Self-assembled π-conjugated chromophores: preparation of one- and two-dimensional nanostructures and their use in photocatalysis.

Photocatalytic systems have attracted research interest as a clean approach to generate energy from abundant sunlight. In this context, developing efficient and robust photocatalytic structures is crucial. Recently, self-assembled organic chromophores have entered the stage as alternatives to both molecular systems and (in)organic semiconductors. Nanostructures made of self-assembled π-conjugated dyes offer, on the one hand, molecular customizability to tune their optoelectronic properties and activities and on the other hand, provide benefits from heterogeneous catalysis that include ease of separation, recyclability and improved photophysical properties. In this contribution, we present recent achievements in constructing supramolecular photocatalytic systems made of chromophores for applications in water splitting, H2O2 evolution, CO2 reduction, or environmental remediation. We discuss strategies that can be used to prepare ordered photocatalytic systems with an emphasis on the effect of packing between the dyes and the resulting photocatalytic activity. We further showcase supramolecular strategies that allow interfacing the organic nanostructures with co-catalysts, molecules, polymers, and (in)organic materials. The principles discussed here are the foundation for the utilization of these self-assembled materials in photocatalysis.

The dawn of hydrogen and halogen bonds and their crucial role in collisional processes probing long-range intermolecular interactions.

This perspective review focuses on the results of an internally consistent study developed in the Perugia laboratory, centered on the fundamental interaction components that, at large intermolecular distances, determine the formation of weak intermolecular hydrogen (HB) and halogen (XB) bonds. This investigation exploits old and novel molecular beam scattering experiments involving several gaseous prototypical systems. In particular, we focus on the kinetic energy dependence of the total (elastic + inelastic) integral cross-sections. Of particular interest is the measure of quantum interference patterns in the energy dependence of cross-sections of targeted systems and their shift compared to that of known reference systems. We interpreted these findings as interaction energy stabilization components, such as charge transfer, σ-hole, and polar flattening, that emerge at intermediate separation distance ranges and selectively manifest for specific geometries of collision complexes. Another significant observable we discuss is the absolute value of the cross-section and its dependence on permanent multipole moments of the collisional partners. Specifically, we show how the spontaneous orientation of rotationally cold and polar molecules, due to the electric field gradient associated with the interaction between permanent multipole moments, can significantly modify the magnitude of the total cross-section, even at high values of the impact parameter. We are confident that the present results can help extend the force field formulation to various interacting systems and carry out molecular dynamics simulations under conditions of application interest.

Butterflies as bioindicators of metal contamination.

Anthropogenic trace metal contamination has significantly increased and has caused many hazardous consequences for the ecosystems and human health. The Terni basin valley (Central Italy) shows a heavy load of pollutants from industrial activities, while the characteristic orography structure of the valley favours air stagnation, thus limiting air pollution dispersal. The present study conducted in 2014 aimed to determine the concentration of ten metals in five species of butterflies at nine sites in the Terni valley along a 21-km-long transect, including both relatively pristine and industrial areas. At sites where soil contamination was high for a given metal, such as for chromium as in the case of site 4 (the closest to the steel plant) and for lead as in the case of site 2 (contaminated by a firing range), higher levels of contamination were observed in the tissues of butterflies. We found a correlation between soil contamination and the concentration of Cr, Al and Sr in the tissues of some species of butterflies. The sensitivity to contamination differed among the five species; in particular, Coenonympha pamphilus was generally the species that revealed the highest concentrations of all the ten trace metals at the sites closer to the industrial area. It is known that C. pamphilus is a sedentary species and that its host plants are the Poaceae, capable of accumulating high quantities of metals in their rhizosphere region, thus providing the link with soil contamination. Therefore, monitoring the metal concentration levels in butterflies might be a good indicator and a control tool of environmental quality, specifically in areas affected by high anthropogenic pollution loads linked to a specific source.

