Noncompliance to iodine supplementation recommendation is a risk factor for iodine insufficiency in Portuguese pregnant women: results from the IoMum cohort.

PURPOSE: After a recommendation for iodine supplementation in pregnancy has been issued in 2013 in Portugal, there were no studies covering iodine status in pregnancy in the country. The aim of this study was to assess iodine status in pregnant women in Porto region and its association with iodine supplementation. METHODS: A cross-sectional study was conducted at Centro Hospitalar Universitário São João, Porto, from April 2018 to April 2019. Pregnant women attending the 1st trimester ultrasound scan were invited to participate. Exclusion criteria were levothyroxine use, gestational age < 10 and ≥ 14 weeks, non-evolutive pregnancy at recruitment and non-signing of informed consent. Urinary iodine concentration (UIC) was measured in random spot urine by inductively coupled plasma-mass spectrometry. RESULTS: Median UIC was 104 µg/L (IQR 62-189) in the overall population (n = 481) of which 19% had UIC < 50 µg/L. Forty three percent (n = 206) were not taking an iodine-containing supplement (ICS) and median UIC values were 146 µg/L (IQR 81-260) and 74 µg/L (IQR 42-113) in ICS users and non-users, respectively (p < 0.001). Not using an ICS was an independent risk factor for iodine insufficiency [adjusted OR (95% CI) = 6.00 (2.74, 13.16); p < 0.001]. Iodised salt use was associated with increased median iodine-to-creatinine ratio (p < 0.014). CONCLUSIONS: A low compliance to iodine supplementation recommendation in pregnancy accounted for a mild-to-moderately iodine deficiency. Our results evidence the need to support iodine supplementation among pregnant women in countries with low household coverage of iodised salt. Trial registration number NCT04010708, registered on the 8th July 2019.

Sulfadiazine removal using green zero-valent iron nanoparticles: A low-cost and eco-friendly alternative technology for water remediation.

In this work, the effectiveness of green zero-valent iron nanoparticles (gnZVIs) for the removal of the antibiotic sulfadiazine (SDZ) from water via adsorption and reduction was tested. Additionally, the effectiveness of this material as a catalyst for the Fenton and photo-Fenton processes was also investigated. This represents the first study concerning the use of gnZVIs for the degradation of a sulfonamide antibiotic. The results obtained indicate that gnZVIs were able to remove up to 58% of SDZ via adsorption and up to 69% via adsorption plus reduction using a SDZ/Fe3+ molar ratio of 1:61.6. Furthermore, gnZVIs showed strong effectiveness as a catalyst for the Fenton and photo-Fenton reactions, with complete SDZ removal in 8 h and 5 min, respectively, using a SDZ/Fe3+/H2O2 molar ratio of 1:38.4:38.4. These results demonstrate that the use of gnZVIs constitutes an attractive and potential alternative technology for water remediation, reducing environmental impact and operational costs.

Effects of single and combined exposures of gold (nano versus ionic form) and gemfibrozil in a liver organ culture of Sparus aurata.

In vitro methods have gained rising importance in ecotoxicology due to ethical concerns. The aim of this study was to assess the single and combined in vitro effects of gold, as nanoparticle (AuNPs) and ionic (Au+) form, and the pharmaceutical gemfibrozil (GEM). Sparus aurata liver organ culture was exposed to gold (4 to 7200 µg·L-1), GEM (1.5 to 15,000 µg·L-1) and combination 80 µg·L-1 gold +150 µg·L-1 GEM for 24 h. Endpoints related with antioxidant status, peroxidative/genetic damage were assessed. AuNPs caused more effects than Au+, increasing catalase and glutathione reductase activities and damaging DNA and cellular membranes. Effects were dependent on AuNPs size, coating and concentration. GEM damaged DNA at an environmentally relevant concentration, 1.5 µg·L-1. Overall, the effects of the combined exposures were higher than the predicted, based on single exposures. This study showed that liver culture can be a useful model to study contaminants effects.

Fe3O4@Au nanoparticles-based magnetoplatform for the HMGA maize endogenous gene electrochemical genosensing.

