Baseline correction method for dynamic pressure gradient modulated comprehensive two-dimensional gas chromatography with flame ionization detection.

A baseline correction method is developed for comprehensive two-dimensional (2D) chromatography (GC × GC) with flame-ionization detection (FID) using dynamic pressure gradient modulation (DPGM). The DPGM-GC × GC-FID utilized porous layer open tubular (PLOT) columns in both dimensions to focus on light hydrocarbon separations. Since DPGM is nominally a stop-flow modulation technique, a rhythmic baseline disturbance is observed in the FID signal that cycles with the modulation period (PM). This baseline disturbance needs to be corrected to optimize trace analysis. The baseline correction method has three steps: collection of a background "blank" chromatogram and multiplying it by an optimized normalization factor, subtraction of the normalization-optimized background chromatogram from a sample chromatogram, and application of Savitzky-Golay smoothing. An alkane standard solution, containing pentane, hexane and heptane was used for method development, producing linear calibration curves (r2 > 0.991) over a broad concentration range (7.8 ppm - 4000 ppm). Further, the limit-of-detection (LOD) and limit-of-quantification (LOQ) were determined for pentane (LOD = 2.5 ppm, LOQ = 8.2 ppm), hexane (LOD = 0.9 ppm, LOQ = 3.0 ppm), and heptane (LOD = 1.9 ppm, LOQ = 6.4 ppm). A natural gas sample separation illustrated method applicability, whereby the DPGM produced a signal enhancement (SE) of 30 for isopentane, where SE is defined as the height of the tallest 2D peak in the modulated chromatogram for the analyte divided by the height of the unmodulated 1D peak. The 30-fold SE resulted in about a 10-fold improvement in the signal-to-noise ratio (S/N) for isopentane. Additional versatility of the baseline correction method for more complicated samples was demonstrated for an unleaded gasoline sample, which enabled the detection (and visual appearance) of trace components.

Volatile Organic Compounds, Bacterial Airway Microbiome, Spirometry and Exercise Performance of Patients after Surgical Repair of Congenital Diaphragmatic Hernia.

The aim of this study was to analyze the exhaled volatile organic compounds (VOCs) profile, airway microbiome, lung function and exercise performance in congenital diaphragmatic hernia (CDH) patients compared to healthy age and sex-matched controls. A total of nine patients (median age 9 years, range 6-13 years) treated for CDH were included. Exhaled VOCs were measured by GC-MS. Airway microbiome was determined from deep induced sputum by 16S rRNA gene sequencing. Patients underwent conventional spirometry and exhausting bicycle spiroergometry. The exhaled VOC profile showed significantly higher levels of cyclohexane and significantly lower levels of acetone and 2-methylbutane in CDH patients. Microbiome analysis revealed no significant differences for alpha-diversity, beta-diversity and LefSe analysis. CDH patients had significantly lower relative abundances of Pasteurellales and Pasteurellaceae. CDH patients exhibited a significantly reduced Tiffeneau Index. Spiroergometry showed no significant differences. This is the first study to report the VOCs profile and airway microbiome in patients with CDH. Elevations of cyclohexane observed in the CDH group have also been reported in cases of lung cancer and pneumonia. CDH patients had no signs of impaired physical performance capacity, fueling controversial reports in the literature.

Micro-fabricated packed metal gas preconcentrator for enhanced monitoring of ultralow concentration of isoprene.

A novel non-silicon-based micro-preconcentration device, as a pretreatment component in a portable gas chromatography system, was developed for the preconcentration one of the trace volatile organic compounds (VOCs) in the exhaled gases, which is one typical biomarker for the chronic liver disease (CLD). The device was designed as an array of manifold-shaped rectangular metal micro-channels with flat dimensions of 16 mm × 12.6 mm and the internal empty volume is 14.4 µL on the copper substrate. Instead of the non-silicon fabrication process, the traditional laser etching technology (LET) was optimized to etch micro-channels, and vacuum diffusion welding (VDW) was applied to form internal channels. The fabricated chip was filled with Carbopack X adsorbent. In the testing, the metal gas preconcentrator (MGP) was installed in a commercial GC (gas chromatography) and nitrogen was used as carrier gas and desorbed gas. With the MPG, up to 352 of concentration factor can be achieved for 10 ppb isoprene. The developed MGP, which has advantages of high strength, low cost, good thermal conductivities, can potentially be used for non-invasive screening of advanced liver fibrosis by monitoring isoprene concentrations in exhaled breath.

