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Fifteen aroma compounds have been determined in their free and glycosylated forms in grapes using dispersive liquid-liquid microextraction with gas chromatography-mass spectrometry. The sample treatment includes a previous solid-liquid extraction stage and subsequent parallel microextraction approaches to preconcentrate total aroma content and the free fraction. Thus, the extraction of the total content of analytes requires previous enzymatic hydrolysis of the bound forms. For preconcentration, chloroform (250 μl) and acetonitrile (1.5 ml) were added to 10 ml of the sample extract in the presence of 0.5 g sodium chloride. The absence of matrix effect in the samples allowed quantification against aqueous external standards. Limits of detection ranged between 5 and 30 ng/g, depending on the compound. Method accuracy was studied through recovery assays, with recoveries in the 82-115% range being obtained. Relative standard deviations for repeatability studies were lower than 12%. Four different samples of grapes were analyzed, being quantified linalool in its free form at concentrations in the 359-470 ng/g range, and benzyl alcohol, 2-phenylethanol, and linalool oxide I and II in their bound forms between 52 and 464 ng/g.

An analytical methodology based on the combination of dispersive magnetic solid-phase extraction (DMSPE) and liquid chromatography-mass spectrometry (LC-MS) is proposed to explore the occurrence of 13 mycotoxins (aflatoxins B1, G1, B2, and G2; deoxynivalenol; T-2 toxin; ochratoxin A; HT-2 toxin; enniatins A, A1, B, and B2; and beauvericin) and their derivatives in natural grass samples. Magnetic microparticles (Fe3O4) coated with polypyrrole (PPy) polymer were used in DMSPE sample treatment as adsorbent phase, and Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy have been used for its characterization. The experimental parameters influencing the adsorption and desorption steps of DMSPE have been optimized. Method validation has been carried out obtaining limits of quantification between 0.07 and 92 μg kg−1 corresponding to enniatin B or A1 and DON, respectively. A total of 83 natural grass samples from 8 dehesa farms were analysed. Enniatin B was found in all the samples (0.29 to 488 μg kg−1 concentration range) followed by enniatin B1 (92.8% of the samples) with a 0.12–137 μg kg−1 concentration range. Moreover, co-occurrence of mycotoxins was studied and between 2 and 5 mycotoxins appeared simultaneously in 97.6% of the samples. Distribution of the contamination according to natural grass location was also investigated. Graphical abstract

Abstract The occurrence of emerging micropollutants (pharmaceuticals, pesticides, personal care products, industrial compounds, etc.) in the environment is considered a major threat to human health and aquatic ecosystems. These micropollutants enter the environment through anthropogenic actions and have been identified in surface, ground, waste, and even in drinking water, in quantities ranging from ng L−1 to µg L−1. Currently, the pollution of the global water cycle with persistent organic pollutants remains one of the major challenges of the twenty-first century. Most of these organic substances are only partially removed by conventional wastewater treatment plants. Particularly, considerable amounts of pharmaceuticals are used in human and veterinary medicine, which are not efficiently removed during conventional wastewater treatments and subsequently continuously enter freshwater systems and even agricultural crops. Accordingly, we have evaluated the effectivity of TiO2 as a photocatalyst in tandem with Na2S2O8 as an oxidant for the treatment of a wastewater effluent polluted with pharmaceutical (atenolol, carbamazepine, clarithromycin, erythromycin, irbesartan, and ketoprofen) residues. Results show that the use of solar heterogeneous photocatalysis by means of band-gap semiconductor materials, especially TiO2 in combination with a strong oxidant such as Na2S2O8, significantly enhances their disappearance from the wastewater effluent. However, the selected pharmaceuticals show a slow degradation in wastewater effluent compared to pure water indicating that the occurrence of dissolved salts and organic carbon in wastewater effluent noticeably slows down the efficiency of the treatment. A single first-order model satisfactorily explains the photocatalytic degradation of the compounds studied for both, pure and wastewater. In the case of wastewater effluent, the highest DT50 values were observed for macrolides (13 and 16 min for erythromycin and clarithromycin, respectively), while the other compounds studied showed DT50 values below 10 min. This methodology has a notorious interest in some areas of the Mediterranean basin with water shortage, such as SE of Spain, where more than 3000 h of sunlight per year are recovered.

A pesar de que la actual Región de Murcia es una de las comunidades autónomas con mayor número de yacimientos de época ibérica, ninguno de ellos ha sido puesto en valor. Esta circunstancia impide una comprensión global del patrimonio ibérico y sitúa a la Región en clara desventaja frente a otras comunidades y provincias que cuentan con amplios programas y rutas de puesta en valor de asentamientos ibéricos. La única excepción a este panorama es el yacimiento de Coimbra del Barranco Ancho (Jumilla, Murcia), donde desde 2006 y sobre todo en los últimos años, se ha trabajado intensamente en su puesta en valor. Sirve pues este caso como ejemplo para las futuras y necesarias actuaciones de salvaguardia y difusión del patrimonio inmueble ibérico en la Región.

