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In this study, the information potential of a two-step sequential extraction procedure was evaluated. For this purpose, first of all the elemental composition of Arctic PM10 samples collected in Ny-Ålesund (Svalbard Islands) from 28 February 2015 to 21 October 2015 was investigated. Enrichment Factors, Principal Component Analysis and Hierarchical Cluster Analysis were performed to identify PM10 sources and to understand the effects of short- and long-range transport processes. The investigation of the potential source areas was also aided by taking into account back-trajectories. Then, the sequential extraction procedure was applied to some of the samples in order to obtain more information on these sources. This approach allowed us to establish that most of the elements prevalently having an anthropogenic origin not only were present in higher concentrations, but they were also more easily extractable in late winter and early spring. This confirms the common statement that the anthropogenic portion of the elements present in a sample is generally loosely bound to the particulate matter structure, and so it is more easily extractable and releasable on the Arctic snowpack. Moreover, in the samples collected in late winter and early spring, even the elements prevalently having a crustal origin were more easily extractable, probably due to the particle size selection occurred during the long-range transport. [ABSTRACT FROM AUTHOR]

In this work, a two-step sequential extraction scheme for the determination of trace elements in Arctic PM10 samples was optimized by using two certified reference materials (CRMs). By means of an experimental design for qualitative variables, the five most common extracting solutions for particulate matter (PM) sequential extraction (high purity water (HPW), 0.032 M HNO3, 0.022 M HCl, 0.11 M CH3COOH, and 0.012 M CH3COOH/CH3COONH4 buffer) and two different extraction methods (stirring and ultrasounds) were compared. The purpose of the study was the identification of the procedure which gives the best estimation of the anthropogenic portion of the elements present in PM10 samples. The use of ultrasounds instead of stirring induced a low but significant decrease of the extraction of all the elements and a decrease in the repeatability of the procedure. Diluted HNO3 was the extractant which allowed to maximize the extraction of anthropogenic elements (As, Cd, Pb, Zn) with respect to crustal ones (Al, Si, Ti). The optimized procedure proved successful in avoiding contaminations and, therefore, suitable to be applied to PM samples having extremely low concentrations, such as samples collected in polar or other remote areas. The chosen procedure was applied to ten Arctic PM10 samples, allowing for a better identification of their sources. Indeed, it was possible to hypothesize that even though the concentrations of As, Cd, K, Mg, Mn, and Ni in spring and summer were different, their mobility and, therefore, their chemical form in the analyzed PM10 samples were probably similar. [ABSTRACT FROM AUTHOR]

Simple Summary: This study is one of the very few phase I trials on intraperitoneal chemotherapy applied as PIPAC. Cisplatin and doxorubicin may be safely used as PIPAC at a dose of 30 mg/m2 and 6 mg/m2, respectively; oxaliplatin can be used at an intraperitoneal dose of 135 mg/m2. No serious adverse event was reported. The dosages achieved to date are the highest ever used in PIPAC. The results of these investigations should be the starting point for further clinical phase II trials regarding repeated PIPAC, possibly associated with systemic chemotherapy. Pressurized Intraperitoneal Aerosol Chemotherapy (PIPAC) is an innovative laparoscopic intraperitoneal chemotherapy approach with the advantage of a deeper tissue penetration. Thus far, oxaliplatin has been administered at an arbitrary dose of 92 mg/m2, cisplatin at 7.5 mg/m2 and doxorubicin 1.5 mg/m2. This is a model-based approach phase I dose escalation study with the aim of identifying the maximum tolerable dose of the three different drugs. The starting dose of oxaliplatin was 100 mg/m2; cisplatin was used in association with doxorubicin: 15 mg/m2 and 3 mg/m2 were the respective starting doses. Safety was assessed according to Common Terminology Criteria for Adverse Events (CTCAE version 4.03). Thirteen patients were submitted to one PIPAC procedure. Seven patients were treated with cisplatin and doxorubicin and 6 patients with oxaliplatin; no dose limiting toxicities and major side effects were found. Common adverse events included postoperative abdominal pain and nausea. The maximum tolerable dose was not reached. The highest dose treated cohort (oxaliplatin 135 mg/m2; cisplatin 30 mg/m2 and doxorubicin 6 mg/m2) tolerated PIPAC well. Serological analyses revealed no trace of doxorubicin at any dose level. Serum levels of cis- and oxaliplatin reached a peak at 60–120 min after PIPAC and were still measurable in the circulation 24 h after the procedure. Cisplatin and doxorubicin may be safely used as PIPAC at a dose of 30 mg/m2 and 6 mg/m2, respectively; oxaliplatin can be used at an intraperitoneal dose of 135 mg/m2. The dosages achieved to date are the highest ever used in PIPAC. [ABSTRACT FROM AUTHOR]

