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HIGHLIGHTS: Microplastics (MPs) and microrubbers (MRs) determined in lichens and mosses around Shiraz. In lichens, MPs mainly thin fibres up to 1 MP g-1; MRs were < 0.1 MP g-1. In mosses, abundances were similar but with a greater fraction of larger, non-fibrous particles. Larger MPs and MRs decreased in abundance with distance and elevation from Shiraz. Around Shiraz, the common moss, Grimmia critina, would be the most suitable biomonitor. Lichens and mosses have been employed as biomonitors of atmospheric particulate pollutants, like metals and industrial solids, for many decades. Here, we evaluated the potential of nine species of crustose and foliose lichens and a widely distributed moss (Grimmia critina) to act as biomonitors of airborne microplastics (MPs) and microrubbers (MRs). About 200 lichens and 40 mosses were sampled across different altitudinal transects in the vicinity of Shiraz City, southwest Iran, and MPs and MRs were quantified and characterised after sample peroxidation. In most species of lichen, MP and MR abundance overall was < 1 g-1 and < 0.1 g-1, respectively, and the majority of plastics were fibres of < 10 µm in diameter and < 1000 µm in length. Respective weight normalised abundances of MPs and MRs were similar in G. critina, but there were greater proportions of both larger (> 1000 µm) and non-fibrous particles among the MPs. In both lichens and moss, there was a greater number of larger MPs and MRs at locations closest to and at the same elevation as Shiraz than at more distant and elevated locations, suggesting an inverse relationship between particle size and distance travelled. Among the lichens, members of the genus Acarospora, with their areolated form, appeared to act as the most suitable biomonitors for MPs and MRs. Overall, however, the wide distribution of the moss, G. crinita, and its ability to intercept and accumulate a broader range of sizes and shapes of MPs and MRs make this species a better choice, at least in the type of environment studied.
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Contaminantes Atmosféricos , Briófitas , Líquenes , Microplásticos , Líquenes/química , Irán , Microplásticos/análisis , Contaminantes Atmosféricos/análisis , Briófitas/química , Monitoreo del Ambiente/métodos , Monitoreo Biológico/métodos , Tamaño de la PartículaRESUMEN
Harmful algal bloom (HAB) toxins consumed by marine predators through fish prey can be lethal but studies on the resulting population consequences are lacking. Over the past approximately 20 years there have been large regional declines in some harbour seal populations around Scotland. Analyses of excreta (faeces and urine from live and dead seals and faecal samples from seal haulout sites) suggest widespread exposure to toxins through the ingestion of contaminated prey. A risk assessment model, incorporating concentrations of the two major HAB toxins found in seal prey around Scotland (domoic acid (DA), and saxitoxins (STX)), the seasonal persistence of the toxins in the fish and the foraging patterns of harbour seals were used to estimate the proportion of adults and juveniles likely to have ingested doses above various estimated toxicity thresholds. The results were highly dependent on toxin type, persistence, and foraging regime as well as age class, all of which affected the proportion of exposed animals exceeding toxicity thresholds. In this preliminary model STX exposure was unlikely to result in mortalities. Modelled DA exposure resulted in doses above an estimated lethal threshold of 1900 µg/kg body mass affecting up to 3.8 % of exposed juveniles and 5.3 % of exposed adults. Given the uncertainty in the model parameters and the limitations of the data these conclusions should be treated with caution, but they indicate that DA remains a potential factor involved in the regional declines of harbour seals. Similar risks may be experienced by other top predators, including small cetaceans and seabirds that feed on similar prey in Scottish waters.
