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This paper reports a laboratorial internship included in the Portuguese Science and Technology promotion program "Internships for Young People in Laboratories (Ciência Viva no Laboratório)", which provided high school students an opportunity to approach the reality of scientific and technological research in a higher education institution. During this internship, students acquired knowledge related to the assessment of the total antioxidant capacity (TAC) of fruits and their byproducts while learning techniques, such as molecular spectrophotometry, as an analytical methodology to measure TAC using the ferric reducing antioxidant power (FRAP) and the total phenolic content (TPC) assays. First, the students were introduced to solid-liquid extraction as a conventional technique to extract antioxidants from the selected matrices. In order to optimize the extraction yield, different solvents, temperatures, and extraction times were used. Then, the students developed skills on TPC and FRAP assays by performing calibration curves using standard antioxidants, namely, gallic acid and ascorbic acid, prior to the measurement of the TAC of fruits (apple and orange) and respective byproducts. Final analysis included TAC values for comparison between fruits and their byproducts and also the influence of the extraction conditions on the TAC levels. At the end, the students presented their findings in a scientific poster and in a postlaboratory quiz. This laboratorial internship has been carried out since 2012 and was designed to be performed during a week, 7 h per day, in groups of two young students.

The acorn, a fruit of the Quercus genus, is abundant in Portugal and offers a high nutritional content, including essential minerals and vitamins, unsaturated fatty acids, and bioactive compounds like tannins, phenolic acids, and flavonoids. Despite their antioxidant properties, excessive consumption of tannins can cause health problems due to their effect on protein bioavailability. This study evaluated two extraction techniques, water immersion at room temperature for seven days and thermal hydrolysis via boiling for 30 min, and their effects on acorns' tannin and mineral content. The results reveal that both extraction methods are viable options for extracting tannins, although they also reduce some important minerals. [ABSTRACT FROM AUTHOR]

Wildfires can cause serious imbalances in ecosystems, primarily at the soil level, making it vulnerable to degradation processes such as erosion. During and after a fire, changes occur in soil properties, including pH, which affects the solubility and availability of nutrients. Currently, there is a great diversity of protocols, some involving normalized standards, to determine soil pH, but there is no consensual or universal analytical method for this parameter, especially in burned soils, in which mineral and organic fractions could have been modified. Therefore, the objective of the present work is to evaluate the effect that variations in these analytical protocols may have on pH results. For this, five methods commonly found in the international bibliography for the analysis of pH of soil in water (pHH2O) were selected and compared to propose the most precise procedure. The analytical methods were applied to 43 soil samples, collected in a plot subjected to prescribed burning in the Parque Natural de Montesinho (Northern Portugal). The studied methods differ in the following protocol items: water suspension ratio (1:2.5 or 1:5), mechanical stirring time in the suspension (10 min or 1 h), and in the resting time for the solid particles to settle (15 min or 8 h). The obtained results point to the suitability of the five methods used for soil pH analysis, indicating that there are no statistically significant differences. However, results also allow suggesting a more appropriate method concerning practical reasons, such as labor in a lab. Thus, to make the analysis process more profitable, M2 is a good option because it uses a small amount of sample (5 g), short agitation (10 min) and settling time (15 min). In turn, M1 and M5, which use a lower proportion of soil (1:2.5) show lower pH variation in the measurements. This fact may be explained by a smaller dilution effect. Considering that these two methods differ in the settling time, it is suggested to apply M1, because only 15 min are required. Therefore, the main conclusion reached with this work is that the measurement of soil pH using M1, i.e., a soil:water ratio of 1:2.5, with agitation of 10 min and settling time of 15 min, is a robust and more expeditious protocol to be applied to soil samples after a fire. [ABSTRACT FROM AUTHOR]

The aims of this study were to characterize the exposure of pregnant women living in Portugal to 3-phenoxybenzoic acid (3-PBA) and to evaluate the association of this exposure with maternal outcomes and newborn anthropometric measures. We also aimed to compare exposure in summer with exposure in winter. Pregnant women attending ultrasound scans from April 2018 to April 2019 at a central hospital in Porto, Portugal, were invited to participate. Inclusion criteria were: gestational week between 10 and 13, confirmed fetal vitality, and a signature of informed consent. 3-PBA was measured in spot urine samples by gas chromatography with mass spectrometry (GC-MS). The median 3-PBA concentration was 0.263 (0.167; 0.458) µg/g creatinine (n = 145). 3-PBA excretion was negatively associated with maternal pre-pregnancy body mass index (BMI) (p = 0.049), and it was higher during the summer when compared to winter (p < 0.001). The frequency of fish or yogurt consumption was associated positively with 3-PBA excretion, particularly during the winter (p = 0.002 and p = 0.015, respectively), when environmental exposure is low. Moreover, 3-PBA was associated with levothyroxine use (p = 0.01), a proxy for hypothyroidism, which could be due to a putative 3-PBA—thyroid hormone antagonistic effect. 3-PBA levels were not associated with the anthropometric measures of the newborn. In conclusion, pregnant women living in Portugal are exposed to 3-PBA, particularly during summer, and this exposure may be associated with maternal clinical features. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous global pollutants that are lipophilic, bioaccumulative and can be both endocrine disruptors and carcinogens. In this study, we measured 18 PAHs among decapod shrimp samples (Palaemon spp.) collected during the spring and autumn from multiple locations along the Portuguese coastal, including local markets and aquaculture farms. ΣPAH concentrations in samples ranged from 3.14 to 320.48 ng/g (ww) with the highest value in this range detected in a sample provided from an aquaculture facility. Fifteen of the 18 scanned PAHs were present in shrimp samples. However, detectable concentrations (0.07 ng/g ww) of the carcinogenic benzo-a-pyrene occurred for a single sample only and approached method detection limits. No significant differences in shrimp ΣPAH concentrations were evident between the spring and autumn seasons. Target hazard quotient estimation suggested low probability of adverse health effects to consumers through consumption of shrimp from the study collection locations. [ABSTRACT FROM AUTHOR]

