Portable X-ray fluorescence (pXRF) calibration for analysis of nutrient concentrations and trace element contaminants in fertilisers

Abstract

With the increasing popularity of local blending of fertilisers, the fertiliser industry faces issues regarding quality control and fertiliser adulteration. Another problem is the contamination of fertilisers with trace elements that have been shown to subsequently accumulate in the soil and be taken up by plants, posing a danger to the environment and human health. Conventional characterisation methods necessary to ensure the quality of fertilisers and to comply with local regulations are costly, time consuming and sometimes not even accessible. Alternatively, using a wide range of unamended and intentionally amended fertilisers this study developed empirical calibrations for a portable handheld X-ray fluorescence (pXRF) spectrometer, determined the reliability for estimating the macro and micro nutrients and evaluated the use of the pXRF for the high-throughput detection of trace element contaminants in fertilisers. The models developed using pXRF for Mg, P, S, K, Ca, Mn, Fe, Zn and Mo had R2 values greater or equal to 0.97. These models also performed well on validation, with R2 values greater or equal to 0.97 (except for Fe, R2val = 0.55) and slope values ranging from 0.81 to 1.44. A second set of models were developed with a focus on trace elements in amended fertilisers. The R2 values of calibration for Co, Ni, As, Se, Cd and Pb were greater than or equal to 0.80. At concentrations up to 1000 mg kg-1, good validation statistics were also obtained; R2 values ranged from 0.97–0.99, except in one instance. The regression coefficients of the validation also had good prediction in the range of 0–100 mg kg-1 (R2 values were from 0.78–0.99), but not as well at lower concentrations up to 20 mg kg-1 (R2 values ranged from 0.10–0.99), especially for Cd. This study has demonstrated that pXRF can measure several major (P, Ca) and micro (Mn, Fe, Cu) nutrients, as well as trace elements and potential contaminants (Cr, Ni, As) in fertilisers with high accuracy and precision. The results obtained in this study is good, especially considering that loose powders were scanned for a maximum of 90 seconds without the use of a vacuum pump.

Recent Progress on Fluorescent Probes in Heavy Metal Determinations for Food Safety: A Review

“…In recent years, portable instruments have been successfully developed to further broaden the practical applicability of XRF. G. E. Acquah et al [47] reported a portable handheld X-ray fluorescence (pXRF) spectrometer to successfully achieve highly accurate and efficient detection of trace heavy metal contaminants (chromium, nickel, and arsenic) in fertilizers. Researchers evaluated the common pXRF method, acid ablation inductively coupled plasma mass spectrometry, and diphenylcarbonyldihydrazide colorimetric methods for the assessment of lead detection in 69 spices worldwide, which helped to reduce lead exposure [48].…”

2023 atomic spectrometry update – a review of advances in X-ray fluorescence spectrometry and its special applications

“…Portable XRF spectrometry was used 68 both for determining macro and micronutrient compositions in fertilisers and for identifying possible contamination with trace elements. Empirical calibrations for 20 elements were constructed using 39 fertiliser samples.…”