Rapid and Complete Digestion of Refractory Geological Samples Using Ultrafine Powder for Accurate Analyses of Trace Elements.

Complete sample digestion is a prerequisite for acquiring high-quality analytical results for geological samples. Closed-vessel acid digestion (bomb) has typically been used for the total digestion of refractory geological samples. However, the long digestion time (4-5 days) and insoluble fluoride complexes still pose challenges for digesting refractory geological samples using this approach. In this study, an efficient and simplified digestion technique combining ultrafine powders from planetary ball milling with bomb digestion was developed for trace element analysis of refractory geological samples: peridotite and granitoid. The method shows two significant improvements compared with previous approaches. (1) By performing dry planetary ultrafine milling, the initial 200 mesh peridotite (<74 µm) could be reduced to 800 mesh (<20 µm) in 6 min at a ball-to-powder mass ratio of approximately 15 using 3 mm tungsten carbide milling balls. (2) Complete peridotite and granitoid dissolution were achieved in approximately 2 h, 60 times faster than what is achievable using previous methods (2 h vs 120 h). Moreover, ultrafine powders effectively suppressed insoluble fluoride formation during bomb digestion. A suite of peridotite and granitoid reference materials were measured to evaluate the stability of this method. This efficient, simple, and reliable sample digestion method could benefit geological, food, environmental, and other fields requiring solid sample decomposition via wet acid, fusion, combustion, or dry ashing.

An Acid-Based Method for Highly Effective Baddeleyite Separation from Gram-Sized Mafic Rocks.

Dating mafic igneous rocks (silica-undersaturated) is difficult for the lack of suitable minerals such as zircons (ZrSiO4) commonly found in the sialic rocks such as granites. In this regard, baddeleyite (ZrO2) has been long recognized as the most important mineral to serve as a geochronometer for dating silica-undersaturated igneous rocks. However, separating baddeleyite is difficult due to its small grain size, typical tabular morphology, and low abundance in samples. The standard water-based separation technique requires kilogram-sized samples and usually has a very low recovery rate. In this study, a new separation method based on the different solubilities of the minerals within HF + HCl + HNO3 reagents was developed to achieve a high recovery of baddeleyite. With ∼19 g of diabase powder, the new method recovers 150-160 baddeleyite grains of 10-100 µm length and 4-50 µm width, an order of magnitude improvement over the water-based separation method, which typically recovers 11-12 similarly sized baddeleyite grains out of the ∼19 g sample. Subsequent secondary ion mass spectrometry U-Pb analyses demonstrate that the baddeleyite grains recovered by the new separation method keep the U-Pb system closed, indicating no Pb loss during acid treatment. Thus, this new method enables the most efficient baddeleyite recovery from gram-sized rocks and is anticipated to greatly contribute to the geochronological study of silica-unsaturated mafic rocks.

Comparative Study of Three Mixing Methods in Fusion Technique for Determining Major and Minor Elements Using Wavelength Dispersive X-ray Fluorescence Spectroscopy.

Accurate analysis using a simple and rapid procedure is always the most important pursuit of analytical chemists. In this study, a new sample preparation procedure, namely the shaker cup (SH) method, was designed and compared with two sample preparation procedures, commonly used in the laboratory, from three aspects: homogeneity of the sample-flux mixture, potential for sample contamination, and sample preparation time. For the three methods, a set of 54 certified reference materials (CRMs) was used to establish the calibration curves, while another set of 19 CRMs was measured to validate the results. In the calibration procedures, the matrix effects were corrected using the theoretical alpha coefficient method combined with the experimental coefficient method. The data of the major oxides (SiO2, TiO2, Al2O3, TFe2O3, MnO, MgO, CaO, Na2O, K2O, and P2O5) and minor elements (Cr, Cu, Ba, Ni, Sr, V, Zr, and Zn) obtained by wavelength dispersive X-ray fluorescence spectroscopy (WD-XRF) were compared using two derivative equations based on the findings by Laurence Whitty-Léveillé. The results revealed that the WD-XRF measured values using the SH method best agreed with the values recommended in the literature.

Sample Digestion and Combined Preconcentration Methods for the Determination of Ultra-Low Gold Levels in Rocks.

The gold abundance in basic rocks, which normally varies between 0.5 and 5 ppb, has served as a very important indicator in many geoscience studies, including those focused on the planetary differentiation, redistribution of elements during the crustal process, and ore genesis. However, because gold is a monoisotopic element that exhibits a nugget effect, it is very difficult to quantify its ultra-low levels in rocks, which significantly limits our understanding of the origin of gold and its circulation between the Earth crust, mantle, and core. In this work, we summarize various sample digestion and combined preconcentration methods for the determination of gold amounts in rocks. They include fire assay, fire assay combined with Te coprecipitation and instrumental neutron activation analysis (INAA) or laser ablation inductively coupled plasma mass spectrometry, fusion combined with Te coprecipitation and anion exchange resins, dry chlorination, wet acid digestion combined with precipitation, ion exchange resins, solvent extraction, polyurethane foam, extraction chromatography, novel solid adsorbents, and direct determination by INAA. In addition, the faced challenges and future perspectives in this field are discussed.