Method comparison study on soot-selective techniques

In a long-term field study at two locations with different air pollution levels several soot-selective measurement techniques were compared with a thermochemical method which measures non-extractable carbon (NEC) detecting the evolved CO₂ by means of coulometric titration. The attenuation measurement technique (aethalometer) and the aerosol photoemission method showed good correlations to NEC for concentrations ranging from 1.6g/m³ to 40.8g/m³. The specific mass absorption coefficient of black carbon with respect to NEC varied between 8.4m²/g and 13.7m²/g with respect to the measurement sites, but the value was found to remain constant at each site independent of seasonal or meteorological variations. The ratio of photoelectric signal to NEC varied between 16 fA·(g/m³)^–1 and 33 fA·(g/m³)^–1 depending on the age of the aerosol. The diurnal variations of that ratio showed strong similarities to the traffic patterns. Additionally a slight temperature dependence of this ratio was found for the aged aerosol with a proportionality factor of – 0.35 fA·(K·g/m³)^–1. With the reflectance measurement technique (smoke shade method) reliable NEC determination was not possible for NEC concentrations 5 g/m³.     

A novel method for the determination of a PCB sum value by enzyme immunoassay to overcome the cross-reactivity problem

Many attempts have been made to detect polychlorinated biphenyls (PCBs) by enzyme immunoassay (ELISA). All known ELISAs to PCBs show characteristic cross-reactivity problems. Without any prior information about the composition of the sample, no quantification of the total PCB content is possible. A chemical approach is shown to solve the cross-reactivity problem by the quantitative dechlorination of all PCB congeners to the single compound biphenyl. For the reductive dechlorination palladium on barium sulfate and ammonium formate were used. The dechlorination procedure was optimized to be performed at room temperature in methanol without the exclusion of oxygen or water. For the development of polyclonal biphenyl-antibodies the synthesis of the hapten biphenylhexanoic acid via Grignard cross-coupling is described and an immunization protocol is given. The purity of the used immunological reagents proved to be very crucial. The whole procedure was tested with spiked soil samples. The detection limit for PCBs (Clophen A50) in soil was 1 mg/kg (3.1 μmol/kg). This corresponds to a biphenyl concentration in methanol of 0.1 mg/L (0.6 μmol/L). Received: 25 September 1998 / Revised: 1 December 1998 / Accepted: 4 December 1998     

Optoacoustic sensor head for depth profiling

-1 (for 0.25 mJ/cm²). The response function of the total experimental setup is derived from the optoacoustic signal of a black absorber, which is necessary to correct theoretical calculations with regard to the finite time response of the detection system. In the case of homogeneous samples, the theory of optoacoustic signal generation is verified, qualitative results are achieved with layered samples. Received: 14 October 1998 / Published online: 24 February 1999     

In-situ atomic force microscopy investigation of aerosols exposed to different humidities

In-situ atomic force microscopy (AFM) studies were performed on aerosol samples showing the potential of a topochemical approach for gaining information on chemical and physical aerosol properties. The behavior of single sub-micron particles has been investigated with respect to changing humidity in the surrounding atmosphere. Volume calculations allowed monitoring of these changes on a quantitative basis. As expected these in-situ experiments showed the restructuring of particles with highly agglomerated chain-like structures induced by condensation and evaporation on a nanometer scale. The particle volumes decreased as the branched chain-like structure changed into a more regular clump-like structure. The degree of restructuring was clearly depending on the chemical surface properties as could be proven for soot-like test aerosol particles. The collapse of the chain-like structure on a nanometer scale was found to be significantly more pronounced for soot particles previously exposed to ozone. Furthermore, in-situ studies were performed on ammonium sulfate test aerosol. Though a distinct deliquescence point typical for salts could not be detected, neither in the topography nor in the phase image, ammonium sulfate test aerosol particles seemed to partially dissolve in humid atmosphere and hence to decrease in volume. Thus, the volume decrease induced by purging with humid nitrogen and subsequent drying which was also observed for a considerable fraction of urban aerosol, could be interpreted in terms of composition and surface properties considering the geometrical structure (i.e. state of agglomeration) of the particles.     

