Changes in air pollution during COVID-19 lockdown in Spain: A multi-city study.

The COVID-19 pandemic has escalated into one of the largest crises of the 21st Century. The new SARS-CoV-2 coronavirus, responsible for COVID-19, has spread rapidly all around the world. The Spanish Government was forced to declare a nationwide lockdown in view of the rapidly spreading virus and high mortality rate in the nation. This study investigated the impact of short-term lockdown during the period from March 15th to April 12th 2020 on the atmospheric levels of CO, SO2, PM10, O3, and NO2 over 11 representative Spanish cities. The possible influence of several meteorological factors (temperature, precipitation, wind, sunlight hours, minimum and maximum pressure) on the pollutants' levels were also considered. The results obtained show that the 4-week lockdown had significant impact on reducing the atmospheric levels of NO2 in all cities except for the small city of Santander as well as CO, SO2, and PM10 in some cities, but resulted in increase of O3 level.

A poly(glycidyl-co-ethylene dimethacrylate) nanohybrid modified with ß-cyclodextrin as a sorbent for solid-phase extraction of phenolic compounds.

A hybrid material made of ß-cyclodextrin anchored to a polymeric network is described and evaluated as a sorbent for solid-phase extraction of phenolic compounds (phenol, cresol isomers, 2-methoxy-4-vinylphenol, 4-ethylphenol, 4-vinylphenol, 4-ethylguaiacol, guaiacol, and eugenol). The polymeric backbone of the sorbent consists of a poly(glycidyl-co-ethylene dimethacrylate) network, whose surface has been modified with ß-cyclodextrin by a click-chemistry based procedure. The resulting material has been characterized by different techniques, and it has shown to be viable as a sorbent for its use in extraction cartridges. In this way, a method for the determination of the above analytes in tea has been validated. Under optimum conditions, the method has good repeatability, with coefficients of variation between 0.6 and 7.2%. In addition, recoveries from spiked samples at the level of 50 µg L-1 are between 57 and 101%. The method has been then applied to the determination of phenolic compounds in the drinkable portion of infusions made from tea bags. The quantification has been carried out by using gas chromatography coupled to a mass spectrometry detector. Following their elution from the sorbent with a mixture of acetonitrile and methanol, the limits of quantification reached are between 4.6 and 400 µg L-1. Results have been compared with those obtained with a reference method by using the paired t-test for comparing individual differences. The solid phase is reusable, and no cyclodextrin is lost during extraction due to its covalent anchoring to the polymeric support. Graphical abstract Schematic representation of the structure and characterization of the hybrid material made of ß-cyclodextrin anchored to a polymeric network. The material is described and evaluated as a sorbent for the solid-phase extraction of phenolic compounds.

Extraction of aflatoxins by using mesoporous silica (type UVM-7), and their quantitation by HPLC-MS.

A solid-phase extraction procedure has been developed by using a sorbent derived from UVM-7 mesoporous silica. The sorbent was applied to the extraction of aflatoxins B1, B2, G1 and G2 from tea samples followed by HPLC with mass spectrometric detection. The sorbent was characterized by transmission electron microscopy, nuclear magnetic resonance, X-ray diffraction and nitrogen adsorption-desorption. UVM-7 is found to be the best solid phase. The amount of solid-phase, type and volume of eluent, pH value and ionic strength and breakthrough volume were optimized. Following the recommended procedure, recoveries between 96.0 and 98.2% were achieved, with RSD values of <5.1%, and the limits of detection are in the range from 0.14 to 0.7 µg·kg-1. The material is reusable. The method was applied to the analysis of real tea samples. A low matrix effect is found, and recoveries are >88%. The results were compared with those obtained by immunoaffinity columns as a reference method. Only low concentrations of aflatoxin G2 were found in some samples, and results obtained with both methods are shown to be statistically sound and comparable. Graphical abstractSchematic representation of a mesoporous silica sorbent (type UVM-7) for the extraction of aflatoxins (AF) from tea by solid-phase extraction (SPE), and its determination by liquid chromatography. The morphology of the material allows to retain the analytes very well.

A city-level analysis of PM2.5 pollution, climate and COVID-19 early spread in Spain.

