Combined Use of Fatty Acid Profiles and Elemental Fingerprints to Trace the Geographic Origin of Live Baits for Sports Fishing: The Solitary Tube Worm (Diopatra neapolitana, Annelida, Onuphidae) as a Case Study.

Diopatra neapolitana Delle Chiaje, 1841 (Annelida, Onuphidae) is one of the most exploited polychaete species in European waters, particularly in Ria de Aveiro, a coastal lagoon in mainland Portugal, where the overexploitation of this resource has led to a generalized decline of local populations. In an attempt to reduce the impact of harvesting, several management actions were implemented, but illegal poaching still fuels a parallel economy that threatens the sustainable use of this marine resource. The present study evaluated the combination of fatty acid profiles and elemental fingerprints of the whole body and jaws, respectively, of D. neapolitana collected from four harvesting locations within Ria de Aveiro in order to determine if their geographic origin could be correctly assigned post-harvesting. Results showed that both fatty acid profiles and elemental fingerprints differ significantly among locations, discriminating the geographic origin with higher accuracy when combining these two natural barcodes than when employing each individually. The present work can, therefore, contribute to the implementation of an effective management plan for the sustainable use of this marine resource, making it possible to detect if D. neapolitana was sourced from no-take zones and if it was collected from the place of origin claimed by live bait traders.

Effects of H2O2 pretreatment on the elemental fingerprints of bivalve shells and their implications for the traceability of geographic origin.

The fraudulent mislabelling of seafood geographic origin has been growing due to complex supply chains and growing consumer demand. To address this issue, seafood traceability tools, such as those based on elemental fingerprints (EF) of bivalve shells, have been successfully used to confirm their harvesting location. However, despite the usefulness of these methodologies, there is still room for optimization. Therefore, this study evaluated the effects of a routine procedure during bivalve shells preparation for ICP-MS analysis - their pretreatment with H2O2 to remove organic components. More specifically, the present study evaluated the effects of H2O2 on i) the elemental fingerprints of shells of two bivalve species (Ruditapes philippinarum and Cerastoderma edule) from four different locations over the north-western and the western Iberian coast, and ii) their influence on the accuracy of models (based on the EF of shells) used to confirm the geographic origin of these species. Significant differences were observed between untreated and pretreated shells of R. philippinarum (p within location ranging from 0.0001 to 0.0011) and C. edule (p ranging from 0.0001 to 0.0007 for C. edule) for both their elemental fingerprints as a whole and several individual elements. The accuracy of the models employed to determine the origin of the two bivalve species, using i) untreated shells, ii) pretreated shells, and iii) both pretreated and untreated shells grouped per location, was high, with the models accurately predicting the geographic origin of 100, 90 and 95% of R. philippinarum and 95, 100 and 95% of C. edule, respectively. These results show that the shifts in the EF of bivalve shells promoted by treating them with H2O2 prior to ICP-MS analysis did not affect the accuracy of the models used to confirm the geographic origin of both bivalve species. Therefore, the need to pre-treat bivalve shells with H2O2 can be dismissed in future studies addressing the traceability of bivalves when using ICP-MS, thus contributing to reducing environmental impacts and economic costs associated with this procedure, as well as the time required to obtain results.

Characterization of percutaneous absorption of calcium, magnesium, and potentially toxic elements in two tailored sulfurous therapeutic peloids: a comprehensive in vitro pilot study.

Pelotherapy treatments in thermal spas, which utilize peloids composed of clay minerals mixed with saltwater or mineral-medicinal water, can have various effects on spa users, ranging from therapeutic to potential adverse reactions. Despite the widespread use of peloids, comprehensive information on the penetration and permeation of essential and potentially toxic elements into deeper layers of the skin during pelotherapy is limited. Understanding the concentrations of these elements is crucial for evaluating therapeutic benefits and ensuring safety. This study investigates the in vitro availability and absorption of calcium, magnesium, and potentially toxic elements in two peloids, considering their formulation matrix. To replicate the pelotherapy methodology, an in vitro permeation experiment was conducted using a vertical diffusion chamber (Franz cells) and a biological system with human skin membranes from five Caucasian women, age range between 25 and 51 years. The experiment involved heating the peloids to 45℃. The results emphasize the possible transport properties of chemical elements in peloids, providing valuable information related to potential therapeutic efficacy and safety considerations. Despite no apparent differences between peloids' chemical composition, the method identified permeation variations among chemical elements. The methodology employed in this study adheres to the guidelines outlined by OECD for analyzing skin absorption through an in vitro approach. Furthermore, it aligns with the associated OECD guidance document for conducting skin absorption studies. The replicability of this methodology not only facilitates the analysis of peloids pre-formulation but also provides a robust means to evaluate the effectiveness of therapeutic elements during topical administration, particularly those with potential toxicity concerns.

