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PubMed2003

Evaluation of relationships between mainstream smoke acetaldehyde and "tar" and carbon monoxide yields in tobacco smoke and reducing sugars in tobacco blends of U.S. commercial cigarettes.

Mainstream (MS) smoke acetaldehyde (AA), carbon monoxide (CO), and "tar" yields and percentage total reducing sugars in the tobacco blends from a Philip Morris USA database of a large number of commercial U.S. cigarettes were analyzed. MS smoke acetaldehyde is significantly correlated with "tar" yield and also with MS smoke carbon monoxide. These correlations are consistent with recently available data, including the 1999 Massachusetts Benchmark Study. MS smoke acetaldehyde yield is not correlated with reducing sugar (RS) concentration in the tobacco blend. For the available data over the time period 1985-1993, the concentration of reducing sugars (mean values for the brands tested) decreased. The correlations found between MS smoke acetaldehyde yield and "tar" and MS smoke carbon monoxide, and the percentage of the variance in AA yield explained by "tar" and MS smoke CO, coupled with the lack of correlation between "tar" normalized MS smoke AA and RS, plus related pyrolysis studies, support the hypothesis that MS smoke acetaldehyde yields are affected more by cigarette design characteristics influencing total smoke production than by tobacco reducing sugars.

Acetaldehyde↗

PubMed1996

Sonolysis of ubiquinone in aqueous solutions. An EPR spin-trapping study.

Free radical formation in aqueous solutions of ubiquinone (coenzyme Qo) induced by ultrasound was studied by EPR and spin trapping with 3,5-dibromo-4-nitrosobenzene sulphonate. When aqueous solutions of ubiquinone were sonicated with 50-kHz ultrasound in the presence of argon or nitrogen, radicals formed by addition of.OH or.H to the double bonds of the ubiquinone ring and methyl radicals were observed as the major spin adducts. The methyl radicals were formed by pyrolysis of ubiquinone. These radicals led to the degradation of ubiquinone. The reduced from of ubiquinone, ubiquinol, was formed by sonication in the presence of argon, and its formation was prevented by addition of native but not of denatured superoxide dismutase. Sodium formate, which scavenges .OH to form CO2-., enhanced ubiquinol formation but partially inhibited the degradation of the ubiquinone ring. No ubiquinol was formed in nitrogen- or oxygen-saturated solutions under our conditions. These results indicate that ubiquinol was formed by reduction of ubiquinone by O2-., which was generated by the sonolysis of argon-saturated water.

Benzenesulfonates↗

PubMed2001

Extraction and characterization of organic matter from surface waters (reservoir of Keddara in Algeria).

The combined XAD-8 and XAD-4 resin procedure for isolating dissolved organic solutes from Keddara reservoir in Algeria was found to isolate 65% of total organic carbon (TOC). Of the 45% of solute adsorbed onto XAD-8 resin, 34% was in the form of fulvic acids, and 11% humic acids. Approximately 19% of the hydrophilic solutes were adsorbed onto XAD-4 resin. Characterization experiments have shown that the three isolated fractions have a low apparent molecular weight investigated by ultrafiltration and fluorescence and low aromaticity as shown by the results of UV-absorbance, the formation potential of total organic halogens (reactivity with chlorine) and the polyhydroxyaromatic (PHA) determined by pyrolysis gas chromatography/mass spectrometry (GC/MS) which show that the isolated fractions are aliphatic as well as aromatic. The low molecular weight and the low aromaticity compared with literature data are due to coagulation and sedimentation of NOM with high molecular weight, which occur naturally in the reservoir. The Keddara reservoir, with low hydraulic loading area and long detention times receiving water with low NOM and high in hardness can be expected to be very effective coagulation and sedimentation basins.

Benzopyrans↗

PubMed2001

Phenols and aromatic hydrocarbons in chimney emissions from traditional and modern residential wood burning.

The emissions from a traditional tiled stove consisted mainly of lignin-related methoxyphenols with antioxidant properties, and 1,6-anhydroglucose from cellulose degradation. A wood stove of presently introduced energy-efficient design for residential heating and hot-water supply was shown to emit small amounts of methoxyphenols and anhydrosugars from primary wood pyrolysis. Secondary harmful components like benzene and polycyclic aromatic hydrocarbons constituted a major portion of the organic emissions. It is concluded that differences in smoke composition are essential to consider in recommendations and rules for proper choices of wood burning devices.

