Long-term contributions of VOC sources and their link to ozone pollution in Bronx, New York City.

Changes in energy and environmental policies along with changes in the energy markets of New York State over the past two decades, have spurred interest in evaluating their impacts on emissions from various energy generation sectors. This study focused on quantifying these effects on VOC (volatile organic compounds) emissions and their subsequent impacts on air quality within the New York City (NYC) metropolitan area. NYC is an EPA nonattainment region for ozone (O3) and likely is a VOC limited region. NYC has a complex coastal topography and meteorology with low-level jets and sea/bay/land breeze circulation associated with heat waves, leading to summertime O3 exceedances and formation of secondary organic aerosol (SOA). To date, no comprehensive source apportionment studies have been done to understand the contributions of local and long-range sources of VOCs in this area. This study applied an improved Positive Matrix Factorization (PMF) methodology designed to incorporate atmospheric dispersion and photochemical reaction losses of VOCs to provide improved apportionment results. Hourly measurements of VOCs were obtained from a Photochemical Assessment Monitoring Station located at an urban site in the Bronx from 2000 to 2021. The study further explores the role of VOC sources in O3 and SOA formation and leverages advanced machine learning tools, XGBoost and SHAP algorithms, to identify synergistic interactions between sources and provided VOC source impacts on ambient O3 concentrations. Isoprene demonstrated a substantial influence in the source contribution of the biogenic factor, emphasizing its role in O3 formation. Notable contributions from anthropogenic emissions, such as fuel evaporation and various industrial processes, along with significant traffic-related sources that likely contribute to SOA formation, underscore the combined impact of natural and human-made sources on O3 pollution. Findings of this study can assist regulatory agencies in developing appropriate policy and management initiatives to control O3 pollution in NYC.

Sorption and attenuation of petroleum VOCs in five unsaturated soils: Microcosms and column experiments.

The fate of volatile organic compounds (VOC) vapors in the unsaturated zone is the basis for evaluating the natural attenuation potential and vapor intrusion risk. Microcosm and column experiments were conducted to study the effects chemical speciation and soil types/properties on the fate of petroleum VOCs in unsaturated zone. The biodegradation and total attenuation rates of the seven VOCs obtained by microcosm experiments in black soil and yellow earth were also generally higher than those in floodplain soil, lateritic red earth, and quartz sand. The VOC vapors in floodplain soil, lateritic red earth, and quartz sand showed slow total attenuation rates (<0.3 d-1). N-pentane, methylcyclopentane, and methylcyclohexane showed lower biodegradation rates than octane and three monoaromatic hydrocarbons. Volatilization into the atmosphere and biodegradation are two important natural attenuation paths for VOCs in unsaturated soil columns. The volatilization loss fractions of different volatile hydrocarbons in all five unsaturated soils were generally in the order: n-pentane (93.5%-97.8%) > methylcyclopentane (77.2%-85.5%) > methylcyclohexane (53.5%-69.2%) > benzene (17.1%-73.3%) > toluene (0-45.7%) > octane (1.9%-34.2%) > m-xylene (0-5.7%). The fractions by volatilization into the atmosphere of all seven hydrocarbons in quartz sand, lateritic red earth, and floodplain soil were close and higher compared to the yellow earth and black soil. Overall, this study illustrated the important roles chemical speciation and soil properties in determining the vapor-phase transport and natural attenuation of VOCs in the unsaturated zone.

Optimal seasonal schedule for the production of isoprene, a highly volatile biogenic VOC.

The leaves of many trees emit volatile organic compounds (abbreviated as BVOCs), which protect them from various damages, such as herbivory, pathogens, and heat stress. For example, isoprene is highly volatile and is known to enhance the resistance to heat stress. In this study, we analyze the optimal seasonal schedule for producing isoprene in leaves to mitigate damage. We assume that photosynthetic rate, heat stress, and the stress-suppressing effect of isoprene may vary throughout the season. We seek the seasonal schedule of isoprene production that maximizes the total net photosynthesis using Pontryagin's maximum principle. The isoprene production rate is determined by the changing balance between the cost and benefit of enhanced leaf protection over time. If heat stress peaks in midsummer, isoprene production can reach its highest levels during the summer. However, if a large portion of leaves is lost due to heat stress in a short period, the optimal schedule involves peaking isoprene production after the peak of heat stress. Both high photosynthetic rate and high isoprene volatility in midsummer make the peak of isoprene production in spring. These results can be clearly understood by distinguishing immediate impacts and the impacts of future expectations.

