Fourier transform and grating-based spectroscopy with a mid-infrared supercontinuum source for trace gas detection in fruit quality monitoring.

We present a multi-species trace gas sensor based on a fast, compact home-built Fourier transform spectrometer (FTS) combined with a broadband mid-infrared supercontinuum (SC) source. The spectrometer covers the spectral bandwidth of the SC source (2 - 4 µm) and provides a best spectral resolution of 1 GHz in 6 seconds. It has a detection sensitivity of a few hundred of ppbv Hz-1/2 for different gas species. We study the performance of the developed spectrometer in terms of precision, linearity, long-term stability, and multi-species detection. We use the spectrometer for measuring fruit-produced volatiles under different atmospheric conditions and compare the performance with a previously developed scanning grating-based spectrometer.

A Searchable Database for Prediction of Emission Compositions from Upstream Oil and Gas Sources.

Atmospheric emissions from oil and gas production operations are composed of multiple hydrocarbons and can have large variations in composition. Accurate estimates of emission compositions are needed to estimate the fate and impacts of emissions and to attribute emissions to sources. This work presents a database, constructed with empirical data and thermodynamic models, that can be queried to estimate hydrocarbon compositions from emission sources present at oil and gas production sites. The database can be searched for matches using between two and seven well parameters as query inputs (gas-to-oil ratio, API gravity, separator pressure, separator temperature, methane molar fraction in produced gas, ethane molar fraction of produced gas, and propane molar fraction in produced gas). Database query performance was characterized by comparing returns from database queries to a test data set. Application of the database to well parameters for tens of thousands of wells in the Barnett, Eagle Ford, and Fayetteville production regions demonstrates variations in emission compositions. Ethane to methane ratio varies by more than an order of magnitude from well to well and source to source. VOC to methane ratios are comparable in variability to ethane to methane ratios for most emission sources, but have a higher variability for emissions from flashing of liquid hydrocarbon tanks.

Projecting the Temporal Evolution of Methane Emissions from Oil and Gas Production Basins.

The methane emission intensity (methane emitted/gas produced or methane emitted/methane produced) of individual unconventional oil and gas production sites in the United States has a characteristic temporal behavior, exhibiting a brief period of decrease followed by a steady increase, with intensities after 10 years of production reaching levels that are 2-10 times the 10 year production-weighted average. Temporal patterns for methane emission intensity for entire production regions are more complex. Historical production data and facility data were used with a detailed basin-wide methane emission model to simulate the collective behavior of tens of thousands of wells and associated midstream facilities. For production regions with few to no new wells being brought to production, and existing wells having reached a mature stage, as in the Barnett Shale production region in north central Texas, the methane emission intensity gradually increases, as natural gas production decreases faster than emissions decrease, following the general pattern exhibited by individual wells. In production regions that are rapidly evolving, either with large numbers of new wells being put into production or with the introduction of source-specific regulations, the behavior is more complex. In the Eagle Ford Shale, which has had both a large number of new wells and the introduction of source-specific regulations, the methane emission intensity stays within relatively narrow bounds but the distribution of sources varies. As source distributions vary, basin-wide propane-to-methane and ethane-to-methane emission ratios vary, impacting methods used in source attribution.

Simultaneous analysis of haloacetonitriles, haloacetamides and halonitromethanes in chlorinated waters by gas chromatography-mass spectrometry.

Nitrogenous classes of disinfection by-products (DBPs), such as haloacetamides (HAAms), haloacetonitriles (HANs) and halonitromethanes (HNMs), while generally present at lower concentrations in disinfected waters than carbonaceous DBPs, such as trihalomethanes or haloacetic acids, have been shown to be more detrimental to human health. While several methods have been shown to be suitable for the analysis of some nitrogenous DBPs (N-DBPs) in disinfected waters, many are unable to quantify HAAms, the most detrimental to health of these three N-DBP classes. Here, we report the first method for the simultaneous analysis of twenty-five N-DBPs (nine HANs, nine HNMs and seven HAAms) in disinfected waters using liquid-liquid extraction followed by gas chromatography-mass spectrometry. The use of a programmable temperature vaporiser injector minimises degradation of the thermally labile HNMs, while avoiding the concomitant decreases in HANs and HAAms which occur when using lower injector temperatures. Extraction parameters, including sample pH, solvent volume, salt addition and sample pre-concentration, were investigated to determine the optimal conditions across all target N-DBPs. Good detection limits were achieved for all analytes (0.8-1.7 µg L-1) and both laboratory and instrumental runtimes were significantly reduced compared to previous methods. The method was validated for the analysis of N-DBPs in drinking, swimming pool and spa waters, and concentrations of up to 41 µg L-1 of some N-DBPs were measured in some pools.

