Association of Smoking with Metabolic Volatile Organic Compounds in Exhaled Breath.

Lung cancer (LC) screening will be more efficient if it is applied to a well-defined high-risk population. Characteristics including metabolic byproducts may be taken into account to access LC risk more precisely. Breath examination provides a non-invasive method to monitor metabolic byproducts. However, the association between volatile organic compounds (VOCs) in exhaled breath and LC risk or LC risk factors is not studied. Exhaled breath samples from 122 healthy persons, who were given routine annual exam from December 2015 to December 2016, were analyzed using thermal desorption coupled with gas chromatography mass spectrometry (TD-GC-MS). Smoking characteristics, air quality, and other risk factors for lung cancer were collected. Univariate and multivariate analyses were used to evaluate the relationship between VOCs and LC risk factors. 7, 7, 11, and 27 VOCs were correlated with smoking status, smoking intensity, years of smoking, and depth of inhalation, respectively. Exhaled VOCs are related to smoking and might have a potential to evaluate LC risk more precisely. Both an assessment of temporal stability and testing in a prospective study are needed to establish the performance of VOCs such as 2,5-dimethylfuranm and 4-methyloctane as lung cancer risk biomarkers.

Exhaled breath metabolomics as a noninvasive diagnostic tool for acute respiratory distress syndrome.

There is a need for biological markers of the acute respiratory distress syndrome (ARDS). Exhaled breath contains hundreds of metabolites in the gas phase, some of which reflect (patho)physiological processes. We aimed to determine the diagnostic accuracy of metabolites in exhaled breath as biomarkers of ARDS. Breath from ventilated intensive care unit patients (n=101) was analysed using gas chromatography and mass spectrometry during the first day of admission. ARDS was defined by the Berlin definition. Training and temporal validation cohorts were used. 23 patients in the training cohort (n=53) had ARDS. Three breath metabolites, octane, acetaldehyde and 3-methylheptane, could discriminate between ARDS and controls with an area under the receiver operating characteristic curve (AUC) of 0.80. Temporal external validation (19 ARDS cases in a cohort of 48) resulted in an AUC of 0.78. Discrimination was insensitive to adjustment for severity of disease, a direct or indirect cause of ARDS, comorbidities, or ventilator settings. Combination with the lung injury prediction score increased the AUC to 0.91 and improved net reclassification by 1.17. Exhaled breath analysis showed good diagnostic accuracy for ARDS, which was externally validated. These data suggest that exhaled breath analysis could be used for the diagnostic assessment of ARDS.

Refining economics of U.S. gasoline: octane ratings and ethanol content.

Increasing the octane rating of the U.S. gasoline pool (currently ∼ 93 Research Octane Number (RON)) would enable higher engine efficiency for light-duty vehicles (e.g., through higher compression ratio), facilitating compliance with federal fuel economy and greenhouse gas (GHG) emissions standards. The federal Renewable Fuels Standard calls for increased renewable fuel use in U.S. gasoline, primarily ethanol, a high-octane gasoline component. Linear programming modeling of the U.S. refining sector was used to assess the effects on refining economics, CO2 emissions, and crude oil use of increasing average octane rating by increasing (i) the octane rating of refinery-produced hydrocarbon blendstocks for oxygenate blending (BOBs) and (ii) the volume fraction (Exx) of ethanol in finished gasoline. The analysis indicated the refining sector could produce BOBs yielding finished E20 and E30 gasolines with higher octane ratings at modest additional refining cost, for example, ∼ 1¢/gal for 95-RON E20 or 97-RON E30, and 3-5¢/gal for 95-RON E10, 98-RON E20, or 100-RON E30. Reduced BOB volume (from displacement by ethanol) and lower BOB octane could (i) lower refinery CO2 emissions (e.g., ∼ 3% for 98-RON E20, ∼ 10% for 100-RON E30) and (ii) reduce crude oil use (e.g., ∼ 3% for 98-RON E20, ∼ 8% for 100-RON E30).

Economic and environmental benefits of higher-octane gasoline.

