Formation of hydroxyl radical from the photolysis of frozen hydrogen peroxide

Hydrogen peroxide (HOOH) in ice and snow is an important chemical tracer for the oxidative capacities of past atmospheres. However, photolysis in ice and snow will destroy HOOH and form the hydroxyl radical (*OH), which can react with snowpack trace species. Reactions of *OH in snow and ice will affect the composition of both the overlying atmosphere (e.g., by the release of volatile species such as formaldehyde to the boundary layer) and the snow and ice (e.g., by the *OH-mediated destruction of trace organics). To help understand these impacts, we have measured the quantum yield of *OH from the photolysis of HOOH on ice. Our measured quantum yields (Phi(HOOH --> *OH)) are independent of ionic strength, pH, and wavelength, but are dependent upon temperature. This temperature dependence for both solution and ice data is best described by the relationship ln(Phi(HOOH --> *OH)) = -(684 +/- 17)(1/T) + (2.27 +/- 0.064) (where errors represent 1 standard error). The corresponding activation energy (Ea) for HOOH (5.7 kJ mol(-1)) is much smaller than that for nitrate photolysis, indicating that the photochemistry of HOOH is less affected by changes in temperature. Using our measured quantum yields, we calculate that the photolytic lifetimes of HOOH in surface snow grains under midday, summer solstice sunlight are approximately 140 h at representative sites on the Greenland and Antarctic ice sheets. In addition, our calculations reveal that the majority of *OH radicals formed on polar snow grains are from HOOH photolysis, while nitrate photolysis is only a minor contributor. Similarly, HOOH appears to be much more important than nitrate as a photochemical source of *OH on cirrus ice clouds, where reactions of the photochemically formed hydroxyl radical could lead to the release of oxygenated volatile organic compounds to the upper troposphere.     

2-Nitrobenzaldehyde as a chemical actinometer for solution and ice photochemistry

2-Nitrobenzaldehyde (2NB) is a convenient, photochemically sensitive, and thermally robust actinometer. Although 2NB has been used in a number of solution and ice experiments in the laboratory, the quantum efficiencies and molar absorptivities of 2NB have not been critically evaluated, especially on ice. Using a series of laboratory and field measurements we have measured the light absorbance and photochemical properties of 2-nitrobenzaldehyde in solution (water and/or acetonitrile) and in/on water ice. Our results show that the molar absorptivities of 2NB are only weakly dependent upon temperature and that the quantum yield is independent of temperature in water; the quantum yield is also independent of wavelength, as shown by past reports. Furthermore, we find that the photochemistry of 2NB in/on water ice is the same as in liquid water. While most studies employing 2NB cite and use a quantum yield of 0.50, based on a review of the literature, and on our new experimental data, we recommend a quantum yield of 0.41 for 2NB photolysis for both solution and water ice.     

Determination of halogenated mono-alcohols and diols in water by gas chromatography with electron-capture detection

We have developed an analytical method for the detection of halogenated alcohols in water with particular focus on 3-chloro-1,2-propanediol and 3-bromo-1,2-propanediol. In this method the target analytes are extracted from water, derivatized with heptafluorobutyric anhydride, and then analyzed with gas chromatography with electron-capture detection. The effects of water, pH and seawater constituents on the method were investigated. Method detection limits for a 5 ml aqueous sample ranged from 0.14 microg l(-1) for 2-bromo-1,3-propanediol to 1.7 microg l(-1) for 1,3-dichloro-2-propanol (1,3DCP).     

Feasibility study of complex wavefield retrieval in off-axis acoustic holography employing an acousto-optic sensor

We propose and experimentally demonstrate a new method for complex-valued wavefield retrieval in off-axis acoustic holography. The method involves use of an intensity-sensitive acousto-optic (AO) sensor, optimized for use at 3.3 MHz, to record the acoustic hologram and a computational method for reconstruction of the object wavefield. The proposed method may circumvent limitations of conventional implementations of acoustic holography and may facilitate the development of acoustic-holography-based biomedical imaging methods.     

