RESUMEN

Mass spectrometry (MS) is an established analytical technique to analyze evolved gas in thermogravimetry (TG). In this study, for the first time a novel SPI-MS technique using an electron beam pumped VUV excimer lamp as photon source (lambda = 126 nm) was employed in conjunction with thermogravimetry. The coupling was achieved with an improved heated interface and adjacent transfer capillary between TG and ion source of a quadrupole mass spectrometer. The feasibility of this approach was proven by investigating semivolatile substances such as long-chain alkanes (heptadecane C17H36), polymers, e.g., polystyrene, polycarbonate, and acrylonitrile-butadiene-styrene, polymer mixtures and blends. Mass spectra with almost no fragmentation were obtained, and quantification of selected substances could be achieved. Polymer mixtures could be distinguished by their SPI mass spectra, and the effect of premixing of polymers has been accessed. Its unique attributes render the TA-SPI-MS method a promising new tool for quantitative and qualitative evaluation of complex organic thermal degradation products.

RESUMEN

Several ionization potentials (IPs) of security relevant substances were determined with single photon ionization time of flight mass spectrometry (SPI-TOFMS) using monochromatized synchrotron radiation from the "Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung" (BESSY). In detail, the IPs of nine explosives and related compounds, seven narcotics and narcotics precursors, and one chemical warfare agent (CWA) precursor were determined, whereas six IPs already known from the literature were verified correctly. From seven other substances, including one CWA precursor, the IP could not be determined as the molecule ion peak could not be detected. For these substances the appearance energy (AE) of a main fragment was determined. The analyzed security-relevant substances showed IPs significantly below the IPs of common matrix compounds such as nitrogen and oxygen. Therefore, it is possible to find photon energies in between, whereby the molecules of interest can be detected with SPI in very low concentrations due to the shielding of the matrix. All determined IPs except the one of the explosive EGDN were below 10.5 eV. Hence, laser-generated 118 nm photons can be applied for detecting almost all security-relevant substances by, e.g., SPI-TOFMS.

Asunto(s)

RESUMEN

Orthogonal acceleration time-of-flight mass spectrometers (oaTOFMS), which are exhibiting a pulsed orthogonal extraction of ion bunches into the TOF mass analyzer from a continuous primary ion beam, are well-suited for continuous ionization methods such as electron impact ionization (EI). Recently an electron beam pumped rare gas excimer lamp (EBEL) was introduced, which emits intensive vacuum UV (VUV) radiation at, e.g., 126 nm (argon excimer) and is well suited as the light source for soft single photon ionization (SPI) of organic molecules. In this paper, a new compact oaTOFMS system which allows switching between SPI, using VUV-light from an EBEL-light source, and conventional EI is described. With the oaTOFMS system, EBEL-SPI and EI mass spectral transients can be recorded at very high repetition rates (up to 100 kHz), enabling high duty cycles and therefore good detection efficiencies. By using a transient recorder card with the capability to perform on-board accumulation of the oaTOF transients, final mass spectra with a dynamic range of 106 can be saved to the hard disk at a rate of 10 Hz. As it is possible to change the ionization modes (EI and SPI) rapidly, a comprehensive monitoring of complex gases with highly dynamic compositions, such as cigarette smoke, is possible. In this context, the EI based mass spectra address the bulk composition (compounds such as water, oxygen, carbon dioxide, etc. in the up to percentage concentration range) as well as some inorganic trace gases such as argon, sulfur dioxide, etc. down to the low ppm level. The EBEL-SPI mass spectra on the other hand are revealing the organic composition down to the lower ppb concentration range.

Asunto(s)

RESUMEN

Soft laser photo-ionization mass spectrometry is presented as a separation dimension hyphenated with gas chromatographic techniques. Single photon ionization (SPI) is a universal soft ionization method which ionizes organic molecules with an ionization potential below 10.5 eV if 118 nm laser radiation is used. The inherently soft ionization of photo ionization techniques can further be utilized together with gas chromatography as a comprehensive two-dimensional separation method (GC x MS), using the GC retention time as first separation dimension and the molecular mass as second separation dimension. Some GC x MS chromatograms of diesel petroleum samples using SPI are presented and discussed. Finally, it is demonstrated that the coupling of soft SPI mass spectrometry with comprehensive two-dimensional gas chromatography (GC x GC) provides a three-dimensional separation technique (GC x GC x SPI-MS).