This work addresses a technological advance applied to the construction of a magnetogenoassay with electrochemical transduction for the maize taxon-specific (HMGA gene) detection using gold-coated magnetic nanoparticles as nanosized platform. Superparamagnetic core-shell Fe3O4@Au nanoparticles (10.4 ±â€¯1.7 nm) were used to assemble the genoassay through the covalent immobilization of HMGA DNA probes onto carboxylated self-assembled monolayers at the nanoparticles surface. A hybridization reaction using sandwich format was selected to prevent inefficient hybridization connected with stable secondary DNA structures using also fluorescein isothiocyanate as DNA signaling tag. The labelling of the hybridization reaction with enzymes allowed the chronoamperometric measurement of the peroxidase activity linked to the nanoplatform located on gold surface. Using this electrochemical magnetogenoassay a linear concentration range from 0.5 to 5 nM and a LOD of 90 pM with a RSD <1.2% was calculated. Certified maize was evaluated without further purification after PCR amplification. This work highlights the efficacy of the electrochemical magnetogenoassay for the HMGA detection, showing its potential as alternative procedure for the verification of the compliance of the legislation.

Electrochemical impedance spectroscopy characterization of beverages.

This paper compares the results of standard chemical analytical processes and electrochemical impedance spectroscopy (EIS) in the characterization of different beverages, namely ground coffee, soluble coffee, coffee substitutes, barley, cow milk, vegetable drinks, tea, plant infusions and plant mixtures. For the two approaches, the similarities between the experimental data are assessed by means of the Euclidean and Canberra distances. The resulting information is processed by means of the multidimensional scaling (MDS) clustering and visualization algorithm. The results of the chemical analytical processes and EIS reveal identical clusters for the two adopted distances. Furthermore, the robustness of the experimental and computational scheme are assessed by means of the Procrustes technique. The results confirm the effectiveness of combining the EIS and MDS.

Preconcentration and sensitive determination of the anti-inflammatory drug diclofenac on a paper-based electroanalytical platform.

This work describes the development of a paper-based platform for highly sensitive detection of diclofenac. The quantification of this anti-inflammatory drug is of importance in clinical (e.g. quality and therapeutic control) and environmental (e.g. emerging contaminant determination) areas. The easy-to-handle platform here described consists of a carbon-ink paper-based working electrode and two metallic wires, provided by a gold-plated standard connector, as reference and counter electrodes. The porous paper matrix enables the preconcentration of the sample, decoupling sample and detection solutions. Thus, relatively large sample volumes can be used, which significantly improves the sensitivity of the method. A wide dynamic range of four orders of magnitude, between 0.10 and 100 µM, was obtained for diclofenac determination. Due to the predominance of adsorption at the lowest concentrations, there were two linear concentration ranges: one comprised between 0.10 and 5.0 µM (with a slope of 0.85 µA µM-1) and the other between 5.0 and 100 µM (with a slope of 0.48 µA µM-1). A limit of detection of 70 nM was achieved with this simple device that provided accurate results with an RSD of ca. 5%. The platform was applied for diclofenac quantification in spiked tap water samples. The versatility of this design enabled the fabrication of a multiplexed platform containing eight electrochemical cells that work independently. The low cost, small size and simplicity of the device allow on-site analysis, which is very useful for environmental monitoring.

Application of experimental design methodology to optimize antibiotics removal by walnut shell based activated carbon.

Three-level Box-Behnken experimental design with three factors (pH, temperature and antibiotic initial concentration) combined with response surface methodology (RSM) was applied to study the removal of Metronidazole and Sulfamethoxazole by walnut shell based activated carbon. This methodology enabled to identify the effects of the different factors studied and their interactions in the response of each antibiotic. The relationship between the independent variable (sorption capacity) and the dependent variables (pH, temperature and antibiotic concentration) was adequately modelled by second-order polynomial equation. The pH factor exerted a significant but distinct influence on the removal efficiency of both antibiotics. The removal of Metronidazole is favoured by increasing pH values, with the maximum value obtained for pH 8 - upper limit of the study domain; while Sulfamethoxazole displays a maximum value around 5.5, with a decrease in the extent of adsorption as the pH increases. The best conditions, predicted by the model, for the removal of the antibiotic Sulfamethoxazole (106.9 mg/g) are obtained at a temperature of 30 °C, initial concentration of 40 mg/L and a pH value of 5.5. For the antibiotic Metronidazole, the highest removal value (127 mg/g) is expected to occur at the maximum levels attributed to each of the factors (pH = 8, Cin = 40 mg/L, T = 30 °C). The results of isotherm experiments (at 20 °C and pH 6) displayed a good agreement with the models predictions. The maximum sorption capacity, estimated by the Langmuir model, was 107.4 mg/g for Metronidazole and 93.5 mg/g for Sulfamethoxazole.

