Quality assurance and quality control of atmospheric organosulfates measured using hydrophilic interaction liquid chromatography (HILIC)

Abstract. ​​​​​​​As a crucial constituent of fine particulate matter (PM2.5), secondary organic aerosols (SOAs) influence public health, regional air quality, and global climate patterns. This paper highlights the use of hydrophilic interaction liquid chromatography (HILIC) which effectively retains strongly polar analytes that might exhibit incomplete or no retention in reverse chromatography, resulting in superior separation efficiency. A HILIC column was used to analyze six standards, environmental standards (1648a and 1649b), and samples collected in urban environments in Guangzhou in the Pearl River Delta region, which serve as valuable reference points for evaluating the organic composition of the atmospheric environment. The results indicate a high degree of accuracy in the analytical method. Sodium octyl-d17 sulfate serves as the internal standard, with a linear correlation coefficient of the six standards, boasting a linear correlation coefficient r ranging from 0.993–0.9991 and a slope, k, of the linear equation from 0.966–1.882. The instrument detection limits (IDLs) are established at 0.03–0.20 µg mL−1, while the method detection limits (MDLs) fall within the range of 0.30–1.75 ng m−3, demonstrating the method's exceptional sensitivity. Since isoprene-derived organosulfates (iOSs) are highly polar due to containing a hydrophilic bond to the hydroxyl group and a hydrophobic bond to the sulfate, and as such showed strong retention using this method, this technique employs sodium ethyl sulfate and sodium octyl sulfate standards for semi-quantitative compound analysis of iOSs. The error in sample analysis (EA) ranged from 12.25 %–95.26 %, and the two standards maintained a consistent recovery rate between 116 %–131 % and 86.4 %–127 %. These findings indicate a high level of precision when semi-quantifying compounds with similar structural characteristics, affirming the analysis method's minimal relative error and underscoring its repeatability, process stability, and the reliability of its results for iOSs. To enhance the method's reliability assessment, the study analyzed polar organic components of standard particulate matter samples (1648a and 1649b), providing precise determinations of several iOSs using this method. Methyltetrol sulfate (m/z 215, C5H11SO7-) is the highest concentration in the ambient samples, up to 67.3 ng m−3 in the daytime. These results serve as valuable reference points for assessing the organic composition of the atmospheric environment.