Evaluation of the reactivity of exhaust from various biodiesel blends as a measure of possible oxidative effects: A concern for human exposure.

Diesel exhaust particles (DEP) are a major constituent of ambient air pollution and are associated with various adverse health effects, posing a major safety and public health concern in ambient and occupational environments. The effects of DEP from various biodiesel blends on biological systems was investigated using glutathione (GSH) as a marker of possible oxidative effects, based on the decrease in the concentration of GSH at physiological pH. The fluorophoric agent 2,3-naphthalenedicarboxaldehyde (NDA) was used as a selective probe of GSH in the presence of any likely interferents via fluorescence detection. Three different polar solvents (acetonitrile, methanol and water) were used to extract DEP generated during the combustion of different biodiesel blends (5%-99%). Oxidation of GSH to the disulfide (GSSG) was confirmed using electrospray ionization mass spectrometry. A decrease in the concentration of GSH was observed in the presence of DEP extracts from all of the biodiesel blends studied, with reaction rates that depend on the biodiesel blend. Interestingly the reactivity peaked at 50% biodiesel (B50) rather than decreasing monotonically with increased biodiesel content, as was expected. Organic solvent DEP extracts showed wider variations in reactivity with GSH, with methanol extracts giving the largest decrease in GSH concentrations. This may imply a more organic nature of the oxidants in the biodiesel exhaust. It is therefore important to consider ways of reducing concentrations of organic components in biodiesel exhaust that can cause different toxic activity before any blend is offered as a preferred alternative to petroleum diesel fuel.

Optical injection unlocking for cavity ringdown spectroscopy.

Continuous wave cavity ringdown spectroscopy requires a rapid termination of the injection of light into the cavity to initiate the decay (i.e., ringdown) event. We demonstrate a technique that accomplishes this through pulsed optical injection of a second laser into the main laser, resulting in 20-100 MHz frequency shifts in the otherwise cavity-locked main laser sufficient to create ringdown events at 3.5 kHz. Data on the frequency shift as a function of both main laser current and relative wavelength are presented, as well as a demonstration that single exponential decays are maintained in the process.

Discrete sums for the rapid determination of exponential decay constants.

Several computational methods are presented for the rapid extraction of decay time constants from discrete exponential data. Two methods are found to be comparably fast and highly accurate. They are corrected successive integration and a method involving the Fourier transform (FT) of the data and the application of an expression that does not assume continuous data. FT methods in the literature are found to introduce significant systematic error owing to the assumption that data are continuous. Corrected successive integration methods in the literature are correct, but we offer a more direct way of applying them which we call linear regression of the sum. We recommend the use of the latter over FT-based methods, as the FT methods are more affected by noise in the original data.

Membrane introduction mass spectrometry of nonpolar hydrocarbons using nitric oxide chemical ionization.

Selectivity enhancement of membrane introduction mass spectrometry of nonpolar alkanes, alkenes, and aromatic hydrocarbons in air samples by application of nitric oxide chemical ionization (NOCI/MIMS) is demonstrated. Membrane methods are useful for separating compounds (usually nonpolar organics) from air and water samples without costly and time-consuming sample preparation, and coupled with mass spectrometry, they provide good sensitivity. But they often suffer from lack of specificity in mixture analysis, particularly for saturated organics. Nitric oxide chemical ionization is able to produce strong unique ion signals for many hydrocarbon test compounds that can be used to identify and quantify the parent neutrals. Our observed detection limits for a number of test compounds were relatively high; however, the method could potentially be useful for environmental analytical applications (e.g., plume tracking) if the monitored compound was at elevated levels or if NOCI/MIMS is coupled with a trapping method.

Solving chemical problems of environmental importance using cavity ring-down spectroscopy.

Cavity ring-down (CRD) is a sensitive variant of traditional absorption spectroscopy that has found increasing use in a number of chemical measurement applications. This review focuses on applications of cavity ring-down spectroscopy that will be of interest to environmental chemists and analytical chemists working on environmental problems. The applications are classified into direct monitoring approaches, indirect analysis methods and ancillary studies and a differentiation is made between field-tested instruments and proof of principle studies.

Ozone modulation of volatile hydrocarbons using membrane introduction mass spectrometry.

A new method that we describe as chemical modulation of volatile hydrocarbons is investigated using ozonolysis pretreatment and membrane introduction mass spectrometry (MIMS). This extension to the MIMS technique is intended to enhance the selectivity of MIMS for measuring hydrocarbons in the complex mixtures often encountered in polluted air samples. The test samples for this study were dilute (parts per billion by volume, ppbv) two-component hydrocarbon mixtures in synthetic air. Ozone reacted to completely suppress the MIMS signal from beta-pinene in a mixture of toluene and beta-pinene and the MIMS signal from cyclohexene in a mixture of cyclohexene and cyclohexane. As expected, the ozone reaction produced little attenuation of the MIMS signal from toluene and cyclohexane in the test mixtures. The basis of the method is that the products of the ozonolysis, which is rapid for alkenes, are polar compounds that are excluded by the membrane used here, as confirmed in this study. Since the modulation only affects unsaturated hydrocarbons (and other similar organic compounds), the method can be used to aid in quantitative analysis of volatile hydrocarbon compounds in air samples for air pollution monitoring.