Unravelling the origin of isoprene in the human body-a forty year Odyssey.

In the breath research community's search for volatile organic compounds that can act as non-invasive biomarkers for various diseases, hundreds of endogenous volatiles have been discovered. Whilst these systemic chemicals result from normal and abnormal metabolic activities or pathological disorders, to date very few are of any use for the development of clinical breath tests that could be used for disease diagnosis or to monitor therapeutic treatments. The reasons for this lack of application are manifold and complex, and these complications either limit or ultimately inhibit the analytical application of endogenous volatiles for use in the medical sciences. One such complication is a lack of knowledge on the biological origins of the endogenous volatiles. A major exception to this is isoprene. Since 1984, i.e. for 40 years, it has been generally accepted that the pathway to the production of human isoprene, and hence the origin of isoprene in exhaled breath, is through cholesterol biosynthesis via the mevalonate (MVA) pathway within the liver. However, various studies between 2001 and 2012 provide compelling evidence that human isoprene is produced in skeletal muscle tissue. A recent multi-omic investigation of genes and metabolites has revealed that this proposal is correct by showing that human isoprene predominantly results from muscular lipolytic cholesterol metabolism. Despite the overwhelming proof for a muscular pathway to isoprene production in the human body, breath research papers still reference the hepatic MVA pathway. The major aim of this perspective is to review the evidence that leads to a correct interpretation for the origins of human isoprene, so that the major pathway to human isoprene production is understood and appropriately disseminated. This is important, because an accurate attribution to the endogenous origins of isoprene is needed if exhaled isoprene levels are to be correctly interpreted and for assessing isoprene as a clinical biomarker.

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.

Atmospheric isoprene and monoterpenes in a typical urban area of Beijing: Pollution characterization, chemical reactivity and source identification.

Continuous observation of isoprene, α-pinene and ß-pinene was carried out in a typical urban area of Beijing from March 2014 to February 2015, using an AirmoVOC online analyzer. Based on the analysis of the ambient level and variation characteristics of isoprene, α-pinene and ß-pinene, the chemical reactivity was studied, and their sources were identified. Results showed that the concentrations of isoprene, α-pinene and ß-pinene in the urban area of Beijing were lower than those in richly vegetated areas; the concentrations of isoprene were at a moderate level compared with those of previous studies of Beijing. Concentrations of isoprene, α-pinene and ß-pinene showed different seasonal, monthly, daily and diurnal variations, and all of the three species showed higher level at night than those in the daytime as a whole, the variations of isoprene, α-pinene and ß-pinene mainly influenced by emission of sources, photochemical reaction, and meteorological parameters. Isoprene was the largest contributor to the total OFP values than α-pinene and ß-pinene. α-Pinene was the largest contributor to the total SOAFP values than isoprene and ß-pinene in autumn, while isoprene was the largest one in other seasons. Isoprene, α-pinene and ß-pinene were derived mainly from biological sources; and α-pinene level were also affected by industrial sources. To reduce the concentrations of isoprene, α-pinene and ß-pinene, it is necessary to scientifically select urban green plant species, and more strict control measures should be taken to reduce the emission of α-pinene from industrial sources, such as artificial flavors and resins synthesis processes.

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.

[The effects of climate change on isoprene emission rate from leaves of Pleioblastus amarus in different regions.] / 气候变化影响下不同地区苦竹异戊二烯排放速率对比.

