Characterisation of the correlations between oxidative potential and in vitro biological effects of PM10 at three sites in the central Mediterranean.

Atmospheric particulate matter (PM) is one of the major risks for global health. The exact mechanisms of toxicity are still not completely understood leading to contrasting results when different toxicity metrics are compared. In this work, PM10 was collected at three sites for the determination of acellular oxidative potential (OP), intracellular oxidative stress (OSGC), cytotoxicity (MTT assay), and genotoxicity (Comet assay). The in vitro tests were done on the A549 cell line. The objective was to investigate the correlations among acellular and intracellular toxicity indicators, the variability among the sites, and how these correlations were influenced by the main sources by using PMF receptor model coupled with MLR. The OPDTTV, OSGCV, and cytotoxicity were strongly influenced by combustion sources. Advection of African dust led to lower-than-average intrinsic toxicity indicators. OPDTTV and OSGCV showed site-dependent correlations suggesting that acellular OP may not be fully representative of the intracellular oxidative stress at all sites and conditions. Cytotoxicity correlated with both OPDTTV and OSGCV at two sites out of three and the strength of the correlation was larger with OSGCV. Genotoxicity was correlated with cytotoxicity at all sites and correlated with both, OPDTTV and OSGCV, at two sites out of three. Results suggest that several toxicity indicators are useful to gain a global picture of the potential health effects of PM.

Inter-annual variability of source contributions to PM10, PM2.5, and oxidative potential in an urban background site in the central mediterranean.

Airborne particulate matter (PM) is studied because of its effects on human health and climate change. PM long-term characterisation allows identifying trends and evaluating the outcomes of environmental protection policies. This work is aimed to study the inter-annual variability of PM2.5 and PM10 concentrations and chemical composition in an urban background site (Italy). A dataset of daily PM2.5 and PM10 was collected in the period 2016-2017, including the content of OC, EC, major water-soluble ions, main metals, and compared to a similar dataset collected in the period 2013-2014. Oxidative potential using DTT assay (dithiothreitol) was evaluated and expressed in DTTV as 0.39 nmol/min·m3 in PM10 and 0.29 in PM2.5 nmol/min·m3. PM source apportionment was computed using the EPA PMF5.0 model and source contributions compared with those of a previous dataset collected between 2013 and 2014. Multi linear regression analysis identified which source contributed (p < 0.05) to the oxidative potential of each size fraction. Inter-annual trends were more evident on PM2.5 with reductions of biomass burning contribution and increases in traffic contribution in the 2016-2017 period. Crustal contributions were similar for the two periods, in both size fractions. Carbonates were comparable in PM10 with a slight increase in PM2.5. Sea spray decreased in PM10. The DTTV of PM2.5 peaked during cold periods, while, the DTTV of the PM10-2.5 fraction peaked in summer, suggesting that different sources, with different seasonality, influence OP in the PM2.5 and PM10-2.5 fractions. Analysis showed that sea spray, crustal, and carbonates sources contribute ∼13.6% to DTTV in PM2.5 and ∼62.4% to DTTV in PM10-2.5. Combustion sources (biomass burning and traffic) contribute to the majority of DTTV (50.6%) in PM2.5 and contribute for ∼26% to DTTV in PM10-2.5. Secondary nitrate contributes to DTTV in both fine and coarse fraction; secondary sulphate contribute to DTTV in PM2.5 with negligible contributions to DTTV in PM10-2.5.

Intrinsic sustainability assessment at technosphere level by adapting entropy based ecologic indicators. A preliminary analysis for some main waste treatment processes.

The present study was developed on the following evidence: "what is considered to be environmentally sustainable in the technosphere has to be in compliance with the development tendency of the ecosphere". Starting from this hypothesis, two entropy-based indicators were proposed: the specific entropy per amount of exergy gained (SEEG); the specific entropy per amount of exergy exploitable in the technosphere (SEEE). These were retrieved from the specific entropy (SE) indicator largely exploited for assessing the health status and the development tendency of ecosystems. Entropy based indicators SEEG and SEEE were used for assessing the environmental sustainability of incineration, anaerobic digestion and composting of waste. The aim of these indicators was to support already available methodologies for environmental impact assessment for better understating the intrinsic sustainability of specific processes, since the only quantification of the emission appears not enough informative for this goal. Concerning the ecosphere, SE minimization follows the Darwinian principle "survival of the fittest", being the fittest ecosystems those able to make the most efficient and effective use and storage of energy and materials, at the lower relative entropy generation. Consequently, the lower are SEEG and SEEE the fittest is the analysed system (i.e. sustainable). Main findings indicate SEEG ranging from 2.471 to 3.705, for incinerator, from 0.007 to 0.106 for anaerobic digestion whereas resulted constant = 0.266 for composting. The SEEE ranged from 0.433 to 0.484 for incinerator, from <0.001 to 0.008 for anaerobic digestion and resulted constant = 0.014 for composting. These preliminary results indicates that processes and system able to return chemicals and materials exploitable at technosphere level were characterized by higher ability in returning exergy flows at the lower entropy increase compared to hose returning only energy.