In this study, the photocatalytic degradation of four fungicides, myclobutanil, penconazole and difenoconazole (triazole compounds) and boscalid (carboxamide), has been examined in different aqueous matrices (tap water, irrigation water and two WWPT effluents). Experiments were conducted at laboratory scale with different reagents—zinc oxide (ZnO), titanium dioxide (TiO2), sodium persulphate (Na2S2O8) and the combined systems ZnO/Na2S2O8 and TiO2/Na2S2O8—in water exposed to UV-LED irradiation. Previously, the effect of catalyst and oxidant loading on the disappearance kinetics of the different fungicides was assessed to know maximum degradation efficiency. The influence of water matrices and pesticide loading in removal effectiveness has been evaluated. It was observed a greater efficiency in processes conducted using the tandems ZnO/Na2S2O8 and TiO2/Na2S2O8 in irrigation and tap waters. Results showed that UV-LED are a suitable alternative for tackling the removal of organic pollutants in water.

One of the consequences of phytosanitary treatments applied to crops is the generation of a great volume of agro-wastewater having pesticide residues. These pollutants can be considered a serious threat to the environment and human health due to their capacity to affect distant areas remaining for a long time after their application. We have assessed the degradation of five pesticides in agro-waste water produced in two farms by the cleaning pesticide containers and phytosanitary treatment equipment used in the farms. For this purpose, a pilot facility was installed in both farms and advanced oxidation treatments were conducted using natural sunlight by means of Na2S2O8 and heterogeneous photocatalysis (TiO2/Na2S2O8). The remaining percentages obtained at the end of the experiments ranged from 5 to 90.1% for chlorantraniliprole, 5 to 82.3% for difenoconazole, 0.02 to 19.1% for metalaxyl, 1.4 to 74.4% for myclobutanil, and 0.3 to 61% for triadimenol. We observed a correlation between the higher remaining percentages and the total initial concentration of pollutant because of other commercial formulations applied in the farms. The results showed that this equipment could be used to eliminate or reduce the presence of pesticide residues in agro-waste water using an innovative facility installed in the farms and a renewable and economical source of energy (sunlight).

This research was to assess the effect of exogenous organic matter (composted sheep manure, CSM) on the sorption, disappearance and leaching of four pesticides (boscalid, flonicamide, myclobutanil ...

Groundwater is a source for drinking water in many countries, and its use is seriously threatened by the leaching of agrochemicals through the soil. With this aim, the oxidation of triclopyr and fluroxypyr in water was investigated at lab-scale using heterogeneous photocatalysis and photo-assisted ozonation combined with hydrogen peroxide H2O2 (peroxone process). For both herbicides, the order of effectiveness of the photo-assisted treatments in pure water were as follows: O3/H2O2>ZnO/Na2S2O8>TiO2/Na2S2O8. Comparing the three types of water, the rate constants through peroxone/UV process were in the order: Pure > Drinking > Leaching water, according to the complexity of the matrix. After two hours of treatment, fluroxypyr was completely removed from pure water, while 90 % and 55 % of its initial mass were removed from drinking and leaching water, respectively. On the other hand, the degradation of triclopyr was significantly slower. In this case, after two hours of illumination the complete degradation was not reached in any case. Owing to the generation of hydroxyl radicals (HO ) the water treatment with O3/H2O2/UV can be considered as an eco-friendly technology, although the substances present in the matrix, mainly in leaching water, can scavenge HO decreasing the photooxidation rate of both herbicides.

The effect of vermicompost added to a loam soil on the leaching behaviour of two herbicides (triclopyr and fluroxypyr) was examined. Mobility of the herbicides was assessed using disturbed soil columns under laboratory conditions. In both cases, the addition of vermicompost significantly increased the sorption of the compounds. For both, DT50 values were slightly higher in the amended soil, due to the increased adsorption. Rate constants (k) calculated according to pseudo-first order model were significantly lower in the case of triclopyr (very persistent), which led to a much lower degradation rate compared to fluroxypyr (persistent) in both unamended and amended soils. Values calculated for the experimental leaching index (ELI) in unamended and amended soils showed medium and high leachability for fluroxypyr (0.31 and 0.29) and triclopyr (0.72 and 0.70), respectively. Other index-based screening models (GUS, RLPI, LIX) also catalogue both herbicides as potential leachers. Results confirm that triclopyr and fluroxypyr may contaminate groundwater resources.

