Antonietta Ianniello

Denuder measurements of gas and aerosol species above Arctic snow surfaces at Alert 2000

Gas and aerosol measurements were made during the Polar Sunrise Experiment 2000 at Alert, Nunavut (Canada), using two independent denuder/filter systems for sampling and subsequent analysis by ion chromatography. Twelve to forty-eight hour samples were taken during a winter (9–21 February 2000) and a spring (17 April–5 May 2000) campaign. During the spring campaign, samples were taken at two different heights above the snow surface to investigate concentration differences. Total particulate NO3− is the most abundant inorganic nitrogen compound during Arctic springtime (mean 137.4 ng m−3). The NO3− fluxes were calculated above the snow surface to help identify processes that control snow–atmosphere exchange of reactive nitrogen compounds. We suggest that the observed fluxes of coarse particle NO3− via snow deposition may contribute to the nitrogen inventory in the snow surface. Measurements of surface snow provide experimental data that constrain the contribution of dry deposition of coarse particle NO3− to <7%. Wet deposition in falling snow appears to be the major contributor to the nitrate input to the snow.

Sources of atmospheric nitrous acid: State of the science, current research needs, and future prospects

Nitrous acid (HONO) plays a key role in tropospheric photochemistry, primarily due to its role as a source of hydroxyl (OH) radicals via its rapid photolysis. OH radicals are involved in photooxidation processes, such as the formation of tropospheric O3 and other secondary atmospheric pollutants (peroxyacetyl nitrate [PAN] and secondary particles). Recent field and modeling studies have postulated the occurrence of a strong and unknown daytime HONO source, but there are still many significant uncertainties concerning the identification and formation mechanisms of these unknown sources. Up to now, five HONO formation pathways are known: direct emission, homogeneous gas-phase reactions, heterogeneous reactions, surface photolysis, and biological processes. In this review paper, the HONO sources proposed to explain the observed HONO budget, especially during daytime, are discussed, highlighting the knowledge gaps that need further investigation. In this framework, it is crucial to have available accurate and reliable measurements of atmospheric HONO concentrations; thus, a short description of HONO measurement techniques currently available is also reported. The techniques are divided into three basic categories: spectroscopic techniques, wet chemical techniques, and off-line methods. Implications: As important OH radical precursor, HONO plays a key role in the atmosphere. OH radicals are involved in photo-oxidation processes, resulting in the formation of tropospheric O3 and secondary pollutants (PAN and secondary particles). The identification of species affecting the oxidation capacity of the atmosphere is crucial for the understanding of the tropospheric chemistry and in determining effective pollution control strategies. Current models underestimate HONO, especially during daytime, since sources are lacking. Although significant uncertainties still exist, some additional sources contributing to HONO budget have been discussed. Advantages and limitations of the currently HONO measurement techniques are also reported.

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.

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.