Characterization of methane emissions from five cold heavy oil production with sands (CHOPS) facilities.

Cold heavy oil production with sands (CHOPS) is a common oil extraction method in the Canadian provinces of Alberta and Saskatchewan that can result in significant methane emissions due to annular venting. Little is known about the magnitude of these emissions, nor their contributions to the regional methane budget. Here the authors present the results of field measurements of methane emissions from CHOPS wells and compare them with self-reported venting rates. The tracer ratio method was used not only to analyze total site emissions but at one site it was also used to locate primary emission sources and quantify their contributions to the facility-wide emission rate, revealing the annular vent to be a dominant source. Emissions measured from five different CHOPS sites in Alberta showed large discrepancies between the measured and reported rates, with emissions being mainly underreported. These methane emission rates are placed in the context of current reporting procedures and the role that gas-oil ratio (GOR) measurements play in vented volume estimates. In addition to methane, emissions of higher hydrocarbons were also measured; a chemical "fingerprint" associated with CHOPS wells in this region reveals very low emission ratios of ethane, propane, and aromatics versus methane. The results of this study may inform future studies of CHOPS sites and aid in developing policy to mitigate regional methane emissions. IMPLICATIONS: Methane measurements from cold heavy oil production with sand (CHOPS) sites identify annular venting to be a potentially major source of emissions at these facilities. The measured emission rates are generally larger than reported by operators, with uncertainty in the gas-oil ratio (GOR) possibly playing a large role in this discrepancy. These results have potential policy implications for reducing methane emissions in Alberta in order to achieve the Canadian government's goal of reducing methane emissions by 40-45% below 2012 levels within 8 yr.

Methane Emissions from Conventional and Unconventional Natural Gas Production Sites in the Marcellus Shale Basin.

There is a need for continued assessment of methane (CH4) emissions associated with natural gas (NG) production, especially as recent advancements in horizontal drilling combined with staged hydraulic fracturing technologies have dramatically increased NG production (we refer to these wells as "unconventional" NG wells). In this study, we measured facility-level CH4 emissions rates from the NG production sector in the Marcellus region, and compared CH4 emissions between unconventional NG (UNG) well pad sites and the relatively smaller and older "conventional" NG (CvNG) sites that consist of wells drilled vertically into permeable geologic formations. A top-down tracer-flux CH4 measurement approach utilizing mobile downwind intercepts of CH4, ethane, and tracer (nitrous oxide and acetylene) plumes was performed at 18 CvNG sites (19 individual wells) and 17 UNG sites (88 individual wells). The 17 UNG sites included four sites undergoing completion flowback (FB). The mean facility-level CH4 emission rate among UNG well pad sites in routine production (18.8 kg/h (95% confidence interval (CI) on the mean of 12.0-26.8 kg/h)) was 23 times greater than the mean CH4 emissions from CvNG sites. These differences were attributed, in part, to the large size (based on number of wells and ancillary NG production equipment) and the significantly higher production rate of UNG sites. However, CvNG sites generally had much higher production-normalized CH4 emission rates (median: 11%; range: 0.35-91%) compared to UNG sites (median: 0.13%, range: 0.01-1.2%), likely resulting from a greater prevalence of avoidable process operating conditions (e.g., unresolved equipment maintenance issues). At the regional scale, we estimate that total annual CH4 emissions from 88 500 combined CvNG well pads in Pennsylvania and West Virginia (660 Gg (95% CI: 500 to 800 Gg)) exceeded that from 3390 UNG well pads by 170 Gg, reflecting the large number of CvNG wells and the comparably large fraction of CH4 lost per unit production. The new emissions data suggest that the recently instituted Pennsylvania CH4 emissions inventory substantially underestimates measured facility-level CH4 emissions by >10-40 times for five UNG sites in this study.

Determination of nitroalkanes in mainstream cigarette smoke by heart-cutting multidimensional gas chromatography system coupled with mass spectrometry detection.