Purpuse: The COVID-19 outbreak has escalated into the worse pandemic of the present century. The fast spread of the new SARS-CoV-2 coronavirus has caused devastating health and economic crises all over the world, with Spain being one of the worst affected countries in terms of confirmed COVID-19 cases and deaths per inhabitant. In this situation, the Spanish Government declared the lockdown of the country. Methods: The variations of air pollution in terms of fine particulate matter (PM2.5) levels in seven representative cities of Spain are analyzed here considering the effect of meteorology during the national lockdown. The possible associations of PM2.5 pollution and climate with COVID-19 accumulated cases were also analyzed. Results: While the epidemic curve was flattened, the results of the analysis show that the 4-week Spanish lockdown significantly reduced the PM2.5 levels in only one city despite the drastically reduced human activity. Furthermore, no associations between either PM2.5 exposure or environmental conditions and COVID-19 transmission were found during the early spread of the pandemic. Conclusions: A longer period applying human activity restrictions is necessary in order to achieve significant reductions of PM2.5 levels in all the analyzed cities. No effect of PM2.5 pollution or weather on COVID-19 incidence was found for these pollutant levels and period of time. Supplementary Information: The online version contains supplementary material available at 10.1007/s40201-022-00786-2.

Mesoporous silica sorbent with gold nanoparticles for solid-phase extraction of organochlorine pesticides in water samples.

In this work, a novel sorbent, based on UVM-7 mesoporous silica doped with Au, has been proposed for organochlorine pesticides extraction. Cartridges containing this material have been applied to the preconcentration of 20 pesticides from water samples, through a solid-phase extraction (SPE) protocol, with their later determination by gas chromatography with an electron capture detector. First, UVM-7 materials were properly characterized by X-ray diffraction, N2 adsorption-desorption, electron microscopy techniques, and UV-Vis spectroscopy, thus confirming their structure and Au incorporation. After optimization of main extraction parameters, recoveries in the range of 80-110% were obtained for most of the analytes, with enrichment factors comprised between 275 and 430. The obtained sensitivity was comparable with other reported methods, with limits of quantification in the range of 0.3-20 ng L-1, thus allowing the determination of these compounds according to European legislation. The developed method has been successfully applied to the analysis of real spiked samples in comparison with a reference method, thus being this sorbent an alternative for organochlorine pesticide enrichment, through a simple, reusable, cheap, and environmentally friendly SPE procedure.

A ß-cyclodextrin sorbent based on hierarchical mesoporous silica for the determination of endocrine-disrupting chemicals in urine samples.

In the present work, a method for the determination of parabens and bisphenol A in urine samples has been developed. For this purpose, a novel hierarchical mesoporous silica doped with ß-cyclodextrin was developed and used as a sorbent for preconcentration and clean-up step, before analyte determination by liquid chromatography coupled to mass spectrometry detector. Disordered silica materials were also synthesized for comparison purposes. All materials were characterized by electron microscopy, X-ray diffraction, porosimetry, nuclear magnetic resonance, thermogravimetric analysis, elemental CNH analysis, and confocal microscopy, and the attachment of cyclodextrins has been proved as well as their uniform distribution in the resulting material. After the optimization of several protocol parameters, good analytical features were achieved, including recoveries in the range of 96-109% for all analytes, as well as relative standard deviations between 8 and 24%. Also, limits of quantification in the range of 0.003-0.19 µg L-1 were obtained in all cases. The developed method was applied to the determination of parabens and bisphenol A in real urine samples in comparison with a reference method using C18 cartridges, including the correction with creatinine content. Target analytes were detected in all analysed samples, with being BPA the most detected compound.

Iron-Doped Bimodal Mesoporous Silica Nanomaterials as Sorbents for Solid-Phase Extraction of Perfluoroalkyl Substances in Environmental Water Samples.

In this work, sorbets based on UVM-7 mesoporous silica doped with Fe were synthesized and applied to solid-phase extraction of perfluoroalkyl substances from environmental water samples. These emerging pollutants were then determined by liquid chromatography coupled with a mass spectrometry detector. Thus, Fe-UVM-7 mesoporous silica materials with different contents of iron, as well as different pore sizes (by using alkyltrimethilamonium bromide surfactants with different organic tail lengths) were synthesized, and their structure was confirmed for the first time by transmission electron microscopy, nitrogen adsorption-desorption, X-ray diffraction, and Raman spectroscopy. After comparison, Fe50-UVM-7-C12 was selected as the best material for analyte retention, and several extraction parameters were optimized regarding the loading and elution step. Once the method was developed and applied to real matrices, extraction efficiencies in the range of 61-110% were obtained for analytes with C8-C14 chain length, both perfluoroalkyl carboxylates, and perfluoroalkyl sulfonates. Likewise, limits of detection in the range of 3.0-8.1 ng L-1 were obtained for all target analytes. In the analysis of real well-water samples, no target compounds were detected. Spiked samples were analyzed in comparison to Oasis WAX cartridges, and statistically comparable results were achieved.