We quantify the economic and environmental benefits of designing U.S. light-duty vehicles (LDVs) to attain higher fuel economy by utilizing higher octane (98 RON) gasoline. We use engine simulations, a review of experimental data, and drive cycle simulations to estimate the reduction in fuel consumption associated with using higher-RON gasoline in individual vehicles. Lifecycle CO2 emissions and economic impacts for the U.S. LDV fleet are estimated based on a linear-programming refinery model, a historically calibrated fleet model, and a well-to-wheels emissions analysis. We find that greater use of high-RON gasoline in appropriately tuned vehicles could reduce annual gasoline consumption in the U.S. by 3.0-4.4%. Accounting for the increase in refinery emissions from production of additional high-RON gasoline, net CO2 emissions are reduced by 19-35 Mt/y in 2040 (2.5-4.7% of total direct LDV CO2 emissions). For the strategies studied, the annual direct economic benefit is estimated to be $0.4-6.4 billion in 2040, and the annual net societal benefit including the social cost of carbon is estimated to be $1.7-8.8 billion in 2040. Adoption of a RON standard in the U.S. in place of the current antiknock index (AKI) may enable refineries to produce larger quantities of high-RON gasoline.

Measuring gas-liquid partition coefficients of aroma compounds by solid phase microextraction, sampling either headspace or liquid.

Hydrophobic compounds are important odorants and nutrients in foods and beverages, as well as environmental contaminants and pharmaceuticals. Factors influencing their partitioning within multi-component systems and/or from the bulk liquid phase to the air are critical for understanding aroma quality and nutrient bioavailability. The equilibrium partitioning of hydrophobic analytes between air and water was analyzed using solid phase microextraction (SPME) in the headspace (HS-SPME) and via direct immersion in the liquid (DI-SPME). The compounds studied serve as models for hydrophobic aroma compounds covering a range of air-water partition coefficients that extends over four orders of magnitude. By varying the total amount of analyte as well as the ratio of vapor to liquid in the closed, static system, the partition coefficient, K(vl), can be determined without the need for an external calibration, eliminating many potential systematic errors. K(vl) determination using DI-SPME in this manner has not been demonstrated before. There was good agreement between results determined by DI-SPME and by HS-SPME over the wide range of partitioning behavior studied. This shows that these two methods are capable of providing accurate, complementary measurements. Precision in K(vl) determination depends strongly on K(vl) magnitude and the ratio of the air and liquid phases.

Dynamic response of gold nanoparticle chemiresistors to organic analytes in aqueous solution.

We investigate the response dynamics of 1-hexanethiol-functionalized gold nanoparticle chemiresistors exposed to the analyte octane in aqueous solution. The dynamic response is studied as a function of the analyte-water flow velocity, the thickness of the gold nanoparticle film and the analyte concentration. A theoretical model for analyte limited mass-transport is used to model the analyte diffusion into the film, the partitioning of the analyte into the 1-hexanethiol capping layers and the subsequent swelling of the film. The degree of swelling is then used to calculate the increase of the electron tunnel resistance between adjacent nanoparticles which determines the resistance change of the film. In particular, the effect of the nonlinear relationship between resistance and swelling on the dynamic response is investigated at high analyte concentration. Good agreement between experiment and the theoretical model is achieved.

Sparse NIR optimization method (SNIRO) to quantify analyte composition with visible (VIS)/near infrared (NIR) spectroscopy (350 nm-2500 nm).

Visual-Near-Infra-Red (VIS/NIR) spectroscopy has led the revolution in high-throughput phenotyping methods used to determine chemical and structural elements of organic materials. In the current state of the art, spectrophotometers used for imaging techniques are either very expensive or too large to be used as a field-operable device. In this study we developed a Sparse NIR Optimization method (SNIRO) that selects a pre-determined number of wavelengths that enable quantification of analytes in a given sample using linear regression. We compared the computed complexity time and the accuracy of SNIRO to Marten's test, to forward selection test and to LASSO all applied to the determination of protein content in corn flour and meat and octane number in diesel using publicly available datasets. In addition, for the first time, we determined the glucose content in the green seaweed Ulva sp., an important feedstock for marine biorefinery. The SNIRO approach can be used as a first step in designing a spectrophotometer that can scan a small number of specific spectral regions, thus decreasing, potentially, production costs and scanner size and enabling the development of field-operable devices for content analysis of complex organic materials.

Research on the effect of wall corrosion and rim seal on the withdrawal loss for a floating roof tank.

