Phase-shift feedback cavity ring-down spectroscopy.

Phase-shift cavity-enhanced techniques have been used to measure optical losses with relatively simple electronics. Instead of measuring the phase shift, in this work the intensity modulation frequency is varied using feedback to keep the phase shift locked to a target value. The modulation frequency then becomes a signal from which cavity losses can be estimated. The technique is applied with a super luminescent diode to measure losses resulting from the addition of acetylene to a cavity containing nitrogen at ambient temperature and pressure. The technique, phase-shift feedback cavity ring down, is compared to phase-shift cavity ring-down spectroscopy.

Integrated fiber optic incoherent broadband cavity enhanced absorption spectroscopy detector for near-IR absorption measurements of nanoliter samples.

An integrated fiber-optic sensor is described that uses incoherent broadband cavity enhanced absorption spectroscopy for sensitive detection of aqueous samples in nanoliter volumes. Absorption was measured in a 100 µm gap between the ends of two short segments of multimode graded-index fiber that were integrated into a capillary using a precision machined V-grooved fixture that allowed for passive fiber alignment. The other ends of the fibers were coated with dielectric mirrors to form a 9.5 cm optical resonator. Light from a fiber-coupled superluminescent diode was directly coupled into one end of the cavity, and transmission was measured using a fiber-coupled silicon photodiode. Dilute aqueous solutions of near infrared dye were used to determine the minimum detectable absorption change of 2.4×10(-4) under experimental conditions in which pressure fluctuations limited performance. We also determined that the absolute minimum detectable absorption change would be 1.6×10(-5) for conditions of constant pressure in which absorption measurement is limited by electronic and optical noise. Tolerance requirements for alignment are also presented.

Stoichiometry of ozonation of environmentally relevant olefins in saturated hydrocarbon solvents.

The double bond-to-ozone reaction stoichiometry was quantified for ozonation of several environmentally relevant unsaturated fatty acids and monoterpenes in saturated hydrocarbon solvents. Olefins with initial concentrations from 30 microM to 3mM were injected in a solvent (n-hexadecane, nonane, or cyclohexane) while an ozone-oxygen mixture was slowly bubbled through the solution. The number of ozone molecules consumed by the injection was quantified in the outgoing flow, and the expected 1:1 double bond-to-ozone reaction stoichiometry was observed only under subambient temperature conditions (T < 250 K). At room temperature, the effective number of double bonds oxidized by each ozone molecule increased to 2-5, with a higher degree of oxidation occurring at lower initial olefin concentrations. The observed enhancement in the stoichiometry is consistent with a competition between direct ozonation and free radical initiated oxidation of double bonds, with free radicals being produced by slow reactions between dissolved ozone and solvent molecules.

Photochemical aging of secondary organic aerosol particles generated from the oxidation of d-limonene.

Secondary organic aerosol (SOA) particles are generated by reacting d-limonene vapor and ozone in a Teflon reaction chamber. The reaction is carried out in either dry or humid air in darkness. The resulting SOA particles are collected on glass fiber filters, and their photochemical properties are probed using a combination of UV photodissociation action spectroscopy and absorption spectroscopy techniques. Photolysis of limonene SOA in the tropospheric actinic region (lambda > 295 nm) readily produces formic acid and formaldehyde as gas-phase products. The UV wavelength dependence of the photolysis product yield suggests that the primary absorbers in SOA particles are organic peroxides. The relative humidity maintained during SOA particle growth is found to have little effect on the UV wavelength dependence of the photolysis product yield. The data suggest that direct photodissociation processes may play an important role in photochemical processing of atmospheric SOA particles.

Ozonolysis and photolysis of alkene-terminated self-assembled monolayers on quartz nanoparticles: implications for photochemical aging of organic aerosol particles.

Photolysis of alkene-terminated self assembled monolayers (SAM) deposited on Degussa SiO(2) nanoparticles is studied following oxidation of SAM with a gaseous ozone/oxygen mixture. Infrared cavity ring-down spectroscopy is used to observe gas-phase products generated during ozonolysis and subsequent photolysis of SAM in real time. Reactions taking place during ozonolysis transform alkene-terminated SAM into a photochemically active state capable of photolysis in the tropospheric actinic window (lambda > 295 nm). Formaldehyde and formic acid are the observed photolysis products. Photodissociation action spectra of oxidized SAM and the observed pattern of gas-phase products are consistent with the well-established Criegee mechanism of ozonolysis of terminal alkenes. There is strong evidence for the presence of secondary ozonides (1,3,4-trioxalones) and other peroxides on the oxidized SAM surface. The data imply that photolysis plays a role in atmospheric aging of primary and secondary organic aerosol particles.

UV photodissociation spectroscopy of oxidized undecylenic acid films.

Oxidation of thin multilayered films of undecylenic (10-undecenoic) acid by gaseous ozone was investigated using a combination of spectroscopic and mass spectrometric techniques. The UV absorption spectrum of the oxidized undecylenic acid film is significantly red-shifted compared to that of the initial film. Photolysis of the oxidized film in the tropospheric actinic region (lambda > 295 nm) readily produces formaldehyde and formic acid as gas-phase products. Photodissociation action spectra of the oxidized film suggest that organic peroxides are responsible for the observed photochemical activity. The presence of peroxides is confirmed by mass-spectrometric analysis of the oxidized sample and an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is observed. The data strongly imply the importance of photochemistry in aging of atmospheric organic aerosol particles.