Assessment of migrating endocrine-disrupting chemicals in bottled acidic juice using type UVM-7 mesoporous silica modified with cyclodextrin.

An innovative material based in type UVM-7 mesoporous silica containing analyte-accessible cyclodextrin units is described and assessed as a selectivity-enhancing sorbent for extracting endocrine-disrupting chemicals from bottled apple juice to subsequently quantify them. The synthesis procedure has been carried out using both ß- and γ-cyclodextrin for their later comparison. Then, a complete analytical method for the isolation and determination of the above analytes has been validated. Following the optimized procedure, recoveries between 94% and 100% have been achieved and good repeatability is obtained with deviations under 6.8% for intra-day and inter-day experiments. The detection limits of the method have been established in the ng L-1 level, which demonstrates the ability to quantify the trace concentrations established by sanitary restrictions. A low matrix effect is found when working with real samples. To end, a comparison with an alternative extraction method using C18 extraction cartridges has been carried out and the results obtained with both procedures are comparable.

Host-guest interactions for extracting antibiotics with a γ-cyclodextrin poly(glycidyl-co-ethylene dimethacrylate) hybrid sorbent.

A procedure for the solid-phase extraction of antibiotics (enoxacin, ofloxacin, norfloxacin, ciprofloxacin, and sparfloxacin) in water has been developed. The sorbent used is based on a poly(glycidyl-co-ethylene dimethacrylate) network, whose previously modified surface has been functionalized with γ-cyclodextrin through a click-chemistry reaction. The architecture of the material has been characterized by thermogravimetric analysis, N2 adsorption-desorption, Raman spectroscopy, confocal microscopy, and scanning electron microscopy, showing good capability to be used as a filler for extraction cartridges. The optimization of the extraction methodology shows good intra-day and inter-day repeatability of the extraction procedure, with coefficients of variation between 2.5 and 5.1% and the possibility of reusing the material at least five times. The detection limits of the method have been established at the µg L-1 level, confirming the possibility of quantifying trace levels. To end, real groundwater samples have been analyzed and the results are comparable with those obtained with a reference method. The proposed material can be used for assessing the presence of antibiotics in aqueous environments through an extraction procedure taking advantage of the presence of γ-cyclodextrin on its structure.

Enhancing extraction performance of organophosphorus flame retardants in water samples using titanium hierarchical porous silica materials as sorbents.

A sorbent for the extraction of organophosphorus flame retardants has been proposed, based on UVM-7 (University of Valencia Materials) mesoporous silica doped with titanium. Designed cartridges have been applied to the extraction and preconcentration of flame retardants in water samples, followed by gas chromatography coupled to a mass spectrometry detector. Firstly, UVM-7 materials with different contents of titanium were synthesized and characterized by several techniques, thus confirming the proper mesoporous architecture. The potential of these materials was assessed in comparison with their morphological properties, resulting Ti50-UVM-7 the best solid phase. Several extraction parameters were also optimized. Analytical parameters were also evaluated, and limits of detection from 0.019 to 0.21 ng mL-1 were obtained, as well as intra-day relative standard deviation below 11% for all analytes. Extraction efficiencies above 80% in water samples were achieved. The reusability of the material was also proved. Finally, the designed protocol was applied for the analysis of real water samples, and quantifiable concentrations of tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and triphenyl phosphate (TPhP) were obtained in some samples. The method was compared with a United States Environmental Protection Agency general method with C18 cartridges.

Cyclodextrins as a Key Piece in Nanostructured Materials: Quantitation and Remediation of Pollutants.

Separation and pre-concentration of trace pollutants from their matrix by reversible formation of inclusion complexes has turned into a widely studied field, especially for the benefits provided to different areas. Cyclodextrins are non-toxic oligosaccharides that are well known for their host-guest chemistry, low prices, and negligible environmental impact. Therefore, they have been widely used as chiral selectors and delivery systems in the pharmaceutical and food industry over time. However, their use for extraction purposes is hampered by their high solubility in water. This difficulty is being overcome with a variety of investigations in materials science. The setting-up of novel solid sorbents with improved properties thanks to the presence of cyclodextrins at their structure is still an open research area. Some properties they can offer, such as an increased selectivity or a good distribution along the surface of a solid support, which provides better accessibility for guest molecules, are characteristics of great interest. This systematic review reports the most significant uses of cyclodextrins for the adsorption of pollutants in different-origin samples based on the works reported in the literature in the last years. The study has been carried out indistinctly for quantitation and remediation purposes.