Asunto(s)

RESUMEN

Resonance-enhanced multiphoton ionization (REMPI) combined with time-of-flight mass spectrometry (TOFMS) is an analytical method capable of on-line monitoring of trace compounds in complex matrices. A necessary prerequisite for substance selective detection is spectroscopic investigation of the target molecules. Several organic nitrogen compounds comprising aliphatic and aromatic amines, nitrogen heterocyclic compounds, and aromatic nitriles are spectroscopically investigated with a tunable narrow bandwidth optical parametric oscillator (OPO) laser system providing a scannable wavelength range between 220 and 340 nm. These species are known as possible precursors in fuel-NO formation from combustion of solid fuels such as biomass and waste. A newly conceived double inlet system was used in this study, which allows rapid change between effusive and supersonic molecular beams. The resulting REMPI spectra of the compounds are discussed with respect to electronic transitions that could be utilized for a selective ionization of these compounds in complex mixtures such as combustion and process gases. The practicability of this approach is demonstrated by wavelength selected on-line REMPI-TOFMS detection of aniline and cyanonaphthalene in the burning chamber of a waste incineration plant. REMPI mass spectra recorded at different excitation wavelengths as well as variations in time show the utilization of species-selective REMPI-TOFMS detection for on-line monitoring of crucial substances in pollutant formation.

Asunto(s)

RESUMEN

On-line analysis of trace and bulk gas compounds in the burning chamber of a waste-incineration plant has been performed, with high temporal resolution, by use of a variety of distinctly different measurement techniques. Time-of-flight mass spectrometry was performed with simultaneous use of three ionization techniques-resonance-enhanced multiphoton ionization (REMPI), single-photon ionization (SPI), and electron-impact ionization (EI). Chemical-ionization mass spectrometry (CIMS), Fourier-transform infrared spectrometry (FTIR), and electrochemical methods were also used. Sampling was conducted by means of a newly developed air-cooled stainless steel lance, to cope with the high temperatures and elevated particle concentrations at the sampling location. Nitrogen species were mainly nitrogen monoxide, ammonia, and hydrogen cyanide (HCN), with a small amount (approximately 0.3%) of aromatic nitrogen compounds. NO, NH(3), and HCN are the main contributors to the NO(x)-formation process in the postulated fuel-NO reaction scheme dominant at this location. The NO recycling process thereby plays a major role. Changes in plant operating conditions have a noticeable impact only when the air supply is varied. For example, reduction of oxygen leads to an increase in the HCN fraction of the total nitrogen content and a decrease in the NO fraction, and vice versa.

Asunto(s)

RESUMEN

Single-photon ionization (SPI) using vacuum ultraviolet (VUV) light produced by an electron beam pumped rare gas excimer source has been coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). The novel device enables real-time on-line monitoring of organic trace substances in complex gaseous matrixes down to the ppb range. The pulsed VUV radiation of the light source is employed for SPI in the ion source of the TOFMS. Ion extraction is also carried out in a pulsed mode with a short time delay with respect to ionization. The experimental setup of the interface VUV light source/time-of-flight mass spectrometer is described, and the novel SPI-TOFMS system is characterized by means of standard calibration gases. Limits of detection down to 50 ppb for aliphatic and aromatic hydrocarbons were achieved. First on-line applications comprised real-time measurements of aromatic and aliphatic trace compounds in mainstream cigarette smoke, which represents a highly dynamic fluctuating gaseous matrix. Time resolution was sufficient to monitor the smoking process on a puff-by-puff resolved basis. Furthermore, human breath analysis has been carried out to detect differences in the breath of a smoker and a nonsmoker, respectively. Several well-known biomarkers for smoke could be identified in the smoker's breath. The possibility for even shorter measurement times while maintaining the achieved sensitivity makes this new device a promising tool for on-line analysis of organic trace compounds in process gases or biological systems.

