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A full-scale passive treatment plant using barium carbonate (BaCO 3 ), the mineral witherite, as a Dispersed Alkaline Substrate (DAS) for strongly contaminated acid mine drainage was implemented for the first time globally at Mina Concepción, located in the Iberian Pyrite Belt (SW Spain). The plant was monitored over a 105-day period, covering the wettest months of the hydrological year and with a mean flow around 4 L s -1 . The AMD treated in the plant exhibits a high strength, with an average sulfate concentration around 1500 mg L -1 and net acidity close to 1000 mg L -1 as CaCO₃ equivalent. According to the above, the loading rate for SO 4 and Fe was around 400 and 80 kg day -1 , respectively. The treatment process produced an alkaline effluent with low metal content. Nearly complete removal of most metal(loid)s was achieved, with significant sulfate decrease to below 500 mg L -1 in the alkaline outflow of the barium carbonate tank. Barium carbonate demonstrated superior performance compared to magnesia, particularly in enhancing alkalinity and lowering net acidity and concentrations of sulfate and manganese. The high efficiency attained by the plant after the barium carbonate treatment is evidenced by compliance with environmental water quality standards for most contaminants., 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 © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Blowouts are wind-formed depressions that help maintain the sediment budget and enhance biodiversity in coastal dunes. However, the drivers controlling their evolution and the temporal scales associated to their genesis, development and decay phases remain unclear. To address this, the morphometric characteristics of a series of blowouts on the Ancão Peninsula (South Portugal) were digitized using imagery from 1972 to 2021, and used to analyse changes in the number of blowouts, total area, morphometric characteristics (width, length, orientation), and elongation rate over time. These data were compared with metocean time series and human activities, allowing the identification of blowout phases, drivers, and associated temporal scales. This work revealed that the blowout genesis phase primarily arised from the impact of physical external factors (e.g., non-storm low-to-moderate winds blowing out sand from dune scarp irregularities formerly created by extreme wave events), creating incisions across the foredune crest, and lasted 1 or 2 years. The blowout development phase, still ongoing, was characterized mainly by blowout expansion and rotation of large blowouts from North-northeast (NNE) to the East-northeast (ENE) controlled by external physical forces at specific times (e.g., low-to-moderate winds) and blowout internal factors (e.g., size and orientation). Complete blowout decay phases were not observed, except the complete artificial sealing of some blowouts due to fencing, which lasted 4 years. These findings suggest that a complete and natural blowout genesis-development-decay cycle could likely take more than five decades, with complex and spatiotemporally variable ecogeomorphic feedbacks driving their evolution. The only phase reversal documented was the reactivation of the artificially sealed blowouts, due to storm impacts. Allowing the dune and blowouts to evolve naturally appears to be the current best approach for the dune management at the studied area., 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 © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Fast detection of viral infections is a key factor in the strategy for the prevention of epidemics expansion and follow-up. Hepatitis C is paradigmatic within viral infectious diseases and major challenges to elimination still remain. Near infrared spectroscopy (NIRS) is an inexpensive, clean, safe method for quickly detecting viral infection in transmission vectors, aiding epidemic prevention. Our objective is to evaluate the combined potential of machine learning and NIRS global molecular fingerprint (GMF) from biobank sera as an efficient method for HCV activity discrimination in serum. GMF of 151 serum biobank microsamples from hepatitis C patients were obtained with a FT-NIR spectrophotometer in reflectance mode. Multiple scatter correction, smoothing and Saviztsky-Golay second derivative were applied. Spectral analysis included Principal Component Analysis (PCA), Bootstrap and L1-penalized classification. Microsamples of 70 µl were sufficient for GMF acquisition. Bootstrap evidenced significant difference between HCV PCR positive and negative sera. PCA renders a neat discrimination between HCV PCR-positive and negative samples. PCA loadings together with L1-penalized classification allow the identification of discriminative bands. Active virus positive sera are associated to free molecular water, whereas water in solvation shells is associated to HCV negative samples. Divergences in the water matrix structure and the lipidome between HCV negative and positive sera, as well as the relevance of prooxidants and glucose metabolism are reported as potential biomarkers of viral activity. Our proof of concept demonstrates that NIRS GMF of hepatitis C patients' sera aided by machine learning allows for efficient discrimination of viral presence and simultaneous potential biomarker identification., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Oscar Barquero reports financial support was provided by Spanish Ministry of Education and Science. If there are other authors, they 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 © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Invasive species are a major threat to global diversity and can interact synergistically or antagonistically with various components of climate change. Using species distribution models (SDMs) at different spatial scales and resolutions, we determined the main variables affecting the distribution of six invasive macroalgae present on European coasts. We also studied occupation of the thermal realized niche and predicted areas potentially at risk of invasion. The climatic variables related to warming had a greater influence on distribution at large scales, while non-climatic variables related to river influence and maritime transport at regional scale. Invaders often seemed to occupy colder areas than in their native area. The combination of SDMs with thermal niche of species is a useful way of clarifying the invasion process. This approach will help in the development of preventive strategies whereby the responsible authorities can implement early detection systems and respond swiftly to the appearance of biopollutants., 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 © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Undiagnosed and untreated human immunodeficiency virus (HIV) infection increases morbidity in the HIV-positive person and allows onward transmission of the virus. Minimizing missed opportunities for HIV diagnosis when a patient visits a healthcare facility is essential in restraining the epidemic and working toward its eventual elimination. Most state-of-the-art proposals employ machine learning (ML) methods and structured data to enhance HIV diagnoses, however, there is a dearth of recent proposals utilizing unstructured textual data from Electronic Health Records (EHRs). In this work, we propose to use only the unstructured text of the clinical notes as evidence for the classification of patients as suspected or not suspected. For this purpose, we first compile a dataset of real clinical notes from a hospital with patients classified as suspects and non-suspects of having HIV. Then, we evaluate the effectiveness of two types of classification models to identify patients suspected of being infected with the virus: classical ML algorithms and two Large Language Models (LLMs) from the biomedical domain in Spanish. The results show that both LLMs outperform classical ML algorithms in the two settings we explore: one dataset version is balanced, containing an equal number of suspicious and non-suspicious patients, while the other reflects the real distribution of patients in the hospital, being unbalanced. We obtain F 1 score figures of 94.7 with both LLMs in the unbalanced setting, while in the balance one, RoBERTa Bio model outperforms the other one with a F 1 score of 95.7. The findings indicate that leveraging unstructured text with LLMs in the biomedical domain yields promising outcomes in diminishing missed opportunities for HIV diagnosis. A tool based on our system could assist a doctor in deciding whether a patient in consultation should undergo a serological test., Competing Interests: Declaration of competing interest None declared., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The Huelva estuary is formed by the common mouths of the Odiel and Tinto Rivers, and inside this ecosystem is the biosphere reserve of the Odiel saltmarshes. This ecosystem has been historically affected by acid mine drainage (AMD) and by releases of pollutants from five phosphoric acid industrial plants and phosphogypsum (PG) waste stacks located in the area. This study carried out a comprehensive assessment of the environmental impact of the biosphere reserve of the Odiel saltmarshes. To this end, it was necessary to find a suitable sedimentary background (Piedras River in our case). To quantify this impact, several pollution indexes were used. According to the values reached by the indexes, this impact was classified as "serious" pollution for most trace elements, excepting the deepest layers, and "low-moderate" pollution for the 238 U-series radionuclides, while no pollution for the 232 Th-series and 40 K radionuclides was found as expected., 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 © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Public health concern associated with the ingestion of microplastics (MPs) released from water packaging materials is increasing. The use of plastic materials for solar disinfection (SODIS) containers has also raised concerns in the SODIS community due to the lack of studies evaluating the presence of MPs in the treated water. In this work, the migration of MPs from poly(ethylene terephthalate, PET) bottles and polypropylene (PP) translucent and transparent jerrycan containers (TJC) into water under natural weathering was investigated using micro-reflectance Fourier Transform Infrared Spectroscopy (µ-FTIR). Containers exposed to sunlight for three months became photodegraded, releasing micro-sized fragments identified as PET, PP and high-density polyethylene (HDPE, from the screw-caps), although with varying degrees of weathering. It is noteworthy that the presence of a clarifying additive in PP formulation did not seem to impact the release of MPs from the containers. The study showed that PP TJC containers released more MPs than PET bottles. Finally, the size of MPs was measured to determine their fate upon ingestion and highlights the need for further studies to understand the safety of these plastic containers for SODIS., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The development of biobased fire-safe thermosets with recyclability heralds the switch for a transition towards a circular economy. In this framework, we introduced a novel high-performance bio-epoxy vitrimer (named GVD), which was fabricated by forming a crosslinking network between bio-epoxy glycerol triglycidyl ether (Gte), varying amounts of reactive flame-retardant agent 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) (0-7 wt%) and a vanillin-based hardener (VA) with imine bonds. For instance, the epoxy vitrimer GVD5, featuring a DOPO content of 5 wt%, achieved a V-0 rating in the vertical burning test (UL-94) and obtained a limiting oxygen index (LOI) value of 31 %, surpassing the performance of pristine epoxy. Furthermore, the peak heat release rate and total heat release of GVD5 were reduced by 38.2 % and 26.3 %, respectively, compared to pristine epoxy. The GVD vitrimers further demonstrated exceptional reprocessability and recyclability, attributed to the presence of dynamic imine bonds within the topological crosslinking network. Remarkably, the epoxy vitrimers maintained the mechanical properties of the parent epoxy. Therefore, this work provides a facile strategy for fabricating high-performance and multi-functional bio-epoxy thermosets., 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 © 2024 Elsevier B.V. All rights reserved.)