A new proposal for the determination of polychlorinated biphenyls in environmental water by using host-guest adsorption.

Polychlorinated biphenyls (PCBs) are ubiquitous environmental pollutants whose wide industrial use has been banned over the years in most countries due to their persistence and bioaccumulation. In fact, the International Agency for Research on Cancer defined them in 2016 as carcinogenic to humans based on sufficient evidence of an increased risk of cancer, being children and pregnant or lactating women the most vulnerable population subgroups. In this work, a new alternative for the determination of polychlorinated biphenyls (PCB28, PCB52, PCB101, PCB138, PCB153, and PCB180) in water samples has been developed by using a cyclodextrin-containing silica microparticulated material as an adsorbent in solid-phase extraction. Gas chromatography coupled to an electron capture detector has been used in the quantification step. The methodology allows quantifying polychlorinated biphenyls at very trace levels, with limits of detection between 0.2 and 1.7 ng L-1. Other parameters such as the repeatability, with coefficients of variation lower than 11%, were likewise established. To end, real water samples were analyzed, and the results were comparable with those obtained with a reference method. The proposed methodology can be utilized for assessing the presence of these compounds in the environment and can come in handy for evaluation and remediation purposes.

Comparison of silica-based materials for organophosphorus pesticides sampling and occupational risk assessment.

A novel air sampler has been designed containing a sorbent based on UVM-7 mesoporous silica doped with Ti. The sorbent has been applied for the determination of organophosphorus pesticides in occupational air, followed by gas chromatography with mass spectrometry detection. Thus, several silica materials with different structures (mesoporous UVM-7 and microporous xerogels) were synthesized, and modified with the addition of Ti and Fe. The structure of these materials was proved by transmission electronic microscopy, energy-dispersive X-ray, X-ray diffraction, nitrogen adsorption-desorption and UV-Vis and Raman spectroscopy. The potential of these materials for the retention of pesticides was evaluated and Ti25-UVM-7 was selected as the best solid phase for analyte sorption. Then, several sampling parameters were optimized and analytical features such as breakthrough volume were determined. Using the designed samplers, quantitative retentions were achieved with recoveries in the range 93-107% for all analytes except for diazinon (82%). RSD values below 13% were obtained. Likewise, the sensitivity of the method was studied, and limits of quantification below 0.5 µg m-3 were obtained for all pesticides. The reusability of the material was also proved. The developed procedure has been applied to the air sampling and occupational risk assessment, during and after methyl-chlorpyrifos application in orange plantations. High concentrations and exposure rates above the limit value for ensure safe work conditions were obtained. At the same time, the air was sampled with XAD-2 samplers as a reference method, and results obtained with both devices were statistically comparable.

Bimodal porous silica nanomaterials as sorbents for an efficient and inexpensive determination of aflatoxin M1 in milk and dairy products.

An extraction procedure was developed for the determination of aflatoxin M1 in milk and dairy products. A sorbent based on UVM-7 mesoporous silica was used as solid phase for the sample clean-up, and the analyte determination was carried out by HPLC coupled to a fluorescence detector. The material architecture was characterized by transmission electronic microscopy, X-ray diffraction, 29Si NMR and nitrogen adsorption-desorption. After the optimization of extraction parameters, the influence of the matrix has been evaluated, obtaining recoveries in the range 78-105% for whole and skimmed milk and yogurt matrix. The reusability of the material was also proved. The sensitivity of the method was also evaluated, and a LOQ (0.015 µg kg-1) below the European legislation limit was obtained. The procedure was successfully applied for the determination of aflatoxin M1 in real samples. The results were compared with those obtained with a reference method, being the results statistically comparable.

Study of silica-structured materials as sorbents for organophosphorus pesticides determination in environmental water samples.

