3D Printing in analytical sample preparation.

In the last 5 years, additive manufacturing (three-dimensional printing) has emerged as a highly valuable technology to advance the field of analytical sample preparation. Three-dimensional printing enabled the cost-effective and rapid fabrication of devices for sample preparation, especially in flow-based mode, opening new possibilities for the development of automated analytical methods. Recent advances involve membrane-based three-dimensional printed separation devices fabricated by print-pause-print and multi-material three-dimensional printing, or improved three-dimensional printed holders for solid-phase extraction containing sorbent bead packings, extraction disks, fibers, and magnetic particles. Other recent developments rely on the direct three-dimensional printing of extraction sorbents, the functionalization of commercial three-dimensional printable resins, or the coating of three-dimensional printed devices with functional micro/nanomaterials. In addition, improved devices for liquid-liquid extraction such as extraction chambers, or phase separators are opening new possibilities for analytical method development combined with high-performance liquid chromatography. The present review outlines the current state-of-the-art of three-dimensional printing in analytical sample preparation.

An integrated automatic system to evaluate U and Th dynamic lixiviation from solid matrices, and to extract/pre-concentrate leached analytes previous ICP-MS detection.

Leached fractions of U and Th from different environmental solid matrices were evaluated by an automatic system enabling the on-line lixiviation and extraction/pre-concentration of these two elements previous ICP-MS detection. UTEVA resin was used as selective extraction material. Ten leached fraction, using artificial rainwater (pH 5.4) as leaching agent, and a residual fraction were analyzed for each sample, allowing the study of behavior of U and Th in dynamic lixiviation conditions. Multivariate techniques have been employed for the efficient optimization of the independent variables that affect the lixiviation process. The system reached LODs of 0.1 and 0.7ngkg-1 of U and Th, respectively. The method was satisfactorily validated for three solid matrices, by the analysis of a soil reference material (IAEA-375), a certified sediment reference material (BCR- 320R) and a phosphogypsum reference material (MatControl CSN-CIEMAT 2008). Besides, environmental samples were analyzed, showing a similar behavior, i.e. the content of radionuclides decreases with the successive extractions. In all cases, the accumulative leached fraction of U and Th for different solid matrices studied (soil, sediment and phosphogypsum) were extremely low, up to 0.05% and 0.005% of U and Th, respectively. However, a great variability was observed in terms of mass concentration released, e.g. between 44 and 13,967ngUkg-1.

226Ra dynamic lixiviation from phosphogypsum samples by an automatic flow-through system with integrated renewable solid-phase extraction.

The release of 226Ra from phosphogypsum (PG) was evaluated by developing a novel tool for fully automated 226Ra lixiviation from PG integrating extraction/pre-concentration using a renewable sorbent format. Eight leached fractions (30mL each one) and a residual fraction were analyzed allowing the evaluation of dynamic lixiviation of 226Ra. An automatic system allows this approach coupling a homemade cell with a 226Ra extraction/pre-concentration method, which is carried out combining two procedures: Ra adsorption on MnO2 and its posterior co-precipitation with BaSO4. Detection was carried out with a low-background proportional counter, obtaining a minimum detectable activity of 7Bqkg-1. Method was validated by analysis of a PG reference material (MatControl CSN-CIEMAT 2008), comparing the content found in fractions (sum of leached fractions + residual fraction) to the reference value. PG samples from Huelva (Spain) were studied. 226Ra average activity concentration of the sum of leached fractions with artificial rainwater at pH 5.4±0.2 was 105±3Bqkg-1d.w. representing a 226Ra lixiviation of 37%; while at pH 2.0±0.2, it was 168±3Bqkg-1 d.w., which represents a 50%. Also, static lixiviation, maintaining the same experimental conditions, was carried out indicating that, for both considered pH, the 226Ra release from PG is up to 50% higher in a dynamic leaching that in a static one, may have both environmental and reutilization implications.