Prediction of the bioavailability of potentially toxic elements in freshwaters. Comparison between speciation models and passive samplers.

The aim of this work is to predict the bioavailability of the Potentially Toxic Elements (PTEs) Cd, Pb, Hg, Ni, Cu, Zn, As, Cr and Se in 6 sites within the Ebro River basin. In situ Diffusive gradient in thin-films (DGTs) and classical sampling have been used and compared. The potentially bioavailable fractions of each PTE was estimated by modelling their chemical speciation using three programs (WHAM 7.0, Visual MINTEQ 3.1 and Bio-met), following the suggestions published in recent European regulations. Results of the equilibrium-based models WHAM 7.0 and Visual MINTEQ 3.1 indicate that As, Cd, Ni, Se and Zn, predominate as free metals ions or forming inorganic soluble complexes. Copper, Pb and Hg bioavailability is conditioned by their affinity to dissolved humic substances. According to Visual MINTEQ 3.1, Cr is subjected to redox reactions, being Cr (VI) present (at low concentrations) in the studied rivers. According to Bio-met model, the bioavailability of Cu and Zn is highly influenced by soluble organic matter and water hardness, respectively. For most PTEs, the bioavailability estimated by deploying DGTs in river waters tends to be slightly lower than the estimation obtained with speciation models, since in real conditions more environmental factors take place comparing to the finite number of parameters considered in models.

Nen d'11 anys amb cefalea persistent i alteració de l'agudesa visual / No disponible

No disponible

Human health risks of formaldehyde indoor levels: An issue of concern.

Formaldehyde is a carcinogenic substance for humans. Exposure to formaldehyde may also cause eye and respiratory tract irritation, as well as skin sensitization. The main indoor sources of formaldehyde are wood-pressed products, insulation materials, paints, varnishes, household cleaning products and cigarettes, among others. Although this chemical is a well-known indoor pollutant, data on indoor concentrations of formaldehyde are still scarce in some countries. In February 2014, 10 homes in Catalonia, Spain, were randomly selected to collect indoor (bedroom and living room) and outdoor air samples. Ten additional samples were also collected at different workplaces (e.g., offices, shops, classrooms, etc.). Formaldehyde air levels found in homes ranged from 10.7 to 47.7 µg m(-3), from 9.65 to 37.2 µg m(-3), and from 0.96 to 3.37 µg m(-3) in bedrooms, living rooms, and outdoors, respectively. Meanwhile, at workplaces, indoor air levels ranged from 5.86 to 40.4 µg m(-3). These levels are in agreement with data found in the scientific literature. Non-carcinogenic risks were above the threshold limit (HQ > 1), and carcinogenic risks were not acceptable either (>10(-4)). Despite the current study limitations, the results confirm that formaldehyde indoor levels are a matter of health concern, which must be taken into account by policymakers and regulatory bodies.

Ecotoxicity of sediments in rivers: Invertebrate community, toxicity bioassays and the toxic unit approach as complementary assessment tools.

The determination of the real toxicity of sediments in aquatic ecosystems is challenging and necessary for an appropriate risk assessment. Different approaches have been developed and applied over the last several decades. Currently, the joint implementation of chemical, ecological and toxicological tools is recommended for an appropriate and successful toxicity risk assessment. We chose the combination of the toxic unit approach with acute pore water tests (Vibrio fischeri, Pseudokirchneriella subcapitata and Daphnia magna) and whole-sediment exposure tests (V. fischeri, Chironomus riparius), together with invertebrate community composition (multivariate analyses) to detect short and long-term responses of the organisms in four rivers of the Iberian Peninsula. High toxicity was detected in three sites (the downstream sites of the Llobregat and the Júcar, and the most upstream site of the Ebro). We identified organophosphate insecticides and metals as the main variables responsible for this toxicity, particularly in the whole-sediment tests. In particular, chlorpyrifos was mostly responsible for the toxicity (TUs) of D. magna, coinciding with the C. riparius mortality (long-term toxicity) in the mentioned sites, and copper was the main pollutant responsible for the short-term toxicity of P. subcapitata. The combination of the different approaches allowed us to detect ecotoxicological effects in organisms and identify the main contributors to the toxicity in these multi-stressed rivers.

