In situ determination of trace elements in Fucus spp. by field-portable-XRF

Fresh and freeze-dried sample sections of the coastal macroalgae, Fucus serratus and F. vesiculosus, and the brackish water macroalga, F. ceranoides, have been analysed for trace elements by field-portable-X-ray fluorescence (FP-XRF) spectrometry using a Niton XL3t in a low density mode with thickness correction. When analysed fresh in a laboratory accessory stand for a period of 200 seconds, As, Br, Fe and Zn were registered in the apex, mid-frond and lower stipe of all species, with detection limits of a few μg g^-1 (As) or a few tens of μg g^-1 (Br, Fe, Zn); when analysed dry under the same conditions, concentrations returned were systematically higher and Cu and Pb were detected in a number of F. ceranoides sections. Concentrations arising from both approaches on a dry weight basis were highly correlated, with deviations from unit slope attributed to the absorption of fluorescent X-rays by internal and surficial water when analysed fresh. With algorithms correcting for the effects of water on mass and X-ray absorption, sections of F. vesiculosus and F. ceranoides were analysed in situ with the XRF connected to a mobile stand and laptop. Dry weight concentrations returned for As and Zn were significantly correlated with respective concentrations subsequently determined by ICP-MS following acid digestion and with a slope close to unity; lower concentrations of Fe returned by ICP were attributed to the incomplete acid digestion of silt particles that evaded an initial cleaning step, while Br concentrations could not be verified independently because of loss of volatile forms during digestion. The in situ determination of trace elements in fucoids by FP-XRF provides a rapid and non-destructive means of monitoring environmental quality and identifying hot-spots of contamination, and enables a research strategy to be developed iteratively that is informed by immediate results.