Speciated VOCs emission estimate for a typical petrochemical manufacturing plant in China using inverse-dispersion calculation method.

Volatile organic compounds (VOCs) play a key role in air pollution of China. Among various sources, petrochemical industry is one of the important contributors, but its VOC emission estimate still exists a big uncertainty. Therefore, this study developed an inverse-dispersion calculation method (IDM), and applied it in a typical petrochemical plant that manufactures ethylene (170 kt/year), polyethylene (100 kt/year), and polypropylene (61 kt/year), and determined the VOC emission amount for this complex industrial area source. Firstly, this study monitored VOC concentrations around this plant in April of 2017, and found that the VOCs at downwind receptors was obviously higher than the level at background, higher by 20.7 ppb on average. This VOC increment was mainly contributed by ethylene (30.4%), propylene (17.8%), pentanes (16.4%), and butanes (13.4%), which is consistent with the knowledge of VOC components emitted from the manufacturing of ethylene, polyethylene, and polypropylene. Then, by using the inverse-dispersion calculation method (IDM), we determined the relationship coefficient γ between source emission rate and ambient concentration for each receptor of each test based on an assumed source emission rate, combined γ with the actual VOC concentrations measured in monitoring tests, and estimated the average VOCs emission of 666.0 tons/year for this plant, including 18.1 tons for ethane, 21.1 tons for propane, 61.6 tons for isobutane, 44.3 tons for n-butane, 79.3 tons for isopentane, 56.8 tons for n-pentane, 115.4 tons for ethylene, 102.5 tons for propylene, 92.7 tons for benzene, and 74.1 tons for toluene. Our IDM estimate was in the same order with the traditional emission factor method estimate (916.4 tons VOCs per year for this plant), and we believed the IDM can be applied to effectively estimate the VOCs emissions for those complicated industrial sources.

Pentane and other volatile organic compounds, including carboxylic acids, in the exhaled breath of patients with Crohn's disease and ulcerative colitis.

A study has been carried out on the volatile organic compounds (VOCs) in the exhaled breath of patients suffering from inflammatory bowel disease (IBD), comprising 136 with Crohn's disease (CD) and 51 with ulcerative colitis (UC), together with a cohort of 14 healthy persons as controls. Breath samples were collected by requesting the patients to inflate Nalophan bags, which were then quantitatively analysed using selected ion flow tube mass spectrometry (SIFT-MS). Initially, the focus was on n-pentane that had previously been quantified in single exhalations on-line to SIFT-MS for smaller cohorts of IBD patients. It was seen that the median concentration of pentane was elevated in the bag breath samples of the IBD patients compared to those of the healthy controls, in accordance with the previous study. However, the absolute median pentane concentrations in the bag samples were about a factor of two lower than those in the directly analysed single exhalations-a good illustration of the dilution of VOCs in the samples of breath collected into bags. Accounting for this dilution effect, the concentrations of the common breath VOCs, ethanol, propanol, acetone and isoprene, were largely as expected for healthy controls. The concentrations of the much less frequently measured hydrogen sulphide, acetic acid, propanoic acid and butanoic acid were seen to be more widely spread in the exhaled breath of the IBD patients compared to those for the healthy controls. The relative concentrations of pentane and these other VOCs weakly correlate with simple clinical activity indices. It is speculated that, potentially, hydrogen sulphide and these carboxylic acids could be exhaled breath biomarkers of intestinal bacterial overgrowth, which could assist therapeutic intervention and thus alleviate the symptoms of IBD.

Volatile Organic Compounds in Exhaled Breath of Idiopathic Pulmonary Fibrosis for Discrimination from Healthy Subjects.