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Floraciones de Algas Nocivas , Animales , Escocia , Medición de Riesgo , Phoca , Toxinas Marinas/análisis , Ácido Kaínico/análogos & derivados , Saxitoxina/análisis , Exposición a Riesgos AmbientalesRESUMEN
The Kuiper Belt object (KBO) Arrokoth, the farthest object in the Solar System ever visited by a spacecraft, possesses a distinctive reddish surface and is characterized by pronounced spectroscopic features associated with methanol. However, the fundamental processes by which methanol ices are converted into reddish, complex organic molecules on Arrokoth's surface have remained elusive. Here, we combine laboratory simulation experiments with a spectroscopic characterization of methanol ices exposed to proxies of galactic cosmic rays (GCRs). Our findings reveal that the surface exposure of methanol ices at 40 K can replicate the color slopes of Arrokoth. Sugars and their derivatives (acids, alcohols) with up to six carbon atoms, including glucose and ribose-fundamental building block of RNA-were ubiquitously identified. In addition, polycyclic aromatic hydrocarbons (PAHs) with up to six ring units (13C22H12) were also observed. These sugars and their derivatives along with PAHs connected by unsaturated linkers represent key molecules rationalizing the reddish appearance of Arrokoth. The formation of abundant sugar-related molecules dubs Arrokoth as a sugar world and provides a plausible abiotic preparation route for a key class of biorelevant molecules on the surface of KBOs prior to their delivery to prebiotic Earth.
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For the last century, the source of sulfur in Earth's very first organisms has remained a fundamental, unsolved enigma. While sulfates and their organic derivatives with sulfur in the S(+VI) oxidation state represent core nutrients in contemporary biochemistry, the limited bioavailability of sulfates during Earth's early Archean period proposed that more soluble S(+IV) compounds served as the initial source of sulfur for the first terrestrial microorganisms. Here, we reveal via laboratory simulation experiments that the three simplest alkylsulfonic acids-water soluble organic S(+IV) compounds-can be efficiently produced in interstellar, sulfur-doped ices through interaction with galactic cosmic rays. This discovery opens a previously elusive path into the synthesis of vital astrobiological significance and untangles fundamental mechanisms of a facile preparation of sulfur-containing, biorelevant organics in extraterrestrial ices; these molecules can be eventually incorporated into comets and asteroids before their delivery and detection on Earth such as in the Murchison, Tagish Lake, and Allende meteorites along with the carbonaceous asteroid Ryugu.
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The decommissioning and normal functioning of nuclear facilities can result in the production and release of airborne particles in the environment. Aquatic biota are expected to be exposed to these particles considering that nuclear facilities are often located near water bodies. Aerosols, such as cement dust, can interact with radionuclides as well as with heavy metals, and therefore elicit not only radiological impacts but also chemical toxicity. In the present study, we aimed to determine the effects of hydrogenated cement particles (HCPs) as a first step before evaluating any radiotoxicity of tritiated cement particles in the marine mussels, Mytilus galloprovincialis. Responses at different levels of biological organisation were assessed, including clearance rate (CR), tissue specific accumulation, DNA damage and transcriptional expression of key stress related genes. Acute (5 h) and medium-term, chronic (11 d) exposures to 1000 µg L-1 HCPs showed that bioaccumulation, assessed using Cu as a proxy and determined by inductively coupled plasma mass spectrometry, was time and tissue dependent. The highest levels of Cu were found in the digestive gland (DG) after 11 d. HCP exposure caused changes in the expression of oxidative and other stress-related genes, including mt20 in DG and gst and sod in the gill after 5 h exposure, while an overexpression of hsp70 in the gill was observed after 11 d. Genotoxic effects in haemocytes were observed after 11 d of HCP exposure. Multivariate analysis indicated that oxidative stress is the most probable factor contributing to overall physiological dysfunction. Our results provide a baseline to perform further studies employing tritiated cement particles. Specifically, future work should focus on the DG since only this tissue showed significant bioaccumulation when compared to the negative control.
