SEARCH · PubMed Health

Results for “Solid Phase Microextraction”

Explore indexed PubMed citations for clinical trials, systematic reviews and public health research. Read source abstracts and follow each citation to its original PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,351 records · Page 75Linked to original sources

PubMed2004

Characterization of polyacrylate membrane-coated fibers used in chemical absorption studies with programmed thermal treatment and FT-IR microscopy.

A polyacrylate (PA) film was coated onto a fused-silica fiber as a permeation membrane in a membrane-coated fiber (MCF) technique and a solid-phase microextraction technique. The molecular changes of the PA membrane after different temperature treatments were studied with FT-IR microscopy. The absorption bands of the PA aliphatic backbone at 2902, 2795, and 2740 cm(-)(1) remained unchanged over the elevated thermal treatments, indicating that the polymer backbone was stable over these conditions. The spectra of the PA membrane remained unchanged when the thermal treatment temperature was under 150 degrees C. When the temperature was 250 degrees C, the O-H stretching band in the -COOH groups of the poly(acrylic acid) at 3315 cm(-)(1) was significantly reduced. When the temperature was higher than 280 degrees C, this O-H band disappeared. These evidences suggested that the PA membrane underwent dehydroxyl reaction to form an anhydride when the thermal treatments were higher than 250 degrees C. Thermal treatments of a deuterated PA MCF confirmed the anhydride formation mechanism. The anhydride formation explained the absorption property of PA MCFs in GC applications where they must be preconditioned at 300 degrees C. The absorption data suggest that a PA fiber does not preferably absorb polar compounds (with permanent dipole moment); instead, it absorbs preferably aromatic compounds.

Journal Article↗

PubMed2004

Determination of total chromium in seawater by isotope dilution sector field ICPMS using GC sample introduction.

A method for the accurate determination of total Cr in seawater by isotope dilution (ID) sector field inductively coupled plasma mass spectrometry (SF-ICPMS) using GC as a means of sample introduction is described. Chromium was reduced to Cr(III) by addition of SO(2)-saturated water and derivatized with trifluoroacetylacetonate (TFA) to form volatile Cr(TFA)(3). Derivatized analyte was either extracted into hexane or directly sampled by solid-phase microextraction (SPME) using a poly(dimethylsiloxane)-coated fused-silica fiber for GC/SF-ICPMS analysis. With medium resolution required to efficiently separate argide, argon chloride and oxide interferences, a concentration of 0.154 +/- 0.013 ng mL(-1) (1 SD, n = 4) was obtained for Cr in NRCC seawater CRM CASS-4 using a 1-microL hexane extract, in agreement with the certified value of 0.144 +/- 0.029 ng mL(-1) (95% confidence interval). A detection limit of 20 pg mL(-1) was achieved. Low-resolution GC/SF-ICPMS in combination with solvent-free SPME sampling effectively eliminated spectroscopic interferences, yielding a concentration of 0.132 +/- 0.004 ng mL(-1) (1 SD, n = 4) for Cr in CASS-4 with a method detection limit of 3.9 pg mL(-1). By comparison, SPME sampling with GC/SF-ICPMS in medium-resolution mode provided a concentration of 0.146 +/- 0.013 ng mL(-1) (1 SD, n = 4) and a method detection limit of 9.1 pg mL(-1).

Chromatography, Gas↗

PubMed2006

An improved approach for accurate quantitation of benzene, toluene, ethylbenzene, xylene, and styrene in blood.