Environmental and human health impact of different powertrain passenger cars in a life cycle perspective. A focus on health risk and oxidative potential of particulate matter components.

Different powertrains passenger cars, homologate in compliance with Euro 6 standard, were compared in a life cycle perspective for assessing both environmental and human health impacts. For this latter aspect, some correlation between the emission of heavy metals, elemental carbon, organic carbon, the oxidative potential of particulate matter and the adverse effect on human health were also analyzed and discussed. Battery electric vehicle (BEV) showed the lower greenhouse gases emissions, from 0.1 kgCO2eq/km to 0.2 kgCO2eq/km but were charged by the higher emissions of freshwater eutrophication and freshwater ecotoxicity, about 6 × 10-6 kgPeq/km and 4 CTUe/km, respectively. Lower resource depletion was detected for cars powered by internal combustion and hybrid powertrains. Amount of particulate matter (PM) emitted resulted lower for petrol-hybrid electric vehicles (Petrol-HEV), of about 5 × 10-5 kgPM2.5eq/km. BEV were charged by the higher values of human toxicity cancer, from about 2 × 10-5 CTUh/km to about 5 × 10-5 CTUh/km whereas Petrol-HEV were credited by the lower impact on human health (DALY/km). The large contribution to PM emission from all the analyzed cars was from tyre and brake wear. Main PM components were elemental (ElC) and organic carbon (OC) compounds. ElC is also a specific marker of PM emitted from traffic. Both ElC and OC were characterized by a strong correlation with the oxidative potential of PM, indicating a threat for human respiratory tract only marginally decreased by the transition from conventional to electric poweretrains vehicles.

Inter-comparison of carbon content in PM10 and PM2.5 measured with two thermo-optical protocols on samples collected in a Mediterranean site.

Scientific interest is focusing on different approaches for characterising organic carbon (OC), elemental carbon (EC) and equivalent black carbon (eBC), although EUSAAR2 protocol has been established and frequently used in EU for regulatory purposes. Discrepancies are observed due to thermal protocols used for OC/EC determinations and the effect of the chemical-physical properties of aerosol using optical measurements for eBC. In this work, a long-term inter-comparison of carbon measurements with two widely used protocols (EUSAAR2 and NIOSH870) was performed on PM2.5 and PM10 samples. The influence of the protocol on the evaluation of secondary organic aerosol (SOC) and on the correlation between EC and eBC was investigated. An extensive check of repeatability gave typical uncertainties of ~ 5% for TC and OC, and ~ 10% for EC for both thermal protocols. Results show that OC is statistically comparable between the two protocols but EC is significantly higher with EUSAAR2, especially during the warm season. The ratio OC/EC is lower with EUSAAR2, also showing a seasonality (lower values in the warm season) not observed with NIOSH870. Despite the differences in OC/EC ratios, the contribution of SOC to OC (~ 50%), evaluated using the EC-tracer method, did not differ significantly between the two protocols and for both size fractions. Further, SOC/OC ratios were comparable in cold and warm periods. eBC/EC ratios larger than one for both protocols were obtained, 1.62 (EUSAAR2) and 1.92 (NIOSH870), and also correlated with the ratio OC/EC for both protocols, especially in the cold season.

Characterization of the water soluble fraction in ultrafine, fine, and coarse atmospheric aerosol.

Water soluble organic carbon significantly contributes to aerosol's carbon mass and its chemical composition is poorly characterized due to the huge number of species. In this study, we determined 94 water-soluble compounds: inorganic ions (Cl-, Br-, I-, NO3-, SO42-,K+, Mg+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2-C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free l- and d-amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The sampling was conducted using a micro-orifice uniform deposit impactor (MOUDI) at the urban area of Mestre-Venice from March to May 2016. The main aim of this work is to identify the source of each detected compound, evaluating its particle size distribution. Clear differences in size distributions were observed for each class of analyzed compounds. The positive matrix factorization (PMF) model was used to identify six factors related to different sources: a) primary biogenic aerosol particles with particle size > 10 µm; b) secondary sulfate contribution; c) biomass burning; d) primary biogenic aerosol particles distributed between 10 and 1 µm; e) an aged sea salt input and f) SOA pinene. Each factor was also characterized by different composition in waters soluble compounds and different particles size distribution.

