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Titanium dioxide nanoparticles (TiO 2 NPs) are widely used in industry as a white pigment (paints, paper industry and toothpastes), photocatalysts (environmental decontamination and photovoltaic cells), inorganic UV filter (sunscreens and personal care products) and as a food additive (E171) and antimicrobial food packaging material. Silver nanoparticles (Ag NPs) are used in photonics, microelectronics, catalysis and medicine due to their catalytic activity, magnetic and optical polarizability, electrical and thermal conductivities and enhanced Raman scattering. They also have antibacterial, antifungal and antiviral activities, as well as anti-inflammatory potential. The huge increase in the use of nano-based products, mainly metallic NPs, implies the presence of nanomaterials in the environment, and hence, the unintentional human ingestion through water or foods (gastrointestinal tract is the main pathway of NPs intake in humans). The presence of TiO 2 NPs and Ag NPs in seafood samples was firstly established using an ultrasound assisted enzymatic hydrolysis procedure and sp-ICP-MS analysis. Several clams, cockles, mussels, razor clams, oysters and variegated scallops, which contain TiO 2 NPs and Ag NPs, were subjected to an in vitro digestion process simulating human gastrointestinal digestion in the stomach and in the small and large intestine to determine the bioaccessibility of these NPs. Caco-2 cells were selected as model of human intestinal epithelium for transport studies because of the development of membrane transporters that are responsible for the uptake of chemicals. Parameters as transepithelial electrical resistance (TEER) and permeability of Lucifer Yellow were studied for establishing cell monolayer integrity. TiO 2 NPs and Ag NPs transport as well as total Ti and Ag concentrations passing through the gastrointestinal epithelial barrier model (0-2 h) were assessed by sp-ICP-MS and ICP-MS in several molluscs., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A method based on asymmetric flow field-flow fractionation (AF4) coupled to ultraviolet-visible (UV-vis) spectroscopy and inductively coupled plasma mass spectrometry (ICP-MS) has been developed for silver nanoparticles (Ag NPs) detection and quantification in bivalve molluscs. Samples were pre-treated using a conventional enzymatic (pancreatin and lipase) hydrolysis procedure (37 °C, 12 h). AF4 was performed using a regenerated cellulose (RC) membrane (10 kDa, 350 μm spacer) and aqueous 5 mM Tris-HCl pH = 7.4 as carrier. AF4 separation was achieved with a program that included a focusing step with tip and focus flows of 0.20 and 3.0 mL min -1 , respectively, and an injection time of 4.0 min. Elution of different size fractions was performed using a cross flow of 3.0 mL min -1 for 15 min, followed by linear cross flow decrease for 7.5 min, and a washing step for 9.4 min with no cross flow. Several bivalve molluscs (clams, oysters and variegated scallops) were analysed for total Ag content (ICP-MS after microwave assisted acid digestion), and for Ag NPs by the method presented here. Results show that Ag NPs are detected at the same elution time than proteins (UV monitoring at 280 and 405 nm), which suggests a certain interaction occurred between Ag NPs with proteins in the enzymatic extracts. AF4-UV-ICP-MS fractograms also suggest different Ag NPs size distributions for selected samples. Membrane recoveries, determined by peak area comparison of fractograms with and without application of cross flow, were within the 49-121% range. Confirmation of the presence Ag NPs in the investigated enzymatic extracts was demonstrated by SEM after an oxidative pre-treatment based on hydrogen peroxide and microwave irradiation., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A procedure for the size characterization and quantification of titanium dioxide (TiO 2 ) nano- and microparticles by Asymmetric Flow Field-Flow Fractionation (AF4) coupled to Dynamic Light Scattering (DLS) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is described. Different strategies for size characterization with size standards and the use of the DLS signal for the estimation of hydrodynamic diameters are evaluated. The procedure has been applied to the characterization of TiO 2 nanoparticles in photocatalytic products and crab sticks (surimis), where TiO 2 is present as E171 food additive. Sizes in the range of 50-90 nm and 160-170 nm were estimated in the different photocatalytic products by AF4-DLS, in good agreement with the sizes predicted by calibration versus SiO 2 and polystyrene standards. In surimis, sizes between 140 and 350 nm were estimated by AF4-DLS, similar to those reported in literature for E171 additive. These results were also compared to those obtained by single particle ICP-MS, which allowed the detection of a nano-sized fraction of TiO 2 present in the four surimis analyzed. Titanium contents in one of the photocatalytic products determined by AF4-ICP-MS was 16.86 ± 2.54 mg g -1 , whereas the alkaline extraction followed by AF4-ICP-MS allowed the determination of TiO 2 content in four surimis at concentration levels in the range of the μg g -1 (from 3.14 ± 0.10 to 14.55 ± 1.46 μg Ti g -1 ), with channel recoveries above 85% in all cases. The method has been validated by comparison with the Ti content determined by ICP-OES after microwaved assisted acid digestion of all the samples. The methodology proposed allows the complete quantification of the (nano)particulate forms of titanium in complex matrices together with their size characterization., 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 © 2020 Elsevier B.V. All rights reserved.)

