Pacific and Yukon Laboratory for Environmental Testing, Science & Technology Branch, Environment and Climate Change, Canada North Vancouver, British Columbia, Canada.
Pacific and Yukon Laboratory for Environmental Testing, Science & Technology Branch, Environment and Climate Change, Canada North Vancouver, British Columbia, Canada.
J Chromatogr A. 2021 Oct 25;1656:462558. doi: 10.1016/j.chroma.2021.462558. Epub 2021 Sep 15.
A rapid and sensitive liquid chromatography (LC) quadrupole time of flight (QTOF) method has been developed for the determination of resin acid concentrations in aqueous pulp and paper effluent related samples. Calibration R of ≥0.995 for twelve resin acids, namely dehydroabietic, 8(14)-abietenic, dihydroisopimaric, levopimaric, neoabietic, pimaric, sandaracopimaric, abietic, isopimaric, palustric, chlorodehydroabietic, and dichlorodehydroabietic acids, was demonstrated in the range 1 µgL to 40 µgL. An improved lower limit of quantitation was achieved without use of complex sample extraction and clean-up procedures undertaken by other published methods. Excellent precision and accuracy results were achieved for dehydroabietic, chlorodehydroabietic, dichlorodehydroabietic, isopimaric (integrated inclusive of all CHO resin acids), dihydroisopimaric and 8(14)-abietenic resin acids, with t-99 percentile detection limits spanning the range 0.05 to 0.07 µgL. While measurement for the CHO resin acids by isopimaric equivalence is considered semi-quantitative and could be an under estimate for the abietic acid component, the developed method demonstrated clear advantage over time consuming, hazardous, and unstable derivatization procedures used for gas chromatography and capillary electrophoresis. The developed LC/QToF method was successfully transferred to an LC triple quadrupole mass spectrometer for routine high throughput trace level analysis. Real world samples, including sea water and estuary water, demonstrated excellent spike recoveries by this procedure, indicating that the method is well suited to the monitoring of industrially derived resin acids in environmental surface waters. While no interferences were observed during routine sample analysis using myristic-1-C acid and palmitic-1-C acid internal standards, these were later substituted by myristic-d and palmitic-d acid in order to improve method robustness for environmental samples where endogenous parent fatty acids could be present.
已开发出一种快速灵敏的液相色谱（LC）四极杆飞行时间（QTOF）方法，用于测定与水性纸浆和造纸废水相关样品中树脂酸的浓度。在 1 µgL 至 40 µgL 的范围内，十二种树脂酸（即去氢枞酸、8(14)-枞烯酸、二氢异枞酸、左旋枞酸、新枞酸、枞酸、沙达树脂酸、枞酸、异枞酸、枞酸、氯去氢枞酸和二氯去氢枞酸）的校准 R 均≥0.995。与其他已发表的方法相比，该方法无需进行复杂的样品提取和净化程序，即可实现更低的定量下限。对于去氢枞酸、氯去氢枞酸、二氯去氢枞酸、异枞酸（包括所有 CHO 树脂酸）、二氢异枞酸和 8(14)-枞烯酸，均获得了出色的精密度和准确度结果，t-99 百分位检测限范围为 0.05 至 0.07 µgL。虽然通过异枞酸等价物测量 CHO 树脂酸被认为是半定量的，并且可能低估了枞酸成分，但与用于气相色谱和毛细管电泳的耗时、危险且不稳定的衍生化程序相比，该方法具有明显的优势。已开发的 LC/QToF 方法已成功转移到 LC 三重四极杆质谱仪，用于常规高通量痕量分析。实际样品，包括海水和河口水，通过该程序证明了良好的加标回收率，表明该方法非常适合监测环境地表水工业衍生的树脂酸。虽然在使用十四烷酸-1-C 和棕榈酸-1-C 内标进行常规样品分析时未观察到干扰，但后来将其替换为十四烷酸-d 和棕榈酸-d 酸，以提高环境样品的方法稳健性，因为可能存在内源性母体脂肪酸。