Purpose Human breath analysis is proposed with increasing frequency as a useful tool in clinical application. We performed this study to find the characteristic volatile organic compounds (VOCs) in the exhaled breath of patients with idiopathic pulmonary fibrosis (IPF) for discrimination from healthy subjects. Methods VOCs in the exhaled breath of 40 IPF patients and 55 healthy controls were measured using a multi-capillary column and ion mobility spectrometer. The patients were examined by pulmonary function tests, blood gas analysis, and serum biomarkers of interstitial pneumonia. Results We detected 85 VOC peaks in the exhaled breath of IPF patients and controls. IPF patients showed 5 significant VOC peaks; p-cymene, acetoin, isoprene, ethylbenzene, and an unknown compound. The VOC peak of p-cymene was significantly lower (p < 0.001), while the VOC peaks of acetoin, isoprene, ethylbenzene, and the unknown compound were significantly higher (p < 0.001 for all) compared with the peaks of controls. Comparing VOC peaks with clinical parameters, negative correlations with VC (r =-0.393, p = 0.013), %VC (r =-0.569, p < 0.001), FVC (r = -0.440, p = 0.004), %FVC (r =-0.539, p < 0.001), DLco (r =-0.394, p = 0.018), and %DLco (r =-0.413, p = 0.008) and a positive correlation with KL-6 (r = 0.432, p = 0.005) were found for p-cymene. Conclusion We found characteristic 5 VOCs in the exhaled breath of IPF patients. Among them, the VOC peaks of p-cymene were related to the clinical parameters of IPF. These VOCs may be useful biomarkers of IPF.

Monitoring of breath VOCs and electrical impedance tomography under pulmonary recruitment in mechanically ventilated patients.

Analysis of exhaled VOCs can provide information on physiology, metabolic processes, oxidative stress and lung diseases. In critically ill patients, VOC analysis may be used to gain complimentary information beyond global clinical parameters. This seems especially attractive in mechanically ventilated patients frequently suffering from impairment of gas exchange. This study was intended to assess (a) the effects of recruitment maneuvers onto VOC profiles, (b) the correlations between electrical impedance tomography (EIT) data and VOC profiles and (c) the effects of recruitment onto distribution of ventilation. Eleven mechanically ventilated patients were investigated during lung recruitment after cardiac surgery. Continuous breath gas analysis by means of PTR-ToF-MS, EIT and blood gas analyses were performed simultaneously. More than 300 mass traces could be detected and monitored continuously by means of PTR-ToF-MS in every patient. Exhaled VOC concentrations varied with recruitment induced changes in minute ventilation and cardiac output. Ammonia exhalation depended on blood pH. The improvement in dorsal lung ventilation during recruitment ranged from 9% to 110%. Correlations between exhaled concentrations of acetone, isoprene, benzene sevoflurane and improvement in regional ventilation during recruitment were observed. Extent and quality of these correlations depended on physico-chemical properties of the VOCs. Combination of continuous real-time breath analysis and EIT revealed correlations between exhaled VOC concentrations and distribution of ventilation. This setup enabled immediate recognition of physiological and therapeutic effects in ICU patients. In a perspective, VOC analysis could be used for non-invasive control and optimization of ventilation strategies.

Sequential biodegradation of complex naphtha hydrocarbons under methanogenic conditions in two different oil sands tailings.

Methane emissions in oil sands tailings ponds are sustained by anaerobic biodegradation of unrecovered hydrocarbons. Naphtha (primarily C6-C10; n- iso- and cycloalkanes) is commonly used as a solvent during bitumen extraction process and its residue escapes to tailings ponds during tailings deposition. To investigate biodegradability of hydrocarbons in naphtha, mature fine tailings (MFT) collected from Albian and CNRL tailings ponds were amended with CNRL naphtha at ∼0.2 wt% (∼2000 mg L-1) and incubated under methanogenic conditions for ∼1600 d. Microbial communities in both MFTs started metabolizing naphtha after a lag phase of ∼100 d. Complete biodegradation/biotransformation of all n-alkanes (except partial biodegradation of n-octane in CNRL MFT) followed by major iso-alkanes (2-methylpentane, 3-methylhexane, 2- and 4-methylheptane, iso-nonanes and 2-methylnonane) and a few cycloalkanes (derivatives of cyclopentane and cyclohexane) was observed during the incubation. 16S rRNA gene pyrosequencing showed dominance of Peptococcaceae and Anaerolineaceae in Albian MFT and Anaerolineaceae and Syntrophaceae in CNRL MFT bacterial communities with co-domination of Methanosaetaceae and "Candidatus Methanoregula" in archaeal populations during active biodegradation of hydrocarbons. The findings extend the known range of hydrocarbons susceptible to methanogenic biodegradation in petroleum-impacted anaerobic environments and help refine existing kinetic model to predict greenhouse gas emissions from tailings ponds.

Real-Time Analysis of Isoprene in Breath by Using Ultraviolet-Absorption Spectroscopy with a Hollow Optical Fiber Gas Cell.

