Supercritical fluid extraction of polychlorinated biphenyls and pesticides from soil. Comparison with other extraction methods.

A comparison is made of supercritical fluid extraction (SFE) with two other techniques widely used for the extraction of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soil. Extraction conditions for the SFE of PCBs and pesticides were first determined. An experimental approach was set up to determine the influence of different extraction parameters such as pressure, extraction time, static and dynamic extraction, restrictor type and collection solvent for off-line SFE. The use of carbon dioxide at 50 degrees C and 20 MPa, 10 min static followed by 20 min dynamic extraction with collection in iso-octane were been found to be the optimum conditions. Two types of soil, with a low and high content of organic carbon, respectively, spiked with 16 PCBs and organochlorine pesticides with a wide range of volatility and polarity at a level of 5 ng/g dry matter, were used as test materials. Conventional solvent extraction gives a good extraction yield for soil with a low content of organic carbon, but for peat soil the recoveries decrease dramatically to 30% for DDE, DDT and PCB 138 and 153. The recoveries with Soxhlet extraction are good, but an extra clean-up step before analysis is necessary. SFE gives good extraction yields for PCBs and organochlorine pesticides, varying between 85 and 105% with a reproducibility of 5% for each component for both types of soil. SFE is a fast, clean and reproducible method for the extraction of PCBs and organochlorine pesticides from these two soil matrices.     

Influence of electron beam irradiation on the impact properties of polystyrene/EPDM rubber blends

The influence of electron beam (EB) irradiation on the impact properties of compatibilized polystyrene/ethylene-propylene-diene-monomer (PS/EPDM) blends was studied. The change in impact value upon irradiation proved to be strongly dependent on the type of compatibilizer used. Using a polystyrene/polybutadiene (SB) diblock copolymer as a compatibilizer, a twofold increase in Izod value could be achieved upon irradiation. Irradiation of a blend using a polystyrene/ethylene-propylene (SEP) copolymer as a compatibilizer resulted in a decrease in impact strength. These observations can be related to a radiation induced increase in interfacial adhesion in case of the SB copolymer, which does not occur for the SEP copolymer. Due to the abundance of double bonds in the SB copolymer, this copolymer reacts very fast upon irradiation and may co-crosslink with, or graft onto the EPDM phase. For the SEP copolymer crosslinking occurs only at much higher doses and is (partly) overruled by chain scission and consequently the adhesion between matrix and dispersed phase will hardly change. This view is supported by analytical methods as FT-IR and NMR as well as from T_g measurements.     

A form of regular variation and its application to the domain of attraction of the double exponential distribution

Probability Theory and Related Fields -     

Evaluation of sugar sorption isotherm measurement by frontal analysis under industrial processing conditions

This paper evaluates frontal analysis for routine sugar isotherm measurements at industrial conditions, that is concentrations up to 400 kg/m3 and a temperature of 60 degrees C. Sugar isotherms for a gel type cation-exchange resin loaded with metal ions were measured in a HPLC setup equipped with a UV detector. It is shown experimentally that isotherms obtained with large concentration steps (step series method) underestimated the isotherm. The underestimation is larger for larger resin particle size. In contrast, isotherms obtained with small concentration steps (staircase method) yielded correct isotherms. The seldom-mentioned change of the sorbent volume during the course of an isotherm measurement is discussed. It is shown that shrinking of 4% cross-linked resin at high sugar concentration has a negligible effect on the isotherm. Furthermore, the isotherms obtained with staircase frontal analysis agreed very well with those obtained with the independent, though more laborious and time-consuming, adsorption-desorption method. Staircase frontal analysis is shown to be convenient and accurate and is therefore recommended for isotherm measurements covering large concentration ranges.     

Downfield γ-gauche and γ-antiperiplanar effects on 13C NMR chemical shifts exerted by thiophene sulphur

The γ-effects of sulphur on ¹³C NMR chemical shifts have been measured in a series of steroidal compounds containing the thiophene ring in different configurations with respect to the rest of the molecule. The data constitute the first example of downfield effects exerted by sulphur on both gauche and antiperiplanar γ-carbons. The γ-gauche effect of sulphur amounts to 1.6–1.8 ppm, the γ-antiperiplanar effect from practically zero to almost 1 ppm.     

Design of a pistonphone

A harmonic pressure generator is developed based on the principle of plane sound waves. The pressure is generated in a cylindrical enclosure by a piston with a flat bottom; the piston is driven by a coil situated in a radial magnetic field. The coil is supplied with an alternating current; the corresponding amplitudes of the piston are measured by a precision accelerometer mounted inside the hollow piston. The apparatus was designed to calibrate the probe microphone described in [1] over a frequency range from 50 to 4000 Hz, with an accuracy of a few percent.     

Cyano-containing ionic liquids for the extraction of aromatic hydrocarbons from an aromatic/aliphatic mixture

Ionic liquids can replace conventional solvents in aromatic/aliphatic extractions, if they have higher aromatic distribution coef- ficients and higher or similar aromatic/aliphatic selectivities. Also physical properties, such as density and viscosity, must be taken into account if a solvent is applied in an industrial extraction process. Cyano-containing ionic liquids have a lower den- sity than the benchmark solvent sulfolane and a higher viscosity. Sulfolane is from a hydrodynamic point of view a better sol- vent than ionic liquids for the aromatic/aliphatic extraction. The most suitable ionic liquids for the extraction of aromatic hy- drocarbons from a mixture of aromatic and aliphatic hydrocarbons are [bmim]C(CN)3, [3-mebupy]N(CN)2, [3-mebupy]C(CN)3, [3-mebupy]B(CN)4 and [mebupyrr]B(CN)4. They have factors of 1.2-2.3 higher mass-based distribution coefficients than sul- folane and a similar or higher, up to a factor of 1.9 higher, aromatic/aliphatic selectivity than sulfolane. The IL [3-mebupy]N(CN)2 is a better extractant for the separation of toluene from a mixture of toluene/n-heptane in a pilot plant Ro- tating Disc Contactor (RDC) than sulfolane.     

Physical properties of 3-methyl-N-butylpyridinium tetracyanoborate and 1-butyl-1-methylpyrrolidinium tetracyanoborate and ternary LLE data of [3-mebupy]B(CN)4 with an aromatic and an aliphatic hydrocarbon at T = 303.2 K and 328.2 K and p = 0.1 MPa

Several physical properties were determined for the ionic liquids 3-methyl-N-butylpyridinium tetracyanoborate ([3-mebupy]B(CN)₄) and 1-butyl-1-methylpyrrolidinium tetracyanoborate ([1-mebupyr]B(CN)₄), viz. liquid density, viscosity, surface tension, thermal stability, and heat capacity over the temperature range from 283.2 K to 475.2 K and at 0.1 MPa. The density and the surface tension were well correlated with linear equations and the viscosity with a Vogel–Fulcher–Tamman equation. The IL [3-mebupy]B(CN)₄ is stable up to a temperature of 480 K and the IL [1-mebupyr]B(CN)₄ up to a temperature of 548 K.Ternary data for the systems {(benzene + n-hexane), or (toluene + n-heptane), or (p-xylene + n-octane + [3-mebupy]B(CN)₄)} were determined at T = 303.2 K and 328.2 K and p = 0.1 MPa. All experimental data were well correlated with the NRTL model. The values of the experimental and calculated aromatic/aliphatic selectivity are in good agreement with each other. The LLE data of [1-mebupyr]B(CN)₄ were only measured in a 10 vol% aromatic feed for the three systems.