geological Survey of Denmark and Greenland (GEUS), Denmark.
Anal Chim Acta. 2022 Feb 8;1193:339227. doi: 10.1016/j.aca.2021.339227. Epub 2021 Nov 2.
For some real-world material systems, estimations of the incompressible sampling variance based on Gy's classical s(FSE) formula from the Theory of Sampling (TOS) show a significant discrepancy with empirical estimates of sampling variance. In instances concerning contaminated soils, coated particular aggregates and mixed material systems, theoretical estimates of sampling variance are larger than empirical estimates, a situation which does not have physical meaning in TOS. This has led us to revisit the development of estimates of s(FSE) from this famous constitutional heterogeneity equation and explore the use of size-density classes for mixed material systems (mixtures of both analyte-enriched and coated particles), an approach which has been mostly unused since Gy's original derivation. This approach makes it possible to avoid taking into account the granulometric and liberation factors from Gy's classical treatment, and present grounds for criticising the use of 'standard' input values of critical parameters such as f: = 0.5, and g: = 0.25. But, as always, the "liberation factor" (l) issue still plays an important role, which is paid due attention. The constitutional heterogeneity formula based on size-density classes is presented in a form that allows for easy implementation in practice, within specified limitations. We present extensive experimental results from real-world systems. Using the "SDCD model" with published data reproduced the relative sampling variances calculated for the standard "mineral-like matrices", but more importantly corrected the relative sampling variance calculated for real contaminants by several orders of magnitudes. In all cases, the recalculated relative sampling variances were decreased to below their corresponding experimental measurements, now fully as expected from TOS, substantiating our development.
对于某些实际的物质系统,基于采样理论(TOS)中 Gy 的经典 s(FSE)公式对不可压缩采样方差的估计与采样方差的经验估计存在显著差异。在涉及污染土壤、涂覆特定颗粒和混合材料系统的情况下,采样方差的理论估计值大于经验估计值,这种情况在 TOS 中没有物理意义。这导致我们重新审视从这个著名的结构异质性方程中估算 s(FSE)的发展,并探索使用大小-密度类来估算混合材料系统(分析物富集和涂覆颗粒的混合物)的采样方差,这种方法自 Gy 最初推导以来大多未被使用。这种方法使得可以避免考虑 Gy 经典处理中的粒度和解放因素,并为批评使用“标准”输入值的临界参数(如 f: = 0.5 和 g: = 0.25)提供了依据。但是,像往常一样,“解放因子”(l)问题仍然起着重要作用,这一点得到了应有的重视。基于大小-密度类的结构异质性公式以一种允许在特定限制内易于在实践中实施的形式呈现。我们提出了来自实际系统的广泛实验结果。使用带有已发表数据的“SDCD 模型”重现了计算标准“类矿物质基质”的相对采样方差,但更重要的是,通过几个数量级校正了计算实际污染物的相对采样方差。在所有情况下,重新计算的相对采样方差都降低到低于其相应的实验测量值,现在完全符合 TOS 的预期,证实了我们的发展。