In this paper, heart-cutting two-dimensional GC/MS (GC-GC/MS) method in combination with a simple sample collection procedure was developed for the determination of 6 nitroalkanes in mainstream cigarette smoke. The method could remove large amounts of impurities on-line in the first polar column by heart-cuts and separate from the left interferences in a second mid-polar column. And the target compounds could be focused at the inlet of the second column by cryo-concentration. Compared to conventional GC/MS, GC-GC/MS achieved a lower noise level and sensitivity at least an order of magnitude higher. Furthermore, the GC-GC/MS method could avoid the false negative and false positive results that appeared in the compared conventional GC/MS analysis. By trapping the vapor phase of 20 cigarettes smoke, the LODs and LOQs of the nitroalkanes were 1.3 to 9.8 and 4.3 to 32.6ng/cigarette, respectively, and all linear correlation efficiencies were larger than 0.999. The validation results also indicate that the method has high accuracy (spiked recoveries between 84% and 102%) and good repeatability (RSD between 7.2% and 9.4%). The developed method was applied to analyze 1 Kentucky reference cigarette (3R4F) and 10 Chinese commercial brands of cigarettes. The research results indicated that nitromethane, nitroethane, 2-nitropropane and 1-nitro-n-pentane were detected in mainstream cigarette smoke, but 1-nitro-n-butane and 2-nitropropane, which were reported by one previous study, were not detected in all cigarette samples.

An investigation of the matrix sensitivity of refinery gas analysis using gas chromatography with flame ionisation detection.

The response of a flame ionisation detector (FID) on a gas chromatograph to methane, ethane, propane, i-butane and n-butane in a series of multi-component refinery gas standards was investigated to assess the matrix sensitivity of the instrument. High-accuracy synthetic gas standards, traceable to the International System of Units, were used to minimise uncertainties. The instrument response exhibited a small dependence on the component amount fraction: this behaviour, consistent with that of another FID, was thoroughly characterised over a wide range of component amount fractions and was shown to introduce a negligible bias in the analysis of refinery gas samples, provided a suitable reference standard is employed. No significant effects of the molar volume, density and viscosity of the gas mixtures on the instrument response were observed, indicating that the FID is suitable for the analysis of refinery gas mixtures over a wide range of component amount fractions provided that appropriate drift-correction procedures are employed.

Natural gas fugitive emissions rates constrained by global atmospheric methane and ethane.

The amount of methane emissions released by the natural gas (NG) industry is a critical and uncertain value for various industry and policy decisions, such as for determining the climate implications of using NG over coal. Previous studies have estimated fugitive emissions rates (FER)--the fraction of produced NG (mainly methane and ethane) escaped to the atmosphere--between 1 and 9%. Most of these studies rely on few and outdated measurements, and some may represent only temporal/regional NG industry snapshots. This study estimates NG industry representative FER using global atmospheric methane and ethane measurements over three decades, and literature ranges of (i) tracer gas atmospheric lifetimes, (ii) non-NG source estimates, and (iii) fossil fuel fugitive gas hydrocarbon compositions. The modeling suggests an upper bound global average FER of 5% during 2006-2011, and a most likely FER of 2-4% since 2000, trending downward. These results do not account for highly uncertain natural hydrocarbon seepage, which could lower the FER. Further emissions reductions by the NG industry may be needed to ensure climate benefits over coal during the next few decades.

Determination of maximal amount of minor gases adsorbed in a shale sample by headspace gas chromatography.

In this paper, we present a novel method for determining the maximal amount of ethane, a minor gas species, adsorbed in a shale sample. The method is based on the time-dependent release of ethane from shale samples measured by headspace gas chromatography (HS-GC). The study includes a mathematical model for fitting the experimental data, calculating the maximal amount gas adsorbed, and predicting results at other temperatures. The method is a more efficient alternative to the isothermal adsorption method that is in widespread use today.

A novel method for the determination of adsorption partition coefficients of minor gases in a shale sample by headspace gas chromatography.

A novel method has been developed for the determination of adsorption partition coefficient (Kd) of minor gases in shale. The method uses samples of two different sizes (masses) of the same material, from which the partition coefficient of the gas can be determined from two independent headspace gas chromatographic (HS-GC) measurements. The equilibrium for the model gas (ethane) was achieved in 5h at 120°C. The method also involves establishing an equation based on the Kd at higher equilibrium temperature, from which the Kd at lower temperature can be calculated. Although the HS-GC method requires some time and effort, it is simpler and quicker than the isothermal adsorption method that is in widespread use today. As a result, the method is simple and practical and can be a valuable tool for shale gas-related research and applications.

Real-time sensing and discrimination of single chemicals using the channel of phi29 DNA packaging nanomotor.