A reliable sample pre-treatment based on enzymatic hydrolysis has been fully optimized and validated for TiO 2 NPs isolation and determination/characterization in surimi (crab sticks). Efficient extractions have been found when using a pancreatin/lipase mixture at pH 7.4 and 37 °C for 12 h under continuous stirring. The proposed sample pre-treatment procedure has been found not to change TiO 2 NPs size distribution, therefore guaranteeing TiO 2 NPs integrity. TiO 2 NPs determination (TiO 2 NPs concentration) and TiO 2 NPs characterization (size distribution) were assessed by single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) working with dwell times in the microsecond range (high frequency of data acquisition). Method validation was performed for TiO 2 NPs concentrations and TiO 2 NPs sizes. Good repeatability (25% and 8% for TiO 2 NPs concentration and TiO 2 NPs most frequent size), and sensitivity (limit of detection of 5.28 × 10 5 NPs g -1 for TiO 2 NPs concentrations, and 31.3-37.1 nm for TiO 2 NPs size) were obtained. Accuracy, calculated through analytical recovery was adequate. Recoveries for TiO 2 NPs standards of 50 and 100 nm were 108 ± 5 and 105 ± 4%, respectively. The proposed methodology was applied to several surimi samples for assessing TiO 2 NPs concentrations and size distribution. Some surimi samples were found to contain TiO 2 NPs (concentrations from 1.40 × 10 7 to 1.19 × 10 9 NPs g -1 ). TiO 2 NPs size distributions were very different among the samples, and some of them showed wide size ranges (the most frequent size varied from 53.8 to 62.1 nm; whereas, the mean size values were within the 73.4-217.5 nm range)., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Objective: We aimed to evaluate the impact of Staphylococcus aureus phenotype (vancomycin MIC) and genotype (agr group, clonal complex CC) on the prognosis and clinical characteristics of infective endocarditis (IE)., Methods: We performed a multicentre, longitudinal, prospective, observational study (June 2013 to March 2016) in 15 Spanish hospitals. Two hundred and thirteen consecutive adults (≥18 years) with a definite diagnosis of S. aureus IE were included. Primary outcome was death during hospital stay. Main secondary end points were persistent bacteraemia, sepsis/septic shock, peripheral embolism and osteoarticular involvement., Results: Overall in-hospital mortality was 37% (n = 72). Independent risk factors for death were age-adjusted Charlson co-morbidity index (OR 1.20; 95% CI 1.08-1.34), congestive heart failure (OR 3.60; 95% CI 1.72-7.50), symptomatic central nervous system complication (OR 3.17; 95% CI 1.41-7.11) and severe sepsis/septic shock (OR 4.41; 95% CI 2.18-8.96). In the subgroup of methicillin-susceptible S. aureus IE (n = 173), independent risk factors for death were the age-adjusted Charlson co-morbidity index (OR 1.17; 95% CI 1.03-1.31), congestive heart failure (OR 3.39; 95% CI 1.51-7.64), new conduction abnormality (OR 4.42; 95% CI 1.27-15.34), severe sepsis/septic shock (OR 5.76; 95% CI 2.57-12.89) and agr group III (OR 0.27; 0.10-0.75). Vancomycin MIC ≥1.5 mg/L was not independently associated with death during hospital nor was it related to secondary end points. No other genotype variables were independently associated with in-hospital death., Conclusions: This is the first prospective study to assess the impact of S. aureus phenotype and genotype. Phenotype and genotype provided no additional predictive value beyond conventional clinical characteristics. No evidence was found to justify therapeutic decisions based on vancomycin MIC for either methicillin-resistant or methicillin-susceptible S. aureus., (Copyright © 2017 European Society of Clinical Microbiology and Infectious Diseases. Published by Elsevier Ltd. All rights reserved.)

