Minimization of water vapor interference in the analysis of non-methane volatile organic compounds by solid adsorbent sampling

Water vapor can be a significant interference in the analysis of air for non-methane volatile organic compounds (NMVOCs) using solid-adsorbent sampling techniques. The adsorbent materials used in sampling cartridges have different hydrophobic characteristics, and it is therefore necessary to characterize solid-adsorbent cartridges over a wide range of humidity. Controlled humidity experiments were performed to assess the extent of water vapor interference when samples are collected onto AirToxics solid-adsorbent cartridges. It was found that elevating the temperature of the cartridge to 10 degrees C above the temperature of the air sample greatly reduced water vapor adsorption and interferences and resulted in > or = 90% recovery of NMVOCs, biogenic VOCs and chlorofluorocarbons. Similar collection efficiencies were obtained at ambient temperature by reducing the relative humidity to > or = 60% in the sample by dilution with dry, scrubbed ambient air. A procedure also was developed and optimized for dry-purging cartridges prior to analysis. However, under optimized conditions, significant losses of C3-C5 compounds still occurred under highly humid conditions. It was determined that these losses were due to reduced retention during sampling rather than loss during the dry purge procedure. The dry purge method was shown to be adequate at high humidities for sampling NMVOCs with retention indices greater than 500.     

Two-Phase Flow in Heterogeneous Porous Media with Non-Wetting Phase Trapping

This article presents a mathematical model describing flow of two fluid phases in a heterogeneous porous medium. The medium contains disconnected inclusions embedded in the background material. The background material is characterized by higher value of the non-wetting-phase entry pressure than the inclusions, which causes non-standard behavior of the medium at the macroscopic scale. During the displacement of the non-wetting fluid by the wetting one, some portions of the non-wetting fluid become trapped in the inclusions. On the other hand, if the medium is initially saturated with the wetting phase, it starts to drain only after the capillary pressure exceeds the entry pressure of the background material. These effects cannot be represented by standard upscaling approaches based on the assumption of local equilibrium of the capillary pressure. We propose a relevant modification of the upscaled model obtained by asymptotic homogenization. The modification concerns the form of flow equations and the calculation of the effective hydraulic functions. This approach is illustrated with two numerical examples concerning oil–water and CO₂–brine flow, respectively.     

Macro-Scale Dynamic Effects in Homogeneous and Heterogeneous Porous Media

It is known that the classical capillary pressure-saturation relationship may be deficient under non-equilibrium conditions when large saturation changes may occur. An extended relationship has been proposed in the literature which correlates the rate of change of saturation to the difference between the phase pressures and the equilibrium capillary pressure. This linear relationship contains a damping coefficient, \tau, that may be a function of saturation. The extended relationship is examined at the macro-scale through simulations using the two-phase simulator MUFTE-UG. In these simulations, it is assumed that the traditional equilibrium relationship between the water saturation and the difference in fluid pressures holds locally. Steady-state and dynamic numerical experiments are performed where a non-wetting phase displaces a wetting phase in homogeneous and heterogeneous domains with varying boundary conditions, domain size, and soil parameters. From these simulations the damping coefficient can be identified as a (non-linear) function of the water saturation. It is shown that the value of increases with an increased domain size and/or with decreased intrinsic permeability. Also, the value of for a domain with a spatially correlated random distribution of intrinsic permeability is compared to a homogeneous domain with equivalent permeability; they are shown to be almost equal.     

Sampling, storage, and analysis of C2-C7 non-methane hydrocarbons from the US National Oceanic and Atmospheric Administration Cooperative Air Sampling Network glass flasks