A highly sensitive and reliable method to sense and identify a single chemical at extremely low concentrations and high contamination is important for environmental surveillance, homeland security, athlete drug monitoring, toxin/drug screening, and earlier disease diagnosis. This article reports a method for precise detection of single chemicals. The hub of the bacteriophage phi29 DNA packaging motor is a connector consisting of 12 protein subunits encircled into a 3.6 nm channel as a path for dsDNA to enter during packaging and to exit during infection. The connector has previously been inserted into a lipid bilayer to serve as a membrane-embedded channel. Herein we report the modification of the phi29 channel to develop a class of sensors to detect single chemicals. The lysine-234 of each protein subunit was mutated to cysteine, generating 12-SH ring lining the channel wall. Chemicals passing through this robust channel and interactions with the SH group generated extremely reliable, precise, and sensitive current signatures as revealed by single channel conductance assays. Ethane (57 Da), thymine (167 Da), and benzene (105 Da) with reactive thioester moieties were clearly discriminated upon interaction with the available set of cysteine residues. The covalent attachment of each analyte induced discrete stepwise blockage in current signature with a corresponding decrease in conductance due to the physical blocking of the channel. Transient binding of the chemicals also produced characteristic fingerprints that were deduced from the unique blockage amplitude and pattern of the signals. This study shows that the phi29 connector can be used to sense chemicals with reactive thioesters or maleimide using single channel conduction assays based on their distinct fingerprints. The results demonstrated that this channel system could be further developed into very sensitive sensing devices.

Rapid analysis of dissolved methane, ethylene, acetylene and ethane using partition coefficients and headspace-gas chromatography.

Analysis of dissolved methane, ethylene, acetylene, and ethane in water is crucial in evaluating anaerobic activity and investigating the sources of hydrocarbon contamination in aquatic environments. A rapid chromatographic method based on phase equilibrium between water and its headspace is developed for these analytes. The new method requires minimal sample preparation and no special apparatus except those associated with gas chromatography. Instead of Henry's Law used in similar previous studies, partition coefficients are used for the first time to calculate concentrations of dissolved hydrocarbon gases, which considerably simplifies the calculation involved. Partition coefficients are determined to be 128, 27.9, 1.28, and 96.3 at 30°C for methane, ethylene, acetylene, and ethane, respectively. It was discovered that the volume ratio of gas-to-liquid phase is critical to the accuracy of the measurements. The method performance can be readily improved by reducing the volume ratio of the two phases. Method validation shows less than 6% variation in accuracy and precision except at low levels of methane where interferences occur in ambient air. Method detection limits are determined to be in the low ng/L range for all analytes. The performance of the method is further tested using environmental samples collected from various sites in Nova Scotia.

[Determination of 1, 1-dichloro-l-nitroethane in air of workplaces by gas chromatography].

OBJECTIVE: To establish a gas chromatography method for detecting the concentration of 1,1-dichloro-1-nitroethane in air of workplaces. METHOD: 1,1-dichloro-1-nitroethane in air of workplaces was collected by activated charcoal tube, absorbed using carbon disulfide and analyzed by Gas Chromatography (FID) with FFAP capillary column. RESULTS: The linear rang of 1,1-dichloro-1-nitroethane in this method was 4.0-858.2 microg/ml, the linear regression formula was Y = 283X-1076, the correlation coefficient was 0.9999, the lowest detection concentration was 0.4 mg/m3 (3L sampling air), the relative standard deviation (RSD) was 1.8%-4.1%, the desorption efficiency was 88.5%-90.6%, the breakthrough volume was > 0.7 mg, the sampling efficiency was 100%, the samples could be kept at ambient temperature for at least 7 days. CONCLUSION: The indicators of this method were conformed to the requirements of "Guide for establishing occupational health standards--Determination methods of air chemicals in workplace". This method could be used to detect 1,1-dichloro-1-nitroethane in air of workplaces.

Exhaled ethane concentration in patients with cancer of the upper gastrointestinal tract - a proof of concept study.

There has been growing interest in the measurement of breath ethane as an optimal non-invasive marker of oxidative stress. High concentrations of various breath alkanes including ethane have been reported in a number of malignancies. Our aim was to investigate the use of novel laser spectroscopy for rapid reporting of exhaled ethane and to determine whether breath ethane concentration is related to a diagnosis of upper gastrointestinal malignancy. Two groups of patients were recruited. Group A (n = 20) had a histo-pathological diagnosis of either esophageal or gastric malignancy. Group B (n = 10) was made up of healthy controls. Breath samples were collected from these subjects and the ethane concentration in these samples was subsequently measured to an accuracy of 0.2 parts per billion, ppb. Group A patients had a corrected exhaled breath ethane concentration of 2.3 +/- 0.8 (mean +/- SEM) ppb. Group B patients registered a mean of 3.1 +/- 0.5 ppb. There was no statistically significant difference between the two groups (p = 0.39). In conclusion, concentrations of ethane in collected breath samples were not significantly elevated in upper gastrointestinal malignancy. The laser spectroscopy system provided a reliable and rapid turnaround for breath sample analysis.