Storage tanks are important parts of volatile organic compound (VOC) fugitive emission sources of the petrochemical industry; the floating roof tank is the main oil storage facility at present. Based on the mechanism of withdrawal loss and the type of rim seal, octane and gasoline were taken as the research objects. A model instrument for simulating the oil loading process by the 316 stainless steel and A3 carbon steel as the test piece was designed, and the film thickness was measured by wet film thickness gauge to investigate the influence of the corrosion of the tank wall and rim seal on the withdrawal loss for floating roof tanks. It was found that withdrawal loss was directly proportional to the shell factor, and the oil thickness of the octane and gasoline increased with the strength of the wall corrosion with the same wall material and rim seal. Compared with the untreated test piece, the oil film thickness of the octane/gasoline was increased by 7.04~8.57 µm/13.14~21.93 µm and 5.59~11.49 µm/11.61~25.48 µm under the corrosion of hydrochloric acid for 32 and 75 h, respectively. The oil film thickness of octane and gasoline decreased with the increasing of the rim seal, and the oil film thickness of the octane decreased by 11.97~28.90% and 37.32~73.83% under the resilient-filled seal and the double seal, respectively. The gasoline dropped by 11.97~31.18% and 45.98~75.34% under the resilient-filled seal and the double seal, respectively. In addition, the tank surface roughness reduced the compression of the rim seal on the tank wall, and the effect of scraping decreased. The API withdrawal loss formula for a floating roof tank was recommended to take into account the effect of the rim seal to improve the accuracy of the loss evaluation. Finally, some measures of reducing the withdrawal loss were proposed.

Investigation of high-speed gas chromatography using synchronized dual-valve injection and resistively heated temperature programming.

High-speed temperature programming is implemented via the direct resistive heating of the separation column (2.3m MXT-5 Silicosteel column with a 180 microm I.D. and a 0.4 microm 5% phenyl/95% dimethyl polysiloxane film). Resistive temperature programming was coupled with synchronized dual-valve injection (with an injection pulse width of 2 ms), producing a complete high-speed gas chromatography (GC) system. A comparison of isothermal and temperature programmed separations of seven n-alkanes (C(6) and C(8)-C(13)) shows a substantial improvement of peak width and peak capacity with temperature programming. The system was further implemented in separations of a mixture of analytes from various chemical classes. Separations of the n-alkane mixture using three different temperature programming rates are reported. A temperature programming rate as high as 240 degrees C/s is demonstrated. The method for determination of temperature programming rate, based on isothermal data, is discussed. The high-speed resistive column heating temperature programming resulted in highly reproducible separations. The highest rate of temperature programming (240 degrees C/s) resulted in retention time and peak width RSD, on average, of 0.5 and 1.4%, respectively, for the n-alkane mixture. This high level of precision was achieved with peak widths-at-half-height ranging from 13 to 36 ms, and retention times ranging from 147 to 444 ms (for n-hexane to n-tridecane).

Determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry.

Analytical methodology was developed and validated for the determination of spiroxamine residues in grapes, must, and wine by gas chromatography/ion trap-mass spectrometry (GC/IT-MS). Two extraction procedures were used: the first involved grapes, must, and wine extraction with alkaline cyclohexane-dichloromethane (9 + 1, v/v) solution, and the second grape extraction with acetone, dichloromethane, and petroleum ether. In both procedures, the extract was centrifuged, evaporated to dryness, and reconstituted in cyclohexane or 2,2,4-trimethylpentane-toluene (9 + 1, v/v), respectively. Spiroxamine diastereomers A and B were determined by GC/IT-MS, and a matrix effect was observed in the case of grapes but not in must and wine. Recovery of spiroxamine from fortified samples at 0.02 to 5.0 mg/kg ranged from 78-102% for grapes and must, with relative standard deviation (RSD) <13%; for red and white wines, recoveries ranged from 90 to 101% with RSD <9%. The limit of quantification was 0.02 mg/kg for grapes, must, and wine or 0.10 mg/kg for grapes, depending on the extraction procedure used.

Transport of hydrocarbons from an emplaced fuel source experiment in the vadose zone at Airbase Vaerløse, Denmark.

An emplaced hydrocarbon source field experiment was conducted in the relatively homogeneous sandy geology of the vadose zone at Airbase Vaerløse, Denmark. The source (10.2 l of NAPL) consisted of 13 hydrocarbons (n-, iso- and cyclo-alkanes and aromates) and CFC-113 as a tracer. Monitoring in the 107 soil gas probes placed out to 20 m from the centre of the source showed spreading of all the compounds in the pore air and all compounds were measured in the pore air within a few hours after source emplacement. Seven of the fourteen compounds were depleted from the source within the 1 year of monitoring. The organic vapours in the pore air migrated radially from the source. The CFC-113 concentrations seemed to be higher in the deeper soil gas probes compared with the hydrocarbons, indicating a high loss of CFC-113 to the atmosphere and the lack of degradation of CFC-113. For the first days after source emplacement, the transport of CFC-113, hexane and toluene was successfully simulated using a radial gas-phase diffusion model for the unsaturated zone. Groundwater pollution caused by the vadose zone hydrocarbon vapours was only detected in the upper 30 cm of the underlying groundwater and only during the first 3 months of the experiment. Only the most water-soluble compounds were detected in the groundwater and concentrations decreased sharply with depth (approximately one order of magnitude within 10 cm depth) to non-detect at 30 cm depth. The groundwater table varied more than 1 m within the measurement period. However that did not influence the direction of the groundwater flow. Approximately 7 months after source emplacement the groundwater table rose more than 1 m within 1 month. That did not cause additional pollution of the groundwater.