Sociodemographic, clinical and criminological characteristics of a sample of Italian Volterra REMS patients.

BACKGROUND: In Italy the Law 9/2012 prescribed the total closure of forensic psychiatric hospitals (OPGs) and the conversion to a care model based on residential units in the community employing only clinical personnel (Residenze per l'Esecuzione delle Misure di Sicurezza - REMS) and fully integrated in public mental health services. The aim of this study is to report sociodemographic, clinical and criminological characteristics of patients admitted in Volterra REMS since it opened on 01/12/15 up to 31/12/17. METHODS: Sociodemographic and clinical information was collected from official documents (clinical files, ward reports) and from patients' personal health records. Psychiatric diagnoses were made by REMS psychiatrists according to the DSM-5 criteria. Criminological information was obtained from patients' criminal records. RESULTS: Volterra REMS patients' characteristics are similar to those of samples of OPGs patients (unmarried socially disadvantaged males with an average age of 40, no offsprings, low education, high rates of Schizophrenia Spectrum Disorders and medical comorbidity). However, the REMS model presents a very high turnover rate: during the study period 61 patients were admitted while 32 were discharged. Being assisted by public mental health services before committing the crime increased the probability of discharge. In non-EU patients long acting injectable antipsychotics were used more frequently than in community ones. Substance-Related Disorders are the main psychiatric comorbidity and resulted as being more frequent in bipolar patients than in other patients. CONCLUSIONS: Due to the high patients' turnover, we expect a progressive change in sociodemographic, clinical and criminological features of the REMS population. The REMS model provides a return for mentally disordered criminals to the care of local public mental health services which are recovering after many years some of their most challenging patients ensuring their deinstitutionalization and reintegration into society.

Application of PMF and CMB receptor models for the evaluation of the contribution of a large coal-fired power plant to PM10 concentrations.

The evaluation of the contribution of coal-fired thermo-electrical power plants to particulate matter (PM) is important for environmental management, for evaluation of health risks, and for its potential influence on climate. The application of receptor models, based on chemical composition of PM, is not straightforward because the chemical profile of this source is loaded with Si and Al and it is collinear with the profile of crustal particles. In this work, a new methodology, based on Positive Matrix Factorization (PMF) receptor model and Si/Al diagnostic ratio, specifically developed to discriminate the coal-fired power plant contribution from the crustal contribution is discussed. The methodology was applied to daily PM10 samples collected in central Italy in proximity of a large coal-fired power plant. Samples were simultaneously collected at three sites between 2.8 and 5.8km from the power plant: an urban site, an urban background site, and a rural site. Chemical characterization included OC/EC concentrations, by thermo-optical method, ions concentrations (NH4(+), Ca(2+), Mg(2+), Na(+), K(+), Mg(2+), SO4(2-), NO3(-), Cl(-)), by high performances ion chromatography, and metals concentrations (Si, Al, Ti, V, Mn, Fe, Ni, Cu, Zn, Br), by Energy dispersive X-ray Fluorescence (ED-XRF). Results showed an average primary contribution of the power plant of 2% (±1%) in the area studied, with limited differences between the sites. Robustness of the methodology was tested inter-comparing the results with two independent evaluations: the first obtained using the Chemical Mass Balance (CMB) receptor model and the second correlating the Si-Al factor/source contribution of PMF with wind directions and Calpuff/Calmet dispersion model results. The contribution of the power plant to secondary ammonium sulphate was investigated using an approach that integrates dispersion model results and the receptor models (PMF and CMB), a sulphate contribution of 1.5% of PM10 (±0.3%) as average of the three sites was observed.

An inter-comparison of PM10 source apportionment using PCA and PMF receptor models in three European sites.

