Microplastics pollution in freshwater fishes in the South of Italy: Characterization, distribution, and correlation with environmental pollutants.

In this study, we investigated the presence, abundance, and chemical nature of microplastics (MPs) in the freshwater fish gastrointestinal tract in the South of Italy, and evaluated the possible correlation between MPs and environmental pollutants. Fifty specimens belonging to five species (Scardinius erythrophthalmus, Barbus barbus, Rutilus rubilio, Leuciscus cephalus, Salmo trutta), from twenty sites were collected. MPs chemical feature was identified by means of Attenuated Total Reflection-Fourier Transform Infrared (ATR-FTIR) and Raman microscopy. MPs were represented by 34.86 % fragments, film, and foam (all together MPs) and 65.14 % by fibers (MFs). The mean number of MPs/MFs per fish ranged from 6.25 ± 4.35 in R. rubilio and 2.26 ± 1.94 in B. barbus. The highest number of MPs/MFs per g of GIT was found in R. rubilio (9.07 ± 9.66), and the lowest in S. erythrophthalmus (0.75 ± 0.53). The highest number of MPs/MFs per fish species was found in L. cephalus (16), and the lowest in S. erythrophthalmus (4). Black predominated in every type of plastic debris identified, followed by blue and white, respectively for MFs and MPs. Polyethylene (PE), polyethylene terephthalate (PET), polystyrene (PS), and polypropylene (PP), were the main plastic polymers found. At fish sampling sites, comparing concentrations in soils of potentially toxic elements and persistent organic pollutants with the number of MPs/MFs in fish, a significant correlation was noted with polychlorinated biphenyls (PCBs) and, in particular, with PCB 105, PCB 118, PCB 156, PCB 157, and PCB 167. A strong correlation was also observed with all types of polycyclic aromatic hydrocarbon (PAHs) particularly with benzo(ghi)perylene, dibenz(a,h)anthracene, benzo(b)fluoranthene, benz(a)anthracene, benzo(a)pyrene, and pyrene. The results of this study would be useful to draft management and action plans, promote intervention plans aiming at removing threats to species and habitats, and address ways of renaturalization.

Characterizing wine terroir using strontium isotope ratios: a review.

This paper presents a detailed review of the use of 87Sr/86Sr isotope systematics for wine provenance studies. The method is based on the principle that the Sr isotope ratio in wine reflects that of the labile fraction of the vineyard soil from which the wine is produced. The review encompasses 87Sr/86Sr data from wine samples published between 1993 and 2021 from terroirs in 22 different countries. The analytical procedures and techniques adopted by the different authors and the range of isotope ratios obtained in the different studies are discussed and evaluated. This study provides a bibliometric analysis of the 87Sr/86Sr isotope approach for wine authentication at different scales. Although limitations are evident when implemented at large (global) scales, we demonstrate that the 87Sr/86Sr isotope tracing technique remains a powerful and reliable tool for determining the geographical origin of wine when combined with detailed knowledge of the geological and soil characteristics of the substrata. For example, this combination of data allows the wines grown in the volcanic soils of Central and Southern Italy to be unambiguously fingerprinted. We present a detailed protocol for the application of the Sr isotope technique to wine authentication.

Particulate matter and polycyclic aromatic hydrocarbon uptake in relation to leaf surface functional traits in Mediterranean evergreens: Potentials for air phytoremediation.

We explored relationships between particulate matter (PM) and polycyclic aromatic hydrocarbon (PAHs) leaf concentrations, uptake rates and leaf surface functional traits in four Mediterranean evergreen trees (Chamaerops humilis, Citrus × aurantium, Magnolia grandiflora, and Quercus ilex) during a dry month. Pollutant leaf concentration at different dates and uptake rate were correlated. We quantified PM by gravimetric analysis, PAHs were extracted from intact and dewaxed leaves and analyzed by GC-MS, and cuticle thickness, number and surface of stomata (Ns and SS) and trichomes (Nt and St) were determined by optical microscopy. Infrared spectroscopy was used to investigate the leaves surfaces composition and assess esterification index (E). Studied species were characterized by unique combinations of functional traits and pollutant uptake capacities. PM10 uptake scaled positively with SS, St and upper cuticle thickness (Tc,u) across species. PM2.5 uptake scaled positively with Tc,u, and thicker cuticles were also associated with greater shares of uptake of hydrophobic PM fractions. Uptakes of different fractions of PAH were generally weakly related to different leaf functional traits, except for some correlations with E and SS. We conclude that both plant surface morphological and chemical leaf traits influence PM and PAH retention, unveiling their potential role in air phytoremediation.

Archaeometric data from the Via dei Sepolcri ceramic workshop in Pompeii (Southern Italy).

