Phthalate esters (PAEs) concentration pattern reflects dietary habitats (δ13C) in blood of Mediterranean loggerhead turtles (Caretta caretta).

Phthalic acid esters (PAEs) are classified as endocrine disruptors, but it remains unclear if they can enter the marine food-web and result in severe health effects for organisms. Loggerhead turtles (Caretta caretta) can be chronically exposed to PAEs by ingesting plastic debris, but no information is available about PAEs levels in blood, and how these concentrations are related to diet during different life stages. This paper investigated, for the first time, six PAEs in blood of 18 wild-caught Mediterranean loggerhead turtles throughout solid-phase extraction coupled with gas chromatography-ion trap/mass spectrometry. Stable isotope analyses of carbon and nitrogen were also performed to assess the resource use pattern of loggerhead turtles. DEHP (12-63 ng mL-1) and DBP (6-57 ng mL-1) were the most frequently represented PAEs, followed by DiBP, DMP, DEP and DOP. The total PAEs concentration was highest in three turtles (124-260 ng mL-1) whereas three other turtles had concentrations below the detection limit. PAEs were clustered in three groups according to concentration in all samples: DEHP in the first group, DBP, DEP, and DiBP in the second group, and DOP and DMP in the third group. The total phthalates concentration did not differ between large-sized (96.3 ± 86.0 ng mL-1) and small-sized (67.1 ± 34.2 ng mL-1) turtles (p < 0.001). However, DMP and DEP were found only in large-sized turtles and DiBP and DBP had higher concentrations in large-sized turtles. On the other hand, DEHP and DOP were found in both small- and large-sized turtles with similar concentrations, i.e. ~ 21.0/32.0 ng mL-1 and ~ 7.1/9.9 ng mL-1, respectively. Winsored robust models indicated that δ13C is a good predictor for DBP and DiBP concentrations (significant Akaike Information criterion weight, AICwt). Our results indicate that blood is a good matrix to evaluate acute exposure to PAEs in marine turtles. Moreover, this approach is here suggested as a useful tool to explain the internal dose of PAEs in term of dietary habits (δ13C), suggesting that all marine species at high trophic levels may be particularly exposed to PAEs, despite their different dietary habitats and levels of exposure.

Visual and Physical Degradation of the Black and White Mosaic of a Roman Domus under Palazzo Valentini in Rome: A Preliminary Study.

Palazzo Valentini, the institutional head office of Città Metropolitana di Roma Capitale, stands in in a crucial position in the Roman archaeological and urban contexts, exactly between the Fora valley, Quirinal Hill slopes, and Campus Martius. It stands on a second-century A.D. complex to which belong, between other archeological remains, two richly decorated aristocratic domus. One of these buildings, the domus A, presents an outward porticoed room with a fourth-century AD central impluvium (open air part of the atrium designed to carry away rainwater) with a black/white tiled mosaic pavement, the preservation status of which is compromised by an incoherent degradation product that has caused gradual detachment of the mosaic tiles. To identify the product and determine the causes of degradation, samples of the product were taken and subjected to SEM-EDS, XRF, NMR, FT-IR and GC-MS analyses. The findings reported in this study can help restorers, archaeologists and conservation scientists in order to improve knowledge about the Roman mosaic, its construction phases, conservation problems and proper solutions.

Ultrafine particle emission from floor cleaning products.

The new particle formation due to the use of cleaning products containing volatile organic compounds (VOCs) in indoor environments is well documented in the scientific literature. Indeed, the physical-chemical process occurring in particle nucleation due to VOC-ozone reactions was deepened as well as the effect of the main influencing parameters (ie, temperature, ozone). Nonetheless, proper quantification of the emission under actual meteo-climatic conditions and ozone concentrations is not available. To this end, in the present paper the emission factors of newly generated ultrafine particles due to the use of different floor cleaning products under actual temperature and relative humidity conditions and ozone concentrations typical of the summer periods were evaluated. Tests in a chamber and in an actual indoor environment were performed measuring continuously particle number concentrations and size distributions during cleaning activities. The tests revealed that a significant particle emission in the nucleation mode was present for half of the products under investigation with emission factors up to 1.1 × 1011 part./m2 (8.8 × 1010 part./mLproduct ), then leading to an overall particle emission comparable to other well-known indoor sources when cleaning wide surfaces.