Immobilised TiO 2 nanotube (TiO 2 -NT) electrodes were grown via electrochemical anodisation in an aqueous solution containing fluoride ions at 10, 20 and 30 V. The photocatalytic (PC) and photoelectrocatalytic (PEC) activity of TiO 2 -NTs electrodes in the oxidation of methanol and the inactivation of bacteria and fungi was studied in different chloride salts electrolytes. Low concentrations of electrochemically generated oxidising species, such as free chlorine, were measured in experiments at pH 8.5 and +1 V of applied potential. Increasing the anodising potential results in longer nanotubes with higher photoactivity. The TiO 2 -NT electrode anodised at 30 V (TiO 2 -NT30V) generates free chlorine with an average concentration of 0.03 mg·L -1 upon illumination with UV-A at +1 V of potential bias. This concentration was enough to achieve 99.99 % of inactivation of a 10 6  CFU·mL -1 Gram-negative bacteria (Escherichia coli) in <3 min and Gram-positive bacteria (Enterococcus faecalis) after 7 min, whereas fungi (Candida albicans) required 15 min. The low production of chlorine was found to have a big impact on the bacteria and fungi inactivation even in not favourable chlorine generation conditions. An in situ investigation of the most influential parameters in the inactivation of some microorganisms with PEC and NT30V electrode has been done. It was found that free chlorine production increases with the length of TiO 2 -NT, with Cl - concentration up to 15 mmol·L -1 and with the application of potential bias. TiO 2 -NT30V photoanode has been demonstrated to produce active chlorine at levels compatible with the water disinfection process, suggesting that the present method could be considered a promising alternative for in situ chlorine-based disinfection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The increase in efficiency achieved by UV LED devices has led to a compelling increase in research reports on UV LED water treatment for consumption in the past few years. This paper presents an in-depth review based on recent studies on the suitability and performance of UV LED-driven processes for water disinfection. The effect of different UV wavelengths and their combinations was analysed for the inactivation of various microorganisms and the inhibition of repair mechanisms. Whereas 265 nm UVC LED present a higher DNA damaging potential, 280 nm radiation is reported to repress photoreactivation and dark repair. No synergistic effects have been proved to exist when coupling UVB + UVC whereas sequential UVA-UVC radiation seemed to enhance inactivation. Benefits of pulsed over continuous radiation in terms of germicidal effects and energy consumption were also analysed, but with inconclusive results. However, pulsed radiation may be promising for improving thermal management. As a challenge, the use of UV LED sources introduces significant inhomogeneities in the light distribution, pushing for the development of adequate simulation methods to ensure that the minimum target dose required for the target microbes is achieved. Concerning energy consumption, selecting the optimal wavelength of the UV LED needs a compromise between the quantum efficiency of the process and the electricity-to-photon conversion. The expected development of the UV LED industry in the next few years points to UVC LED as a promising technology for water disinfection at a large scale that could be competitive in the market in the near future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Freshwaters are considered among the most endangered ecosystems globally due to multiple stressors, which coincide in time and space. These local stressors typically result from land-use intensification or hydroclimatic alterations, among others. Despite recent advances on multiple stressor effects, current knowledge is still limited to manipulative approaches minimizing biological and abiotic variability. Thus, the assessment of multiple stressor effects in real-world ecosystems is required. Using an extensive survey of 50 stream reaches across North Portugal, we evaluated taxonomic and functional macroinvertebrate responses to multiple stressors, including marked gradients of nutrient enrichment, flow reduction, riparian vegetation structure, thermal stress and dissolved oxygen depletion. We analyzed multiple stressor effects on two taxonomic (taxon richness, Shannon-diversity) and two trait-based diversity indices (functional richness, functional dispersion), as well as changes in trait composition. We found that multiple stressors had additive effects on all diversity metrics, with nutrient enrichment identified as the most important stressor in three out of four metrics, followed by dissolved oxygen depletion and thermal stress. Taxon richness, Shannon-diversity and functional richness responded similarly, whereas functional dispersion was driven by changes in flow velocity and thermal stress. Functional trait composition changed along a major stress gradient determined by nutrient enrichment and oxygen depletion, which was positively correlated with organisms possessing fast-living strategies, aerial respiration, adult phases, and gathering-collector feeding habits. Overall, our results reinforce the need to consider complementary facets of biodiversity to better identify assembly processes in response to multiple stressors. Our data suggest that stressor interactions may be less frequent in real-word streams than predicted by manipulative experiments, which can facilitate mitigation strategies. By combining an extensive field survey with an integrative consideration of multiple biodiversity facets, our study provides new insights that can help to better assess and manage rivers in a global change context., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

The amount of wastewater processed in treatment plants is increasing following more strict environmental regulations. Treatment facilities are implementing upgrades to abate the concentrations of nutrients and contaminants and, thus, reduce their effects on receiving systems. Although many studies characterized the chemical composition and ecotoxicological effects of treated wastewater, its environmental effects are still poorly known, as receiving water bodies are often subjected to other stressors. We performed a field manipulative experiment to measure the response of invertebrate assemblages to one year of tertiary-treated wastewater discharges. We poured treated wastewater from an urban wastewater treatment plant into the lower-most 100-m of a previously unpolluted stream (3.6 % daily flow on average) while using another upstream reach as control. The positive correlation between effect sizes of abundance changes and IBMWP scores suggested assemblage modifications were following taxa tolerance to ecological impairment. The treatment increased the temporal variability of SPEAR organic , EPT relative abundance, and invertebrate functional redundancy. Our results show that even in this best-case scenario of tertiary-treated and highly diluted wastewater, the abundance of the most sensitive taxa in the aquatic assemblages is reduced. Further improvements in wastewater treatments seem necessary to ensure these effluents do not modify receiving water ecosystems., 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 © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

It is accepted that Microplastic (MP) biofilms accumulates antibiotic-resistant bacteria (ARB) and antibiotic-resistant genes (ARGs) in water. ARB/ARGs and MPs are emerging pollutants of concern due to various associated health risks. The objective of this study was to 1) investigate the ARB community in a pilot-scale wastewater treatment plant (WWTP) effluent, 2) to study and visualize the ARB/ARGs in MP biofilm grown in WWTP effluent and tap water, and 3) to analyze microplastic adherent ARB/ARGs in the biofilm and planktonic ARB/ARGs in the filtrate under controlled conditions. Results indicated the dominance of Pseudomonas, Aeromonas, and Bacillus among isolated ARB in WWTP effluent. Representative resistance strains were incubated in 300 mL water containing commercial polystyrene beads of 300550 μm diameter (MP) in a series of batch experiments. Microbiological, molecular, and microscopic analyses were performed by enumeration, 16srRNA, real-time polymerase chain reaction (qPCR), and Field Emission-Scanning Electron Microscopy (FEG-SEM) techniques. The analyzed viable ARB indicated an increasing trend in MP biofilms between days 3 and 5. It further decreased on days 7 and 9. The prevalence of ARB in the filtrate and MP biofilm varied as a function of time and TOC level, while no significant impacts were observed for minor temperature variation, low antibiotic pressure, and increased MP mass with few exceptions. Relative abundance of ARGs (vanA, sul1) and integron integrase gene (intl1) in MP biofilm were significantly different across different TOC levels, time, and antibiotic pressure. ARGs and intl1 were detected in the MP biofilm in tap water and WWTP effluent on day 30., 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 © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The feasibility to manufacture scaffolds of poly-lactic acid reinforced with Zn particles by fused filament fabrication is demonstrated for the first time. Filaments of 2.85 mm in diameter of PLA reinforced with different weight fractions of μm-sized Zn - 1 wt.% Mg alloy particles (in the range 3.5 to 17.5 wt.%) were manufactured by a double extrusion method in which standard extrusion is followed by precision extrusion in a filament-maker machine. Filaments with constant diameter, negligible porosity and a homogeneous reinforcement distribution were obtained for Zn weight fractions of up to 10.5%. It was found that the presence of Zn particles led to limited changes in the physico-chemical properties of the PLA that did not affect the window temperature for 3D printing nor the melt flow index. Thus, porous scaffolds could be manufactured by fused filament fabrication at 190 °C with poly-lactic acid/Zn composites containing 3.5 and 7 wt.