Petroleum and Environmental Geochemistry Group, Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK.
Environ Sci Technol. 2011 Nov 15;45(22):9806-15. doi: 10.1021/es202606d. Epub 2011 Oct 20.
The large volumes, acute toxicity, estrogenicity, and antiandrogenicity of process-affected waters accruing in tailings ponds from the operations of the Alberta oil sands industries pose a significant task for environmental reclamation. Synchronous fluorescence spectra (SFS) suggest that oil sands process-affected water (OSPW) may contain aromatic carboxylic acids, which are among the potentially environmentally important toxicants, but no such acids have yet been identified, limiting interpretations of the results of estrogenicity and other assays. Here we show that multidimensional comprehensive gas chromatography-mass spectrometry (GCxGC-MS) of methyl esters of acids in an OSPW sample produces mass spectra consistent with their assignment as C(19) and C(20) C-ring monoaromatic hydroxy steroid acids, D-ring opened hydroxy and nonhydroxy polyhydrophenanthroic acids with one aromatic and two alicyclic rings and A-ring opened steroidal keto acids. High resolution MS data support the assignment of several of the so-called 'O3' species. When fractions of distilled, esterified, OSPW acid-extractable organics were examined, the putative aromatics were mainly present in a high boiling fraction; when examined by argentation thin layer chromatography, some were present in a fraction with a retardation factor between that of the methyl esters of synthetic monoalicyclic and monoaromatic acids. Ultraviolet absorption spectra of these fractions indicated the presence of benzenoid moieties. SFS of model octahydro- and tetrahydrophenanthroic acids produced emissions at the characteristic excitation wavelengths observed in some OSPW extracts, consistent with the postulations from ultraviolet spectroscopy and mass spectrometry data. We suggest the acids originate from extensive biodegradation of C-ring monoaromatic steroid hydrocarbons and offer a means of differentiating residues at different biodegradation stages in tailings ponds. Structural similarities with estrone and estradiol imply that such compounds may account for some of the environmental estrogenic activity reported in OSPW acid-extractable organics and naphthenic acids.
从阿尔伯塔油砂作业中尾矿池产生的大量、急性毒性、雌激素和抗雄激素的加工影响水，对环境整治构成了重大任务。同步荧光光谱（SFS）表明，油砂加工影响水（OSPW）可能含有芳香羧酸，这些酸是潜在的重要环境毒物之一，但尚未鉴定出这些酸，限制了对雌激素和其他测定结果的解释。在这里，我们表明，对 OSPW 样品中酸的甲酯进行多维综合气相色谱-质谱（GCxGC-MS）分析，产生的质谱与将其分配为 C（19）和 C（20）C 环单芳香羟基甾体酸、D 环开环羟基和非羟基多氢化菲并酸一致，具有一个芳香环和两个脂环，以及 A 环开环甾体酮酸。高分辨率 MS 数据支持几种所谓的“O3”物质的分配。当蒸馏、酯化、OSPW 酸可萃取有机物的馏分被检查时，假定的芳烃主要存在于高沸点馏分中；当用银离子薄层色谱法检查时，一些存在于一个介于合成单脂环和单芳烃酸甲酯之间的滞后因子的馏分中。这些馏分的紫外吸收光谱表明存在苯环部分。模型八氢和四氢化菲并酸的 SFS 产生了在一些 OSPW 提取物中观察到的特征激发波长的发射，与紫外光谱和质谱数据的假设一致。我们认为这些酸源自 C 环单芳香甾体烃的广泛生物降解，并提供了一种区分尾矿池不同生物降解阶段残留物的方法。与雌酮和雌二醇的结构相似性表明，这些化合物可能是 OSPW 酸可萃取有机物和环烷酸中报道的一些环境雌激素活性的原因。
