Effect of forced aeration on the biogeochemical cycle of nutrients and metal(loid)s as a remedy for hypoxia in a permanently stratified estuary (Gulf of Trieste, northern Adriatic Sea).

The Timavo River estuary (northern Adriatic Sea) is characterised by strong thermohaline stratification that keeps the deep waters hypoxic. The consequence is an harmful algal bloom at the surface in summer that can be mitigated with a forced aeration system installed at the bottom to improve water oxygenation. The nutrient and metal(loid) cycle was investigated, before and during reoxygenation, using an in situ benthic chamber coupled with sampling and analyses of the water column, sediments and porewater. Dissolved oxygen (DO) decreased along the water column and quickly within the benthic chamber when aeration was not in operation, resulting in hypoxia (2.29 mg L-1) at the bottom and consequent increase in nutrient and metal(loid) concentrations. In contrast, DO levels increased during the activation of the forced aeration system, which proved effective in mitigating oxygen depletion and the efflux of metal(loid)s and nutrients into the overlying water.

Exposure to gallium arsenide nanoparticles in a research facility: a case study using molecular beam epitaxy.

We evaluated GaAs nanoparticle-concentrations in the air and on skin and surfaces in a research facility that produces thin films, and to monitored As in the urine of exposed worker. The survey was over a working week using a multi-level approach. Airborne personal monitoring was implemented using a miniature diffusion size classifier (DiSCMini) and IOM sampler. Environmental monitoring was conducted using the SKC Sioutas Cascade Impactor to evaluate dimensions and nature of particles collected. Surfaces contamination were assessed analyzing As and Ga in ghost wipes. Skin contamination was monitored using tape strips. As and Ga were analyzed in urines collected every day at the beginning and end of the shift. The greatest airborne exposure occurred during the cutting operations of the GaAs Sample (88883 np/cm3). The highest levels of contamination were found inside the hood (As max = 1418 ng/cm2) and on the laboratory floor (As max = 251 ng/cm2). The average concentration on the worker's skin at the end of the work shift (3.36 ng/cm2) was more than 14 times higher than before the start of the shift. In weekly urinary biomonitoring an average As concentration of 19.5 µg/L, which was above the Società Italiana Valori di Riferimento (SIVR) reference limit for the non-occupational population (2.0 - 15 µg/L), but below the ACGIH limit (30 µg/L). Overall, airborne monitoring, surface sampling, skin sampling, and biomonitoring of worker confirmed the exposure to As of workers. Systematic cleaning operations, hood implementation and correct PPE management are needed to improve worker protection.

Probing the effectiveness of barrier creams against human skin penetration of nickel powder.

OBJECTIVE: Barrier creams (BCs) are marketed as locally applied medical devices or cosmetic products to protect the skin from exposure to chemicals and irritants. Generally, the mechanism of action of such products is mainly due to the formation of a superficial thin film between the skin and the irritant or sensitizer, thus reducing or totally blocking the cutaneous penetration of such agents. Specifically, studies focusing on the effectiveness of commercial protective creams to prevent nickel cutaneous penetration are extremely scarce. The aim of the current work, therefore, is to evaluate the protective role of a commercially available barrier cream for nickel and compare the results with a simple moisturizing, following exposure to Ni powder. METHODS: Marketed BCs were evaluated and tested. Human skin absorption of Ni was studied in vitro using static Franz diffusion cells. RESULTS: Our results demonstrate that the application of both formulations caused a reduction of Ni inside the skin (8.00 ± 3.35 µg cm-2 for the barrier cream and 22.6 ± 12.6 µg cm-2 for the general moisturizing product), with the specialized barrier cream being statistically (p = 0.015) more efficient on forming a protective barrier, thus evidencing the importance of some ingredients in such formulations on the nickel dermal accumulation. CONCLUSIONS: The composition of the formulations based on film-forming or chelating agents may play an imperative role in reducing the cutaneous penetration of Ni.

