The Identification of Polynuclear Aromatic Hydrocarbon (PAH) Derivatives in Mutagenic Fractions of Diesel Particulate Extracts

Abstract

The soluble organic fraction (SOF) of particulate matter from diesel exhaust (from point sources, ambient air, etc.) contains hundreds of organic constituents. Normal-phase high pressure liquid chromatography (HPLC) has been used to separate the SOF into sub-fractions suitable for subsequent chemical analysis and bioassays. These fractions consist of non-polar(PAH), moderately polar (transition) and highly polar constituents. The non-polar fractions have been well characterized and consist of PAH and aliphatic hydrocarbons. The specific compounds present in the transition and polar fractions are for the most part unknown. This analytical information has been difficult to obtain since these compounds are highly labile, polar, of low volatility and in very low concentrations when compared to the bulk of material found in the SOF. Mutagenicity tests using the Ames Salmonella typhimurium assay indicate that the transition fraction accounts for most of the mutagenicity when compared to the non-polar (PAH) and polar fractions.

A variety of chromatographic and mass spectrometric techniques are described that have been used to determine the composition of the HPLC fractions. More than one hundred species have been identified in the transition fraction of diesel particulate matter using high resolution gas chromatography (HRGC)/high resolution mass spectrometry (HRMS), HPLC and direct-probe high resolution mass spectrometry. It has been found that the transition fraction contains mostly PAH derivatives consisting of hydroxy, ketone, quinone, carboxaldehyde, acid anhydride and dihydroxy derivatives of PAH. Three nitro-PAH species have been tentatively identified and 1-nitropyrene positively identified in the transition fraction. The 1-nitropyrene was found to account for approximately 45% and 30% of the direct-acting mutagenicity observed for the transition fraction and total extract, respectively. The HPLC separation procedure was shown to give better than 95% recovery of the mass and mutagenic activity. The problem of PAH oxidation during the analytical procedures and possible effect on bioassay results are discussed.     

Charge transfer and stability of NFE random alloys

The stability of random alloys is determined primarily by a balance between the energy of the volume change upon alloy formation (elastic energy), and the charge transfer between atomic cells. The charge transfer in homovalent, nearly free electron alloys was determined by taking the wave function to be that of the free atoms inside the ion cores, and to be plane waves in the interstitial regions. For a given valence, it was possible to establish an electronegativity series based on charge transfer, to determine charge transfer as a function of composition, and to compute the energy of alloy formation. The theory properly accounts for the formation of alloys of the alkali and alkaline earth metals, and shows why so few such alloys form.     

Noise suppression using the coherent onion peeler

An innovative noise suppression algorithm, called the coherent onion peeler (COP) (patent detained) is derived by minimizing the error in the coherent subtraction of the data from a single plane wave model. The COP solution "collapses" for all beamforming algorithms to the same solution at the complex hydrophone FFT level. Thus, any beamformer can be applied to the residual FFTs after the COP has been applied. The COP is applied to the strongest interferer first and the residual FFTs represent the acoustic field with this interferer coherently "peeled back" like the outer skin of an onion. This procedure can be repeated any number of times to coherently suppress the noise from all interferers present. A new nonadaptive beamformer is developed that "blends" together the best beam pattern properties of conventional beamforming (CBF) near array design frequency and the generalized fourier integral method (GFIM) at very low frequencies (VLF). In between these frequency extremes, the GFIM-CBF Blend (patent pending) (G-C Blend) is a frequency-dependent weighted average of both individual beamformers. COP and G-C Blend are applied to the broadband noise emitted by the tow ship, which severely degrades the performance of the towed array; COP reduced this broadband noise by over 19 dB in a single pass.