Widespread exposure to benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS) and the potential for this exposure to cause health effects drives the need to develop improved methods for measuring exposure. In this work, we demonstrate our latest assay for quantifying BTEXS in blood and characterize sources of both positive and negative biases. This method involves blood sample collection using common techniques followed by static headspace sampling using solid-phase microextraction and gas chromatography/mass spectrometry analysis. We found that the greatest and unexpected source of positive bias was from contamination of butyl rubber materials used in sample preparation consumables such as Vacutainer stoppers, syringe plungers, and sample vial septa. Conversely, the primary cause of negative bias observed was from the diffusion loss of BTEXS from blood during transfer into sample vials. By minimizing or eliminating these and other sources of bias, we improved method accuracy and precision to within 10% while maintaining low-picogram per milliliter detection. Furthermore, upon comparison of these results with those from other laboratories, we observe substantially lower blood BTEXS levels reported to date for nonoccupationally exposed nonsmokers. A relatively unbiased method, as such, will help elucidate any potential associations between adverse health effects and human exposure to low levels of BTEXS.

Benzene↗

PubMed2006

Generating multiple independent retention index data in dual-secondary column comprehensive two-dimensional gas chromatography.

A method producing simultaneously three retention indexes for compounds has been developed for comprehensive two-dimensional gas chromatography by using a dual secondary column approach (GC x 2GC). For this purpose, the primary flow of the first dimension column was equally diverted into two secondary microbore columns of identical geometry by means of a three-way flow splitter positioned after the longitudinally modulated cryogenic system. This configuration produced a pair of comprehensive two-dimensional chromatograms and generated retention data on three different stationary phases in a single run. First dimension retention indexes were determined on a polar SolGel-Wax column under linear programmed-temperature conditions according to the van den Dool approach using primary alcohol homologues as the reference scale. Calculation of pseudoisothermal retention indexes in both second dimensions was performed on low-polarity 5% phenyl equivalent polysilphenylene/siloxane (BPX5) and 14% cyanopropylphenyl/86% dimethylpolysiloxane (BP10) columns. To construct a retention correlation map in the second dimension separation space upon which KovAts indexes can be derived, two methods exploiting "isovolatility" relationships of alkanes were developed. The first involved 15 sequential headspace samplings of selected n-alkanes by solid-phase microextraction (SPME), with each sampling followed by their injection into the GC at predetermined times during the chromatographic run. The second method extended the second dimension retention map and consisted of repetitive introduction of SPME-sampled alkane mixtures at various isothermal conditions incremented over the temperature program range. Calculated second dimension retention indexes were compared with experimental values obtained in conventional one-dimensional GC. A case study mixture including 24 suspected allergens (i.e., fragrance ingredients) was used to demonstrate the feasibility and potential of retention index information in comprehensive 2D-GC.

Journal Article↗

PubMed1999

Determination of lead in blood and urine by SPME/GC.

Lead is the most frequently quantitated toxic metal in biological matrixes. In this paper, a method is described for lead determination in whole blood and urine using solid-phase microextraction (SPME) gas chromatography. Lead ion is first derivatized with sodium tetraethylborate to form tetraethyllead, which is then extracted from the headspace over the sample by SPME. The analytical procedure was optimized for coating selection, pH, extraction time, and effect of salt. The relative standard deviation was less then 10% for both urine and blood samples. The limit of detection was 3 and 4 ppb; the limit of quantification is 5 and 10 ppb for urine and blood samples, respectively. Good linearity was found for both urine and blood samples when PDMS coating was used. The standard addition method was used for quantitation. Certified urine and blood samples were analyzed, and good accuracy was obtained.

Borates↗

PubMed1999

Identification of proteins in complexes by solid-phase microextraction/multistep elution/capillary electrophoresis/tandem mass spectrometry.

A method to directly identify proteins in complex mixtures by solid-phase microextraction (micro-SPE)/multistep elution/capillary electrophoresis (CE)/tandem mass spectrometry (MS/MS) is described. A sheathless liquid-metal junction interface is used to interface CE and electrospray ionization MS/MS. A subfemtomole detection limit is achieved for protein identification through database searching using MS/MS data. The SPE serves as a semiseparation dimension using an organic-phase step-elution gradient in combination with the second separation dimension for increased resolving power of complex peptide mixtures. This approach improves the concentration detection limit for CE and allows more proteins in complex mixtures to be identified. A 75-protein complex from yeast ribosome is analyzed using this method and 80-90% of the proteins in the complex can be identified by searching the database using the MS/MS data from a complete analysis. This multidimensional CE/MS/MS methodology provides an alternative to multidimensional liquid chromatography/MS/MS for direct identification of small amounts of protein in mixtures.

