Color, origen botánico y composición del polen apícola

El polen es conocido por el hombre desde la antigüedad como alimento potencial (SAENZ, 1978). Por su contenido en proteínas, hidratos de carbono, lípidos, minerales y vitaminas, representa la fuente insustituible de la alimentación de las larvas y abejas jóvenes, siendo indispensable para su crecimiento. Esta interesante composición permite. asegurar su uso en la alimentación humana ya que además de lo mencionado anteriormente posee 20 de los 22 aminoácidos de nuestras proteínas (PERIS, 1984). En la actualidad existe una tendencia generalizada hacia el uso de productos naturales, por lo que el polen es cada vez más apreciado con objeto de paliar las carencias de nuestra alimentación actual. Este producto no se menciona en el Código Alimentario Español (1967) citándose desde 1976 dentro de la Reglamentación Técnico Sanitaria sobre preparados alimenticios para regímenes dietéticos y jo especiales (BOE, 1976). Figura registrado, por una parte como polen de flores en productos de parafarmacia en el apartado de regímenes tradicionales y por otra, como especialidad farmacéutica (desde 1987) dentro de los urológicos en forma de comprimidos, conteniendo las fracciones oleosoluble e hidrosoluble del polen

A Synthetic Quality Index to Evaluate the Functional Stability of Soil Microbial Communities After Perturbations

[Abstract] Soil stability includes both resistance, the ability to withstand a perturbation or stress, and resilience, the ability to recover to pre perturbation levels. The functional stability of soil microbial communities is of paramount importance for the ecosystem functioning. We investigated the differences in the stability (resistance and resilience) of three enzyme activities (hydrolytic, laccase and peroxidase) in three different forest (holm oak, black pine and beech) soils after addition of PAHs (phenanthrene, pyrene and benzo[a]pyrene) with different molecular weights. Furthermore, we proposed a new soil quality index (MAI) based on the measured enzyme activity values, useful to quantify the ecological impact of soil perturbations (PAH exposure in our case). The degradation rates of different PAHs follow their complexity, slowing with increasing of PAH molecular weight in all soil types. Moreover, we found higher microbial resistance to PAH perturbation in “broad scale” enzyme activity (hydrolase), in respect to the two “narrow-niche” enzyme activities (laccase and peroxidase). The results demonstrate a higher functional stability in soils with a higher content of recalcitrant organic matter (soil under pine), compared to soils with higher content of labile organic matter (soil under holm oak). In particular, laccase activity is less affected by phenanthrene and pyrene addition in soil under pine; peroxidase activity shows a higher resistance and resilience in soil under beech for all PAHs added. Resistance and/or resilience to PAH contamination, observed for hydrolytic functional stability in the three soils, is mainly due to the high diversity of enzymes expressing this type of catalytic activity

Development of an Analytical Procedure to Analyze Microplastics in Edible Macroalgae Using an Enzymatic-Oxidative Digestion

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] Besides being food and a refuge to marine species, macroalgae are a powerful and renewable economic resource. However, they may introduce microplastics (MPs) in the trophic chain. We developed a reliable analytical method to characterize and quantify MPs in common and edible macroalgae. Several digestion methods and filters, along with various measurement options, were studied. A new enzymatic-oxidative protocol with a unique final filtration was selected and validated with a mixture of 5 commercial macroalgae (Undaria pinnatifida spp, Porphyra spp, Ulva spp, Laminaria ochroleuca and Himanthalia elongate). Further, it was shown that washing the macroalgae to release MPs is suboptimal and the potential adhesion of MPs to macroalgae was evaluated. A filter subsampling strategy that scans 33.64 % of its surface reduced the time required to characterize <70 μm particles and fibres directly on the 47 mm diameter filter using an IR microscope (1 sample/day).This work is a part of the projects MicroplastiX (Grant PCI2020-112145, JPI Oceans Project supported by MCIN/AEI/10.13039/501100011033 and by the European Union “Next Generation EU/PRTR”) and LAnd-Based solutions for PLAStics in the Sea, LABPLAS, (Grant H2020-101003954 supported by the EU H2020 program). The Program “Consolidación e Estructuración de Unidades de Investigación Competitivas” of the Galician Government (Xunta de Galicia) is also acknowledged (Grant ED431C 2021/56). Funding for open access charge: Universidade da Coruña/CISUGXunta de Galicia; ED431C 2021/5