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Bioacumulación , Daño del ADN , Mytilus , Contaminantes Químicos del Agua , Animales , Mytilus/efectos de los fármacos , Mytilus/metabolismo , Contaminantes Químicos del Agua/toxicidad , Contaminantes Químicos del Agua/metabolismo , Materiales de Construcción , Branquias/metabolismo , Branquias/efectos de los fármacos , Estrés Oxidativo/efectos de los fármacos , Metales Pesados/toxicidad , Metales Pesados/metabolismoRESUMEN
Orthocarboxylic acidsâorganic molecules carrying three hydroxyl groups at the same carbon atomâhave been distinguished as vital reactive intermediates by the atmospheric science and physical (organic) chemistry communities as transients in the atmospheric aerosol cycle. Predicted short lifetimes and their tendency to dehydrate to a carboxylic acid, free orthocarboxylic acids, signify one of the most elusive classes of organic reactive intermediates, with even the simplest representative methanetriol (CH(OH)3)âhistorically known as orthoformic acidânot previously been detected experimentally. Here, we report the first synthesis of the previously elusive methanetriol molecule in low-temperature mixed methanol (CH3OH) and molecular oxygen (O2) ices subjected to energetic irradiation. Supported by electronic structure calculations, methanetriol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies and the detection of photoionization fragments. The first synthesis and detection of methanetriol (CH(OH)3) reveals its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition. These findings progress our fundamental understanding of the chemistry and chemical bonding of methanetriol, hydroxyperoxymethane (CH3OOOH), and hydroxyperoxymethanol (CH2(OH)OOH), which are all prototype molecules in the oxidation chemistry of the atmosphere.
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BACKGROUND: Polycystic ovary syndrome (PCOS) represents a significant global health burden requiring urgent attention. This common chronic endocrine and cardiometabolic condition affects around 1 in 10 women and individuals assigned female at birth, with significant adverse effects on well-being, quality of life, and mental health, as well as serious and complex long-term health consequences. International guidelines for best health care practice recommend the provision of comprehensive cognitive behavioral interventions to support self-management and improve health outcomes for those living with PCOS. Web-based health interventions have the potential to meet this need in an accessible and scalable way. OBJECTIVE: We aim to identify barriers to self-management and psychological well-being in women with PCOS and adapt a web-based self-management program to provide a prototype digital support intervention for them. METHODS: We adapted an existing support program (HOPE) for PCOS using the antecedent target measure approach. We conducted qualitative interviews with 13 adult women living with PCOS, 3 trustees of a patients with PCOS advocacy charity, and 4 endocrinologists to identify "antecedents" (barriers) to self-management and psychological well-being. Framework analysis was used to identify potentially modifiable antecedents to be targeted by the novel intervention. At a national conference, 58 key stakeholders (patients and health professionals) voted for the antecedents they felt were most important to address. We used research evidence and relevant theory to design a prototype for the PCOS intervention. RESULTS: Voting identified 32 potentially modifiable antecedents, relating to knowledge, understanding, emotions, motivation, and behaviors, as priorities to be targeted in the new intervention. A modular, web-based prototype HOPE PCOS intervention was developed to address these, covering six broad topic areas (instilling HOPE for PCOS; managing the stress of PCOS; feeding your mind and body well; body image, intimacy, and close relationships; staying healthy with PCOS; and keeping PCOS in its place). CONCLUSIONS: We identified barriers to self-management and psychological well-being in women with PCOS and used these to adapt a web-based self-management program, tailoring it for PCOS, which is a comprehensive group intervention combining education, empowerment, lifestyle management, peer support with cognitive behavioral tools, and goal-setting (to be delivered by peers or codelivered with health care professionals). The modular structure offers flexibility to adapt the program further as new clinical recommendations emerge. The intervention has the potential to be delivered, evaluated for feasibility, and, if effective, integrated into health care services. Self-management interventions are not designed to replace clinical care; rather, they serve as an additional source of support. The HOPE PCOS program conveys this message in its content and activities. Future research should evaluate the prototype intervention using primary outcomes such as measures of psychological well-being, self-management self-efficacy, depression, anxiety, and PCOS-related quality of life. They should also assess the intervention's acceptability, scalability, and cost-effectiveness.