% of Zn and at 170 °C when the Zn content was 10.5 wt.% with excellent dimensional accuracy and mechanical properties., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Assessing the spatial and temporal changes in ecosystems is essential to account for natural capital contribution to human well-being. However, various methods to quantify these changes challenge the development of reliable values which can be integrated into national statistical accounts. Following the international system of environmental-economic accounting framework, which recently adopts an ecosystem accounting standard. We present a novel approach to develop an ecosystem extent account from existing ecosystem classifications. This study shows the spatial and statistical extent account of 26 ecosystems (i.e. forests, grasslands, croplands, and urban, among others) between 1970 and 2015 at the national scale. Extent accounts were developed at a resolution of 25 m and provided reliable information on how ecosystem types have changed over time in Spain. Our results reflect three main patterns in the extension account: (i) an increase in forest ecosystems, (ii) a considerable decrease in agroecosystems (especially annual croplands), and (iii) substantial development of urban areas. To the best of our knowledge, this method is the first attempt to develop a robust methodology to measure the extent of ecosystems at the national level. The proposed approach is crucial for a strong knowledge of ecosystem dynamics and their implications for ecosystem conditions and services at a national level. This has potential applications in urban planning, green infrastructure development, and multiple uses for territory management and policies, integrating natural capital into official statistics and mainstreaming ecosystems into national-level planning and monitoring processes., 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 © 2022 Elsevier B.V. All rights reserved.)

The quality of water bodies has been decreasing over time. Urban wastewater treatment plants (UWWTPs) are key players to avoid that potentially toxic micropollutants reach the environment, and advanced treatment processes are being applied to address this issue. However, several variables have to be taken into account, particularly environmental sustainability. The aim of this study is to assess the life cycle impacts of combining UVC with different oxidants - hydrogen peroxide (H 2 O 2 ), peroxymonosulfate (PMS) and persulfate (PS) -, considering different concentrations (0.05, 0.20 and 0.50 mM) and UVC dosages of 42, 63 and 170 J/L, corresponding to UV contact times of 4, 7 and 18 s in a specific industrial equipment. UVC/PMS was the worst performing process (despite being able to achieve removals similar to UVC/H 2 O 2 ), followed by UVC/PS. Both would only be preferred relatively to H 2 O 2 if much lower concentrations of PMS or PS could be used to achieve the same removal of micropollutants (10 times lower was not enough). Additionally, PMS and PS production contributes more to the environmental footprint than the electricity use, unlike H 2 O 2 . Therefore even if considering lower treatment times when using sulfate-based oxidants, these will still be more impactful than using H 2 O 2 at the studied conditions. Based on both avoided and generated impacts, H 2 O 2 is the best option environmentally. In this case, the environmental impacts are more affected by an increase in treatment time rather than by an increase in the H 2 O 2 concentration. It is thus best to opt for a higher concentration and the lowest treatment time possible for a significant ecotoxicity reduction. Electricity is a relevant parameter in all cases and its impact can be reduced in nearly all endpoint categories by opting for cleaner energy sources., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Solar technologies constitute an excellent alternative for water treatment in low-income countries where the poverty of a large part of the population hinders their access to safe water. From a technical point of view, the use of compound parabolic collectors (CPC) has been consolidated in the last decades. However, the relatively high cost of tooling conventional manufacturing processes for these collectors makes them difficult to afford in the most impoverished regions. This work presents the development of low-cost CPC and parabolic through solar collectors (PTC) by 3D printing of the structure and the use of recycled reflective materials. Besides, open-source hardware has been used to control system operation, including a supplementary UV LED system to compensate for the operation under low solar irradiance. Regarding the tested reflective materials, an optimum is obtained using an aluminium adhesive sheet that leads to an efficiency of 80% compared to a commercial CPC made of high-quality anodised aluminium, being the cost 20 times lower. On the other hand, incorporating a low-cost solar tracking system in a printed PTC reactor could lead to efficiencies up to 300% compared to the commercial CPC, while the cost was 4.5 times lower. Finally, the LED compensation system was successfully validated, allowing the operation with a constant treatment capacity during operation in cloudy conditions. In conclusion, the developed collectors are high-performance solar water treatment systems with a significantly lower investment cost, making them affordable worldwide., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Climate change is increasing the frequency of extreme climate events, causing profound impacts on forest function and composition. Late frost defoliation (LFD) events, the loss of photosynthetic tissues due to low temperatures at the start of the growing season, might become more recurrent under future climate scenarios. Therefore, the detection of changes in late-frost risk in response to global change emerges as a high-priority research topic. Here, we used a tree-ring network from southern European beech (Fagus sylvatica L.) forests comprising Spain, Italy and the Austrian Alps, to assess the incidence of LFD events in the last seven decades. We fitted linear-mixed models of basal area increment using different LFD indicators considering warm spring temperatures and late-spring frosts as fixed factors. We reconstructed major LFD events since 1950, matching extreme values of LFD climatic indicators with sharp tree-ring growth reductions. The last LFD events were validated using remote sensing. Lastly, reconstructed LFD events were climatically and spatially characterized. Warm temperatures before the late-spring frost, defined by high values of growing-degree days, influenced beech growth negatively, particularly in the southernmost populations. The number of LFD events increased towards beech southern distribution edge. Spanish and the southernmost Italian beech forests experienced higher frequency of LFD events since the 1990s. Until then, LFD events were circumscribed to local scales, but since that decade, LFD events became widespread, largely affecting the whole beech southwestern distribution area. Our study, based on in-situ evidence, sheds light on the climatic factors driving LFD occurrence and illustrates how increased occurrence and spatial extension of late-spring frosts might constrain future southern European beech forests' growth and functionality. Observed alterations in the climate-phenology interactions in response to climate change represent a potential threat for temperate deciduous forests persistence in their drier/southern distribution edge., Competing Interests: Declaration of competing interest The authors declare no conflict of interests., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Research Question: Do donor spermatozoa improve IVF outcomes after first oocyte donation failure?, Design: Retrospective, multicentre study including couples undergoing oocyte donation cycles using autologous or donor spermatozoa after a failed first attempt. Male partners were further characterized as normozoospermic or oligoasthenoteratospermic, i.e. fewer than 5 million motile progressive spermatozoa in the ejaculate. The main outcomes measured were live birth rate (LBR) per embryo transfer, LBR per number of embryos transferred, and cumulative LBR (CLBR) considering oocytes consumed in the previous donation cycles., Results: Analysis comprised 6065 cycles of oocyte donation failure; among these, subgroup analyses by sperm quality comprised 4113 cycles with severe male factor and 1150 cycles with suboptimal/normal spermatozoa. Sperm replacement in the first cycle after failure increased LBR per embryo transfer (OR 2.21, 95% CI 1.7-2.8, P < 0.001) and per number of embryos transferred (OR 2.46, 95% CI 1.9-3.1, P < 0.001) for normospermic and oligoasthenoteratospermic men. Replacement by the third cycle after failure was less beneficial (LBR per embryo transfer: OR 1.35, 95% CI 0.9-2.1, P = 0.16; LBR per embryos transferred: OR 1.33, 95% CI 0.9-2.0, P = 0.186). Kaplan-Meier curves of CLBR per oocyte fertilized with autologous or donor spermatozoa were statistically different (P < 0.001) and demonstrate how each additional oocyte may affect success based on sperm source (donor/autologous)., Conclusions: Donor spermatozoa improved outcomes when used after an initial failed oocyte donation cycle. The CLBR curves can be used to determine the cumulative chances of live birth using either autologous or donor spermatozoa, providing guidance on when to replace spermatozoa., (Copyright © 2021 Reproductive Healthcare Ltd. Published by Elsevier Ltd. All rights reserved.)