Applicability of single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) using dwell times equal to or shorter than 100 μs has been tested for assessing titanium dioxide nanoparticles (TiO 2 NPs) in bivalve mollusks. TiO 2 NPs isolation from fresh mollusk tissues was achieved by ultrasound assisted enzymatic hydrolysis procedure using a pancreatin/lipase mixture. Optimum extraction conditions imply ultrasonication (60% amplitude) for 10 min, and 7.5 mL of a solution containing 3.0 g L -1 of pancreatin and lipase (pH 7.4). The developed method was found to be repeatable (repeatability of 17% for the over-all procedure, TiO 2 NPs concentration of 5.33 × 10 7  ± 8.89 × 10 6 , n = 11), showing a limit of detection of 5.28 × 10 6 NPs g -1 , and a limit of detection in size of 24.4-30.4 nm, based on the 3σ criteria, and on the 3σ/5 σ criteria, respectively. The analytical recovery within the 90-99% range (use of TiO 2 NPs standards of 50 nm at 7 and 14 μg L -1 as Ti). Several bivalve mollusks (clams, cockles, mussels, razor clams, oysters and variegated scallops) were analyzed for total titanium (ICP-MS after microwave assisted acid digestion), and for TiO 2 NPs by the proposed method. TiO 2 NPs concentrations were within the 2.36 × 10 7 -1.25 × 10 8 NPs g -1 range, and the most frequent sizes were from 50 to 70 nm., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Many regions of Latin America are widely reported for the occurrence of high arsenic (As) in groundwater and surface water due to a combination of geological processes and/or anthropogenic activities. In this paper, we review the available literature (both in English and Spanish languages) to delineate human As exposure pathways through the food chain. Numerous studies show that As accumulations in edible plants and crops are mainly associated with the presence of high As in soils and irrigation waters. However, factors such as As speciation, type and composition of soil, and plant species have a major control on the amount of As uptake. Areas of high As concentrations in surface water and groundwater show high As accumulations in plants, fish/shellfish, livestock meat, milk and cheese. Such elevated As concentrations in food may result in widespread health risks to local inhabitants, including health of indigenous populations and residents living close to mining industries. Some studies show that As can be transferred from the water to prepared meals, thereby magnifying the As content in the human diet. Arsenic speciation might also change during food preparation, especially during high temperature cooking, such as grilling and frying. Finally, the review of the available literature demonstrates the necessity of more rigorous studies in evaluating pathways of As exposure through the human food chain in Latin America., (Copyright © 2011 Elsevier B.V. All rights reserved.)

During decades, in semiarid rainfed Aragon, intensive soil tillage and low crop residue input have led to the loss of soil structure and soil degradation. Conservation tillage and cropping intensification can improve soil structure in these areas. The objective of this study was to determine the influence of three different tillage systems (traditional tillage, reduced tillage and no-tillage) under two cropping systems (fallow-barley rotation and barley monoculture) on soil aggregation dynamics during a cropping season. A decrease in tillage intensity resulted in a higher mean size of dry aggregates and a greater water aggregate stability in both cropping systems particularly under no-tillage.