Spectrometric methods for the determination of chlorine in crude oil and petroleum derivatives — A review

• Critical evaluation of spectrometric methods for chlorine in petroleum products.
• Reviews on element determination in petroleum have not address the case of chlorine.
• Peculiarities of the spectrometric determination of Cl in petroleum are discussed.
• The spectrometric approaches are detailed and compared to the official methods.
• New trends in chlorine determination in petroleum products are indicated.

Chlorine determination in crude oil is made in order to guarantee that the oil does not contain levels of this element that might cause damages in the oil processing equipment. In petroleum products, the determination of chlorine is made, for instance, to evaluate if there are proper concentrations of organochloride compounds, which are used as additives. Such determinations are currently performed following official guidelines from the ASTM International and from the United States Environmental Protection Agency as well as protocols indicated by the Universal Oil Products. X-ray fluorescence spectroscopy plays an important role in many of these official methods. In contrast, other spectrometric methods based on optical and mass detection are plagued by limitations related to both the fundamental characteristics of non-metals and to the complex sample matrices, which reflects in the small number of articles devoted to these applications. In this review, the current status of the spectrometric methods, especially the role played by X-ray fluorescence spectrometry, is evaluated in terms of the determination of chlorine in crude oil and petroleum derivatives. Comparison of the performance of the methods, limitations and potential new approaches to ensure proper spectrometric determinations of chlorine is indicated.