Asunto(s)

RESUMEN

A new built instrument suitable for laser desorption-single photon ionization time-of-flight mass spectrometry (LD-SPI-TOFMS) with use of Vacuum-UV photons with a wavelength of 118 nm was used for the analysis of organic compounds. Fragmentation-free analysis of a variety of substances was achieved for desorption experiments with pure compounds desorbed from quartz glass filters applying low desorption energies. It was further found that the rate of fragmentation is strongly dependent on the desorption energy. Matrix effects were investigated by desorption experiments utilizing soot spiked with several organic compounds.The characteristics of the desorption process are assessed in more detail and the impact on the analysis of ambient particulate matter (PM) samples on filters are discussed. First results obtained from the application of the technique to the analysis of organic compounds from ambient PM are presented. Furthermore, possibilities of future developments of the method, in particular for analysis of ambient PM, are discussed.

RESUMEN

The application of soft ionization methods for mass spectrometry (MS), such as single-photon ionization (SPI) using vacuum ultraviolet (VUV) light, provides powerful analytical instrumentation for real-time on-line monitoring of organic substances in gaseous matrixes. A compact and mobile quadrupole mass spectrometer (QMS) system using a novel electron beam pumped rare gas VUV lamp for SPI has been developed for on-line analysis of organic trace compounds (ppb concentrations). The VUV radiation of the light source is employed for SPI in the ion source of the QMS. The concept of the interfacing of the VUV light source with the QMS is described and the SPI-QMS is characterized. On-line detection limits down to 50 ppb for benzene, toluene, and m-xylene were achieved. The instrument is well suited for continuous measurements of aromatic and aliphatic trace compounds and can therefore be used for on-line monitoring of trace compounds in dynamically fluctuating process gases. First measurements of gas standards, petrochemical samples, and on-line monitoring of automotive exhaust are presented.

RESUMEN

The emission of particulate matter and gaseous compounds during combustion of wood and refuse-derived fuel in a small batch reactor is investigated by laser mass-spectrometric on-line measurement techniques for gas-phase analysis and simultaneous registration of physical aerosol properties (number size distribution). The gas-phase composition is addressed by a laser-based mass spectrometric method, namely, vacuum-UV single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS). Particle-size distributions are measured with a scanning mobility particle sizer. Furthermore, a photoelectric aerosol sensor is applied for detection of particle-bound polycyclic aromatic hydrocarbons. The different phases of wood combustion are distinguishable by both the chemical profiles of gas-phase components (e.g., polycyclic aromatic hydrocarbons, PAH) and the particle-size distribution. Furthermore, short disturbances of the combustion process due to air supply shortages are investigated regarding their effect on particle-size distribution and gas-phase composition, respectively. It is shown that the combustion conditions strongly influence the particle-size distribution as well as on the emission of particle-bound polycyclic aromatic hydrocarbons.

Asunto(s)

RESUMEN

This paper reports on a newly developed mobile mass spectrometer for comprehensive on-line analysis of complex gas mixtures such as ambient air or industrial process gases. Three ionization methods, namely, the resonance-enhanced multiphoton ionization (REMPI), vacuum-ultraviolet single-photon ionization (SPI), and electron impact ionization (EI) are implemented in this instrument and can be operated (quasi-) simultaneously. By means of this setup, a wide range of compounds can be analyzed due to the unique ionization selectivitiy and sensitivity profiles provided by the different ionization techniques. The mass spectrometer is designed for field application even under severe conditions. The REMPI technique is suitable for the selective and soft ionization (without fragmentation) of aromatic compounds at trace level (ppbv/pptv). The also soft but less selective SPI technique with 118-nm vacuum-ultraviolet laser pulses is used as a second laser-based ionization method. Mass spectra obtained by this technique show profiles of most organic compounds (aliphatic and aromatic species) and of some low IP inorganic substances (e.g., ammonia, nitrogen oxide) down to ppbv concentrations. In addition to the laser-based ionization techniques, EI ionization can be used for analysis of the bulk components such as water, oxygen, nitrogen, and carbon dioxide as well as for detection of inorganic minor components such as HCN or HCl from combustion flue gases at ppmv concentration levels. Each method yields specific mass spectrometric information of the sample composition. Special techniques have been developed to combine the three ionization methods in a single mass spectrometer and to allow the quasi-parallel application of all three ionization techniques.