A breath analysis system based on ultraviolet-absorption spectroscopy was developed by using a hollow optical fiber as a gas cell for real-time monitoring of isoprene in breath. The hollow optical fiber functions as an ultra-small-volume gas cell with a long path. The measurement sensitivity of the system was evaluated by using nitric-oxide gas as a gas sample. The evaluation result showed that the developed system, using a laser-driven, high-intensity light source and a 3-m-long, aluminum-coated hollow optical fiber, could successfully measure nitric-oxide gas with a 50 ppb concentration. An absorption spectrum of a breath sample in the wavelength region of around 200-300 nm was measured, and the measured spectrum revealed the main absorbing components in breath as water vapor, isoprene, and ozone converted from oxygen by radiation of ultraviolet light. The concentration of isoprene in breath was estimated by multiple linear regression. The regression analysis results showed that the proposed analysis system enables real-time monitoring of isoprene during the exhaling of breath. Accordingly, it is suitable for measuring the circadian variation of isoprene.

The potential of the mevalonate pathway for enhanced isoprenoid production.

The cytosol-localised mevalonic acid (MVA) pathway delivers the basic isoprene unit isopentenyl diphosphate (IPP). In higher plants, this central metabolic intermediate is also synthesised by the plastid-localised methylerythritol phosphate (MEP) pathway. Both MVA and MEP pathways conspire through exchange of intermediates and regulatory interactions. Products downstream of IPP such as phytosterols, carotenoids, vitamin E, artemisinin, tanshinone and paclitaxel demonstrate antioxidant, cholesterol-reducing, anti-ageing, anticancer, antimalarial, anti-inflammatory and antibacterial activities. Other isoprenoid precursors including isoprene, isoprenol, geraniol, farnesene and farnesol are economically valuable. An update on the MVA pathway and its interaction with the MEP pathway is presented, including the improvement in the production of phytosterols and other isoprenoid derivatives. Such attempts are for instance based on the bioengineering of microbes such as Escherichia coli and Saccharomyces cerevisiae, as well as plants. The function of relevant genes in the MVA pathway that can be utilised in metabolic engineering is reviewed and future perspectives are presented.

National review of ambient air toxics observations.

UNLABELLED: Ambient air observations of hazardous air pollutant (HAPs), also known as air toxics, derived from routine monitoring networks operated by states, local agencies, and tribes (SLTs), are analyzed to characterize national concentrations and risk across the nation for a representative subset of the 187 designated HAPs. Observations from the National Air Toxics Trend Sites (NATTS) network of 27 stations located in most major urban areas of the contiguous United States have provided a consistent record of HAPs that have been identified as posing the greatest risk since 2003 and have also captured similar concentration patterns of nearly 300 sites operated by SLTs. Relatively high concentration volatile organic compounds (VOCs) such as benzene, formaldehyde, and toluene exhibit the highest annual average concentration levels, typically ranging from 1 to 5 µg/m(3). Halogenated (except for methylene chloride) and semivolatile organic compounds (SVOCs) and metals exhibit concentrations typically 2-3 orders of magnitude lower. Formaldehyde is the highest national risk driver based on estimated cancer risk and, nationally, has not exhibited significant changes in concentration, likely associated with the large pool of natural isoprene and formaldehyde emissions. Benzene, toluene, ethylbenzene, and 1,3-butadiene are ubiquitous VOC HAPs with large mobile source contributions that continue to exhibit declining concentrations over the last decade. Common chlorinated organic compounds such as ethylene dichloride and methylene chloride exhibit increasing concentrations. The variety of physical and chemical attributes and measurement technologies across 187 HAPs result in a broad range of method detection limits (MDLs) and cancer risk thresholds that challenge confidence in risk results for low concentration HAPs with MDLs near or greater than risk thresholds. From a national monitoring network perspective, the ability of the HAPs observational database to characterize the multiple pollutant and spatial scale patterns influencing exposure is severely limited and positioned to benefit by leveraging a variety of emerging measurement technologies. IMPLICATIONS: Ambient air toxics observation networks have limited ability to characterize the broad suite of hazardous air pollutants (HAPs) that affect exposures across multiple spatial scales. While our networks are best suited to capture major urban-scale signals of ubiquitous volatile organic compound HAPs, incorporation of sensing technologies that address regional and local-scale exposures should be pursued to address major gaps in spatial resolution. Caution should be exercised in interpreting HAPs observations based on data proximity to minimum detection limit and risk thresholds.