Based on the RCP2.6, RCP4.5, RCP6.0 and RCP8.5 climate change scenarios produced by the global climate model NorESM1-M and plant isoprene emissions model, the effects of climate change on the isoprene emission rate from leaves of Pleioblastus amarus in Yixing City of Jiangsu Province, Longmen County of Guangdong Province, Yulong Naxi Autonomous County of Yunnan Province and Wanyuan City of Sichuan Province were simulated. The differences of isoprene emission rate from leaves of P. amarus distributed in four regions were compared under future climate change scenarios. The results showed that mean annual air temperature would increase, annual precipitation and radiation intensity would greatly fluctuate, with the coexistence of increasing and decreasing trends in the four regions. In the baseline scenario, daily mean emission rate of isoprene from leaves of P. amarus was 71-470 µg·g-1·d-1, and annual mean value was 25954-171231 µg·g-1·a-1. The daily and annual emission rates in the four regions decreased with the order of Longmen, Yixing, Wanyuan and Yulong. Compared with the baseline scenario, daily mean emission rate of isoprene from leaves of P. amarus was about 4-45 µg·g-1·d-1 higher in future climate change scenario, and which was about 23, 29, 4, and 14 µg·g-1·d-1 higher than that in baseline in Yixing, Longmen, Yulong and Wanyuan, respectively. In addition, the emission rate of isoprene from leaves of P. amarus was more than 5% higher in the future climate change scenario than that in the baseline scenario, which was higher in Wanyuan and Yixing (>13%) than and lower in Longmen and Yulong (>5%). All the four regions reached the highest rate under RCP8.5 scenario (increased by about 11%-18%). Compared with the baseline scenario, annual emission rate of isoprene in the future climate change scenario was about 1500-17000 µg·g-1·a-1, and which was about 8560-13208 µg·g-1·a-1 higher in Yixing, 10862-16131 µg·g-1·a-1 higher in Longmen, 1574-3028 µg·g-1·a-1 higher in Yulong, 5288-8532 µg·g-1·a-1 higher in Wanyuan. In addition, the increasing rate of annual isoprene emission rates was 6%-14%. The rates in Yixing (8%-12%) and Wanyuan (8%-14%) were higher than that in the other two regions, the rate in Yulong (6%-12% increase) was the lowest, with all four regions increasing substantially (9%-14%) under RCP8.5 scenario. The results suggested that climate change would have different effects on the rate of isoprene emissions from leaves of P. amarus distributed in diffe-rent regions.

Characterization of volatile organic compounds and the impacts on the regional ozone at an international airport.

In this study, the measurement of volatile organic compounds (VOCs) was conducted at Beijing Capital International Airport (ZBAA) and a background reference site in four seasons of 2015. Total concentrations of VOCs were 72.6 ±â€¯9.7, 65.5 ±â€¯8.7, 95.8 ±â€¯11.0, and 79.2 ±â€¯10.8 µg/m3 in winter, spring, summer, and autumn, respectively. The most abundant specie was toluene (10.1%-17.4%), followed by benzene, ethane, isopentane, ethane, acetylene, and n-butane. Seasonal variations of VOCs were analyzed, and it was found that the highest concentration occurring in summer, while the lowest in spring. For the diurnal variation, the concentration of VOCs in the daytime (9:00-15:00) was less than that at night (15:00-21:00) obviously. Ozone Formation Potential (OFP) was calculated by using Maximum Incremental Reactivity (MIR) method. The greatest contribution to OFP from alkenes and aromatics, which accounted for 27.3%-51.2% and 36.6%-58.6% of the total OFP. The WRF-CMAQ model was used to simulate the impact of airport emissions on the surrounding area. The results indicated that the maximum impact of VOCs emissions and all sources emissions at the airport on O3 was 0.035 and -23.8 µg/m3, respectively. Meanwhile, within 1 km from the airport, the concentration of O3 around the airport was greatly affected by airport emitted.

Microbial cycling of isoprene, the most abundantly produced biological volatile organic compound on Earth.

Isoprene (2-methyl-1,3-butadiene), the most abundantly produced biogenic volatile organic compound (BVOC) on Earth, is highly reactive and can have diverse and often detrimental atmospheric effects, which impact on climate and health. Most isoprene is produced by terrestrial plants, but (micro)algal production is important in aquatic environments, and the relative bacterial contribution remains unknown. Soils are a sink for isoprene, and bacteria that can use isoprene as a carbon and energy source have been cultivated and also identified using cultivation-independent methods from soils, leaves and coastal/marine environments. Bacteria belonging to the Actinobacteria are most frequently isolated and identified, and Proteobacteria have also been shown to degrade isoprene. In the freshwater-sediment isolate, Rhodococcus strain AD45, initial oxidation of isoprene to 1,2-epoxy-isoprene is catalyzed by a multicomponent isoprene monooxygenase encoded by the genes isoABCDEF. The resultant epoxide is converted to a glutathione conjugate by a glutathione S-transferase encoded by isoI, and further degraded by enzymes encoded by isoGHJ. Genome sequence analysis of actinobacterial isolates belonging to the genera Rhodococcus, Mycobacterium and Gordonia has revealed that isoABCDEF and isoGHIJ are linked in an operon, either on a plasmid or the chromosome. In Rhodococcus strain AD45 both isoprene and epoxy-isoprene induce a high level of transcription of 22 contiguous genes, including isoABCDEF and isoGHIJ. Sequence analysis of the isoA gene, encoding the large subunit of the oxygenase component of isoprene monooxygenase, from isolates has facilitated the development of PCR primers that are proving valuable in investigating the ecology of uncultivated isoprene-degrading bacteria.