The first full study of heavy metal(loid)s in western-European hedgehogs (Erinaceus europaeus) from Portugal.

The western-European hedgehog (Erinaceus europaeus) is an insectivore with a wide distribution in Portugal and a potential tool for biomonitoring relevant One Health hazards, including heavy metal(loid)s' pollution. The aim of this study was to positively contribute to the current knowledge about the metal(loid) pollution in Portugal. Forty-six hedgehogs (from rescue centres; with known provenance) were necropsied. Sex, age category and weight were determined. Spines, liver and kidney were collected, and metalloid concentrations were determined by inductively coupled plasma mass spectrophotometry (ICP-MS). In general, results did not present alarming metal(loid) concentrations, with the exception of cadmium (Cd) (in the kidneys) and copper (Cu). Hedgehogs from Viana do Castelo and Viseu showed elevated concentrations of arsenic (As) and Castelo Branco presented concerning values of cadmium (Cd). Adult and heavier hedgehogs tended to present higher levels of metal(loid)s. Sex does not seem to significantly affect the metal(loid)s' concentrations. Further analysis would be needed to prioritize areas with detail and allow the application of the necessary mitigation strategies.

Heavy metals and metalloids in wild boars (Sus Scrofa) - a silent but serious public health hazard.

Wild boars (Sus scrofa) are part of the hunting economy and are highly consumed in the Iberian Peninsula, including in the Castile and Leon regions. As zoonotic diseases, chemical pollutants in wild boars' internal tissues should be interpreted as evidence of environmental contamination and a matter of concern for animal, human and ecosystem health; in other words, a One Health concern. Twenty-eight wild boars' livers and kidneys (n = 28) from Castile and Leon were submitted to metal(loid) determination (As, Cd, Co, Cr, Cu, Ni, Pb, and Zn) with inductively coupled plasma mass spectrophotometry (ICP-MS) and histopathological exam. Cd levels, especially in the kidneys (7.063 ± 7.271 mg/kg dw), were the most concerning results, considering the calculated maximum values for consumption (EC No. 915/2023) (2.491 mg/kg dw or 1.0 mg/kg ww). Wild boars with hydropic changes in the liver presented higher concentrations of Ni. Thus, the metal(loid) contamination of wild boar carcasses seems to be a "no trace" but very relevant problem that should raise awareness of a more accurate monitoring program and other strategies to avoid public health consequences.

Domestication shapes the endophytic microbiome and metabolome of Salicornia europaea.

AIMS: We aim at understanding the effect of domestication on the endophytic microbiome and metabolome of Salicornia europaea and collecting evidence on the potential role of microbial populations and metabolites in the adaptation of plants to different ecological contexts (wild vs crops). METHODS AND RESULTS: Samples were collected from a natural salt marsh (wild) and an intensive crop field (crop). High-throughput sequencing of the 16S rRNA gene, gas chromatography-mass spectrometry (GC-MS) and ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) were used to analyze the endophytic bacterial communities and the metabolite profiles of S. europaea roots, respectively. The elemental analysis of the plant shoots was performed by Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS).Overall, significant differences were found between the microbiome of wild and cultivated plants. The later showed a higher relative abundance of the genera Erythrobacter, Rhodomicrobium, and Ilumatobacter than wild plants. The microbiome of wild plants was enriched in Marinobacter, Marixanthomonas, and Thalassospira. The metabolite profile of crop plants revealed higher amounts of saturated and non-saturated fatty acids and acylglycerols. In contrast, wild plants contained comparatively more carbohydrates and most macroelements (i.e. Na, K, Mg, and Ca). CONCLUSIONS: There is a strong correlation between plant metabolites and the endosphere microbiome of S. europaea. In wild populations, plants were enriched in carbohydrates and the associated bacterial community was enriched in genes related to primary metabolic pathways such as nitrogen metabolism and carbon fixation. The endosphere microbiome of crop plants was predicted to have higher gene counts related to pathogenesis. Crop plants also exhibited higher amounts of azelaic acid, an indicator of exposure to phytopathogens.