Image reconstruction in optoacoustic tomography for dispersive acoustic media

Conventional image reconstruction methods for optoacoustic tomography (OAT) assume an idealized, non-dispersive acoustic medium. However, the linear attenuation coefficient and the phase velocity of acoustic waves propagating in soft tissue depend on temporal frequency and satisfy a known dispersion law. These frequency-dependent effects are incorporated into an optoacoustic wave equation, and a corresponding reconstruction method for OAT is developed. The improvement in image fidelity that can be achieved over conventional reconstruction methods is demonstrated by use of computer-simulation studies.     

Invariance of a Shift-Invariant Space in Several Variables

In this article we study invariance properties of shift-invariant spaces in higher dimensions. We state and prove several necessary and sufficient conditions for a shift-invariant space to be invariant under a given closed subgroup of \mathbb R^d{\mathbb {R}^d}, and prove the existence of shift-invariant spaces that are exactly invariant for each given subgroup. As an application we relate the extra invariance to the size of support of the Fourier transform of the generators of the shift-invariant space. This work extends recent results obtained for the case of one variable to several variables.     

Benzimidazole carbamate residues in milk: Detection by Surface Plasmon Resonance-biosensor, using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method for extraction

A surface plasmon resonance (SPR) biosensor screening assay was developed and validated to detect 11 benzimidazole carbamate (BZT) veterinary drug residues in milk. The polyclonal antibody used was raised in sheep against a methyl 5(6)-[(carboxypentyl)-thio]-2-benzimidazole carbamate protein conjugate. A sample preparation procedure was developed using a modified QuEChERS method. BZT residues were extracted from milk using liquid extraction/partition with a dispersive solid phase extraction clean-up step. The assay was validated in accordance with the performance criteria described in 2002/657/EC. The limit of detection of the assay was calculated from the analysis of 20 known negative milk samples to be 2.7 μg kg⁻¹. The detection capability (CCβ) of the assay was determined to be 5 μg kg⁻¹ for 11 benzimidazole residues and the mean recovery of analytes was in the range 81-116%. A comparison was made between the SPR-biosensor and UPLC-MS/MS analyses of milk samples (n = 26) taken from cows treated different benzimidazole products, demonstrating the SPR-biosensor assay to be fit for purpose.     

Meson exchange and the theory of finite fermi systems

The spin-dependent parameters g₀ and g'₀ in Migdal's theory of finite Fermi systems are studied. Assuming their values to be such as to reproduce the M1 states in ²⁰⁸Pb at 7 and 8 MeV, the origin of these (large) values in meson-exchange contributions to the nucleon-nucleon force is studied. Pion exchange contributes little, because of cancellation between matrix elements from the spin-spin and tensor components. The largest, nearly equal, contributions to g₀ and g'₀ come from p-meson exchange. In order to explain the large values needed for g₀ and g'₀, the tensor coupling of the ρ-meson must be substantially larger than the effective ones found in current phenomenological potentials, such as the Reid soft-core and Hamada-Johnston ones. The large value of the coupling needed follows from work analyzing nucleon form factors.     

Region-of-interest imaging in differential phase-contrast tomography

Differential phase-contrast tomography, also known as beam-deflection tomography, is a method for reconstructing an object's refractive index distribution from knowledge of differential projection data that describe beam deflection angles. We describe and demonstrate an approach to determining regions of interest within an object from truncated differential projection data.     

Strain-induced post-curing of acrylate networks

The mechanical properties and network structure of photocurable polymers are strongly dependent on processing conditions. Here it is reported that highly crosslinked acrylate systems undergo unexpected additional post-curing during DMTA measurements, resulting in an increase in glass-transition temperature (T_g). A detailed study of the conditions under which this increase in T_g takes place unequivocally shows that a small (0.1%) oscillatory strain applied above T_g is responsible for additional cross-linking reactions. The effect of strain-induced post-curing is confirmed by applying post-curing treatments under oscillatory shear strain in rheological tests. Different acrylate systems were characterized and the results show that the strain induced post-curing depends on the network structure of the polymer. In polymer networks with an initial high crosslink density the effect is pronounced while in polymers with an initial lower crosslink density no shift in T_g is observed.