Source apportionment of aerosol is an important approach to investigate aerosol formation and transformation processes as well as to assess appropriate mitigation strategies and to investigate causes of non-compliance with air quality standards (Directive 2008/50/CE). Receptor models (RMs) based on chemical composition of aerosol measured at specific sites are a useful, and widely used, tool to perform source apportionment. However, an analysis of available studies in the scientific literature reveals heterogeneities in the approaches used, in terms of "working variables" such as the number of samples in the dataset and the number of chemical species used as well as in the modeling tools used. In this work, an inter-comparison of PM10 source apportionment results obtained at three European measurement sites is presented, using two receptor models: principal component analysis coupled with multi-linear regression analysis (PCA-MLRA) and positive matrix factorization (PMF). The inter-comparison focuses on source identification, quantification of source contribution to PM10, robustness of the results, and how these are influenced by the number of chemical species available in the datasets. Results show very similar component/factor profiles identified by PCA and PMF, with some discrepancies in the number of factors. The PMF model appears to be more suitable to separate secondary sulfate and secondary nitrate with respect to PCA at least in the datasets analyzed. Further, some difficulties have been observed with PCA in separating industrial and heavy oil combustion contributions. Commonly at all sites, the crustal contributions found with PCA were larger than those found with PMF, and the secondary inorganic aerosol contributions found by PCA were lower than those found by PMF. Site-dependent differences were also observed for traffic and marine contributions. The inter-comparison of source apportionment performed on complete datasets (using the full range of available chemical species) and incomplete datasets (with reduced number of chemical species) allowed to investigate the sensitivity of source apportionment (SA) results to the working variables used in the RMs. Results show that, at both sites, the profiles and the contributions of the different sources calculated with PMF are comparable within the estimated uncertainties indicating a good stability and robustness of PMF results. In contrast, PCA outputs are more sensitive to the chemical species present in the datasets. In PCA, the crustal contributions are higher in the incomplete datasets and the traffic contributions are significantly lower for incomplete datasets.

Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter in Venice air.

Harbours are important hubs for economic growth in both tourism and commercial activities. They are also an environmental burden being a source of atmospheric pollution often localized near cities and industrial complexes. The aim of this study is to quantify the relative contribution of maritime traffic and harbour activities to atmospheric pollutant concentration in the Venice lagoon. The impact of ship traffic was quantified on various pollutants that are not directly included in the current European legislation for shipping emission reduction: (i) gaseous and particulate PAHs; (ii) metals in PM10; and (iii) PM10 and PM2.5. All contributions were correlated with the tonnage of ships during the sampling periods and results were used to evaluate the impact of the European Directive 2005/33/EC on air quality in Venice comparing measurements taken before and after the application of the Directive (year 2010). The outcomes suggest that legislation on ship traffic, which focused on the issue of the emissions of sulphur oxides, could be an efficient method also to reduce the impact of shipping on primary particulate matter concentration; on the other hand, we did not observe a significant reduction in the contribution of ship traffic and harbour activities to particulate PAHs and metals. Graphical abstract Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter and evaluation of the effect of an European Directive on air quality in Venice.

Comparison of PM10 concentrations and metal content in three different sites of the Venice Lagoon: an analysis of possible aerosol sources.

The Venice Lagoon is exposed to atmospheric pollutants from industrial activities, thermoelectric power plants, petrochemical plants, incinerator, domestic heating, ship traffic, glass factories and vehicular emissions on the mainland. In 2005, construction began on the mobile dams (MOSE), one dam for each channel connecting the lagoon to the Adriatic Sea as a barrier against high tide. These construction works could represent an additional source of pollutants. PM10 samples were taken on random days between 2007 and 2010 at three different sites: Punta Sabbioni, Chioggia and Malamocco, located near the respective dam construction worksites. Chemical analyses of V, Cr, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl and Pb in PM10 samples were performed by Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) and results were used to identify the main aerosol sources. The correlation of measured data with meteorology, and source apportionment, failed to highlight a contribution specifically associated to the emissions of the MOSE construction works. The comparison of the measurements at the three sites showed a substantial homogeneity of metal concentrations in the area. Source apportionment with principal component analysis (PCA) and positive matrix factorization (PMF) showed that a four principal factors model could describe the sources of metals in PM10. Three of them were assigned to specific sources in the area and one was characterised as a source of mixed origin (anthropogenic and crustal). A specific anthropogenic source of PM10 rich in Ni and Cr, active at the Chioggia site, was also identified.

A(2A) adenosine receptor binding parameters in platelets from patients affected by pathological gambling.