Simultaneous determination of organophosphorus pesticides and phthalates in baby food samples by ultrasound-vortex-assisted liquid-liquid microextraction and GC-IT/MS.

Baby foods are either a soft, liquid paste or an easily chewed food since babies lack developed muscles and teeth to chew effectively. Babies typically move to consuming baby food once nursing or formula is not sufficient for the child's appetite. Some commercial baby foods have been criticized for their contents. This article focuses on the simultaneous determination of organophosphorus pesticides and phthalates by means of a method based on ultrasound-vortex-assisted liquid-liquid microextraction coupled with gas chromatography-ion trap mass spectrometry (GC-IT/MS). The protocol developed allowed the determination of six phthalates [dimethyl phthalate, diethyl phthalate, dibutyl phthalate, isobutyl cyclohexyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate] and 19 organophosphorus pesticides. Freeze-dried product samples (0.1-0.2 g) were dissolved in 10 mL of warm distilled water along with 5 µL of an internal standard (anthracene at 10 mg mL-1 in acetone): the choice of extraction solvent was studied, with the most suitable being n-heptane, which is used for phthalate determination in similar matrices. The solution, held for 5 min in a vortex mixer and for 6 min in a 100-W ultrasonic bath to favor solvent dispersion and consequently analyte extraction, was centrifuged at 4000 rpm for 30 min. Then 1 µL was injected into the GC-IT/MS system (SE-54 capillary column; length 30 m, inner diameter 250 µm, film thickness 0.25 µm). All analytical parameters investigated are discussed in depth. The method was applied to real commercial freeze-dried samples: significant contaminant concentrations were not found. Graphical abstract Simultaneous and sensitive determination of organophosphorus pesticides and phthalates in baby foods by the ultrasound-vortex-assisted liquid-liquid microextraction Öªgas chromatography-ion trap mass spectrometry procedure. 1 methacrifos, 2 pirofos, 3 phorate, 4 seraphos, 5 diazinon, 6 etrimphos, 7 dichlofenthion, 8 chlorpyrifos-methyl, 9 pirimiphos-methyl, 10 malathion, 11 chlorpyrifos, 12 parathion-ethyl, 13 pirimiphos-ethyl, 14 bromophos, 15 chlorfenvinphos, 16 bromophos-ethyl, 17 stirophos, 18 diethion, 19 coumaphos, A dimethyl phthalate, B diethyl phthalate, C dibutyl phthalate, D butyl cyclohexyl phthalate, E benzyl butyl phthalate, F bis(2-ethylhexyl) phthalate, IS internal standard.

Sensitive multiresidue method by HS-SPME/GC-MS for 10 volatile organic compounds in urine matrix: a new tool for biomonitoring studies on children.

A HS-SPME method coupled with GC-MS analysis has been developed for simultaneously measuring the concentration of 10 volatile organic compounds (VOCs) (benzene, toluene, ethylbenzene, o-, m-, and p-xylene, methyl tert-butyl ether, ethyl tert-butyl ether, 2-methyl-2-butyl methyl ether, and diisopropyl ether) in urine matrix as a biomonitoring tool for populations at low levels of exposure to such VOCs. These compounds, potentially toxic for human health, are common contaminants of both outdoor and indoor air, as they are released by autovehicular traffic; some of them are also present in environmental tobacco smoke (ETS). Thus, the exposure to these pollutants cannot be neglected and should be assessed. The low limits of detection and quantification (LODs and LOQs <6.5 and 7.5 ng L(-1), respectively) and the high reproducibility (CVs <4 %) make the developed method suited for biomonitoring populations exposed at low levels such as children. Further, the method is cost-effective and low in time-consumption; therefore, it is useful for investigating large populations. It has been applied to children exposed to traffic pollution and/or ETS; the relevant results are reported, and the relevant implications are discussed.

Visible light caffeic acid degradation by carbon-doped titanium dioxide.