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Metals may be associated with plastics as additives arising from manufacture or through acquisition from the environment, but these associations are often poorly defined or referred to synonymously when considering metal availability. In this study, samples of plastic litter (n = 22) have been collected from various environmental and industrial compartments of Lublin Province, Poland, and fractionated according to polymer type (polyethylene, polyethylene terephthalate, nylon, expanded polystyrene, polypropylene, and "mixed") before being micronised to < 2 mm. Composites (n = 89) were subjected to two phases of a standardised and widely employed sequential extraction protocol (Bureau Communautaire de Reference; BCR) in order to define available (acid-soluble and exchangeable) and residual (soluble in boiling aqua regia) concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn. For a given metal, total content, calculated by summing available and residual components, was highly variable, both between locations and amongst polymer categories, reflecting the heterogeneous distribution of a multitude of different additives. Overall, however, concentrations were greatest for Fe, with medians of several hundred to several thousand mg kg-1 amongst the different polymers, and lowest for Cd, Co, and Ni, where nearly all concentrations were below 10 mg kg-1. Median percentage metal availabilities were greatest for expanded polystyrene and were above 25% for Mn and Zn and below 10% for Cr and Fe in all polymer types. These observations are largely, but not entirely, attributed to the relative contributions of metals acquired from the environment and metals present as additives and residues. Significantly, the approach employed allows direct comparisons of metal availability in plastics with metal availability in environmental solids in order to evaluate the overall impacts of plastics in metal risk assessments.
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Metales Pesados , Metales Pesados/análisis , Cadmio , Poliestirenos , Monitoreo del Ambiente/métodos , Medición de RiesgoRESUMEN
BACKGROUND: Individuals with rare kidney diseases account for 5-10% of people with chronic kidney disease, but constitute more than 25% of patients receiving kidney replacement therapy. The National Registry of Rare Kidney Diseases (RaDaR) gathers longitudinal data from patients with these conditions, which we used to study disease progression and outcomes of death and kidney failure. METHODS: People aged 0-96 years living with 28 types of rare kidney diseases were recruited from 108 UK renal care facilities. The primary outcomes were cumulative incidence of mortality and kidney failure in individuals with rare kidney diseases, which were calculated and compared with that of unselected patients with chronic kidney disease. Cumulative incidence and Kaplan-Meier survival estimates were calculated for the following outcomes: median age at kidney failure; median age at death; time from start of dialysis to death; and time from diagnosis to estimated glomerular filtration rate (eGFR) thresholds, allowing calculation of time from last eGFR of 75 mL/min per 1·73 m2 or more to first eGFR of less than 30 mL/min per 1·73 m2 (the therapeutic trial window). FINDINGS: Between Jan 18, 2010, and July 25, 2022, 27â285 participants were recruited to RaDaR. Median follow-up time from diagnosis was 9·6 years (IQR 5·9-16·7). RaDaR participants had significantly higher 5-year cumulative incidence of kidney failure than 2·81 million UK patients with all-cause chronic kidney disease (28% vs 1%; p<0·0001), but better survival rates (standardised mortality ratio 0·42 [95% CI 0·32-0·52]; p<0·0001). Median age at kidney failure, median age at death, time from start of dialysis to death, time from diagnosis to eGFR thresholds, and therapeutic trial window all varied substantially between rare diseases. INTERPRETATION: Patients with rare kidney diseases differ from the general population of individuals with chronic kidney disease: they have higher 5-year rates of kidney failure but higher survival than other patients with chronic kidney disease stages 3-5, and so are over-represented in the cohort of patients requiring kidney replacement therapy. Addressing unmet therapeutic need for patients with rare kidney diseases could have a large beneficial effect on long-term kidney replacement therapy demand. FUNDING: RaDaR is funded by the Medical Research Council, Kidney Research UK, Kidney Care UK, and the Polycystic Kidney Disease Charity.
