Effects of temperature and soil on yields and identities of light gases (H-2, CH4, C2H2, C2H4, C2H6, CO, and CO2) and polycyclic aromatic hydrocarbons (PAH) from thermal treatment of a pyrene-contaminated (5 wt%) soil in the absence of oxygen were determined for a U.S. EPA synthetic soil matrix prepared to proxy U.S. Superfund soils. Shallow piles (140-170 mg) of contaminated soil particles and as controls, neat (non-contaminated) soil (140-160 mg), neat pyrene (10-15 mg), neat sand (230 mg), and pyrene-contaminated sand (160 mg), were heated in a ceramic boat inside a 1.65 cm i.d. pyrex tube at temperatures from 500 to 1100 degrees C under an axial flow of helium. Volatile products spent 0.2-0.4 s at temperature before cooling. Light gases, PAH and a dichloromethane extract of the residue in the ceramic boat, were analyzed by gas chromatography or high pressure liquid chromatography (HPLC). Over 99% pyrene removal was observed when heating for a few tens of seconds in all investigated cases, i.e., at 500, 650, 750, 1000, and 1100 degrees C for soil, and 750 and 1000 degrees C for sand. However, each of these experiments gave significant yields (0.2-16 wt% of the initial pyrene) of other PAH, e.g., cyclopenta[cd]pyrene (CPP), which mutates bacterial cells and human cells in vitro. Heating pyrene-polluted soil gave pyrene conversions and yields of acetylene, CPP, and other PAH exceeding those predicted from similar, but separate heating of neat soil and neat pyrene. Up to 750 degrees C, recovered pyrene, other PAH, and light gases accounted for all or most of the initial pyrene whereas at 1000 and 1100 degrees C conversion to soot was significant. A kinetic analysis disentangled effects of soil-pyrene interactions and vapor phase pyrolysis of pyrene. Increase of residence time was found to be the main reason for the enhanced conversion of pyrene in the case of the presence of a solid soil or sand matrix. Light gas species released due to the thermal treatment, such as acetylene and methane, lead the formation of other, pyrene-derived PAH, e.g., methylpyrenes, cyclopenta[cd]pyrene, and benzo[a]pyrene. Implications of these findings for the chemistry of soil thermal decontamination and for diagnosing potential defects in soil thermal cleaning, e.g., incomplete elimination of targeted pollutants and formation of adverse by-products, are discussed. (c) 2005 Elsevier B.V. All rights reserved.