A novel sorbent based on a UVM-7 mesoporous silica doped with Ti has been synthesized and used for solid-phase extraction of several organophosphorus pesticides in environmental water samples followed by gas chromatography coupled to a nitrogen-phosphorus selective detector. Thus, mesoporous silica materials doped with Ti and Fe as well as immobilized cyclodextrin silica-based supports were prepared and morphologically characterized by several techniques such as transmission electronic microscopy, nitrogen adsorption-desorption and X-ray diffraction. These sorbents were comparatively evaluated, and Ti25-UVM-7 material was selected as the best solid phase. After optimization of extraction parameters such as amount of solid-phase, type and volume of eluent, pH and ionic strength and breakthrough volume, recoveries between 81% and 104.5% were achieved, with RSD values below 7.8% and 12% for intra-day and inter-day repeatability respectively. Moreover, limits of quantification in the range 0.5-4.4 µg L-1 were achieved for all target compounds using mass spectrometry detector. In addition, the developed method was applied for analysis of real water samples and it was validated with commercial C18 cartridges. Matrix effect was demonstrated in complex environmental matrices and the good reusability of synthesized material was also proved.

Design, characterization and comparison of materials based on ß and γ cyclodextrin covalently connected to microporous silica for environmental analysis.

Determination of organic pollutants in environmental samples presents great difficulties due to the lack of sensitivity and selectivity in many of the existing analytical methods. In this work, the efficiency of materials based on silica structures containing bounded γ-cyclodextrin has been evaluated to determinate phenolic compounds and polycyclic aromatic hydrocarbons in air and water samples, respectively, in comparison with materials made of ß-cyclodextrin. According to the results obtained for the material characterization, the new γ-cyclodextrin solid phase does not apparently present any porosity when used in air samples, but it has been shown to work efficiently for the preconcentration of polycyclic aromatic hydrocarbons in water, with recoveries around 80%. In addition, the use of the ß-cyclodextrin material for phenolic compounds sampling can be highlighted with recoveries between 83% and 95%, and recoveries for 4-vinylphenol and 2-methoxy-4-vinylphenol have been especially improved in comparison with the use of materials containing trapped ß-cyclodextrin in our previous researches. The observed phenomena can be explained on the basis of the analyte molecules size and the diameter of the cyclodextrin cavities, the influence of the cyclodextrin type in the material structure as well as on the interactions taking place with the pollutants and the influence of the matrix type in the retention and desorption mechanisms.

Comparison of the solid-phase extraction efficiency of a bounded and an included cyclodextrin-silica microporous composite for polycyclic aromatic hydrocarbons determination in water samples.

Solid-phase extraction is one of the most important techniques for sample purification and concentration. A wide variety of solid phases have been used for sample preparation over time. In this work, the efficiency of a new kind of solid-phase extraction adsorbent, which is a microporous material made from modified cyclodextrin bounded to a silica network, is evaluated through an analytical method which combines solid-phase extraction with high-performance liquid chromatography to determine polycyclic aromatic hydrocarbons in water samples. Several parameters that affected the analytes recovery, such as the amount of solid phase, the nature and volume of the eluent or the sample volume and concentration influence have been evaluated. The experimental results indicate that the material possesses adsorption ability to the tested polycyclic aromatic hydrocarbons. Under the optimum conditions, the quantification limits of the method were in the range of 0.09-2.4µgL(-1) and fine linear correlations between peak height and concentration were found around 1.3-70µgL(-1). The method has good repeatability and reproducibility, with coefficients of variation under 8%. Due to the concentration results, this material may represent an alternative for trace analysis of polycyclic aromatic hydrocarbons in water trough solid-phase extraction.

Determination of phenolic compounds in air by using cyclodextrin-silica hybrid microporous composite samplers.

An analytical method for the determination of phenolic compounds in air samples based on the use of cyclodextrin-silica hybrid microporous composite samplers is proposed. The method allows the determination of phenol, guaiacol, cresol isomers, eugenol, 4-ethylphenol and 4-ethylguaiacol in workplaces according to the Norm UNE-EN 1076:2009 for active sampling. Therefore, the proposed method offers an alternative for the assessment of the occupational exposure to phenol and cresol isomers. The detection limits of the proposed method are lower than those for the NIOSH Method 2546. Storage time of samples almost reaches 44 days. Recovery values for phenol, guaiacol, o-cresol, m-cresol, p-cresol, 4-ethylguaiacol, eugenol and 4-ethylphenol are 109%, 99%, 102%, 94%, 94%, 91%, 95% and 102%, respectively with a coefficient of variation below 6%. The method has been applied to the assessment of exposure in different areas of a farm and regarding the quantification of these compounds in the vapors generated by burning incense sticks and an essential oil marketed as air fresheners. The acquired results are comparable with those provided from a reference method for a 95% of confidence level. The possible use of these samplers for the sampling of other toxic compounds such as phthalates is evaluated by qualitative analysis of extracts from incense sticks and essential oil samples.