Air Pollution↗

PubMed2002

Determination of firefighter exposure to polycyclic aromatic hydrocarbons and benzene during fire fighting using measurement of biological indicators.

In accomplishing their duties, firefighters are potentially exposed to a vast array of toxic combustion and pyrolysis products such as benzene, carbon monoxide, acrolein, nitrogen dioxide, and polycyclic aromatic hydrocarbons. Exposure to PAH and benzene was assessed by means of urinary measurements of 1-hydroxypyrene and t,t-muconic acid, respectively. All urine samples were collected from 43 firefighters during a period extending for 20 h following the end of exposure during a fire. A control sample was also obtained from each participant after at least four days without involvement in fire fighting activities. Only one control 1-hydroxypyrene measurement exceeded the value of 0.32 micromol/mol creatinine considered as the 95th percentile of a normal reference population in this study. Following exposure, 38 percent of the maximum values of all samples collected from each firefighter exceeded this reference value. The highest single value observed in this study was 3.6 micromol/mol creatinine. None of the control samples had a t,t-muconic acid concentration above the limit of detection. A large number (81%) of post-fire samples also had nonquantifiable concentrations of this metabolite. Among 43 firefighters in this study, 17 had measurable excretion of this metabolite in any of the urine samples after fire fighting and, of the latter group, only 6 had t,t-muconic acid concentrations exceeding 1.1 mmol/mol creatinine, a value considered to correspond to a benzene-air concentration of approximately 1 ppm according to the literature. There is clear evidence that fire fighting activities are associated with exposure to PAH above environmental background, as assessed by 1-hydroxypyrene measurements, despite the use of protective equipment. However, in comparison with observations made in other cohorts of industrial workers with known polycyclic aromatic hydrocarbons exposure, firefighters' exposure in this study was low. Similarly, based on t,t-muconic acid determinations, exposure to benzene was rather low in this study. For both contaminants, observation of low exposure could be due to either low concentrations of the contaminant during fire fighting or to the efficiency of protective equipment worn.

Adult↗

PubMed2003

Folpet permeation through nitrile gloves.

The aim of this study was to investigate whether two different brands of unsupported and unlined nitrile gloves protected against aqueous emulsions of a Folpet wettable powder (50% Folpet) using an ASTM type-I-PTC 600 permeation cell at 30.0 +/- 0.1 degrees C held in a shaking water bath. An analytical method to determine Folpet using the internal standard method was first developed based on gas chromatography-mass spectrometry (GC-MS), and gas chromatography-electron capture detection (GC-ECD). A novel pyrolysis GC-ECD technique that quantified the thermal degradation product phthalimide had pg sensitivity suitable to detect the trace amounts of Folpet that permeated. The on-column conversion was (68.0 +/- 9.5) percent at 170 degrees C over the folpet injected mass range of 3 to 148 pg. The challenge solution in the permeation cell was 1.4 mg/mL aqueous emulsion of Folpet wettable powder, and 2-propanol was the collection solvent. After evaporation of the collection solvent, the time weighted average rate of permeation of Folpet through SafeSkin nitrile (an exams type of glove) after 8 hours was (42.1 +/- 2.9) ng/cm(2)/min compared with (2.04 +/- 0.69) ng/cm(2)/min for the Sol-Vex nitrile (industrial chemical resistant), the latter being about 21 times more protective and also near the limits of detection. The respective values after 4 hours of exposure were (28.4 +/- 1.2) and (0.65 +/- 0.36) ng/cm(2)/min. Diagnostic reflectance infrared minima of both challenge and collection sides of the gloves showed small changes in wave number and intensity values after 8 hours of exposure, with Folpet being detected in dried spots on the challenge side. GC-ECD-based permeation and IR reflectance data indicated high chemical resistance of the Sol-Vex gloves to an aqueous emulsion of Folpet.

Chromatography, Gas↗

PubMed2002

Evaluation of OC/EC speciation by thermal manganese dioxide oxidation and the IMPROVE method.