The removal of the phenolic compound, caffeic acid, by photodegradation has been investigated using carbon-doped titanium dioxide particles as a photocatalyst under visible light. UV-vis absorption spectroscopy and gas chromatography-ion trap mass spectrometry analyses revealed a substrate concentration dependence of the removal of caffeic acid from a water solution. The k2 and t(0.5) parameters of each reaction were calculated by fitting kinetics data to a second-order kinetic adsorption model. To evaluate the photodegradation event, the effect of the adsorption process on the whole degradation was also monitored in the absence of light. Adsorption isotherm studies supported by ζ potential and scanning electron microscopy data demonstrated the pivotal role of the absorption mechanism. It was found that the whole photodegradation process is governed by a synergic mechanism in which adsorption and photodegradation are involved. This study, centered on the removal of caffeic acid from aqueous solutions, highlights the potential application of this technology for the elimination of phenolic compounds from olive mill wastewater, a fundamental goal in both the agronomical and environmental fields.

State-of-art of the legislation on odour emissions with a focus on the Italian studies.

This review would like to point out the state-of-art of the European legislation for the odour pollution determination and management. Odour is generated by a mixture of more or less volatile and persistent compounds that surround us in daily life. European directives impose the use of corresponding technical standards for the application of the limits imposed. The different approaches (chemicals and/or olfactometries) and integrated evaluation methods for measuring and characterizing odour, even if in a very different way in the European territories, will be reviewed and commented. Specifically, the authors will describe and comment the main procedures for odour concentration determination (e.g., multigas sensors, electronic sensors for odour monitoring). It is important to note that the definition of odour does not take into account if an odour is "good" or "bad", but only if it exists. The limit value must guarantee a total equivalent level of environmental protection and does not involve a greater polluting load in the environment. Further, a deep revision of the Italian situation in terms of legislation and studies, will complete the paper.

Atmospheric bulk depositions: state-of-the-art and European legislative framework with focus on Italy.

The determination of total atmospheric deposition (bulk) is an essential tool to assess the state of environmental contamination and the consequent exposure of the population to persistent organic pollutants (POPs) through the intake of contaminated food. Over the past 20 years, international authorities and the European Union through various pieces of legislation have emphasised the importance of conducting monitoring and studies on depositions to better understand their impact on the environment and human health without setting reference values. Despite the absence of such values, several European countries, through national laws, have adopted limit values and/or guideline values for the deposition fluxes of some organic (dioxins, furans, polychlorinated biphenyls and polycyclic aromatic hydrocarbons) and inorganic persistent pollutants (metals). The aim of this review is both to summarise the present European legislation on depositions both to discuss the different legislations adopted by the various member states. Furthermore, a focus of this paper will be dedicated to the Italian legislation, where there is currently no specific guideline values for POPs in atmospheric deposition. In any case, some national authorities in Italy, such as the National Institute of Health (ISS) and the Regional Environmental Protection Agencies (ARPA), have conducted numerous monitoring activities on depositions, providing the scientific community and policymakers with numerous data on which to establish national reference values.

There's Something in What We Eat: An Overview on the Extraction Techniques and Chromatographic Analysis for PFAS Identification in Agri-Food Products.

Per- and polyfluorinated alkyl substances (PFASs) are a group of anthropogenic chemicals used in a range of industrial processes and consumer products. Recently, their ubiquitous presence in the environment as well as their toxicological effects in humans have gained relevant attention. Although the occurrence of PFASs is widely investigated in scientific community, the standardization of analytical method for all matrices still remains an important issue. In this review, we discussed extraction and detection methods in depth to evaluate the best procedures of PFAS identification in terms of analytical parameters (e.g., limits of detection (LODs), limits of quantification (LOQs), recoveries). Extraction approaches based on liquid-liquid extraction (LLE), alkaline digestion, and solid phase extraction (SPE), followed by liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) analysis are the main analytical methods applied in the literature. The results showed detectable recoveries of PFOA and PFOS in meat, milk, vegetables, eggs products (90.6-101.2% and of 89.2-98.4%), and fish (96-108%). Furthermore, the low LOD and LOQ values obtained for meat (0.00592-0.01907 ng g-1; 0.050 ng g-1), milk (0.003-0.009 ng g-1; 0.010-0.027 ng g-1), fruit (0.002-0.009 ng g-1; 0.006-0.024 ng g-1), and fish (0.00369-0.017.33 ng g-1; 0.05 ng g-1) also confirmed the effectiveness of the recent quick, easy, cheap, effective, rugged, and safe method (QuEChERS) for simple, speedy, and sensitive ultra-trace PFAS analysis.