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Fallo Renal Crónico , Insuficiencia Renal Crónica , Insuficiencia Renal , Humanos , Tasa de Filtración Glomerular , Riñón , Fallo Renal Crónico/epidemiología , Fallo Renal Crónico/terapia , Fallo Renal Crónico/etiología , Radar , Enfermedades Raras , Sistema de Registros , Insuficiencia Renal/epidemiología , Insuficiencia Renal Crónica/epidemiología , Insuficiencia Renal Crónica/terapia , Insuficiencia Renal Crónica/complicaciones , Reino Unido/epidemiología , Recién Nacido , Lactante , Preescolar , Niño , Adolescente , Adulto Joven , Adulto , Persona de Mediana Edad , Anciano , Anciano de 80 o más AñosRESUMEN
Microplastics and other microscopic debris are a concern in the coastal environment but measurements in the water column and sediment are often problematic and rely on non-standardised and highly variable methodologies. To this end, we explore the potential of different species of temperate-cold marine macroalgae as passive biomonitors of anthropogenic microparticles at three contrasting locations in southwest England. Specifically, fronds from samples of fucoids and Ulva lactuca (n = 9 in total, and three from each location) have been sectioned and analysed directly under a microscope and anthropogenic microparticles counted and subsequently characterised for chemical composition. Microparticles were heterogeneously distributed throughout sections from the same sample. However, on a dry weight basis, combined microparticle concentrations for each sample ranged from about 7.5 g-1 to 110 g-1, and from about 0.2 cm-2 to 0.9 cm-2, and for a given species were higher in samples from a semi-enclosed harbour and urban beach than in samples from a protected beach facing the open sea. These values compare with published concentrations of microplastics and microfibres reported for the regional water column on the order of 0.1 m-3. Most particles were cellulosic (e.g., rayon) and petroleum-based (mainly polyester and polyethylene terephthalate) fibres but plastic fragments were also present on most samples. Glass retroreflective beads derived from road markings were also present at up to 18 g-1 on fucoids from the urban beach because of its proximity to a stormwater effluent. Most microparticles were adhered to the smooth parts of the macroalgal surface but some displayed wrapping around edges and creases or entrapment by appendages. The practical and environmental implications of macroalgae passively capturing significant quantities of anthropogenic microparticles are discussed.
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Algas Comestibles , Algas Marinas , Ulva , Contaminantes Químicos del Agua , Microplásticos/análisis , Plásticos/análisis , Monitoreo Biológico , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/métodos , Agua/análisisRESUMEN
Masses of plastic and other anthropogenic debris on beaches of inner Seychelles and derived from 53 organised clean-ups have been analysed. Debris and plastic densities ranged from 0.0011 to 0.1622 kg m-2 and 0.0004 to 0.1179 kg m-2, respectively, and data from successive cleans of the same beach resulted in respective median accumulation rates of 0.0293 and 0.0137 g m-2 d-1. There was no dependence of density or accumulation on beach location/aspect or season, but there were significant inverse relationships with beach area. This effect was attributed to most debris and plastic being trapped on the backshore by rocks and vegetation, and the areal proportion of backshore increasing with decreasing beach size. Plastic is derived from local littering and more distal sources, with polyethylene terephthalate bottles, flip-flops and Styrofoam fragments making important contributions. Without intervention and an increased risk of coastal flooding with climate change, beached debris on Seychelles is predicted to increase.
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Ciencia Ciudadana , Residuos , Residuos/análisis , Plásticos , Seychelles , Monitoreo del Ambiente/métodos , PlayasRESUMEN
Waste disposal in landfills remains a global concern. Despite technological developments, landfill leachate poses a hazard to ecosystems and human health since it acts as a secondary reservoir for legacy and emerging pollutants. This study provides a systematic and scientometric review of the nature and toxicity of pollutants generated by landfills and means of assessing their potential risks. Regarding human health, unregulated waste disposal and pathogens in leachate are the leading causes of diseases reported in local populations. Both in vitro and in vivo approaches have been employed in the ecotoxicological risk assessment of landfill leachate, with model organisms ranging from bacteria to birds. These studies demonstrate a wide range of toxic effects that reflect the complex composition of leachate and geographical variations in climate, resource availability and management practices. Based on bioassay (and other) evidence, categories of persistent chemicals of most concern include brominated flame retardants, per- and polyfluorinated chemicals, pharmaceuticals and alkyl phenol ethoxylates. However, the emerging and more general literature on microplastic toxicity suggests that these particles might also be problematic in leachate. Various mitigation strategies have been identified, with most focussing on improving landfill design or leachate treatment, developing alternative disposal methods and reducing waste volume through recycling or using more sustainable materials. The success of these efforts will rely on policies and practices and their enforcement, which is seen as a particular challenge in developing nations and at the international (and transboundary) level. Artificial intelligence and machine learning afford a wide range of options for evaluating and reducing the risks associated with leachates and gaseous emissions from landfills, and various approaches tested or having potential are discussed. However, addressing the limitations in data collection, model accuracy, real-time monitoring and our understanding of environmental impacts will be critical for realising this potential.