Misidentification of PVC Microplastics in Marine Environmental Samples

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] Poly(vinylchloride), PVC, is the third most demanded polymer in Europe although its presence in marine ecosystems, surprisingly, is scarcely observed. This does not reflect neither its production nor its widespread usage. Therefore, it is imperative to understand why this may happen. PVC is the least stable of the high-tonnage produced polymers as it has the highest sensitivity towards UV radiation and, therefore, photo-degradation is of maximum relevance. The big amount of additives included in PVC formulations, weathering and the different treatments required to isolate it from environmental samples can modify the surface of PVC microplastics, making their spectral identification/quantification an analytical challenge. All these factors can lead to large PVC underestimations in environmental studies, in which other polymers like PE, PP or PS outstand. Further, the fact that the infrared spectrum of weathered PVC can be confounded with that of PE is of most relevance and, therefore, remarkable misidentifications and/or wrong quantifications may occur. In this work some relevant factors that can explain the low percentages of PVC reported in the literature are discussed and special emphasis is made on the need for suitable spectroscopic databases that include PVC weathered standards. This has been confirmed by the results of a detailed study of PVC weathering under pilot-scale conditions, monitoring its spectroscopic and physical changes over time.This work is part of the project MicroplastiX (Grant PCI2020-112145) supported by the JPI_Oceans Program and by MCIN/AEI/10.13039/501100011033 and the European Union “Next Generation EU”/PRTR”; by the LAnd-Based solutions for PLAStics in the Sea (LABPLAS) Grant H2020- 101003954 and “ChemPlas” Project supported by the Agencia Estatal de Investigación (Grant PID2019-108857RB-C31/AEI/10.13039/501100011033). The Program ‘Consolidación e Estructuración de Unidades de Investigación Competitivas” of the Galician Government (Xunta de Galicia) is also acknowledged (Grant ED431C 2021/56). Funding for open access charge: Universidade da Coruña/CISUGXunta de Galicia; ED431C 2021/5

Adsorption of Pesticides and Personal Care Products on Pristine and Weathered Microplastics in the Marine Environment. Comparison Between Bio-Based and Conventional Plastics

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] The hydrophobicity of persistent organic pollutants (POPs) makes them adsorb on microplastics in the marine environment, affecting their distribution, persistence, or their transfer to the trophic chain. Fragrances and non-polar pesticides can be adsorbed by microplastics in the marine environment because of their physico-chemical characteristics. In this work, the adsorption of two pesticides (α-endosulfan and chlorpyrifos) and 6 musk fragrances (musk xylene, musk ketone, musk moskene, galaxolide, tonalide, and celestolide) on polyamide (PA6) (a petroleum based polymer) and on polyhydroxybutyrate (PHB) (biopolymer) in seawater was studied, considering also the effect of water temperature and plastic weathering. Results show higher adsorption of the selected pollutants for PHB than PA, being PA more affected by the water temperature and the plastic weathering. The highest percentage of adsorption was achieved in most cases at 24 h. In addition, this process was irreversible, as it showed the leaching assays. Besides, this work revealed that plastics mitigate the degradation of α-endosulfan in aquatic media (hydrolysis), showing that plastics can act as inhibitors of degradation of POPs, increasing its persistence in the environment.This work was supported by the Spanish Inter-Ministerial Science and Technology Commission and by the European Union through the European Regional Development Fund (ERDF) through the ARPA-ACUA (CTM2016-77945-C3-3-R) project, and JPI_Oceans 2019 MicroplastiX (PCI2020-112145) and RISBIOPLAS (CHEMPLAS, PID2019-108857RB-C3/AEI/10.13039/501100011033) projects, financed by the Spanish Ministery of Science and Innovation. Financial support is also acknowledged by the Program of Consolidation and Structuring of Units of Competitive Investigation of the University System of Galicia (Xunta de Galicia) potentially co-financed by ERDF in the frame of the operative Program of Galicia 2021–2024 (reference: ED431C 2021/56). Funding for open access charge: Universidade da Coruña/CISUGXunta de Galicia; ED431C 2021/5

Mixed-Mode Chromatography of Mixed Functionalized Analytes as the Homologues of Benzalkonium Chloride. Application to Pharmaceutical Formulations