An analytical technique was developed to analyze light non-methane hydrocarbons (NMHC), including ethane, propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, isoprene, benzene and toluene from whole air samples collected in 2.5l-glass flasks used by the National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Global Monitoring Division (NOAA ESRL GMD, Boulder, CO, USA) Cooperative Air Sampling Network. This method relies on utilizing the remaining air in these flasks (which is at below-ambient pressure at this stage) after the completion of all routine greenhouse gas measurements from these samples. NMHC in sample aliquots extracted from the flasks were preconcentrated with a custom-made, cryogen-free inlet system and analyzed by gas chromatography (GC) with flame ionization detection (FID). C2-C7 NMHC, depending on their ambient air mixing ratios, could be measured with accuracy and repeatability errors of generally < or =10-20%. Larger deviations were found for ethene and propene. Hexane was systematically overestimated due to a chromatographic co-elution problem. Saturated NMHC showed less than 5% changes in their mixing ratios in glass flask samples that were stored for up to 1 year. In the same experiment ethene and propene increased at approximately 30% yr(-1). A series of blank experiments showed negligible contamination from the sampling process and from storage (<10 pptv yr(-1)) of samples in these glass flasks. Results from flask NMHC analyses were compared to in-situ NMHC measurements at the Global Atmospheric Watch station in Hohenpeissenberg, Germany. This 9-months side-by-side comparison showed good agreement between both methods. More than 94% of all data comparisons for C2-C5 alkanes, isoprene, benzene and toluene fell within the combined accuracy and precision objectives of the World Meteorological Organization Global Atmosphere Watch (WMO-GAW) for NMHC measurements.     

Gas chromatography system for the automated, unattended, and cryogen-free monitoring of C2 to C6 non-methane hydrocarbons in the remote troposphere

An unattended, automated, on-line, cryogen-free, remotely controlled gas chromatography (GC) system was developed and has been deployed for more than 1 year for the continuous determination of C(2) to C(6) hydrocarbons at an observatory located at 2225 m elevation, on the summit caldera of an inactive volcano on the island of Pico, Azores. The GC instrument is tailored to the measurement challenges at this remote and high altitude site. All consumable gases are prepared in situ. Total power use remains below 700 W at all times. Sample collection and analysis is performed without use of cryogen. Hydrocarbons are concentrated on a one-stage trapping/injection system consisting of a Peltier-cooled multi-bed solid adsorbent trap. Analytes are detected after thermal desorption and separation on an alumina-PLOT (porous-layer open tubular) column by flame ionization detection (FID). Sample focusing, desorption, separation and detection parameters were thoroughly investigated to ensure quantitative collection and subsequent injection onto the GC system. GC operation is controlled remotely and data are downloaded daily. Sample volumes (600 and 3000 ml) are alternated for analysis of C(2) to C(3) and C(3) to C(6) hydrocarbons, respectively. Detection limits are in the low parts per trillion by volume (pptv) range, sufficient for quantification of the compounds of interest at their central North Atlantic lower free troposphere background concentrations.     

Evaluation of solid adsorbent materials for cryogen-free trapping-gas chromatographic analysis of atmospheric C2-C6 non-methane hydrocarbons

Nine commercial solid adsorbent materials (in order of decreasing surface area: Carboxen 1000, Carbosieve S III, molecular sieve 5A, molecular sieve 4A, silica gel, Carboxen 563, activated alumina, Carbotrap and Carboxen 1016) were investigated for their ability to trap and release C2-C6 non-methane hydrocarbons (NMHCs) in atmospheric samples for subsequent thermal desorption gas chromatography-flame ionization detection analysis (GC-FID). Recovery rates for 23 NMHCs and methyl chloride (CH3Cl) were determined. A microtrap filled with the three adsorbents Carbosieve S III, Carboxen 563 and Carboxen 1016 was found to allow for the analysis of the widest range of target analytes. A detection limit of approximately 3pptC [parts per trillion (carbon)] in a 1l air sample and a linear response over a wide range of volatilities and sample volumes was determined for this configuration. Water vapor in the sample air was found to causes interference in trapping and subsequent chromatographic analysis of light NMHCs. A Peltier-cooled, regenerable water trap inserted into the sample flow path was found to mitigate these problems and to allow quantitative and reproducible results for all analytes at all tested humidity conditions.     