A municipal solid waste incinerator (MSWI) was installed in a peripheral area of the city of Turin. In this study, we evaluated the contribution of this plant to the massive concentration of PM 10 , to its chemical composition and to the distribution of the lead isotopes during the start-up phase.We assessed the inorganic composition of PM 10 collected in the vicinity of the Turin incinerator by inductively coupled plasma atomic emission spectroscopy (ICP-AES), magnetic sector inductively coupled plasma mass spectrometer (SF-ICP-MS) and ion chromatography (IC). The lead isotope ratios in PM 10 samples were determined by SF-ICP-MS by a method developed and optimized using experimental design approach. Element trends and data chemometric treatment evidence that the vehicular traffic, increased in this area due to the opening of the MSWI plant, and, to a lesser degree, the direct incinerator emissions influence As, Cd, Cr, Cu, Ba, Mo, Pb, Sn and Zn concentrations. As a whole, however, the element concentrations in PM 10 and the Enrichment Factors (EFs) were comparable with the values reported for other urban sites and target pollutant concentrations of MSWI emissions, namely Cd, Cr, Cu and Pb, were lower than in PM 10 emitted from older MSWIs. This confirms that incinerators of new installation have a lower impact on atmospheric PM 10 composition thanks to stricter current legislation and up-to-date technologies. The lead isotope ratios investigation allowed to distinguish the diverse sources (crustal, vehicular traffic and MSWI) that influence lead concentration in PM 10 collected near incinerator during start-up phase. Image 1 • The impact of a new MSWI on air quality during start-up phase was evaluated. • Element concentration changes are mainly due to an increased vehicular traffic. • Pollutant concentrations of MSWI emissions are lower than those of older MSWIs. • Pb isotope ratios show traffic, MSWI emissions and soil dust as main PM 10 sources. [ABSTRACT FROM AUTHOR]

Modern incinerator plants are equipped with an efficient system for the removal of pollutants and, hence, the gas and particle emissions are generally extremely low. However, it is possible that malfunctions, together with specific meteorological conditions, temporarily cause significant emissions. In this study, the evolution of the inorganic composition of PM10 samples collected in the vicinity of the Turin incinerator before and after its commissioning was assessed. The purpose was to identify the PM sources present in the area, and to evaluate if the operation of the incinerator caused an increase of the concentration of some species. Significant differences were registered among the composition of samples collected in 2012 and 2014, as the latter year was characterized by higher concentrations of Al, As, Ba, Ca, K, Na, Ni, Pb, Sr, and Zn. Considering the position of the incinerator and of the monitoring station, it seems that this increment was not directly caused by the plant emissions. The most probable source of these elements is the highway vehicular traffic, which might have increased due to the travelling of trucks carrying wastes to the incinerator. However, a direct contribution deriving from the incinerator emissions cannot be excluded. [ABSTRACT FROM AUTHOR]

Magnetic Nanoparticles (MNPs) are of great interest in biomedicine, due to their wide range of applications. During recent years, one of the most challenging goals is the development of new strategies to finely tune the unique properties of MNPs, in order to improve their effectiveness in the biomedical field. This review provides an up-to-date overview of the methods of synthesis and functionalization of MNPs focusing on Iron Oxide Nanoparticles (IONPs). Firstly, synthesis strategies for fabricating IONPs of different composition, sizes, shapes, and structures are outlined. We describe the close link between physicochemical properties and magnetic characterization, essential to developing innovative and powerful magnetic-driven nanocarriers. In conclusion, we provide a complete background of IONPs functionalization, safety, and applications for the treatment of Central Nervous System disorders. [ABSTRACT FROM AUTHOR]

The potential of utilizing inorganic constituents in processed animal proteins (PAPs) for species identification in animal feeds was investigated, with the aim of using these constituents to ensure the quality and authenticity of the products. This study aimed to quantify the inorganic content across various PAP species and assess whether inorganic analysis could effectively differentiate between PAP species, ultimately aiding in the identification of PAP fractions in animal feeds. Four types of PAPs, namely bovine, swine, poultry, and fish-based, were analyzed and compared to others made up of feathers of vegetal-based feed. Also, three insect-based PAPs (Cricket, Silkworm, Flour Moth) were considered in this study to evaluate the differences in terms of the nutrients present in this type of feed. Ionic chromatography (IC) was used to reveal the concentrations of NO 3 - , NO 2 , Cl - , and SO 4 2- , and inductively coupled plasma optical emission spectroscopy (ICP-OES) to detect Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, P, Si, Sr, Ti, and Zn. The application of multivariate chemometric techniques to the experimental results allowed us to determine the identification capability of the inorganic composition to identify correlations among the variables and to reveal similarities and differences among the different species. The results show the possibility of using this component for discriminating between different PAPS; in particular, fish PAPs are high in Cd, Sr, Na, and Mg content; swine PAPs have lower metal content due to high fat; feathers and vegetal feed have similar Al, Si, and Ni, but feathers are higher in Fe and Zn; and insect PATs have nutrient levels comparable to PAPs of other origins but are very high in Zn, Cu, and K.