A new technique for measurement of glufosinate (GLU), glyphosate (GLY) and its metabolite aminomethylphosphonic acid (AMPA) using liquid chromatography with tandem mass spectrometry with a triple quadrupole (LC-QqQ-MS/MS) is proposed for the analysis of vegetables, agricultural soil and irrigation water. An ion-pair liquid–liquid microextraction (IP-LLME) procedure using 9-fluorenylmethyl chloroformate as the derivatizing reagent, methyl isobutyl ketone as the extraction solvent and hexadecyltrimethylammonium bromide as the ion-pair reagent was performed for preconcentration purposes, because the herbicides are present at very low concentrations. Limits of quantification (LOQs) of 0.5 ng mL−1, 2.5 μg kg−1 and 1.6 μg kg−1 were obtained for water, vegetables and soil, respectively. Repeatability and reproducibility were calculated using the relative standard deviation, and values ranged between 6 and 11%, depending on the analyte. Enrichment factors were 62, 60 and 85 for GLY, GLU and AMPA, respectively.

The photocatalytic properties of silk fibroin (SF) incorporating TiO2 nanoparticles using an electrospinning technique were examined. Electrospun SF/TiO2 mats were successfully prepared and characterized by different techniques (XRD, FE-SEM, XPS, XDS, FTIR and BET). The photocatalytic efficiency of these materials were assessed by their ability to degrade four pesticides (boscalid, hexythiazox, pyraclostrobin and trifloxystrobin) in water exposed to solar irradiation. The effect of catalyst loading on the disappearance kinetics of the different pesticides was studied in order to determine the maximum degradation efficiency. The degradation rate significantly increases upon adding the TiO2. However, no significant differences (p < 0.05) were observed when the TiO2 loading was increased from 25 to 50 mg for most compounds. Thus, SF mats with 25 mg of TiO2 were selected. Therefore, a new and simple approach to produce materials with photocatalytic activity, safety and potential application in the purification of water contaminated by pesticides has been developed.

The main objective of this study was to learn the leachability of three widely used triazole fungicides (flutriafol, myclobutanil and triadimenol) in clay-loam soil to assess the risk of groundwater pollution by means of leaching potential indices (LPIs). For this, sorption, degradation and leaching experiments were conducted in a lab to evaluate the behaviour of the fungicides in a typical semiarid Mediterranean soil (calcareous Regosol). The sorption study was carried out following the batch equilibrium method. The degradation test was performed in aerobic and dark conditions (21 °C) for 60 days. Finally, the leaching potential was assessed using disturbed soil columns. Samples of soil and water were analysed by HPLC-MS2. Low adsorption in the soil (log KOC ≤ 2.5) was observed for the three fungicides. The half-lives ranged from 79 to 136 days for triadimenol and flutriafol, respectively, showing moderate to high persistence in soil. All fungicides were detected in leachates with percentages ranging from 12% (triadimenol) to 26% (myclobutanil) of the initial mass added. Concentrations found in total leachates (13, 17 and 23 µg L−1 for triadimenol, flutriafol and myclobutanil, respectively) were in all cases higher than the maximum admissible concentration (0.1 µg L−1) established by the EU for groundwater. In accordance with the screening indices used (GUS, RLPI, LIX and ELI), all fungicides behave as mobile or very mobile compounds. The findings suggest that the studied fungicides are candidates to pollute groundwater resources, mainly in areas with intensive yearly rainfall regimes.

Scientific literature is full of works studying the removal of different pollutants from water through different Advanced Oxidation Processes (AOPs). Many of them only suggest it is reused for agricultural purposes or for small crops in pots. This study is based on the reuse of reclaimed agricultural wastewater contaminated with four insecticides (chlorantraniliprole, imidacloprid, pirimicarb and thiamethoxam) for growing lettuce in field conditions. First, solar photocatalysis with TiO2/Na2S2O8 was used on a pilot plant in a sunny area (Murcia, SE of Spain) as an environmentally friendly technology to remove insecticide residues and their main reaction intermediates from contaminated water. The necessary fluence (H, kJ m−2) to accomplish 90% removal (H90) ranged from 0.12 to 1212 kJ m−2 for pirimicarb and chlorantraniliprole, respectively. Only six (derived from imidacloprid, pirimicarb and thiametoxam) of 18 transformation intermediate products studied were detected in reclaimed water during the photoperiod (2000 kJ m-2 of accumulated UVA radiation) although all of them were totally photodegraded after a fluence of 1250 kJ m-2. Secondly, reclaimed agro-wastewater was used to irrigate two lettuce crops grown under greenhouse conditions and under agricultural field conditions. In no cases, insecticide residues nor their TIPs were noticed above their respective LOQs (limits of quantification) in soil and lettuce samples (between 0.03 and 0.04 μg kg−1 for pirimicarb and 2.49 and 2.23 μg kg−1 for thiamethoxam, respectively) when they were irrigated with reclaimed water, while residues of the four insecticides and some of their intermediates were found in soil and lettuce by the end of cultivation when they were irrigated with non-reclaimed contaminated water. According to the results, this technology can be applied in a sustainable way, mainly in areas with water scarcity and high solar radiation, contributing to water utilisation in drought areas and the use of renewable energy.