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Inteligencia Artificial , Ecotoxicología , Instalaciones de Eliminación de Residuos , Humanos , Monitoreo del Ambiente/métodos , Política Ambiental , Eliminación de Residuos/métodos , Medición de Riesgo , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/toxicidadRESUMEN
The release of microfibres from fabrics during laundering represents an important source of plastic and natural microfibres to aquatic environments. Garment age - how long the garment has been used - could be a key factor influencing the rate of release, yet most studies of microfibre shedding have only assessed newly manufactured products. To this end, we quantified microfibre release during laundering in domestic washing machines from polyester (PES) and cotton garments (n = 38) used in real-life conditions for periods between 1 and 31 years with different use intensities. In addition, to better understand the factors involved in microfibre releases, fibre composition (different PES percentages) and type of garments (T-shirts, polo shirts, uniforms, sports shirts, and sweatshirts) were examined. All garments released microfibres during washing, while the older garments presented higher releases for clothing with a PES/cotton blend. In general, older garments (15-31 years) released nearly twice as many fibres when washed than newer garments (1-10 years). The mass of microfibres released was consistently greater in garments with a higher proportion of cotton than PES (up to 1.774 mg g-1 in 2% PES and 0.366 mg g-1 in 100% PES fabrics), suggesting that cotton might be released more readily such that the relative proportion of PES in the garments could increase over time. Additionally, SEM images showed fibre damage, with fibres from the older garments exhibiting more peeling and splitting. While it is important to note that the overall environmental footprint is undoubtedly reduced by keeping garments in use for longer periods of time, older garments were shown to release more microfibres.
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Lavandería , Poliésteres , Textiles , Lavandería/métodos , VestuarioRESUMEN
OBJECTIVE: To describe the experiences and opinions of general practitioners (GPs) in England regarding patients having access to their full online GP health records. DESIGN: Convenience sample, online survey. PARTICIPANTS: 400 registered GPs in England. MAIN OUTCOME MEASURES: Investigators measured GPs' experiences and opinions about online record access (ORA), including patient care and their practice. RESULTS: A total of 400 GPs from all regions of England responded. A minority (130, 33%) believed ORA was a good idea. Most GPs believed a majority of patients would worry more (364, 91%) or find their GP records more confusing than helpful (338, 85%). Most GPs believed a majority of patients would find significant errors in their records (240, 60%), would better remember their care plan (280, 70%) and feel more in control of their care (243, 60%). The majority believed they will/already spend more time addressing patients' questions outside of consultations (357, 89%), that consultations will/already take significantly longer (322, 81%) and that they will be/already are less candid in their documentation (289, 72%) after ORA. Nearly two-thirds of GPs believed ORA would increase their litigation (246, 62%). CONCLUSIONS: Similar to clinicians in other countries, GPs in our sample were sceptical of ORA, believing patients would worry more and find their records more confusing than helpful. Most GPs also believed the practice would exacerbate work burdens. However, the majority of GPs in this survey also agreed there were multiple benefits to patients having online access to their primary care health records. The findings of this survey also contribute to a growing body of contrastive research from countries where ORA is advanced, demonstrating clinicians are sceptical while studies indicate patients appear to derive multiple benefits.
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Médicos Generales , Humanos , Actitud del Personal de Salud , Inglaterra , Atención al Paciente , Derivación y Consulta , Encuestas y CuestionariosRESUMEN
Pharmaceuticals are recognised as environmental contaminants of emerging concern (CECs) due to their increasing presence in the aquatic environment, along with high bioactivity linked to their therapeutic use. Therefore, information on environmental levels is urgently required. This study examined the presence of a range of common pharmaceuticals in oysters and mussels intended for human consumption from England and Wales using stable isotope dilution tandem mass spectrometry. A range of compounds were detected in bivalve tissue, with the Selective Serotonin Reuptake Inhibitor antidepressant sertraline being most abundant, reaching a maximum concentration of 22.1 ng/g wet weight shellfish tissue. Levels of all pharmaceuticals showed seasonal and geographical patterns. A dietary risk assessment revealed that the levels of pharmaceuticals identified in bivalve molluscs represent a clear hazard, but not a risk for the consumer. This study highlights the requirement for further monitoring of the presence of pharmaceuticals and other CECs in bivalve molluscs.