This study addresses the widespread use of UV filters (UVFs) in cosmetic and solar products due to the negative effects of UV radiation, particularly in relation to melanoma risk. While these filters offer protection, their extensive application raises concerns about their environmental and health impacts. Organic UVFs, in particular, have been associated with endocrine disruption in aquatic species and coral reef damage. To mitigate these concerns, regulatory limits have been imposed on certain UVFs. Current analytical techniques for UVF determination, such as HPLC-PDA and HPLC-MS/MS, offer high accuracy but are expensive and lack on-site monitoring capabilities. In response, this research aims to develop a rapid and cost-effective method, utilizing voltammetry for organic UVF quantification in complex matrices like sunscreens. Additionally, HPLC-PDA and HPLC-MS/MS are employed for electrochemical methods and device validation. This approach not only addresses the need for efficient UVF analysis but also provides a basis for regulatory compliance and environmental stewardship in the cosmetics industry.

Iron, a crucial element in our environment, plays a vital role in numerous natural processes. Understanding the presence and concentration of iron in the environment is very important as it impacts various aspects of our planet's health. The on-site detection and speciation of iron are significant for several reasons. In this context, the present work aims to evaluate the applicability of voltammetry for the on-site determination of iron and its possible speciation using a portable voltammetric analyzer. Voltammetry offers the advantage of convenience and cost-effectiveness. For iron (III) determination, the modification of a glassy carbon electrode (GCE) with an antimony-bismuth film (SbBiFE) using the acetate buffer (pH = 4) as a supporting electrolyte was used. The technique adopted was Square Wave Adsoptive Cathodic Stripping Voltammetry (SW-AdCSV), and we used 1-(2-piridylazo)-2-naphthol (PAN) as the iron (III) ligand. Linearity, repeatability, detection limit, and accuracy were determined using synthetic solutions; then, a Standard Reference Material (SRM) of 1643f Trace Elements in Water (iron content: 93.44 ± 0.78 µg L -1 ) was used for validation measurements in the real matrix. the accuracy of this technique was found to be excellent since we obtained a recovery of 103.16%. The procedure was finally applied to real samples (tap, lake, and seawater), and the results obtained were compared via Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The amount of iron found was 207.8 ± 6.6 µg L -1 for tap water using voltammetry and 200.9 ± 1.5 µg L -1 with ICP-OES. For lake water, 171.7 ± 3.8 µg L -1 , 169.8 ± 4.1 µg L -1 , and 187.5 ± 5.7 µg L -1 were found using voltammetry in the lab both on-site and using ICP-OES, respectively. The results obtained demonstrate the excellent applicability of the proposed on-site voltammetric procedure for the determination of iron and its speciation in water.

The determination of the authenticity of extra virgin olive oils (EVOOs) has become more interesting in recent years. Italy is the first country in Europe in terms of number of Protected Designation of Origin (PDO) oils, which connects consumers to a feeling of tradition and thus to higher quality standards. This work focused on the consideration of the inorganic content as a possible marker of EVOOs. Ten vegetable oils (VOs), eight Italian EVOOs and seven not Italian EVOOs were analyzed. After pretreatment by acid mineralization, Al, Ba, Ca, Cu, Fe, K, Li, Mg, Mn, Na, P, Sb, Se and Zn were determined by ICP-OES. The electrochemical properties of a selected group of EVOOs and other vegetal oils of different botanical origin were investigated by voltammetry. Carbon paste electrodes (CPEs) were prepared. The features observed in the voltammograms reflect the reactions of electroactive compounds, which are present in the oils. A chemometric treatment of the results was performed to assess the possibility to distinguish (i) the region of provenience considering the inorganic profile; and (ii) the plant species from which each oil was obtained on the basis of the current profile registered during voltammetric analysis. Inorganic composition seems to be a useful marker for the assessment of the geographical origin of an EVOO. The EVOO-CPEs voltammetry seems to have a good ability to distinguish the plant species of origin. This method could be useful to monitor the conservation status of the oils, as the redox profile is linked to the oxidative degradation state.

