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In this paper, a method of ultrasound-assisted low-pressure closed acid digestion followed by inductively coupled plasma mass spectrometry (ICP-MS) analysis was proposed for trace element quantification in rock samples. By using 1.5 mL of a binary acid mixture of HNO3–HF with a ratio of 2:1, rock powder samples of 50 mg were completely decomposed in 12 h at 140 °C after 4 h of ultrasonic treatment with or without pressure relief procedure. The element extraction efficiency of this method was evaluated via the yielded relative errors (REs) of the trace elements in a series of geological standard reference materials (SRMs) with compositions from basic to acidic. It was found that the contents of trace elements (i.e., 36 metal elements from Li to U) in basalt BCR-2, diabase W-2a, andesite AGV-2, granodiorite GSP-2, and granite GSR-1 were comparable with the reported reference values, giving REs with absolute values less than 10%. It was also found that clear solutions without sample powder residues by naked-eye observation can be obtained when using the low-pressure closed decomposition method without ultrasonic pretreatment. The quantification results, however, were found to be negatively biased for most of the studied trace elements, and, in particular, the content bias of Zr in SRM GSP-2 was down to −86.28% due to the low extraction efficiency of refractory minerals of the low-pressure closed digestion method. By applying this proposed digestion strategy, the decomposition property of the ternary combination of HNO3–HF–mannitol in terms of trace element quantification accuracy was also investigated. Results showed that the concentrations of trace elements in the studied SRMs were consistent with the reference values, giving REs within ±6.94%, which revealed that there was no deterioration of extraction efficiencies of trace elements and neglected mass interferences from mannitol. This study demonstrated the essential role of ultrasound irradiation in rock sample decomposition to achieve the high extraction efficiency of trace elements under a low-pressure environment, and the developed approach with promising future applications in geoscience exhibited considerable merits, including a high extraction efficiency, feasible digestion process, less time consumption, and lower safety associated risks.

Tourmaline, a boron-bearing mineral, has been extensively applied as a geothermometer, provenance indicator, and fluid-composition recorder in geological studies. In this paper, the decomposition capability of an HF-HNO3–mannitol mixture for a tourmaline sample was investigated in detail for the first time, and a wet acid digestion method based on the boron–mannitol complex for accurate boron determination in tourmaline by inductively coupled plasma mass spectrometry (ICP-MS) was proposed. With a digestion temperature of 140 °C, tourmaline samples of 25 mg (±0.5 mg) can be completely decomposed by a ternary mixture, which consisted of 0.6 mL of HF, 0.6 mL of HNO3, and 0.7 mL of 2% mannitol (wt.), via a continuous heating treatment of 36 h. Following gentle evaporation at 100 °C, the sample residues were re-dissolved using 2 mL of 40% HNO3 solution (wt.) and diluted to about 2.0 × 105-fold by a two-step method using 2% HNO3 solution (wt.). The boron contents in a batch of parallel tourmaline samples were then determined by ICP-MS, and results showed that the boron concentration levels were in a range of 3.20–3.44% with determination RSDs less than 4.0% (n = 5). It was found that the boron concentrations obtained at the mass of 10B were comparable with results from the measurements at the mass of 11B. This revealed that the usage of 2% mannitol with a quantity as high as 0.7 mL in this developed approach did not exhibit significant effect on the quantification accuracy of boron at the mass of 11B. It was also found that the processes including fluoride-forming prevention and fluoride decomposition deteriorated the boron-reserving efficiency of mannitol for tourmaline, causing the averaged boron contents to vary from 2.25% to 3.57% (n = 5). Furthermore, the stability of the boron–mannitol complex under 185 °C by applying the laboratory high pressure-closed digestion method was evaluated, which showed that there existed a 60.36% loss of boron compared to that under 140 °C by using this proposed approach. For this ternary mixture, the tourmaline decomposing efficiency was found to be weakened prominently using 100 °C as the digestion temperature, and tourmaline powders can be observed even after 72 h of continuous heating with B contents within 1.09–1.23% (n = 5). To assess the accuracy of this developed method, the boron recovery of anhydrous lithium tetraborate was studied. It was found that the boron recoveries were within 96.59–102.12% (RSD < 1%, n = 5), demonstrating the accuracy and reliability of this proposed method, which exhibits advantages of high B preserving efficiency, and giving concentration information of both B and trace elements simultaneously. By applying such a boron–mannitol complex-based wet acid digestion method, the chemical composition of boron and trace elements in three tourmaline samples from different pegmatites were quantified, which provided valuable information to distinguish regional deposits and the associated evolution stages.

