Developing Matrix-Matched Empirical Calibrations for EDXRF Analysis of Peat-Alternative Growth Media

A key reason for the widespread use of peat-based growth media in horticulture is their reliable nutrient availability when supplemented with fertilisers. However, due to environmental concerns over continued peat-extraction and use, peat-alternatives (e.g., coir, wood fibre, composted bark, biochar) are increasingly being used commercially. These alternative media often blend multiple materials, making it crucial to understand elemental composition and nutrient interactions between components. This study evaluates whether benchtop Energy Dispersive X-ray Fluorescence (EDXRF) can provide a rapid method for determining the elemental composition of peat-alternative components.

Representative growing media components (peat, coir, wood fibre, composted bark, biochar, horticultural lime, perlite, slow-release fertilisers, and trace-element fertiliser) were blended in different ratios to generate industry-representative mixes. Individual components and prepared mixes were dried and milled to ≤80 μm. An industry-representative mix (QC-50: 50% peat, 30% wood fibre, 10% composted bark, 10% coir, with fertiliser and lime additions) and 100% peat were analysed by EDXRF (Rigaku NEX-CG) for P, K, Mg, Ca, S, Fe, Mn, Zn, Cu and Mo, and compared against ICP-OES reference measurements. The instrument’s fundamental parameters (FP) method using a plant-based organic materials library showed large discrepancies relative to ICP-OES (relative differences: 268–390 084%) for most elements in both QC-50 and peat, with the exception of Ca in QC-50 (11%). These results confirm that the FP approach combined with loose-powder preparation is unsuitable for accurate elemental analysis of organic growing media.

An empirical calibration was subsequently developed using 18 matrix-matched standards (CRMs, in-house growing media and individual component standards). Matrix matching is challenging because mixes are mostly organic by volume, yet variable inorganic amendments (e.g., lime, fertilisers, and sometimes perlite) can strongly influence XRF absorption/enhancement effects. Calibration performance was optimised iteratively using QC-50 as the validation sample, until relative differences were <15% for all elements. When applied to 100% peat, agreement with ICP-OES results improved substantially for some macro-elements (e.g. Mg 10%, Ca 1%, S 19%) but remained poor for most trace elements (28–96%), demonstrating limited transferability of this calibration method across different elements and matrices tested.

Overall, these results demonstrate that loose powder preparation does not provide sufficiently robust accuracy for EDXRF analysis of organic growing media even with meticulous empirical matrix-matched calibration. We are therefore developing a pressed pellet method using a low-cost wax binder to improve sample homogeneity (packing density) and calibration transferability. Twenty unknown mixes will be analysed using both loose powder and pressed-pellet calibrations, and agreement with reference data (ICP-OES) will confirm method validation, supporting the development of EDXRF as a novel approach for growing media analysis.