Mercury (Hg) and its compounds are highly toxic for humans and ecosystems, and their chemical forms determine both their behavior and transportation as well as their potential toxicity for human beings. Determining the various species of an element is therefore more crucial than understanding its overall concentration in samples. For this reason, several studies focus on the development of new analytical techniques for the identification, characterization, and quantification of Hg compounds. Commercially available, hyphenated technology, such as HPLC-ICP-MS, supports the rapid growth of speciation analysis. This review aims to summarize and critically examine different approaches for the quantification of mercury species in different samples using HPLC-ICP-MS. The steps preceding the quantification of the analyte, namely sampling and pretreatment, will also be addressed. The scenarios evaluated comprehend single and multi-element speciation analysis to create a complete guide about mercury content quantification., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Favilli, Giacomino, Malandrino, Inaudi, Diana and Abollino.)

Aluminium is the most common substrate in studies using impactors for the measurement of the number or the weight of size-segregated atmospheric particulate matter (PM), as its characteristics perfectly fit impactor requirements. However, its use is not recommended by manufacturers when one of the purposes of the study is the determination of the metal content in the sample. The aim of this work was to develop an efficient analytical procedure for the removal and acid digestion of PM samples collected on aluminium foils by a cascade impactor to perform the determination of metals. The possibility of performing the trace metal analysis of PM samples collected using aluminium foils is of great importance, as it allows the determination of an accurate size distribution and the elemental composition of the PM collected on each impactor stage. Two procedures were optimised by using different digestion and analysis techniques. Both procedures were then applied to the two halves of several Dekati low-pressure impactor (DLPI) samples, and the results were critically compared. The two procedures proved to be effective in the determination of extremely low concentrations of a large suite of analytes in different size fractions of PM emitted by a brake system.

The electronic properties of a charge-transfer (donor-acceptor) semiconducting organic co-crystal, Perylene:F4-TCNQ (PE:F4) (the donor, D, is PE and the acceptor, A, is 2,3,5,6-tetrafluoro-7,7,8,8 tetracyanoquinodimethane (F4)) in its 3 : 2 stoichiometry, are experimentally and theoretically studied. This is performed by means of electron paramagnetic resonance (EPR) and solid state electrochemical techniques, such as cyclic voltammetry (CV) measurements on single crystals. In particular, solid state electrochemistry proves to be an effective tool to probe, on a macroscopic scale, the electronic characteristics of the co-crystal. However, EPR highlights the presence of spin ½ radicals localized on F4 molecules, possibly linked to defects. The experimental findings are discussed on the basis of density functional theory (DFT) based calculations, carried out using both the projector augmented wave (PAW), with "periodic boundary conditions" (pbc), method and the localized orbitals, molecular cluster, approach. In particular, a satisfying agreement is found between the experimental, 0.336 eV (electrochemical), and theoretical, 0.303 eV (PAW), band gaps. Differences with the reported optical bandgap are discussed considering excitonic effects.

A measurement and speciation procedure for the determination of total mercury (Hg TOT ), inorganic mercury (Hg IN ), and methylmercury (CH 3 Hg) was developed and the applicability for on-site determination was demonstrated. A simple, portable sample pretreatment procedure was optimized to extract the analytes. Home-made columns, packed with a new sorbent material called CYXAD (CYPHOS 101 modified Amberlite XAD), were used to separate the two forms of the analyte. Hg TOT and CH 3 Hg were determined by anodic stripping voltammetry (ASV), using a solid gold electrode (SGE). Two certified reference materials (BCR-463 Tuna Fish and Tuna Fish ERM-CE 464) and eight fresh fishes were analyzed. Then, the results that were obtained following the optimized portable procedure were compared with the concentrations obtained, using a direct mercury analyzer (DMA). This quantification, using the two techniques, demonstrated the good performance of the proposed method.