Electrophoresis, Capillary↗

PubMed2000

Source identification of underground fuel spills by solid-phase microextraction/high-resolution gas chromatography/genetic algorithms.

Solid-phase microextraction (SPME), capillary column gas chromatography, and pattern recognition methods were used to develop a potential method for typing jet fuels so a spill sample in the environment can be traced to its source. The test data consisted of gas chromatograms from 180 neat jet fuel samples representing common aviation turbine fuels found in the United States (JP-4, Jet-A, JP-7, JPTS, JP-5, JP-8). SPME sampling of the fuel's headspace afforded well-resolved reproducible profiles, which were standardized using special peak-matching software. The peak-matching procedure yielded 84 standardized retention time windows, though not all peaks were present in all gas chromatograms. A genetic algorithm (GA) was employed to identify features (in the standardized chromatograms of the neat jet fuels) suitable for pattern recognition analysis. The GA selected peaks, whose two largest principal components showed clustering of the chromatograms on the basis of fuel type. The principal component analysis routine in the fitness function of the GA acted as an information filter, significantly reducing the size of the search space, since it restricted the search to feature subsets whose variance is primarily about differences between the various fuel types in the training set. In addition, the GA focused on those classes and/or samples that were difficult to classify as it trained using a form of boosting. Samples that consistently classify correctly were not as heavily weighted as samples that were difficult to classify. Over time, the GA learned its optimal parameters in a manner similar to a perceptron. The pattern recognition GA integrated aspects of strong and weak learning to yield a "smart" one-pass procedure for feature selection.

Algorithms↗

PubMed2000

Speciation of alkyllead and inorganic lead by derivatization with deuterium-labeled sodium tetraethylborate and SPME-GC/MS.

A method for full speciation and determination of alkyllead and inorganic lead(II) in aqueous samples was developed. This was accomplished by in situ derivatization with deuterium-labeled sodium tetraethylborate NaB(C2D5)4 (DSTEB). The derivatization was carried out directly in the aqueous sample and the derivatives were extracted from the headspace by a solid-phase microextraction (SPME) fiber. The extracted analytes were then transferred to a GC/MS or a GC/FID for separation and detection. The research presented demonstrates that SPME and the derivatization reagent DSTEB can be used successfully for the speciation of Pb2+, Pb(CH3)3+, Pb(C2H5)3+, and Pb(C2H5)4 in water samples. All derivatives, Pb(C2D5)4, (CH3)3Pb(C2D5), (C2H5)3Pb(C2D5), and Pb(C2H5)4, are separated using an SBP-5 column. This method was applied to monitor degradation of tetraethyllead in water. This is the first report of ethylation by DSTEB for full speciation of methyllead, ethyllead, and inorganic lead compounds. This approach can be extended to other organometallic compounds as demonstrated for ethyltin speciation. This full speciation method will aid in monitoring occurrence, pathways, toxicity, and biological effects of these compounds in the environment. It is easily adopted for field analysis.

Borates↗

PubMed2000

Development of a hollow waveguide sampler for detection of chlorinated aromatic compounds in soils.

