nitrogen-dioxide and sodium-nitrate

Nitrate and halide ions coexist in a number of environmental systems, including sea salt particles, the Arctic snowpack, and alkaline dry lakes. However, little is known about potential synergisms between halide and nitrate ions. The effect of sea salt on NO(3)(-) photochemistry at 311 nm was investigated at 298 K using thin films of deliquesced NaNO(3)-synthetic sea salt mixtures. Gas phase NO(2), NO, and halogen products were measured as a function of photolysis time using NO(y) chemiluminescence and atmospheric pressure ionization mass spectrometry (API-MS). The production of NO(2) increases with the halide-to-nitrate ratio, and is similar to that for mixtures of NaCl with NaNO(3). Gas phase halogen production also increased with the halide-to-nitrate ratio, consistent with NO(3)(-) photolysis yielding OH which oxidizes halide ions in the film. Yields of gas phase halogens and NO were strongly dependent on the acidity of the solution, while that of NO(2) was not. An additional halogen formation mechanism in the dark involving molecular HNO(3) is proposed that may be important in other systems such as reactions on surfaces. These studies show that the yield of Br(2) relative to NO(2) during photolysis of halide-nitrate mixtures could be as high as 35% under some atmospheric conditions.

Topics: Atmosphere; Atmospheric Pressure; Bromides; Chlorides; Halogens; Nitrates; Nitrogen Dioxide; Oxidation-Reduction; Photochemistry; Photolysis; Seawater; Sodium Chloride; Temperature; Water

Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen lead to replacement of chloride ion by nitrate ion. Studies of the photochemistry of a model system were carried out using deliquesced mixtures of NaCl and NaNO3 on a Teflon substrate. Varying molar ratios of NaCl to NaNO3 (1 : 9 Cl- : NO3-, 1 : 1 Cl- : NO3-, 3 : 1 Cl- : NO3-, 9 : 1 Cl- : NO3-) and NaNO3 at the same total concentration were irradiated in air at 299 +/- 3 K and at a relative humidity of 75 +/- 8% using broadband UVB light (270-380 nm). Gaseous NO2 production was measured as a function of time using a chemiluminescence NO(y) detector. Surprisingly, an enhanced yield of NO2 was observed as the chloride to nitrate ratio increased. Molecular dynamics (MD) simulations show that as the Cl- : NO3- ratio increases, the nitrate ions are drawn closer to the interface due to the existence of a double layer of interfacial Cl- and subsurface Na+. This leads to a decreased solvent cage effect when the nitrate ion photodissociates to NO2+O*-, increasing the effective quantum yield and hence the production of gaseous NO2. The implications of enhanced NO2 and likely OH production as sea salt aerosols become processed in the atmosphere are discussed.

Topics: Atmosphere; Computer Simulation; Ions; Kinetics; Models, Chemical; Nitrates; Nitrogen Dioxide; Photochemistry; Photolysis; Sodium Chloride; Spectrophotometry, Ultraviolet; Surface Properties; Time Factors; Ultraviolet Rays

Mitoxantrone [1,4-dihydroxy-5,8-bis[[2-[(2-hydroxyethyl)amino]ethyl] amino]-9,10-anthracenedione, MXH2] is a novel anticancer agent frequently employed in the chemotherapy of leukemia and breast cancer. Earlier studies have shown that metabolic oxidation to reactive 1,4-quinone or/and 5,8-diiminequinone intermediates may be an important mechanism of activation of this agent, pertinent to its cytotoxic action in vivo. Here we report that in the presence of nitrite ions (NO2-), MXH2 undergoes oxidation by the mammalian enzyme lactoperoxidase (LPO) and hydrogen peroxide and that the process proceeds at a rate that is proportional to NO2- concentration. In contrast, when MXH2 was exposed to LPO/H2O2 in the absence of nitrite, oxidation of the drug was either completely absent or markedly inhibited. These experiments were carried out using concentrated solutions of MXH2 (approximately 100 microM) at near neutral pH where dimers of the drug predominate. We propose that oxidation of MXH2 is mediated by an LPO/ H2O2 metabolite of NO2-, most likely the .NO2 radical. Because in mitoxantrone therapy the drug is administered intravenously, it is directly exposed to nitrogen oxides and other free radicals produced by blood components. It is therefore possible that the ability of mitoxantrone to react with the nitrogen dioxide radical may be relevant to the biological action of the drug in vivo.

Topics: Animals; Antineoplastic Agents; Free Radicals; Hydrogen Peroxide; Hydrogen-Ion Concentration; Lactoperoxidase; Mitoxantrone; Nitrates; Nitrogen Dioxide; Oxidation-Reduction; Spectrometry, Fluorescence