Numerical,wind-tunnel,and atmospheric evaluation of a turbulent ground-based inlet sampling system

The use of inlets for transferring aerosols from the environment to instrumentation can introduce uncertainty in the measurement of aerosol properties. Aerosol loss during this process is a non-negligible issue that may bias the subsequent measurements. These loss mechanisms include aspiration at the inlet head and deposition/evaporation/condensation during transport through the sampling lines. Coarse-mode aerosol is significantly impacted by the aspiration and inertial loss mechanisms within an inlet system. This work uses wind tunnel experiments to investigate aerosol losses through the Storm Peak Laboratory’s (SPL) new aerosol inlet system. The inlet is used extensively for both intensive field campaigns and long-term aerosol monitoring. The results of numerical simulations of the SPL aerosol inlet sampling efficiency are provided at several wind speeds, and experimental results demonstrate the system has a 50% cut off for the coarse-mode at an aerodynamic diameter of approximately 13?μm and wind speed of 0.5?m s^?1. This investigation will lead to improved accuracy of in situ aerosol measurements at SPL and this system can be replicated at other atmospheric stations.

Copyright © 2019 American Association for Aerosol Research     

A variant human IgG1-Fc mediates improved ADCC

Ribosome display was applied to the Fc region of human immunoglobulin G (IgG1) to select for improved binding to human FcγRIIIa, the receptor expressed on human natural killer cells that mediates antibody-dependent cellular cytotoxicity (ADCC). A library of human Fcγ1 variants was generated using error-prone polymerase chain reaction, and subjected to multiple rounds of ribosome display selection against progressively decreasing concentrations of soluble human FcγRIIIa, to enrich for improved binders. Radioimmunoassay and alphascreen analyses of the aglycosylated IgG-Fc output revealed variants with improved binding to FcγRIIIa relative to wild-type IgG-Fc. Subsequent expression in human (HEK-EBNA) cells generated glycosylated IgGs with modified activity in ADCC assays. One particular variant, 125_B01 triggered enhanced ADCC (EC(50) up to four-fold reduced with increased maximal lysis) relative to wild-type antibody, having more equal levels of ADCC for each allotype (V158/F158) of FcγRIIIa. Deconvolution of individual replacements within the variant showed that improved function arose from the Phe243Leu replacement within the CH2 domain, rather than the CH3 domain replacements Thr393Ala or His433Pro. Surprisingly, the oligosaccharide profiles of 125_B01 indicated more oligosaccharide chains lacking fucose, or with bisecting N-acetylglucosamine relative to wild-type IgG1, which correlates with improved function and the replacement Phe243Leu that is a carbohydrate contact residue within the C(H)2 domain.     

A flow cell for transient voltammetry and in situ grazing incidence X-ray diffraction characterization of electrocrystallized cadmium(II) tetracyanoquinodimethane

An easy to fabricate and versatile cell that can be used with a variety of electrochemical techniques, also meeting the stringent requirement for undertaking cyclic voltammetry under transient conditions in in situ electrocrystallization studies and total external reflection X-ray analysis, has been developed. Application is demonstrated through an in situ synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) characterization of electrocrystallized cadmium (II)-tetracyanoquinodimethane material, Cd(TCNQ)₂, from acetonitrile (0.1 mol dm⁻³ [NBu₄][PF₆]). Importantly, this versatile cell design makes SR-GIXRD suitable for almost any combination of total external reflection X-ray analysis (e.g., GIXRF and GIXRD) and electrochemical perturbation, also allowing its application in acidic, basic, aqueous, non-aqueous, low and high flow pressure conditions. Nevertheless, the cell design separates the functions of transient voltammetry and SR-GIXRD measurements, viz., voltammetry is performed at high flow rates with a substantially distended window to minimize the IR (Ohmic) drop of the electrolyte, while SR-GIXRD is undertaken using stop-flow conditions with a very thin layer of electrolyte to minimize X-ray absorption and scattering by the solution.     

Impact of mass balance calculations on adsorption capacities in microporous shale gas reservoirs

Determination of the adsorbed reservoir capacity of gas shales by adsorption analyses as done routinely by mass balance maybe in significant error if the effects of pore-size dependent void volume (porosity) is not considered. It is shown here that with increasing pressure, helium, which is invariably used to measure void volume, can access pores that are not available for adsorption to gases with larger kinetic diameters as highlighted by experiments with zeolites of known pore-size distribution. Helium can diffuse and/or adsorb in restricted pores of the microporous samples, as indicated by a larger void volume with pressure. The error in adsorption calculations due to helium void volume calibrations for high pressure methane isotherms is most significant with low organic-carbon content, moisture-equilibrated shales and mudrocks in which the overall adsorptive capacity is low. In such samples negative adsorption can be calculated due to the void volume of helium used in the mass balance calculations exceeding the void volume to methane – a reflection of greater pore-space accessibility of the smaller helium molecule than methane. The amount of the error introduced by using helium void volume in mass balance calculations is pore-size and pore-size distribution dependent. Organic-rich shales and mudrocks or coals which do not show negative methane adsorption also maybe in error but the error is masked by their larger adsorbed gas capacities. Such findings underline the importance of analysis gas-type as kinetic diameter size will influence the penetrability/diffusion of the gas through the sample and hence the calculated adsorbed gas capacities.     

