A High-temperature and High-pressure Sintered Calcite Ceramic Reference Material CAL-D for in Situ Trace Element Microanalysis of Calcite by LA-ICP-MS

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is commonly employed for in situ microanalysis of elemental mass fractions in calcite samples.However, the evaluation of its accuracy is questioned due to the scarcity of homogeneous and matrix-matched reference materials (RMs).In this research, we successfully synthesized multielemental doped calcite ceramic RMs (CAL-D) through a combined approach involving hydrothermal synthesis and hightemperature and high-pressure sintering (HTHPs) methods.Electron probe microanalysis (EPMA) and X-ray diffraction (XRD) confirmed that CAL-D was matrix-matched with natural calcite.The homogeneity of trace element distribution was assessed using LA-ICP-MS, encompassing both within-unit and between-unit homogeneity assessments.The analysis reveals 40 elements with relative standard deviation (RSD) <10% in both within-unit and between-unit tests.Among them, 27 elements (Sc, Mn, Ni, Cu, Ga, Sr, Y, Nb, In, Sn, Ba, Ta, Bi, Th, La, Ce, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) demonstrate RSD values below 5%.There are 36 elements that passed the t-test evaluation in a 6-month stability examination.These findings indicate that CAL-D satisfies the requirements for matrix-matched and homogeneous LA-ICP-MS RMs, demonstrating its suitability for quantitative calibration of trace element mass fractions in natural calcite.Atom.Spectrosc.2025, 46(4), 362-371.Table 1.Compilation of currently published carbonate RMs for LA-ICP-MS analysis RMs name Homogeneity Limitations Ref. MACS-3 33 elements (RSD<10%) 10-30 m particle size causes non-uniform ablation; Poor cohesion 1,47 MACS-3NP 33 elements (RSD<10%) Moisture absorption, poor cohesion, high porosity, and low hardness 47 CGSP-A 34 elements (RSD<20%) Moisture absorption, poor cohesion, high porosity, and low hardness 29 CGSP-B 29 elements (RSD<20%) Moisture absorption, poor cohesion, high porosity, and low hardness 29 CGSP-C 27 elements (RSD<20%) Moisture absorption, poor cohesion, high porosity, and low hardness 29 CGSP-D 32 elements (RSD<20%) Moisture absorption, poor cohesion, high porosity, and low hardness 29 OOID 29 elements (RSD<10%) Moisture absorption, poor cohesion, high porosity, and low hardness 26 NFHS-2-NP 25 elements (RSD<20%) Moisture absorption, poor cohesion, high porosity, and low hardness 24 JCp-1 B, Mg, Sr, U (RSD<10%) conservation regulations, low trace element 26,47 JCp-1NP 16 elements (RSD<10%) conservation regulations, low trace element 47 JCt-1 Li, B, Na, Si, Fe, Sr (RSD<10%) conservation regulations, low trace element 26,47 JCt-1NP 11 elements (RSD<10%) conservation regulations, low trace element 26,47