Metal bioavailability in freshwater sediment samples and their influence on ecological status of river basins.

The general aim of this work has been to check the ecological impact of metals on the Ebro river basin. In order to evaluate this, metal behavior considering water, sediment as well as metal bioaccumulation in fish has been studied. Total concentrations of metals, as well as the potentially bioavailable fraction of metals in sediment has also been analyzed by the application of the sequential extraction method (BCR method). In order to evaluate the influence of metal pollution on the river ecological status, according to the Water Framework Directive (WFD), diverse biological indices such as macroinvertebrates (IBMWP), diatoms (IPS) and macrophytes (IVAM), have been considered from an integrated point of view. Considering both water and sediment, metals which contributed in higher extend to the reduction of biological quality have been demonstrated to be Pb and Zn, as they presented a negative influence on macroinvertebrates, diatoms and macrophytes communities. As and Cr that seemed to have a significant influence on macroinvertebrates and diatoms too, while Ni negatively influenced only diatom communities. This study also demonstrated that monitoring programs only based on total metal determination in water are inefficient, as metals present even at undetectable concentrations in water are strongly accumulated in fish. Moreover, the high concentrations of Hg found in sediments indicated that this river basin may present pollution problems regarded to this metal, as demonstrated by the high Hg levels found in fish.

Assessment of sediment ecotoxicological status as a complementary tool for the evaluation of surface water quality: the Ebro river basin case study.

According to the European Water Framework Directive (WFD), assessment of surface water status is based on ecological and chemical status that is not always in coherence. In these situations, ecotoxicity tests could help to obtain a better characterization of the ecosystems. The general aim of this work is to design a methodology to study the ecotoxicological status of freshwater systems. This could be useful and complementary to ecological status, for a better ecological characterization of freshwater systems. For this purpose, sediments from thirteen sampling sites within the Ebro river watershed (NE Spain) were collected for ecotoxicity characterization. The ecotoxicity of pore water has been evaluated employing the test organisms Vibrio fischeri, Pseudokirschneriella subcapitata and Daphnia magna, while whole sediment ecotoxicity was evaluated using Vibrio fischeri, Daphnia magna, Nitzschia palea and Chironomus riparius. An analysis of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) was performed to evaluate the sediment toxicity associated to bioavailable metals. Moreover, data about priority pollutants defined by the WFD in water, sediment and fish as well as data of surface water status of each sampling point were provided by the Monitoring and Control Program of the Ebro Water bodies. In general terms, whole sediment bioassays have shown more toxicity than pore water tests. Among the different organisms used, P. subcapitata and C. riparius were the most sensitive in pore water and whole sediment, respectively. Our evaluation of the ecotoxicological status showed high coincidences with the ecological status, established according to the WFD, especially when ecosystem disruption due to numerous stressors (presence of metals and organic pollution) was observed. These results allow us to confirm that, when chemical stressors affect the ecosystem functioning negatively, an ecotoxicological approach, provided by suitable bioassays in pore water and whole sediment, could detect these changes with accurate sensitivity.

Síndrome de varón 46, XX (SRY +) asociado a Enfermedad de Crohn. A propósito de un caso / 46, XX (SRY +) male syndrome associated with Crohn disease. A case report

