A newly developed, mobile laser mass spectrometer (resonance-enhanced multiphoton ionization - time-of-flight mass spectrometer, REMPI-TOFMS) was applied to on-line measurements at a waste incineration pilot plant. REMPI-TOFMS combines the optical selectivity of resonance-enhanced multiphoton ionization with a time-of-flight mass analysis to give a two-dimensional analytical method. Special care was taken to build up a sampling and inlet system suitable for on-line measurements of large, semivolatile polycyclic aromatic hydrocarbons (PAHs). An effusive molecular beam inlet in combination with a fixed frequency UV laser (Nd:YAG at 266 nm or KrF excimer at 248 nm) was used. Under these conditions, many different PAHs can be ionized selectively from the complex flue gas matrix. For example, the achieved detection limit for naphthalene is in the 10 parts-per-trillion by volume (pptv) concentration range. Calibration was performed by using external concentration standards supplied in low ppbv concentrations. The instrumentation is sufficiently robust to be operated under industrial conditions at incineration plants, for instance. The REMPI mass spectra can be acquired at 5-50 Hz. Time profiles of the concentrations of different PAHs in the flue gas were monitored with a time resolution of 200 ms. Significant variations in the concentration profile of several PAHs up to mass 276 amu (e.g., benzo[ghi]perylene) and methylated PAHs have been observed while combustion parameters were changing. In summary, it was demonstrated that laser mass spectrometry (REMPI-TOFMS) enables a real-time on-line trace analysis of combustion flue gases or industrial process gases.

A newly developed compact and mobile time-of-flight mass spectrometer (TOFMS) for on-line analysis and monitoring of complex gas mixtures is presented. The instrument is designed for a (quasi-)simultaneous application of three ionization techniques that exhibit different ionization selectivities. The highly selective resonance-enhanced multiphoton ionization (REMPI) technique, using 266-nm UV laser pulses, is applied for selective and fragmentationless ionization of aromatic compounds at trace levels (parts-per-billion volume range). Mass spectra obtained using this technique show the chemical signature solely of monocyclic (benzene, phenols, etc.) and polycyclic (naphthalene, phenathrene, indol, etc.) aromatic species. Furthermore, the less selective but still fragmentationless single photon ionization (SPI) technique with 118-nm VUV laser pulses allows the ionization of compounds with an ionization potential below 10.5 eV. Mass spectra obtained using this technique show the profile of most organic compounds (aliphatic and aromatic species, like nonane, acetaldehyde, or pyrrol) and some inorganic compounds (e.g., ammonia, nitrogen monoxide). Finally, the nonselective ionization technique laser-induced electron-impact ionization (LEI) is applied. However, the sensitivity of the LEI technique is adjusted to be fairly low. Thus, the LEI signal in the mass spectra gives information on the inorganic bulk constituents of the sample (i.e., compounds such as water, oxygen, nitrogen, and carbon dioxide). Because the three ionization methods (REMPI, SPI, LEI) exhibit largely different ionization selectivities, the isolated application of each method alone solely provides specific mass spectrometric information about the sample composition. Special techniques have been developed and applied which allow the quasi-parallel use of all three ionization techniques for on-line monitoring purposes. Thus, a comprehensive characterization of complex samples is feasible jointly using the characteristic advantages of the three ionization techniques. Laboratory applications show results on rapid overview characterization of mineral oil-based fuels and coffee headspace. The first reported field applications include timely resolved on-line monitoring results on automobile exhausts and of waste incineration flue gas.

Irradiation (UV/Vis λ > 290 nm) under nitrogen and oxygen atmosphere significantly affected the structure of dissolved humic material (DHM). Photobleaching of the DHM solution occurred essentially under O 2 atmosphere in conjunction with a decrease in average molecular weight and an increase in acidity due to the disaggregation and photooxidation processes. The structural changes were followed by various separation and analytical methods including capillary zone electrophoresis (CZE), gel permeation chromatography (GPC), Fourier transformation infrared (FTIR), and one-and two-dimensional nuclear magnetic resonance spectroscopy (NMR) as well as pyrolysisfield ionization mass spectrometry (Py-FIMS). The structural investigations showed selective degradations of DHM, especially under oxygen atmosphere. Structures of lignic and lipidic origin were the most photolabile as compared to carbohydrates, alkylbenzenes, or N-containing structures that accumulated in the system. Under nitrogen atmosphere the acids remained fairly stable. Indirect photolysis seems to be the major pathway in degradation of DHM subjected to UV/Vis irradiation.

The amount of volatile organic compounds (VOCs) in indoor air, usually called TVOC (total volatile organic compounds), has been measured using different definitions and techniques which yield different results. This report recommends a definition of TVOC referring to a specified range of VOCs and it proposes a method for the measurement of this TVOC entity. Within the specified range, the measured concentrations of identified VOCs (including 64 target compounds) are summed up, concentrations of non‐identified compounds in toluene equivalents are added and, together with the identified VOCs, they give the TVOC value. The report reviews the TVOC concept with respect to its usefulness for exposure assessment and control and for the prediction of health or comfort effects. Although the report concludes that at present it is not possible to use TVOC as an effect predictor, it affirms the usefulness of TVOC for characterizing indoor pollution and for improving source control as required from the points of view of health, comfort, energy efficiency and sustainability.

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The chiral herbicide dichlorprop (2,4-dichlorophenoxy-2-propionic acid), which is sold and applied as the racemic mixture, was observed to degrade completely in soil within 31 days, with a half-life of 6.6 d. Degradation occurred with enantiomeric selectivity, indicating biologically mediated reactivity as opposed to strictly abiotic degradation. The S-(−)-isomer degraded significantly faster (t 1/2 = 4.4 d) than the R-(+)-isomer (t 1/2 = 8.7 d); this is contrary to other published results that show selective degradation of the R-(+)-enantiomer, although in other media. Soil samples taken from a field plot at increasing time intervals after application of Foxtril, a commercial herbicide formulation, were solvent-extracted and analyzed for total dichlorprop by capillary zone electrophoresis (CZE), using an acetate buffer at pH 4.7. Heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin, a chiral reagent, was then added to the buffer to effect separation of the (+)- and (−)-isomers of dichlorprop. Baseline resolution allowed calculation of relative concentrations (enantiomer ratios) of the two isomers. CZE is a fast and efficient technique for the analysis of ionic organic species (such as the anion of dichlorprop), including their enantiomers, in pesticide formulations as well as in environmental samples. It thus was possible to analyze Foxtril directly after dilution with water for ioxynil (2,6-diiodo-4-cyanophenol) as well as for dichlorprop. Ioxynil also was detected in the soil extract on the day of application. The hydrolysis product [methyl 2-nitro-5-(2,4-dichlorophenoxy) benzoic acid] of bifenox methyl ester, another herbicide component of Foxtril, was detected in the soil samples taken at 17 and 31 d.

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