Isoprene Emissions and Ozone Formation in Urban Conditions: A Case Study in the City of Rio de Janeiro.

The potential role of isoprene oxidative processes, as well as the possible impact of air pollution on isoprene emissions, are more important in tropical cities, surrounded by rainforests. In this study, the contribution of isoprene to ozone formation was determined considering different scenarios, mainly volatile organic compounds/NO x (VOC/NO x ) ratios, and typical atmospheric conditions for the city of Rio de Janeiro, where more than 36% of the urbanized area is covered by vegetation. Ozone isopleths and incremental reactivity coefficients (IR) were evaluated to understand the direct contribution of isoprene to ground-level ozone formation and the negative impact of anthropogenic NO x emissions on the natural atmospheric balance. Although isoprene accounted for only 2.7% of the total VOC mass, excluding the isoprene concentration from the model reduced the maximum ozone value by 14.1%. The calculated IR coefficient (grams of O3 formed per gram of added isoprene) was 2.2 for a VOC/NO x ratio of 8.86.

Air sampling unit for breath analyzers.

The paper presents a portable breath sampling unit (BSU) for human breath analyzers. The developed unit can be used to probe air from the upper airway and alveolar for clinical and science studies. The BSU is able to operate as a patient interface device for most types of breath analyzers. Its main task is to separate and to collect the selected phases of the exhaled air. To monitor the so-called I, II, or III phase and to identify the airflow from the upper and lower parts of the human respiratory system, the unit performs measurements of the exhaled CO2 (ECO2) in the concentration range of 0%-20% (0-150 mm Hg). It can work in both on-line and off-line modes according to American Thoracic Society/European Respiratory Society standards. A Tedlar bag with a volume of 5 dm3 is mounted as a BSU sample container. This volume allows us to collect ca. 1-25 selected breath phases. At the user panel, each step of the unit operation is visualized by LED indicators. This helps us to regulate the natural breathing cycle of the patient. There is also an operator's panel to ensure monitoring and configuration setup of the unit parameters. The operation of the breath sampling unit was preliminarily verified using the gas chromatography/mass spectrometry (GC/MS) laboratory setup. At this setup, volatile organic compounds were extracted by solid phase microextraction. The tests were performed by the comparison of GC/MS signals from both exhaled nitric oxide and isoprene analyses for three breath phases. The functionality of the unit was proven because there was an observed increase in the signal level in the case of the III phase (approximately 40%). The described work made it possible to construct a prototype of a very efficient breath sampling unit dedicated to breath sample analyzers.

Exhaled isoprene for monitoring recovery from acute hypoxic stress.

Hypoxia-like incidents in-flight have increased over the past decade causing severe safety concerns across the aviation community. As a result, the need to monitor flight crews in real-time for the onset of hypoxic conditions is paramount for continued aeronautical safety. Here, hypoxic events were simulated in the laboratory via a reduced oxygen-breathing device to determine the effect of recovery gas oxygen concentration (21% and 100%) on exhaled breath volatile organic compound composition. Data from samples collected both serially (throughout the exposure), prior to, and following exposures yielded 326 statistically significant features, 203 of which were unique. Of those, 72 features were tentatively identified while 51 were verified with authentic standards. A comparison of samples collected serially between recovery and hypoxia time points shows a statistically significant reduction in exhaled breath isoprene (2-methyl-1,3-butadiene, log2 FC -0.399, p = 0.005, FDR = 0.034, q = 0.033), however no significant difference in isoprene abundance was observed when comparing recovery gases (21% or 100% O2, p = 0.152). Furthermore, examination of pre-/post-exposure 1 l bag breath samples illustrate an overall increase in exhaled isoprene abundance post-exposure (log2 FC 0.393, p = 0.005, FDR = 0.094, q = 0.033) but again no significant difference between recovery gas (21% and 100%, p = 0.798) was observed. A statistically significant difference in trend was observed between isoprene abundance and recovery gases O2 concentration when plotted against minimum oxygen saturation (p = 0.0419 100% O2, p = 0.7034 21% O2). Collectively, these results suggest exhaled isoprene is dynamic in the laboratory ROBD setup and additional experimentation will be required to fully understand the dynamics of isoprene in response to acute hypoxic stress.

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.

Concentration- and flux-based dose-responses of isoprene emission from poplar leaves and plants exposed to an ozone concentration gradient.