Lack of knowledge about iodine has been suggested as a risk factor for iodine deficiency in pregnant women, but no studies have addressed this issue in Portugal. So, the aim of this study was to investigate iodine knowledge among Portuguese pregnant women and its association with iodine status. IoMum, a prospective observational study, included 485 pregnant women recruited at Centro Hospitalar e Universitário de S. João, Porto, between the 10th and 13th gestational weeks. Partial scores for knowledge on iodine importance, on iodine food sources or on iodised salt were obtained through the application of a structured questionnaire. Then, a total iodine knowledge score was calculated and grouped into low, medium and high knowledge categories. Urinary iodine concentration (UIC) was measured in spot urine samples by inductively coupled plasma MS. Of the pregnant women, 54 % correctly recognised iodine as important to neurocognitive development, 32 % were unable to identify any iodine-rich food and 71 % presented lack of knowledge regarding iodised salt. Of the women, 61 % had a medium total score of iodine knowledge. Knowledge on iodine importance during pregnancy was positively associated with iodine supplementation and also with UIC. Nevertheless, median UIC in women who correctly recognised the importance of iodine was below the cut-off for adequacy in pregnancy (150 µg/l). In conclusion, knowledge on iodine importance is positively associated with iodine status. Despite this, recognising iodine importance during pregnancy may not be sufficient to ensure iodine adequacy. Literacy-promoting actions are urgently needed to improve iodine status in pregnancy. [ABSTRACT FROM AUTHOR]

The role of milk and dairy products in supplying iodine to pregnant women is unknown in Portugal. The aim of this study was to evaluate the association between milk and dairy product consumption and the iodine status of pregnant women in the IoMum cohort of the Oporto region. Pregnant women were recruited between 10 and 13 weeks of gestation, when they provided a spot urine sample and information on lifestyle and intake of iodine-rich foods. Urinary iodine concentration (UIC) was determined by inductively coupled plasma MS. A total of 468 pregnant women (269 iodine supplement users and 199 non-supplement users) were considered eligible for analysis. Milk (but not yogurt or cheese) intake was positively associated with UIC, in the whole population (P = 0·02) and in the non-supplement users (P = 0·002), but not in the supplement users (P = 0·29). In non-supplement users, adjusted multinomial logistic regression analysis showed that milk consumption <3 times/month was associated with a five times increased risk of having UIC < 50 µg/l when compared with milk consumption ≥2 times/d (OR 5·4; 95 % CI 1·55, 18·78; P = 0·008). The highest UIC was observed in supplement users who reported consuming milk once per d (160 µg/l). Milk, but not yogurt or cheese, was positively associated with iodine status of pregnant women. Despite the observed positive association, daily milk consumption may not be sufficient to ensure adequate iodine intake in this population. [ABSTRACT FROM AUTHOR]

Investigation during 11-month period was performed to study the presence of caffeine in the Lis River in Leiria Town in Portugal, and a monitoring during 9-month period was realized to check the contribution of the human pollution of two wastewater treatment plants (WWTPs) that discharge their effluents to the studied river. The samples were collected in five sampling points along the river and in two influents and two effluents of the studied WWTPs. Caffeine was detected in all ninety-one collected samples. The caffeine concentration ranged from 25.3 to 321 ng/L in the river samples, from 112 to 1927 ng/L in the WWTP effluents, and from 9478 to 83,901 ng/L in the WWTP influents. The highest concentration in the river was detected in the two sampling points located after the effluent discharge points and reached 315 and 321 ng/L. Risk assessment was performed for three trophic levels using the risk quotient calculation and revealed that caffeine do not cause toxic effect on Daphnia magna and on fish but could be possibly toxic to algae. The results proved that caffeine can be an effective indicator of human-born pollution. [ABSTRACT FROM AUTHOR]