Effects and bioaccumulation of gold nanoparticles in the gilthead seabream (Sparus aurata) - Single and combined exposures with gemfibrozil.

Gold nanoparticles (AuNPs) are found in a wide range of applications and therefore expected to present increasing levels in the environment. There is however limited knowledge concerning the potential toxicity of AuNPs as well as their combined effects with other pollutants. Hence, the present study aimed to investigate the effects of AuNPs alone and combined with the pharmaceutical gemfibrozil (GEM) on different biological responses (behaviour, neurotransmission, biotransformation and oxidative stress) in one of the most consumed fish in southern Europe, the seabream Sparus aurata. Fish were exposed for 96 h to waterborne 40 nm AuNPs with two coatings - citrate and polyvinylpyrrolidone (PVP), alone or combined with GEM. Antioxidant defences were induced in liver and gills upon both AuNPs exposure. Decreased swimming performance (1600 µg.L-1) and oxidative damage in gills (4 and 80 µg.L-1) were observed following exposure to polyvinylpyrrolidone coated gold nanoparticles (PVP-AuNPs). Generally, accumulation of gold in fish tissues and deleterious effects in S. aurata were higher for PVP-AuNPs than for cAuNPs exposures. Although AuNPs and GEM combined effects in gills were generally low, in liver, they were higher than the predicted. The accumulation and effects of AuNPs showed to be dependent on the size, coating, surface charge and aggregation/agglomeration state of nanoparticles. Additionally, it was tissue' specific and dependent on the presence of other contaminants. Although, gold intake by humans is expected to not exceed the estimated tolerable daily intake, it is highly recommended to keep it on track due to the increasing use of AuNPs.

Genotoxicity of gold nanoparticles in the gilthead seabream (Sparus aurata) after single exposure and combined with the pharmaceutical gemfibrozil.

Due to their diverse applications, gold nanoparticles (AuNPs) are expected to increase of in the environment, although few studies are available on their mode of action in aquatic organisms. The genotoxicity of AuNPs, alone or combined with the human pharmaceutical gemfibrozil (GEM), an environmental contaminant frequently detected in aquatic systems, including in marine ecosystems, was examined using gilthead seabream erythrocytes as a model system. Fish were exposed for 96 h to 4, 80 and 1600 µg L-1 of 40 nm AuNPs with two coatings - citrate or polyvinylpyrrolidone; GEM (150 µg L-1); and a combination of AuNPs and GEM (80 µg L-1 AuNPs + 150 µg L-1 GEM). AuNPs induced DNA damage and increased nuclear abnormalities levels, with coating showing an important role in the toxicity of AuNPs to fish. The combined exposures of AuNPs and GEM produced an antagonistic response, with observed toxic effects in the mixtures being lower than the predicted. The results raise concern about the safety of AuNPs and demonstrate interactions between them and other contaminants.

A multibiomarker approach highlights effects induced by the human pharmaceutical gemfibrozil to gilthead seabream Sparus aurata.

Lipid regulators are among the most prescribed human pharmaceuticals worldwide. Gemfibrozil, which belongs to this class of pharmaceuticals, is one of the most frequently encountered in the aquatic environment. However, there is limited information concerning the mechanisms involved in gemfibrozil effects to aquatic organisms, particularly to marine organisms. Based on this knowledge gap, the current study aimed to assess biochemical and behavioral effects following a sublethal exposure to gemfibrozil (1.5, 15, 150, 1500 and 15,000 µg L-1) in the estuarine/marine fish Sparus aurata. After the exposure to 1.5 µg L-1 of gemfibrozil, fish had reduced ability to swim against a water flow and increased lipid peroxidation in the liver. At concentrations between 15-15,000 µg L-1, the activities of some enzymes involved in antioxidant defense were induced, appearing to be sufficient to prevent oxidative damage. Depending on the organ, different responses to gemfibrozil were displayed, with enzymes like catalase being more stimulated in gills, whereas glutathione peroxidase was more activated in liver. Although there were no obvious concentration-response relationships, the integrated biomarker response version 2 (IBRv2) analysis revealed that the highest concentrations of gemfibrozil (between 150-15,000 µg L-1) caused more alterations. All the tested concentrations of gemfibrozil induced effects in S. aurata, in terms of behavior and/or oxidative stress responses. Oxidative damage was found at a concentration that is considered environmentally relevant, suggesting a potential of this pharmaceutical to impact fish populations.

