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Biomedical subjects

A Colmsjö

Publications and source records attributed to A Colmsjö.

15 recordsLinked to original sources

Response mechanisms of thermionic detectors with enhanced nitrogen selectivity.

The response mechanisms of a thermionic detector with enhanced nitrogen selectivity operating in an inert gas environment were investigated. According to accepted theory, the analyte has to contain electronegative functional groups in order for negative ions to be formed by the extraction of electrons from the thermionic source. This leads to a selective detector response for compounds containing nitro groups or multiple halogens. However, in the tests described here, polycyclic aromatic nitrogen hydrocarbons (PANHs), acridines, and carbazoles were used as reference substances. These compounds contain no electronegative functional groups. None of the investigated acridines exhibited any response from the detector, but carbazoles generated a strong structure-related detector response. By examining partial charges for all hydrogens of all individual carbazoles and acridine, it was demonstrated that the acidic hydrogen atom attached to the nitrogen heteroatom of the carbazoles has a strong influence on the detector response. Ionization of carbazoles may occur by dissociation of the nitrogen-hydrogen bond during contact with the thermionic surface. Support for this theory was provided by the linear relationship between the relative detector response and the deprotonization energy of the carbazoles (coefficients of determination of 0.90 and 0.98 for linear and quadratic models, respectively, were obtained). Further, there appeared to be no linear relationship between the detector response and electron affinity of the carbazoles, (R2 value, 0.32). Thus, the mechanism involved in ionization of the carbazoles is probably not direct electron transfer from the thermionic surface to the carbazoles. Principal component analysis (PCA) showed that the thermal conductivity of chemically inert detector gases also has an influence on the detector response. The investigated gases were helium, neon, nitrogen, carbon dioxide, and argon. It was found that thermal conductivity can be used to rank the detector response for the carbazoles, and there was no discernible response when helium, which has the highest thermal conductivity, was used as the detector gas.

Journal Article↗

Determination of gaseous toluene diisocyanate by use of solid-phase microextraction with on-fibre derivatisation.

An SPME method was developed for sampling gaseous 2,4-toluene diisocyanate (2,4-TDI) involving derivatisation of the isocyanate by reacting with dibutylamine (DBA). The TDI-DBA derivative thus formed was determined by LC-MS-MS utilising atmospheric pressure chemical ionisation (APCI). As a first step, DBA was loaded onto a poly(dimethylsiloxane)/divinylbenzene (PDMS-DVB) fibre coating by direct vapour-phase extraction of a highly concentrated diethyl ether solution of DBA. The DBA-loaded fibre was then exposed to an artificially generated atmosphere of gaseous 2,4-TDI. The linearity of the method ranged from 52.8 to 3100 microg m(-3) (6.8 to 400 ppbv) with a sampling time of 60 min. The proposed method has been applied to 2,4-TDI determination in an artificially generated dynamic standard atmosphere, yielding an approximate method detection limit (MDL) of 2 microg m(-3) (0.25 ppbv). This concentration is one twentieth of the Occupational Safety and Health Administration (OSHA) 8-hour time-weighted average (TWA) exposure limit. The sampler with the PDMS-DVB-DBA coating was found to be stable and retains the required amount of DBA for at least 10 days, an important feature for sampling systems with potential in-situ applications.

Journal Article↗

Development of a personal isocyanate sampler based on DBA derivatization on solid-phase microextraction fibers.

The design and evaluation of a portable diffusive sampler for isocyanates is described. The sampler employs dibutylamine (DBA) loaded onto 60-microm polydimethylsiloxane-divinylbenzene (PDMS-DVB) solid-phase microextraction (SPME) fibers. The DBA-isocyanate derivative is then desorbed by sonication and analyzed by LC-MS using atmospheric pressure chemical ionization (APCI). The samplers are calibrated (i.e. the uptake rate is calculated) by exposing them to a known concentration of hexamethylene diisocyanate (HDI) in a standard gas-generation chamber. The uptake rate for the proposed method, at room temperature (25 degrees C), is 1.13 pg (min ppb(v))(-1) and the method detection limit is 3.2 microg m(-3), equivalent to less than 10% of the airborne time-weighted average (TWA) exposure limits recommended by both the National Institute for Occupational Safety and Health (NIOSH) and the American Conference of Governmental Industrial Hygienists (ACGIH). Practical points that should be considered when using the SPME device as a diffusive sampler are discussed.