In this paper, a Fourier transform infrared (FT-IR) spectroscopic method for detection of chlorinated aromatic compounds in soils was developed. The sensing device of this method was based on an infrared hollow waveguide, the inner surface of which was coated with a hydrophobic film. Vaporized chlorinated aromatic compounds from soils were trapped onto the hydrophobic film of the hollow waveguide sampler following detection by FT-IR spectrometry. The extraction process in this method was similar to the headspace solid-phase microextraction (HSSPME) in principle. Means of increasing the speed of transfer of the vaporized organic species to the sampler were also studied. Results indicated that, with a negative pressure on the end of the sampler, the speed of transfer increased significantly. Vapor pressures of the analytes were used as an indication to test the limitation of this method in the analysis of organic compounds in soils. Results showed that analytes with vapor pressures lower than 12 Torr could be detected quantitatively. The typical R-square of the regression on the concentration and IR signals was around 0.99 and the typical detection limits were in the range of hundreds of parts per billion.

Hydrocarbons, Aromatic↗

PubMed2001

Sorption of pyrene to dissolved humic substances and related model polymers. 1. Structure--property correlation.

Solid-phase microextraction (SPME) was employed to determine sorption coefficients for pyrene on dissolved humic substances (DHS) of various origins and also on model polymers to gain a better understanding of the relationships between sorption potential and sorbent structures. The sorption potential of DHS from very different sources is described by an empirical two-parameter correlation involving the polarity (O/H atomic ratio) and the aromaticity (epsilon 280 nm) as descriptors. On the other hand, sorption experiments with well-defined model polymers, poly(acrylic acid) esters, led to the conclusion that aliphatic chains may be more effective than aromatic moieties in binding PAHs. The molecular weight of the model sorbents was found to have a significant influence on the sorption potential.

Fluorescent Dyes↗

PubMed2002

Methyl tert-butyl ether (MTBE) in river and wastewater in Germany.

An overview of methyl tert-butyl ether (MTBE) concentrations in German river water (315 samples) and wastewater (82 samples) is given. In the agglomerated area of Frankfurt/M, several samples of surface water, wastewater, and industrial effluents were analyzed for its MTBE content from 1999 to 2001. MTBE was analyzed by a combination of headspace-solid-phase microextraction and gas chromatography-mass spectrometry (HS-SPME/GC-MS). Rhine and Main water concentrations of MTBE in the lower parts of the rivers were approximately 250 ng/L and 200 ng/L, respectively. The concentrations increased from the upper parts of the rivers to its mouths. Water from the Elbe, Neckar, and Weser rivers showed lower MTBE concentrations, and the ether was not detected in the Danube river. Generally, higher MTBE concentrations were detected at urban agglomerations compared to rural areas. Small urban creeks without significant industrial input showed MTBE concentrations of approximately 50 ng/L, and it was hardly detectable in small rural creeks. Higher MTBE concentrations in river water were correlated with increased concentrations of the oxygenate measured in precipitation. Most MTBE concentrations in river water fell in the range of 50-200 ng/L (32%), 10-50 ng/L (28%), and 200-1000 ng/L (26%). MTBE concentrations in German surface water and air are 3-17 times lower compared to Californian data. Wastewater samples from influents of two sewage plants showed MTBE concentrations of approximately 100-300 ng/L, and a loading of 2-37 kg/a was calculated. An eliminated MTBE percentage of roughly 30-35% of MTBE in the plants was estimated. Industrially influenced samples of river water or public wastewater and industrial effluents showed MTBE concentrations of up to 2267 ng/L and 28 microg/L, respectively. This input has not been considered before because only 1.5% of the produced amount of MTBE in Germany is used for industrial processes, but it should not be neglected because MTBE is very persistent in water.

California↗

PubMed2002

Occurrence of methyl tert-butyl ether (MTBE) in riverbank fiftered water and drnking water produced by riverbank filtration. 2.

