In situ analysis of 8-Oxo-7,8-dihydro-2′-deoxyguanosine oxidation reveals sequence- and agent-specific damage spectra

Guanine is a major target for oxidation in DNA, with 8-oxo-7,8-dihydro- 2′-deoxyguanosine (8-oxodG) as a major product. 8-oxodG is itself significantly more susceptible to oxidation than guanine, with the resulting damage consisting of more than 10 different products. This complexity has hampered efforts to understand the determinants of biologically relevant DNA oxidation chemistry. To address this problem, we have developed a high mass accuracy mass spectrometric method to quantify oxidation products arising site specifically in DNA. We applied this method to quantify the role of sequence context in defining the spectrum of damage products arising from oxidation of 8-oxodG by two oxidants: nitrosoperoxycarbonate (ONOOCO2 -), a macrophage-derived chemical mediator of inflammation, and the classical one-electron oxidant, riboflavin-mediated photooxidation. The results reveal the predominance of dehydroguanidinohydantoin (DGh) in 8-oxodG oxidation by both oxidants. While the relative quantities of 8-oxodG oxidation products arising from ONOOCO2 - did not vary as a function of sequence context, products of riboflavin-mediated photooxidation of 8-oxodG were highly sequence dependent. Several of the 8-oxodG oxidation products underwent hydrolytic conversion to new products with half-lives of 2-7 h. The results have implications for understanding the chemistry of DNA oxidation and the biological response to the damage, with DNA damage recognition and repair systems faced with a complex and dynamic set of damage targets. © 2012 American Chemical Society

Atmospheric trace elements in aerosols observed over the Southern Ocean and coastal East Antarctica

Atmospheric aerosol samples were collected over the Southern Ocean (SO) and coastal East Antarctica (CEA) during the austral summer of 2010/11. Samples were analysed for trace elements, including Na, Mg, K, Al, Fe, Mn, Ni, Cd and Se, by inductively coupled plasma mass spectrometry (ICP-MS). The mean atmospheric concentrations over the SO were 1100 ng m−3 for Na, 190 ng m−3 for Mg, 150 ng m−3 for Al, 14 ng m−3 for Fe, 0.46 ng m−3 for Mn and 0.25 ng m−3 for Se. Over CEA, the mean concentrations were 990 ng m−3 for Na, 180 ng m−3 for Mg, 190 ng m−3 for Al, 26 ng m−3 for Fe, 0.70 ng m−3 for Mn and 0.29 ng m−3 for Se. Particle size distributions, enrichment factors (EFs) and correlation analysis indicate that Na, Mg and K mainly came from the marine source, while Al, Fe and Mn were mainly from the crustal source, which also contributed to Mg and K over CEA. High EFs were associated with Ni, Cd and Se, suggesting likely contributions from mixed sources from the Antarctic continent, long-range transport, marine biogenic emissions and anthropogenic emissions. Sea-salt elements (Na, Mg, K) were mainly accumulated in the coarse mode, and crustal elements (Al, Fe, Mn) presented a bimodal size distribution pattern. Bioactive elements (Fe, Ni, Cd) were enriched in the fine mode, especially with samples collected over the SO, possibly affecting biogeochemical cycles in this oceanic region