Applying Artificial Neural Networks to Oxidative Stress Biomarkers in Forager Honey Bees (Apis mellifera) for Ecological Assessment.

Insect pollinators provide an important ecosystem service that supports global biodiversity and environmental health. The study investigates the effects of the environmental matrix on six oxidative stress biomarkers in the honey bee Apis mellifera. Thirty-five apiaries located in urban, forested, and agricultural areas in Central Italy were sampled during the summer season. Enzyme activities in forager bees were analyzed using an artificial neural network, allowing the identification and representation of the apiary patterns in a Self-Organizing Map. The SOM nodes were correlated with the environmental parameters and tissue levels of eight heavy metals. The results indicated that the apiaries were not clustered according to their spatial distribution. Superoxide dismutase expressed a positive correlation with Cr and Mn concentrations; catalase with Zn, Mn, Fe, and daily maximum air temperature; glutathione S-transferase with Cr, Fe, and daily maximal air temperature; and glutathione reductase showed a negative correlation to Ni and Fe exposure. This study highlights the importance of exploring how environmental stressors affect these insects and the role of oxidative stress biomarkers. Artificial neural networks proved to be a powerful approach to untangle the complex relationships between the environment and oxidative stress biomarkers in honey bees. The application of SOM modeling offers a valuable means of assessing the potential effects of environmental pressures on honey bee populations.

The role of precursor states in the stereo-dynamics of elementary processes.

The present perspective review focuses on the role of the precursor state, controlling the dynamical evolution of elementary processes, whose structure and stability are often difficult to characterize on quantitative grounds. In particular, such a state depends on the critical balance of weak intermolecular forces operative at long and intermediate separation distances. In this paper, a complementary problem has been properly addressed, concerning the suitable formulation of the intermolecular forces involved, defined in terms of a limited number of parameters and applicable in the whole space of the relative configurations of interacting partners. Important help to the solution of such a problem has been provided by the phenomenological method which adopts semi-empirical and empirical formulas to represent the basic features of the leading interaction components. Such formulas are defined in terms of a few parameters directly or indirectly related to the fundamental physical properties of the interacting partners. In this way, the basic features of the precursor state controlling its stability and its dynamical evolution have been defined in an internally consistent way for several elementary processes, having apparently different natures. Particular attention has been paid to the chemi-ionization reactions: they are treated as prototype oxidation processes for which all electronic rearrangements affecting stability and evolution of the precursor state, coincident with the reaction transition state, have been characterized in great detail. The obtained information appears to be in the perspective of general interest for many other elementary processes, difficult to investigate in the same detail since many other effects mask their basic features.

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.

Sex and seasonal differences in metal accumulation of selected tissues in red swamp crayfish from Lake Trasimeno (Umbria, Italy).

Concentrations of essential metals (Cu, Co, Cr, Fe, Ni, Mn, and Zn) and non-essential and toxic metals (Ag, Cd, Hg, and Pb) were quantified in hepatopancreas and abdominal muscle for 73 specimens (37 males and 36 females) of Procambarus clarkii from Lake Trasimeno (Italy) in a year's campaign (July 2018 to June 2019). Elemental concentrations determined in crayfish differed in tissues, seasons, and gender. Both sexes showed lower concentrations in abdominal muscle than in hepatopancreas. Essential metals accumulated in higher concentrations in both tissues than non-essential elements, while associations between essential metals were stronger, especially for females; however, a strong correlation was also observed between Cu and Ag in both sexes. No significant differences in concentrations were recorded between sexes for all seasons; contrarily, significant differences among the total seasonal concentrations (males plus females) were observed only for essential metals and for Ag. Seasonal Toxic Contamination Index (TCI) for Cr, Ni, Cu, Zn, Cd, Pb, and Hg were calculated to assess the toxicity level of metals in the sediments. TCI higher than 1 was detected for Ni only in summer, confirming the close connection between the fluctuating hydrological levels of the shallow Lake Trasimeno, strongly dependent on precipitation, and the metal contamination levels of sediments.

