Concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs) in liver samples of different marine mammals (1984-2009)

Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984-2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9-C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006.

NADW Photodegradation FTICR-MS

Duplicate, filtered samples of North Atlantic Deep Water (NADW) were irradiated for 28 days in a solar simulator. Duplicate dark controls were placed alongside the irradiated samples. After 28 days, samples were extensively photo-degraded based upon colored dissolved organic matter (CDOM) photo-bleaching (> 95%). Samples were solid phase extracted using PPL resin to isolate, concentrate and desalt the dissolved organic matter (DOM) in the samples. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) enabled 3024 molecular formulas to be identified in the dark control. Photo-degradation decreased molecular diversity, with 2402 formulas assigned post-irradiation. Molecular formulas were classified based upon their photo-lability as 1) photo-resistant; 2) photo-labile; and, 3) photo-produced. Photo-resistant DOM made up 73% of all formulas and was dominated by highly unsaturated molecular signatures consistent with carboxylic-rich alicyclic molecules, suggesting that these apparently bio-refractory compounds may also survive multiple passages through sunlit surface waters and thus accumulate for timeframes exceeding ocean ventilation. Photo-labile DOM was enriched in low molecular weight formulas, aromatic molecular formulas, and sulfur and phosphorous containing formulas. Compounds containing both sulfur and nitrogen were particularly photo-labile and may represent an underappreciated component of the photo-reactive CDOM pool. Photo-produced DOM was enriched in higher molecular weight formulas, as well as aliphatic and peptide formulas. Molecular formulas are indexed by their photo-lability classification in the supplementary information.

(Table 1) Salinity and dissolved organic carbon concentration of marine water (ANT-XIX/2) and mangrove porewater (Brazil)

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

Maize Stress DIESI-MS Data and R Script

Climatic change is an increasing challenge for agriculture that is driving the development of suitable crops in order to ensure supply for both human nutrition and animal feed. In this context, it is increasingly important to understand the biochemical responses of cells to environmental cues at the whole system level, an aim that is being brought closer by advances in high throughput, cost-efficient plant metabolomics. To support molecular breeding activities, we have assessed the economic, technical and statistical feasibility of using direct mass spectrometry methods to evaluate the physiological state of maize (Zea mays L.) plants grown under different stress conditions.