Ambient particulate samples are routinely analyzed for organic and elemental carbon (OC/EC) using either thermal manganese dioxide oxidation (TMO) or thermal volatilization-pyrolysis correction methods, such as the Interagency Monitoring of PROtected Visual Environments (IMPROVE) method with correction by reflectance, or a variation of the National Institute of Occupational Safety and Health (NIOSH) Method 5040 using thermal optical transmittance (TOT). With TMO, EC is modeled after the oxidation properties of submicron graphite and needle coke by MnO2, and is the fraction of total carbon (TC) that is not oxidized at >525 degrees C. In thermal volatilization methods, EC is the fraction of TC that accounts for the light extinction properties of the sample at the start of analysis. Chow et al. (2001) compared IMPROVE and NIOSH methods implemented on the same instrument using 60 samples of various types and found that NIOSH EC was lower than IMPROVE. This study compares total, organic, and elemental carbon measurements from the TMO and IMPROVE thermal optical reflectance (TOR) methods using a sample set consisting of 60 IMPROVE nonurban, 16 Korean urban, 10 Hong Kong urban, and 14 synthetic carbon black samples.

Carbon↗

PubMed2005

Investigation of nitrogen-bearing species in catalytic steam gasification of poultry litter.

The production of broiler chickens has become one of the largest sectors in U.S. agriculture, and the growing demand for poultry has led to an annual production growth rate of 5%. With increased demand for poultry, litter management has become a major challenge in the agriculture industry. Although the catalytic steam gasification has been accepted as a possible and feasible method for litter management, concern has been expressed about the presence of nitrogen and phosphorus containing species in the fuel gas and/or in the final solid residue. The possible release of phosphorus as phosphine gas in the fuel gas can have an adverse impact on the environment. Similarly, possible release of ammonia from the nitrogen containing species is also not acceptable. Hence, under partial U.S. Department of Agriculture support, a study was conducted to examine the fate and the environmental impact of the nitrogen- and phosphorus-containing species released during catalytic steam gasification of poultry litter. From various preliminary tests, it was concluded that most (approximately 100%) of the phosphorus would remain in the residue, and some (20-70%) of the nitrogen would end up as ammonia in the fuel gas. The effects of temperature, catalyst loading, and type of catalyst on ammonia liberation were studied in a muffled furnace setup at atmospheric pressure. The fraction of nitrogen released as ammonia was found to decrease with an increase in temperature during pyrolysis and steam gasification. It also decreased with an increase in catalyst loading.

Animals↗

PubMed2005

Quantification of monosaccharide anhydrides by liquid chromatography combined with mass spectrometry: application to aerosol samples from an urban and a suburban site influenced by small-scale wood burning.

Levels of the monosaccharide anhydride (MA) levoglucosan and its isomeric compounds galactosan and mannosan were quantified in the PM10 fraction (particulate matter < or = 10 microm in aerodynamic diameter) of ambient aerosols from an urban (Oslo) and a suburban (Elverum) site in Norway, both influenced by small-scale wood burning. MAs are degradation products of cellulose and hemicellulose, and levoglucosan is especially emitted in high concentrations during pyrolysis and combustion of wood, making it a potential tracer of primary particles emitted from biomass burning. MAs were quantified using a novel high-performance liquid chromatography/ high-resolution mass spectrometry-time of flight method. This approach distinguishes between the isomeric compounds of MAs and benefits from the limited sample preparation required before analysis, and no extensive derivatization step is needed. The highest concentrations of levogucosan, galactosan, and mannosan (sigmaMA) were recorded in winter because of wood burning for residential heating (sigmaMA(MAX) = 1,240 ng m(-3)). This finding was substantiated by a relatively high correlation (R2 = 0.64) between the levoglucosan concentration and decreasing ambient temperature. At the suburban site, sigmaMA accounted for 3.1% of PM10, whereas the corresponding level at the urban site was 0.6%. The mass size distribution of MAs associated with atmospheric aerosols was measured using a Berner cascade impactor. The size distribution was characterized with a single mode at 561 nm. Ninety-five percent of the mass concentration of the MAs was found to be associated with particles < 2 micro.m. A preliminary attempt to estimate the contribution of wood burning to the mass concentration of PM10 in Oslo using levoglucosan as a tracer indicates that 24% comes from wood burning. This is approximately a factor of 2 lower than estimated by the AirQUIS dispersion model.

Aerosols↗

PubMed2001

MAP: microwave-assisted extraction of fatty acids and Py/GC/MS analysis of selected insects.