OBJECTIF: Les crèmes de barrière (CB) sont commercialisées en tant que dispositifs médicaux ou produits cosmétiques appliqués localement pour protéger la peau contre l'exposition aux produits chimiques et irritants. En général, le mécanisme d'action de ces produits est principalement dû à la formation d'un film mince superficiel entre la peau et l'irritant ou le sensibilisant, réduisant ainsi ou bloquant totalement la pénétration cutanée de ces agents. Plus précisément, les études portant sur l'efficacité des crèmes protectrices commercialisées pour prévenir la pénétration cutanée du nickel sont extrêmement rares. L'objectif du projet en cours est donc d'évaluer le rôle protecteur d'une crème barrière disponible dans le commerce contre le nickel et de comparer les résultats à un simple hydratant après une exposition à la poudre de Ni. MÉTHODES: Des CB commercialisées ont été évaluées et testées. L'absorption cutanée du Ni dans la peau humaine a été étudiée in vitro à l'aide de cellules de diffusion statiques de Franz. RÉSULTATS: Nos résultats démontrent que l'application des deux formulations a entraîné une réduction du taux de Ni à l'intérieur de la peau (8,00 ± 3,35 µg·cm-2 pour la crème barrière et 22,6 ± 12,6 µg·cm-2 pour le produit hydratant ordinaire), la crème barrière spécialisée étant statistiquement (p = 0,015) plus efficace pour former une barrière protectrice, démontrant ainsi l'importance de certains ingrédients dans ces formulations sur l'accumulation dermique du nickel. CONCLUSIONS: La composition des formulations basées sur des agents de formation de film ou de chélation peut jouer un rôle nécessaire pour réduire la pénétration cutanée du Ni.

Reduced Tiara-like Palladium Complex for Suzuki Cross-Coupling Reactions.

The design of highly active and structurally well-defined catalysts has become a crucial issue for heterogeneous catalysed reactions while reducing the amount of catalyst employed. Beside conventional synthetic routes, the employment of polynuclear transition metal complexes as catalysts or catalyst precursors has progressively intercepted a growing interest. These well-defined species promise to deliver catalytic systems where a strict control on the nuclearity allows to improve the catalytic performance while reducing the active phase loading. This study describes the development of a highly active and reusable palladium-based catalyst on alumina (Pd8 /Al2 O3 ) for Suzuki cross-coupling reactions. An octanuclear tiara-like palladium complex was selected as active phase precursor to give isolated Pd-clusters of ca. 1 nm in size on Al2 O3 . The catalyst was thoroughly characterised by several complementary techniques to assess its structural and chemical nature. The high specific activity of the catalyst has allowed to carry out the cross-coupling reaction in 30 min using only 0.12 mol % of Pd loading under very mild and green reaction conditions. Screening of various substrates and selectivity tests, combined with recycling and benchmarking experiments, have been used to highlight the great potentialities of this new Pd8 /Al2 O3 catalyst.

Evaluating the role of protective creams on the cutaneous penetration of Ni nanoparticles.

There is an increase of application of Nickel in the form of nanoparticles (NiNPs) in several fields including modern metallurgy, bioengineering, and medicine. Such growth of the areas of application is actually accompanied with an increase of exposure to Nickel, thus an intensification of the negative effects, the most frequent being the allergic contact dermatitis. Indeed, due to their smaller size, and therefore their higher surface area, NiNPs can release more Ni ions compared to bulk material, that can penetrate and permeate through the skin. To reduce the Ni cutaneous penetration, barrier creams (BC) are applied on the skin surface. There is little information, however, on the efficiency of such commercial protective creams on decreasing Ni cutaneous penetration. For this reason, the objective of the current study was to investigate the protective role of one commercially available formulation for Ni (Nik-L-Block™ containing a chelating agent) and one moisturizing cream (Ceramol 311 basic cream without chelating agent), following exposure to NiNPs, using in vitro Franz cells, as well as the cytotoxicity of NiNPs in primary human dermal fibroblasts was studied. Our results demonstrated that although both tested formulations can decrease Ni accumulation in the skin (4.13 ± 1.74 µg/cm2 for Nik-L-Block™ and 7.14 ± 1.46 µg/cm2 for Ceramol 311 basic cream); there are significant differences between the two creams (p = 0.004). Based on the experimental evidence, we therefore conclude that the composition of such formulations has an imperative role for dermal uptake of Ni. Finally, NiNPs showed no cytotoxic effect on cultured human dermal fibroblasts after 24 and 72 h.