RESUMEN

A newly conceived compact and mobile time-of flight mass spectrometer (TOFMS) for real-time monitoring of highly complex gas mixtures is presented. The device utilizes two selective and sensitive soft ionization techniques, viz., resonance-enhanced multiphoton ionization (REMPI) and single-photon ionization (SPI) in a (quasi)-simultaneous mode. Both methods allow a fragmentationless ionization. The REMPI method selectively addresses aromatic species, while with SPI applying vacuum ultaviolet light (118 nm) in principle all compounds with an ionization potential below 10.5 eV are accessible. This provides comprehensive information of the chemical composition of complex matrixes. The combustion and pyrolysis behavior of five organic materials typically used in steel processing in China was studied. The trace amounts of organic compounds in the gas phase during combustion and pyrolysis were monitored selectively and sensitively by real-time SPI/REMPI-TOFMS. The measurements were carried out at several constant temperatures in the range from 300 to 1190 degrees C in both synthetic air and nitrogen. Timely resolved mass spectra reveal the formation and subsequent growth of aromatic molecules. At lower temperatures, highly alkylated PAHs predominate, while at temperatures above 800 degrees C, the more stable benzene and PAHs without side chains prevail. Potential hyphenation of SPI/REMPI-TOFMS to methods of thermal analysis is discussed.

RESUMEN

Fast on-line detection of organic compounds from complex mixtures, such as industrial process gas streams, require selective and sensitive analytical methods. One feasible approach for this purpose is the use of mass spectrometry (MS) with a selective and soft (fragment-free) ionization technique, such as chemical ionization (CI) or photo ionization (PI). Single photon ionization (SPI) with vacuum ultraviolet (VUV) light is a particularly sof tionization technique, well-suited for detection of both aromatic and aliphatic species. Problematic, however, is the generation of the VUV light. In general, the vacuum ultraviolet (VUV) light sources for SPI-MS are based either on lasers (e.g., 118-nm radiation generated by frequency-tripling of the third harmonic of a Nd:YAG laser) or on conventional VUV lamps, such as deuterium lamps. Althoughthe laser-based techniques are very sophisticated and expensive, the conventional lamps have serious drawbacks regarding their optical parameters, such as low-output power, low spectral power density, and broad emission bands. In this work, a novel excimer VUV light source, in which an electron beam is used to form rare gas excimer species, is used. The excimer VUV light sourceproduces brilliant and intense VUV light. The novel VUV light source was coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). A special interface design, including optical (VUV optics) as well as electronic measures (e.g., pulsed ion extraction) was realized. The use of the excimer VUV lamp for SPI will allow the realization of very compact, rugged, and sensitive SPI-TOFMS devices, which preferably will be adapted for process analytical application or monitoring issues (e.g., chemical warfare detection). The excimer VUV-lamp technology delivers VUV light with a good beam quality and high-output power at low costs. Furthermore, it allows changing the emitted wavelength as well as the bandwidth of the excimer VUV lamp in t he 100-200-nm region by changing the gas filling. Consequently, SPI-TOFMS with an excimer light source is a fast detection technique that can be used for online monitoring, for example, in environmental studies or industrial manufacturing processes. In this paper, technology and characteristics of the new excimer light source, as well as the combination with the TOFMS, are presented. Furthermore, a first characterization of the SPI-TOFMS instrument, regarding analytical parameters such as detection limits and selectivity, is given. This includes a discussion of potential improvements that probably will be achievable within a future prototype genertation. Finally, first applications of the system for on-line measurement of organic trace species in a complex gas mixture (here, motorcycle exhaust gas) are presented.

RESUMEN

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.

RESUMEN

A total of 624 respiratory specimens from 543 patients (418 Belgian, 110 Rwandan, and 15 Colombian patients) were tested for the presence of Mycobacterium tuberculosis by the Mycobacterium Tuberculosis Direct Test (MTDT, Gen-Probe). Compared to culture, the MTDT on 497 samples of sputum or broncho-alveolar lavage from Belgium had a sensitivity, specificity and positive and negative predictive value of 86.4%, 96.0%, 50.0% and 99.3% respectively. The pooled results for Rwanda (112 specimens) and Colombia (15 specimens) were 97.8%, 65.7%, 88.2%, 92% respectively. After resolution of discrepant results by taking into account the clinical data, the results for the Belgian patients were 86.9%, 96.2%, 52.6%, 99.3% respectively, and for the Rwandan-Colombian patients 98.1%, 100%, 100% and 92% respectively. Results could be improved by testing more than one specimen from each patient and the inclusion of an internal control to detect inhibitors of the reaction. Culture remains necessary for drug susceptibility tests and the isolation and identification of non-tuberculous mycobacteria.