Bioaccessibility by perspiration uptake of minerals from two different sulfurous peloids.

The risks associated with the use of peloids in thermal centers, spas, or at home, must be tested to develop appropriate safety guidelines for peloids formulations and the release of substances of high concern. Additionally, the beneficial effects of some elements on human health should be assessed to aid in interpreting the therapeutic action and effectiveness of pelotherapy on dermatological or osteomuscular disorders. Therefore, a methodology was developed to better understand the biogeochemical behavior of the elements in formulated peloids. Two peloids were formulated with the same clay and two different sulfurous mineral-medicinal waters for 90 days, with light stirring every 15 days. Bentonite clay, with a high content of smectite and Ca and Mg as the main exchangeable cations, and high heat capacity, was used. The selected mineral-medicinal waters were collected from two Portuguese thermal centers with recognized therapeutic efficacy for rheumatic, respiratory and dermatological pathologies. The peloids were used without drying and withdrawn directly from the maturation tank, and a mixture of bentonite and demineralized water was prepared as a reference sample. A stabilized, ready-to-use, artificial perspiration test was used to simulate the peloids' interaction with skin. Thirty-one elements extracted from the two prepared peloids were analyzed using ICP-MS. The data were analyzed and related to the mineralogical composition of the original clay and supernatant composition of the maturation tanks. The content of some potentially toxic elements and metals' bioaccessibility by perspiration showed very low solubility and undetectable amounts extracted from the studied samples. This analytical method provided reliable information on dermal exposure and the identification of some elements that may enter the systemic circulation, requiring implementation of surveillance and control measures.

Enhanced Gastric/Lung Arsenic Bioaccessibility from Lignite Fly Ashes: Comparing Bioaccessibility Rates with Multiple Environmental Matrices.

Inorganic arsenic (As), a carcinogenic element to humans, is among the most dangerous and flammable substances that coal-burning plants could release. When coal is burned, large portions of arsenic are captured on fly-ash (FA) particles, but it could also contribute significantly to stack emissions of fine fly-ash particles. The aim of this study was to evaluate the oral and respiratory bioaccessibility of arsenic in lignite fly-ash (LFA) samples, and their contribution to total As exposure. Arsenic bioaccessibility fractions via ingestion and inhalation showed significant differences, suggesting the presence of highly soluble As-bearing phases in the studied LFA samples. The bioaccessible As fractions (BAF%) in the simulated gastric fluids (UBM protocol, ISO 17924:2018) showed a range of 45-73%, while the pulmonary bioaccessibility rates in the simulated lung fluid (artificial lung fluid (ALF)) exhibited significantly enhanced levels ranging from 86% to 95%. The obtained arsenic bioaccessibility rates were compared with previous data for multiple environmental matrices such as soil and dust-related materials, revealing that LFA exhibited significantly higher bioaccessibility (%) for the inhalation pathway.

High Levels of Heavy Metal(loid)s Related to Biliary Hyperplasia in Hedgehogs (Erinaceus europaeus).

Heavy metal(loid) pollution of ecosystems is a current One Health problem. The liver is one of the most affected organs in cases of acute or chronic exposure to abnormal amounts of these substances, inducing histopathologic lesions. In order to assess the influence of heavy metal(loids), forty-five European hedgehogs (Erinaceus europaeus) were submitted to necropsy, and liver samples were collected for a routine histopathology exam and metal(loid)s determination (As, Cd, Co, Cr, Cu and Pb) by ICP-MS. Age was estimated during the necropsy exam. Biliary hyperplasia was the most frequent lesion observed (16/45; 35.56%). No statistically significant associations were found between biliary hyperplasia and age or sex. Metal(loid)s' concentrations were higher in animals with biliary hyperplasia (except for As). There was a statistically significant difference for both Cd and Co. For As, Cd and Co, cubs and juveniles animals showed significantly lower concentrations than elder individuals. Only for Pb were significant differences found between females and males. As described in the literature, exposure to metal(loid)s may be a cause of biliary hyperplasia, although further research (including the use of biochemical methods) is needed to support these results. To the authors' knowledge, this is the first report of this association in hedgehogs.

Interplay of Seasonality, Major and Trace Elements: Impacts on the Polychaete Diopatra neapolitana.

