The NMR free induction decay from a spinning sample having inhomogeneous anisotropic interactions (chemical shifts, first order quadrupole couplings) takes the form of a train of rotational spin echoes. The Fourier transform of the echo envelope is a sharp spectrum from which the effects of anisotropy have been removed. The Fourier transform of the echo shape contains information concerning the anisotropies: This information can be extracted by a moment analysis. The effects of localized homonuclear spin–spin interactions are to convert the ’’isotropic’’ spectrum into a characteristic powder pattern. Second order quadrupole coupling produces a similar effect. It is shown in this case that the usual second-order level shifts cannot be used to calculated this pattern, which must be described by a proper average Hamiltonian theory. Finally it is shown that rotational spin echoes provide a convenient means of studying very slow random molecular rotations (τc≲1 sec).

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Particle size distributions of light-duty vehicle brake wear debris are reported with careful attention paid to avoid sampling biases. Electrical low-pressure impactor and micro-orifice uniform deposit impactor measurements yield consistent size distributions, and the net particulate matter mass from each method is in good agreement with gravimetric filter measurements. The mass mean diameter of wear debris from braking events representative of urban driving is 6 microm, and the number-weighted mean is 1-2 microm for three currently used classes of lining materials: low metallic, semimetallic, and non-asbestos organic (NAO). In contrast, the wear rates are very material dependent, both in number and mass of particles, with 3-4 times higher emissions observed from the low metallic linings as compared to the semimetallic and NAO linings. Wind tunnel and test track measurements demonstrate the appearance of micron size particles that correlate with braking events, with approximately 50% of the wear debris being airborne for the test vehicle in this study. Elemental analysis of the wear debris reveals a consistent presence of the elements Fe, Cu, and Ba in both dynamometer and test track samples.

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The question of the validity of the average Hamiltonian theory is discussed. This is derived from consideration of the Floquet theorem for periodic systems. A perturbation scheme is developed and shown to give an average Hamiltonian equivalent to that obtained from the Magnus expansion. The convergence condition is shown to depend on the existence of resonances. These results are applied to a discussion of pulse spinlocking experiments.

Abstract. The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm−3 h of OH exposure). Therefore, the contribution of light-duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3–7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11–15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the timescale of these experiments, the mixture of organic vapors emitted by newer vehicles appears to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the nonmethane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. By comparing this study with a companion study of diesel trucks, we conclude that both primary PM emissions and SOA production for light-duty gasoline vehicles are much greater than for late-model (2007 and later) on-road heavy-duty diesel trucks.