Sources and trends of trace elements and polycyclic aromatic hydrocarbons in a shallow lake in the Mediterranean area from sediment archives of the Anthropocene.

In this study, the anthropogenic contamination in Trasimeno lake (Central Italy) was investigated using three sediment cores spanning over the last 150 years (Anthropocene) to identify the primary sources of pollution and quantify the level of contaminant enrichment in the basin. First, based on the relative cumulative frequency and linear regression methods, we obtained a geochemical baseline for the lake using the deeper parts of the sediment cores. The geochemical baseline allowed us to determine the values of trace elements enrichment factors. On this knowledge, as a second result, we were able to reconstruct the natural sources and the anthropogenic impact on the lake with a biennial resolution. This goal has been obtained by combining different inorganic and organic chemical proxies such as trace elements, polycyclic aromatic hydrocarbons, and lead isotope ratios and exploiting both principal component and factor analysis to associate chemical proxies to human-driven contamination processes. Five different groups of elements have been identified, one of which is of natural origin and four of anthropogenic origin. In particular, it was possible to identify the times and impacts of the industrial activities during the Second World War, which dispersed heavy metals in sediments. Moreover, we found evidence of the recent human activities that have characterized the surroundings of the basin, such as Pb inputs related to the use of gasoline and the enrichment of certain elements generally used in agricultural activities (such as P, Cu, and Mn) due to the development of this sector in the last 40 years.

Molecular beam scattering experiments on noble gas-propylene oxide: Total integral cross sections and potential energy surfaces of He- and Ne-C3H6O.

The interactions of He and Ne with propylene oxide have been investigated with the molecular beam technique by measuring the total (elastic + inelastic) integral cross section as a function of collision velocity. Starting from the analysis of these experimental data, potential energy surfaces, formulated as a function of the separation distance and orientation of propylene oxide with respect to the interacting partners, have been built: The average depth of potential wells (located at intermediate separation distances) has been characterized by analyzing the observed "glory" quantum effects, and the strength of long-range attractions has been obtained from the magnitude and the velocity dependence of the smooth component of measured cross sections. The surfaces, tested and improved against new ab initio calculations of minima interaction energies at the complete basis set level of theory, are defined in the full space of relative configurations. This represents a crucial condition to provide force fields useful to carry out, in general, important molecular property simulations and to evaluate, in the present case, the spectroscopic features and the dynamical selectivity of weakly bound complexes formed by propylene oxide, a prototype chiral species, during collisions in interstellar clouds and winds, in the space and planetary atmospheres. The adopted formulation of the interaction can be readily extended to similar systems, involving heavier noble gases or diatomic molecules (H2, O2, and N2) as well as to propylene oxide dimers.

Population Ecology and Genetic Diversity of the Invasive Alien Species Procambarus clarkii in Lake Trasimeno (Italy).

The deliberate or accidental introduction of invasive alien species (IAS) causes negative ecological and economic impacts altering ecosystem processes, imperiling native species and causing damage to human endeavors. A monthly monitoring program was performed in Lake Trasimeno (Central Italy) from July 2018 to July 2019 in order to provide an upgrade of the population ecology of Procambarus clarkii and to assess the genetic diversity by analyzing the relationships among mitochondrial DNA diversity. Our results confirmed that P. clarkii is well acclimatized in the lake, revealing a stable population structure favored by the resources and conditions typical of this ecosystem, which seem to be optimal for the maintenance of the species. Four distinct mitochondrial haplotypes were detected, but one of them was clearly overrepresented (76%), suggesting that a single predominant introduction event may have occurred in this area, likely followed by secondary events. The identification of the typical genetic variants provides a better understanding of the evolutionary scenarios of P. clarkii in this biotope and it can be helpful in management plans concerning the expanding populations of this invasive alien species.

