Prediction of gas collection efficiency and particle collection artifact for atmospheric semivolatile organic compounds in multicapillary denuders

A modeling approach is presented to predict the sorptive sampling collection efficiency of gaseous semivolatile organic compounds (SOCs) and the artifact caused by collection of particle-associated SOCs in multicapillary diffusion denuders containing polydimethylsiloxane (PDMS) stationary phase. Approaches are presented to estimate the equilibrium PDMS–gas partition coefficient (K_pdms) from a solvation parameter model for any compound, and, for nonpolar compounds, from the octanol–air partition coefficient (K_oa) if measured K_pdms values are not available. These estimated K_pdms values are compared with K_pdms measured by gas chromatography. Breakthrough fraction was measured for SOCs collected from ambient air using high-flow (300 L min⁻¹) and low-flow (13 L min⁻¹) denuders under a range of sampling conditions (−10 to 25 °C; 11–100% relative humidity). Measured breakthrough fraction agreed with predictions based on frontal chromatography theory using K_pdms and equations of Golay, Lövkvist and Jönsson within measurement precision. Analytes included hexachlorobenzene, 144 polychlorinated biphenyl congeners, and polybrominated diphenyl ethers 47 and 99. Atmospheric particle transmission efficiency was measured for the high-flow denuder (0.037–6.3 μm diameter), and low-flow denuder (0.015–3.1 μm diameter). Particle transmission predicted using equations of Gormley and Kennedy, Pich, and a modified filter model, agreed within measurement precision (high-flow denuder) or were slightly greater than (low-flow denuder) measured particle transmission. As an example application of the model, breakthrough volume and particle collection artifact for the two denuder designs were predicted as a function of K_oa for nonpolar SOCs. The modeling approach is a necessary tool for the design and use of denuders for sorptive sampling with PDMS stationary phase.     

Fast implementation of sparse iterative covariance-based estimation for source localization

Fast implementations of the sparse iterative covariance-based estimation (SPICE) algorithm are presented for source localization with a uniform linear array (ULA). SPICE is a robust, user parameter-free, high-resolution, iterative, and globally convergent estimation algorithm for array processing. SPICE offers superior resolution and lower sidelobe levels for source localization compared to the conventional delay-and-sum beamforming method; however, a traditional SPICE implementation has a higher computational complexity (which is exacerbated in higher dimensional data). It is shown that the computational complexity of the SPICE algorithm can be mitigated by exploiting the Toeplitz structure of the array output covariance matrix using Gohberg-Semencul factorization. The SPICE algorithm is also extended to the acoustic vector-sensor ULA scenario with a specific nonuniform white noise assumption, and the fast implementation is developed based on the block Toeplitz properties of the array output covariance matrix. Finally, numerical simulations illustrate the computational gains of the proposed methods.     

Photokinetic analysis of PRODAN and LAURDAN in large unilamellar vesicles from multivariate frequency-domain fluorescence

This paper describes a multivariate photokinetic analysis of the membrane phase dependence of PRODAN and LAURDAN photokinetics in DMPC vesicles. Decay data, arranged in the form of Fourier transformed emission-decay matrices (FT-EDMs), were collected as a function of temperature around the gel phase transition temperature. Each matrix was partitioned into the emission spectra and decay profiles of the underlying emission components using methods based on principal components analysis. The analysis revealed that both probes typically emit at least three spectral components, which vary in intensity as the membrane undergoes gel to liquid-crystalline phase transitions: a locally excited species (lambda max approximately 415 nm), a charge-transfer species (lambda max approximately 435 nm), and a solvent relaxed species (lambda max approximately 490 nm). In contrast to previous reports, the most red-shifted species is not photoexcited, but evolves from the locally excited species and does not exhibit the dynamic Stokes' shifts associated with conventional solvent relaxation. The primary difference in the emission of the two probes is the prominence of the charge-transfer species in the LAURDAN emission.