In this work, a reliable and robust in situ non-matrix-matched calibration method is proposed for element composition determination in scheelite samples. With external calibration against the silicate glass standard reference material NIST SRM 610, the concentrations of both major elements (Ca and W) and trace elements (Si, Fe, Mo, Y, rare earth elements, etc.) in scheelite are determined using an ArF 193 nm excimer nanosecond laser ablation-inductively coupled plasma mass spectrometer (LA-ICP-MS). Here, the ablation was performed by hole drilling under a helium (He) environment using a laser spot size of 35 μm and a laser repetition of 5 Hz, and the aerosols were then transported to a quadrupole ICP-MS by a mixture of He and make-up gas argon (Ar) with a total gas flow rate of 1.6 L/min. Results showed that there was no apparent matrix effect between the NIST SRM 610 and scheelite by this proposed method. With internal standardization against W, the obtained concentrations of CaO and WO3 were found to yield an average matrix CaO/WO3 mass fraction ratio of 0.245 (2σ = 0.003, n = 19), which agreed well with the value of 0.243 (2σ = 0.002, n = 15) from electron probe microanalysis (EPMA). Furthermore, the accuracy of trace element analyses with this proposed non-matrix-matched calibration in situ method was evaluated by comparing the concentration results with those from bulk analysis by solution nebulizer ICP-MS (SN-ICP-MS). It was found that the quantification results from LA-ICP-MS and SN-ICP-MS were comparable, in particular showing a relative concentration bias of the total ∑REE+Y contents of less than 2%. This confirmed that scheelites can be accurately analyzed in situ by LA-ICP-MS without matrix-matched calibration standards. By using this developed in situ method, the element compositions in a series of scheelite samples from different W-associated deposits in China were successfully quantified, promising further genetic process investigation and associated geologic activities of the polymetallic resources.

In this paper, a boron–mannitol complex wet acid digestion method proposed for the accurate determination of boron in silicate samples by inductively coupled plasma mass spectrometry (ICP-MS) was investigated in detail for the first time. With the addition of 50 μL of mannitol (2% wt.) into the mixture of 0.6 mL of concentrated HF and 30 μL of concentrated HNO3, the 50 mg of silicate sample was effectively decomposed after being heated overnight with optional pre-ultrasonic treatment. Following fluoride formation prevention by 8% HNO3 (wt.) and fluoride decomposition using 6% HCl (wt.), the samples were fluxed in 2.0 mL of 40% HNO3 (wt.) for 4 h and aged overnight. By diluting 1000-fold using 2% HNO3 (wt.) solution, the samples were directly quantified by an ICP-MS, showing boron recoveries of the standard materials including diabase W-2, basalt JB-2a, and rhyolite JR-2 in the range of 95.5–105.5% (n = 5). For this wet acid method, it was found that the contents of boron had no obvious difference under digestion temperatures of 65, 100, and 140 °C. It was also found that the ICP-MS quantification accuracy deteriorated at the mass of 11B when boron content was about 7250 ng yielding positive bias with average recoveries of 115.5–119.8% (n = 5), while the determination results remained unaffected at the mass of 10B. Furthermore, the digestion efficiency of boron by laboratory high-pressure closed digestion method was assessed. The boron recoveries with samples treated by the high-pressure closed digestion method were found to vary within 49.5–98.0% (n = 5) and even lowered down to 31.1% when skipping pressure relief procedure. The long-term quantification stability study showed that the boron content generally declined in one month for the high-pressure closed digestion method and exhibited no significant changes for the proposed method. By applying such an improved boron–mannitol complex digestion method, the boron concentration in the studied silicate standard materials were accurately determined, providing critical data for further boron isotope analyses and associated geochemical studies. This in-depth method investigation for silicate boron determination demonstrates the feasibility of this boron–mannitol complex strategy under a wide digestion temperature of 65–140 °C, and also sheds light on the extensive applications of boron as a geological tracer.

This work presents the long-term determination accuracy study of ICP-QMS for rare earth elements (REEs) in geological matrices. Following high-pressure closed acidic decomposition, REEs are measured repetitively across seven months by ICP-QMS. Under optimum experimental conditions (including spray chamber temperature, gas flow rate, sampling depth, etc.), the REE contents in geological standard materials from basic (basalt BCR-2 and BE-N) to intermediate (andesite AGV-2) and up to acidic (granite GSR-1) show good agreement with the certified values, giving relative errors below 10%. Here, the influence of two storage materials (perfluoroalkoxy PFA and polypropylene PP) on the long-term determination accuracy of REEs has also been monitored. It is found that the relative errors of REEs using a PFA container range from −6.6 to 6.3% (RSDs < 6.0%), while that using a PP container are within −4.0 to 3.9% (RSDs < 4.6%). By using PP material as a solution storage container, the accuracy of REEs quantification in a series of real geological samples are checked, showing the RSDs of less than 5.0%. This work first clarifies the long-term stability of REEs quantification by ICP-QMS covering two types of storage materials, confirming the reasonability of PP material as a daily storage container in terms of higher data precision and lower cost.