Evidence on the formation of dimers of polycyclic aromatic hydrocarbons in a laminar diffusion flame.

The role of polycyclic aromatic hydrocarbons (PAHs) in the formation of nascent soot particles in flames is well established and yet the detailed mechanisms are still not fully understood. Here we provide experimental evidence of the occurrence of dimerization of PAHs in the gas phase before soot formation in a laminar diffusion methane flame, supporting the hypothesis of stabilization of dimers through the formation of covalent bonds. The main findings of this work derive from the comparative chemical analysis of samples extracted from the gas to soot transition region of a laminar diffusion methane flame, and highlight two different groups of hydrocarbons that coexist in the same mass range, but show distinctly different behavior when processed with statistical analysis.

On the benefits of using multivariate analysis in mass spectrometric studies of combustion-generated aerosols.

The intricate chemistry of the carbonaceous particle surface layer (which drives their reactivity, environmental and health impacts) results in complex mass spectra. In this respect, detailed molecular-level analysis of combustion emissions may be challenging even with high-resolution mass spectrometry. Building on a recently proposed comprehensive methodology (encompassing all stages from sampling to data reduction), we propose herein a comparative analysis of soot particles produced by three different sources: a miniCAST standard generator, a laboratory diffusion flame and a single cylinder internal combustion engine.

Dimers of polycyclic aromatic hydrocarbons: the missing pieces in the soot formation process.

The soot nucleation process, defined as the transition from molecular precursors to condensed matter, is the less understood step in the whole soot formation process. The possibility that polycyclic aromatic hydrocarbon (PAH) dimers, especially those containing moderate-sized PAHs, can play a major role in soot nucleation is a very controversial issue. Although PAH dimers have often been considered as potential soot precursors, their formation is not thermodynamically favored at a typical flame temperature, their binding energies being considered too weak to allow them to survive in this environment.

A comprehensive protocol for chemical analysis of flame combustion emissions by secondary ion mass spectrometry.

Rationale: Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is used to provide detailed information on the surface chemical composition of soot. An analytical protocol is proposed and tested on a laboratory flame, and the results are compared with our previous measurements provided by two-step laser mass spectrometry (L2MS).

Methods: This work details: (1) the development of a dedicated apparatus to sample combustion products from atmospheric flames and deposit them on substrates suitable for TOF-SIMS analysis; (2) the choice of the deposition substrate and the material of the sampling line, and their effect on the mass spectra; (3) a method to separate the contributions of soot and condensable gas based on impact deposition; and finally (4) post-acquisition data processing.