[Abstract] In this work, a retention behavior based on mixed-mode reversed-phase (RP)/hydrophilic interaction liquid chromatography (HILIC) was observed for benzalkonium chloride (BAK) using a core-shell column functionalized with biphenyl groups. Although in the literature, the U-shaped retention was reported for polar compounds in mixed functionalized phases, in the present work, the behavior was dependent upon the chemical structure of the analyte with mixed functionality (ammonium group, a benzyl group and an alkyl chain) and on the high selectivity of the chromatographic column. The bimodal retention was observed for the four BAK homologues using a content of acetonitrile from 65 to 95% in the mobile phase. The data were adjusted to polynomial equations which allow for modeling and predicting the U-shaped retention. The salt concentration (50 and 100 mM), anion (formate and acetate) and cation (ammonium and triethylammonium) of the salt, pH (4 and 5) in the mobile phase were studied in order to understand their influence on the two retention modes. Significant electrostatic interactions were involved in the two retention modes, especially with a content of acetonitrile higher that 90%. Linear relationships between the retention factors of the four homologues were found in a wide range of %acetonitrile when the salt and triethylamine concentration, pH and nature of salt were changed. The differences found on the retention of the homologues, when increasing the alkyl chain length, were more significant in the RP mode due to predominant hydrophobic interactions. A pH decrease and a salt concentration increase caused a retention decrease for both modes. A decrease on of the retention was observed when acetate anion was replaced by formate anion. The different order of the polynomial equations according to the used mobile phase confirmed its relevant role in the interactions with the analytes and stationary phase. A mobile phase was selected (85% acetonitrile, pH 4 and 100 mM ammonium formate) for the BAK determination in cutaneous, otic and ophthalmic formulations with different active pharmaceutical ingredients and excipients. Low sample volume (500 μL) and short analysis time ( 0.999, % RSD <4.5% for intra-day precision and <5.8% for inter-day precision, and recoveries in the 92–105% range) was obtained.This work was supported by Xunta de Galicia, Spain (Programa de Consolidación y Estructuración de Unidades de Investigación Competitivas- Program for the Consolidation and Structuring of Competitive Research Units ED431C 2017/28-2017-2020)Xunta de Galicia; ED431C 2017/28-2017-202

Filtration of Biopolymer PHB Particles Loaded With Synthetic Musks Does Not Cause Significant Bioaccumulation in Marine Mussels

[Abstract] The role of the biopolymer polyhydroxybutyrate (PHB, <250 µm) as a vehicle of a synthetic musks mixture (celestolide, galaxolide, tonalide, musk xylene, musk moskene and musk ketone) to Mytilus galloprovincialis was investigated. For 30 days, virgin PHB, virgin PHB+musks (6.82 µg g-1) and weathered PHB+musks, were daily spiked into tanks containing mussels, followed by a 10-day depuration period. Water and tissues samples were collected to measure exposure concentrations and accumulation in tissues. Mussels were able to actively filter microplastics in suspension but the concentration of the musks found in tissues (celestolide, galaxolide, tonalide) were markedly lower than the spiked concentration. Estimated Trophic Transfer Factors suggest that PHB will only play a minor role on musks accumulation in marine mussels, even if our results suggest a slightly extended persistence in tissues of musks loaded to weathered PHB.We thank AIMPLAS for in-kind supplying customized PHB polymers. This study was funded by AEI/10.13039/501100011033 (Spanish Government) through the ARPA-ACUA (CTM2016–77945-C3) and RISBIOPLAS (PID2019–108857RB-C32) project

Monitorization of Polyamide Microplastics Weathering Using Attenuated Total Reflectance and Microreflectance Infrared Spectrometry