Soil nitrogen (N) availability is a key driver of soil-atmosphere greenhouse gas (GHG) exchange, yet we are far from understanding how increases in N deposition due to human activities will influence the net soil-atmosphere fluxes of the three most important GHGs: nitrous oxide (N 2 O), methane (CH 4 ) and carbon dioxide (CO 2 ). We simulated four levels of N deposition (10, 20 and 50 kg N ha -1  yr -1 , plus unfertilised control) to evaluate their effects on N 2 O, CH 4 and CO 2 soil fluxes in a semiarid shrubland in central Spain. After 8 years of experimental fertilisation, increasing N availability led to a consistent increase in N 2 O emissions, likely due to simultaneous increases in soil microbial nitrification and/or denitrification processes. However, only intermediate levels of N fertilisation reduced CH 4 uptake, while increasing N fertilisation had no effects on CO 2 fluxes, suggesting complex interactions between N deposition loads and GHG fluxes. Our study provides novel insight into the responses of GHGs to N deposition in drylands, forecasting increases in N 2 O emissions, and decreases in CH 4 uptake rates, with likely consequences to the on-going climate change., 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.)

Solar water disinfection (SODIS) is a simple, inexpensive and sustainable Household Water Treatment (HWT) that is appropriate for low-income countries or emergency situations. Usually, SODIS involves solar exposure of water contained in transparent polyethylene terephthalate (PET) bottles for a minimum of 6 h. Sunlight, especially UVB radiation, has been demonstrated to photoinactivate bacteria, viruses and protozoa. In this work, an in-depth study of the optical and mechanical properties, weathering and production prices of polymeric materials has been carried out to identify potential candidate materials for manufacturing SODIS devices. Three materials were ruled out (polystyrene (PS), polyvinyl chloride (PVC) and polyethylene (PE)) and four materials were initially selected for study: polymethylmethacrylate (PMMA), polypropylene (PP), polycarbonate (PC) and polyethylene terephthalate (PET). These plastics transmit sufficient solar radiation to kill waterborne pathogens with production costs compensated by their durability under solar exposure. A predictive model has been developed to quantitatively estimate the radiation available for SODIS inside the device as a function of the material and thickness. This tool has two applications: to evaluate design parameters such as thickness, and to estimate experimental requirements such as solar exposure time. In this work, this model evaluated scenarios involving different plastic materials, device thicknesses, and pathogens (Escherichia coli bacterium, MS2 virus and Cryptosporidium parvum protozoon). The developed Solar UV Calculator model is freely available and can be also applied to other customized materials and conditions., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

In this work a new method for the determination of 5-hydroxymethylfurfural (HMF) in cereal and insect bars has been developed and validated. The method consisted of a solid-liquid extraction (SLE) followed by a solid phase extraction (SPE), employing functionalized mesostructured silica as sorbent, and prior to high-performance liquid chromatography coupled to mass spectrometry analysis (HPLC-MS/MS). Mesostructured silica with a large pore (SBA-15-LP) functionalized with aminopropyl- groups (SBA-15-LP-NH 2 ), octyl- groups (SBA-15-LP-C8) and bifunctionalized with both organic ligands (SBA-15-LP-C8-NH 2 ) were prepared, characterized and tested for this purpose. The optimal conditions showed that the best extraction solvent was water acidified with HCl (pH 1.0) and the best material for SPE was SBA-15-LP-NH 2 (recoveries near 100%). Results were compared with other analogous commercial sorbent (Discovery® DSC-NH 2 ), evaluated under similar conditions, and SBA-15-LP-NH 2 sorbent showed better recoveries than the commercial one (62 ± 1%). The developed method was validated and good detection and quantification limits (MDL: 11 µg kg -1 and MQL: 38 µg kg -1 ), good precision in terms of repeatability and within-laboratory reproducibility (RSD < 8%) and good accuracy (recoveries between 99-102%) were obtained. The method was successfully applied to the determination of HMF in different samples of cereals and insect bars. In all the samples analysed, high concentrations of HMF (ranging from 336 to 962 mg kg -1 ) have been found., Competing Interests: Declaration of Competing Interest The authors have declared no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

We report on the formation of two novel multifunctional isomorphous (4,4) square-grid 2D coordination polymers based on 1H-indazole-5-carboxylic acid. To the best of our knowledge, these complexes are the first examples of 2D-coordination polymers constructed with this novel ligand. We have analysed in detail the structural, magnetic and anti-parasitic properties of the resulting materials. In addition, the capability of inhibiting nitric oxide production from macrophage cells has been measured and was used as an indirect measure of the anti-inflammatory response. Finally, the photocatalytic activity was measured with a model pollutant, i.e. vanillic acid (phenolic compound), with the aim of further increasing the functionalities and applicability of the compounds., Competing Interests: Declaration of competing interest There is no any conflict of interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Hollow mesoporous silica nanoparticles (HMSNs) consist of a network of cavities confined by mesoporous shells that have emerged as promising tools for drug delivery or diagnostic. The physicochemical properties of HMSNs are dictated by the synthesis conditions but which conditions affect which property and how it impacts on biological interactions is unclear. Here by changing the concentration of the structure-directing agent (SDA), the pH and the ratio between SDA and added salt (NaCl) we determine the effects in size, morphology, surface charge and density or degree of compaction (physicochemical properties) of HMSNs and define their impact on their biological interactions with human colon cancer or healthy cells at the level of cellular uptake and viability. Increased size or density/degree of compaction of HMSNs increases their cytotoxicity. Strikingly, high salt concentrations in the synthesis medium leads to a spiky-shell morphology that provokes nuclear fragmentation and irreversible cell damage turning HMSNs lethal and unveiling intrinsic therapeutic potential. This strategy may open new avenues to design HMSNs nanoarchitectures with intrinsic therapeutic properties without incorporation of external pharmaceutical ingredients., 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.)

