Long-range transport and deposition on the Arctic snowpack of nuclear contaminated particulate matter.

The primary environmental concern related to nuclear power is the production of radioactive waste hazardous to humans and the environment. The main scientific and technological problems to address this are related to the storage and disposal of the nuclear waste and monitoring the dispersion of radioactive species into the environment. In this work, we determined an anomalously high 14C activity, well above the modern natural background, on surface and seasonal snow sampled in early May 2019 on glaciers in the Hornsund fjord area (Svalbard). Due to the lack of local sources, the high snow concentrations of 14C suggest long-range atmospheric transport of nuclear waste particles from lower latitudes, where nuclear power plants and treatment stations are located. The analysis of the synoptic and local meteorological data allowed us to associate the long-range transport of this anomalous 14C concentration to an intrusion event of a warm and humid air mass that likely brought pollutants from Central Europe to the Arctic in late April 2019. Elemental and organic carbon, trace element concentration data, and scanning electron microscopy morphological analysis were performed on the same snow samples to better constrain the transport process that might have led to the high 14C radionuclide concentrations in Svalbard. In particular, the highest 14C values found in the snowpack (> 200 percent of Modern Carbon, pMC) were associated with the lowest OC/EC ratios (< 4), an indication of an anthropogenic industrial source, and with the presence of spherical particles rich in iron, zirconium, and titanium which, altogether, suggest an origin related to nuclear waste reprocessing plants. This study highlights the role of long-range transport in exposing Arctic environments to human pollution. Given that the frequency and intensity of these atmospheric warming events are predicted to increase due to ongoing climate change, improving our knowledge of their possible impact to Arctic pollution is becoming urgent.

Spatiotemporal correlation of urban pollutants by long-term measurements on a mobile observation platform.

We conducted a three-year campaign of atmospheric pollutant measurements exploiting portable instrumentation deployed on a mobile cabin of a public transport system. Size selected particulate matter (PM) and nitrogen monoxide (NO) were measured at high temporal and spatial resolution. The dataset was complemented with measurements of vehicular traffic counts and a comprehensive set of meteorological covariates. Pollutants showed a distinctive spatiotemporal structure in the urban environment. Spatiotemporal autocorrelations were analyzed by a hierarchical spatiotemporal statistical model. Specifically, particles smaller than 1.1 µm exhibited a robust temporal autocorrelation with those at the previous hour and tended to accumulate steadily during the week with a maximum on Fridays. The smallest particles (mean diameter 340 nm) showed a spatial correlation distance of ≈600 m. The spatial correlation distance reduces to ≈ 60 m for particle diameters larger than 1.1 µm, which also showed peaks at the stations correlated with the transport system itself. NO showed a temporal correlation comparable to that of particles of 5.0 µm of diameter and a correlating distance of 155 m. The spatial structure of NO correlated with that of the smallest sized particles. A generalized additive mixed model was employed to disentangle the effects of traffic and other covariates on PM concentrations. A reduction of 50% of the vehicles produces a reduction of the fine particles of -13% and of the coarse particle number of -7.5%. The atmospheric stability was responsible for the most significant effect on fine particle concentration.

Characterization of long-range transported bioaerosols in the Central Mediterranean.

Airborne bacteria were characterized over a 2-y period via high-throughput massive sequencing of 16S rRNA gene in aerosol samples collected at a background mountain European Monitoring and Evaluation Programme (EMEP) Network site (Monte Martano, Italy) located in the Central Mediterranean area. The air mass origin of nineteen samples was identified by air mass modelling and a detailed chemical analysis was performed. Four main origins (Saharan, North-western, North-eastern, and Regional) were identified, and distinct microbial communities were associated with these air masses. Samples featured a great bacterial diversity with Protobacteria being the most abundant phylum, and Sphingomonas followed by Acidovorax, Acinetobacter and Stenotrophomonas the most abundant genera of the dataset. Bacterial genera including potential human and animal pathogens were more abundant in European and in Regional samples compared to Saharan samples; this stressed the relevance of anthropic impact on bacterial populations transported by air masses that cross densely populated areas. The principal aerosol chemical characteristics and the airborne bacterial communities were correlated by cluster analysis, similarity tests and non-metric multidimensional scaling analysis, explaining most of the variability observed. However, the strong correlation between bacterial community structure and air mass origin hampered the possibility to disentangle the effects of variations in bacterial populations and in dust provenance on variations in chemical variables.

Deposition processes over complex topographies: Experimental data meets atmospheric modeling.

The present paper describes the assessment of the atmospheric deposition processes in a basin valley through a multidisciplinary approach based on the data collected within an extensive physico-chemical characterization of the soils, combined with the local meteorology. Surface soil cores were collected on a NNW-SSE transect across the Terni basin (Central Italy), between the Monti Martani and the Monti Sabini chains (956 m a.s.l.), featuring the heavily polluted urban and industrial enclave of Terni on its bottom. Airborne radiotracers, namely 210Pb and 137Cs, have been used to highlight atmospheric deposition. We observed an increased deposition flux of 210Pb and 137Cs at sites located at the highest altitudes, and the associated concentration profiles in soil allowed to evaluate the role of atmospheric deposition. We also obtained a comprehensive dataset of stable anthropogenic pollutants of atmospheric origin that showed heterogeneity along the transect. The behavior has been explained by the local characteristic of the soil, by seeder-feeder processes promoted by the atmospheric circulation, and was reconciled with the concentration profile of radiotracers by factor analysis. Finally, the substantial impact of the local industrial activities on soil profiles and the role of the planetary boundary layer has been discussed and supported by simulations employing a Lagrangian dispersion model.