[Near infrared spectra (NIR) analysis of octane number by wavelet denoising-derivative method].

Derivative can correct baseline effects and also increase the level of noise. Wavelet transform has been proven an efficient tool for de-noising. This paper is directed to the application of wavelet transfer and derivative in the NIR analysis of octane number (RON). The derivative parameters, as well as their effects on the noise level and analytic accuracy of RON, have been studied in detail. The results show that derivative can correct the baseline effects and increase the analytic accuracy. Noise from the derivative spectra has great detriment to the analysis of RON. De-noising of wavelet transform can increase the S/N and improve the analytical accuracy.

Intrinsic isotope effects suggest that the reaction coordinate symmetry for the cytochrome P-450 catalyzed hydroxylation of octane is isozyme independent.

The mechanism of the omega-hydroxylation of octane by three catalytically distinct, purified forms of cytochrome P-450, namely, P-450b, P-450c, and P-450LM2, was investigated by using deuterium isotope effects. The deuterium isotope effects associated with the omega-hydroxylation of octane-1,1,1-2H3, octane-1,8-2H2, and octane-1,1,8,8-2H4 by all three isozymes were determined. From these data the intrinsic isotope effects were calculated and separated into their primary and secondary components. The primary intrinsic isotope effect for the reaction ranged from 7.69 to 9.18 while the secondary intrinsic isotope effect ranged from 1.13 to 1.25. Neither the primary nor secondary isotope effect values were statistically different for any of the isozymes investigated. These data are consistent with a symmetrical transition state for a mechanism involving initial hydrogen atom abstraction followed by hydroxyl radical recombination which is essentially independent of the specific isozyme catalyzing the reaction. It is concluded that (1) in general the porphyrin-[FeO]3+ complex behaves as a source of a triplet-like oxygen atom, (2) the regioselectivity for the site of oxidation is dictated by the apoprotein of the specific isozyme of cytochrome P-450 catalyzing the reaction, and (3) the maximum primary intrinsic isotope effect for any cytochrome P-450 catalyzed oxidation of a carbon center is about 9, assuming no tunneling effects.

Unknown bisethylisooctanollactone isomers in industrial waste water. Isolation, identification and occurrence in surface water.

Unknown bisethylisooctanollactone isomers (BIOL isomers) which are chemical by-products of butyraldehyde synthesis, were isolated from industrial waste water applying various purification methods with subsequent semi-preparative high-performance liquid chromatography. Through interpretation of mass spectra after gas chromatographic separation the individual BIOL isomers were identified as stereoisomers of 2,4-diethyl-3-n-propyl-delta-valerolactone. Thus, it was possible for the first time to quantify the BIOL isomers in the river Rhine, Germany, with a mean sum concentration of 1.6 microg l(-1). A regular analysis performed over a period of almost two years of the river Rhine always gave the same ratio among the individual isomers. Drinking water production out of such water was studied, revealing that activated carbon filtration led to a 95% reduction of the BIOL concentration. Additional subsoil passage and a subsequent slowsand filtration led to a total elimination due to microbial degradation. Even if the BIOL isomers proved not to be relevant to drinking water, their behavior in the aquatic environment needs to be more thoroughly investigated since these compounds have been discharged for many years in high amounts into the river Rhine.

Gas chromatographic column for the storage of sample profiles.

The concept of a sample retention column that preserves the true time profile of an analyte of interest is studied. This storage system allows for the detection to be done at convenient times, as opposed to the nearly continuous monitoring that is required by other systems to preserve a sample time profile. The sample storage column is essentially a gas chromatography column, although its use is not the separation of sample components. The functions of the storage column are the selective isolation of the component of interest from the rest of the components present in the sample and the storage of this component as a function of time. Using octane as a test substance, the sample storage system was optimized with respect to such parameters as storage and readout temperature, flow rate through the storage column, column efficiency and storage time. A 3-h sample profile was collected and stored at 30 degrees C for 20 h. The profile was then retrieved, essentially intact, in 5 min at 130 degrees C.

Assessment of pareto calibration, stability, and wavelength selection.