From Collection or Archaeological Finds? A Non-Destructive Analytical Approach to Distinguish between Two Sets of Bronze Coins of the Roman Empire.

This study stems from the need for numismatics to establish whether there may be relationships between a group of 103 bronze coins from the Roman era found in archaeological excavations on the Cesén Mountain (Treviso, Italy) and a group of 117 coins kept at the Museum of Natural History and Archaeology in Montebelluna (Treviso, Italy). The chemists were delivered six coins with neither pre-agreements nor further information on the origin of the coins. Therefore, the request was to hypothetically assign the coins to the two groups on the basis of similarities and differences in their surface composition. Only non-destructive analytical techniques were allowed to be used to characterize the surface of the six coins taken blindly from the two sets. The elemental analysis of each coins' surface was carried out by µ-XRF. To better observe the morphology of the coins' surfaces, SEM-EDS was used. Compounds covering the coins coming from both corrosion processes (patinas) and the deposition of soil encrustations were also analyzed by means of the FTIR-ATR technique. The molecular analysis confirmed the presence of silico-aluminate minerals on some coins, unequivocally indicating a provenance from clayey soil. Some soil samples, collected from the archaeological site of interest, were analyzed to verify whether the encrusted layer on coins could contain chemical components compatible with them. This result, together with the chemical and morphological investigations, led us to subdivide the six target coins into two groups. The first group is made up of two coins coming from the set of coins from excavation (found in the subsoil) and from the set from open air finds (coins found in the top layer of the soil). The second group is made up of four coins that are devoid of characteristics corresponding to exposure to soil contact for long periods of time and, moreover, their surface compounds could suggest a different provenance. The analytical results of this study made it possible to correctly assign all six coins to the two groups of finds and support numismatics, which was unconvinced in considering all coins to come from the same finding site only on the basis of archaeological documentations.

A Multi-Analytical Approach on Silver-Copper Coins of the Roman Empire to Elucidate the Economy of the 3rd Century A.D.

In this study, 160 silver-copper alloy denarii and antoniniani from the 3rd century A.D. were studied to obtain their overall chemical composition. The approach used for their characterisation is based on a combination of physical, chemical, and chemometric techniques. The aim is to identify and quantify major and trace elements in Roman silver-copper coins in order to assess changes in composition and to confirm the devaluation of the currency. After a first cataloguing step, µ-EDXRF and SEM-EDX techniques were performed to identify the elements on the coins' surface. A micro-destructive sampling method was employed on a representative sample of the coins to quantify the elements present in the bulk. The powder obtained from drilling 12 coins (keeping the two categories of coins separate) was dissolved in an acidic medium; heated and sonicated to facilitate dissolution; and then analysed by ICP-AES and ICP-MS. The two currencies had different average alloy percentages; in particular, the % difference of Ag was about 8%. The other elements were found in concentrations <1 wt%. Of these, the element highest in concentration were Pb and Sn, which is in agreement with the literature. The multivariate analysis performed on the data acquired revealed two groups of coins, corresponding to the two currencies.

Transdermal permeation of inorganic cerium salts in intact human skin.

The stratum corneum protects the body against external agents, such as metals, chemicals, and toxics. Although it is considered poorly permeable to them, comprising the major barrier to the permeation of such substances, it may become a relevant gate of entry for such molecules. Cerium (Ce) is a lanthanide that is widely used in catalytic, energy, biological and medicinal applications, owing to its intrinsic structural and unique redox properties. Cerium salts used to produce cerium oxide (CeO2) nanostructures can potentially come into contact with the skin and be absorbed following dermal exposure. The objective of this study was to investigate the percutaneous absorption of three inorganic Ce salts: cerium (III) chloride (CeCl3); cerium (III) nitrate (Ce(NO3)3) and ammonium cerium (IV) nitrate (Ce(NH4)2(NO3)6), which are commonly adopted for the synthesis of CeO2 using in vitro - ex vivo technique in Franz diffusion cells. The present work shows that Ce salts cannot permeate intact human skin, but they can penetrate significantly in the epidermis (up to 0.29 µg/cm2) and, to a lesser extent in dermis (up to 0.11 µg/cm2). Further studies are required to evaluate the potential effects of long-term exposure to Ce.