Five new coordination polymers (CPs) constructed of aminopyridine-2-carboxylate (ampy) ligand have been synthesized and fully characterized. Three of them correspond to metal-organic chains built from the coordination of ampy to sodium and lanthanides with formulae [MNa(ampy) 4 ] n (M = terbium (2), erbium (1) and ytterbium (3)) resembling a previously reported dysprosium material which shows anticancer activity. On another level, the reaction of Hampy with cobalt and copper ions ({[CoK(ampy) 3 (H 2 O) 3 ](H 2 O) 3 } n (4) and [Cu(ampy) 2 ] n (5)) lead to CPs with variable dimensionalities, which gives the opportunity of analyzing the structural properties of this new family. Lanthanide materials display solid state intense photoluminescent emissions in both the visible and near-infrared region and exhibit slow relaxation of magnetization with frequency dependence of the out-of-phase susceptibility. More interestingly, in our search for multifunctional materials, we have carried out antitumor measurements of these compounds. These multidisciplinary studies of metal complexes open up the possibility for further exploring the applications in the fields of metal-based drugs., Competing Interests: Declaration of competing interest There is not any conflict of interest., (Copyright © 2020. Published by Elsevier Inc.)

Adopting an integrative approach that explicitly includes the different facets of biodiversity is crucial to assess the response of biological communities to changing environments. The identification of the optimal climatic conditions where communities maximize their functional, phylogenetic and taxonomic diversity is useful to compare whether the optima of the different facets of biodiversity match. Using a wide climatic gradient across Europe, we quantified the functional, phylogenetic and taxonomic diversity of epiphytic macrolichen communities, which are valuable early-warning ecological indicators. We ordinated 22 environmental variables and simultaneously illustrated non-parametric regressions of the diversity metrics against the climatic space using the 'hilltop plot' method to detect the climatic conditions in which the different diversity facets peaked and to compare the match between them. Functional diversity predicted at least part of the peaks of phylogenetic and taxonomic diversity, but phylogenetic and taxonomic hotspots did not overlap. Epiphytic macrolichen communities maximized their functional and phylogenetic diversity in the southernmost forests, with the Mediterranean region appearing as a biodiversity hotspot. Regarding the studied traits, photobiont type and growth form showed clearly defined optima while the quantitative physiological traits and families' optima did not show this pattern in response to climate. The different facets of biodiversity were not surrogates of each other highlighting the need for an integrative approach to assess the effect of environmental changes on communities and to establish conservation priorities. As functional traits mediated the response of lichen communities to climate, preserving high functional diversity might indirectly preserve high phylogenetic and taxonomic diversity. Relevant ecological indicators useful to develop rapid assessment methods to evaluate the effects of climatic changes include the photobiont type and growth form. The lack of relation between quantitative traits and climate call for further research to unveil their role as ecological indicators of small-scale variables or as effect traits., 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.)

This work aimed to study the effect of the combination of Sodium hypochlorite, the most used disinfectant by the vegetable industry, with a natural antimicrobial, benzyl-isothiocyanate (BITC), considering cutting surface and contact time, on the reduction of Salmonella in fresh-cut produce in washing operations under typical industrial conditions. Overall, the combinations of disinfectant and process parameters resulted in a mean reduction of Salmonella of 2.5 log CFU/g. According to statistical analysis, free chlorine and BITC concentrations, contact time and cut size exerted a significant effect on the Salmonella reduction (p ≤ 0.05). The optimum combination of process parameter values yielding the highest Salmonella reduction was a lettuce cut size of 15 cm 2 washed for 110 s in industrial water containing 160 mg/L free chlorine and 40 mg/L BITC. A predictive model was also derived, which, as illustrated, could be applied to optimize industrial disinfection and develop probabilistic Exposure Assessments considering the effect of washing process parameters on the levels of Salmonella contamination in leafy green products. The present study demonstrated the efficacy of chlorine to reduce Salmonella populations in fresh-cut lettuce while highlighting the importance of controlling the washing process parameters, such as, contact time, cut size and concentration of the disinfectant to increase disinfectant efficacy and improve food safety., (Copyright © 2019. Published by Elsevier Ltd.)

A series of copper-functionalized SBA-15 (Santa Barbara Amorphous) materials containing the ligands triethoxysilylpropylmaleamic acid (maleamic) or triethoxy-3-(2-imidazolin-1-yl)propylsilane (imidazoline) have been prepared. The nanostructured silica-based systems SBA-maleamic, SBA-imidazoline, SBA-maleamic-Cu and SBA-imidazoline-Cu were characterized by several methods observing that the functionalization took place mainly inside the pores of the mesoporous system. The antimicrobial behaviour of the synthesized materials against Staphylococcus aureus and Escherichia coli was tested observing a very potent activity of the copper-functionalized systems (minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) values for SBA-maleamic-Cu of ca. 31.25 μg/mL, which correspond with ca. 1.13 μg/mL of Cu). A study of the oxidative stress promoted by the synthesized materials showed that the SBA-maleamic-Cu and the SBA-imidazoline-Cu were able to increase the reactive oxygen species (ROS) production in S. aureus by 427% and 373%, respectively, while this increase was slightly lower in E. coli (387 and 324%, respectively). Furthermore, an electrochemical study was carried out in order to determine if these materials interact with lysine or alanine to validate a potential antimicrobial mechanism based on the inhibition of the synthesis of the peptidoglycan of the bacterial wall. Finally, these studies were also performed to determine the potential interaction of the copper-containing materials with glutathione in order to assess if they are able to perturb the metabolism of this tripeptide., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2018. Published by Elsevier Inc.)

Despite distinct roles of soil microbes in regulating carbon (C) respiration in diverse environments, it remains unclear whether microbial taxonomic and functional attributes can consistently predict soil C emissions across contrasting ecosystems. Here, we conducted a large-scale sampling event across two contrasting croplands (rice and wheat-corn crop rotation) to identify specific soil microbial phylotypes and functional genes associated with soil respiration rates. The results of structural equation modeling indicated that bacterial community composition had a strong link with C respiration rates in the two contrasting cropland types; however, this link was weaker for fungal communities. More importantly, we found that the relative abundances of bacterial Solirubrobacterales&#95;480-2, Myxococcales&#95;mle1-27 and fungal Westerdykella had consistently negative correlation with respiration rates across paddy and upland soils. We also identified taxa that are significantly correlated to C respiration in the paddy (e.g. Methylocaldum) and upland soils (e.g. Kribbella), respectively. Further, we found multiple associations between functional genes involved in microbial C metabolism and soil respiration rates. Our findings provide novel insights into understanding microbial predictors of soil CO 2 emissions in diverse croplands, which have important implications for improving C emission predictions in terrestrial ecosystems., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Estuaries are very sensitive ecosystems to human activities and the natural evolution of their drainage basins located upstream. Pollution derived from human activities, such as historical mining or recent industrial wastes, can significantly affect their environmental quality. This paper analyzes the silver and copper contents of four cores extracted in two estuaries of SW Spain. Its chronology and vertical evolution allow to differentiate the effects of several pollution episodes (natural, Roman, 19th-20th centuries) on its different sedimentary environments in the last 6 million years. Possible future applications are included in the fields of environmental management or even education., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The shift in ecosystem multifunctionality during ecosystem succession (years to decades) remains largely unexplored. In this study, we used a 120-year-old pine temperate forest chronosequence (1: 1-19 years, stage 2: 20-39 years, stage 3: 40-59 years, stage 4: 60-79 years, stage 5: 80-99 years, stage 6: 100-120 years) to evaluate the role that time plays in shaping ecosystem multifunctionality (nutrient cycling, carbon stocks, water regulation, decomposition and wood production), and found that, over the first century, ecosystem functioning gradually increased every ~50 years. Such a result was maintained for individual groups of ecosystem functions and services including nutrient cycling, carbon stocks, decomposition and wood production. Plant diversity and soil stoichiometry (C:N ratio) were the major environmental predictors for the changes in ecosystem multifunctionality during forest secondary succession. Plant diversity increased during ecosystem succession and was positively related to ecosystem multifunctionality. The soil C:N ratio decreased during ecosystem succession and was negatively related to multifunctionality. Our results suggest that increases in aboveground resource heterogeneity (higher plant diversity) and organic matter quality (lower soil C:N ratios) could help explain the increases in multifunctionality over a century of forest development. Our work illustrates the importance of time in shaping multifunctionality during the first century of ecosystem succession, and further provide important insights for the management of temperate forest ecosystems., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Preparation of new sorbents specific to DNA has a great significance in many biomedical fields. This study reports a new sorbent with high surface area and porosity to immobilize nucleic acids having both high molecular weight like genomic DNA (gDNA) for potential use in therapy of some immune system disease and low molecular weight like plasmid DNA (pDNA) for diagnosis, gene therapy and DNA vaccination. For this aim, silica-based pore-expanded SBA-15 nanoparticles with aminopropyl-trimethoxysilane (APTMS) for decoration of Fe +3 ions (PE SBA-15-APTMS/Fe +3 ) were synthesized to get high surface area for high adsorption, and embedded into cryogel column for obtaining interconnected pores to avoid diffusion limitation of DNA samples because of their viscosity features. SEM, XRD, BET, and FTIR techniques were used for characterization of samples. Synthesized hybrid column showed a superior adsorption capacity of 751.5 mg/g NP for gDNA at pH 6 with an initial concentration of 2.0 mg/mL. Hybrid column presented excellent performance for pDNA when evaluated with agarose gel electrophoresis., (Copyright © 2019. Published by Elsevier B.V.)