A portable measurement and speciation procedure for inorganic mercury (Hg IN ) and methylmercury (CH 3 Hg) was developed. A portable sample pretreatment was optimized to determine total mercury content. A new home-made sorbent (CYXAD, CHYPOS 101 modified Amberlite XAD), was prepared to separate Hg IN and CH 3 Hg. Mercury species were determined using square wave anodic stripping voltammetry (SW-ASV) with a solid gold electrode (SGE) and using a portable potentiostat. A certified reference material, five freeze-dried samples and three fresh samples were analysed with conventional voltammetric analyzer, after dissolution of the samples in microwave oven, and with a portable potentiostat after the mild eating procedure. The results obtained by SW-ASV were compared with those obtained using Direct Mercury Analyser (DMA). The quantification with the portable method is comparable to that obtained with the DMA. Retention tests showed the selectivity of CYXAD for Hg IN , its stability and the possibility to re-use the same aliquot of resin., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Transition metals play a key role in the pathogenic potential of urban particulate matter (PM). However, air quality regulations include exposure limits only for metals having a known toxic potential like Pb, As, Cd, and Ni, neglecting other transition metals like Fe and Cu. Fe and Cu are mainly found in the water-soluble fraction of PM. However, a fraction of the ions may persist strongly bound to the particles, thus potentially acting as surface reactive sites. The contribution of surface ions to the oxidative potential (OP) of PM is likely different from that of free ions since the redox activity of metals is modulated by their local chemical environment. The aim of this study was to investigate how Fe and Cu bound to carbonaceous particles affect the OP and associated toxicity of PM toward epithelial cells and macrophages. Carbonaceous nanoparticles (CNPs) having well-defined size were loaded with controlled amounts of Cu and Fe. The effect of Cu and Fe on the OP of CNPs was evaluated by electronic paramagnetic resonance (EPR) spectroscopy associated with the spin-trapping technique and correlated with the ability to induce cytotoxicity (LDH, WST-1), oxidative stress (Nrf2 translocation), and DNA damage (comet assay) on lung macrophages (NR8383) and/or epithelial cells (RLE-6TN). The release of pro-inflammatory cytokines (TNF-α, MCP-1, and CXCL2) by macrophages and epithelial cells was also investigated. The results indicate a major contribution of surface Cu to the surface reactivity of CNPs, while Fe has a minor role. At the same time, Cu increases the cytotoxicity of CNPs and their ability to induce oxidative stress and DNA damage. In contrast, surface Fe increases the release of pro-inflammatory cytokines by macrophages. Overall, these results confirm the role of Cu and Fe in PM toxicity and suggest that the total metals content in PM might be a better indicator of pathogenicity than water-soluble metals.

Alzheimer's disease (AD) is the most common form of dementia, characterized by a complex etiology that makes therapeutic strategies still not effective. A true understanding of key pathological mechanisms and new biomarkers are needed, to identify alternative disease-modifying therapies counteracting the disease progression. Iron is an essential element for brain metabolism and its imbalance is implicated in neurodegeneration, due to its potential neurotoxic effect. However, the role of iron in different stages of dementia is not clearly established. This study aimed to investigate the potential impact of iron both in cerebrospinal fluid (CSF) and in serum to improve early diagnosis and the related therapeutic possibility. In addition to standard clinical method to detect iron in serum, a precise quantification of total iron in CSF was performed using graphite-furnace atomic absorption spectrometry in patients affected by AD, mild cognitive impairment, frontotemporal dementia, and non-demented neurological controls. The application of machine learning techniques, such as clustering analysis and multiclassification algorithms, showed a new potential stratification of patients exploiting iron-related data. The results support the involvement of iron dysregulation and its potential interaction with biomarkers (Tau protein and Amyloid-beta) in the pathophysiology and progression of dementia., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Ficiarà, Boschi, Ansari, D'Agata, Abollino, Caroppo, Di Fede, Indaco, Rainero and Guiot.)

In this work, a two-step sequential extraction scheme for the determination of trace elements in Arctic PM 10 samples was optimized by using two certified reference materials (CRMs). By means of an experimental design for qualitative variables, the five most common extracting solutions for particulate matter (PM) sequential extraction (high purity water (HPW), 0.032 M HNO 3 , 0.022 M HCl, 0.11 M CH 3 COOH, and 0.012 M CH 3 COOH/CH 3 COONH 4 buffer) and two different extraction methods (stirring and ultrasounds) were compared. The purpose of the study was the identification of the procedure which gives the best estimation of the anthropogenic portion of the elements present in PM 10 samples. The use of ultrasounds instead of stirring induced a low but significant decrease of the extraction of all the elements and a decrease in the repeatability of the procedure. Diluted HNO 3 was the extractant which allowed to maximize the extraction of anthropogenic elements (As, Cd, Pb, Zn) with respect to crustal ones (Al, Si, Ti). The optimized procedure proved successful in avoiding contaminations and, therefore, suitable to be applied to PM samples having extremely low concentrations, such as samples collected in polar or other remote areas. The chosen procedure was applied to ten Arctic PM 10 samples, allowing for a better identification of their sources. Indeed, it was possible to hypothesize that even though the concentrations of As, Cd, K, Mg, Mn, and Ni in spring and summer were different, their mobility and, therefore, their chemical form in the analyzed PM 10 samples were probably similar. Graphical abstract.

