Due to urbanization and industrialization, water pollution is now one of the major environmental challenges of the twenty-first century. Considering the increasing of agricultural and non-agricultural settings in the last decades, the investigation of the relationship between such pesticides and urban stormwater is critical to understand how urban, residential, and industrialized areas can affect environmental safety. Recently, scientific interest has grown in stormwater chemical characterization with the aim to define its impacts in the environment and possibly to make it potable water. In this context, glyphosate, glufosinate, and their degradation products have been identified as the key knowledge gap for the chemical characterization of stormwater. Research investments are needed for a better understanding of the highly polar pesticides to estimate their load, source, and dispersion of urban runoff due to residential use of herbicides. Furthermore, a more comprehensive study of wet and dry deposition and spray drift should be considered for a correct evaluation of source apportionment.

• Chemical characterisation of aerosol was performed in 12 size ranges. • Source apportionment of Venice size-segregated aerosol was carried out. • Impact of ship traffic was studied for the first time on particles below 1 μm. • Impact of ship traffic is higher in nanoparticles compared to larger particles.

Dissolved organic matter (DOM) plays an important role in the environment by influencing the transport and distribution of organic and inorganic components through different processes: the retention, mobilization, and bio-availability of potentially toxic elements (PTEs). The aim of the present study is to examine the dimensional characterization of humic acids (HA) extracted from soil matrix, as well as to analyze the metal distribution among different ligand classes. The molecular size distribution of the HA extract from soil showed three dimensional classes: 52 KDa, 4.5 KDa, and 900 Da. HPSEC-ICP-MS measurements demonstrated that the dimensional classes, relative to first two fractions, bind the largest part of metals. The complexing capacity of HA was evaluated to assess the pollutants mobility in the environmental system. In particular, cadmium (Cd) and copper (Cu) complexation was investigated due to the great concern regarding their bio-availability and toxicity in natural waters. The complexing capacity of HA solution (20 mg/L) was measured by titration using a high-performance size exclusion chromatography (HP-SEC) coupled to an inductively coupled mass spectrometry (ICP-MS). Results obtained by this technique are compared with those obtained by anodic stripping voltammetry (ASV) to investigate the effects of kinetic lability of complexes on measurements carried by HPSEC-ICP-MS. In this study, results of ligand concentrations and stability constants obtained via the two techniques are assessed considering the detection window associated to the applied analytical methodology. Results obtained using the two analytical techniques showed that Cd is complexed by two classes of ligands. However, the ligand concentration values obtained using the two techniques are different, because the detection window associated to the two methodologies; the complexing capacity, which was obtained as sum of the two classes of ligands, were 33 nmol/L and 9 nmol/L for ASV and HPSEC-ICP-MS, respectively. The copper complexing capacities determined by the two methodologies are comparable: 166 and 139 nmol/L for ASV and HPSEC-ICP-MS, respectively. However, the results of Cu titration differ for the two techniques, highlighting only one class of ligands when ASV was used, and two classes when HPSEC-ICP-MS was employed. Differences on results obtained by the two techniques are explained considering the kinetic lability of complexes; the results show that, differently from previous studies, also Cu complexes can be kinetically labile, if one technique with high reaction time is used, as well some cadmium complexes are sufficient stable to be determined by HPSEC-ICP-MS.