Polychaetes are known to be good bioindicators of marine pollution, such as inorganic contamination. Major and trace elements are commonly present in sediment and may be accumulated by polychaetes such as the tubiculous Diopatra neapolitana. In this study, D. neapolitana individuals were collected in the autumn, winter, spring, and summer of 2018/2019 from the Ria de Aveiro lagoon (western Portugal) to understand how seasonality influences element accumulation. The impact of the interaction of seasonality and elements on oxidative status, energy metabolism, and oxidative damage was also assessed. The obtained results showed that the activity of the antioxidant enzymes catalase, glutathione S-transferases, and non-protein thiol levels were higher in summer and that superoxide dismutase, lipid peroxidation, and electron transport system activity increased in winter. The lowest glycogen levels were observed during spring, and protein carbonylation was the highest during autumn. These results could mainly be related to high temperatures and the bioaccumulation of Al, As, Mn, and Zn. Energy-related parameters increased during spring and autumn, mainly due to the bioaccumulation of the same elements during spring and summer. Lipid damage was higher during winter, which was mainly due to salinity and temperature decreases. Overall, this study demonstrates that seasonality plays a role in element accumulation by polychaetes and that both impact the oxidative status of D. neapolitana.

Sorption and post-sorption performances of Cd, Pb and Zn onto peat, compost and biochar.

The development of waste-derived sorbents to immobilize potentially toxic elements (PTEs) is a promising strategy, contributing to the achievement of sustainable development goals (SDGs). Therefore, this study aimed to assess the sorption performance of cadmium (Cd), lead (Pb) and zinc (Zn), comparing sorbents derived from organic fraction of municipal solid waste (composts and biochars) with peat. The physicochemical characterization, equilibrium of sorption, post-sorption analyzes and bioaccessibility were investigated. Results showed that the sorbents have distinct characteristics; however, each material have their particularities favorable to sorption. For instance, peat and composts have the highest cation exchange capacity (800-1100 mmolc kg-1), while biochar produced at 700 °C has the highest specific surface area (91.21 m2 g-1). The sorption equilibrium data revealed the actual sorption capacity and was well explained by the Freundlich and Langmuir isotherms and, in some cases, by the Dubinin-Radushkevich model. Post-sorption analyzes indicated the occurrence of several sorption mechanisms, driven by the physicochemical properties. Electrostatic interaction stood out for peat and compost. The FTIR spectrum for peat proved the complexation with oxygenated functional groups. The composts showed variations in the released cations (e.g. Ca2+ and K+), indicating cation exchange. Differently, for biochars, the XRD patterns showed that precipitation or coprecipitation seems to be one of the main mechanisms, especially for Cd and Pb. Regarding human bioaccessibility, the results of the gastric phase simulation (pH∼1.20) revealed lower percentages of Pb (33-81%) than Cd (91-99%) or Zn (82-99%), especially for the highest concentrations. Nevertheless, in numerical terms, all bioaccessible concentrations inspire care. In conclusion, among the sorbents, composts and biochars presented the best sorption performances and, therefore, have great potential for environmental applications. Furthermore, the bioaccessibility findings indicate that these assays, still little used in experiments with sorbents, are an important tool that should be better explored in the assessment of the environmental risk associated with contamination.

Chemical characterization of riverine sediments affected by wastewater treatment plant effluent discharge.

This study was aimed at assessing the contribution of wastewater treatment effluents to the contamination profile of the sediments of receiving waterways. Three wastewater treatment plants (WWTP) were addressed, encompassing different population equivalent sizes, urbanization degrees and treatment methods translating differences in expected contamination patterns. Within each WWTP system, the assessment targeted the effluent and sediment samples collected upstream and downstream the effluent discharge point; contaminants belonging to several concerning chemical classes (metals and metalloids; pesticides; pharmaceuticals and personal care products, PPCPs; and polycyclic aromatic hydrocarbons, PAHs) were quantified both in effluent and sediment samples. Clear associations between contaminants present in the effluent and corresponding sediment samples were not always verified. In fact, a noticeable difference between the number or abundance of contaminants detected in effluents and in sediments, suggesting that effluents are not always the most likely source (e.g. PAHs). However, sediment contaminants that were likely sourced by the effluents were also identified (e.g. PPCPs). Sediment analysis offers an important historical view of contamination, especially in flowing recipient ecosystems where any characterization over the water matrix is ephemeral and linking exclusively to the moment of sampling. Hence, sediments should be considered for the establishment of WWTP operational benchmarks regulating the emission of contaminants, which is currently focused mostly on effluent composition thus potentially over/underestimating the longer-term impact of effluent discharge in the recipient waterways.