A Microwave-Assisted Process (MAP) solvent extraction procedure was used in conjunction with GC/MS analysis to investigate the chemical composition of dried silkworm, dried earthworm, silkworm droppings, and cicada nymph skin. Selected insect samples were also analyzed by pyrolysis-GC-MS. Silkworm and earthworm generated fatty acids, sterols and phenol derivatives. Cicada nymph skin was analyzed by pyrolysis/GC/MS and generated mainly heterocyclic compounds. The data indicated that insects can retain environmental contaminants such as 2,6-bis(1,1-dimethylethyl)-4-methyl phenol (BHT) and as such could be used as biological indicators. In addition, some of the therapeutic characteristics associated with insects could be attributed to the chemicals ingested from plant sources.

Air Pollutants↗

PubMed2003

Detecting crack and other cocaine use with fastpatches.

A continuing social problem is presented by the large number of individuals who use crack cocaine. Recent research has identified unique pyrolysis products of crack or burned cocaine as anhydroecgonine methylester (AEME) and ecgonidine (ECD) through gas chromatography/mass spectrometry (GC/MS) that allow for the detection of crack use distinct from other cocaine use. However, there have been no large-scale studies to document the presence and prevalence of these substances in sweat. A new sweat-testing appliance called a fastpatch was developed for this study. Through mild heating and a slightly larger collection pad than a standard Pharmchek( trade mark ) sweat patch, this product shows the promise of shorter required wear periods than standard sweat patches, and possibly longer time-periods of detected use. One hundred and eighty subjects wore 360 fastpatch prototypes (one per hand). However, subsequent analysis determined that only one patch per subject was needed to obtain sufficient sweat eluate for GC/MS. Cocaine use was detected in sweat of 92% of subjects through GC/MS, comparing favorably with 91% with EMIT urinalysis. Crack metabolites were detected in 54% of subjects. The predominant analyte detected was AEME. There were no significant differences in detection rates between 15-, 20- and 30-minute wear periods. All wear periods detected both cocaine use in general and crack use successfully. These results suggest that crack use as distinct from other cocaine use can be detected in sweat and that fastpatches are a promising new way to detect drugs of abuse.

Administration, Cutaneous↗

PubMedDate not supplied

Mutagenicity of rubber vulcanization gases in Salmonella typhimurium.

Gases formed by rubber and rubber additives in the vulcanization process were collected with a laboratory-scale glass apparatus. Mutagenicity testing of the vulcanization gases by the Salmonella/microsome test was conducted with strains TA1535, TA1538, TA98, and TA100 in the absence and presence of a metabolizing system from rat liver homogenates. The mutagenicity of gases derived by heating chloroprene rubber and ethylene propylene rubber was established with both base substitution- and frameshift-sensitive strains and that of a styrene-butadiene rubber was established with the base substitution-sensitive stain TA100. Tests on pyrolysis gases from a butadiene acrylonitrile rubber revealed only toxic effects. Curing systems, additives, and filling materials from various sources were represented in the material. Gases were collected at temperature levels corresponding to both mixing and curing of these particular rubbers in the industrial operations. Attempts were made to correlate the mutagenicity of the gases to the presence of mutagenic components in the rubber mixtures.

Acrylonitrile↗

PubMed1993

The Bhopal accident and methyl isocyanate toxicity.

The Bhopal accident, the world's worst industrial disaster, in which nearly 40 metric tons of methyl isocyanate (MIC) was released from the Union Carbide pesticide plant, occurred nearly 10 yr ago during the night of December 2 and 3, 1984. Over 3000 people residing in areas adjacent to the plant died of pulmonary edema within 3 d of the accident. Follow-up studies revealed pulmonary, ophthalmic, reproductive, immunologic, neurological, and hematologic toxicity among the survivors. Despite high reactivity, MIC can traverse cell membranes and reach distant organs, perhaps as a reversible conjugate with glutathione, which may explain some of the systemic effects of MIC. MIC can be degraded as a result of pyrolysis and interaction with water, but none of the breakdown products can duplicate the toxicity observed in Bhopal and in animal models. MIC may be the most toxic of all isocyanates because of its very high vapor pressure relative to other isocyanates and because of its ability to exert toxic effects on numerous organ systems.

Accidents, Occupational↗

PubMedDate not supplied

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↗

PubMed1993

Evaluation of shipboard formation of a neurotoxicant (trimethylolpropane phosphate) from thermal decomposition of synthetic aircraft engine lubricant.