OBJETIVO: Presentar el caso de un paciente de fenotipo masculino con testículos y pene de tamaño ligeramente disminuido diagnosticado de azoospermia no obstructiva. Revisión de la literatura. MATERIAL Y MÉTODOS: Exploración física, perfil hormonal, espermiograma, ultrasonografía genital, cariotipo y análisis citogenético mediante microarrays KaryoNIM. RESULTADOS: La exploración clínica mostró un fenotipo masculino con testes y pene disminuidos de tamaño y obesidad. Las determinaciones hormonales evidenciaron un hipogonadismo hipergonadotropo. El estudio seminal mostró una azoospermia y la ecografía genital un aparato genital masculino normal. El cariotipo fue 46,XX, normal de mujer, y el estudio citogenético mostró la traslocación de material genético del cromosoma Y al cromosoma X, incluyendo el gen SRY. La biopsia testicular evidenció la presencia de hialinización tubular con células de Sertoli maduras, sin línea germinal y acusada hiperplasia de células de Leydig. Comentarios y conclusión: El síndrome de varón con cariotipo 46,XX es una etiología inusual de azoospermia. Su asociación a patologías autoinmunes no está actualmente bien aclarada. Aunque la única opción disponible para tratar el problema reproductivo es el uso de semen de donante, el abordaje de estos pacientes debe ser multidisciplinar

OBJECTIVES: To present the case of a patient showing male phenotype with testes and penis size slightly decreased, which was diagnosed with non-obstructive azoospermia. Review of the literature. MATERIAL AND METHODS: Physical examination, hormonal profile, semen analysis, genital ultrasound scan, karyotype and cytogenetic microarray analysis (KaryoNIM). RESULTS: Clinical examination showed a male phenotype with decreased size of testes and penis and obesity. Hormonal determinations evidenced hypergonadotropic hypogonadism. The seminal study showed azoospermia and genital ultrasound a normal male genital tract. Karyotype 46,XX, normal woman, and the cytogenetic study showed the translocation of genetic material from chromosome Y to chromosome X, including the SRY gene. Testicular biopsy showed the presence of tubular hyalinization with mature Sertoli cells, absent germ line and pronounced hyperplasia of Leydig cells. Comments and conclusion: 46,XX male is a rare genetic condition of non-obstructive azoospermia. The association to autoimmune diseases needs to be clarified. Although sperm donation remains the only fertility treatment currently available multidisciplinary approach should be adopted in the management of 46,XX individuals

Integrated study of metal behavior in Mediterranean stream ecosystems: a case-study.

The objective of the present work was to assess the ecosystem status of Francolí river (Catalonia, Spain), a Mediterranean stream basin with contrasting human influences. An integrated approach was designed by combining physicochemical, biological and ecotoxicological analyses. The content of metals (As, Cd, Cr, Co, Cu, Hg, Ni, Pb, and Zn) was analyzed in samples of water, benthic sediments and aquatic macroinvertebrates. In addition, the potentially bioavailable fraction of metals in water and sediments was determined by using diffusive gradient in thin-films (DGTs) and sequential extraction of sediments (BCR), respectively. The biological quality was evaluated through aquatic macroinvertebrate communities, while the ecotoxicological status was assessed by Microtox(®) with Vibrio fischeri. Finally, an analysis of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) was performed to evaluate the sediment toxicity associated to metal content. According to the results, DGTs and BCR are suitable methodologies to predict the potential bioavailable fraction of metals in freshwater systems. Moreover, ecotoxicity evaluation by means of V. fischeri, in combination with the chemical characterization and the biological quality assessment, should be complementarily used to get a better diagnose of freshwater systems.

In vitro tests to assess toxic effects of airborne PM(10) samples. Correlation with metals and chlorinated dioxins and furans.

