Trace Rare Earth Element Detection in Food and Agricultural Products Based on Flow Injection Walnut Shell Packed Microcolumn Preconcentration Coupled with Inductively Coupled Plasma Mass Spectrometry

With the extensive use of rare earth elements (REEs) in agriculture as fertilizer and feed additives, the concentration of REEs has increased in environmental and biological samples and finally impaired human health by food chain accumulation. The determination of trace REEs has gained considerable importance because of their toxicity and increasing occurrence. In this work, walnut shell has been used as the green adsorbent in online preconcentration and detection of REEs in food and agricultural products coupled with inductively coupled plasma mass spectrometry (ICP-MS). Because of the porous surface and abundant −COO^– groups on the walnut shell surface, the walnut shell-packed microcolumn provides high adsorption efficiency and high tolerable capacity for coexisting ions. Under the optimized conditions, the adsorption efficiency of the walnut shell packed microcolumn was as high as 98.9% for 15 REEs, and the tolerable concentration ratios were between 2000 and 80 000 000 for 37 kinds of coexisting interfering ions. The enhancement factors achieved were 79–102 for 15 REEs with a sample loading volume of 4.7 mL. The detection limits were in the range of 2–34 pg g^–1. The relative standard deviation for 11 replicate preconcentrations of 2.5 ng L^–1 REEs solution ranged from 0.5 to 2.0%. The present method was successfully applied to selective determination of REEs in 4 environmental and biological certified reference materials and 18 locally collected food and agricultural products