Sorption of arsenic by composts and biochars derived from the organic fraction of municipal solid wastes: Kinetic, isotherm and oral bioaccessibility study.

The historic contamination of water and soils by arsenic (As) is an extremely alarming environmental and public health issue worldwide. This study investigated the relationship between As sorption and physicochemical properties of composts and biochars derived from the organic fraction of municipal solid wastes (OFMSW) towards the development of promising sorbents with value-added solid wastes management solutions. The sorbents were characterized and their effectiveness on the As sorption was tested. Several isothermal and kinetic sorption models were used for the prediction of sorption. Composts did not show promising sorption capacities, and in some cases, the As immobilization was practically null. In contrast, biochars achieved higher sorption performance, and the experimental data fitted well on Dubinin-Rabushkevich and Langmuir models, with higher R2 values. The maximum sorption capacities of BC700 estimated by such models were 6.495 and 170.252 mg g-1, respectively, whereas those of BC500 estimated by D-R and Langmuir models were only 0.066 and 0.070 mg g-1, respectively. In sorption kinetics, As was retained onto biochars at a faster first stage, reaching equilibrium after approximately 1 h and 2 h for initial concentrations of 10 and 100 mg L-1. The pseudo-second-order, Ritchie's second-order, Ritchie's, and Elovich models more adequately described the sorption kinetics of As onto biochars with high R2 values. Overall, the complexation and precipitation were predominant mechanisms for As sorption by OFMSW-derived biochars. Furthermore, the mathematical models indicated contributions arise from physisorption and external and internal diffusion mechanisms. Although BC700 can immobilize large As amounts, the gastric phase of the oral bioaccessibility test revealed more than 80% of the sorbed As could be released under conditions similar to a human stomach (pH~1.2). Such conclusions have given important insights about the refining of effective and eco-friendly remediation technologies for the management and rehabilitation of As-contaminated soil and water, particularly in developing countries.

Assessing the elemental fingerprints of cockle shells (Cerastoderma edule) to confirm their geographic origin from regional to international spatial scales.

Geographic origin is directly linked to the quality and commercial value of bivalves. The globalization of the seafood trade and the increasing number of fraudulent practices in the bivalves industry has prompted consumers to become increasingly aware on the geographic origin of the seafood they consume. To enhance consumers' confidence and allow authorities to effectively enforce regulations and contain risks that threaten public health, fast and accurate tools must be made available to confirm claims along the trade chain on the geographic origin of bivalves. In the present study the efficiency of using the elemental fingerprints of a small-homogenized subsample of the shell of common cockles (Cerastoderma edule) to confirm their harvesting location is evaluated at different spatial scales: i) regional (along the Galician coast (Spain) - Espasante, Barallobre, Rio Anllóns, Camariñas, Muros, Noia, Carril, Grove, Combarro, Placeres, Moaña, and Baiona), ii) national (along the Portuguese coast - Ria de Aveiro, Óbidos lagoon, Tagus estuary, Sado estuary and Ria Formosa), and iii) international (along the Northeast Atlantic coast - Hejeltefjorden (Norway), Nykobing Mors (Denmark), Sylt (Germany), Slikken van Viane (Netherlands), Roscoff (France), Plymouth (England), Swansea (Wales), Ria de Aveiro (Portugal) and Oualidia (Morocco). Results confirm that elemental fingerprints of bivalve shells are significantly different among locations and that they can be successfully used with high accuracy to discriminate the geographic origin of cockles at all spatial scales surveyed (97.2% at regional scale, 99.3% at national scale and 100% at international scale). Overall, elemental fingerprints of a small-homogenized subsample of the shell showed to be a replicable, low cost and fast tool to reliably trace the place of origin of cockles sampled at different spatial scales, with success rate of discrimination directly increasing with distance between collection sites.

Nano-Fe2O3 as a tool to restore plant growth in contaminated soils - Assessment of potentially toxic elements (bio)availability and redox homeostasis in Hordeum vulgare L.