Inhalation is an important exposure pathway to airborne pollutants such as heavy metals, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and particulate matter. Chronic exposure to those chemicals, which form part of complex environmental mixtures, may mean important human health risks. In the present study, the suitability of different in vitro tests to evaluate the toxic effects of air PM(10) pollutants is investigated. In addition, it is also assessed how to distinguish the contribution of chemical pollutants to toxicity. Sixty-three air samples were collected in various areas of Catalonia (Spain), and the levels of ecotoxicity, cytotoxicity and genotoxicity were evaluated. Aqueous acidic extractions of quartz fiber filters, where PM(10) had been retained, were performed. The photo-luminescent bacteria Vibrio fischeri (Microtox®) bioassay was performed to assess ecotoxicity. Moreover, MTT and Comet Assays, both using human lung epithelial cells A549 as target cells, were applied to assess the cytotoxicity and genotoxicity of air samples, respectively. The results show that Microtox® is an excellent screening test to perform a first evaluation of air quality, as it presented a significant correlation with chemical contaminants, contrasting with MTT Assay. Although none of the samples exhibited genotoxicity, a high correlation was found between this in vitro test and carcinogenic agents. Urban samples from traffic-impacted areas would be significantly more toxic. Finally, environmental temperature was identified as a key parameter, as higher values of ecotoxicity were found in winter.

Relationship between pollutant content and ecotoxicity of sewage sludges from Spanish wastewater treatment plants.

Chemical and ecotoxicological properties of 28 sewage sludge samples from Spanish wastewater treatment plants were studied in order to assess their suitability for agricultural purposes. Sludge samples were classified into five categories according to specific treatment processes in terms of digestion (aerobic/anaerobic) and drying (mechanical/thermal). Composted samples, as indicative of the most refined process, were also considered. Sludges were subjected to physical-chemical characterization, being the sludge stabilization degree respirometrically assessed. The concentrations of seven metals (Cd, Cr, Cu, Pb, Zn, Ni, Hg) and organic substances (phenolic compounds, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polychlorinated naphthalenes, polybrominated diphenyl ethers, and perfluorinated compounds) were determined. Finally, two ecotoxicological tests were performed: i) Microtox® toxicity test with Vibrio fischeri, and ii) root elongation test with Allium cepa, Lolium perenne and Raphanus sativus seeds. Significant differences were found in the following parameters: dry matter, electrical conductivity, nitrogen, organic matter and its stability, phytotoxicity and ecotoxicity, depending on the sludge treatment. In turn, no significant differences were found between categories in the concentrations of most metals and organic pollutants, with the exception of free phenolic compounds. Furthermore, no correlation between total heavy metal burden and ecotoxicity was observed. However, a good correlation was found between phenolic compounds and most ecotoxicological tests. These results suggest that sludge stability (conditioned by sludge treatment) might have a greater influence on sludge ecotoxicity than the pollutant load. Composting was identified as the treatment resulting in the lowest toxicity.

Novel approach for assessing heavy metal pollution and ecotoxicological status of rivers by means of passive sampling methods.

In order to study the pollution of fluvial ecosystems, it is necessary to analyze not only the levels of chemical contaminants in water, but also those accumulated in the sediment matrix, as well as to assess its ecotoxicological status. Eleven Catalan (Spain) river sections (one sampling point per river) located near urban and industrial areas were sampled during winter of 2009. Water pollutants were collected by using passive samplers as Diffusive Gradient in Thin-Films (DGTs) and Semi-Permeable Membrane Devices (SPMDs). Point water samples were also collected. The concentrations of potentially toxic elements (PTE) in water, filtered water, DGTs and sediment samples were analyzed. Aqueous and organic solvent extracts of sediments samples and organic extracts of SPMDs were performed to assess acute toxicity to Vibrio fischeri by Microtox(®), and chronic toxicity to the green alga Pseudokirschneriella subcapitata. Microtox(®) test was also performed with DGT extracts. The results show that metals content of Catalan river waters are below the freshwater screening US EPA benchmarks, excepting some industrial areas (for Hg, Pb, and Zn). In contrast, sediments levels of some rivers were far above freshwater sediment screening US EPA benchmarks (for Zn, As, Cr, Pb, Ni, Hg, and Mn), particularly in the most industrialized areas. A good correlation was found between toxicity values of extracts (from sediments and DGTs) and PTE levels in sediments. The current results support the suitability of using combined point and passive sampling methods for assessing the chemical and ecotoxicological status of aqueous environments.