Equilibrium sampling of persistent and bioaccumulative compounds in soil and sediment: comparison of two approaches to determine equilibrium partitioning concentrations in lipids

The equilibrium sampling in silicone is increasingly applied to measure freely dissolved concentrations and chemical activities within bioaccumulation research of hydrophobic organic chemicals. Two equilibrium methods were applied to PCB-contaminated soil and sediment, and directly calibrated with respect to equilibrium partitioning concentrations in lipids (C(lipid,partitioning)): (i) Solid phase microextraction in the headspace above the sample (HS-SPME) required optimization for its application to PCBs, and it was calibrated above external partitioning standards in olive oil. (ii) Equilibrium sampling with internally coated glass jars with varying thicknesses of silicone (PDMS) resulted in proportionality between coating and analyte mass, which confirmed several validity criteria. C(lipid,partitioning) was here determined as product of PDMS concentration and PDMS to lipid partition ratio. The results of the two methods were in good agreement and thus validated each other. Finally, the coated glass jar method was applied to field sediment containing invertebrates, which lead to C(lipid,partitioning) that were about two times higher than measured lipid-normalized concentrations in the organisms. Temperature differences and animal lipid structure were discussed as possible reasons for this discrepancy. Both methods combine high analytical performance, reduced equilibration times and new calibration possibilities, which makes them suited for bioaccumulation research and environmental monitoring.     

Sex Pheromone of the Pine Sawfly, Gilpinia pallida: Chemical Identification, Synthesis, and Biological Activity

We present the identification of the sex pheromone in the pine sawfly, Gilpinia pallida, including analysis of the female pheromone content, male antennal response and attraction in the field, and synthesis of the most active pheromone component. Several 3,7-dimethyl-2-alkanols were identified from female whole-body extracts, including some compounds with a 2R configuration. This is the first observation of such compounds in a pine sawfly species. Antennae of male G. pallida responded strongly in electroantennograph (EAG) recordings to the (2S,3R,7R)-isomers of the propionates of 3,7-dimethyl-2-tridecanol, 3,7-dimethyl-2-tetradecanol, and 3,7-dimethyl-2-pentadecanol, as well as to the acetates of the tri- and pentadecanols (the acetate of the tetradecanol was not tested). The propionate of (2S,3R,7R)-3,7-dimethyl-2-tetradecanol caught more males in the field than the corresponding isomer of tri- or pentadecanol. We suggest that the (2S,3R,7R)-isomer of 3,7-dimethyl-2-tetradecanol is likely the main sex pheromone precursor in G. pallida, with a subsidiary role for the (2S,3R,7R)-isomer of the tridecanol. Preparation of highly pure (2R,3R,7R)- and (2S,3R,7R)-stereoisomers of 3,7-dimethyl-2-tetradecanol, including the biological active esters, was performed via chemoenzymatic methods and is described in detail.     

Directional velocity estimation using a spatio-temporal encoding technique based on frequency division for synthetic transmit aperture ultrasound

This paper investigates the possibility of flow estimation using spatio-temporal encoding of the transmissions in synthetic transmit aperture imaging (STA). The spatial encoding is based on a frequency division approach. In STA, a major disadvantage is that only a single transmitter (denoting single transducer element or a virtual source) is used in every transmission. The transmitted acoustic energy will be low compared to a conventional focused transmission in which a large part of the aperture is used. By using several transmitters simultaneously, the total transmitted energy can be increased. However, to focus the data properly, the signals originating from the different transmitters must be separated. To do so, the pass band of the transducer is divided into a number of subbands with disjoint spectral support. At every transmission, each transmitter is assigned one of the subbands. In receive, the signals are separated using a simple filtering operation. To attain high axial resolution, broadband spectra must be synthesized for each of the transmitters. By multiplexing the different waveforms on different transmitters over a number of transmissions, this can be accomplished. To further increase the transmitted energy, the waveforms are designed as linear frequency modulated signals. Therefore, the full excitation amplitude can be used during most of the transmission. The method has been evaluated for blood velocity estimation for several different velocities and incident angles. The program Field II was used. A 128-element transducer with a center frequency of 7 MHz was simulated. The 64 transmitting elements were used as the transmitting aperture and 128 elements were used as the receiving aperture. Four virtual sources were created in every transmission. By beamforming lines in the flow direction, directional data were extracted and correlated. Hereby, the velocity of the blood was estimated. The pulse repetition frequency was 16 kHz. Three different setups were investigated with flow angles of 45, 60, and 75 degrees with respect to the acoustic axis. Four different velocities were simulated for each angle at 0.10, 0.25, 0.50, and 1.00 m/s. The mean relative bias with respect to the peak flow for the three angles was less than 2%, 2%, and 4%, respectively.     

Improved temperature precision in rotational coherent anti-stokes raman spectroscopy with a modeless dye laser

Single-shot thermometry with dual-broadband rotational coherent anti-Stokes Raman spectroscopy that employs amplified spontaneous emission from a broadband modeless dye laser has been examined. Evaluation of single-shot spectra of air, N2, and O2 showed an improved temperature precision at room temperature compared with the precision obtained with a conventional dye laser. A comparison was also made between the use of single-mode and multimode Nd:YAG lasers as sources for narrowband radiation, and in all cases the single-mode Nd:YAG laser resulted in higher precision. The experimental results are compared with theoretical predictions.     

