Giulio Esposito

Nitrate postdeposition processes in Svalbard surface snow

The snowpack acts as a sink for atmospheric reactive nitrogen, but several postdeposition pathways have been reported to alter the concentration and isotopic composition of snow nitrate with implications for atmospheric boundary layer chemistry, ice core records, and terrestrial ecology following snow melt. Careful daily sampling of surface snow during winter (11–15 February 2010) and springtime (9 April to 5 May 2010) near Ny-Alesund, Svalbard reveals a complex pattern of processes within the snowpack. Dry deposition was found to dominate over postdeposition losses, with a net nitrate deposition rate of (0.6 ± 0.2) μmol m A2 d A1 to homogeneous surface snow. At Ny-Alesund, such surface dry deposition can either solely result from long-range atmospheric transport of oxidized nitrogen or include the redeposition of photolytic/bacterial emission originating from deeper snow layers. Our data further confirm that polar basin air masses bring 15 N-depleted nitrate to Svalbard, while high nitrate δ(18 O) values only occur in connection with ozone-depleted air, and show that these signatures are reflected in the deposited nitrate. Such ozone-depleted air is attributed to active halogen chemistry in the air masses advected to the site. However, here the Ny-Alesund surface snow was shown to have an active role in the halogen dynamics for this region, as indicated by declining bromide concentrations and increasing nitrate δ(18 O), during high BrO (low-ozone) events. The data also indicate that the snowpack BrO-NO x cycling continued in postevent periods, when ambient ozone and BrO levels recovered.

Improved Time-Resolved Measurements of Inorganic Ions in Particulate Matter by PILS-IC Integrated with a Sample Pre-Concentration System

A particle-into-liquid sampler coupled with ion chromatograph (PILS-IC) for the on-line measurement of inorganic ions has been modified by the insertion of two ion-exchange pre-concentration cartridges that enrich the sample during the period of the IC analysis. The limits of detection of the modified instrument were 10-15 times lower and the time coverage 24 times higher (from 2 to 48 min per hour) than those of the original PILS-IC setup. The instrumental performance in terms of recovery and break-through volume from the cartridges was satisfactory. The modified PILS-IC was operated in comparison with a diffusion denuder line and with a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) during a short intensive measurement period organized in the framework of the European Monitoring and Evaluation Programme (EMEP), a co-operative program for monitoring and evaluation of the long-range transmission of the air pollutants in Europe. The instrument showed a quantitative response in agreement with the results of the diffusion lines, and an ability to trace fine concentration variations not so different from the performance of the much more complex HR-TOF-AMS. From the time patterns of the ion concentrations measured by the modified PILS-IC, it was possible to obtain useful information about the variations in the air quality and in the strength of the particulate matter sources. Copyright 2015 American Association for Aerosol Research

Characterisation and cleaning of biogas from sewage sludge for biomethane production

This study investigates the conversion of sewage sludge from wastewater treatment plants (WWTP) into biomethane for automotive fuel or grid injection. A prototype plant was monitored in Northern Italy, based on vacuum swing adsorption (VSA) on synthetic zeolite 13×: this biogas upgrading method is similar to pressure swing adsorption (PSA) and commonly used for other kinds of biomass. Measurements of biogas inlet, biomethane outlet and off-gas were performed including CH4, CO2, CO, H2, O2, N2, HCl, HF, NH3, H2S and volatile organic compounds (VOCs). Critical levels were observed in the biogas for of H2S and HCl, whose concentrations were 1570 and 26.8 mg m-3, respectively. On the other hand, the concentration of halogenated VOCs (including tetrachloroethylene and traces of perfluoroalkilated substances, PFAS) and mercaptans were relatively low. A simultaneous and reversible adsorption on 13× zeolite was achieved for H2S and CO2, and carbon filters played a minor role in desulfurisation. The presence of HCl is due to clarifying agents, and its removal is necessary in order to meet the required biomethane characteristics: an additional carbon-supported basic adsorbent was successfully used to remove this contaminant. This study also highlights the interference of CO2 towards HCl if sampling is performed in compliance with the new EU standard for biomethane. High total volatile silicon (TVS) was confirmed in sewage sludge biogas, with a major contribution of siloxane D5: the suitability of this compound as an indicator of total siloxanes is discussed. Results demonstrate that volatile methyl siloxanes (VMS) do not represent a critical issue for the VSA upgrading methodology.

Bayesian Spatiotemporal Modeling of Urban Air Pollution Dynamics

This work deals with the spatiotemporal analysis of urban air pollution dynamics in the town of Perugia (Central Italy) using high-frequency and size resolved data on particular matter (PM). Such data are collected by an Optical Particle Counter (OPC) located on a cabin of the Minimetro, a public transport system that moves on a monorail on a line transect of the town. Hierarchical Bayesian models are used that allow to model a quite large dataset and include an autoregressive term in time, in addition to spatially correlated random effects. Models are fitted for three response variables (fine and coarse particle counts, nitric oxide concentration) and using covariate information such as temperature and humidity. Results show a large temporal autocorrelation, relatively larger for particle counts; moreover, all variables show a significant spatial correlation, with larger ranges for fine PM rather than for coarse PM and nitric oxide concentration.