Oxidation products of a-pinene represent a fraction of organic matter in the environmental aerosol. alpha-pinene is one of most abundant monoterpenes released in the atmosphere by plants, located typically in boreal, temperate and tropical forests, This primary compound reacts with atmospheric oxidants, such as O-3, O-2, OH radicals and NOx, through the major tropospheric degradation pathway for many monoterpenes under typical atmospheric condition. Although several studies identified a series of by-products deriving from the alpha-pinene photo-oxidation in the atmosphere, such as pinic and cis-pinonic acid, the knowledge of the mechanism of this process is partially still lacking. Thus, the investigation of the distribution of these acids in the different size aerosol particles provides additional information on this regard. The aim of this study is twofold. First, we aim to improve the existing analytical methods for the determination of pinic and cis-pinonic acid in aerosol samples, especially in terms of analytical sensitivity and limits of detection (LOD) and quantification (LOQ). We even attempted to increase the knowledge of the alpha-pinene photo oxidation processes by analysing, for the first time, the particle-size distribution up to nanoparticle level of pinic and cis-pinonic acid. The analysis of aerosol samples was carried out via high-performance liquid chromatography coupled to a triple quadrupole mass spectrometer. The instrumental LOD values of cis-pinonic and pinic acid are 1.6 and 1.2 ng L-1 while LOQ values are 5.4 and 4.1 ng L-1, respectively. Samples were collected by MOUDI II (TM) cascade impactor with twelve cut-sizes, from March to May 2016 in the urban area of Mestre-Venice (Italy). The range concentrations in the aerosol samples were from 0.1 to 0.9 ng m(-3) for cis-pinonic acid and from 0.1 to 0.8 ng m(-3) for pinic acid.

ABSTRACTTrace and rare earth elements from a sediment core from Lake Petén Itzá (Guatemala) depict the geochemical dynamics affecting the lake from ∼5500 a BP to the present. This timing encompasses the Preclassic (4000–1700 a BP) and Classic Periods (1700−1000 a BP) when thriving Maya societies extensively cleared land for agriculture. We demonstrate that this land use occurred during times of increased precipitation, where both processes resulted in increased erosion. Rare earth element ratios depict high precipitation rates between 3000 and 1000 a BP, correlating with an increase in allochthonous silicate input and low organic carbon in the ‘Maya Clay’ stratigraphic section, where this layer is ascribed to intensive anthropogenic land use. Cesium anomalies provide additional evidence for runoff due to high rainfalls and amplified by anthropogenic impacts. The Petén Itzá core contains anomalous spikes of arsenic and mercury, and these peaks correspond to documented volcanic eruptions and therefore are probably natural. The geochemical composition of sediments and palynological records indicate re‐growth of the forest after ∼900 a BP. This increased forest vegetation coincides with the timing of the decline in Maya agriculture.

In order to study the role of sediment re-suspension and deposition versus the role of organic complexation, we investigated the speciation of cadmium (Cd), copper (Cu) and lead (Pb) in samples collected in the Venice Lagoon during several campaigns from 1992 to 2006. The increment in Cd and Pb concentration in the dissolved phases, observed in the central and northern basins, can be linked to important alterations inside the lagoon caused by industrial and urban factors. The study focuses on metal partition between dissolved and particulate phases. The analyses carried out in different sites illustrate the complex role of organic matter in the sedimentation process. While Cd concentration in sediments can be correlated with organic matter, no such correlation can be established in the case of Pb, whose particulate concentration is related only to the dissolved concentration. In the case of Cu, the role of organic complexation remains unclear.

The concentrations of water-soluble compounds (ions, carboxylic acids, amino acids, sugars, phenolic compounds) in aerosol and snow have been determined at the coastal Italian base “Mario Zucchelli” (Antarctica) during the 2014–2015 austral summer. The main aim of this research was to investigate the air-snow transfer processes of a number of classes of chemical compounds and investigate their potential as tracers for specific sources. The composition and particle size distribution of Antarctic aerosol was measured, and water-soluble compounds accounted for 66% of the PM10 total mass concentration. The major ions Na+, Mg2+, Cl− and SO42− made up 99% of the total water soluble compound concentration indicating that sea spray input was the main source of aerosol. These ionic species were found mainly in the coarse fraction of the aerosol resulting in enhanced deposition, as reflected by the snow composition. Biogenic sources were identified using chemical markers such as carboxylic acids, amino acids, sugars and phenolic compounds. This study describes the first characterization of amino acids and sugar concentrations in surface snow. High concentrations of amino acids were found after a snowfall event, their presence is probably due to the degradation of biological material scavenged during the snow event. Alcohol sugars increased in concentration after the snow event, suggesting a deposition of primary biological particles, such as airborne fungal spores.