Modeling Kinetic Interphase Mass Transfer for Two-Phase Flow in Porous Media Including Fluid–Fluid Interfacial Area

Interphase mass transfer in porous media takes place across fluid–fluid interfaces. At the field scale, this is almost always a kinetic process and its rate is highly dependent on the amount of fluid–fluid interfacial area. Having no means to determine the interfacial area, modelers usually either neglect kinetics of mass transfer and assume local equilibrium between phases or they estimate interfacial area using lumped parameter approaches (in DNAPL pool dissolution) or a dual domain approach (for air sparging). However, none of these approaches include a physical determination of interfacial area or accounts for its role for interphase mass transfer. In this work, we propose a new formulation of two-phase flow with interphase mass transfer, which is based on thermodynamic principles. This approach comprises a mass balance for each component in each phase and a mass balance for specific interfacial area. The system is closed by a relationship among capillary pressure, interfacial area, and saturation. We compare our approach to an equilibrium model by showing simulation results for an air–water system. We show that the new approach is capable of modeling kinetic interphase mass exchange for a two-phase system and that mass transfer correlates with the specific interfacial area. By non-dimensionalization of the equations and variation of Peclet and Damköhler number, we make statements about when kinetic interphase mass transfer has to be taken into account by using the new physically based kinetic approach and when the equilibrium model is a reasonable simplification.     

High-capacity NO2 denuder systems operated at various temperatures (298–473?K)

In this study, we investigated several coatings for high-temperature, high-capacity, and high-efficiency denuder-based NO₂ removal, with the scope to face the harsh conditions and requirements of automotive exhaust gas sampling. As first coating, we propose a potassium iodide (KI)/polyethylene glycol coating with a high removal efficiency (ε?>?98?%) for about 2?h and 50?ppm NO₂ at room temperature (298?K). At elevated temperatures (423?K), the initial capacity (100?ppmh) is decreased to 15?ppmh. Furthermore, this is the first proposal of the ionic liquid methyl-butyl-imidazolium iodide ([BMIm⁺][I^?]) as denuder coating material. At room temperature, this ionic liquid exhibits far greater capacity (300?ppmh) and NO₂ removal efficiency (ε?>?99.9?%) than KI. Nevertheless, KI exhibits a slightly (~10?%) higher capacity at elevated temperatures than [BMIm⁺][I^?]. Both coatings presented are suitable for applications requiring selective denuding of NO₂ at temperatures up to 423?K.     

On accuracy and efficiency of the CESE-method of C. S. Chang for one-dimensional unstaedy flow computation

About twenty years ago a NASA-group around S. C. Chang began to develop a method using space-time domains as elements for unstaedy flow computation. There are two kinds of elements. One within which the linearized form of the underlying differential equation is satisfied and one whithin which space-time flux is conserved. Therefore the method is called conservation-element solution-element or shortly CESE. Applied to one-dimensional flow equations we show conditions under which the method in the version of Jerez et al. [1] is - second order accurate and - more efficient than Lax-Wendroff type methods. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Immunological determination of triazine pesticides bound to soil humic acids (bound residues)

An immunological method for the determination of triazine herbicides covalently bound to soil humic acids has been developed. A sandwich-immunoassay has been performed, based on both polyclonal humic acid-antibodies and monoclonal triazineantibodies. A peroxidase-labelled third antibody has been used for the photometric detection. A triazine-humic acid conjugate served as calibration standard. The coupling density for this conjugate has been determined by measuring the difference of free amino groups both with ninhydrin and with the trinitrobenzene sulfonic acid method. In addition, the coupling density has been confirmed by scintillation counting using a ¹⁴C-atrazine derivative. Due to nonspecific interactions between antibody proteins and humic acids, different blocking steps had to be performed. Finally, the assay has been applied to a triazine contaminated soil sample. Humic acids (including bound residues) have been extracted by diluted sodium carbonate solution. Concentrations of bound atrazine residues have been found in the range of 2 mg/kg soil on fields where triazine herbicides has been applied over a period of 21 years. These results are comparable to both the applied amount and the nonextractable fraction.     

In-situ-Photoemission an PAH-beschichteten Aerosolen

Summary The principles of in-situ photoemission from PAH (polycyclic aromatic hydrocarbons)-covered aerosols are presented. The particles are illuminated by UV light causing photoelectron emission. The occurrence of positively charged particles acts as a measure of particle coverage by photoemitting PAHs. The positively charged particles are counted by means of an aerosol electrometer. High photoyields are found with particulate PAHs consisting of molecules with a planar structure and a high -electron density.