The inorganic component of hazelnuts was considered as a possible marker for geographical allocation and for the assessment of technological impact on their quality. The analyzed samples were Italian hazelnuts of the cultivar Tonda Gentile Romana and Turkish hazelnuts of the cultivars Tombul , Palaz and Çakildak . The hazelnuts were subjected to different drying procedures and different conservative methods. The concentration of 13 elements, namely Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, Sn, Sr and Zn, were quantified by inductively coupled plasma optical emission spectroscopy (ICP-OES). All the samples were previously digested in a microwave oven. Before proceeding with the analysis of the samples, the whole procedure was optimized and tested on a certified reference material. The results show that the inorganic component: (i) can represent a fingerprint, able to identify the geographical origin of hazelnuts, becoming an important quality marker for consumer protection; (ii) is strongly influenced by the treatments undergone by the investigated product during all the processing stages. A pilot study was also carried out on hazelnuts of the cultivar Tonda Gentile Trilobata Piemontese , directly harvested from the plant during early development to maturity and analyzed to monitor the element concentration over time., Competing Interests: The authors declare no conflict of interest.

A simple procedure for field fish sample pretreatment was developed. This treatment in combination with square wave anodic stripping voltammetry (SW-ASV) with solid gold electrodes (SGE) and gold nanoparticle-modified glassy carbon electrodes (AuNPs-GCE) was applied for the determination of total mercury content. A certified reference material (CRM, Tuna Fish BCR 463) , ten freeze-dried samples of canned tuna and two fresh fish samples were analysed both with a bench-top voltammetric analyser after microwave digestion and with a portable potentiostat after mild eating using a small commercial food warmer. The results obtained by the two SW-ASV approaches and by a Direct Mercury Analyser (DMA), the official method for mercury determination, were in very good agreement. In particular, (i) the results obtained with in field procedure are consistent with those obtained with the conventional microwave digestion; (ii) the presence of gold nanoparticles on the active electrode surface permits an improvement of the analytical performance in comparison to the SGE: the Limit of Quantification (LOQ) for mercury in fish-matrix was 0.1 μg L -1 (Hg cell concentration), corresponding to 0.06 mg kg -1 wet fish, which is a performance comparable to that of DMA. The pretreatment proposed in this study is very easy and applicable to fresh fish; in combination with a portable potentiostat, it proved to be an interesting procedure for on-site mercury determination.

One of the most challenging goals in pharmacological research is overcoming the Blood Brain Barrier (BBB) to deliver drugs to the Central Nervous System (CNS). The use of physical means, such as steady and alternating magnetic fields to drive nanocarriers with proper magnetic characteristics may prove to be a useful strategy. The present review aims at providing an up-to-date picture of the applications of magnetic-driven nanotheranostics agents to the CNS. Although well consolidated on physical ground, some of the techniques described herein are still under investigation on in vitro or in silico models, while others have already entered in-or are close to-clinical validation. The review provides a concise overview of the physical principles underlying the behavior of magnetic nanoparticles (MNPs) interacting with an external magnetic field. Thereafter we describe the physiological pathways by which a substance can reach the brain from the bloodstream and then we focus on those MNP applications that aim at a nondestructive crossing of the BBB such as static magnetic fields to facilitate the passage of drugs and alternating magnetic fields to increment BBB permeability by magnetic heating. In conclusion, we briefly cite the most notable biomedical applications of MNPs and some relevant remarks about their safety and potential toxicity., Competing Interests: The authors declare no conflict of interest.

The presence of certain metals naturally contained inside raw materials (e.g., pigments) used to produce cosmetics for make-up may represent a serious concern for the final quality and safety of the product. The knowledge of the total concentration of metals is not sufficient to predict their reactivity and their toxicological profile. For these reasons, we set up a comprehensive approach to characterize the content of Co, Cr, and Ni in two raw materials for cosmetic production, a black iron oxide and a pearly pigment, and in a finished product, pearly powder eye shadow. Namely, besides the total metal concentrations, the speciation of chromium and the bioaccessibility of the three metals were assessed. Since no standard method is so far available for hexavalent chromium extraction from cosmetic samples, three approaches were compared (EPA 3060A method, IRSA 16 method, and a Na 3 PO 4 extraction). Results show that Na 3 PO 4 extraction is the most selective one. Cr(VI) was undetectable in black iron oxide and present at very low concentrations (about 0.3 mg/kg) in pearly pigment and in the pearly powder eye shadow samples. The extracted Cr(VI) concentrations are not related to the total Cr content in the samples. Bioaccessibility studies were performed by in vitro extractions with synthetic lacrimal fluids and sweat. Despite the wide range of metal concentrations in the samples, the amounts of bioaccessible elements were undetectable or very low (less than 0.4 mg/kg), thus suggesting that metals in the three samples are present in inert forms. Graphical abstract The possible leaching of metals from cosmetics to biological fluids. Spectroscopic and chromatographic techniques provide complementary information for an integrated bioanalytical approach to risk characterization.