Evaluating microplastic emission from takeaway containers: A Micro-Raman approach across diverse exposure scenarios.

Based on inconsistencies observed in literature regarding microplastic levels released by takeaway plastic containers, this study investigates the release from takeaway containers composed of polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET). To simulate real-world conditions, experiments were conducted using Milli-Q water at room temperature, 100 °C, and at pH 4.5. Containers were subjected to 20-min exposure with agitation, and microplastics were quantified via optical microscopy, with micro-Raman spectroscopy to confirm the particle polymeric nature. The results indicate that PET and PS containers released microplastic in varying quantities: 9 and 1 at room temperature, 7 and 3 in acidified water, and 17 and 30 at 100 °C, respectively. The particle sizes ranged between 13 and 32 µm. Notably, no microplastics were detected from PP containers under any tested conditions. This study underscores the significant release of microplastics from PET and PS containers, particularly at elevated temperatures, suggesting that PP may represent a safer alternative.

Evaluation of the Content of Minerals, B-Group Vitamins, Tocols, and Carotenoids in Raw and In-House Cooked Wild Edible Plants.

Notwithstanding the increased interest in wild edible plants, little is known on how some domestic thermal processes can affect their content. The aim of this study was to investigate the amounts of minerals, B1 and B2 vitamins, tocols, and carotenoids in raw, boiled, and steamed wild edible plants, namely, Sonchus asper (L.) Hill s.l., Sonchus oleraceus L., Cichorium intybus L., and Beta vulgaris L. var cicla. All vegetables were confirmed as high sources of lutein (from 6 to 9 mg/100 g) and ß-carotene (from 2 to 5 mg/100 g). Quite high amounts of violaxanthin and neoxanthin were found. Alfa-tocopherol and γ-tocopherol were the main tocols, with same contents in raw and processed vegetables (about 2.5 mg/100 g). The most abundant macro element and trace element were, respectively, potassium and iron. B1 and B2 vitamins were found in low amounts in almost all plants, with the exception of thiamine in Beta vulgaris (about 1.6 mg/100 g). Boiling led to a significant loss of minerals (up to 60%) and B-group vitamins (up to 100%), while, among carotenoids, it only affected violaxanthin levels (up to 90%). Steamed vegetables showed only a slight reduction, about 20%, in ß-carotene and lutein, with a marked decrease in violaxanthin and neoxanthin. One hundred grams of all fresh and cooked plants can be claimed as a source of vitamin A and E.

Diversity of plant pollen sources, microbial communities, and phenolic compounds present in bee pollen and bee bread.

The pollination of several crops, as well as wild plants, depends on honeybees. To get the nutrients required for growth and survival, honeybee colonies are dependent on pollen supply. Bee pollen (BP) is partially packed in honeycomb cells and processed into beebread (BB) by microbial metabolism. The composition of pollen is highly variable and is mainly dependent on ecological habitat, geographical origin, honey plants, climatic conditions, and seasonal variations. Although there are important differences between the BP and the BB, little comparative chemical and microbiological data on this topic exists in the literature, particularly for samples with the same origin. In this study, BP and BB pollen samples were collected from two apiaries located in the Campania and Molise regions of Southern Italy. Phenolic profiles were detected via HPLC, while antioxidant activity was determined by ABTS·+ and DPPH· assay. The next-generation sequencing (NGS) based on RNA analysis of 16S (rRNA) and internal transcribed spacer (ITS2) regions were used to investigate the microbial community (bacteria and fungi) and botanical origin of the BP and BB. Chemical analysis showed a higher content of flavonols in BP (rutin, myricetin, quercetin, and kaempferol), while in BB there was a higher content of phenolic acids. The NGS analysis revealed that the microbial communities and pollen sources are dependent on the geographical location of apiaries. In addition, diversity was highlighted between the microbial communities present in the BP and BB samples collected from each apiary.

Validation of a novel derivatization method for GC-ECD determination of acrylamide in food.