This work aimed to evaluate the potential of Fe2O3 nanoparticles (nano-Fe2O3) to alleviate potentially toxic elements (PTEs) - induced stress in barley plants (Hordeum vulgare L.), focusing on bioaccumulation patterns and on plant growth and redox homeostasis. To achieve this goal, plants grew in two agricultural soils, contaminated by different levels of PTEs, collected from an industrial area, previously amended, or not, with 1% (w/w) nano-Fe2O3. After 14 d of growth, biometric parameters were evaluated, along with the analysis of PTEs bioaccumulation and biochemical endpoints. After exposure to contaminated soils, plant development was greatly affected, as evidenced by significant decreases in root length and biomass production. However, upon co-treatment with nano-Fe2O3, lower inhibitory effects on biometric parameters were observed. Regarding the oxidative damage, both soils led to increases in lipid peroxidation and superoxide anion concentration, though hydrogen peroxide levels were only increased in the most contaminated soil. In general, these changes in the oxidative stress markers were accompanied by an upregulation of different antioxidant mechanisms, whose efficiency was even more powerful upon soil amendment with nano-Fe2O3, thus lowering PTEs-induced oxidative damage. Altogether, the present study revealed that nano-Fe2O3 can protect the growth of barley plants under contaminated soils.

Successful Use of Geochemical Tools to Trace the Geographic Origin of Long-Snouted Seahorse Hippocampus guttulatus Raised in Captivity.

The global market of dried seahorses mainly supplies Traditional Chinese Medicine and still relies on blurry trade chains that often cover less sustainable practices targeting these pricey and endangered fish. As such, reliable tools that allow the enforcement of traceability, namely to confirm the geographic origin of traded seahorses, are urgently needed. The present study evaluated the use of elemental fingerprints (EF) in the bony structures of long-snouted seahorses Hippocampus guttulatus raised in captivity in two different locations (southern Portugal and Northern Spain) to discriminate their geographic origin. The EF of different body parts of H. guttulatus were also evaluated as potential proxies for the EF of the whole body, in order to allow the analysis of damaged specimens and avoid the use of whole specimens for analysis. The contrasting EF of H. guttulatus raised in the two locations allowed their reliable discrimination. Although no single body part exactly mimicked the EF of the whole body, seahorse trunks, as well as damaged specimens, could still be correctly allocated to their geographic origin. This promising forensic approach to discriminate the geographic origin of seahorses raised in captivity should now be validated for wild conspecifics originating from different locations, as well as for other species within genus Hippocampus.

Environmental Impact Assessment in the Former Mining Area of Regoufe (Arouca, Portugal): Contributions to Future Remediation Measures.

The W-Sn Regoufe mine, closed since the 1970s, was once intensively exploited for tungsten concentrates. Throughout its activity, considerable amounts of arsenopyrite-rich mine wastes were produced and, to this day, are still exposed to weathering conditions. Thus, this work aims at assessing soil contamination, using a combination of chemical, physicochemical and mineralogical analyses and sequential selective chemical extraction of the main potentially toxic elements (PTEs) in topsoils. Results show that Regoufe soils are enriched in most of the PTEs associated with the ore assemblage, but As and Cd contents far outstrip both international and national guidelines. The estimated contamination factor reveals that 67% of soil samples are classified as highly to ultra-highly contaminated. Similar distribution patterns, with the main focus around the unsealed mine adits, are observed when spatially projecting the modified degree of contamination (mCd) and arsenic contents. Fe-oxyhydroxides and organic matter demonstrate to have a preponderant role in the retention of Cd and As. In fact, despite the high PTE contents in soils, local surface waters are characterised by low metal(loid) contents and nearly neutral pH, with PTE concentrations below national thresholds for irrigation waters.

Sources of carbohydrates on bulk deposition in South-Western of Europe.

Scarce information is available concerning the presence of carbohydrates in rainwater. The existence of carbohydrates in bulk deposition at the town of Estarreja (Portugal), at industrial (I) and background (BG) locals, in winter and spring seasons 2016, was assessed. Seventeen carbohydrates and related compounds were identified: monosaccharides (ribose, arabinose, xylose, glucose, galactose, fructose), disaccharides (sucrose, trehalose, maltose, cellobiose), polyols (arabinitol, xylitol, myo-inositol, mannitol, glucitol, maltitol), and the anhydromonosaccharide levoglucosan. Higher content of carbohydrates was observed in spring (BG: 670 nM; I: 249 nM) than in winter (BG: 168 nM; I: 195 nM), and fructose was the carbohydrate with the highest contribution in both seasons (spring: 32%/44% (I/BG); winter: 24% (at both sites)). Fructose, myo-inositol, glucose and sucrose showed higher volume-weighted averages (VWA) concentrations in spring than in winter, possibly due to biogenic emissions typical of spring, such as pollen, and fungal spores for myo-inositol. Fructose may have derived from isomerization of glucose in biomass burning, namely in winter. Levoglucosan and galactose presented higher VWA concentration in winter than in spring, suggesting a seasonal effect related with the biomass combustion. The carbohydrates VWA concentrations were similar for samples associated with maritime and terrestrial air masses, indicating that local sources were their main contributors. Source assessment of carbohydrates by factor analysis suggested: biogenic sources for the arabinitol, myo-inositol, glucose, fructose and sucrose; soil dust for the trehalose; and anthropogenic sources from biomass burning for the galactose, arabinose and levoglucosan. The bulk deposition showed to be fundamental on removing carbohydrates from the atmosphere.