Monitoring the interfacial capacitance at self-assembled phosphate monolayers on gold electrodes upon interaction with calcium and magnesium

Electrochemical impedance spectroscopy has been used to evaluate the change in interfacial capacitance upon calcium and magnesium coordination to a phosphate-modified electrode. The phosphate electrode was prepared via immobilization of phosphorylated, thiol-containing, serine analogues onto gold. Upon subjection to calcium and magnesium, a substantial drop in capacitance was observed. Magnesium displayed the largest influence on the capacitance: a 27% capacitance drop was observed upon introduction of a 1 mM solution of magnesium ions. The lowered capacitance is a result of a change in the potential and charge distribution at the film/electrolyte interface as the cations coordinate to the phosphate groups. Moreover, the relationship between electrode potential and capacitance has been investigated and reveals a significant difference between monovalent and divalent cations. As complementary information, infrared reflection absorption spectra of the phosphorylated monolayer having different counterions are presented. The results reported in this paper indicate that the phosphorylated amino acid analogue monolayers could be used in investigations of the biochemically important coordination of calcium and magnesium to phosphates and phosphorylated amino acids.     

High frame-rate blood vector velocity imaging using plane waves: simulations and preliminary experiments

Conventional ultrasound methods for acquiring color images of blood velocity are limited by a relatively low frame-rate and are restricted to give velocity estimates along the ultrasound beam direction only. To circumvent these limitations, the method presented in this paper uses 3 techniques: 1) The ultrasound is not focused during the transmissions of the ultrasound signals; 2) A 13-bit Barker code is transmitted simultaneously from each transducer element; and 3) The 2-D vector velocity of the blood is estimated using 2-D cross-correlation. A parameter study was performed using the Field II program, and performance of the method was investigated when a virtual blood vessel was scanned by a linear array transducer. An improved parameter set for the method was identified from the parameter study, and a flow rig measurement was performed using the same improved setup as in the simulations. Finally, the common carotid artery of a healthy male was scanned with a scan sequence that satisfies the limits set by the Food and Drug Administration. Vector velocity images were obtained with a frame-rate of 100 Hz where 40 speckle images are used for each vector velocity image. It was found that the blood flow approximately followed the vessel wall, and that maximum velocity was approximately 1 m/s, which is a normal value for a healthy person. To further evaluate the method, the test person was scanned with magnetic resonance (MR) angiography. The volume flow derived from the MR scanning was compared with that from the ultrasound scanning. A deviation of 9% between the 2 volume flow estimates was found.     

The effect of a local mesh refinement on hydraulic modelling of river meanders

Large-scale river models are generally discretized by relatively large mesh cells resulting in bathymetry discretization errors and numerical effects. These hydraulic models are generally calibrated by altering the bed roughness to compensate for these errors and effects. Consequently, the calibrated roughness values are mesh-dependent while generally local mesh refinements are executed after model calibration to study the effects of river interventions. This study shows both the errors caused by bathymetry discretization and numerical effects for locally refined meshes. First, schematised river meanders with a flat bed in the transverse flow direction are analysed to isolate the induced numerical effects by the mesh. Afterwards, a case study is considered to verify if similar mesh influences are found in natural river meanders. Curvilinear, triangular and hybrid (combination of curvilinear and triangular cells) meshes are used with different resolutions. The analysis shows that in the schematised river meanders lower depth-averaged flow velocities and larger water depths are simulated with coarser meshes. In the case study, substantial differences in hydrodynamics between the meshes are obtained suggesting that the bathymetry discretization is more influential than the numerical effects. Finally, it was found that triangular meshes, and rivers with narrow meander bends, are most sensitive to mesh resolution. Especially in these cases, it is desirable to refine the mesh at the desired locations before model calibration.     

Formation of Amylose‐Lipid Complexes and Effects of Temperature Treatment. Part 1. Monoglycerides

The formation of amylose‐lipid complexes of form I (amorphous structure) and form II (crystalline structure) during heating was studied by differential scanning calorimetry (DSC) for a range of monoglycerides and for monoglyceride mixtures. The temperature treatment applied to amylose‐monoglyceride‐mixtures were either the first scan in DSC (10 °C/min, 15‐144 °C) or a prolonged heat treatment where the samples were kept at 100 °C for 24 h before being analysed in DSC. The temperature treatment influenced which type of complex was formed, and how much, whereas the thermal stability (as judged from the transition peak temperature) was only marginally influenced. It is shown in this study that all the investigated monoglycerides were able to give complex form I as well as complex form II, although the conditions for the formation differed between the monoglycerides. It was found that a simple DSC‐scan was enough for formation of complex form II for the shortest monoglycerides (glycerol monocaprin, glycerol monolaurin and glycerol monomyristin), whereas in case of the longer monoglycerides and monoglyceride mixtures the prolonged heat treatment was required for formation of complex form II. Moreover, the monoglyceride mixtures gave only form II at conditions where the individual components in the mixtures gave both form I and form II.