Estimation and usefulness of measurement uncertainty from sampling at different spatial scales: microns to kilometres

Measurements made on samples are the basis of most scientific decision, but always contain uncertainty. Much of this uncertainty arises from how the samples are taken, and this can be quantified using the Duplicate Method, which can be applied at any spatial scale, from kilometre to microns.
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Estimation and usefulness of measurement uncertainty from sampling at different spatial scales: microns to kilometres - Environmental Geochemistry and Health

Uncertainty of measurement values (MU) is crucial to their reliable geochemical interpretation. MU can be estimated using the Duplicate Method, which requires the taking of a small proportion of duplicated samples, and can be applied at any spatial scale. The distance between the duplicated samples is selected to reflect the effect of analyte heterogeneity on the measurement result (i.e. estimated concentration) within each sampling target, at the particular scale of investigation. Three published case studies, at different spatial scales, are used to explain how the Duplicate Method can be applied to estimate MU. They also illustrate how MU can be used to improve geochemical interpretation and validate measurement procedures (that include sampling) by judging their fitness for purpose. At the kilometre scale, measurements from the GEMAS survey of agricultural soils across Europe are used to estimate their MU for the first time. The MU for 53 elements range from an uncertainty factor of 1.01 to over 10. The MU contributes more that 20% to the total variance for 8 of the 53 elements, showing that the measurement procedure was not fit for purpose in those cases. At the micron scale, measurements of oxygen isotopes in candidate quartz reference materials had MU that was dominated by its sampling component, caused by sometimes unacceptable heterogeneity. A third case study of Pb in soils at 12 UK sites showed that the Duplicate Method can also be used to quantify the heterogeneity (as factor 1.03 to 2.4), and that it can indicate different possible sources of an element.

Uncertainty of measurement values (MU) is crucial to their reliable geochemical interpretation. MU can be estimated using the Duplicate Method, which requires the taking of a small proportion of duplicated samples, and can be applied at any spatial scale. The distance between the duplicated samples is selected to reflect the effect of analyte heterogeneity on the measurement result (i.e. estimated concentration) within each sampling target, at the particular scale of investigation. Three published case studies, at different spatial scales, are used to explain how the Duplicate Method can be applied to estimate MU. They also illustrate how MU can be used to improve geochemical interpretation and validate measurement procedures (that include sampling) by judging their fitness for purpose. At the kilometre scale, measurements from the GEMAS survey of agricultural soils across Europe are used to estimate their MU for the first time. The MU for 53 elements range from an uncertainty factor of 1.01 to over 10. The MU contributes more that 20% to the total variance for 8 of the 53 elements, showing that the measurement procedure was not fit for purpose in those cases.

Effect of increasing levels of measurement uncertainty on clarity of geochemical maps of Europe
Effect of increasing measurement uncertainty on clarity of (GEMAS) geochemical maps of Europe, from acceptably low levels for As, Pb to unacceptably high level for Pt

At the micron scale, measurements of oxygen isotopes in candidate quartz reference materials had MU that was dominated by its sampling component, caused by sometimes unacceptable heterogeneity. A third case study of Pb in soils at 12 UK sites showed that the Duplicate Method can also be used to quantify the heterogeneity (as factor 1.03 to 2.4), and that it can indicate different possible sources of an element. 

https://doi.org/10.1007/s10653-024-01888-6

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Earth Sciences
Physical Sciences > Earth and Environmental Sciences > Earth Sciences
Analytical Chemistry
Physical Sciences > Chemistry > Analytical Chemistry
Measurement Science and Instrumentation
Physical Sciences > Physics and Astronomy > Applied and Technical Physics > Measurement Science and Instrumentation

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