Fitness centres (FC) represent a unique indoor microenvironment. Exercising on regular basis provides countless health benefits and improves overall well-being, but if these facilities have poor indoor air quality, the respective exercisers might be subjected to some adverse risks. Considering the limited existent data, this work aimed to evaluate particulate pollution (PM 10, PM 2.5 , and ultrafine particles – UFP) in indoor air of FC and to estimate the respective risks for occupants (both staff and exercising subjects). Sampling was conducted during 40 consecutive days of May–June 2014 in general fitness areas, studios and classrooms (for group activities) of four different fitness centres (FC1–FC4) situated within Oporto metropolitan area, Portugal. The results showed that across the four FC, PM 10 ranged between 5 and 1080 μg m −3 with median concentrations (15–43 μg m −3 ) fulfilling the limit (50 μg m −3 ) of Portuguese legislation in all FC. PM 2.5 (medians 5–37 μg m −3 ; range 5–777 μg m −3 ) exceeded thresholds of 25 μg m −3 at some FC, indicating potential risks for the respective occupants; naturally ventilated FC exhibited significantly higher PM ranges ( p < 0.05). Similarly, UFPs (range 0.5–88.6 × 10 3 # cm −3 ) median concentrations were higher (2–3 times) at FC without controlled ventilation systems. UFP were approximately twice higher ( p < 0.05) during the occupied periods (mean of 9.7 × 10 3 vs . 4.8 × 10 3 # cm −3 ) with larger temporal variations of UFP levels observed in general fitness areas than in classrooms and studios. Cardio activities (conducted in studios and classrooms) led to approximately twice the UFPs intakes than other types of exercising. These results indicate that even short-term physical activity (or more specifically its intensity) might strongly influence the daily inhalation dose. Finally, women exhibited 1.2 times higher UFPs intake than men thus suggesting the need for future gender-specific studies assessing UFP exposure. [ABSTRACT FROM AUTHOR]

Bathing water quality standards are based on international standards and legislations. However, in Europe, only the microbiological parameters are to be accomplished. Recent research has focused on chemical indicators that can determine human fecal contaminants in water. Therefore, the suitability of caffeine as a chemical marker of seawater pollution in the north Portuguese coastal area in the Atlantic Ocean during the bathing season was assessed in this study. The quality of water from the coasts of five cities was monitored. 101 seawater samples were collected from 14 beaches, and their water quality was classified as sufficient, good, and excellent. Caffeine was detected in all samples in concentration range of 18 to 525 ng/L. The highest average concentration of caffeine was found in seawater samples collected in July from beaches classified as having sufficient water quality, which were located in cities with high population density and high tourist affluence. [ABSTRACT FROM AUTHOR]

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 µg kg−1for fluazifop-p-butyl to 50 µg kg−1for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits. [ABSTRACT FROM AUTHOR]

Ibuprofen is amongst the most worldwide consumed pharmaceuticals. The present work presents the first data in the occurrence of ibuprofen in Portuguese surface waters, focusing in the north area of the country, which is one of the most densely populated areas of Portugal. Analysis of ibuprofen is based on pre-concentration of the analyte with solid phase extraction and subsequent determination with liquid chromatography coupled to fluorescence detection. A total of 42 water samples, including surface waters, landfill leachates, Wastewater Treatment Plant (WWTP), and hospital effluents, were analyzed in order to evaluate the occurrence of ibuprofen in the north of Portugal. In general, the highest concentrations were found in the river mouths and in the estuarine zone. The maximum concentrations found were 48,720 ng L in the landfill leachate, 3,868 ng L in hospital effluent, 616 ng L in WWTP effluent, and 723 ng L in surface waters (Lima river). Environmental risk assessment was evaluated and at the measured concentrations only landfill leachates reveal potential ecotoxicological risk for aquatic organisms. Owing to a high consumption rate of ibuprofen among Portuguese population, as prescribed and non-prescribed medicine, the importance of hospitals, WWTPs, and landfills as sources of entrance of pharmaceuticals in the environment was pointed out. Landfill leachates showed the highest contribution for ibuprofen mass loading into surface waters. On the basis of our findings, more studies are needed as an attempt to assess more vulnerable areas. [ABSTRACT FROM AUTHOR]

This study focused on the occurrence of several EDCs including bisphenol A, estrone (E1), the 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) in fourteen rivers of Portugal. Samples analysis revealed a widespread contamination of BPA especially in Ave, Cávado, Douro, Ferro, Sousa and Vizela Rivers. Achieving 98.4 ng/L for the highest concentration. The estrogens achieved above the method quantification limit (MQL) were E1 in Águeda River and E2 in Ave, Lima and Tâmega Rivers. The maximum concentration detected for E1 was 26.9 ng/L. EE2 was detected only below MQL. [ABSTRACT FROM AUTHOR]

