Empirical relationship between precision and ultra-trace concentrations of PCDD/Fs and dioxin-like PCBs in biological matrices

Dioxin analysis in food and feed can be characterized as an analytical application where very high accuracy is required at very low levels of contamination. Gas chromatography (GC) in combination with 13C-label isotope dilution (ID) high resolution mass spectrometry (HRMS) is the reference congener-specific technique characterized by pronounced selectivity, precision and trueness at parts-per-trillion (ppt) and sub-parts-per-trillion (sub-ppt) levels. The quality of the analytical data produced routinely by a laboratory should be adequate for its intended purpose, i.e., one will seek a compromise between the cost and time needed and the consequences of incorrect decisions due to erroneous results. The requirements for reproducibility are usually dependent on the analyte concentrations and have been expressed in various empirical functions. While Horwitz or modified functions are widely useful for many purposes, it would be difficult to expect these functions to cover every analytical problem. This study reports on precision characteristics achieved by the GC-ID-HRMS reference method for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in food and feed in two interlaboratory method-performance studies among expert laboratories with long-standing experience in this field. Striking linear functions in log scale between reproducibility standard deviation and congener's level over a concentration range of 10(-8)-10(-14)g per g fresh weight are observed. The data fit very well to a Horwitz-type function of the form sR=0.153c0.904, where sR and c are dimensionless mass ratios expressed in pg g(-1) on fresh weight, regardless of the nature of the toxic congeners, food and feed matrices, or sample preparation methods. We demonstrate that the proposed function is suitable for use as a fitness-for-purpose criterion for proficiency assessment in interlaboratory comparisons on dioxins and related compounds in food.