Atomic spectrometric methods for the determination of metals and metalloids in automotive fuels--a review.

Gasoline, diesel, ethanol and more recently also biodiesel are the four types of fuel used for automobile, truck and other transportation vehicle. The presence of metallic and metalloid species in automotive fuels is undesirable, except in the form of additives in order to improve specific characteristics of the fuel. Metallic or metalloid elements may derive from the raw product, such as nickel and vanadium in petroleum-based fuel or phosphorus in biodiesel, or they may be introduced during production and storage, such as copper, iron, nickel and zinc in case of petroleum-based fuel and alcohol or sodium and potassium in the case of biodiesel. The most famous additive to fuel is undoubtedly lead, the use of which has been banned or drastically reduced now in many countries of the world. The problems related to the trace element content may be economic, such as fuel degradation and poisoning of automotive catalysts, and/or environmental, such as the emission of metal compounds to the atmosphere. The analytical methods that have been developed for metal and metalloid quantification in automotive fuel are reviewed in this article. The main atomic spectrometric techniques used for trace metal and metalloid determination in fuels, particularly atomic absorption spectrometry with flames, graphite furnaces and with chemical vapor generation, and inductively coupled plasma coupled with optical emission and mass spectrometry are presented, including the different sample preparation procedures proposed for these techniques.

Identification of alkyl carbazoles and alkyl benzocarbazoles in Brazilian petroleum derivatives.

Carbozoles are important compounds in crude oils, as they may be used as geochemical tracers, being the major type of nitrogen compounds in petroleum. At the same time, they are regarded as undesirable due to the problems they may cause in the refining process, such as catalyst poisoning, corrosion, gum or color formation in final products. As separation and identification of carbazoles are challenging goals, this work presents a chromatographic method, made of a pre-fractionation on neutral alumina followed by the separation and identification of two classes of carbazoles using FeCl(3)/Chromossorb W and gas chromatograph with mass spectrometer (GC/MS) (SIM-single ion monitoring mode) analysis. For the first time, a series of alkyl carbazoles and alkyl benzocarbazoles were identified in heavy gas oil (HGO) and atmospheric residue of distillation (ARD) obtained from Brazilian petroleum.