Genotoxicity of gemfibrozil in the gilthead seabream (Sparus aurata).

Widespread use of pharmaceuticals and suboptimal wastewater treatment have led to increased levels of these substances in aquatic ecosystems. Lipid-lowering drugs such as gemfibrozil, which are among the most abundant human pharmaceuticals in the environment, may have deleterious effects on aquatic organisms. We examined the genotoxicity of gemfibrozil in a fish species, the gilthead seabream (Sparus aurata), which is commercially important in southern Europe. Following 96-h waterborne exposure, molecular (erythrocyte DNA strand breaks) and cytogenetic (micronuclei and other nuclear abnormalities in cells) endpoints were measured. Gemfibrozil was positive in both endpoints, at environmentally relevant concentrations, a result that raises concerns about the potential genotoxic effects of the drug in recipient waters.

Development of a multi-residue method for the determination of human and veterinary pharmaceuticals and some of their metabolites in aqueous environmental matrices by SPE-UHPLC-MS/MS.

The aim of the present work was to develop and validate a multi-residue method for the analysis of 33 human and veterinary pharmaceuticals (non-steroidal anti-inflammatory drugs (NSAIDs)/analgesics, antibiotics and psychiatric drugs), including some of their metabolites, in several aqueous environmental matrices: drinking water, surface water and wastewaters. The method is based on solid phase extraction (SPE) followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) and it was validated for different aqueous matrices, namely bottled water, tap water, seawater, river water and wastewaters, showing recoveries between 50% and 112% for the majority of the target analytes. The developed analytical methodology allowed method detection limits in the low nanograms per liter level. Method intra- and inter-day precision was under 8% and 11%, respectively, expressed as relative standard deviation. The developed method was applied to the analysis of drinking water (bottled and tap water), surface waters (seawater and river water) and wastewaters (wastewater treatment plant (WWTP) influent and effluent). Due to the selectivity and sensitivity of the optimized method, it was possible to detect pharmaceuticals in all the aqueous environmental matrices considered, including in bottled water at concentrations up to 31ngL-1 (salicylic acid). In general, non-steroidal anti-inflammatory drugs/analgesics was the therapeutic group most frequently detected, with the highest concentrations found in wastewaters (acetaminophen and the metabolite carboxyibuprofen at levels up to 615 and 120µgL-1, respectively).

Determination of pharmaceuticals in groundwater collected in five cemeteries' areas (Portugal).

There are growing public attention and concern about the possibility of ecosystem and human health effects from pharmaceuticals in environment. Several types of environmental samples were target of studies by the scientific community, namely drinking water, groundwater, surface water (river, ocean), treated water (influent and effluent), soils, and sediments near to Wastewater Treatment Plants or near to others potential sources of contaminations. Normally, studies in the cemeteries areas are for historical and architectural research and questions of the potential risk for adverse impact of cemeteries in environment have never received enough attention. However, this risk may exist when cemeteries are placed in areas that are vulnerable to contamination. The objective of the present work was the determination of pharmaceuticals (nonsteroidal anti-inflammatory/analgesics, antibiotics and psychiatric drugs) in groundwater samples collected inside of the cemeteries areas. Acetaminophen, salicylic acid, ibuprofen, ketoprofen, nimesulide, carbamazepine, fluoxetine, and sertraline were the pharmaceuticals achieved in the analysed samples. None of the studied antibiotics were detected. The highest concentration was obtained for salicylic acid (in the range of 33.7 to 71.0ng/L) and carbamazepine (between 20.0 and 22.3ng/L), respectively. By the cluster analysis similarity between carbamazepine and fluoxetine was achieved.

Characterization of green zero-valent iron nanoparticles produced with tree leaf extracts.