A predictive method for volatile organic compounds emission from soil: Evaporation and diffusion behavior investigation of a representative component of crude oil.

Pipelines are convenient, economical and widely used mode of transportation of crude oil. However, the inevitable or otherwise accidents during such transport of crude oil lead to large scale oil spills, which consequently result in both soil and air pollution. When such pollution occurs, crude oil VOC concentrations in air, soil pollution evaluation and VOC propagation in soil provide important evidence for airborne detection of oils spills. Therefore, several issues, including determination method for VOC, isotherm parameters of VOC sorption on soil surfaces, and VOC diffusion flux simulation, are significant. In our previous study, n-butane and n-pentane were proved to be the maximum VOCs in studied crude oils. Therefore, a predictive method using n-pentane as a representative component is proposed in this paper. Firstly, a headspace solid phase microextraction (SPME) method was developed for determination of n-pentane in non-equilibrium mass transfer conditions. Secondly, Brunauer-Emmett-Teller (BET) analysis with liquid nitrogen was carried out to predict isotherm parameters for n-pentane. Finally, two models were used to predict the emission process. Probably influenced by gas vapor density below and above the soil layer, the experimental data amounted to 74% of the deduced value from the simplified analytical model. However, the free diffusion model fitted well with the experimental results.

Pitfalls in the analysis of volatile breath biomarkers: suggested solutions and SIFT-MS quantification of single metabolites.

The experimental challenges presented by the analysis of trace volatile organic compounds (VOCs) in exhaled breath with the objective of identifying reliable biomarkers are brought into focus. It is stressed that positive identification and accurate quantification of the VOCs are imperative if they are to be considered as discreet biomarkers. Breath sampling procedures are discussed and it is suggested that for accurate quantification on-line real time sampling and analysis is desirable. Whilst recognizing such real time analysis is not always possible and sample collection is often required, objective recognition of the pitfalls involved in this is essential. It is also emphasized that mouth-exhaled breath is always contaminated to some degree by orally generated compounds and so, when possible, analysis of nose-exhaled breath should be performed. Some difficulties in breath analysis are mitigated by the choice of analytical instrumentation used, but no single instrument can provide solutions to all the analytical challenges. Analysis and interpretation of breath analysis data, however acquired, needs to be treated circumspectly. In particular, the excessive use of statistics to treat imperfect mass spectrometry/mobility spectra should be avoided, since it can result in unjustifiable conclusions. It is should be understood that recognition of combinations of VOCs in breath that, for example, apparently describe particular cancer states, will not be taken seriously until they are replicated in other laboratories and clinics. Finally, the inhibiting notion that single biomarkers of infection and disease will not be identified and utilized clinically should be dispelled by the exemplary and widely used single biomarkers NO and H2 and now, as indicated by recent selected ion flow tube mass spectroscopy (SIFT-MS) results, triatomic hydrogen cyanide and perhaps pentane and acetic acid. Hopefully, these discoveries will provide encouragement to research workers to be more open-minded on this important and desirable issue.

Volatile sulphur compound measurement with OralChroma(TM): a methodological improvement.

The instrumental measurement of volatile sulphur compounds is a common practice to assess halitosis. One of the most widespread devices for that purpose is OralChroma(TM), a combination of a semiconductor gas sensor and a compact gas chromatograph (GC) system. Several lines of evidence indicate that although the hardware of OralChroma(TM) is fit for the precise measurement of volatile sulphur compounds (VSCs), its software needs revision to allow that precision. In this study we sought to develop software to solve this problem, and to test the utility of the new software in a population of patients and controls. The results were also compared with VSC measurements performed with Halimeter(®), another widespread device, so as to assess the correlation. A set of measurements involving volunteers (21 controls and 14 oral cancer patients) were conducted. The analysis of the chromatograms recorded by OralChroma(TM) indicated that the majority of the studied breath samples contained significant amounts of isoprene (the peak was around 100 s) and acetaldehyde (the peak was around 350 s), therefore OralChroma(TM) was also calibrated for both isoprene and acetaldehyde. A linear relationship was found between the concentration (in the range of 80-1400 ppbv for acetaldehyde and 40-560 ppbv for isoprene) and the area under the corresponding peak. In numerous cases the concentrations of VSCs calculated by the software of OralChroma(TM) required revision. In the new software, the concentrations of the VSCs, isoprene and acetaldehyde were determined by fitting the chromatograms with the sum of six Gaussian functions. Based on the findings of the present study we conclude that our new software allows an improved and instantaneous evaluation of OralChroma(TM) chromatograms with the additional possibility of determining the isoprene and acetaldehyde concentrations from breath samples.

