The principle, technical details, and performance of the long path extinction spectrometer (LOPES), a new folded-path extinction cell with a spectral range from the mid-UV (200 nm) to the near infrared (1015 nm), is presented. Using nonabsorbing glass beads the measured extinction spectrum of LOPES was validated by Mie calculations and was compared with scattering coefficients in the visible measured by a three-color integrating nephelometer (TSI, mod. 3563). For absorbing aerosols (here soot and biomass burning aerosol with single-scattering albedos of about 0.2 and 0.74 at 550 nm), LOPES was combined with a TSI 3563 nephelometer to determine the wavelength-dependent absorption coefficients from the difference of the extinction and scattering coefficients. These absorption coefficients were found to agree with the measurements by two state-of-the-art absorption techniques, the multiangle absorption photometry (MAAP) and photoacoustic spectrometry (PAS), which measure the absorption coefficient at the single wavelength of 532 nm and 670 nm, respectively. Finally, based on a comprehensive analysis of the TSI 3563 nephelometer errors and their propagation into the determination of the absorption coefficients from the LOPES and nephelometer data, we discuss implications for improving in situ measurements of the optical properties of atmospheric aerosols.

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The ability of ultraviolet resonance Raman spectroscopy (UVRRS) to determine structural, environmental, and analytical information concerning low-concentration aqueous biomolecules makes it a powerful bioanalytical and biophysical technique. Unfortunately, its utility has been limited by experimental requirements that preclude in situ or in vivo studies in most cases. We have developed the first high-performance fiber-optic probes suitable for long-term use in pulsed UVRRS applications in the deep- UV (DUV, 205-250 nm). The probes incorporate recently developed improved ultraviolet (IUV) fibers that do not exhibit the rapid solarization and throughput decay that previously hampered the use of optical fibers for delivering pulsed, DUV light. A novel 90 degrees mirrored collection geometry is used to overcome the inner-filtering effects that plague flush-probe geometries. The IUV fibers are characterized with respect to their efficacy at transmitting pulsed, DUV laser light, and prototype probes are used to obtain pulsed UVRRS data of aromatic amino acids, proteins, and hormones at low concentrations with 205-240-nm pulsed excitation. Efficient probe geometries and fabrication methods are presented. The performance of the probes in examining resonance-enhanced Raman signals from absorbing chromophores is investigated, and the optimal excitation wavelength is shown to be significantly red-shifted from the maximum of the resonance Raman enhancement profile. Generally applicable procedures for determining optimal experimental conditions are also introduced.

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