BACKGROUND/AIMS: A structural and functional interaction between A(2A) adenosine receptors and D(2) dopamine receptors has been implicated in the pathophysiology of impulse control disorders. The aim of this study was to use platelet membranes to assess A(2A) adenosine receptor affinity and density in patients affected by pathological gambling (PG; which is classified as a specific impulse control disorder) with respect to those of control subjects. METHODS: Twelve drug-free PG patients and 12 age- and sex-matched healthy controls were enrolled in the study. PG was diagnosed according to the Structured Clinical Interview for DSM-IV - Patient Version 2.0 and the South Oaks Gambling Screen. A(2A) adenosine receptor binding parameters were evaluated using a [(3)H]ZM(241385) binding assay; affinity and density (B(max)) were determined by means of saturation binding studies with platelet membranes. RESULTS: The A(2A) adenosine receptor binding affinity was found to be significantly higher in patients affected by PG than in healthy subjects; in contrast, no significant differences in B(max) were observed between the 2 groups. CONCLUSIONS: The elevated A(2A) adenosine receptor binding affinity in platelets from PG patients with respect to control subjects demonstrates for the first time a change in adenosine receptor parameters, and it suggests the involvement of the adenosine system in this pathology. The previously demonstrated hyperactivity of the dopamine system in PG may modulate the A(2A) adenosine receptor, supporting a role for this receptor as a peripheral marker of dopamine dysfunction. Because it is not possible to directly measure the D(2) dopamine receptor in human platelets, these data are particularly relevant to the detection of dopamine dysfunction.

Sexual dysfunctions and suicidality in patients with bipolar disorder and unipolar depression.

INTRODUCTION: Impairment in sexual function is frequent and underestimated in patients with mental disorders, particularly in those with mood disorders. Few studies have examined the relationship between sexual dysfunctions and the clinical characteristics of mood disorders. AIM: The aim of the present study was to explore the frequency of sexual dysfunctions in patients with bipolar I disorder (BD) and unipolar depression (UD) with respect to control subjects, as well as their relationship with suicidality. MAIN OUTCOME MEASURES: Assessments included: the Structured Clinical Interview for Diagnostic and Statistical Manual of Mental Disorders Fourth Edition (SCID-I/P), the 24-item Brief Psychiatric Rating Scale and the Mood Spectrum Self-Report, a questionnaire exploring lifetime mood spectrum symptomatology including symptoms of sexual functioning and suicidality. METHODS: A consecutive sample of 142 patients (60 BD and 82 UD) and a comparison group of 101 control subjects were recruited in a multicenter study involving 11 academic departments of psychiatry. RESULTS: Lifetime impairment in the sexual response cycle, including desire, excitement, and ability to achieve orgasm, was significantly more common in patients with mood disorders compared with control subjects. Increase in sexual activity and promiscuity were significantly more common in patients with BD vs. the other two groups. Lifetime dysfunctions in all three phases of the sexual response cycle explored were significantly associated with lifetime suicide attempts in patients with BD and with thoughts of death in patients with UD. In BD patients, the lifetime presence of periods with frequent changes of sexual partners was significantly associated with thoughts of death. CONCLUSIONS: Our findings suggest the importance of assessing sexual dysfunctions in patients with either BD or UD, as they may be clinically helpful in identifying phenotypes of mood disorders characterized by high suicidality.

Electrochemical and spectroscopic behavior of iron(III) porphyrazines in Langmuir-Schafer films.

Thin films of a newly synthesized iron(III) porphyrazine, LFeOESPz ( L = ClEtO, OESPz = ethylsulfanylporphyrazine), have been deposited by the Langmuir-Schafer (LS) technique (horizontal lifting) on ITO or gold substrates. Before deposition, the floating films have been investigated at the air-water interface by pressure/area per molecule (pi/ A) experiments, Brewster angle microscopy (BAM) and UV-vis reflection spectroscopy (RefSpec). The complex reacts with water subphase (pH 6.2) forming the mu-oxo dimer, which becomes the predominant component of the LS films ( LS-Fe) as indicated by optical, IR, XPS, and electrochemical data. LS-Fe multilayers exhibit, between open circuit potential (OCP) and +0.90 V (vs SCE), two independent peak pairs with formal potentials, E surf (I) and E surf(II) of +0.56 V and +0.78 V, respectively. According to dynamic voltammetric and coulometric experiments the peak pair at +0.56 V is attributed to one-electron process at the iron(III) centers on the monomer, while the peak pair at +0.78 V is associated to a four-electron process involving mu-oxo-dimer oligomers. LS-Fe films prove to be quite stable electrochemically between OCP and +0.90 V. The electrochemical stability decreases, however, when the potential range is extended both anodically and cathodically outside these limits, due to formation of new species. Upon incubation with TCA solutions, LS-Fe films show remarkable changes in the UV-vis spectra, which are consistent with a significant mu-oxo dimer --> monomer conversion. Addition of TCA to the electrochemical cell using a LS-Fe film as working electrode, results in a linear increase of a cathodic current peak near -0.40 V as the TCA concentration varies in the 0.1-2.0 mM range. This behavior is interpreted in terms of TCA inducing a progressive change in the composition of the LS-Fe films in favor of the monomeric iron(III) porphyrazine, which is responsible for the observed increase in the cathodic current near -0.40 V.