Recent work has shown that ridge regression (RR) is Pareto to partial least squares (PLS) and principal component regression (PCR) when the variance indicator Euclidian norm of the regression coefficients, //p//, is plotted against the bias indicator root mean square error of calibration (RMSEC). Simplex optimization demonstrates that RR is Pareto for several other spectral data sets when //p// is used with RMSEC and the root mean square error of evaluation (RMSEE) as optimization criteria. From this investigation, it was observed that while RR is Pareto optimal, PLS and PCR harmonious models are near equivalent to harmonious RR models. Additionally, it was found that RR is Pareto robust, i.e., models formed at one temperature were then used to predict samples at another temperature. Wavelength selection is commonly performed to improve analysis results such that bias indicators RMSEC, RMSEE, root mean square error of validation, or root mean square error of cross-validation decrease using a subset of wavelengths. Just as critical to an analysis of selected wavelengths is an assessment of variance. Using wavelengths deemed optimal in a previous study, this paper reports on the variance/bias tradeoff. An approach that forms the Pareto model with a Pareto wavelength subset is suggested.

Aroma compound analysis of Eruca sativa (Brassicaceae) SPME headspace leaf samples using GC, GC-MS, and olfactometry.

The aroma compounds of rocket salad (Eruca sativa) SPME headspace samples of fresh leaves were analyzed using GC, GC-MS, and olfactometry. More than 50 constituents of the Eruca headspace could be identified to be essential volatiles, responsible for the characteristic intense green; herbal; nutty and almond-like; Brassicaceae-like (direction of cabbage, broccoli, and mustard); and horseradish-like aroma of these salad leaves. As aroma impact compounds, especially isothiocyanates, and derivatives of butane, hexane, octane, and nonane were identified. 4-Methylthiobutyl isothiocyanate (14.2%), cis-3-hexen-1-ol (11.0%), cis-3-hexenyl butanoate (10.8%), 5-methylthiopentyl isothiocyanate (9.3%), cis-3-hexenyl 2-methylbutanoate (5.4%), and 5-methylthiopentanenitrile (5.0%) were found in concentrations higher than 5.0% (calculated as % peak area of GC analysis using a nonpolar column).

Recovery of dodecane, octane and toluene spills in sandpacks using ethanol.

This paper is an extension of the work of Grubb et al. on the recovery of lighter-than-water non aqueous phase liquids (LNAPLs) from sandpacks. Dodecane, toluene and octane (500 mL each) were used to simulate fresh and weathered petroleum spills. The ethanol flooding experiments evaluated the feasibility of recovering the LNAPLs from unconfined uniform sandpacks in a quasi two-dimensional apparatus. A combined pure ethanol and 50/50 (vol.%) ethanol-water blend flooding strategy successfully mobilized and recovered the simulated large-volume LNAPL spills (10x greater than previous studies). At flow rates < 7 m per day, the toluene and octane recoveries were approximately 84.9 and 88.1%, respectively, which are considered impressive as no optimization was even attempted.

Exposures to benzene and other volatile compounds from active and passive smoking.

Personal exposures and breath concentrations of approximately 20 volatile organics were measured for 200 smokers and 322 nonsmokers in New Jersey and California. Smokers displayed significantly elevated breath levels of benzene, styrene, ethylbenzene, m + p-xylene, o-xylene, and octane. Significant increases in breath concentration with number of cigarettes smoked were noted for the first four aromatic compounds. Based on direct measurements of benzene in mainstream cigarette smoke, it is calculated that a typical smoker inhales 2 mg benzene daily, compared to 0.2 mg/day for the nonsmoker. Thus, cigarette smoking may be the most important source of exposure to benzene for about 50 million citizens of the United States. Passive smokers exposed at work had significantly elevated levels of aromatics in their breath. Indoor air levels in homes with smokers were significantly greater than in nonsmoking homes during fall and winter but not during spring and summer. The average annual increase in homes with smokers was 3.6 microgram/m3 for benzene and 0.5 microgram/m3 for styrene--an approximate 50% relative increase in each case. Thus, exposure to benzene and styrene may be increased for the approximately 60% of children and other nonsmokers living in homes with smokers.

[Analysis of PAHs by Shpol'skii fluorescence spectra in low temperature].

The factors affecting Shpol'skii fluorescence spectra have been investigated on a spectrofluorimeter coupled with a cryospectral system connected by optical fibres, and quasi-linear spectra were obtained. In combination with the synchronous fluorescence technique, the capability of spectral resolution in Shpol'skii spectra is illustrated. The result indicates that Shpol'skii fluorescence spectra may become a routine analytical tool for PAHs.