In the last decades nanotechnology has become increasingly important because it offers indisputable advantages to almost every area of expertise, including environmental remediation. In this area the synthesis of highly reactive nanomaterials (e.g. zero-valent iron nanoparticles, nZVI) is gaining the attention of the scientific community, service providers and other stakeholders. The synthesis of nZVI by the recently developed green bottom-up method is extremely promising. However, the lack of information about the characteristics of the synthetized particles hinders a wider and more extensive application. This work aims to evaluate the characteristics of nZVI synthesized through the green method using leaves from different trees. Considering the requirements of a product for environmental remediation the following characteristics were studied: size, shape, reactivity and agglomeration tendency. The mulberry and pomegranate leaf extracts produced the smallest nZVIs (5-10 nm), the peach, pear and vine leaf extracts produced the most reactive nZVIs while the ones produced with passion fruit, medlar and cherry extracts did not settle at high nZVI concentrations (931 and 266 ppm). Considering all tests, the nZVIs obtained from medlar and vine leaf extracts are the ones that could present better performances in the environmental remediation. The information gathered in this paper will be useful to choose the most appropriate leaf extracts and operational conditions for the application of the green nZVIs in environmental remediation.

Polycyclic aromatic hydrocarbons: levels and phase distributions in preschool microenvironment.

This work aims to characterize levels and phase distribution of polycyclic aromatic hydrocarbons (PAHs) in indoor air of preschool environment and to assess the impact of outdoor PAH emissions to indoor environment. Gaseous and particulate (PM1 and PM(2.5)) PAHs (16 USEPA priority pollutants, plus dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were concurrently sampled indoors and outdoors in one urban preschool located in north of Portugal for 35 days. The total concentration of 18 PAHs (ΣPAHs) in indoor air ranged from 19.5 to 82.0 ng/m(3) ; gaseous compounds (range of 14.1-66.1 ng/m(3)) accounted for 85% ΣPAHs. Particulate PAHs (range 0.7-15.9 ng/m(3)) were predominantly associated with PM1 (76% particulate ΣPAHs) with 5-ring PAHs being the most abundant. Mean indoor/outdoor ratios (I/O) of individual PAHs indicated that outdoor emissions significantly contributed to PAH indoors; emissions from motor vehicles and fuel burning were the major sources.

Utilization of food industry wastes for the production of zero-valent iron nanoparticles.

The proper disposal of the several types of wastes produced in industrial activities increases production costs. As a consequence, it is common to develop strategies to reuse these wastes in the same process and in different processes or to transform them for use in other processes. This work combines the needs for new synthesis methods of nanomaterials and the reduction of production cost using wastes from citrine juice (orange, lime, lemon and mandarin) to produce a new added value product, green zero-valent iron nanoparticles that can be used in several applications, including environmental remediation. The results indicate that extracts of the tested fruit wastes (peel, albedo and pulp fractions) can be used to produce zero-valent iron nanoparticles (nZVIs). This shows that these wastes can be an added value product. The resulting nZVIs had sizes ranging from 3 up to 300 nm and distinct reactivities (pulp>peel>albedo extracts). All the studied nanoparticles did not present a significant agglomeration/settling tendency when compared to similar nanoparticles, which indicates that they remain in suspension and retain their reactivity.

Commercial squids: characterization, assessment of potential health benefits/risks and discrimination based on mineral, lipid and vitamin E concentrations.

The most consumed squid species worldwide were characterized regarding their concentrations of minerals, fatty acids, cholesterol and vitamin E. Interspecific comparisons were assessed among species and geographical origin. The health benefits derived from squid consumption were assessed based on daily minerals intake and on nutritional lipid quality indexes. Squids contribute significantly to daily intake of several macro (Na, K, Mg and P) and micronutrients (Cu, Zn and Ni). Despite their low fat concentration, they are rich in long-chain omega-3 fatty acids, particularly docosahexaenoic (DHA) and eicosapentanoic (EPA) acids, with highly favorable ω-3/ω-6 ratios (from 5.7 to 17.7), reducing the significance of their high cholesterol concentration (140-549 mg/100g ww). Assessment of potential health risks based on minerals intake, non-carcinogenic and carcinogenic risks indicated that Loligo gahi (from Atlantic Ocean), Loligo opalescens (from Pacific Ocean) and Loligo duvaucelii (from Indic Ocean) should be eaten with moderation due to the high concentrations of Cu and/or Cd. Canonical discriminant analysis identified the major fatty acids (C14:0, C18:0, C18:1, C18:3ω-3, C20:4ω-6 and C22:5ω-6), P, K, Cu and vitamin E as chemical discriminators for the selected species. These elements and compounds exhibited the potential to prove authenticity of the commercially relevant squid species.