Bank filtration of river or lake water represents an efficient and natural purification process used for the drinking water production in many countries and at an amount of about 15-16% in Germany. From experiences over decades particularly at the river Rhine and Elbe, it is known that the occurrence of persistent pollutants in river water can represent a problem for the quality of drinking water produced by bank filtration. The common detection of the gasoline additive methyl tert-butyl ether (MTBE) in drinking water and the announced phase-out of the oxygenate in the U.S. show that MTBE can contaminate large water amounts due to its physicochemical properties. The MTBE situation in the U.S differs from Europe, and significantly lower concentrations in the German environment can be expected. Average MTBE concentrations of 200-250 ng/L in the Lower Main and Lower Rhine river in 2000/2001 were reported. At two sites at the Lower Rhine and Lower Main rivers MTBE concentrations in bank filtered water (n = 22), recovering well water, raw water, and drinking water produced by the water utility at the Lower Rhine site (n = 30) and tap water at Frankfurt/M City (n = 13) were analyzed from 1999 to 2001. Sample analysis is performed by a combination of headspace-solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC/MS) with a detection limit of 10 ng/L and a relative standard deviation of 11%. At the Lower Rhine site up to 80 m from the river an average MTBE concentration of 88 ng/L in riverbank filtered water, recovering well water, and raw water (n = 7) and of 43-110 ng/L in drinking water (n = 3) result. At the Lower Main site up to 400 m from the river MTBE concentrations from 52 to 250 ng/L (n = 7) were measured. Tap water samples at Frankfurt/M (mean of 35 ng/L, maximum of 71 ng/L) were in the same range as MTBE amounts in drinking water at the Lower Rhine site. Measured MTBE amounts eliminated by bank filtration at the Lower Rhine site are comparable to other contaminants. The results of this study show that concentrations measured in river water and drinking water are approximately 2-3 orders of magnitude lower than the U.S. drinking water standard of 20-40 microg/L, represent trace-level concentrations, and are not of major concern nowadays. However, the unfavorable combination of the occurrence of nonpoint MTBE emissions and the persistent behavior of the ether in water even at low concentrations should not be neglected in future discussion. The reported MTBE concentrations are relevant for precautionary aspects. MTBE concentrations in German river water show a tendency toward increasing concentrations since 1999, and in the future possible higher concentrations could represent a risk for the quality of drinking water that is being produced by water utility using bank filtered river water.

Filtration↗

PubMed2002

Detection of volatile organometal chloride species in model atmosphere above seawater and sediment.

The principal route for release of organometallic species into the atmosphere is currently considered to be the biological or chemical formation of saturated volatile compounds such as dimethylmercury, metal hydrides, etc. Model experiments conducted in our laboratory pointto the release of extremely toxic, volatile organotin, -lead, -mercury, and -arsenic species that have been detected as the chlorides in the gas phase above seawater and sediment mixtures. As the sediment was sterilized prior to the analytical study, any bioformation of volatile metal species was excluded. The most probable account of these observations is the naturally occurring formation of metal chlorides, fueled by the abundance of chloride ion (or other halides) present in seawater and many other natural environments. This raises the suggestion that the release of toxic trace elements to the atmosphere by environmental processes may be seriously underestimated. A conservative projection, based on laboratory data, suggests that the emission of butyltin into the atmosphere may reach as high as 150 ng/m2 of water/yr from a polluted marine environment, suggesting a very significant level of release of butyltin from seawater at the global level. For the sampling and determination of volatile metal species, solid-phase microextraction combined with inductively coupled plasma time-of-flight mass spectrometry has been used. This new analytical system is capable of detection of semivolatile, thermally unstable compounds such as the class encompassing metal halide species.

Biotransformation↗

PubMed2002

Investigation of the volatile organic substances that cause the characteristic odor of pentachlorophenol treated wood utility poles.

The nature of the volatile organic compounds that could be at the origin of the characteristic odor of treated wood utility poles was investigated by the study of compositional changes in the chromatographic profiles of fresh-pentachlorophenol (PCP) solvent samples and weathered samples collected from an in-service red pine pole. Over 99 peaks were identified in the chromatogram of the fresh solvent from which a large portion of the C3-, C4-, C5-, C6-alkylbenzene isomers and early eluting n-alkanes was missing from the analysis of weathered samples. Three domains in the chromatographic profile (volatile, semivolatile, and nonvolatile components) were confirmed by assessing the headspace of fresh-PCP solvent samples using direct syringe sampling and solid-phase microextraction. A first level of field validation was achieved using an emission cell for measuring substances emanating from sapwood specimens at different temperatures. The average latent heat of vaporization (deltaHvap) of the PCP-solvent components was estimated at 99.9 kJ/mol from these results. Finally, the analysis of airborne substances at a treating plant and a utility pole storage site confirmed that the C4-, C5-, and C6-alkylbenzene isomers could contribute to the characteristic odor perceived by humans.