The present article provides chemical, paleontological and mineralogical data obtained during an archaeometric characterization of 40 samples (33 pottery sherds, 5 clay samples, 1 sand sample and 1 red earth pigment) collected in the Via dei Sepolcri ceramic workshop in Pompeii, Italy. The workshop was still active during the 79 CE eruption of Mt. Vesuvius and the archaeometric data obtained in our investigation reveal distinct differences between pottery and geological raw materials belonging to an early 'Phase 1' production (from the beginning of the 1st century CE to the 62 CE earthquake) and a subsequent 'Phase 2' production (from the 62 CE earthquake to the 79 CE eruption). These data inform the discussions and interpretations presented in the article entitled "A pottery workshop in Pompeii unveils new insights on the Roman ceramics crafting tradition and raw materials trade", edited by Grifa et al. [1].

The Tomb of the Diver and the frescoed tombs in Paestum (southern Italy): New insights from a comparative archaeometric study.

The Tomb of the Diver has been subject for many decades of fierce debate among archaeologists and classicists. Since its discovery in 1968, some scholars have considered it a unique example of the lost tradition of Greek painting, others have emphasized Etruscan or Italic parallels. More recently, a possible local production has been suggested. With the aim of trying to solve the archaeological question, an archaeometric comparison among this well-known artwork and several frescoed tombs coming from Hellenistic and Lucan necropolis was carried out. The multi-analytical study was focused on the identification of peculiar features of executive techniques and raw materials since the first period of the archaeological site. The analytical investigation has been preliminary based on a non-destructive approach, performed in-situ by portable equipment including imaging diagnostics and compositional spectroscopic techniques for identifying pigments and the conservation state of original painted surface; subsequently, a further deepening by using destructive techniques was performed in-lab for the mortar-based supports characterization. Archaeometric study suggested that technological choices slightly changed in a time span of about two centuries, highlighting important markers that allow clustering the contemporary artistic productions. Moreover, a comparison with mortars from temples decorations was provided to better understand the whole artistic context. The archaeometric data showed that the Tomb of the Diver could be traced back to a local artisanal tradition and therefore is neither Etruscan nor Greek, but the first and foremost an expression of the local elite culture of Paestum.

Surface modified natural zeolites (SMNZs) as nanocomposite versatile materials for health and environment.

The present research deals with the evaluation of a clinoptilolite-rich rock, occurring in the Nizný Hrabovec deposit (Slovakia), for high-value technological applications based on sorption and in vitro release of nonsteroidal anti-inflammatory drugs (i.e., ibuprofen sodium salt). This georesource was surface modified (SMNZ) using four cationic surfactants. Results demonstrate that ibuprofen sorption is very fast and SMZNs can sorb up to ˜26 mg/g of drug as a function of the type of counterion and morphology of surfactant, as well as the hydrophobicity and molecular structure of the drug. Maximum sorption capacities observed for all SMNZs are fully comparable to other adsorbent carriers usually used for removal of contaminants in wastewaters. Sorption of ibuprofen is controlled by a dual mechanism: external anionic exchange and partition into the hydrophobic portion of the patchy bilayer. A prompt drug release in simulated intestinal fluid (SIF) was also observed, making this natural material also suitable to provide rapid soothing effects in potential pharmacological applications. Comparing the results of this study with other recent investigations, a good technological performance of clinoptilolite-rich rock can be inferred despite the relatively low zeolite content (˜56 wt.%).

The characterization of natural gemstones using non-invasive FT-IR spectroscopy: New data on tourmalines.

Fourteen samples of tourmaline from the Real Museo Mineralogico of Federico II University (Naples) have been characterized through multi-methodological investigations (EMPA-WDS, SEM-EDS, LA-ICP-MS, and FT-IR spectroscopy). The samples show different size, morphology and color, and are often associated with other minerals. Data on major and minor elements allowed to identify and classify tourmalines as follows: elbaites, tsilaisite, schorl, dravites, uvites and rossmanite. Non-invasive, non-destructive FT-IR and in-situ analyses were carried out on the same samples to validate this chemically-based identification and classification. The results of this research show that a complete characterization of this mineral species, usually time-consuming and expensive, can be successfully achieved through non-destructive FT-IR technique, thus representing a reliable tool for a fast classification extremely useful to plan further analytical strategies, as well as to support gemological appraisals.

Adsorption of the mycotoxin zearalenone by clinoptilolite and phillipsite zeolites treated with cetylpyridinium surfactant.