Pesticides are among the most widely used chemicals in the world. Because of the widespread use of agricultural chemicals in food production, people are exposed to low levels of pesticide residues through their diets. Scientists do not yet have a total understanding of the health effects of these pesticide residues. This work aims to determine differences in terms of pesticide residue content in Portuguese strawberries grown using different agriculture practices. The Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method was conducted and shown to have good performance for multiclass pesticides extraction in strawberries. The screening of 25 pesticides residue was performed by gas chromatography-tandem mass spectrometry. In quantitative validation, acceptable performances were achieved with recoveries of 70-120 and <12 % residual standard deviation for 25 pesticides. Good linearity was obtained for all the target compounds, with highly satisfactory repeatability. The limits of detection were in the range of 0.1-28 μg/kg. The method was applied to analyze strawberry samples from organic and integrated pest management (IPM) practices harvested in 2009-2010. The results showed the presence of fludioxonil, bifenthrin, mepanipyrim, tolylfluanid, cyprodinil, tetraconazole, and malathion when using IPM below the maximum residue levels. [ABSTRACT FROM AUTHOR]

The total lipid content and lipidic profile of seaweeds harvested in the North Coast and purchased in Portugal were determined in this paper. The amount of total lipids in the different species of seaweeds varied between 0.7 ± 0.1% (Chondrus crispus) and 3.8 ± 0.6% (Ulva spp.). Regarding the fatty acid content, polyunsaturated fatty acids (PUFA) ranged between 0–35%, with Ulva spp. presenting the highest amount; monounsaturated fatty acids (MUFA) varied between 19 and 67%; and saturated fatty acids (SFA) were predominant in C. crispus (45–78%) and Gracilaria spp. (36–79%). Concerning the nutritional indices, the atherogenicity index (AI) was between 0.4–3.2, the thrombogenicity index (TI) ranged from 0.04 to 1.95, except for Gracilaria spp., which had a TI of 7.6, and the hypocholesterolemic/hypercholesterolemic ratio (HH) values ranged between 0.88–4.21, except for Gracilaria spp., which exhibited values between 0.22–9.26. The n6/n3 ratio was below 1 for most of the species evaluated, except for Ascophyllum nodosum, which presented a higher value, although below 2. Considering the PUFA/SFA ratio, seaweeds presented values between 0.11–1.02. The polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHCs) contamination of seaweeds under study was also quantified, the values found being much lower than the maximum levels recommended for foodstuff. [ABSTRACT FROM AUTHOR]

The present work aimed at studying Saccorhiza polyschides extracts obtained by subcritical water extraction as a potential source of essential macro and trace elements, aiming for its potential application as a biofertilizer. The mineral composition, as well as sulfate, chlorine and iodine, total organic matter, and total nitrogen content, were determined on the extracts obtained from seaweeds harvested during low tide at the northern Portuguese coast. The selected parameters are important for a biofertilizer. Among the macronutrients, the most abundant was K (15.7 ± 0.2 g/L), followed by Na (5.46 ± 0.11 g/L), S (1.52 ± 0.06 g/L), Ca (1.09 ± 0.11 g/L), and Mg (1.02 ± 0.08 g/L). Several important micronutrients (Zn, B, Cl, P, Mo, V, Se, and I) have also been found in the extracts. The total organic matter was 34.1 ± 0.3 g/L. The extracts present low levels of toxic compounds such as Ni, Cd, and Pb. Considering the composition of the obtained extracts, these can find application in the development of fertilization products. The composition of subcritical water extracts of S. polyschides suggests that they may have important characteristics as a biofertilizer and can be an option in biofortification experiments with essential nutrients. The method can be easily scaled up which makes it attractive for agricultural applications. [ABSTRACT FROM AUTHOR]

Antibiotics are the most consumed therapeutic classes worldwide and are released to the environment in their original form as well as potentially active metabolites and/or degradation products. Consequences of the occurrence of these compounds in the environment are primarily related to bacterial resistance development. This work presents a validated analytical method based on solid phase extraction (SPE) using HLB cartridges, followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) for quantification of seven different fluoroquinolone antibiotics, namely ciprofloxacin (CPF), enrofloxacin (ENR), lomefloxacin (LOM), norfloxacin (NOR), ofloxacin (OFL), prulifloxacin (PLF) and moxifloxacin (MOX) and its application to detect the target compounds in influents and effluents of wastewater treatment plants (WWTP). Linearity was established through calibration curves in solvent and matrix match using internal calibration method in the range of 50–1300 ng L−1 and all the fluoroquinolones showed good linear fit (r2 ≥ 0.991). Accuracy ranged between 80.3 and 92.9%, precision was comprised between 7.2 and 14.6%, and 10.7 and 18.1% for intra- and inter-batch determinations, respectively. Method detection and quantification limits ranged from 6.7 to 59.0 ng L−1 and 22.3–196.6 ng L−1, respectively. Influents and effluents of fifteen WWTPs of North of Portugal were analyzed. OFL was the fluoroquinolone found at the highest concentration, up to 4587.0 ng L−1 and 987.9 ng L−1, in influent and effluent, respectively. NOR and PLF were not detected. Image 1 • FQs were analyzed in thirty WWTP samples (influent and effluent) from fifteen WWTPs. • High concentration of ciprofloxacin and ofloxacin was found in WWTP influents. • Ofloxacin was quantified in most of all WWTP effluents. • Important information about FQs in WWTP with different removal systems. The present works characterizes WWTP influents and effluents regarding seven different fluoroquinolone antibiotics in fifteen Portuguese northern WWTPs with diverse operational features and treatment procedures. [ABSTRACT FROM AUTHOR]