Breath metabolite response to major upper gastrointestinal surgery.

BACKGROUND: Esophagectomy and gastrectomy are associated with profound metabolic changes and significant postoperative morbidity. The aim of this prospective clinical study was to determine whether breath analysis can offer novel insight into the surgical metabolic response and identify biomarkers of postoperative complications, including lung injury. METHODS: Breath samples were collected preoperatively and at 24, 48, 72, 96 and 168 h after esophagectomy (n = 25) and gastrectomy (n = 15). Targeted analysis of four prominent breath metabolites was performed by selected ion flow-tube mass spectrometry. Patients with nonsurgical lung injury (community-acquired pneumonia) were recruited as positive controls. RESULTS: Perioperative starvation and subsequent reintroduction of nutritional input were associated with significant changes in breath acetone levels. Breath acetone levels fell after esophagectomy (P = 0.008) and were significantly lower than in gastrectomy patients at postoperative time points 48 (P < 0.001) and 72 h (P < 0.001). In contrast, concentrations of isoprene increased significantly after esophagectomy (P = 0.014). Pneumonia was the most frequently observed postoperative complication (esophagectomy 36% and gastrectomy 7%). The concentration of hydrogen cyanide was significantly lower in the breath of patients who developed pneumonia, 72 h after surgery (P = 0.008). Exhaled hydrogen cyanide (P = 0.001) and isoprene (P = 0.014) were also reduced in patients with community-acquired pneumonia compared with healthy controls. CONCLUSIONS: Selected ion flow-tube mass spectrometry can be used as a totally noninvasive resource to monitor multiple aspects of metabolic alterations in the postoperative period. Exhaled concentrations of several prominent metabolites are significantly altered after major upper gastrointestinal surgery and in response to pneumonia.

Volatile organic compounds in bile can diagnose malignant biliary strictures in the setting of pancreatic cancer: a preliminary observation.

BACKGROUND: Ascertaining the nature of biliary strictures is challenging. The role of volatile organic compounds (VOCs) in bile in determining the cause of biliary strictures is not known. OBJECTIVE: To identify potential VOCs in the headspaces (gas above the sample) of bile in patients with malignant biliary strictures from pancreatic cancer. DESIGN: Prospective cross-sectional study. SETTING: Referral center. PATIENTS: Prospective study in which bile was aspirated in 96 patients undergoing ERCP for benign and malignant conditions. MAIN OUTCOME MEASUREMENTS: Selected ion flow tube mass spectrometry (VOICE200R SIFT-MS instrument; Syft Technologies Ltd, Christchurch, New Zealand) was used to analyze the headspace and to build a predictive model for pancreatic cancer. RESULTS: The headspaces from 96 bile samples were analyzed, including 24 from patients with pancreatic cancer and 72 from patients with benign biliary conditions. The concentrations of 6 compounds (acetaldehyde, acetone, benzene, carbon disulfide, pentane, and trimethylamine [TMA]) were increased in patients with pancreatic cancer compared with controls (P < .05). By using receiver-operating characteristic curve analysis, we developed a model for the diagnosis of pancreatic cancer based on the levels of TMA, acetone, isoprene, dimethyl sulfide, and acetaldehyde. The model [10.94 + 1.8229* log (acetaldehyde) + 0.7600* log (acetone) - 1.1746* log (dimethyl sulfide) + 1.0901* log (isoprene) - 2.1401 * log (trimethylamine) ≥ 10] identified the patients with pancreatic cancer (area under the curve = 0.85), with 83.3% sensitivity and 81.9% specificity. LIMITATIONS: Sample size. CONCLUSIONS: The measurement of biliary fluid VOCs may help to distinguish malignant from benign biliary strictures. Further studies are warranted to validate these observations. (Clinical Trial Registration Number NCT01565460.).

Determination of breath isoprene and acetone concentration with a needle-type extraction device in gas chromatography-mass spectrometry.

