Valente Roque Jussara, Rodrigues Marcella Ferreira, M Dufrayer Gabriel Henry, Medeiros Júnior Iris, de Carvalho Rogério Mesquita, da Silva Lima Gesiane, Dos Santos Gabriel Franco, Vaz Boniek Gontijo
Institute of Chemistry, Federal University of Goiás, Goiânia, GO 74690-900, Brazil.
CENPES, PETROBRAS, Rio de Janeiro, RJ 21941-915, Brazil.
J Am Soc Mass Spectrom. 2024 Sep 4;35(9):2128-2135. doi: 10.1021/jasms.4c00172. Epub 2024 Aug 24.
Naphthenic acids (NAs) naturally occur in crude oil and its associated produced water, presenting significant challenges, such as corrosion, in refinery apparatus and ecotoxicity in aquatic habitats. This study delineates a multivariate method to quantify NAs in produced water via electrospray ionization coupled with high-resolution Orbitrap mass spectrometry (ESI-Orbitrap MS). By employing liquid-liquid extraction, followed by direct infusion ESI(-)-Orbitrap MS, we characterized and quantified NAs employing a partial least-squares regression (PLS) model enhanced by the ordered predictor selection (OPS) algorithm. Thirty-six produced water samples were utilized, with 24 allocated for calibration and 12 designated for validation. The PLS-OPS model demonstrated notable accuracy in predicting NA concentrations in simulated and actual produced water samples ranging from ∼30 to 300 mg·L. This methodology offers a rapid yet robust alternative for quantifying NAs using mass spectrometry augmented by PLS and the OPS. Its significance is underscored by its potential to equip the petroleum industry with a swift and reliable monitoring mechanism for NAs in produced water, thereby aiding in mitigating environmental and operational risks.
环烷酸（NAs）天然存在于原油及其伴生水之中，给炼油设备带来了诸如腐蚀等重大挑战，同时也对水生生境具有生态毒性。本研究描述了一种多变量方法，通过电喷雾电离结合高分辨率轨道阱质谱（ESI-Orbitrap MS）对采出水中的环烷酸进行定量分析。通过液液萃取，随后直接进样ESI(-)-Orbitrap MS，我们采用了由有序预测变量选择（OPS）算法增强的偏最小二乘回归（PLS）模型对环烷酸进行表征和定量分析。使用了36个采出水样本，其中24个用于校准，12个用于验证。PLS-OPS模型在预测模拟和实际采出水样本中环烷酸浓度方面表现出显著的准确性，浓度范围约为30至300 mg·L。该方法为使用由PLS和OPS增强的质谱法对环烷酸进行定量分析提供了一种快速且可靠的替代方法。其重要性体现在它有可能为石油行业提供一种快速且可靠的采出水中环烷酸监测机制，从而有助于降低环境和运营风险。