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] The EU goal to reduce marine plastic litter by ca. 30% by 2020 stressed the need to deploy analytical methods to ascertain the polymeric nature of a residue. Furthermore, as plastics age under natural conditions and usual databases do not include their weathered spectra, (micro)plastics in environmental samples may be unidentified. In this paper, polyamide (nylon) microplastics weathering was monitored because of its ubiquity in household commodities, clothes, fishery items and industry, whose residues end up frequently in the environment. Infrared spectra (ATR and microreflectance) and Scanning Electron Microscopy (SEM) images were collected periodically while exposing nylon to controlled weathering. It was seen that ATR was more sensitive than microreflectance to monitor the structural evolution of polyamide and that the spectra and the surface of weathered microplastics showed remarkable differences with the pristine material, which stresses the need for considering its evolution when identifying microplastics in environmental studies. The evolution of six band ratios related to the chemical evolution of this polymer are presented. SEM images revealed the formation of secondary microplastics at the most advanced weathering stages of polyamide.This work was supported through the JPI-Oceans BASEMAN and MicroplastiX projects, sponsored by the Spanish Ministry of Science and Innovation (Agencia Estatal de Investigación) -partially financed by the European Regional Development Fund program- (Grants: PCIN-2015-170-C02-01; PCIN- PCI2020-112145 and CTM2016-77945-C3-3-R, ARPA-ACUA). The Program ‘Consolidación e Estructuración de Unidades de Investigación Competitiva’ of the Galician Government (Xunta de Galicia) is also acknowledged (Grant: ED431C-2017/28)Xunta de Galicia; ED431C-2017/2

New Ways for the Advanced Quality Control of Liquefied Natural Gas

[Abstract] Currently, gas chromatography is the most common analytical technique for natural gas (NG) analysis as it offers very precise results, with very low limits of detection and quantification. However, it has several drawbacks, such as low turnaround times and high cost per analysis, as well as difficulties for on-line implementation. With NG applications rising, mostly thanks to its reduced gaseous emissions in comparison with other fossil fuels, the necessity for more versatile, fast, and economic analytical methods has augmented. This work summarizes the latest advances to determine the composition and physico-chemical properties of regasified liquid natural gas, focusing on infrared spectroscopy-based techniques, as well as on data processing (chemometric techniques), necessary to obtain adequate predictions of NG properties.Part of this work was performed under the EMPIR 16ENG09 project ‘Metrological support for LNG and LBG as transport fuel (LNG III)’. This project has received funding from the EMPIR programme co-financed by the Participant States and from the European Union’s Horizon 2020 Research and Innovation programme. Mestrelab, Reganosa and Naturgy are acknowledged for hiring the services of the Group of Applied Analytical Chemistry for FTIR method development. The Program “Consolidación e Estructuración de Unidades de Investigación Competitivas” of the Galician Government (Xunta de Galicia) is also acknowledged (Grant ED431C 2021/56).Xunta de Galicia; ED431C 2021/5

A Reliable Method for the Isolation and Characterization of Microplastics in Fish Gastrointestinal Tracts Using an Infrared Tunable Quantum Cascade Laser System

[Abstract] Societal and environmental concern due to frequent reports of microplastics in fish stomachs raised as they may accumulate along the trophic chain. The request for analysing microplastics in fish stresses two major analytical issues: sample treatment and final characterization. The, so far, workhorse for chemical characterization is infrared spectroscopy which is time-consuming. Here, a quantum cascade laser-based device is used to accelerate the characterization stage. Its novelty poses new challenges for sample processing and particle handling because the unknown particles must be transferred to a reflective slide. In this study, three sample digestion protocols (alkaline-oxidative with H2O2, and alkaline-oxidative with NaClO and enzymatic-oxidative) and three different procedures to transfer the filter cake to reflective slides are compared. A simplified enzymatic-oxidative digestion (validated through an interlaboratory exercise) combined with a Syncore® automatic evaporation system and a Laser Direct Infrared Imaging (LDIR) device is proposed first time as a reliable and relatively fast method to treat gastrointestinal tracts of fish. Analytical recoveries were studied using samples of Scomber scombrus and they were ca. 100% for big –i.e., >500 μm- and ca. 90% for medium –i.e., 200–300 μm- particles and ca. 75% for 10 μm thick fibres.This research was supported by the LAnd-Based Solutions for PLAstics in the Sea Project (LABPLAS Project), Grant Agreement No. 101003954, under the European Union's Horizon 2020 research and innovation programme, and the Integrated approach on the fate of MicroPlastics (MPs) towards healthy marine ecosystems Project (MicroplastiX project), Grant PCI2020-112145, supported by the JPI_Oceans Program and by MCIN/AEI/10.13039/501100011033 and the European Union “Next Generation EU/PRTR”. The Program ‘Consolidación e Estructuración de Unidades de Investigación Competitivas” of the Galician Government (Xunta de Galicia) is also acknowledged (Grant ED431C 2021/56)Xunta de Galicia; ED431C 2021/5