Air Pollutants, Occupational↗

Characterization of thermally generated aerosols from polyurethane foam.

Isocyanates constitute a group of highly reactive chemicals used on a large scale for the production of flexible polyurethane (PUR) foam. Exposure to isocyanates is known to produce irritation of the mucous membranes and the eyes. Isocyanates also have strong sensitizing properties and may cause occupational asthma. It is therefore important to monitor isocyanate emissions at workplaces. To obtain information for the improvement of isocyanate samplers and for health risk assessments of exposure, the emitted aerosol from two types of flexible PUR foam subjected to thermal degradation was characterized. Particle size distribution and toluene diisocyanate (TDI) concentration in the emitted aerosols were measured. Thermal degradation of flexible PUR foam at temperatures from 250 to 300 degrees C produced an aerosol with a geometric mean particle diameter of 30-50 nm. Between 5% and 9% of the PUR foam was emitted as TDI, and 2% to 6% of TDI monomers were found in the particle phase under the experimental conditions used. The 2,6-TDI isomer was more abundant in the gas phase than in the particle phase.

Aerosols↗

Dynamic microwave-assisted extraction.

An apparatus for extraction of solid matrices has been constructed which utilizes a microwave technique for heating in a dynamic mode. During the extraction, fresh solvent is continuously pumped through the extraction cell, which is maintained at a slight overpressure in order to keep the solvent in a liquid state. The extraction efficiency, which can be easily monitored, has been investigated in a factorial design and validated for polycyclic aromatic hydrocarbons in a reference sediment sample (EC-1). Important parameters were found to be temperature and duration of extraction. Flow-rate had no significant first-order effect on the recovery, but interaction effects with flow-rate were found to be significant. The dynamic microwave-assisted extraction apparatus was demonstrated to yield recoveries equivalent to Soxhlet extraction, but in a much shorter time. Each extraction of EC-1 typically takes 40 min.

Chromatography, High Pressure Liquid↗

Dietary and ethanol induced alterations of the toxikokinetics of toluene in humans.

This study was undertaken to evaluate the influence of a carbohydrate restricted diet, a subacute ethanol intake, and their combined effect on the kinetics of toluene in humans. Eight healthy male volunteers were exposed by inhalation at four different occasions to 200 mg/m3 2H8-toluene for two hours at a work load of 50 W after a one week low (30%) carbohydrate (CH) diet or high (60%) CH diet with (+EtOH) or without (-EtOH) ethanol consumption (47 g ethanol) on the evening before exposure. Deuterium labelled toleune was used to measure the excretion of hippuric acid originating from toluene separately from hippuric acid from other sources. The results indicated that subacute ethanol consumption combined with a carbohydrate restricted diet, may enhance the metabolism of toluene in humans at an exposure concentration of 200 mg/m3. The cumulative amount of hippuric acid excreted in the urine up to 20 hours after the end of exposure in % of the net uptake of toluene was enhanced by 22% (p = 0.05) in the low CH + EtOH compared with the low CH-EtOH experiment. The apparent blood clearance of toluene was 37% higher in the low CH + EtOH than in the low CH-EtOH experiment, but this effect was not statistically significant (p = 0.1). There were no significant changes in the kinetics of toluene as a result of a low carbohydrate diet alone. Neither did subacute ethanol intake without the combination with a carbohydrate restricted diet influence the kinetics of toluene.

Adolescent↗

Toxicokinetics of toluene and urinary excretion of hippuric acid after human exposure to 2H8-toluene.

