{"title":"Optimized sample cleanup for compound-specific isotope analysis of polycyclic aromatic hydrocarbons in complex environmental samples","authors":"Md Samrat Alam , Jason M.E. Ahad , Colin A. Cooke","doi":"10.1016/j.orggeochem.2025.104966","DOIUrl":null,"url":null,"abstract":"<div><div>Compound-specific isotope analysis (CSIA) using gas chromatography – isotope ratio mass spectrometry is a powerful tool to discriminate sources of polycyclic aromatic hydrocarbons (PAHs). However, interferences from co-eluting peaks often prevent accurate isotopic measurements in complex environmental samples. Purification of sample extracts is thus a crucial analytical step. In this study, we report a rapid and effective cleanup method using high-performance liquid chromatography (HPLC) that provides high integrity isolation of PAHs suitable for CSIA. The method reported here was effective at purifying both parent and alkylated PAHs from several highly complex matrices, including river sediments, bitumen, petroleum coke, and wildfire ash. HPLC separation removed much of the interfering aromatic unresolved complex mixture (UCM) and significantly improved chromatography, yielding well-resolved PAH peaks with high intensities and signal-to-noise ratios. Recoveries and purities of target compounds following HPLC separation were 70 ± 13% and 97 ± 5%, respectively. No noticeable differences (± 0.5‰) were observed in the carbon isotope values (δ<sup>13</sup>C) of standards subjected to extraction and HPLC purification steps, indicating negligible isotopic fractionation associated with the protocol. The δ<sup>13</sup>C values for individual PAHs in samples were comparable to those previously reported for the same sample types, further demonstrating this method’s high level of accuracy and precision. Additionally, this technique allows for isotopic characterisation of a larger number of 4- to 5-ring PAHs compared to many previous studies due to removal of much of the later-eluting UCM, potentially providing greater insight into source discrimination and understanding of PAH deposition and transformation processes. While the focus of this investigation was on PAHs, this technique could be adapted to other problematic compounds targeted for CSIA.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"203 ","pages":"Article 104966"},"PeriodicalIF":2.6000,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Geochemistry","FirstCategoryId":"89","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0146638025000397","RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"GEOCHEMISTRY & GEOPHYSICS","Score":null,"Total":0}
引用次数: 0
Abstract
Compound-specific isotope analysis (CSIA) using gas chromatography – isotope ratio mass spectrometry is a powerful tool to discriminate sources of polycyclic aromatic hydrocarbons (PAHs). However, interferences from co-eluting peaks often prevent accurate isotopic measurements in complex environmental samples. Purification of sample extracts is thus a crucial analytical step. In this study, we report a rapid and effective cleanup method using high-performance liquid chromatography (HPLC) that provides high integrity isolation of PAHs suitable for CSIA. The method reported here was effective at purifying both parent and alkylated PAHs from several highly complex matrices, including river sediments, bitumen, petroleum coke, and wildfire ash. HPLC separation removed much of the interfering aromatic unresolved complex mixture (UCM) and significantly improved chromatography, yielding well-resolved PAH peaks with high intensities and signal-to-noise ratios. Recoveries and purities of target compounds following HPLC separation were 70 ± 13% and 97 ± 5%, respectively. No noticeable differences (± 0.5‰) were observed in the carbon isotope values (δ13C) of standards subjected to extraction and HPLC purification steps, indicating negligible isotopic fractionation associated with the protocol. The δ13C values for individual PAHs in samples were comparable to those previously reported for the same sample types, further demonstrating this method’s high level of accuracy and precision. Additionally, this technique allows for isotopic characterisation of a larger number of 4- to 5-ring PAHs compared to many previous studies due to removal of much of the later-eluting UCM, potentially providing greater insight into source discrimination and understanding of PAH deposition and transformation processes. While the focus of this investigation was on PAHs, this technique could be adapted to other problematic compounds targeted for CSIA.
期刊介绍:
Organic Geochemistry serves as the only dedicated medium for the publication of peer-reviewed research on all phases of geochemistry in which organic compounds play a major role. The Editors welcome contributions covering a wide spectrum of subjects in the geosciences broadly based on organic chemistry (including molecular and isotopic geochemistry), and involving geology, biogeochemistry, environmental geochemistry, chemical oceanography and hydrology.
The scope of the journal includes research involving petroleum (including natural gas), coal, organic matter in the aqueous environment and recent sediments, organic-rich rocks and soils and the role of organics in the geochemical cycling of the elements.
Sedimentological, paleontological and organic petrographic studies will also be considered for publication, provided that they are geochemically oriented. Papers cover the full range of research activities in organic geochemistry, and include comprehensive review articles, technical communications, discussion/reply correspondence and short technical notes. Peer-reviews organised through three Chief Editors and a staff of Associate Editors, are conducted by well known, respected scientists from academia, government and industry. The journal also publishes reviews of books, announcements of important conferences and meetings and other matters of direct interest to the organic geochemical community.