Surface‐enhanced Raman spectra of dimethoate and omethoate

Surface‐enhanced Raman scattering (SERS) spectra are presented and analyzed for two important organophosphate pesticides, dimethoate (DMT) and omethoate (OMT). Very detailed SERS spectra were obtained by aggregated Ag hydrosols, both in aqueous suspension and dried on a glass substrate. The SERS and ordinary Raman spectra of DMT do not resemble each other, suggesting that a chemical reaction immediately occurs when DMT is adsorbed onto the metal surface. We propose that the reaction product is OMT, which is the oxygen analog of DMT, on the basis of the Raman and SERS spectra of OMT. Further support is derived from the calculated Raman spectra of DMT and OMT. Minor wavenumber and intensity differences that are observed between the SERS spectra of DMT reaction product and those of OMT could be related to different metal/adsorbate interaction modes. The results can be useful in the development of new analytical methods for the determination of pesticide residues in food. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental and semi-detailed kinetic modeling study of decalin oxidation and pyrolysis over a wide range of conditions

Decalin is the simplest polycyclic alkane (polynaphtenic hydrocarbon) found in liquid fuels (jet fuels, Diesel). In order to better understand the combustion characteristics of decalin, this study provides new experimental data for its oxidation in a jet-stirred reactor. For the first time, stable species concentration profiles were measured in a jet-stirred reactor at a constant mean residence time of 0.1 s and 0.5 s at respectively 1 and 10 atm, over a range of equivalence ratios (? = 0.5–1.5) and temperatures (750–1350 K). The oxidation of decalin under these experimental conditions was modeled using a semi-detailed chemical kinetic reaction mechanism (11,000 reactions involving 360 species) derived from a previously proposed scheme for the ignition of the same fuel in a shock-tube. The proposed mechanism that includes both low- and high-temperature chemistry shows reasonably good agreement with the present experimental data set. It can also represent well decalin pyrolysis and oxidation data available in the literature. Reaction path analyses and sensitivity analyses were conducted to interpret the results.     

Charge distributions in low-energy nuclear fission and their relevance to fission dynamics

Radiochemical and energy loss techniques have been used to measure fragment charge distributions in the systems ²²⁹Th(n_th, f), ²³⁵U(n_{3 MeV}, f) and ²⁵²Cf(s, f). Together with those previously obtained [^{233, 235}U(n_th, f) and ^{239, 241}Pu(n_th, f] the results show that these charge distributions depend very sensitively on both the fissioning species and the initial excitation energy. Very strong even-odd effects are present, for example in the charge distribution of ²²⁹Th(n_th, f) while they almost disappear in ²³⁵U(n_{3 MeV}, f). In the ²²⁹Th(n_th f) and ²⁵²Cf(s, f) cases, kinetic energy distributions of the fragments have been obtained. Fragments with even charges are more energetic, on average, than fragments with odd charges. The results are discussed in terms of a rather small probability for pair breaking during the transition from saddle-point to scission. The relationship between even-odd effects in charge distributions and fine structures in mass distributions is also investigated.     

Measurement of charge distributions for 229Th(nth,f) and 232U(nth,f)

A gas ΔE ? E_R telescope has been used to measure charge yields and their correlations with kinetic energies for ²²⁹Th and ²³²U. Even-charge yields are enhanced compared with odd-charge yields for both fissioning systems; this enhancement increases for events with higher kinetic energy. The mean odd-even effect $\text{δ}{}_{\mathrm{<mtext>p</mtext>}}\text{is}\text{= (40±4)\%}\text{for}{}^{229}\text{Th}$; it is $\text{(21 ± 3)\%}\text{for}{}^{232}\text{U-the same as for}{}^{233}\text{U}\text{((22.1±2.1)\%)}\text{and}{}^{235}\text{U}\text{((23.7±0.7)\%)}$. The energy-integrated δ_p and δ_p for different energy windows, vary strongly as a function of charge (Z) due to the underlying shells. The δ_p averaged over Z increases fast with kinetic energy, contrary to the existing results for ²³³U and ²³⁵U, where δ_p flattens off at low energies. For both systems, the most probable kinetic energy ē shows a strong odd-even stagger; the mean odd-even effect on energy, $\text{δE}{}_{\mathrm{<mtext>K</mtext>}}{}^{\mathrm{<mtext>o?e</mtext>}}\text{,}\text{is}\text{1.4 ± 0.3}\text{MeV for}{}^{229}\text{Th, and}\text{1.7±0.4}\text{MeV for}{}^{232}\text{U}\text{—}$ the latter is about twice the value for ${}^{233}\text{U}\text{(0.95 ± 0.09}\text{MeV}\text{)}\text{and}{}^{235}\text{U}\text{(0.7}\text{MeV}\text{)}$. These results are discussed in terms of the existing models.     

Projectile fragments from 86 MeV/nucleon 12C induced reactions

An 86 MeV/nucleon ¹²C beam has been used to bombard targets of C, Ag and Au. Energy spectra of reaction products with Z = 3?6 and A = 6?12 have been measured at angles between 3° and 20°. A simple fragmentation model, while predicting approximately the gross features of the data, fails to describe the results in detail.     

Nuclear charge distributions from 4π-β measurements on mass separated fragments from235U(n th,f)

A 4π-β detector was used at the Lohengrin mass separator to measure theβ-activity of mass chains 91, 93, 94, 95, 137 and 139 produced in the thermal neutron induced fission of²³⁵U. This activity was analysed intoZ-yields. The different possible corrections were considered and applied to the data. TheZ-yields from this work are compared with the diverse existing results obtained with other methods. The need for and significance of this method to determine theZ-distribution of fission fragments of the heavy group is discussed.     

Aerosol optical properties measured in Argentina: wavelength dependence and variability based on sun photometer measurements

This paper deals with the spectral dependence and time variability of Ångström wavelength exponent scaling law (α), which is the spectral varying slope of the logarithmic relationship between aerosol optical depths (τ) and the wavelength (λ). It is commonly used to retrieve intensive air masses optical properties such as aerosol size distribution from extensive quantities (τ) and Ångström turbidity coefficient (β). This spectral variation of α is studied at different wavelengths from measurements taken by ground-based sun photometer covering from near-infrared to ultraviolet range. We analyze the spectral measurement of aerosols optical depths at eight specific selected wavelengths from 340 to 1020 nm using the sun photometer measurements from AErosol RObotic NETwork (AERONET) from NASA. Data from the entire year 2000 were used from instruments deployed at two different sites covering the regions of Argentina as northcentral at Cordoba CETT (31.5S, 64.4W) and “pampa húmeda” at Buenos Aires CEILAP (34.5S, 58.5W). A new approach of Ångström wavelength exponent spectral variation was developed to take into account with a more accurate precision the significant curvature appearing in the logarithmic relation between τ and λ. Using the direct spectral solar radiation set, time series of Ångström coefficient of turbidity and wavelength scaling law was computed with a day to day data base clustering with uncertainty lower than 0.01 in the optical depth reconstruction over the bulk sun photometer measurements. Temporal series of constant and spectral dependence of wavelength exponent scaling law and turbidity coefficient was derived and shown to vary in space and time. Different meteorological forcing for both sites was evidenced using a regression coefficient analysis to well assess the spectral dependence of wavelength exponent coefficient due to the different cumulating mode of particles and air masses origin at different sites. This spectral decomposition is a key issue in aerosols analysis of steady state and regional scale intrusion episodes with strong connection to their potential contribution of pollution episodes in air-quality problems on urban environment.