Air Pollutants↗

PubMed2003

Hydroxyaldehyde products from hydroxyl radical reactions of Z-3-hexen-1-ol and 2-methyl-3-buten-2-ol quantified by SPME and API-MS.

Hydroxyaldehyde products of the OH radical-initiated reactions (in the presence of NO) of two volatile vegetative emissions, Z-3-hexen-1-ol and 2-methyl-3-buten-2-ol, were examined to assess the qualitative and quantitative potential of two analysis techniques (1) sampling by Solid-Phase MicroExtraction (SPME) with on-fiber derivatization followed by gas chromatographic analyses and (2) in situ analysis by negative ion mode atmospheric pressure ionization mass spectrometry (API-MS). The compounds were chosen because reaction mechanisms predict hydroxyaldehyde products, and reliable coproduct yield data are available. The API-MS analyses showed product ion peaks attributed to the NO2- adducts of 3-hydroxypropanal and dihydroxynitrates from Z-3-hexen-1-ol, and a formation yield of 3-hydroxypropanal of 44% was derived. Product ion peaks attributed to NO2- adducts of glycolaldehyde [HOCH2CHO], 2-hydroxy-2-methylpropanal [(CH3)2C(OH)CHO], and dihydroxynitrates were observed by API-MS from 2-methyl-3-buten-2-ol, and a formation yield of 2-hydroxy-2-methylpropanal of 16% was obtained. In experiments with SPME sampling, the formation yields of hydroxycarbonyls measured as their oxime derivatives were as follows: from Z-3-hexen-1-ol, propanal, 56 +/- 8%; 3-hydroxypropanal, 101 +/- 24%; and from 2-methyl-3-buten-2-ol, 2-hydroxy-2-methylpropanal, 31 +/- 4%. Both the API-MS and SPME analyses provided product information, and hydroxycarbonyl yields from the SPME data are in reasonable agreement with previously measured formation yields of coproducts.

Chemistry Techniques, Analytical↗

PubMed2005

Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene.

1,3-Butadiene and isoprene (2-methyl-1,3-butadiene) are emitted into the atmosphere in vehicle exhaust and, in the case of isoprene, from vegetation. We have investigated the formation and further reaction of products of their hydroxyl radical-initiated reactions using atmospheric pressure ionization mass spectrometry (API-MS) and solid-phase microextraction fibers precoated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl compounds, with subsequent analysis by thermal desorption and gas chromatography with flame ionization detection (SPME/GC-FID) or MS detection. Products attributed as HOCH2CH=CHCHO and HOCH2CH=CHCH2ONO2 (and isomers) from 1,3-butadiene; HOCD2CD=CDCDO and HOCD2CD=CDCD2ONO2 (and isomers) from 1,3-butadiene-d6; HOCH2C(CH3)=CHCHO and/or HOCH2CH=C(CH3)CHO, and HOCH2C(CH3)=CHCH2ONO2 (and isomers) from isoprene; and HOCD2C(CD3)=CDCDO and/or HOCD2CD=C(CD3)CDO, and HOCD2C(CD3)=CDCD2ONO2 (and isomers) from isoprene-d8 were observed as their NO2- adducts in the API-MS analyses. The hydroxycarbonyls were observed from SPME/GC-FID analyses of the 1,3-butadiene and isoprene reactions as their oximes, together with acrolein, glycolaldehyde, and glyoxal from the 1,3-butadiene reaction. A rate constant for the reaction of OH radicals with 4-hydroxy-2-butenal of (5.7 +/- 1.4) x 10(-11) cm3 molecule(-1) s(-1) at 298 +/- 2 K was derived, and formation yields of acrolein and 4-hydroxy-2-butenal from the 1,3-butadiene reaction of 58 +/- 10% and 25 (+15/-10)%, respectively, were determined. Analogous experiments showed that the two C5-hydroxycarbonyls formed from isoprene have rate constants for their reactions with OH radicals of (1.0 +/- 0.3) x 10(-10) cm3 molecule(-1) s(-1) and (4 +/- 2) x 10(-11) cm3 molecule(-1) s(-1) and a combined yield of approximately 15%, although isomer-specific identification of the hydroxycarbonyls was not achieved.

