3D printed stir bar sorptive extraction coupled with high performance liquid chromatography for trace estrogens analysis in environmental water samples

Background: Any imaginary shape with good preparation reproducibility can be made by 3D printing technology, and it has been applied in various fields. Comparatively, its applications in sample pre-treatment are relatively less, most of which involves making extraction sorbents and producing non-functionalized devices for support assistance. 3D printing has not been applied to fabricate stir bars in stir bar sorptive extraction, mainly due to the lacking of suitable printing feedstocks. This work aimed to fabricate stir bars by 3D printing, reducing the manufacturing cost and steps and improving preparation reproducibility. (90)Results: By using fused deposition modeling technique and porous filament printing feedstock, stir bars were fabricated without any modifications. Adsorption performance of 3D printed stir bars were investigated for substances with different structures and polarities. Five estrogens with adsorption efficiencies of over 80 % were selected as the representatives. The 3D printed stir bars exhibited good preparation reproducibility (2.9-4.4 %) and higher extraction recoveries (73-81 %) for five estrogens than commercial polydimethylsiloxane coated stir bars (13-69 %) in a shorter time (90 vs 120 min). They showed long lifespan (160 times) with good mechanical properties and merited reduced manufacturing cost (0.064 $ per bar) and manual operation. A method of stir bar sorptive extraction coupled with high performance liquid chromatography was proposed for trace analysis of estrogens in environmental water. Under the optimized conditions, the linear ranges for estrogens were 0.5-200 mu g/L with LODs of 0.13-0.17 mu g/L. (136)Significance: The feasibility of fused deposition modeling in stir bar fabrication was demonstrated, along with the potential of porous filament printing feedstock as the sorbent for substances with medium polarity. 3D printed stir bars were featured with excellent preparation reproducibility, long lifespan, and good mechanical properties. The stir bar fabrication method can be used for mass production with minimal differences in products perfor-mance. (62)