Major, minor and trace elements were determined in freshwater of lacustrine systems in Terra Nova Bay, along Victoria Land coast, Antarctica, as well as in algae and mosses. The samples were collected during some of the sampling campaigns between 2007 and 2011 (and the one of 2002) within the framework of the Italian National Program of Research in Antarctica (PNRA). Data were processed with chemometric techniques. Results showed that elements typically considered as potential anthropogenic pollutants (e.g. As, Pb, Zn, Cu and Ni) present a strong correlation with the lithogenic elements (e.g. Al, Si, Fe) in all matrices, suggesting that their origin is connected to natural phenomena. Metal concentrations in vegetation samples are in the same range as previously published data. The obtained results were compared with older literature data (since the early '90s) from the same lacustrine systems, in order to present a historical overview of element concentrations. This approach furnishes important information on surface water evolution as a function of time. A considerable variability was observed in metal concentrations but no clear trend was identified. This suggests that their concentration evolution is hardly correlated to specific natural or anthropic phenomena. No evidence of an increase of concentrations over time was apparent. Our results represent new important data about metal concentrations in lacustrine systems in Antarctica, furnishing ranges of values that can be considered as a reference. These data, therefore, could be used to detect or monitor future local and/or global anthropogenic contaminations., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The applicability to the determination of mercury in tuna of square wave anodic stripping voltammetry (SW-ASV) conducted at both solid gold electrode (SGE) and a gold nanoparticle-modified glassy carbon electrode (AuNPs-GCE) was demonstrated. Mercury content in two certified materials and in ten samples of canned tuna was measured. The performances of the electrodes were compared with one another as well as with two spectroscopic techniques, namely cold vapour atomic absorption spectroscopy (CV-AAS) and a direct mercury analyser (DMA). The results found pointed out that both SW-ASV approaches were suitable and easy-to-use method to monitor mercury concentration in tunas, since they allowed accurate quantification at concentration values lower than the maximum admissible level in this matrix ([Hg]=1mg/kg wet weight,ww ). In particular, mercury detection at the AuNPs-GCE showed a LOQ in fish-matrix of 0.1μg/l, corresponding to 0.06mg/kg ww , with performance comparable to that of DMA., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A work on the characterization of the air quality in the city of Turin was carried out in different sampling periods, reflecting early autumn and winter conditions, including a snow episode during the early 2012 European cold wave. The concentrations of 13 elements in eight size fractions of the aerosol were determined using inductively coupled plasma-mass spectrometry. The collection was carried out with a Andersen MkII cascade impactor. The size distribution of elements allowed the identification of three main behavioural types: (a) elements associated with coarse particles (Cd, Cr, Cu, Fe, Mn, Mo and Sn); (b) elements found within fine particles (As, Co, Pb and V) and (c) elements spread throughout the entire size range (Ni and Zn). Principal Component Analysis allowed to examine the relationships between the inorganic elements and to infer about their origin. Chemometric investigation and assessment of similarity in the distribution led to similar conclusions on the sources. The concentration of gaseous trace pollutants (O3, NOx and VOCs) was determined. The concentrations of these pollutants are scarcely correlated with the metal contents of all the size classes of the PM. The differences found in the O3, NO2 and VOCs levels of the two winter campaigns due to the high photochemical reactivity in the period after the snow episode, do not reflect in differences in the metals distribution in the PM. Since PM metals, NOx and VOC have common sources, this behaviour is due to relevant differences in the transformation and deposition processes., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The results on elemental composition of aerosol (PM10) sampled during 2011 in Piedmont region (Italy) are interpreted using meteorological data, Enrichment Factors (EF), chemometric processing by Principal Component Analysis (PCA), Factor Analysis (FA) and Hierarchical Cluster Analysis (HCA). Daily concentrations of about 30 elements were measured using HR-ICP-MS in five monitoring sites. A clear seasonal pattern, with higher concentrations in autumn and winter, was observed, particularly in the urban sites. Levels of As, Cd, Ni and Pb in most of the samples were within the limits imposed by the European legislation. Spatial differences in PM10 and metal concentrations were significant, with rural and urban sites showing different metal patterns, indicating different sources. K and Ca were used, respectively, as marker of biomass burning and industrial marker (cement plant); EFs showed that Ca was enriched just in one area and K was enriched only in the winter period considered and in some stations. Data analysis through PCA, FA and HCA allowed us to identify correlations among the investigated elements and similarities between sampling sites in order to individuate specific emission sources, such as non-exhaust vehicle emission., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Glyceric Macerates (GMs) and Mother Tinctures (MTs) are liquid preparations obtained from plant buds (for GMs) and flowers, leaves or roots (for MT) by extraction with a mixture of solvents. Their quality depends on the quality of the plant materials and on the preparation procedures. In this work we determined the concentrations of major, minor and trace elements in buds, flowers and other plant components and in