This study explores the enhancement of UV-C tertiary treatment by sulfate radical based Advanced Oxidation Processes (SR-AOPs), including photolytic activation of peroxymonosulfate (PMS) and persulfate (PS) and their photocatalytic activation using Fe(II). Their efficiency was assessed both for the inactivation of microorganisms and the removal or micropollutants (MPs) in real wastewater treatment plant effluents. Under the studied experimental range (UV-C dose 5.7-57 J/L; UV-C contact time 3 to 28 s), the photolysis of PMS and PS (0.01 mM) increased up to 25% the bacterial removal regarding to UV-C system. The photolytic activation of PMS led to the total inactivation of bacteria (≈ 5.70 log) with the highest UV-C dose (57 J/L). However, these conditions were insufficient to remove the MPs, being required oxidant's dosages of 5 mM to remove above 90% of carbamazepine, diclofenac, atenolol and triclosan. The best efficiencies were achieved by the combination of PMS or PS with Fe(II), leading to the total removal of the MPs using a low UV-C dosage (19 J/L), UV-C contact time (9 s) and reagent's dosages (0.5 mM). Finally, high mineralization was reached (>50%) with photocatalytic activation of PMS and PS even with low reagent's dosages., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This research reports for the first time the full-scale application of different homogeneous Advanced Oxidation Processes (AOPs) (H 2 O 2 /UV-C, PMS/UV-C and PMS/Fe(II)/UV-C) for the removal of antibiotics (ABs) and antibiotic resistance genes (ARGs) from wastewater effluent at Estiviel wastewater treatment plant (WWTP) (Toledo, Spain). AOPs based on the photolytic decomposition of H 2 O 2 and peroxymonosulfate tested at low dosages (0.05-0.5 mM) and with very low UV-C contact time (4-18 s) demonstrated to be more efficient than UV-C radiation alone on the removal of the analyzed ABs. PMS (0.5 mM) combined with UV-C (7 s contact time) was the most efficient treatment in terms of AB removal: 7 out of 10 ABs detected in the wastewater were removed more efficiently than using the other oxidants. In terms of ARGs removal efficiency, UV-C alone seemed the most efficient treatment, although H 2 O 2 /UV-C, PMS/UV-C and PMS/Fe(II)/UV-C were supposed to generate higher concentrations of free radicals. The results show that treatments with the highest removal of ABs and ARGs did not coincide, which could be attributed to the competition between DNA and oxidants in the absorption of UV photons, reducing the direct photolysis of the DNA. Whereas the photolytic ABs removal is improved by the generation of hydroxyl and sulfate radicals, the opposite behavior occurs in the case of ARGs. These results suggest that a compromise between ABs and ARGs removal must be achieved in order to optimize wastewater treatment processes., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Pseudo-persistent organic pollutants, such as anionic surfactants (AS), are nowadays among the more complex problems that threaten the aquatic environments and other environmental compartments. The present work describes the identification and efficiency of a consortium, isolated from Algerian industrial wastewater, to remove three anionic surfactants (i.e., sodium dodecylbenzenesulfonate (SDBS), sodium dodecyl sulfate (SDS) and sodium lauryl ether sulfate (SLES)). The genetic analysis of 16S rRNA indicated that these strains are Alcaligenes faecalis, Enterobacter cloacae and Serratia marcescens. Under aerobic conditions, pH 7.0 and optimum temperature of 30 °C, the mixed consortium allowed to degrade 85.1% of initial SDBS amount after 144 h of incubation with half-life of 20.8 h. While E. cloacae and S. marcescens pure strains eliminated 46% and 41% less SDBS respectively. Evenly, SDS was degraded at only 23.71% by A. faecalis strain. However, the degradation capacity of SDS by the consortium was very high (94.2%) with a half-life of 9.8 h. The SLES anionic surfactant showed a lower biodegradation by the consortium (47.53%) due to the presence of ether oxide units in the chemical structure of SLES which induced toxicity to the medium. The investigation of the biodegradation of this type of organic pollutants by microorganisms has recently become a key issue for the environmental protection area., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Considering the progressive depletion of groundwater quantity and the alteration of superficial and groundwater quality in the Madrid region, a highly populated area with extended urbanizations in the north and agricultural activities in the south, we conducted a monitoring study over a period of 2.5 years (2015-2017). The study was conducted in the Jarama-Tajuña shallow alluvial aquifer system located southeast of Madrid, where the exploitation of the aquifer and the Jarama river have increased exponentially in the last decade being affected by both urban and agricultural activities. Our aims were to provide: i) a geochemical characterization of the surface and groundwater properties; ii) identify the process responsible for the geochemical evolution and mineralization of the waters; iii) assess the water quality (i.e. nitrates, ammonia, sodium and chloride as potential contaminants) and the water suitability for irrigation (SAR, Wilcox, KI and MH indexes); and iv) identify the main sources of contamination in the area. A set of plots, ion ratios, correlation coefficients, multivariate statistical analyses and indexes were performed. Results indicated that rock weathering largely controls the hydrogeochemistry of the system and that wastewater treatment plant discharges and agricultural practices significantly affect the composition of the water, causing an important decline of both surface and groundwater chemical quality. Nonetheless, water suitability for irrigation is admissible. Thus, taking additional measures to increase its quality are not necessary. With this study we aimed to establish a base line to evaluate future changes in the groundwater properties from the Madrid region enabling the planners and policy makers to develop a strategy to mitigate the impact of the exponential increase of urban and agriculture activities on groundwater resources., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Two novel materials based on periodic mesoporous organosilica (PMO) with cationic amine-bridged ligands, (styrylmethyl)bis(triethoxysilylpropyl)ammonium chloride (PMO-STPA) and bis(3-triethoxysilylpropyl)amine (PMO-TEPA), were synthesized in this work to obtain materials with reverse-phase/strong anionic exchange mixed-mode or strong anionic exchange retention mechanism, respectively. The resulting materials were comprehensively characterized and showed functionalization with cationic amine-bridged ligands, and values of surface areas characteristic of mesoporous materials (higher than 100m 2 /g). These materials were evaluated for the off-line solid-phase extraction (SPE) of a mixture of six phenoxy acid herbicides (fenoprop, mecoprop, dichlorprop, 2-(4-chlorophenoxy)propionic acid (4-CPPA), 2-(3-chlorophenoxy)propionic acid (3-CPPA), 2-phenoxypropionic acid (2-PPA)) from water samples previous to their analysis by CE with diode-array detection using a dual chiral selector system (20mM of heptakis(2,3,6-tri-O-methyl)-β-CD (TM-β-CD) and 7mM of (2-hydroxypropyl)-β-CD (HP-β-CD) dissolved in 50mM phosphate buffer, pH 7.0) which enabled the simultaneous enantiomeric separation of the six phenoxy acid herbicides in 11min. SPE parameters were optimized and recoveries obtained for PMO-STPA and PMO-TEPA sorbents were compared. Under the optimized conditions, it was demonstrated that using 100mg of PMO-STPA sorbent, a maximum preconcentration factor (PF) of 1500 was achieved with 750mL of standard solution, allowing recoveries between 75.5 and 112.2%, with good repeatability (RSD=1.9-8.7%, n=6). Analytical characteristics of the method were evaluated in terms of precision, linearity and accuracy with method quantitation limits (MQL) between 0.4 and 14.3μg/L. The developed method was applied to the analysis of river samples and effluents from wastewater treatment plants, with recoveries ranging from 78.3 to 107.5%., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Two novel periodic mesoporous organosilica materials were synthesized with a neutral phenylene-bridged ligand, 1,4-bis(trimethoxysilylethyl)benzene, one of them using tetraethyl orthosilicate as additional silica source (PMO-TMSEB-1 and PMO-TMSEB-2). A third material was also synthesized with 1,4-bis(triethoxysilyl)benzene