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Bivalvos , Ostreidae , Animales , Humanos , Estaciones del Año , Bivalvos/química , Ostreidae/química , Mariscos/análisis , Preparaciones Farmacéuticas , Monitoreo del AmbienteRESUMEN
A high temperature phenyl-mediated addition-cyclization-dehydrogenation mechanism to form peri-fused polycyclic aromatic hydrocarbon (PAH) derivatives-illustrated through the formation of dibenzo[e,l]pyrene (C24H14)-is explored through a gas-phase reaction of the phenyl radical (C6H5Ë) with triphenylene (C18H12) utilizing photoelectron photoion coincidence spectroscopy (PEPICO) combined with electronic structure calculations. Low-lying vibrational modes of dibenzo[e,l]pyrene exhibit out-of-plane bending and are easily populated in high temperature environments such as combustion flames and circumstellar envelopes of carbon stars, thus stressing dibenzo[e,l]pyrene as a strong target for far-IR astronomical surveys.
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Cellulose acetate fibres from cigarette filters represent a form of microplastic that has received little attention in the environment. In this study, a ground composite of spent, smoked filter material (FM) has been used to investigate the role of cellulose acetate fibres as a source and a sink of trace metals (Cd, Co, Cu, Ni, Pb and Zn) in coastal waters. FM suspended in river water and seawater and mixtures thereof representative of an estuarine gradient resulted in the leaching of pre-existent metals derived from the combustion of tobacco, with mean percentages of release ranging from about 40 for Pb to nearly 90 for Cd, Co and Zn. Addition of 40 µg L-1 of each metal to FM suspensions incubated for 48 h yielded mean partition coefficients (KDs) ranging from <10 L kg-1 for Co to > 100 L kg-1 for Cu, Pb and Zn, with Cu and Ni displaying a net increase in KD with increasing salinity. Adsorption is interpreted in terms of hydrophobic interactions between metal-organic complexes and the cellulose acetate surface, and in support of this assertion KDs exhibited a significant, positive relationship with published metal-humic acid binding constants. The findings of this study improve our understanding of the role of cellulosic microfibres more generally in transporting trace metals in aquatic systems.
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Metales Pesados , Productos de Tabaco , Oligoelementos , Contaminantes Químicos del Agua , Cadmio , Plomo , Plásticos , Oligoelementos/análisis , Contaminantes Químicos del Agua/análisis , Metales Pesados/análisis , Monitoreo del Ambiente/métodosRESUMEN
Surface and subsurface sediment samples (n = 16) from the highly urbanised inner Thames Estuary (UK) have been physically and chemically characterised and analysed for anthropogenic microdebris. Sediments were gravelly sands throughout and were heavily contaminated by lead (Pb, up to 12,500 mg kg-1) and zinc (Zn, up to 9500 mg kg-1). Microfibres of mm-dimensions and retroreflective glass microbeads (median diameter = 188 µm) used in road markings were the most abundant types of microdebris present, and concentrations (as numbers, N) on a dry weight basis were spatially heterogeneous (ranging from about 4000 to 60,000 N kg-1 and 100 to 28,000 N kg-1, respectively). Nevertheless, concentrations of the two types of particle were significantly correlated and both displayed an inverse, non-linear relationship with sediment grain size. Road marking paint fragments of different colours were detected in most cases (n = 13) but quantification was difficult because of analytical constraints related to size, shape, colour, fragmentation and encrustation. Concentrations of up to about 500 mg kg-1 Pb were determined in isolated paint fragments but road paint particles are unlikely to make a significant contribution to Pb pollution in Thames Estuary sediments. Overall, our observations suggest that stormwater runoff is a significant source of multiple types of anthropogenic microdebris in urban estuaries, with additional, direct atmospheric deposition contributing to microfibre accumulation. More generally, it is recommended that studies of microplastics consider additional debris and sediment characteristics for a better understanding of their sources and transport.