This paper proposes a new method for quantitative analysis of acrylamide in cereal-based foods and potato chips. The method uses reaction with trifluoroacetic anhydride, and analyses the resulting derivative by use of gas chromatography with electron-capture detection (GC-ECD). The effects of derivatization conditions, including temperature, reaction time, and catalyst, on the acylation reaction were evaluated. Chromatographic analysis was performed on an SE-54 capillary column. Under the optimum conditions, good retention and peak response were achieved for the acrylamide derivative. The analytical method was fully validated by assessment of LODs and LOQs (1 ng g(-1) and 25 ng g(-1), with relative standard deviations (RSD) 2.1 and 3.6, respectively), linearity (R = 0.9935 over the range 0.03-10 µg g(-1)), and extraction recovery (>96%, with RSD below 2.0, for acrylamide spiked at 1, 20, 50, and 100 ng g(-1); 99.8% for acrylamide content >1000 ng g(-1)). The method requires no clean-up of the acrylamide derivative before injection. The method has been successfully used to determine acrylamide levels in different commercial cereal-based foods, French fries, and potato chips.

GC models for separation optimization in pressure-tuneable tandem capillary columns operated isothermally. Part 1: Theoretical aspects.

GC column selectivity can be continuously adapted to suit analytical needs using a flow-tuneable tandem system. Its application for the separation of complex mixtures requires a deep understanding of the theory in this area. Although a number of researchers have developed specific models, a general and exhaustive theory is still missing. In this paper, we have made an implementation of pre-existing models on tandem-column assemblies operated isothermally. In particular, we have investigated the effect of column length and diameter, phase thickness, and oven temperature on chromatographic parameters, such as capacity factor, selectivity, and intrinsic resolution. A new approach for the correct choice of the working temperature has been proposed.

Instrumental neutron activation analysis and statistical approach for determining baseline values of essential and toxic elements in hairs of high school students.

The possibility to have reference values in clinical chemistry is really important and hair is an ideal tissue for tracing human health conditions. This study performed on 131 hair samples of high school students gives a better knowledge of element levels (i.d., As, Cd, Cr, Cu, Fe, Hg, Mn, S, Sb, Se, Sn and Zn) in subjects not exposed to specific contamination. A nuclear analytical technique, Instrumental Neutron Activation Analysis, has been employed for determining such species. These data can be used as tentative reference values in human hairs. The ratios among metals give important considerations on the general aspect of human health: the reference value represents an evaluation of the essential metabolic functions whereas an imbalance could be a factor influencing the rising of some pathologies, even if it is not an index of particular metabolic deficiency. A comparison with Italian studies shows a good agreement whereas some little discrepancies are evident with International studies. Further, a statistical approach (cluster analysis, Canonical Discriminant Analysis) was applied for determining the reference values. Taking in account these reference values a relationship with the environmental and pollutant compartments was studied confirming the starting hypothesis.

Determination of interesting toxicological elements in PM2.5 by neutron and photon activation analysis.

Human activities introduce compounds increasing levels of many dangerous species for environment and population. In this way, trace elements in airborne particulate have a preeminent position due to toxic element presence affecting the biological systems. The main problem is the analytical determination of such species at ultratrace levels: a very specific methodology is necessary with regard to the accuracy and precision and contamination problems. Instrumental Neutron Activation Analysis and Instrumental Photon Activation Analysis assure these requirements. A retrospective element analysis in airborne particulate collected in the last 4 decades has been carried out for studying their trend. The samples were collected in urban location in order to determine only effects due to global aerosol circulation; semiannual samples have been used to characterize the summer/winter behavior of natural and artificial origin. The levels of natural origin element are higher than those in other countries owing to geological and meteorological factors peculiar to Central Italy. The levels of artificial elements are sometimes less than those in other countries, suggesting a less polluted general situation for Central Italy. However, for a few elements (e.g., Pb) the levels measured are only slight lower than those proposed as air ambient standard.

Are Microplastics a Macro Issue? A Review on the Sources of Contamination, Analytical Challenges and Impact on Human Health of Microplastics in Food.

