Water-soluble organic compounds (WSOC) often represent a large fraction of the total organic mass found in the atmospheric aerosol. They play a very important role in determining the ability of aerosol particles to act as cloud condensation nuclei (CCN), influencing cloud and fog formation and cloud albedo. Molecular characterization of WSOC in fogwater samples was achieved using a twostage ion-trap mass spectrometer equipped with electrospray ionization (ESIMS/MS). Negative ionization conditions in the electrospray interface finalized our characterization of the acidic fraction of WSOC that comprises both monoand di-carboxylic acids and polycarboxylic acids for which a similarity was suggested with naturally occurring humic (or fulvic) acids, and which are sometimes referred to in the literature as humic-like substances (HULIS). Molecular structure elucidation was accomplished using several model compounds and exploiting mass spectral resolution for compound separation. Single compound identification was attempted by recording typical MS/MS fragmentation pathways of model substances and comparing them with actual sample pathways in order to establish specific correspondences. Besides this spectrum-matching identification process, MS/MS interpretation led to several hypothetical structures for HULIS, extending the comprehension of their chemical nature. Suwannee River fulvic acid, proposed as a suitable model for representing the complex mixtures of HULIS in cloud and water aerosol extracts, was also analyzed, and the data obtained were compared with those from WSOC.

Our aim was to enhance the spontaneous slow-frequency EEG activity during the resting state using oscillating transcranial direct currents (tDCS) with a stimulation frequency that resembles the spontaneous oscillations of sleep onset. Accordingly, in this preliminary study, we assessed EEG after-effects of a frontal oscillatory tDCS with different frequency (0.8 vs. 5 Hz) and polarity (anodal, cathodal, and sham). Two single-blind experiments compared the after effects on the resting EEG of oscillatory tDCS [Exp. 1=0.8 Hz, 10 subjects (26.2 ± 2.5 years); Exp. 2=5 Hz, 10 subjects (27.4 ± 2.4 years)] by manipulating its polarity. EEG signals recorded (28 scalp derivations) before and after stimulation [slow oscillations (0.5-1 Hz), delta (1-4 Hz), theta (5-7 Hz), alpha (8-12 Hz), beta 1 (13-15 Hz) and beta 2 (16-24 Hz)] were compared between conditions as a function of polarity (anodal vs. cathodal vs. sham) and frequency of stimulation (0.8 vs. 5 Hz). We found a significant relative enhancement of the delta activity after the anodal tDCS at 5 Hz compared to that at 0.8 Hz. This increase, even though not reaching the statistical significance compared to sham, is concomitant to a significant increase of subjective sleepiness, as assessed by a visual analog scale. These two phenomena are linearly related with a regional specificity, correlations being restricted to cortical areas perifocal to the stimulation site. We have shown that a frontal oscillating anodal tDCS at 5 Hz results in an effective change of both subjective sleepiness and spontaneous slow-frequency EEG activity. These changes are critically associated to both stimulation polarity (anodal) and frequency (5 Hz). However, evidence of frequency-dependence seems more unequivocal than evidence of polarity-dependence.

We investigated the association between rapid eye movement (REM) density (REMd) and electroencephalogram (EEG) activity during non-rapid eye movement (NREM) and REM sleep, within the re-assessment, in a large sample of normal subjects, of the reduction of oculomotor activity in REM sleep after total sleep deprivation (SD). Coherently with the hypothesis of a role of homeostatic sleep pressure in influencing REMd, a negative correlation between changes in REMd and slow-wave activity (SWA) was expected. A further aim of the study was to evaluate if the decreased REMd after SD affects ultradian changes across sleep periods. Fifty normal subjects (29 male and 21 female; mean age=24.3 ± 2.2 years) were studied for four consecutive days and nights. Sleep recordings were scheduled in the first (adaptation), second (baseline) and fourth night (recovery). After awakening from baseline sleep, a protocol of 40 h SD started at 10:00 hours. Polysomnographic measures, REMd and quantitative EEG activity during NREM and REM sleep of baseline and recovery nights were compared. We found a clear reduction of REMd in the recovery after SD, due to the lack of REMd changes across cycles. Oculomotor changes positively correlated with a decreased power in a specific range of fast sigma activity (14.75-15.25 Hz) in NREM, but not with SWA. REMd changes were also related to EEG power in the 12.75-13.00 Hz range in REM sleep. The present results confirm the oculomotor depression after SD, clarifying that it is explained by the lack of changes in REMd across sleep cycles. The depression of REMd can not simply be related to homeostatic mechanisms, as REMd changes were associated with EEG power changes in a specific range of spindle frequency activity, but not with SWA.

A conspicuous fraction of the water soluble organic compounds (WSOC) in fog and fine aerosol samples is composed by monosaccharide anhydrides, such as levoglucosan and its stereoisomers, galactosan and mannosan. Levoglucosan is produced exclusively during wood combustion processes, making it a very useful tracer for plant combustion emissions in the atmosphere. This paper describes a new experimental approach, based on electrospray-tandem mass spectrometry (ESI-MS/MS), for the identification of levoglucosan in fog water samples. The analytical method proposed allows to identify the specific sugar anhydrides directly in the liquid phase without the need of any derivatization process.