Nine male volunteers were exposed to 2H8-toluene (200 mg/m3 for two hours during a workload of 50 W) via inspiratory air with the aid of a breathing valve and mouthpiece. Labelled toluene was used to differentiate between hippuric acid originating from exposure to toluene and hippuric acid normally excreted in urine. The total uptake of toluene was 2.2 (standard deviation (SD) 0.2) mmol, or 50% of the amount inhaled. Four hours after the end of exposure 1.4 (SD 0.3) mmol or 65% of the total uptake had been excreted in urine as 2H-hippuric acid and 20 hours after the end of exposure the cumulative excretion of 2H-hippuric acid was 1.8 (SD 0.3) mmol, or 78% of the total uptake. By contrast the cumulative excretion of labelled plus unlabelled hippuric acid exceeded the total uptake of toluene already after four hours. The excretion rate of 2H-hippuric acid was highest, about 5 mumol/min, during exposure and the SD between the subjects was low. The background concentrations of unlabelled hippuric acid in urine were high, however, and there were large differences between subjects. These findings confirm earlier indications that for low exposure, urinary hippuric acid concentration cannot be used for biological monitoring of exposure to toluene.

Adolescent↗

Occupational implications of the chlorofluorocarbon ban in Sweden.

Limitations on the use of full halogenated chlorofluorocarbons (CFCs) may create occupational environmental problems. These are currently largely unknown, because the toxicology of most CFC substitutes is unknown. Therefore, toxicity testing of CFC substitutes is necessary, and this can best be done before their use commences. Destruction of CFC and materials containing CFC could generate new chemical compounds, especially during incineration. In addition, problems with higher noise and vibration levels may occur when CFC substitutes are employed, and we should keep in mind that occupational environment problems could also develop when new routines are introduced for transporting, storing, and handling new materials.

Humans↗

Four different b-type cytochromes in the halophilic archaebacterium, Halobacterium halobium.

The halophilic archaebacterium, Halobacterium halobium has been found to contain four different b-type cytochromes. The four components were recognized by their potentiometric characteristics in situ in their functional environment in the membrane of H. halobium. Oxidation-reduction midpoint potentials of these four b-type cytochromes were determined to be +261, +160, +30, and -153 mV, respectively. We also demonstrate that the pathway involved in the transport of reducing equivalents from succinate to oxygen proceeds through the b-type cytochromes with oxidation-reduction midpoint potentials of +261 and +161 mV. The cytochrome with oxidation-reduction midpoint potential of -153 mV was not substrate reducible by NADH but was chemically reducible by dithionite. Antimycin inhibits reduction of b-type cytochrome in the succinate pathway, but has no effect on b-type cytochrome reduction when reducing equivalents are provided by NADH. The carbon monoxide difference spectrum of H. halobium membranes shows at least one carbon monoxide-binding b-type cytochrome, indicating a terminal oxidase. A scheme for electron transport in H.halobium involving the b-type cytochromes and terminal oxidase is suggested.

Antimycin A↗

Oxidation-reduction potentials and absorption spectra of two b-type cytochromes from the halophilic archaebacterium, Halobacterium halobium.

The oxidation-reduction midpoint potentials were determined for two b-type cytochromes, which had been solubilized from the membrane of Halobacterium halobium and partially purified. The two b-type cytochromes have oxidation-reduction midpoint potentials of 175 and 7 mV, respectively. These b-type cytochromes could also be resolved by difference absorption spectroscopy, which revealed one b-type cytochrome with absorption maximum (alpha-peak) at 558 nm, reducible by ascorbate-tetramethyl-p-phenylenediamine, and the other with absorption maximum (alpha-peak) at 560 nm, reducible by dithionite. Different substrates such as succinate, NADH, and alpha-glycerophosphate were used to study the b-type cytochromes in situ when bound to the membrane in a functional state. Reducing equivalents from succinate and alpha-glycerophosphate appear to enter the respiratory chain at the 175 mV b-type cytochrome. Cytochrome a3 is spectrophotometrically shown to be present in the membrane of H. halobium.