ligand (PMO-TESB-1) which use has scarcely been reported. The three materials were evaluated as solid-phase extraction (SPE) sorbents for the off-line extraction of a mixture of seven drugs of different nature (duloxetine, terbutaline, econazole, propranolol, verapamil, metoprolol, and betaxolol) from water samples. Subsequent simultaneous enantiomeric analysis by CE, using sulfated-β-cyclodextrin (2% w/v) dissolved in a 25 mM phosphate buffer (pH 3.0) and a voltage of -20 kV (negative polarity) was carried out. Enantiomeric resolutions ranging from 2.4 to 8.5 were obtained in an analysis time of 16 min. After optimization of SPE parameters, it was shown that using just 100 mg of PMO-TESB-1 as sorbent, a preconcentration factor of 400 with 200 mL solution was achieved, allowing recoveries between 80.5 and 103.1% (except for terbutaline), with good repeatability (% RSD = 2-8 %, n = 5). Analytical characteristics of the method were evaluated in terms of precision, linearity and accuracy with method quantitation limits between 5.6 and 21.9 μg/L. The developed method was applied to the analysis of spiked wastewater samples collected in different treatment plants, with recoveries between 73.9 and 102.9% except for econazole with recovery values ranging between 58.5 and 72.4%., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The high chemical stability and the low biodegradability of a vast number of micropollutants (MPs) impede their correct treatment in urban wastewater treatment plants. In most cases, the chemical oxidation is the only way to abate them. Advanced Oxidation Processes (AOPs) have been experimentally proved as efficient in the removal of different micropollutants at lab-scale. However, there is not enough information about their application at full-scale. This manuscript reports the application of three different AOPs based on the addition of homogeneous oxidants [hydrogen peroxide, peroxymonosulfate (PMS) and persulfate anions (PS)], in the UV-C tertiary treatment of Estiviel wastewater treatment plant (Toledo, Spain) previously designed and installed in the facility for disinfection. AOPs based on the photolytic decomposition of oxidants have been demonstrated as more efficient than UV-C radiation alone on the removal of 25 different MPs using low dosages (0.05-0.5 mM) and very low UV-C contact time (4-18 s). Photolysis of PMS and H 2 O 2 reached similar average MPs removal in all the range of oxidant dosages, obtaining the highest efficiency with 0.5 mM and 18 s of contact time (48 and 55% respectively). Nevertheless, PMS/UV-C reached slightly higher removal than H 2 O 2 /UV-C at low dosages. So, these treatments are selective to degrade the target compounds, obtaining different removal efficiencies for each compound regarding the oxidizing agent, dosages and UV-C contact time. In all the cases, H 2 O 2 /UV-C is more efficient than PMS/UV-C, comparing the ratio cost:efficiency (€/m 3 ·order). Even H 2 O 2 /UV-C treatments are more efficient than UV-C alone. Thus, the addition of 0.5 mM of H 2 O 2 compensates the increased of UV-C contact time and therefore the increase of electrical consumption, that it should be need to increase the removal of MPs by UV-C treatments alone., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Vegetation filters (VFs), a type of land application system, are a robust technology based on natural treatment mechanisms for the removal of wastewater contaminants. Their capacity to attenuate emerging organic contaminants (EOCs) has not yet been evaluated. The present study reports the results of a 2-year EOC monitoring carried out using a poplar VF receiving wastewater primarily treated by an Imhoff tank. The compounds selected included analgesics, a β-adrenergic blocker, stimulants, an anticonvulsant, an anti-depressant, an anti-inflammatory, an antibiotic and analgesic and stimulant metabolites. EOCs were analysed in the Imhoff tank effluent, in the infiltrated water at a depth of 90cm and in the groundwater at a depth of 10m. The results demonstrated that EOC attenuation was more significant in the first 90cm than in the rest of the soil profile. The removal efficiency for all of the selected EOCs was higher than 90% with the exception of ketoprofen, which may pose a higher threat of groundwater contamination. The observed attenuation correlated with the hydrophobicity and charge state of the EOCs. The higher persistence of the metabolites 4-AAA and 4-FAA shows that progression in the degradation pathway does not always imply a mitigation of contamination., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Since the last decade, the metal composite nanostructures have evolved as promising candidates in regard to their wide applications in the fields of science and engineering. Recently, several investigators identified the titanium based nanomaterials as excellent agents for multifunctional environmental and biomedical applications. In this perspective, we have developed a series of zinc-doped (2 and 5%) titanium oxide-based nanomaterials using various reaction conditions and calcination temperatures (TZ1-TZ3: calcined at 500°C, TZ4-TZ6: calcined at 600°C and TZ7-TZ9: calcined at 700°C). The calcined materials (TZ1 to TZ9) were thoroughly analyzed by several physico-chemical characterization methods. The increase of the calcination temperature results in significant changes of the textural properties of the nanostructured materials. In addition, the increase of the calcination temperature leads to the formation of anatase/rutile mixtures with higher quantity of rutile. Furthermore, incorporation of zinc changes the morphology of the obtained nanoparticles. The materials were studied in the photodegradation of methylene blue observing that materials calcined at lower temperatures (TZ1-TZ3) have higher photocatalytic activity than those of the materials calcined at 600°C (TZ4-TZ6), rutile-based systems TZ7-TZ9 are not active. Based on the background literature of titanium and zinc based nanostructures in therapeutic angiogenesis, we have explored the pro-angiogenic properties of these materials using various in vitro and in vivo assays. The zinc-doped titanium dioxide nanostructures (TZ5 and TZ6) exhibited increased cell viability, proliferation, enhanced S-phase cell population, increased pro-angiogenic messengers (ROS: reactive oxygen species and NO: nitric oxide) production and promoted in vivo blood vessel formation in a plausible mechanistic p38/STAT3 dependent signaling cascade. Altogether, the results of the present study showcase these zinc doped-titanium oxide nanoparticles as promising candidates for environmental (water-remediation) and therapeutic angiogenic applications., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Chemotherapy is a cancer treatment modality that uses drugs to kill tumor cells. A typical chemotherapeutic protocol consists of several drugs delivered in cycles of three weeks. We present mathematical analyses demonstrating the existence of a maximum time between cycles of chemotherapy for a protocol to be effective. A mathematical equation is derived, which relates such a maximum time with the variables that govern the kinetics of the tumor and those characterizing the chemotherapeutic treatment. Our results suggest that there are compelling arguments supporting the use of dose-dense protocols. Finally, we discuss the limitations of these protocols and suggest an alternative., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A SBA-15 type mesoporous silica was synthesized and bi-functionalized with octadecylsilane (C18) or octylsilane (C8), and sulfonic acid (SO 3 - ) groups in order to obtain materials with reversed-phase/strong cation-exchange mixed-mode retention mechanism. The resulting hybrid materials (SBA-15-C18-SO 3 - and SBA-15-C8-SO 3 - ) were comprehensively characterized. They showed high surface area, high pore volume and controlled porous size. Elemental analysis of the materials revealed differences in the amount of C18 and C8. SBA-15-C18-SO 3 - contained 0.19mmol/g of C18, while SBA-15-C8-SO 3 - presented 0.54mmol/g of C8. The SO 3 - groups anchored to the silica surface of the pore walls were 0.20 and 0.09mmol/g, respectively. The bi-functionalized materials were evaluated as SPE sorbents for the multi-residue extraction of 26 veterinary drug residues in meat samples using ultra-high-performance liquid chromatography coupled to mass spectrometry detector (UHPLC-MS/MS). Different sorbent amounts (100 and 200mg) and organic solvents were tested to optimize the