In recent years, human populations' exposure to microplastics via foods is becoming a topic of concern. Although microplastics have been defined as "emerging contaminants", their occurrence in the environment and food is quite dated. This systematic review aims to investigate the discrepancies which are characterizing the research in the microplastics field in foods, with particular regard to sample preparations, microplastics' concentrations and their effect on humans. For the selection of papers, the PRISMA methodology was followed. Discrepancies in the methodological approaches emerged and in the expression of the results as well, underlying the urgency in the harmonization of the methodological approaches. Uncertainties are still present regarding the adverse effects of microplastics on the human body. The scientific evidence obtained thus far is, in fact, not sufficient to demonstrate a concrete negative effect. This review has clearly underlined the need to standardise laboratory approaches to obtain useful results for better food safety management.

Microplastic contamination in commercial salt: An issue for their sampling and quantification.

Sea salt can be considered as a vector of microplastics in the human body. In this work, the sea salts collected from three Italian salterns has been solubilized in MilliQ water and filtered to extract microplastics. The visual quantification of microplastics with a stereomicroscope was carried out on the bases of their size, followed by a classification taking into account their physical characteristics. ATR-FTIR and Raman spectroscopy were used to identify the polymeric type of microplastics. Their significant presence has been revealed: 1653 ± 29 microplastics/kg of sea salt. In total, 80.6 % of microplastics have a fiber shape, 18.9 % a fragmented shape and 2.7 % are sphere. The size of microplastics has been analysed, indicating that the most frequent is between 0 and 500 µm. Polypropylene, polyamide and polyethylene were identified as the most frequent types of polymers. This research could be of global relevance given the significant export of Italian salt to foreign countries.

The Presence of Ultra-Traces of Persistent Organic Pollutants (POPs) and Heavy Metals in Some Areas of Molise: The Importance of a "Blank" in Public Health Studies.

The emission of chemicals into the environment has increased in a not negligible way as a result of the phenomenon of globalization and industrialization, potentially also affecting areas always considered as "uncontaminated". In this paper, five "uncontaminated" areas were analyzed in terms of the presence of polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs), comparing them with an "environmental blank". Chemical analyses were carried out using standardized protocols. The 'environmental blank' results revealed the presence of Cu (<64.9 µg g-1), Ni (<37.2 µg g-1), and Zn (<52.6 µg g-1) as HMs and fluorene (<17.0 ng g-1) and phenanthrene (<11.5 ng g-1) as PAHs. However, regarding the results of the pollution status of the areas under study, fluorene (#S1, 0.34 ng g-1; #S2, 4.3 ng g-1; #S3, 5.1 ng g-1; #S4, 3.4 ng g-1; #S5, 0.7 ng g-1) and phenanthrene (#S1, 0. 24 ng g-1; #S2, 3.1 ng g-1; #S3, 3.2 ng g-1; #S4, 3.3 ng g-1; #S5, 0.5 ng g-1) were found in all areas, while the other PAHs investigated were detected at a concentration averaging less than 3.3 ng g-1. HMs were found in all of the investigated areas. In particular, Cd was detected in all areas with an average concentration of less than 0.036 µg g-1, while Pb was absent in area #S5, but present in the other areas with an average concentration of less than 0.018 µg g-1.

Characteristics of Commercial and Raw Pellets Available on the Italian Market: Study of Organic and Inorganic Fraction and Related Chemometric Approach.

Air pollution and the increasing production of greenhouse gases has prompted greater use of renewable energy sources; the EU has set a target that the use of green energy should be at 32 percent by 2030. With this in mind, in the last 10 years, the demand for pellets in Italy has more than doubled, making Italy the second largest consumer in Europe. The quality of the pellets burned in stoves is crucial to indoor and outdoor pollution. Among other parameters, moisture and ash are used to classify pellets according to EN ISO 17225:2014. This work involved the analysis of the organic and inorganic fraction of both some finished products on the Italian market and some raw materials (e.g., wood chips) sampled according to the technical standard EN 14778:2011. The analytical results showed the presence of some substances potentially harmful to human health such as formaldehyde, acetone, toluene and styrene for the organic fraction and nickel, lead and vanadium for the inorganic fraction. The chemometric approach showed that it is the inorganic fraction which is most responsible for the diversification of the samples under study. The detection of some substances may be a warning bell about the impact of such materials, both for the environment and for human health.