Respiratory bioaccessibility and solid phase partitioning of potentially harmful elements in urban environmental matrices.

Studies regarding the role of geochemical processes in urban environmental matrices (UEM) and their influence on respiratory bioaccessibility in humans are scarce in humid tropical regions, especially in Brazil. Contaminated UEM are potentially hazardous to humans if particles <10 µm in diameter are inhaled and reach the tracheobronchial region. In this study, we evaluated samples collected in Brazilian UEMs with a large environmental liability left by former mining industries and in a city with strong industrial expansion. UEM samples were classified into soil, sediment and mine tailings according to the characteristics of the collection sites. The respiratory bioaccessibility of potentially harmful elements (PHE) was evaluated using artificial lysosomal fluid (ALF, pH 4.5), and the BCR-sequential extraction was performed to evaluate how the respiratory bioaccessibility of the PHE was related to the solid phase partitioning. The bioaccessible fraction (BAF) ranged from 54 to 98% for Cd; 21-89% for Cu; 46-140% for Pb, 35-88% for Mn and; 41-84% for Zn. The average BAF of the elements decreased in the following order: Soil: Cd > Pb > Mn > Zn > Cu; Tailing: Pb > Cd > Zn > Mn > Cu; and Sediments: Pb > Mn > Cd > Zn > Cu. BCR-fractions were useful to predict the PHE bioaccessibility (R2 = 0.79-0.98), thus suggesting that particle geochemistry and mineralogy can influence PHE behaviour in the pulmonary fluid. Therefore, this approach provides a combination of quantitative and qualitative data, which allows us to carry out a more realistic assessment of the current situation of the potentially contaminated site and possible alternatives for decision making by the stakeholders.

In vitro assessment of oral and respiratory bioaccesibility of trace elements of environmental concern in Greek fly ashes: Assessing health risk via ingestion and inhalation.

Fly ash engender significant environmental and human health problems due to enhanced contents of potentially harmful trace elements (TrElems). This study aims to evaluate human exposure to TrElems via a combined ingestion (i.e., oral bioaccessibility) and inhalation (i.e., respiratory bioaccessibility) pathway. Five fly ash samples were collected from power plants operating in the main lignite basins of Greece, while the ingestible (<250 µm) and inhalable (<10 µm) particle size fractions were utilized. The Unified Bioaccessibility Method (UBM) was utilized to assess the oral bioaccessibility, while the respiratory bioaccessible fractions were extracted using the Artificial Lysosomal Fluid (ALF). All studied FAs exhibited significantly higher contents in Ba, Cr, Ni, V and Zn. Cadmium was presented relative enriched in the finer size fraction (<10 µm), while Ba, Co, Cr, Cu, Mn, Ni and V were depleted. The UBM-extractable concentrations fluctuated greatly among the studied FAs, while notably lower bioaccessible contents were recorded in the gastrointestinal phase. On the other hand, ALF-extractable concentrations were surprisingly higher than the corresponding UBM-extractable ones in the gastric phase. The oral bioaccessibility of the studied TrElems ranged from 12.5 to 100%, while respiratory bioaccessibility presented high values exceeding 45% on average. A significant effect of fly ash type on human bioaccessibility was revealed. Thus, high-Ca FAs exhibited significantly higher bioaccessibility of the studied TrElems via ingestion, while a relatively higher bioaccessibility via inhalation was observed for high-Si FAs. Regarding non-carcinogenic health risk via ingestion and inhalation, Cr and Co exhibited the highest HQing and HQinh values, however there were significantly lower than safe level (HQ < 1). On the contrary, Cr was the dominant contributor to carcinogenic risk with CR values being well above threshold or even tolerable risk levels.