Accumulation and spatial distribution of arsenic and phosphorus in the fern Pityrogramma calomelanos evaluated by micro X-ray fluorescence spectrometry

The accumulation and spatial distribution of arsenic and phosphorus in the As-hyperaccumulator fern Pityrogramma calomelanos were investigated by micro-energy dispersive X-ray fluorescence spectrometry (mu-EDXRF). Ferns were grown in half-strength Hoagland nutrient solution without and with 1.0, 10 or 30 x 10(-3) mol L-1 As during three weeks. Microchemical As and P maps in different areas of the pinna were obtained by mu-EDXRF, and the same elements were also determined in pelletized powdered samples from the pinna, stipe and root. The reference method for the determination of As and P in the fern samples was a validated method based on microwave-assisted acid digestion followed by ICP OES analysis. Correlations between X-ray characteristic emission intensities and the corresponding As and P mass fractions obtained from the analysis of pelletized test samples exhibited linear correlation coefficients higher than 0.98 (n = 42). Better root mean square errors of prediction (RMSEPs) were obtained when different calibration models were built with pinna, stipe and root test samples separately. Arsenic was accumulated mainly in the pinna midrib, secondary veins, and apical and marginal regions of the pinnule of P. calomelanos, causing alterations in the P distribution. The proposed mu-EDXRF method is an appropriate analytical tool for simultaneously mapping As and P in P. calomelanos. In addition, useful information for either environmental monitoring or phytoremediation studies regarding As contamination is properly obtained.