The electrooxidative behavior of pravastatin (PRV) in aqueous media was studied by square-wave voltammetry at a glassy-carbon electrode (GCE) and at a screen-printed carbon electrode (SPCE). Maximum peak current intensities in a pH 5.0 buffer were obtained at +1.3 V vs. AgCl/Ag and +1.0 V vs. Ag for the GCE and SPCE surface respectively. Validation of the developed methodologies revealed good performance characteristics and confirmed their applicability to the quantification of PRV in pharmaceutical products, without significant sample pretreatment. A comparative analysis between the two electrode types showed that SPCEs are preferred as an electrode surface because of their higher sensitivity and the elimination of the need to clean the electrode's surface for its renewal, which frequently is, if not always, the rate-limiting step in voltammetric analysis. [ABSTRACT FROM AUTHOR]

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75–100mgL−1. The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9–39.5, 18.6–32.0 and 32.3–50.4mgg−1, respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents. [Copyright &y& Elsevier]

The occurrence of 33 pharmaceuticals and metabolites was evaluated along the Lis river and in the influents and effluents of two wastewater treatment plants (WWTPs) located along the river. Results indicate that pharmaceuticals, such as ibuprofen, ketoprofen, carbamazepine and fluoxetine, and the metabolite salicylic acid are widespread along the Lis river, showing 100% of detection frequency, at levels up to 1.3 μg L –1 . The number of molecules detected increased along the river, with 11 molecules in the source, 15 upstream WWTP 1, 16 downstream WWTP 1 and upstream WWTP 2 and 19 downstream WWTP 2. The highest concentrations were often found downstream near the river mouth. Different possible sources of contamination of the Lis river were identified, namely WWTP effluents, untreated wastewaters and livestock production. Nevertheless, the discharge of WWTP effluents appeared to be the most pronounced, given that, in general, it was noticed an increase in the concentration of pharmaceuticals downstream of the WWTPs. WWTP effluents contributed with a total mass load of pharmaceuticals into the Lis river between 470 and 2317 mg/d/1000 inhabitants. Non-steroidal anti-inflammatory drugs/analgesics were the therapeutic group with a high contribution to the total mass load of pharmaceuticals entering the Lis river, followed by psychiatric drugs and antibiotics. No seasonal variation was observed for the detected concentrations of pharmaceuticals. At the levels detected in the Lis river, sulfamethoxazole, clarithromycin, azithromycin and ibuprofen showed to have potential risk for aquatic organisms. These findings show that further studies embracing different environmental compartments (water, sediment and biota) are needed, in order to evaluate the partition/distribution of pharmaceuticals, their metabolites and transformation products in the environment as well as to predict their possible impact to non-target organisms and, in a last instance, to human health. [ABSTRACT FROM AUTHOR]

Abstract: Air pollution represents a serious risk not only to environment and human health, but also to historical heritage. In this study, air pollution of the Oporto Metropolitan Area and its main impacts were characterized. The results showed that levels of CO, PM10 and SO2 have been continuously decreasing in the respective metropolitan area while levels of NOx and NO2 have not changed significantly. Traffic emissions were the main source of the determined polycyclic aromatic hydrocarbons (PAHs; 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in air of the respective metropolitan area. The mean concentration of 18 PAHs in air was 69.9±39.7ngm−3 with 3–4 rings PAHs accounting for 75% of the total ΣPAHs. The health risk analysis of PAHs in air showed that the estimated values of lifetime lung cancer risks considerably exceeded the health-based guideline level. Analytical results also confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere. FTIR and EDX analyses showed that gypsum was the most important constituent of black crusts of the characterized historical monument Monastery of Serra do Pilar classified as “UNESCO World Cultural Heritage”. In black crusts, 4–6 rings compounds accounted approximately for 85% of ΣPAHs. The diagnostic ratios confirmed that traffic emissions were the major source of PAHs in black crusts; PAH composition profiles were very similar for crusts and PM10 and PM2.5. [Copyright &y& Elsevier]

Abstract: This study reports the levels of nitrate and nitrite of 34 vegetable samples, including different varieties of cabbage, lettuce, spinaches, parsley and turnips, collected in several locations of an intensive agricultural area (Modivas, Vila do Conde, northern Portugal). Nitrate levels ranged between 54 and 2440mg kg−1, while nitrite levels ranged between 1.1 and 57mg kg−1. The maximum residue levels established for nitrate in spinach and lettuce samples were not exceeded. Nitrate and nitrite levels reported in the literature for the same type of samples are reviewed, as well as the contribution of vegetables to nitrate and nitrite dietary exposure of populations. [Copyright &y& Elsevier]

