Abstract. Understanding the sources of volatile organic compounds (VOCs) is essential for ground-level ozone and secondary organic aerosol (SOA) abatement measures. We made VOC measurements at 27 sites and online observations at an urban site in Beijing from July 2009 to January 2012. Based on these measurement data, we determined the spatial and temporal distribution of VOCs, estimated their annual emission strengths based on their emission ratios relative to carbon monoxide (CO), and quantified the relative contributions of various sources using the chemical mass balance (CMB) model. These results from ambient measurements were compared with existing emission inventories to evaluate the spatial distribution, species-specific emissions, and source structure of VOCs in Beijing. The measured VOC distributions revealed a hotspot in the southern suburban area of Beijing, whereas current emission inventories suggested that VOC emissions were concentrated in downtown areas. Compared with results derived from ambient measurements, the annual inventoried emissions of oxygenated VOC (OVOC) species and C2–C4 alkanes may be underestimated, while the emissions of styrene and 1,3-butadiene may be overestimated by current inventories. Source apportionment using the CMB model identified vehicular exhaust as the most important VOC source, with the relative contribution of 49%, in good agreement with the 40–51% estimated by emission inventories. The relative contribution of paint and solvent utilization obtained from the CMB model was 14%, significantly lower than the value of 32% reported by one existing inventory. Meanwhile, the relative contribution of liquefied petroleum gas (LPG) usage calculated using the CMB model was 6%, whereas LPG usage contribution was not reported by current emission inventories. These results suggested that VOC emission strengths in southern suburban area of Beijing, annual emissions of C2–C4 alkanes, OVOCs and some alkenes, and the contributions of solvent and paint utilization and LPG usage in current inventories all require significant revisions.

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The thermal decomposition of 3,4-dihydro-2H-pyran (DHP, C~H B O ) has been investigated by two methods: in shock waves with the laser-schlieren technique using mixtures of 5 and 10% DHP in krypton over 900-1500 K, 110-560 torr; in a flow tube having a reaction pressure 0.5 torr above atmospheric, using the decomposition of allylethyl ether as an internal standard, and covering 663-773 K. The retro-DielsAlder dissociation to the stable acrolein and ethylene is the dominant channel for all conditions. Precise rate constants (rms deviation of 10%) were obtained for this process over the indicated temperature ranges. Unimolecular falloff is evident in the shock-tube results, and RRKM calculations also predict a slight falloff a t the lower temperatures. These RRKM calculations use a routine vibration model transition state and agree closely with the high-temperature data when (AE)down is a fured 400 cm-'. Arrhenius expressions for k, derived from the two measurements are in close accord and also consistent with most previous studies of this reaction. 0 1995 John Wiley & Sons, Inc.

The structural phase transition of a single-crystal Ni lattice upon dissolving Ta solute atoms is investigated by means of molecular-dynamics simulations with a realistic n-body Ni-Ta potential. It is found that when the solute concentration is within 9-19 at. % of Ta, the accumulated strain results in a martensitic phase transition, i.e., face-centered-cubic ͑fcc͒ Ni transforms into a face-centered-orthorhombic-͑fco͒ like structure through shearing, and that when the solute concentration is over 21 at. % of Ta, the Ni lattice collapses and turns into an amorphous state. Comparatively, for the case of an initial hcp Ni lattice, the same martensitic and amorphization transitions also take place. The former hcp-fco transition, however, is mainly through atomic rearrangement as well as readjustment of lattice parameters, and the resultant state is almost perfect single crystal with no shearing bands. Besides, the above structural transitions are frequently in association with a dramatic softening in shear elastic moduli.

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