A comparison of oxidative stress in smokers and non-smokers: an in vivo human quantitative study of n-3 lipid peroxidation.

BACKGROUND: Cigarette smoking is believed to cause oxidative stress by several mechanisms, including direct damage by radical species and the inflammatory response induced by smoking, and would therefore be expected to cause increased lipid peroxidation. The aim was to carry out the first study of the relationship of smoking in humans to the level of n-3 lipid peroxidation indexed by the level of ethane in exhaled breath. METHODS: Samples of alveolar air were obtained from 11 smokers and 18 non-smokers. The air samples were analyzed for ethane using mass spectrometry. RESULTS: The two groups of subjects were matched with respect to age and gender. The mean cumulative smoking status of the smokers was 11.8 (standard error 2.5) pack-years. The mean level of ethane in the alveolar breath of the group of smokers (2.53 (0.55) ppb) was not significantly different from that of the group of non-smokers (2.59 (0.29) ppb; p = 0.92). With all 29 subjects included, the Spearman rank correlation coefficient between ethane levels and cumulative smoking status was -0.11 (p = 0.58), while an analysis including only the smokers yielded a corresponding correlation coefficient of 0.11 (p = 0.75). CONCLUSION: Our results show no evidence that cigarette smoking is related to increased n-3 lipid peroxidation as measured by expired ethane.

Intercomparison of infrared cavity leak-out spectroscopy and gas chromatography-flame ionization for trace analysis of ethane.

Comparison of two different methods for the measurement of ethane at the parts-per-billion (ppb) level is reported. We used cavity leak-out spectroscopy (CALOS) in the 3 microm wavelength region and gas chromatography-flame ionization detection (GC-FID) for the analysis of various gas samples containing ethane fractions in synthetic air. Intraday and interday reproducibilities were studied. Intercomparing the results of two series involving seven samples with ethane mixing ratios ranging from 0.5 to 100 ppb, we found a reasonable agreement between both methods. The scatter plot of GC-FID data versus CALOS data yields a linear regression slope of 1.07 +/- 0.03. Furthermore, some of the ethane mixtures were checked over the course of 1 year, which proved the long-term stability of the ethane mixing ratio. We conclude that CALOS shows equivalent ethane analysis precision compared to GC-FID, with the significant advantage of a much higher time resolution (<1 s) since there is no requirement for sample preconcentration. This opens new analytical possibilities, e.g., for real-time monitoring of ethane traces in exhaled human breath.

[New method of mixed gas infrared spectrum analysis based on SVM].

A new method of infrared spectrum analysis based on support vector machine (SVM) for mixture gas was proposed. The kernel function in SVM was used to map the seriously overlapping absorption spectrum into high-dimensional space, and after transformation, the high-dimensional data could be processed in the original space, so the regression calibration model was established, then the regression calibration model with was applied to analyze the concentration of component gas. Meanwhile it was proved that the regression calibration model with SVM also could be used for component recognition of mixture gas. The method was applied to the analysis of different data samples. Some factors such as scan interval, range of the wavelength, kernel function and penalty coefficient C that affect the model were discussed. Experimental results show that the component concentration maximal Mean AE is 0.132%, and the component recognition accuracy is higher than 94%. The problems of overlapping absorption spectrum, using the same method for qualitative and quantitative analysis, and limit number of training sample, were solved. The method could be used in other mixture gas infrared spectrum analyses, promising theoretic and application values.

[Determination of residual epoxyethane in medical instruments by headspace capillary gas chromatography].

OBJECTIVE: To establish a method of determining the residual epoxyethane in medical instruments. METHOD: An HP-5 capillary column (30 m x 0.32 mm x 0.25 microm), an FID detecter and an oven were used in the determination. The oven temperature was kept at 120 degrees C for 8 minutes, the example inlet temperature was kept at 200 degrees C, while the detecter temperature was kept at 250 degrees C. RESULT: The method has a linear range between 5.1920-51.920 microg, (r = 0.997, n = 6). The average rate of recovery of the injecter is 103.3%. The average rate of recovery of the infusion devices is 81.04%. CONCLUSION: The method has been proved to be convenient, sensitive and accurate. It is suitable for the determination of residual organic solvents in medical instruments.