The goal of this study was to examine how IQ changes (the Flynn effect) among school-aged children in Portugal behaved over a period of 25 years (1991, 2008 and 2016) that registered major economic transformations in the country. The country's initial move to prosperity was followed by a recent move into recession, which might affect IQ gains. Changes in IQ by level of intellectual ability were also inspected. Children's scores on Raven's Coloured Progressive Matrices in Portugal were compared between the years 1991, 2008 and 2016. Differences in IQs were calculated according to Flynn's (1987) procedures. In addition, percentile distributions of children's scores in the period of economic growth (between 1991 and 2008) were compared for inspection of IQ changes across levels of intellectual ability. Results showed an IQ gain of 2.6 points per decade from 1991 to 2008, followed by a smaller increase (of 1.7 points per decade) from 2008 to 2016, with negative gains observed for seven-, eight- and 10-year-old children. The gains in IQ from 1991 to 2008 have occurred mainly for lower levels of intellectual ability. IQ relative gains accompanied the country's economic fluctuations, and children in lower levels of intellectual ability seemed to have benefitted the most from the economic growth. The trends in the country are suggestive of the influence of economic fluctuations on family dynamics, which, although moderated by education, have consequences for children's cognitive development. • Portuguese school children's IQ has increased over the past 25 years. • IQ gains were smaller after 2008. • The gains in IQ have occurred mainly for lower levels of intellectual ability. [ABSTRACT FROM AUTHOR]

Obesity is a worldwide multifactorial disease linked to persistent pollutants exposure amongst other factors. Humans are daily exposed to an assort of pollutants, such as polychlorinated biphenyls, brominated flame retardants and synthetic musks. These, also known as endocrine disruptors, were all found in human adipose tissue, the preferable matrix for the assessment of long-time accumulation. There are several accounts of hazardous effects of polychlorinated biphenyls and brominated flame retardants on the human organism, whereas for synthetic musks little is still known. Hence, in this study, the levels of polychlorinated biphenyls, brominated flame retardants, and synthetic musks were measured in samples of adipose tissue from 188 Obese Portuguese Women (subcutaneous or scAT and visceral or vAT). After which, associations between pollutants levels and several biochemical parameters from assorted of metabolic processes were studied. Brominated flame retardants were not found in any sample analysed, synthetic musks were found in all the samples analysed (100 % detection frequency) with median levels of 0.4 ± 0.6 μg/g in scAT and 0.4 ± 0.7 μg/g in vAT and polychlorinated biphenyls were found in the majority of samples (<90 % detection frequency) with median levels of 0.1 ± 0.3 μg/g in both tissues. Median concentrations of synthetic musks and polychlorinated biphenyls were similar between scAT and vAT. In total 315 associations were achieved with pollutants levels in adipose tissue, including 273 Spearman's correlations (146 negative and 127 positive). Additionally, 3 multiple linear regressions were achieved. Synthetic musks behave differently than polychlorinated biphenyls and other well-known persistent pollutants in the human body. Synthetic musks behaviour is yet poorly known and their high levels and detection frequencies enforces the need for more studies about their impact on human health. Understanding how these chemicals alter the metabolism is crucial knowledge and hopefully will contribute to improving the treatment and follow-up of obesity in the female population., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The goal of this work was to examine whether elevated iodine intake was associated with adverse effects on IQ among school-age children in Portugal. In a representative sample of children from the north of the country, IQ percentiles by age (assessed with Raven’s Colored Progressive Matrices) were dichotomized to <50 (“below-average” IQs) and ≥50. Morning urine iodine concentrations, corrected for creatinine, were dichotomized to <250 µg/g and ≥250 µg/g, according to the European Commission/Scientific Committee on Food’s tolerable upper level of daily iodine intake for young children. Data were examined with Chi-square tests, logistic regression, and GLM univariate analysis. The sample (N = 1965) was classified as generally iodine-adequate (median urinary iodine concentration = 129 µg/L; median iodine-to-creatinine ratio = 126 µg/g) according to the WHO’s criteria. A greater proportion of children in the ≥250 µg/g group had below-average IQs, compared to children with less than 250 µg/g (p = 0.037), despite a sizable (though non-significant) proportion of children in the less-than-250 µg/g group also presenting below-average IQs, at the bottom of the iodine distribution (<50 µg/g). The proportion of below-average IQs increased with increasingly elevated iodine concentrations (p = 0.047). The association remained significant after the adjustment for confounders, with the elevated iodine group showing increased odds of having below-average IQs when compared with the non-elevated iodine group (OR 1.55; 95% CI 1.11−2.17; p = 0.011). Consistently, the former group presented a lower mean IQ than the latter (p = 0.006). High iodine intake was associated with lower IQs even in a population classified as iodine-adequate. These results bear on child cognition and on initiatives involving iodine supplementation.