Acrolein↗

PubMed2005

Sediment dilution method to determine sorption coefficients of hydrophobic organic chemicals.

Sorption coefficients of hydrophobic organic chemicals (HOC) to sediments and soils can easily be underestimated in traditional batch experiments, especially because analysis of the aqueous concentration often includes compounds sorbed to colloidal organic matter. In this work, a "sediment dilution approach" has been combined with measurements of freely dissolved concentrations to determine sorption coefficients of five chlorobenzenes and two chloroanilines in spiked sediment and of two unknown chemicals in field-contaminated sediment. A range of sediment suspensions with different sediment-water ratios was made. Freely dissolved concentrations in these suspensions were measured by negligible depletion solid-phase microextraction (nd-SPME). Sediment-water sorption coefficients (KD) were derived from the decrease of the freely dissolved concentrations as a function of the "dilution factor" (DF = volume water/mass sediment). The determined sorption coefficients were very similar to literature values. The experimental setup provides sorption coefficients without the need for total extractions, and the negligible depletion SPME technique does not require phase separation. The proposed method might be an alternative for batch equilibrium experiments to determine sorption coefficients.

Adsorption↗

PubMed2005

1,4-hydroxycarbonyl products of the OH radical initiated reactions of C5-C8 n-alkanes in the presence of NO.

Alkanes account for approximately 50% of nonmethane organic compounds present in urban atmospheres. Previous studies have shown that hydroxycarbonyls are important products ofthe OH radical initiated reactions of > or = C5 n-alkanes, but isomer-specific identifications and quantifications of these products have not been carried out. In this work, we have used solid-phase microextraction fibers precoated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl-containing compounds with subsequent analyses by combined gas chromatography-mass spectrometry (GC-MS) and GC with flame ionization detection (GC-FID). GC-MS analyses showed the presence of the oximes of 5-hydroxy-2-pentanone and 4-hydroxypentanal from the n-pentane reaction; 5-hydroxy-2-hexanone, 6-hydroxy-3-hexanone, and 4-hydroxyhexanal from the n-hexane reaction; 5-hydroxy-2-heptanone, 6-hydroxy-3-heptanone, 1-hydroxy-4-heptanone, and 4-hydroxyheptanal from the n-heptane reaction; and 5-hydroxy-2-octanone, 6-hydroxy-3-octanone, 7-hydroxy-4-octanone, and 4-hydroxyoctanal from the n-octane reaction. The formation yields of these 1,4-hydroxycarbonyls were determined from GC-FID analyses. By use of the yields of 1,4-hydroxycarbonyls formed from n-hexane, n-heptane, and n-octane at 50% relative humidity (and those from n-pentane at both 5 and 50% relative humidity), then formation of 1,4-hydroxycarbonyls accounts for 54% of the reaction products from n-pentane, 57% from n-hexane, 51% from n-heptane, and 53% from n-octane. Combined with previously measured yields of carbonyls, alkyl nitrates, and hydroxyalkyl nitrates, we can now accountfor approximately 74-118% of the products formed from the n-pentane through n-octane reactions.

Aldehydes↗