First discrete iron(II) records from Dome C (Antarctica) and the Holtedahlfonna glacier (Svalbard).

Fe(II) is more soluble and bioavailable than Fe(III) species, therefore the investigation of their relative abundance and redox processes is relevant to better assess the supply of bioavailable iron to the ocean and its impact on marine productivity. In this context, we present a discrete chemiluminescence-based method for the determination of Fe(II) in firn matrices. The method was applied on discrete samples from a snow pit collected at Dome C (DC, Antarctica) and on a shallow firn core from the Holtedahlfonna glacier (HDF, Svalbard), providing the first Fe(II) record from both Antarctica and Svalbard. The method showed low detection limits (0.006 ng g-1 for DC and 0.003 ng g-1 for the HDF) and a precision ranging from 3% to 20% RSD. Fe(II) concentrations ranged between the LoD and 0.077 ng g-1 and between the LoD and 0.300 ng g-1 for the Antarctic and Arctic samples, respectively. The Fe(II) contribution with respect to the total dissolved Fe was comparable in both sites accounting, on average, for 5% and 3%, respectively. We found that Fe(II) correctly identified the Pinatubo/Cerro Hudson eruption in the DC record, demonstrating its reliability as volcanic tracer, while, on the HDF core, we provided the first preliminary insight on the processes that might influence Fe speciation in firn matrices (i.e. organic ligands and pH influences).

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.

Source, timing and dynamics of ionic species mobility in the Svalbard annual snowpack.

Nearly all ice core archives from the Arctic and middle latitudes (such as the Alps), apart from some very high elevation sites in Greenland and the North Pacific, are strongly influenced by melting processes. The increases in the average Arctic temperature has enhanced surface snow melting even of higher elevation ice caps, especially on the Svalbard Archipelago. The increase of the frequency and altitude of winter "rain on snow" events as well as the increase of the length of the melting season have had a direct impact on the chemical composition of the seasonal and permanent snow layers due to different migration processes of water-soluble species, such as inorganic ions. This re-allocation along the snowpack of ionic species could significantly modify the original chemical signal present in the annual snow. This paper aims to give a picture of the evolution of the seasonal snow strata with a daily time resolution to better understand: a) the processes that can influence deposition b) the distribution of ions in annual snow c) the impact of the presence of liquid water on chemical re-distribution within the annual snow pack. Specifically, the chemical composition of the first 100 cm of seasonal snow on the Austre Brøggerbreen Glacier (Spitsbergen, Svalbard Islands, Norway) was monitored daily from the 27th of March to the 31st of May 2015. The experimental period covered almost the entire Arctic spring until the melting season. This unique dataset gives us a daily picture of the snow pack composition, and helps us to understand the behaviour of cations (K+, Ca2+, Na+, Mg2+) and anions (Br-, I-, SO42-, NO3-, Cl-, MSA) in the Svalbard snow pack. We demonstrate that biologically related depositions occur only at the end of the snow season and that rain and melting events have different impacts on the snowpack chemistry.

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.

Leading Interaction Components in the Structure and Reactivity of Noble Gases Compounds.

The nature, strength, range and role of the bonds in adducts of noble gas atoms with both neutral and ionic partners have been investigated by exploiting a fine-tuned integrated phenomenological-theoretical approach. The identification of the leading interaction components in the noble gases adducts and their modeling allows the encompassing of the transitions from pure noncovalent to covalent bound aggregates and to rationalize the anomalous behavior (deviations from noncovalent type interaction) pointed out in peculiar cases. Selected adducts affected by a weak chemical bond, as those promoting the formation of the intermolecular halogen bond, are also properly rationalized. The behavior of noble gas atoms excited in their long-life metastable states, showing a strongly enhanced reactivity, has been also enclosed in the present investigation.

Evaluation of geochemical baselines and metal enrichment factor values through high ecological quality reference points: a novel methodological approach.