Concentration- and flux-based O3 dose-responses of isoprene emission from single leaves and whole plants were developed. Two poplar clones differing in O3 sensitivity were exposed to five O3 levels in open-top chambers for 97 d: charcoal-filtered ambient air (CF), non-filtered ambient air (NF) and NF plus 20 ppb (NF + 20), 40 ppb (NF + 40) and 60 ppb (NF + 60). At both leaf and plant level, isoprene emission was significantly decreased by NF + 40 and NF + 60 for both clones. Although intra-specific variability was found when the emissions were up-scaled to the whole plant, both leaf- and plant-level emissions decreased linearly with increasing concentration-based (AOT40, cumulative exposure to hourly O3 concentrations >40 ppb) and flux-based indices (PODY , cumulative stomatal uptake of O3  > Y nmol O3 m-2 PLA s-1 ). AOT40- and POD7 -based dose-responses performed equally well. The two clones responded differently to AOT40 and similarly to PODY (with a slightly higher R2 for POD7 ) when the emission was expressed as change relative to clean air. We thus recommend POD7 as a large-scale risk assessment metric to estimate isoprene emission responses to O3 in poplar.

The application of chromatographic breath analysis in the search of volatile biomarkers of chronic kidney disease and coexisting type 2 diabetes mellitus.

Chromatographic studies on breath composition are aimed at finding volatile markers useful for medical diagnostics or in screening investigations. Studies leading to the development of screening breath tests are especially important for the diagnostics of chronic kidney disease (CKD) and type 2 diabetes mellitus (T2DM). The aim of the presented study was to confirm diagnostic usefulness of chosen volatile compounds detected in breath, which are suggested as potential biomarkers of renal dysfunction and diabetes. Breath analysis were carried out in three groups: 10 healthy volunteers, 10 patients with CKD and 10 patients with CKD and T2DM. All exhaled air samples were analyzed using gas chromatograph (Agilent 6890GC) coupled with mass spectrometer (5975MSD). Thermal desorption was applied as the enrichment method. TMA was detected only in CKD patients. Higher breath concentrations of methanethiol (MeSH) were observed in CKD patients with coexisting diabetes than in patients with renal dysfunction only or in the healthy group. There was a tendency of increasing MeSH concentration in breath with increasing total glutathione in plasma (r=0.53, p=0.0026). Also, a trend of increasing dimethylsulfide (DMS) levels detected in breath was noticed with an increase of hydrogen sulfide concentration in plasma (r=0.74; p=0.00001) as well as with aspartate aminotransferase (AST), (r=0.61; p=0.001). The presented results suggest the possibility of applying TMA, MeSH, and DMS detection in breath as diagnostic methods.

Anesthetic synergy between two n-alkanes.

OBJECTIVE: N-butane and n-pentane can both produce general anesthesia. Both compounds potentiate γ-aminobutyric acid type A (GABAA) receptor function, but only butane inhibits N-methyl-d-aspartate (NMDA) receptors. It was hypothesized that butane and pentane would exhibit anesthetic synergy due to their different actions on ligand-gated ion channels. STUDY DESIGN: Prospective experimental study. ANIMALS: A total of four Xenopus laevis frogs and 43 Sprague-Dawley rats. METHODS: Alkane concentrations for all studies were determined via gas chromatography. Using a Xenopus oocyte expression model, standard two-electrode voltage clamp techniques were used to measure NMDA and GABAA receptor responses in vitro as a function of butane and pentane concentrations relevant to anesthesia. The minimum alveolar concentrations (MAC) of butane and pentane were measured separately in rats, and then pentane MAC was measured during coadministration of 0.25, 0.50 or 0.75 times MAC of butane. An isobole with 95% confidence intervals was constructed using regression analysis. A sum of butane and pentane that was statistically less than the lower-end confidence bound isobole indicated a synergistic interaction. RESULTS: Both butane and pentane dose-dependently potentiated GABAA receptor currents over the study concentration range. Butane dose-dependently inhibited NMDA receptor currents, but pentane did not modulate NMDA receptors. Butane and pentane MAC in rats was 39.4±0.7 and 13.7±0.4 %, respectively. A small but significant (p<0.03) synergistic anesthetic effect with pentane was observed during administration of either 0.50 or 0.75×MAC butane. CONCLUSIONS: Butane and pentane show synergistic anesthetic effects in vivo consistent with their different in vitro receptor effects. CLINICAL RELEVANCE: Findings support the relevance of NMDA receptors in mediating anesthetic actions for some, but not all, inhaled agents.

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.