Multi-elemental analysis of ready-to-eat "baby leaf" vegetables using microwave digestion and high-resolution continuum source atomic absorption spectrometry.

The mineral content (phosphorous (P), potassium (K), sodium (Na), calcium (Ca), magnesium (Mg), iron (Fe), manganese (Mn), zinc (Zn) and copper (Cu)) of eight ready-to-eat baby leaf vegetables was determined. The samples were subjected to microwave-assisted digestion and the minerals were quantified by High-Resolution Continuum Source Atomic Absorption Spectrometry (HR-CS-AAS) with flame and electrothermal atomisation. The methods were optimised and validated producing low LOQs, good repeatability and linearity, and recoveries, ranging from 91% to 110% for the minerals analysed. Phosphorous was determined by a standard colorimetric method. The accuracy of the method was checked by analysing a certified reference material; results were in agreement with the quantified value. The samples had a high content of potassium and calcium, but the principal mineral was iron. The mineral content was stable during storage and baby leaf vegetables could represent a good source of minerals in a balanced diet. A linear discriminant analysis was performed to compare the mineral profile obtained and showed, as expected, that the mineral content was similar between samples from the same family. The Linear Discriminant Analysis was able to discriminate different samples based on their mineral profile.

Iron oxide/gold core/shell nanomagnetic probes and CdS biolabels for amplified electrochemical immunosensing of Salmonella typhimurium.

There is an imminent need for rapid methods to detect and determine pathogenic bacteria in food products as alternatives to the laborious and time-consuming culture procedures. In this work, an electrochemical immunoassay using iron/gold core/shell nanoparticles (Fe@Au) conjugated with anti-Salmonella antibodies was developed. The chemical synthesis and functionalization of magnetic and gold-coated magnetic nanoparticles is reported. Fe@Au nanoparticles were functionalized with different self-assembled monolayers and characterized using ultraviolet-visible spectrometry, transmission electron microscopy, and voltammetric techniques. The determination of Salmonella typhimurium, on screen-printed carbon electrodes, was performed by square-wave anodic stripping voltammetry through the use of CdS nanocrystals. The calibration curve was established between 1×10(1) and 1×10(6) cells/mL and the limit of detection was 13 cells/mL. The developed method showed that it is possible to determine the bacteria in milk at low concentrations and is suitable for the rapid (less than 1h) and sensitive detection of S. typhimurium in real samples. Therefore, the developed methodology could contribute to the improvement of the quality control of food samples.

Application of green zero-valent iron nanoparticles to the remediation of soils contaminated with ibuprofen.

Zero-valent iron nanoparticles (nZVIs) are often used in environmental remediation. Their high surface area that is associated with their high reactivity makes them an excellent agent capable of transforming/degrading contaminants in soils and waters. Due to the recent development of green methods for the production of nZVIs, the use of this material became even more attractive. However, the knowledge of its capacity to degrade distinct types of contaminants is still scarce. The present work describes the study of the application of green nZVIs to the remediation of soils contaminated with a common anti-inflammatory drug, ibuprofen. The main objectives of this work were to produce nZVIs using extracts of grape marc, black tea and vine leaves, to verify the degradation of ibuprofen in aqueous solutions by the nZVIs, to study the remediation process of a sandy soil contaminated with ibuprofen using the nZVIs, and to compare the experiments with other common chemical oxidants. The produced nZVIs had nanometric sizes and were able to degrade ibuprofen (54 to 66% of the initial amount) in aqueous solutions. Similar remediation efficiencies were obtained in sandy soils. In this case the remediation could be enhanced (achieving degradation efficiencies above 95%) through the complementation of the process with a catalyzed nZVI Fenton-like reaction. These results indicate that this remediation technology represents a good alternative to traditional and more aggressive technologies.