Cytochrome b Group↗

Some chloro derivatives of polynuclear aromatic hydrocarbons are potent mutagens in Salmonella typhimurium.

A series of chlorinations of some polynuclear aromatic hydrocarbons (PAH) were carried out and the products were tested for mutagenicity on Salmonella typhimurium TA98 and TA100. We conclude that the chlorination of certain PAHs with low mutagenicity, such as pyrene and benzo[e]pyrene, resulted in the formation of two types of product. The chlorination of pyrene was studied in some detail. The major products of this chlorination were chloro-substituted pyrenes. These compounds showed an S9-dependent mutagenicity and were identified as 1-chloro-, 1,6-dichloro-, 1,8-dichloro- and 1,3-dichloropyrene. On tester strain TA100 the mutagenic effect ranged from 1.4 to 14 revertants/nmol, 1,3-dichloropyrene being the most potent of the isomers. Minor products eluting from a chromatograph in a more polar fraction than the major products were also formed. These compounds were less stable than the major products and were identified as pyrene with chloro additions in the 4- and 5-positions, with various chloro substituents at other positions. These minor products showed a high mutagenic effect on Salmonella in the absence of S9. The mutagenic effect on strain TA100 ranged from 10 to 15 revertants per ng which is at least 40 and 4000 times higher than for 1-nitropyrene and pyrenequinones, respectively. These unstable chloro derivatives of pyrene are difficult to analyse chemically because they are easily degraded and give rise to the more stable 4-chloropyrene.

Mass Spectrometry↗

Speciation of mercury excreted in feces from individuals with amalgam fillings.

Investigators established methods for the analysis of total mercury (Hg-total), oxidized mercury and mercury bound to sulfhydryl groups (Hg-S), mercury vapor (Hg0), and mercury from amalgam particles (APs) in fecal samples. Two individuals consumed mercury as a mercury-cysteine complex mercury vapor, and mercury from amalgam particles, and the cumulative excretion of mercury in feces was followed. Investigators found that 80% of the mercury from amalgam particles and mercury bound to sulfhydryl groups was excreted, but only 40% of the mercury vapor was excreted. Speciation of mercury excreted in feces from 6 individuals with a moderate loading of amalgam fillings showed that most of the mercury originating from the fillings consisted of oxidized mercury, which was probably bound to sulfhydryl-containing compounds. The proportion of amalgam particles in fecal samples from these individuals was low, and it did not exceed 26% of the total amount of mercury excreted.

Adult↗

Construction and evaluation of an aerosol generating apparatus for combustion products from polyurethane foam.

A system has been constructed and evaluated for generating aerosols from combustion or pyrolysis of various cross-linked polymers. The system consists of an aerosol generator and an aerosol chamber with a sampling compartment designed for various samplers and sampling probes. A geared electric motor assembly is used to lower a polymer strip into the controlled atmosphere of a quartz-lined furnace. The polymer used in this investigation was a polyurethane foam (PUF) based on toluene diisocyanate (TDI). Combustion of the PUF was conducted in filtered air at a temperature of 300 degrees C. The particle number concentration of the generated aerosol was measured by light scattering in the particle size range from 0.1 micron to greater than 5 microns. Air samples were collected periodically in impinger flasks using dibutylamine (DBA) in toluene as derivatization reagent. The TDI-DBA derivatives from the impinger samples were analyzed with high performance liquid chromatography. The aerosol generating system was found to generate a stable, reproducible, and predictable concentration of particles and TDI monomer. Three partial least squares models were created to evaluate the generator. The investigated responses were the TDI concentration, the particle number concentration, and the stability of the particle number concentration during the generating process. The factor with most impact on the concentrations of the generated aerosol was found to be the interaction between linear feeding rate of the polymer strip and the flow rate of combustion gas. For stability the linear feeding rate was the most important.

Aerosols↗