Airborne bacteria and persistent organic pollutants associated with an intense Saharan dust event in the Central Mediterranean.

In this paper, we present a comprehensive taxonomic survey of the bacterial community and accurate quantification of polycyclic aromatic hydrocarbons (PAHs) associated with an intense Saharan dust advection, which impacted Central Mediterranean area in the whole 2014-2015 period. This work is part of an intensive field campaign at the EMEP regional background site of Monte Martano (Central Italy), considered well representative of long-range transport in the Central Mediterranean area. 22 samples have been characterized in their provenance region and have been considered for the chemical and biological characterization. The event described in the present paper was exceptionally intense at the sampling site allowing a detailed evaluation of the dust load on a regional scale, an estimation of the impact of PAH based on the Toxic Equivalency Factor methodology and a thorough characterization of the airborne bacterial fraction performed by High Throughput Sequencing approach. Afterward, we cultured viable bacteria and evaluated several enzymatic activities and conducted UV survival tests. Principal findings include: (i) the striking evidence that, during the Saharan dust event, a highly diverse and abundant bacterial community was associated with PAH concentrations higher than the yearly mean; (ii) the tangible presence of cultivable microbes; (iii) the proof that the isolates recovered from Saharan dust had the potential to be metabolically active and that almost all of them were able to persist following UV radiation exposure. Comparisons of results for the present case study with mean values for the 2014-2015 experimental campaign are presented. The bacterial community and chemical speciation associated with the Saharan dust advection were specific and very different from those associated with other air masses. The particular case of North-Western Atlantic, which represents one of the most typical advection route reaching the sampling site is discussed in detail.

Functional exploratory data analysis for high-resolution measurements of urban particulate matter.

In this work we propose the use of functional data analysis (FDA) to deal with a very large dataset of atmospheric aerosol size distribution resolved in both space and time. Data come from a mobile measurement platform in the town of Perugia (Central Italy). An OPC (Optical Particle Counter) is integrated on a cabin of the Minimetrò, an urban transportation system, that moves along a monorail on a line transect of the town. The OPC takes a sample of air every six seconds and counts the number of particles of urban aerosols with a diameter between 0.28 µm and 10 µm and classifies such particles into 21 size bins according to their diameter. Here, we adopt a 2D functional data representation for each of the 21 spatiotemporal series. In fact, space is unidimensional since it is measured as the distance on the monorail from the base station of the Minimetrò. FDA allows for a reduction of the dimensionality of each dataset and accounts for the high space-time resolution of the data. Functional cluster analysis is then performed to search for similarities among the 21 size channels in terms of their spatiotemporal pattern. Results provide a good classification of the 21 size bins into a relatively small number of groups (between three and four) according to the season of the year. Groups including coarser particles have more similar patterns, while those including finer particles show a more different behavior according to the period of the year. Such features are consistent with the physics of atmospheric aerosol and the highlighted patterns provide a very useful ground for prospective model-based studies.

Anion-dependent tendency of di-long-chain quaternary ammonium salts to form ion quadruples and higher aggregates in benzene.

The self-aggregation tendency of [N(CH(3))(2)(C(18)H(37))(2)]X [1X; X(-)=BF(4) (-), PF(6) (-), OTf(-), NTf(2) (-), BPh(4) (-), BTol(4) (-), BAr(F-), and B(C(6)F(5))(4) (-)] salts to form ion quadruples (IQs) and higher aggregates (HAggs) in [D(6)]benzene is investigated by means of diffusion NMR spectroscopy. The experimental results indicate that salts containing small anions (1BF(4), 1PF(6), and 1OTf) are present in solution as IQs even at the lowest investigated concentration of C=5×10(-5) M and show a limited tendency to further self-aggregate, reaching a maximum average aggregation number (N=V(H)/V(H)(0IP), where V(H)=measured hydrodynamic volume and V{H}{0IP}=hydrodynamic volume of the ion pair) of about 6-8 (C=0.050-0.100 M). Salts with larger counterions [1BPh(4), 1BTol(4), 1BAr(F), and 1B(C(6)F(5))(4)] form instead ion pairs at low concentration but steadily self-aggregate (especially the non-fluorinated ones) on increasing their concentration up to N values exceeding 50 (C=0.030-0.050 M). 1NTf(2) behaves in an intermediate fashion. The self-aggregation tendency of salts is quantified by formulating the dependence of V(H) on C by means of the equations of indefinitive aggregation models. The following rankings for the formation of IQs and HAggs are obtained: IQs: 1BF(4)≈1PF(6)≈1OTf> 1NTf(2)>1B(C(6)F(5))(4)≥1BPh(4)≥1BTol(4)≥1BAr(F); HAggs: 1BTol(4)>1BPh(4)> 1NTf(2)>1B(C(6)F(5))(4)> 1BAr(F)>1BF(4)≈1PF(6)≈1OTf. Interionic NOE NMR studies and DFT calculations were conducted in order to determine the relative anion-cation orientation in the self-aggregating units.