In this study, organozeolites were prepared by treatment of the natural zeolites (clinoptilolite and phillipsite) with cetylpyridinium chloride (CP) equivalent to 50 and 100% of their external cation exchange capacities (ECEC). Organoclinoptilolites (ZCPs) and organophillipsites (PCPs) were characterized by FTIR spectroscopy, thermal analysis, determination of the point of zero charge and zeta potential. Adsorption of zearalenone (ZEN) by ZCPs and PCPs at pH 3 and 7 was investigated. Results showed that adsorption of ZEN increases with increasing amounts of CP at the zeolitic surfaces for both ZCPs and PCPs but the adsorption mechanism was different. Adsorption of ZEN by ZCPs followed a linear type of isotherm at pH 3 and 7 while ZEN adsorption by PCPs showed non linear (Langmuir and Freundlich) type of isotherm at both pH values. Different interactions between the ZEN molecule (or ion) and ZCPs and PCPs occurred: partition (linear isotherms) and adsorption in addition to partition (non linear isotherms), respectively. For the highest level of organic phase at the zeolitic surfaces, the maximum adsorbed amount of ZEN was 5.73mg/g for organoclinoptilolite and 6.86mg/g for organophillipsite at pH 3. Slightly higher adsorption: 6.98mg/g for organoclinoptilolite and 7.54mg/g for organophillipsite was achieved at pH 7. The results confirmed that CP ions at both zeolitic surfaces are responsible for ZEN adsorption and that organophillipsites are as effective in ZEN adsorption as organoclinoptilolites.

Surface modified natural zeolite as a carrier for sustained diclofenac release: A preliminary feasibility study.

In view of zeolite potentiality as a carrier for sustained drug release, a clinoptilolite-rich rock from California (CLI_CA) was superficially modified with cetylpyridinium chloride and loaded with diclofenac sodium (DS). The obtained surface modified natural zeolites (SMNZ) were characterized by confocal scanning laser microscopy (CLSM), powder X-ray diffraction (XRPD) and laser light scattering (LS). Their flowability properties, drug adsorption and in vitro release kinetics in simulated intestinal fluid (SIF) were also investigated. CLI_CA is a Na- and K-rich clinoptilolite with a cationic exchange ability that fits well with its zeolite content (clinoptilolite=80 wt%); the external cationic exchange capacity is independent of the cationic surfactant used. LS and CLSM analyses have shown a wide distribution of volume diameters of SMNZ particles that, along with their irregular shape, make them cohesive with scarce flow properties. CLSM observation has revealed the localization of different molecules in/on SMNZ by virtue of their chemical nature. In particular, cationic and polar probes prevalently localize in SMNZ bulk, whereas anionic probes preferentially arrange themselves on SMNZ surface and the loading of a nonpolar molecule in/on SMNZ is discouraged. The adsorption rate of DS onto SMNZ was shown by different kinetic models highlighting the fact that DS adsorption is a pseudo-second order reaction and that the diffusion through the boundary layer is the rate-controlling step of the process. DS release in an ionic medium, such as SIF, can be sustained for about 5h through a mechanism prevalently governed by anionic exchange with a rapid final phase.

Anion exchange selectivity of surfactant modified clinoptilolite-rich tuff for environmental remediation.

Lately, the functionalization of industrial minerals with high technological properties, such as natural zeolites, is shaping as a promising approach in environmental sphere. In fact, under the specific conditions, the surface functionalization via adsorption of cationic surfactants reverses the surface charge of the mineral, enabling zeolites to simultaneously interact either with organic contaminants or inorganic anions. This aspect allows zeolites to be used in the remediation of contaminated fluids. The present research shed new light on some still not fully understood aspects concerning exchange kinetics such as anion-exchange mechanisms and selectivity of surface modified minerals. For this purpose the mineralogical characterization and the surface properties evaluation (X Ray Powder Diffraction, chemical analysis, thermal analysis, ECEC and AEC) of a clinoptilolite-rich tuff were performed, and the anion exchange isotherms of the sample, modified with hexadecyltrimethylammonium chloride or bromide (HDTMA-Cl/-Br), were determined. Ion-exchange equilibrium data of uni-uni valent reaction were obtained by solutions containing Br(-), Cl(-), NO3(-) or ClO4(-). Liquid phase was analysed via high performance liquid chromatography. Thermodynamic quantities (Ka and ΔG(0)) were determined and compared with the Hofmeister series. The value of the ECEC, calculated in batch conditions, was about 137 mmol/kg, in good agreement with that evaluated in dynamic conditions, while the AEC data were different for the SMNZ-Br and -Cl samples, amounting to 137 and 106 mmol/kg, respectively, thus indicating a different compactness of the bilayer formed in the two cases. Moreover, the anion isotherm results and the mathematical evaluation of the thermodynamic parameters, demonstrated the good affinity of SMNZ-Br towards chloride, nitrate and perchlorate, and of SMNZ-Cl for nitrate and perchlorate, also endorsing the possibility of using the same thermodynamic approach developed to describe cation exchange selectivity in zeolites. Finally, it was also verified that the zeolite modified with HDTMA-Cl is able to better exploit its anion exchange capacity compared to the same zeolite modified with HDTMA-Br.