Calibration system and analytical considerations for quantitative sesquiterpene measurements in air

Sesquiterpenes (C15H24, SQT) are semi-volatile organic compounds emitted from vegetation and are of interest for air quality considerations because of their suspected contribution to the formation of secondary aerosol. This article investigates the application of a capillary diffusion method for the generation of standard atmospheres of 16 SQT and four other related semi-volatile compounds. This instrument subsequently has been used in the testing of analytical materials, protocols and calibration of air sampling methods. SQT DB-1 retention indices, vapor pressures at 25 and 75 degrees C, and diffusion coefficients were determined. A quantitative, on-line GC method yielded improved results (median relative standard deviation of 5.0-6.1%) for the diffusion rate determination in comparison to a gravimetric approach (median relative standard deviation 18%). The GC method also allowed identifying errors in the gravimetric method stemming from residual solvent evaporation, impurities, and chemical analyte losses. Stainless steel, glass, nickel and PTFE tubing that were tested for transfer lines and a sampling loop had to be kept at temperatures in excess of approximately 110 degrees C in order to prevent significant analytical errors from the stickiness of SQT to these materials. In addition to SQT analysis, results from this research provide general guidelines for gas-phase analysis of related compounds in the C14-C16 volatility range.     

Monotone nonlinear finite‐volume method for nonisothermal two‐phase two‐component flow in porous media

This article presents a new nonlinear finite‐volume scheme for the nonisothermal two‐phase two‐component flow equations in porous media. The face fluxes are approximated by a nonlinear two‐point flux approximation, where transmissibilities nonlinearly depend on primary variables. Thereby, we mainly follow the ideas proposed by Le Potier combined with a harmonic averaging point interpolation strategy for the approximation of arbitrary heterogeneous permeability fields on polygonal grids. The behavior of this interpolation strategy is analyzed, and its limitation for highly anisotropic permeability tensors is demonstrated. Moreover, the condition numbers of occurring matrices are compared with linear finite‐volume schemes. Additionally, the convergence behavior of iterative solvers is investigated. Finally, it is shown that the nonlinear scheme is more efficient than its linear counterpart. Copyright © 2016 John Wiley & Sons, Ltd.     

Effective equations for two-phase flow in porous media: the effect of trapping on the microscale

In this article, we consider a two-phase flow model in a heterogeneous porous column. The medium consists of many homogeneous layers that are perpendicular to the flow direction and have a periodic structure resulting in a one-dimensional flow. Trapping may occur at the interface between a coarse and a fine layer. Assuming that capillary effects caused by the surface tension are in balance with the viscous effects, we apply the homogenization approach to derive an effective (upscaled) model. Numerical experiments show a good agreement between the effective solution and the averaged solution taking into account the detailed microstructure.     

Modeling Concentration Distribution and Deformation During Convection-Enhanced Drug Delivery into Brain Tissue

Convection-enhanced drug delivery is a technique where a therapeutic agent is infused under positive pressure directly into the brain tissue. For predicting the final concentration distribution and optimizing infusion rate and catheter placement, numerical models can be of great help. However, despite advances in modeling this process, often the infused agent does not reach the targeted region prescribed in the modeling phase. In this study, patient-specific brain structure and parameters, obtained from diffusion tensor imaging (DTI), are implemented in a numerical model which describes the flow and transport in an elastic deformable matrix. To our knowledge, this is the first time that information from DTI is used in a numerical model which includes both transport of a therapeutic agent and tissue deformation. Fractional anisotropy (FA) is used to distinguish between gray and white matter and tortuosity to differentiate between inside and outside the brain tissue. One voxel in the DT-image is represented by one element of the numerical grid. The DT-images were in addition used to determine the orientation of the white matter fiber tracts and calibrate permeability and diffusion coefficients found in the literature. Values chosen for the porosity and Lamé parameters are also based on those found in the literature. Given realistic literature values, the calibration of the permeability and diffusion tensors are shown to be successful. Our result shows that preferential flow occur in direction of the white matter fiber tracts. The current model assumes linear deformation, corresponding to small porosity changes. But, because large porosity changes occur that may adversely affect drug transport, non-linear deformations should be included in the future.