We investigated the elemental composition and water-soluble-organic compounds (WSOC) present in size-segregated airborne particulate matter to better understand: (1) the distribution of the water-soluble fraction of trace elements (TE), rare earth elements (REE) and WSOCs among different particulate sizes, and (2) the transport processes of aerosol towards the Arctic zone. Samples were collected at Ny-Alesund in the Svalbard Islands (78°55′07″N, 11°53′30″E) from 19 April to 14 September 2010. Water-soluble TE and REE were measured with the aim of recognising reliable tracers of specific sources, which may prove crucial in cost-effective strategies of air pollution control. The TE and REE content, especially in the finest fractions of aerosols in remote areas, is primarily due to long-range transport. It gives valuable information on the global circulation and on the contribution of human activities to aerosol composition (Birmili et al. in Environ Sci Technol 40:1144–1153, 2006; Fernández-Espinosa et al. in Atmos Environ 38:873–886, 2004; Song et al. in Atmos Environ 35:5277–5286, 2001). On the same samples, we also determined water-soluble organic tracers as specific source indicators: levoglucosan and methoxyphenols from biomass burning, acrylamide from anthropogenic origin and amino acids from primary production. These results were discussed in previous papers (Scalabrin et al. in Atmos Chem Phys 12:10453–10463, 2012; Zangrando et al. in Environ Sci Technol 47:8565–8574, 2013).

The concentration and particle-size distribution of ionic species in Antarctic aerosol samples were determined to investigate their potential sources, chemical evolution, and transport. We analyzed aerosol samples collected at two different Antarctic sites: a coastal site near Victoria Land close to the Italian Research Base “Mario Zucchelli”, and another site located on the Antarctic plateau, close to Italian-French Concordia Research Station. We investigated anionic compounds using ion-chromatography coupled to mass spectrometry, and cationic species through capillary ion chromatography with conductometry. Aerosol collected close to the coast was mainly characterized by sea salt species such as Na + , Mg 2+ , and SO 4 2− . These species represented a percentage of 88% of the total sum of all detected ionic species in the aerosol samples from the coastal site. These species were mainly distributed in the coarse fraction, confirming the presence of primary aerosol near the ocean source. Aerosol collected over the Antarctic plateau was characterized by high acidity, with nss-SO 4 2− , NO 3 − , and methanesulfonic acid as the most abundant species. These species were mainly distributed in the <0.49 μm fraction, and they had a behavior of a typical secondary aerosol, where several chemical and physical processes occurred.

Despite geographical isolation and almost complete absence of human settlements, Antarctica is affected by Persistent Organic Pollutants (POPs): the traces of these impacts are recorded in the snow. Although POPs were detected in Antarctica decades ago, there are still large knowledge gaps and a comprehensive understanding of their fundamental patterns is lacking. In this study, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs, including the non-Aroclor PCB-11), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) were measured in surface snow samples from five selected locations of Northern Victoria Land. To our knowledge this is the first study providing ground-based measurements of PCDD/Fs, PCB-11 and PBDEs in Antarctic surface snows, including the plateau. Long-range atmospheric transport (LRAT) followed by regional redistribution were hypothesized as governing sources of POPs to the Antarctic Plateau, but also local pollution from human activities was found. Sub-pgL−1 levels of PCDD/Fs were detected in the coastal samples, while PCBs (ΣPCBs 110-580pgL−1) generally showed a decrease with respect to the past decades. Similar concentrations of PBDEs (ΣBDEs 130–340pgL−1) were found, mainly attributable to the congeners BDE-47 and BDE-99. PAHs (ΣPAHs 0.65–140ngL−1) were the most abundant compounds in all sites with an unexpected high value near a refueling point. Possible source areas of contamination were investigated by means of the HYSPLIT model.