MIL-L-23699 lubricants that are composed principally of trimethylolpropane triheptanoate (TMP) and tricresyl phosphate (TCP) have been shown to form a neurotoxicant, trimethylolpropane phosphate (TMPP), during pyrolysis and/or combustion. Mechanistically, TMPP is thought to irreversibly inhibit the GABA-mediated inhibitory response and thereby produce epileptiform clonic/tonic seizures with convulsions followed by death. Thermal decomposition of MIL-L-23699 lubricant produces TMPP under laboratory conditions, but this product has not been detected in the workplace following actual fires. This study has examined whether TMPP is produced during an actual shipboard fire by placing the synthetic lubricant in a fire environment aboard the ex-U.S.S. Shadwell, Mobile, Alabama. Both biological and chemical analyses were performed on the thermally decomposed lubricant to ensure detection of the neurotoxic material. Under the conditions of this study, the formation of TMPP during a shipboard fire was confirmed. The implications of this finding for safe management of post-fire cleanup are discussed.

Bridged Bicyclo Compounds, Heterocyclic↗

PubMedDate not supplied

Characterization of particulate matter in carbon-graphite/epoxy advanced composite material smoke.

The physical and chemical properties of the particulate fraction of carbon-graphite/epoxy advanced composite material (cgeACM) smoke were measured to address concerns regarding potential health hazards posed by the release of fibers during pyrolysis of this material. Filter, low-pressure cascade impactor, and electrostatic precipitator samples were collected from cgeACM smoke in which the aerosol concentration ranged from 0.20 to 5.39 g/m3. Fibers were found in the smoke among individual, spherical, or nearly spherical particles and chain aggregates. The fibers had a mean count diameter of 0.54 micron and an average length of 2.84 microns. However, fibers accounted for approximately 0.3% of the particles counted. The smoke aerosols (including fibers) had mass median aerodynamic diameters (MMAD) ranging from 1.4 to 1.9 microns with standard geometric deviations ranging from 1.6 to 1.8, and hence more than 88% of the particles were in the thoracic size range (MMAD < or = 4.0 microns). All particles were composed primarily of carbon, silicon, sulfur, and oxygen with traces of other metals. By comparison fibers were composed almost exclusively of silicon.

Air Pollutants↗

PubMedDate not supplied

Volatile organic compounds produced during irradiation of mail.

In 2001, Bacillus anthracis spores were delivered through the United States postal system in a series of bioterrorist acts. Controls proposed for this threat included sanitization with high-energy electrons. Solid phase microextraction was used with gas chromatography/mass spectrometry for field sampling and analysis of volatile compounds apparently produced from polymeric materials such as cellulose and plastics, immediately following processing of mail at a commercial irradiation facility. Solid phase microextraction and direct sampling of air into a cryogenically cooled temperature programmable inlet were used in the laboratory for gas chromatography/mass spectrometry analysis of air in contact with irradiated mail, envelopes only (packaged identically to mail), and air inside irradiated plastic mail packaging bags (with neither mail nor envelopes). Irradiated mail or envelope systems produced hydrocarbons such as propane, butane, pentane, hexane, heptane, methylpentanes, and benzene; and oxygen-containing compounds such as acetaldehyde, acrolein, propionaldehyde, furan, 2-methylfuran, methanol, acetone, 2-butanone, and ethanol. In addition to hydrocarbons, methyl and ethyl nitrate were detected in irradiated bags that contained only air, suggesting reactive nitrogen species formed from air irradiation reacted with hydroxy-containing compounds to give nitro esters. The similarities of volatile compounds in irradiated systems containing paper to those observed by researchers studying cellulose pyrolysis suggests common depolymerization and degradation mechanisms in each case. These similarities should guide additional work to examine irradiated mail for chemical compounds not detectable by methods used here.

Air Pollution, Indoor↗

PubMed2001

Mercury adsorption onto pyrolyzed waste paper.

The ability of pyrolyzed waste paper to remove mercury from aqueous solutions by physicochemical adsorption was investigated. Defibered waste newsprint was pyrolyzed in a nitrogen atmosphere at 300 degrees C for 3 h. The pyrolysis residue showed high affinity to inorganic divalent mercury species. To investigate the adsorption characteristics, the factors affecting mercury adsorption were examined. The adsorbent was efficient in capturing mercury in neutral and basic media, although limited adsorption occurred in acidic media. The extent of the adsorption was also dependent upon the solution temperature and initial concentration of mercury in solution. The adsorption followed both the Langmuir and Freundlich isotherms.

Adsorption↗