No abstract

In the present study, carbon and bromine isotope effects during UV-photodegradation of bromophenols in aqueous and ethanolic solutions were determined. An anomalous relatively high inverse bromine isotope fractionation (εreactive position up to +5.1‰) along with normal carbon isotope effect (εreactive position of -12.6‰ to -23.4‰) observed in our study may be attributed to coexistence of both mass-dependent and mass-independent isotope fractionation of C-Br bond cleavage. Isotope effects of a similar scale were observed for all the studied reactions in ethanol, and for 4-bromophenol in aqueous solution. This may point out related radical mechanism for these processes. The lack of any carbon and bromine isotope effects during photodegradation of 2-bromophenol in aqueous solution possibly indicates that C-Br bond cleavage is not a rate-limiting step in the reaction. The bromine isotope fractionation, without any detectable carbon isotope effect, that was observed for 3-bromophenol photolysis in aqueous solution probably originates from mass-independent fractionation.

We developed an analytical method for precise and accurate analysis of δ(34)S, δ(81)Br, and δ(37)Cl in individual anionic species by coupled ion chromatography (IC) and multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The method is based on the online separation and purification of ions by IC prior to their isotope analysis by MC-ICPMS. The developed technique significantly simplifies δ(34)S, δ(81)Br, and δ(37)Cl analysis in environmental samples. In cases when several anionic species of the same element are present in the sample, they might be analyzed in a single analytical run. Major isobaric interferences for the analyzed elements were reduced by using "dry" plasma conditions and applying sufficient mass resolution power. The sample-standard bracketing technique was used for instrumental drift correction. In the case of δ(34)S analysis, precisions up to 0.15‰ (1sd) have been achieved for analytes containing down to 5 nmol of S; for δ(81)Br, the attained precision was 0.1‰ (1sd) for analytes containing down to 0.6 nmol of Br. Precisions of 0.2‰ have been obtained for δ(37)Cl with analytes containing 0.7 μmol of Cl. Robustness of the developed analytical method, as well as high precisions and accuracies, has been demonstrated for the laboratory standard solutions and for environmental samples.

The adhesion of explosive particles to substrates with tailored chemical nature was analyzed by atomic force microscopy (AFM). Four different explosives were studied: TNT, RDX, HMX, and PETN. Two types of measurements were performed: in the first, a self-assembled monolayer (SAM) with different end groups was deposited on the tip and used to measure adhesion forces to an explosive particle surface. In the second type of experiment, the explosive particle was glued to the cantilever, and its adhesion force to a SAM-covered gold-plated glass substrate was measured. All experiments were performed both in ambient air and under water. The study shows that −OH and −C6H5 end groups lead to increased adhesion. In addition, we found that capillary forces have significantly contributed to the adhesion of explosive particles.