BACKGROUND: Isoprene in human breath is said to be related to cholesterol metabolism, and the possibility of the correlations with some clinical parameters has been studied. However, at this stage, no clear benefit of breath isoprene has been reported for clinical diagnosis. In this work, isoprene and acetone concentrations were measured in the breath of healthy and obese subjects using a needle-type extraction device for subsequent analysis in gas chromatography-mass spectrometry (GC-MS) to investigate the possibility of these compounds as an indicator of possible diseases. METHODS: After measuring intraday and interday variations of isoprene and acetone concentrations in breath samples of healthy subjects, their concentrations were also determined in 80 healthy and 17 obese subjects. In addition, correlation between these breath concentrations and the blood tests result was studied for these healthy and obese subjects. RESULTS: The results indicated successful determination of breath isoprene and acetone in this work, however, no clear correlation was observed between these measured values and the blood test results. CONCLUSIONS: Breath isoprene concentration may not be a useful indicator for obesity or hypercholesterolemia.

Detection of potential chronic kidney disease markers in breath using gas chromatography with mass-spectral detection coupled with thermal desorption method.

The analytical potential of chromatographic breath analysis towards detection of compounds suggested as markers of chronic kidney disease (CKD) was tested. Until now, trimethylamine (TMA) considered as a potential marker of renal disorder was detected mainly in plasma. Detection of TMA in breath was rarely undertaken due to analytical difficulties associated with amines' properties. The results of our investigations confirmed that an application of thermal desorption (TD) and gas chromatography with mass-spectral detection (GC/MS) allows direct detection of TMA in breath. The preliminary studies allowed to determine the breath composition in case of patients suffering from CKD and to compare the obtained results to a control group. Breath samples were collected from 14 patients and 9 healthy volunteers. TMA was detected in all patients suffering from CKD in the range 1.76-38.02ppb, but not in the control group. Acetone and isoprene were present in the exhaled air of all examined persons. The concentration of acetone was in the range of 26.52-329.46ppb in the patient group and 73.11-437.14ppb in the control group. Isoprene was detected in the range 57.17-329.8ppb among CKD patients and 27.99-143.77ppb in healthy volunteers. Additionally aliphatic hydrocarbons and sulfur compounds were determined in breath as compounds which could be essential in case of diseases coexisting with CKD. Apart from TMA and pentane no statistically significant differences were found using our analytical technique. TMA was detected in the breath of all patients with CKD and in none of breath samples in control group. TMA seems to be a promising marker of CKD.

Atmospheric pressure chemical ionization mass spectrometry of pyridine and isoprene: potential breath exposure and disease biomarkers.

Volatile organic compounds (VOCs) in exhaled human breath can serve as potential disease-specific and exposure biomarkers and therefore can reveal information about a subject's health and environment. Pyridine, a VOC marker for exposure to tobacco smoke, and isoprene, a liver disease biomarker, were studied using atmospheric pressure chemical ionization mass spectrometry (APCI-MS). While both molecules could be detected in low-ppb levels, interactions of the ionized analytes with their neutral forms and ambient air led to unusual ion/molecule chemistry. The result was a highly dynamic system and a nonlinear response to changes in analyte concentration. Increased presence of ambient water was found to greatly enhance the detection limit of pyridine and only slightly decrease that of isoprene. APCI-MS is shown to be a promising analytical tool in breath analysis with good detection limits, but its application requires a better understanding of the ion/molecule chemistry that may affect VOC quantification from a chemically complex system such as human breath.

Source signature of volatile organic compounds from oil and natural gas operations in northeastern Colorado.

An extensive set of volatile organic compounds (VOCs) was measured at the Boulder Atmospheric Observatory (BAO) in winter 2011 in order to investigate the composition and influence of VOC emissions from oil and natural gas (O&NG) operations in northeastern Colorado. BAO is 30 km north of Denver and is in the southwestern section of Wattenberg Field, one of Colorado's most productive O&NG fields. We compare VOC concentrations at BAO to those of other U.S. cities and summertime measurements at two additional sites in northeastern Colorado, as well as the composition of raw natural gas from Wattenberg Field. These comparisons show that (i) the VOC source signature associated with O&NG operations can be clearly differentiated from urban sources dominated by vehicular exhaust, and (ii) VOCs emitted from O&NG operations are evident at all three measurement sites in northeastern Colorado. At BAO, the reactivity of VOCs with the hydroxyl radical (OH) was dominated by C(2)-C(6) alkanes due to their remarkably large abundances (e.g., mean propane = 27.2 ppbv). Through statistical regression analysis, we estimate that on average 55 ± 18% of the VOC-OH reactivity was attributable to emissions from O&NG operations indicating that these emissions are a significant source of ozone precursors.