Every year, after grape harvesting, high quantities of vine-canes are generated. Due to the high amount of bioactive compounds present in this woody material, several studies reported their potential to be used in different sustainable applications. However, before employing vine-canes in this kind of products, their safety needs to be assessed. A robust method for identification and quantification of 30 environmental contaminants (12 organochloride pesticides (OCPs), 6 organophosphorus pesticides (OPPs), 5 polychlorinated biphenyls (PCBs) and 7 brominated flame retardants (BFRs)) in vine-canes was developed. For that, the extraction and clean-up procedures were optimized, namely the vine-canes size, the QuEChERS (quick, easy, cheap, effective, rugged and safe) composition and the amount of carbon used in the dispersive-solid phase extraction (d-SPE). Suitable analytical parameters were obtained: linearity (r 2 ) >0.99 for all the studied compounds and for the solvent and matrix-matched standards; relative standard deviation (RSD) below 14%; and mean recoveries for two spiking levels (10 and 20 μg/kg) between 75 and 103%, excepting for the PCBs that ranged between 59 and 105%. The limit of detection (LOD) and quantification (LOQ) ranged between 0.38 and 1.09 and 1.26 to 3.64 μg/kg, respectively. Regarding the analysis of 19 vine-cane samples, corresponding to four different varieties (Touriga Nacional, Tinta Roriz, Alvarinho, and Loureiro) collected in four different years in the North of Portugal, five contaminants (aldrin, 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p'-DDE), α-hexachlorocyclohexane (α-HCH), 2,4,4'-trichlorobiphenyl (PCB28), and 2,2',4,5,5'-pentachlorobiphenyl (PCB101)) were detected. However, only α-HCH (5.85 ± 0.32 to 5.99 ± 0.25 μg/kg) and aldrin (2.44 ± 0.15 μg/kg) were quantified above the LOQ. The screening of environmental contaminants in vine-canes is essential to waste valorization, especially if the goal is to apply them in products for human consumption., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The development of coastal regions has contributed to the intensification of environmental contamination, which can accumulate in aquatic biota, such as shrimps. These crustaceans, besides being delicious and being a good source of nutrients, can also accumulate environmental pollutants. Amongst others, these include organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), brominated flame retardants (BFRs), polychlorinated biphenyls (PCBs) and synthetic musks (SMs). These pollutants, classified as endocrine disruptors, are related to adverse effects in humans and since one of the major routes of exposition is ingestion, this is a cause for concern regarding their presence in food. The aim of the present study was to quantify the presence of environmental pollutants in shrimp samples and in the water from their habitat along the northwest Portuguese coast. In seawater samples, only two OCPs (lindane and DDD) and one BFR (BTBPE) were detected, and in shrimp samples, one OCP (DDD) and three SMs (HHCB, AHTN and ketone) were found. Bioaccumulation and the risk assessment of dietary exposure of SMs in shrimp samples were investigated. It was observed that all shrimp samples analyzed significantly presented bioaccumulation of the three SMs found. Concentrations of SMs detected in shrimp samples do not present a health risk for the adult Portuguese population.

This work characterizes the dimension and the exceptionality of 2017 large- and mega-fires that occurred in the center region of Portugal through the assessment of their impact on the ambient levels of particulate matter (PM 10 and PM 2.5 ), retrieved from local monitoring stations, and the associated public health risks. PM 10 and PM 2.5 concentrations were increased during the occurrence of large fires and megafires, with daily concentrations exceeding the European/national guidelines in 7-14 and 1-12 days of 2017 (up to 704 µg/m 3 for PM 10 and 46 µg/m 3 for PM 2.5 ), respectively. PM 10 concentrations were correlated with total burned area (0.500 < r < 0.949; p > 0.05) and with monthly total burned area/distance 2 (0.500 < r < 0.667; p > 0.05). The forest fires of 2017 took the life of 112 citizens. A total of 474 cases of hospital admissions due to cardiovascular diseases and 3524 cases of asthma incidence symptoms per 100,000 individuals at risk were assessed due to exposure to 2017 forest fires. Real-time and in situ PM methodologies should be combined with protection action plans to reduce public health risks. Portuguese rural stations should monitor other health-relevant pollutants (e.g., carbon monoxide and volatile organic compounds) released from wildfires to allow performing more robust and comprehensive measurements that will allow a better assessment of the potential health risks for the exposed populations.

To our knowledge, this is the first study in Portugal for the analysis of both antibiotics and psychiatric drugs in river waters from Douro and Leça rivers and its sediments. Samples were extracted using solid phase extraction and QuEChERS procedures and the analysis was performed using liquid chromatography with tandem mass spectrometry. Higher number of pharmaceuticals and higher concentrations were found in the Leça river for the two matrices under study. The highest detection frequency for the twenty-seven pharmaceuticals was observed for fluoxetine with 83.3% in both matrices. None of the studied antibiotics were detected in water collected in the Douro river however six antibiotics (azithromycin, ciprofloxacin, clarithromycin, moxifloxacin, ofloxacin, and trimethoprim) were found in the Leça river. Further, the analysis of sediments exhibits the occurrence of sulfamethoxypyridazine in the Douro river and azithromycin in the Leça river. The highest concentration was observed in Leça river for azithromycin in the river water (2,819 ng/L) and sediments (43.2 ng/g). Carbamazepine, citalopram, fluoxetine, sertraline, trazodone, and venlafaxine were the psychiatric drugs detected in river waters and sediments with more diazepam as water river contamination. Concentrations ranged from