extraction procedure. Both silicas showed big extraction potential and were successful in the extraction of the target analytes. The mixed-mode retention mechanism was confirmed by comparing both silicas with SBA-15 mesoporous silica mono-functionalized with C18 and C8. Best results were achieved with 200mg of SBA-15-C18-SO 3 - obtaining recoveries higher than 70% for the majority of analytes., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this paper a chiral stationary phase (CSP) was prepared by the immobilization of a β-CD derivative (3,5-dimethylphenylcarbamoylated β-CD) onto the surface of amino-functionalized spherical ordered mesoporous silica (denoted as SM) via a urea linkage using the Staudinger reaction. The CSP was packed into fused silica capillaries 100μm I.D. and evaluated by means of nano-liquid chromatography (nano-LC) and capillary electrochromatography (CEC) using model compounds for the enantio- and the diastereomeric separation. The compounds flavanone, 2'-hydroxyflavanone, 4'-hydroxyflavanone, 6-hydroxyflavanone, 4'-methoxyflavanone, 7-methoxyflavanone, hesperetin, hesperidin, naringenin, and naringin were studied using reversed and polar organic elution modes. Baseline stereoisomer resolution and good results in terms of peak efficiency and short analysis time of all studied flavonoids and flavanones glycosides were achieved in reversed phase mode, using as mobile phase a mixture of MeOH/H 2 O, 10mM ammonium acetate pH 4.5 at different ratios. For the polar organic mode using 100% of MeOH as mobile phase, the CSP showed better performances and the baseline chiral separation of several studied compounds occurred in an analysis time of less than 10min. Good results were also achieved by CEC employing two different mobile phases. The use of MeOH/H 2 O, 5mM ammonium acetate buffer pH 6.0 (90/10, v/v) was very effective for the chiral resolution of flavanone and its methoxy and hydroxy derivatives., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Novel nanomaterials based on doped TiO2 nanoparticles with different morphological, textural and band-gap properties have been synthesized using scalable methods. The influence of synthetic parameters such as titanium source (titanium(IV) isopropoxide and titanium(IV) butoxide), doping quantity (0%, 2% or 5% Zn), acidic solution for the hydrolysis reaction (ascorbic acid, nitric acid) and calcination temperatures (500°C and 600°C) was simultaneously investigated. The obtained nanomaterials were characterized by different methods and photocatalytic tests of methylene blue (MB) degradation under UV-light were conducted to determine their activity. The results revealed that the synthesized nanomaterials are porous aggregates with very high crystallinity and are mainly composed of the anatase phase; although their physical properties vary depending on the different synthetic parameters employed. These changes are able to modify the apparent rate constant of the degradation of MB up to one order of magnitude, indicating, substantial changes in their photoactivity. Hybrid materials TiO2-Pd nanoparticles have also been prepared, characterized and tested for hydrogen production using photocatalytic methanol reforming where supported palladium nanoparticles acted as co-catalyst. Furthermore, the hybrid materials TiO2-Pd nanoparticles were studied in photocatalytic tests of methylene blue degradation under visible LED-light. The results obtained in the production of hydrogen from the photocatalytic reforming of methanol by hybrid materials suggest that the reported hybrid systems could be suitable photocatalysts for future sustainable hydrogen production upon tuning of the morphological, textural and band gap energy properties to allow processes to be carried out under visible light., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A quick, sensitive and selective analytical reversed-phase multi-residue method using ultra-high performance liquid chromatography coupled to an ion-trap mass spectrometry detector (UHPLC-IT-MS/MS) operating in both positive and negative ion mode was developed for the simultaneous determination of 23 veterinary drug residues (β-blockers, β-agonists and Non-Steroidal Anti-inflammatory Drugs (NSAIDs)) in meat samples. The sample treatment involved a liquid-solid extraction followed by a solid-phase extraction (SPE) procedure. SBA-15 type mesoporous silica was synthetized and modified with octadecylsilane, and the resulting hybrid material (denoted as SBA-15-C18) was applied and evaluated as SPE sorbent in the purification of samples. The materials were comprehensively characterized, and they showed a high surface area, high pore volume and a homogeneous distribution of the pores. Chromatographic conditions and extraction procedure were optimized, and the method was validated according to the Commission Decision 2002/657/EC. The method detection limits (MDLs) and the method quantification limits (MQLs) were determined for all the analytes in meat samples and found to range between 0.01-18.75μg/kg and 0.02-62.50μg/kg, respectively. Recoveries for 15 of the target analytes ranged from 71 to 98%. In addition, for comparative purpose SBA-15-C18 was evaluated towards commercial C18 amorphous silica. Results revealed that SBA-15-C18 was clearly more successful in the multi-residue extraction of the 23 mentioned analytes with higher recovery values. The method was successfully tested to analyze prepacked preparations of mince bovine meat. Traces of propranolol, ketoprofen and diclofenac were detected in some samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Two different silica based (MSU-2 and MCM-41) curcumin loaded mesoporous materials V3 and V6 were synthesized and characterized by several physico-chemical techniques. Release kinetic study revealed the slow and sustained release of curcumin from those materials in blood simulated fluid (pH: 7.4). The materials V3 and V6 were found to be biocompatible in non-cancerous CHO cell line while exhibiting significant cytotoxicity in different cancer cells (human lung carcinoma cells: A549, human breast cancer cells: MCF-7, mouse melanoma cells: B16F10) compared to pristine curcumin indicating the efficacy of the mesoporous silica materials based drug delivery systems (DDSs). The generation of intracellular reactive oxygen species (ROS) and down regulation of anti-apoptotic protein leading to the induction of apoptosis were found to be the plausible mechanisms behind the anti-cancer activity of these DDSs. These results suggest that curcumin-loaded drug delivery system may be successfully employed as an alternative treatment strategy for cancer therapeutics through a nanomedicine approach in near future., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The increasing human presence in Antarctica and the waste it generates is causing an impact on the environment at local and border scale. The main sources of anthropic pollution have a mainly local effect, and include the burning of fossil fuels, waste incineration, accidental spillage and wastewater effluents, even when treated. The aim of this work is to determine the presence and origin of 30 substances of anthropogenic origin considered to be, or suspected of being, endocrine disruptors in the continental waters of the Antarctic Peninsula region. We also studied a group of toxic metals, metalloids and other elements with possible endocrine activity. Ten water samples were analyzed from a wide range of sources, including streams, ponds, glacier drain, and an urban wastewater discharge into the sea. Surprisingly, the concentrations detected are generally similar to those found in other studies on continental waters in other parts of the world. The highest concentrations of micropollutants found correspond to the group of organophosphate flame retardants (19.60-9209ngL(-1)) and alkylphenols (1.14-7225ngL(-1)); and among toxic elements the presence of aluminum (a possible hormonal modifier) (1.7-127µgL(-1)) is significant. The concentrations detected are very low and insufficient to cause acute or subacute toxicity in aquatic organisms. However, little is known as yet of the potential sublethal and chronic effects of this type of pollutants and their capacity for bioaccumulation. These results point to the need for an ongoing system of environmental monitoring of these substances in Antarctic continental waters, and the advisability of regulating at least the most environmentally hazardous of these in the Antarctic legislation., (Copyright © 2016 Elsevier Inc. All rights reserved.)