the GMs and MTs obtained from them by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) after microwave mineralization. To the best of our knowledge, this procedure has been applied for the first time here to the analysis of buds. We have taken into account spectral interferences and other causes of errors. Analogies and differences with regard to the method reported by European Pharmacopoeia for heavy metal determination in herbal drugs have been highlighted. The experimental results have been interpreted with chemometric techniques. No significant contamination was detected during the manufacturing step. Element concentrations in GMs and MTs, taking into account their daily dosages, are lower than acceptable intake levels., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Element mobility and availability in natural solid matrices can be studied with single and sequential extraction procedures; such procedures provide reliable and useful information only if the experiments are correctly planned and executed and the results are properly interpreted. Chemometrics can be a valuable tool for these aims, especially taking into account the large amounts of data generated with extraction essays and the complexity of the processes under investigation. This review deals with the application of chemometrics in research studies involving single and sequential extractions on soils or sediments, for several purposes: the development and optimization of the extraction conditions, the calculation of element fractionation, the visual illustration of the experimental results, the acquisition of different areas of information, including relationships among variables, similarities and differences among samples, causes of the observed behaviour (e.g. source identification), risk assessment, models and predictions of future events. In Part I of the review, following an overview on extraction procedures, the applications of univariate and bivariate chemometric methods are reported; then the principles of multivariate techniques for pattern recognition based on variable reduction, their applications and the main findings obtained are addressed., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Single and sequential extraction procedures are used for studying element mobility and availability in solid matrices, like soils, sediments, sludge, and airborne particulate matter. In the first part of this review we reported an overview on these procedures and described the applications of chemometric uni- and bivariate techniques and of multivariate pattern recognition techniques based on variable reduction to the experimental results obtained. The second part of the review deals with the use of chemometrics not only for the visualization and interpretation of data, but also for the investigation of the effects of experimental conditions on the response, the optimization of their values and the calculation of element fractionation. We will describe the principles of the multivariate chemometric techniques considered, the aims for which they were applied and the key findings obtained. The following topics will be critically addressed: pattern recognition by cluster analysis (CA), linear discriminant analysis (LDA) and other less common techniques; modelling by multiple linear regression (MLR); investigation of spatial distribution of variables by geostatistics; calculation of fractionation patterns by a mixture resolution method (Chemometric Identification of Substrates and Element Distributions, CISED); optimization and characterization of extraction procedures by experimental design; other multivariate techniques less commonly applied., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The aim of this work is to evaluate the efficiency of the determination of As(III) by anodic stripping voltammetry (ASV) using a lateral gold electrode and to study the modifications of the electrode surface during use. Potential waveforms (differential pulse and square wave), potential scan parameters, deposition time, deposition potential and surface cleaning procedure were examined for they effect on arsenic peak intensity and shape. The best responses were obtained with differential pulse potential wave form and diluted 0.25 M HCl as supporting electrolyte. The repeatability, linearity, accuracy and detection limit of the procedure and the interferences of cations and anions in solution were evaluated. The applicability of the procedure for As(III) determination in drinking waters was tested. Cyclic voltammetry (CV) was used to study the electrochemical behaviour of As(III) and for the daily monitoring of electrode surface. Also scanning electron microscopy (SEM) analysis was used to control the electron surface. Finally we evaluated the possibility to apply the equations valid for flow systems also to a stirred system, in order to calculate the number of electrons transferred per molecule during the stripping step., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The possibility of using mosses as environmental indicators of metal pollution has been investigated. Mosses of the species Bryum argenteum were collected from different parts of Piedmont (Italy), ranging from highly polluted areas to nearly uncontaminated mountain areas. Periodical samplings were planned in every site on a monthly base, in order to check variations of metal uptake throughout one year; correlations with pluviometric and thermal patterns were investigated for all sampling stations. On every moss sample 20 elements, ranging from major (K, P, Al, Ca, Fe and Mg) to minor (Mn, Na, Ti and Zn) and trace (As, Ba, Cd, Co, Cr, Cu, Li, Ni, Pb and Sr), were quantitatively determined by inductively coupled plasma-atomic emission spectrometry or graphite furnace-atomic absorption spectrometry, depending on the needed sensitivity. Statistical analyses, carried out with principal component analysis and cluster analysis methods, revealed that a good correlation exists between metal content in mosses and pollution degree in the areas sampled.