Maternal High‐Fat‐Diet Programs Rat Offspring Liver Fatty Acid Metabolism

In offspring exposed in utero to a maternal diet high in fat (HF), we have previously demonstrated that despite similar birth weights, HF adult offspring at 6 months of age had significantly higher body weights, greater adiposity, and increased triacylglycerol (TAG) levels as compared to controls. We hypothesized that a maternal HF diet predisposes to offspring adiposity via a programmed increase in the synthesis of monounsaturated fatty acids in the liver and hence increased substrate availability for liver TAG synthesis. We further hypothesized that programmed changes in offspring liver fatty acid metabolism are associated with increased liver expression of the lipogenic enzyme stearoyl‐CoA desaturase‐1 (SCD‐1). Female rats were maintained on a HF diet rich in monounsaturated fatty acids (MUFA) prior to and throughout pregnancy and lactation. After birth, newborns were nursed by the same dam, and all offspring were weaned to control diet. Plasma and liver fatty acid compositions were determined using gas chromatography/mass spectrometry. Fatty acid C16 desaturation indices of palmitoleic/palmitic and (vaccenic + palmitoleic)/palmitic and the C18 desaturation index of oleic/stearic were calculated. Liver protein abundance of SCD‐1 was analyzed in newborns and adult offspring. Plasma and liver C16 desaturation indices were decreased in HF newborns, but increased in the adult offspring. Liver SCD‐1 expression was increased in the HF adult offspring. These data show that the maternal HF diet during pregnancy and lactation increases offspring liver SCD‐1 protein abundance and alters the liver C16 desaturase pathway.     

Smart carboxymethylchitosan hydrogels that have thermo‐ and pH‐responsive properties

Thermo‐responsive poly(N‐isopropylacrylamide) (poly(NIPAAm)) and pH‐responsive poly(N,N′‐diethylaminoethyl methacrylate) (poly(DEAEMA)) polymers were grafted to carboxymethylchitosan (CMC) via radical polymerization to form highly water swellable hydrogels with dual responsive properties. Ratios of CMC, NIPAAm to DEAEMA used in the reactions were finely adjusted such that the thermo and pH responsiveness of the hydrogels was retained. Scanning electron microscopy (SEM) indicated the formation of an internal porous structure for the swollen CMC hydrogels upon incorporation of poly(NIPAAm) and poly(DEAEMA). Effect of temperature and pH changes on water swelling properties of the hydrogels was investigated. It was found that the water swelling of the hydrogels was enhanced when the solution pH was under basic conditions (pH 11) or the temperature was below its lower critical solution temperature (LCST). These responsive properties can be used to regulate releasing rate of an entrapped drug from the hydrogels, a model drug, indomethacin was used to demonstrate the release. These smart and nontoxic CMC‐based hydrogels show great potential for use in controlled drug release applications with controllable on‐off switch properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41505.     

A single series representation of multiple independent ARMA processes

This article shows that multiple independent time series from the same ARMA process can be represented by a single univariate ARMA time series through an interleaving of the original series. Using this result, existing univariate modelling software can be used to fit a single ARMA time series model simultaneously to multiple independent realizations of the same ARMA process. The interleaving approach and its properties will be presented and compared with alternative estimation options. It will be applied to the modelling of 66 years of daily maximum temperatures for Perth, Western Australia and to other time series models.     

The use of small angle neutron scattering with contrast matching and variable adsorbate partial pressures in the study of porosity in activated carbons

The porosity of a typical activated carbon is investigated with small angle neutron scattering (SANS), using the contrast matching technique, by changing the hydrogen/deuterium content of the absorbed liquid (toluene) to extract the carbon density at different scattering vector (Q) values and by measuring the p/p₀ dependence of the SANS, using fully deuterated toluene. The contrast matching data shows that the apparent density is Q-dependent, either because of pores opening near the carbon surface during the activation processor or changes in D-toluene density in nanoscale pores. For each p/p₀ value, evaluation of the Porod Invariant yields the fraction of empty pores. Hence, comparison with the adsorption isotherm, shows that the fully dry powder undergoes densification when liquid is added. An algebraic function is developed to fit the SANS signal at each p/p₀ value hence yielding the effective Kelvin radii of the liquid surfaces as a function of p/p₀. These values, when compared with the Kelvin equation, show that the resultant surface tension value is accurate for the larger pores but tends to increase for small (nanoscale) pores. The resultant pore size distribution is less model-dependent than for the traditional methods of analyzing the adsorption isotherms.     

Sulfur-Tolerant NOx Storage Traps: An Infrared and Thermodynamic Study of the Reactions of Alkali and Alkaline-Earth Metal Sulfates

The sulfur tolerance of a barium-containing NO_x storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 °C. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NO_x storage capacity to give sulfur-tolerant NO_x traps.     

A model of ammonia volatilisation from a dairy farm: an examination of abatement strategies

A model (MAST) to calculate the mass flow of NH₃ through amodel dairy farm has been developed. Updated emission factors for UKagriculturewere used to examine different abatement strategies available for a typicaldairy farm. A range of annual NH₃ emissions was calculated for bothslurry and FYM based dairy systems. Emission for the slurry based system ranged between 27 kg NH₃-N ha^–1 yr^–1, achieved using a combination of abatementstrategies, and 107 kg NH₃-N ha^–1 yr^–1, calculated for a worst casescenario. For FYM, this range was between 33 and 86 kg NH₃-Nha^–1 yr^–1. The greatest reductionswereachieved by manipulating options linked to fertiliser usage and manureapplication.