Asunto(s)

Asunto(s)

RESUMEN

Multiresistant tuberculoses are on the increase. The conversion rates in "additional" therapy are only modest. 17 multiresistant patients and 6 treatment-refractory tuberculoses were treated by us with ofloxacin-cycloserin-protionamide-INH. 16 of these patients were HIV positive. 21 patients converted after 3 months of treatment by the latest. 3 patients died of HIV syndrome. There was otherwise no difference between HIV positive and HIV negative patients. As a rule, the combination was well tolerated. In multiresistant tuberculosis, it is mandatory to administer at least 3 drugs to which there is no resistance.

Asunto(s)

RESUMEN

This prospective randomised study compares 100 each HIV negative und HIV positive patients suffering from pulmonary tuberculosis, under hospital conditions. Both groups are similar in respect of age and sex. Tuberculin anergy exists in 24% of the patients of the HIV positive group. Symptomatology and complaints are analogous. HIV positive patients excrete a greater quantity of tuberculosis bacilli. There is no difference between both groups in respect of sputum conversion. The HIV negative group has a comparatively greater number of tuberculous cavities, whereas the positive group has more infiltrations. Radiological regression is more rapid and marked in the HIV-negative group, and weight increase is also superior, plus a definite regression of the sedimentation reaction and correction of anaemias. Drug tolerance is equally good in both groups. There is a difference in respect of social status and profession.

Asunto(s)

RESUMEN

OBJECTIVES: To study the demographic, clinical, radiographic and diagnostic features, the clinical course and therapeutic response of pulmonary cryptococcosis in HIV-1-infected patients. DESIGN: Retrospective review. SETTING: The Department of Medicine of an urban reference hospital in Central Africa. METHODS: All the records of HIV-1-infected patients with pulmonary cryptococcosis were reviewed retrospectively with regard to the parameters described above. RESULTS: Over a 3-year period, pulmonary cryptococcosis was diagnosed in 37 HIV-1-infected Rwandan patients (21 men, 16 women; mean age, 35 years; range, 26-55 years). Twenty-nine patients (78%) had primary pulmonary cryptococcosis. Cough (94%), weight loss (65%), fever (51%), dyspnoea (46%), thoracic pain (30%), headache (13%) and haemoptysis (8%) were the predominant clinical findings. A diffuse interstitial infiltrate on chest radiograph was observed in 76% of the patients, an alveolar pattern in 19%, mediastinal and/or hilar adenopathy in 11%, nodules and pleural effusion each in 5%. Bronchoalveolar lavage, with a yield of 82%, was found to be the most sensitive diagnostic procedure. Screening of cryptococcal antigen in the serum failed to detect cases of primary pulmonary cryptococcosis. Twelve patients with primary pulmonary cryptococcosis treated with itraconazole as acute and maintenance therapy were all protected against disseminated cryptococcal disease; seven out of 10 (70%) of those who did not receive a specific anticryptococcal drug developed disseminated cryptococcal disease. CONCLUSION: Pulmonary cryptococcosis is not a rare complication of HIV-1 infection in Rwanda. Its clinical and radiographic patterns are non-specific and bronchoalveolar lavage is the procedure of choice for its diagnosis. The natural history of untreated primary pulmonary cryptococcosis is disseminated cryptococcal disease. Itraconazole is highly effective in the prevention of disseminated cryptococcal disease in patients with primary pulmonary cryptococcosis.

Asunto(s)

RESUMEN

In a placebo-controlled double-blinded study with ten healthy volunteers and ten patients with obstructive airway disease, the effect of the test compound on respiratory function was measured. Results show that in healthy persons as well patients with obstructive lung disease of slight to moderate degree respiratory functions were not impaired.

Asunto(s)