In this study, we propose a new approach to estimate geochemical local baselines and enrichment factor values for metals in riverine sediments. The goal is to describe catchment areas characterized by intensive and spread anthropogenic activities, for which it is challenging to identify undisturbed sites to utilize as reference. The case study is the Nestore river basin (Central Italy). Our approach is based on the use of ecological quality as a criterion to select the reference points in the normalization processes of metal baselines. The rationale is to assume that the sediments with a better environmental quality are anthropogenically least impaired. On these grounds, we detected geochemical local baselines and enrichment factor values of various metals (Ca, Co, Cr, Cu, Mn, Ni, Pb, Se, Sr, and Zn). Also, this approach allowed highlighting a major level of pollution for the most downstream site of Nestore river and its left tributaries.

Plant-microorganisms interaction promotes removal of air pollutants in Milan (Italy) urban area.

Plants and phyllosphere microorganisms may effectively contribute to reducing air pollution in cities through the adsorption and biodegradation of pollutants onto leaves. In this work, during all seasons, we sampled atmospheric particulate matter (PM10) and leaves of southern magnolia Magnolia grandiflora and deodar cedar Cedrus deodara, two evergreen plant species widespread in the urban area of Milan where the study was carried out. We then quantified Polycyclic Aromatic Hydrocarbons (PAHs) both in PM10 and on leaves and used sequencing of 16S rRNA gene, shotgun metagenomics and qPCR analyses to investigate the microbial communities hosted by the sampled leaves. Taxonomic and functional profiles of epiphytic bacterial communities differed between host plant species and seasons and the microbial communities on leaves harboured genes involved in the degradation of hydrocarbons. Evidence collected in this work also suggested that the abundance of hydrocarbon-degrading microorganisms on evergreen leaves increased with the concentration of hydrocarbons when atmospheric pollutants were deposited at high concentration on leaves, and that the biodegradation on the phyllosphere can contribute to the removal of PAHs from the urban air.

The Halogen-Bond Nature in Noble Gas-Dihalogen Complexes from Scattering Experiments and Ab Initio Calculations.

In order to clarify the nature of the halogen bond (XB), we considered the prototype noble gas-dihalogen molecule (Ng-X2) systems, focusing on the nature, range, and strength of the interaction. We exploited data gained from molecular beam scattering experiments with the measure of interference effects to obtain a suitable formulation of the interaction potential, with the support of high-level ab initio calculations, and charge displacement analysis. The essential interaction components involved in the Ng-X2 adducts were characterized, pointing at their critical balance in the definition of the XB. Particular emphasis is devoted to the energy stability of the orientational Ng-X2 isomers, the barrier for the X2 hindered rotation, and the influence of the X2 electronic state. The present integrated study returns reliable force fields for molecular dynamic simulations in Ng-X2 complexes that can be extended to systems with increasing complexity and whose properties depend on the selective formation of XB.

Molecular Beam Scattering Experiments as a Sensitive Probe of the Interaction in Bromine-Noble Gas Complexes.

This paper reports for the first time molecular beam experiments for the scattering of He, Ne, and Ar by the Br2 molecule, with the aim of probing in detail the intermolecular interaction. Measurements have been performed under the experimental condition to resolve the glory pattern, a quantum interference effect observable in the collision velocity dependence of the integral cross section. We analyzed the experimental data with a reliable potential model defined as a combination of an anisotropic van der Waals component with the additional contribution due to charge transfer and polar flattening effects related to the formation of an intermolecular halogen bond. The model involves few parameters, whose values are related to fundamental physical properties of the interacting partners, and it allows an internally consistent comparison of the stability of the gas-phase adducts formed by Br2 moiety with different noble gases as well as homologous complexes with the Cl2 molecule. The same model appears to be also easily generalized to describe the interaction of diatomic halogen molecules in the excited B(3Π) electronic state where the halogen bond contribution tends to vanish and more anisotropic van der Waals components dominate the structure of the complexes with noble gases.