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.

Multivariate statistical methods are proposed for the analysis of the physical properties of limestone cement, natural hydraulic lime and pozzolana-lime mortars admixed with water-repellents. The relationship between the physical properties and the durability of the mortars is evaluated by principal component analysis (PCA) and linear regression models. PCA allows to visualize (i) three groups of mortars according to the binder used and the structural/mechanical properties; (ii) the durability in relation to the mortar properties in simulated conditions. Linear regression models allow to identify and quantify associations between properties, composition and durability. (C) 2015 Elsevier Ltd. All rights reserved.

The concentrations of 19 elements in wild and genetically modified Nicotiana langsdorffii (N. langsdorffii) exposed to Chromium (VI) and to water deficit were determined and compared to provide new information about their response to abiotic stress. Genetic modifications by GR and RolC genes (encoding for the rat glucocorticoid receptor and for Agrobacterium rhizogenes RolC, respectively) were investigated because they induce significant, but only partially known changes in the plant response to stress. Simultaneous determination of Al, As, Ba, Ca, Cd, Co, Cr, Cs, Cu, Fe, K, Mg, Mn, Na, Pb, Rb, Sr, V and Zn was carried out by ICP-MS equipped with a collision/reaction cell (ICP-ORS-MS). The methodology was optimised by testing the grinding, homogenisation, digestion and analysis procedures, to reduce the uncertainty of the experimental results and to identify statistically significant differences between nine sample pools, for a total of 75 samples. The quality control procedure was carried out by blank control and by evaluating the detection limits and repeatability. Trueness was assessed by analysing certified reference material, NIST 1573a. Significant differences were observed in the uptake and accumulation of several elements in the wild-type N. langsdorffii samples, either with respect to the plants submitted to water deficit and exposure to Cr(VI) or with respect to the genetically modified plants. The differences were highlighted by principal component analysis (PCA). The analysis of the element content of the whole plant, combined with the data found in the literature, allows us to hypothesise effects on the metabolic mechanism controlling the uptake and translocation of elements inside the vegetal organism. Because genetic and chemical stress decreases the nutrient concentration in the whole plant, we can say that the uptake at root level is affected. The increase in concentration of elements such as As, Sr and Al indicates a decreased selectivity in the uptake of potentially toxic elements and, consequently, highlights the effects on the plant's metabolic processes.

Size distribution and selected element concentrations of atmospheric particulate matter (PM) were investigated in the Venice Lagoon, at three sites characterised by different anthropogenic influence. The PM10 samples were collected in six size fractions (10–7.2, 7.2–3.0, 3.0–1.5, 1.5–0.95; 0.95–0.49 and <0.49μm) with high volume cascade impactors, and the concentration of 17 elements (Al, As, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, V, Zn) was determined by inductively coupled plasma quadrupole mass spectroscopy. More than 1year of sampling activities allowed the examination of seasonal variability in size distribution of atmospheric particulates and element contents for each site.At all the stations, particles with an aerodynamic diameter <3μm were predominant, thus accounting for more than 78% of the total aerosol mass concentration. The highest PM10 concentrations for almost all elements were found at the site which is more influenced by industrial and urban emissions. Similarity in size distribution of elements at all sites allowed the identification of three main behavioural types: (a) elements found mainly within coarse particles (Ca, Mg, Na, Sr); (b) elements found mainly within fine particles (As, Cd, Ni, Pb, V) and (c) elements with several modes spread throughout the entire size range (Co, Cu, Fe, K, Zn, Mn).Factor Analysis was performed on aerosol data separately identified as fine and coarse types in order to examine the relationships between the inorganic elements and to identify their origin. Multivariate statistical analysis and assessment of similarity in the size distribution led to similar conclusions on the sources.