The chemical composition and daily mineral intake (DMI) of six macro (calcium, magnesium, sodium, potassium, phosphorous, and chloride) and four microminerals (copper, iron, manganese, and zinc) were determined in four types of Portuguese breads (white wheat, maize, wheat/maize, and maize/rye breads). Samples were processed with microwave assisted digestion and mineral composition was determined with a high-resolution continuum-source atomic absorption spectrometer with flame and graphite furnace. Bread contributes to an equilibrated diet since it is rich in several minerals (0.21 mg/100 g of copper in wheat bread to 537 mg/100 g of sodium in maize/rye bread). Maize/rye bread presented the highest content of all minerals (except phosphorous and chloride), while the lowest levels were mainly found in wheat bread. Median sodium concentrations (422-537 mg/100 g) represented more than 28% of the recommended daily allowance, being in close range of the maximum Portuguese limit (550 mg/100 g). Maize/rye bread exhibited the highest DMI of manganese (181%), sodium (36%), magnesium (32%), copper (32%), zinc (24%), iron (22%), potassium (20%), and calcium (3.0%). A Principal Component Analysis (PCA) model based on the mineral content allowed the differentiation among white wheat, maize, and maize/rye bread. Zinc, magnesium, manganese, iron, phosphorus, potassium, copper, and calcium proved to be good chemical markers to differentiate bread compositions.

3-Phenoxybenzoic acid (3-PBA) is a shared metabolite of several synthetic pyrethroid pesticides (SPs) resulting from environmental degradation of parent compounds and thus occurs frequently as a residue in samples. Hence, the importance of 3-PBA evaluation after pyrethroid application. There is a gap of analytical methods to determine 3-PBA in soil samples. Therefore, an analytical method that combines the solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC/MS) detection has been developed for the determination of 3-PBA in soil samples. The analytical method was validated in terms of linearity, sensitivity, intra- and inter-day batch precisions, recoveries, and quantification limits. An SPE method using a Strata X cartridge allows obtaining limits of detection and quantification equal to 4.0 and 13.3 ng g -1 , respectively. Under optimized conditions, the method average recovery levels ranged from 70.3 to 93.5% with a relative standard deviation below 3.4%. Method intra- and inter-day precision was under 5.0 and 4.8%, respectively. The developed method was applied to 11 agricultural soil samples in the north of Portugal. The developed methodology allowed for the determination of the pyrethroid metabolite, 3-PBA, in agricultural soil samples at levels of few ng g -1 . Graphical abstract ᅟ.

The occurrence of seven pharmaceuticals and two metabolites belonging to non-steroidal anti-inflammatory drugs and analgesics therapeutic classes was studied in seawaters. A total of 101 samples covering fourteen beaches and five cities were evaluated in order to assess the spatial distribution of pharmaceuticals among north Portuguese coast. Seawaters were selected in order to embrace different bathing water quality (excellent, good and sufficient). Acetaminophen, ketoprofen and the metabolite hydroxyibuprofen were detected in all the seawater samples at maximum concentrations of 584, 89.7 and 287 ng L(-1), respectively. Carboxyibuprofen had the highest seawater concentration (1227 ng L(-1)). The temporal distribution of the selected pharmaceuticals during the bathing season showed that, in general, higher concentrations were detected in August and September. The environmental risk posed by the pharmaceuticals detected in seawaters towards different trophic levels (fish, daphnids and algae) was also assessed. Only diclofenac showed hazard quotients above one for fish, representing a potential risk for aquatic organisms. These results were observed in seawaters classified as excellent bathing water. Additional data is needed in order to support the identification and prioritization of risks posed by pharmaceuticals in marine environment., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40-67ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57μg/L., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LC-PAD). Calibration curves were linear in the range of 0.5-10 mg L⁻¹ for all compounds studied. The average recoveries, measured at 0.1 mg kg⁻¹ wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

The evaluation of benzene in different environments such as indoor (with and without tobacco smoke), a city area, countryside, gas stations and near exhaust pipes from cars running on different types of fuels was performed. The samples were analyzed using gas chromatography (GC) with flame ionization detection (FID) and tandem mass spectrometric detection (MS/MS) (to confirm the identification of benzene in the air samples). Operating conditions for the GC-MS analysis were optimized as well as the sampling and sample preparation. The results obtained in this work indicate that i) the type of fuel directly influences the benzene concentration in the air. Gasoline with additives provided the highest amount of benzene followed by unleaded gasoline and diesel; ii) the benzene concentration in the gas station was always higher than the advisable limit established by law (5 μg m⁻³) and during the unloading of gasoline the achieved concentration was 8371 μg m⁻³; iii) the data from the countryside (Taliscas) and the urban city (Matosinhos) were below 5 μg m⁻³ except 5 days after a fire on a petroleum refinery plant located near the city; iv) it was proven that in coffee shops where smoking is allowed the benzene concentration is higher (6 μg m⁻³) than in coffee shops where this is forbidden (4 μg m⁻³). This method may also be helpful for environmental analytical chemists who use GC-MS/MS for the confirmation or/and quantification of benzene.