Assessment of dermal absorption of beryllium and copper contained in temple tips of eyeglasses.

Dermal exposure to hazardous substances such as chemicals, toxics, metallic items and other contaminants may present substantial danger for health. Beryllium (Be) is a hazardous metal, especially when inhaled and/or in direct contact with the skin, associated with chronic beryllium disease (CBD) and Be sensitization (BeS). The objective of this study was to investigate the percutaneous penetration of beryllium and copper contained in metallic items as eyeglass temple tips (specifically BrushCAST® Copper Beryllium Casting Alloys containing Be 0.35 < 2.85%; Cu 95.3-98.7%), using Franz diffusion cells. This work demonstrated that the total skin absorption of Cu was higher (8.86%) compared to Be (4.89%), which was expected based on the high percentage of Cu contained in the eyeglass temple tips. However, Be accumulated significantly in the epidermis and dermis (up to 0.461 µg/cm2) and, to a lesser extent, in the stratum corneum (up to 0.130 µg/cm2) with a flux of permeation of 3.52 ± 4.5 µg/cm2/hour and lag time of 2.3 ± 1.3 h, after cutaneous exposure of temple tip into 1.0 mL artificial sweat for 24 h. Our study highlights the importance of avoiding the use of Be alloys in items following long-term skin contact.

Percutaneous metals absorption following exposure to road dust powder.

The skin constitutes a protective barrier to external physical and chemical aggressions. Although it is constantly exposed to various xenobiotics, it is generally considered poorly permeable to them, as for example metal ions, becoming unfortunately an entry route of such substances. Metals may penetrate inside the skin inducing more or less local effects such as skin sensitization and potential metals diffusion into the bloodstream. The objective of the study was to investigate the percutaneous penetration of metals in vitro - ex vivo in Franz cell with intact as well damaged skin applying a road dust powder. Moreover, porcine and human skins were compared. This study demonstrated that, after the application of a road dust powder on the skin, metals can penetrate and permeate this cutaneous membrane. From this experimental analysis, in intact skin lead (Pb) achieved the highest skin absorption in both human and porcine skin, while skin absorption profile of cobalt (Co) was the lowest in human skin than the one in porcine model. The concentrations of Ni present in receiving solution were higher compared to other metals in all experiments performed. The present work, definitely shows that metals permeation through damaged skin is accelerated than intact skin, as a result of the weaker cutaneous barrier function. According to published data, pig skin appeared as a suitable model for human skin. Our results confirmed that skin absorption of metals can be relevant in environmental exposures.

Secondary Formation of Aromatic Nitroderivatives of Environmental Concern: Photonitration Processes Triggered by the Photolysis of Nitrate and Nitrite Ions in Aqueous Solution.

Aromatic nitroderivatives are compounds of considerable environmental concern, because some of them are phytotoxic (especially the nitrophenols, and particularly 2,4-dinitrophenol), others are mutagenic and potentially carcinogenic (e.g., the nitroderivatives of polycyclic aromatic hydrocarbons, such as 1-nitropyrene), and all of them absorb sunlight as components of the brown carbon. The latter has the potential to affect the climatic feedback of atmospheric aerosols. Most nitroderivatives are secondarily formed in the environment and, among their possible formation processes, photonitration upon irradiation of nitrate or nitrite is an important pathway that has periodically gained considerable attention. However, photonitration triggered by nitrate and nitrite is a very complex process, because the two ionic species under irradiation produce a wide range of nitrating agents (such as •NO2, HNO2, HOONO, and H2OONO+), which are affected by pH and the presence of organic compounds and, in turn, deeply affect the nitration of aromatic precursors. Moreover, aromatic substrates can highly differ in their reactivity towards the various photogenerated species, thereby providing different behaviours towards photonitration. Despite the high complexity, it is possible to rationalise the different photonitration pathways in a coherent framework. In this context, this review paper has the goal of providing the reader with a guide on what to expect from the photonitration process under different conditions, how to study it, and how to determine which pathway(s) are prevailing in the formation of the observed nitroderivatives.