In light of foreseen global climatic changes, we can expect crops to be subjected to several stresses that may occur at the same time, but information concerning the effect of long-term exposure to a combination of stresses on fruit yield and quality is scarce. This work looks at the effect of a long-term combination of salinity and high temperature stresses on tomato yield and fruit quality. Salinity decreased yield but had positive effects on fruit quality, increasing TSS, acidity, glucose, fructose and flavonols. High temperatures increased the vitamin C content but significantly decreased the concentration of some phenolic compounds (hydroxycinnamic acids and flavanones) and some carotenoids (phytoene, phytofluene and violaxanthin). An idiosyncrasy was observed in the effect of a combination of stresses on the content of homovanillic acid O-hexoside, lycopene and lutein, being different than the effect of salinity or high temperature when applied separately. The effect of a combination of stresses may differ from the effects of a single stress, underlining the importance of studying how stress interactions may affect the yield and quality of crops. The results show the viability of exploiting abiotic stresses and their combination to obtain tomatoes with increased levels of health-promoting compounds.

Although the use of shade cloths is an economic and common practice to mitigate the effect of high temperatures in greenhouse crops in warm areas, the decrease of solar radiation may alter some physiological processes of the plant, modifying their nutritional needs and ultimately affecting production and quality. In this paper we study the effect of nitrogen dose and its interaction with the use of shade cloths on the quality of tomatoes, with particular attention paid to their bioactive compound content. The treatments consisted of three levels of N (14, 7 and 3 mM), combined with two levels of light intensity, control (100% light), and shading (60% light) provided by shade cloth. Shading adversely affected the production of tomatoes cultivated with 14 mM N, although a lower dose of N offset the negative effect of shade on performance. Shading did not affect the concentration of sugars in the fruit, but decreased the phenolic compound and vitamin C contents. By contrast, a decrease in the dose of N increased the concentration of phenolic compounds at 100% light and that of vitamin C with and without shading. Shading decreased the concentration of β-carotene only in the case of plants grown with the highest concentration of N. The concentration of lycopene, contrary to that observed for all other metabolites of interest, increased with shading. Under these shading conditions, the decrease in the dose of N did not affect the β-carotene and lycopene concentrations.

As a consequence of phytosanitary treatments on crops a volume of agro-waste water containing pesticide residues from remnants and rinse of the treatment machinery is usually generated. These residues can become a danger to the environment and human health. Therefore, three pilot facility located in different farms were developed and used for wastewater detoxification containing four neonicotinoid insecticides (thiamethoxam, imidacloprid, acetamiprid and thiacloprid) by means of heterogeneous photocatalysis (TiO2 in tandem with Na2S2O8) and natural sunlight. Previously, the catalyst load (300 mg L−1) and oxidant concentration (300 mg L−1) were optimized at lab-scale using a photoreactor. The remaining percentage of the insecticides were in the range 0–47% for thiamethoxam, 0.1–33% for imidacloprid, 2–66% for acetamiprid and 0.02–60% for thiacloprid of the total initial mass. The observed differences for each insecticide in same farm could be due to total initial concentration of pollutant due to others pesticides (non-neonicotinoid insecticides) used in the farms, and the different physical-chemicals characteristics of the water used to fill and wash of treatment equipment. The results obtained have demonstrated a cost-effective viable alternative to degrade the neonicotinoids insecticide residues contained in these agro-wastewater, with an innovative and energetically efficient facility placed in the farms.

The photocatalytic efficiency of magnetic nanoparticles using different coatings between Fe3O4 and semiconductor oxides (ZnO and TiO2) was evaluated by their capability to degrade four insecticides (etoxazole, fenpyroximate, flonicamid and metaflumizone) in water exposed to sunlight. Magnetic particles coated with SiO2 (MSPs) showed higher photodegradation activity. Sol-gel TiO2-SiO2 coated TiO2 P25 magnetic particles (MSTi2Ps) and sol-gel ZnO-SiO2 coated ZnO magnetic particles (MSZn2Ps) were more efficient than magnetic particles consisting of a silica undercoat followed by a TiO2- or ZnO- sol-gel coating as the photocatalytic layer for catalysing the removal of these pesticides. Finally, the addition of Na2S2O8 increased the photooxidation activity of both MSTi2Ps and MSZn2Ps. A comparison of the semiconductor oxides showed MSZn2Ps to be the most effective for the removal of the studied pollutants. As a consequence, the tandem MSZn2Ps/Na2S2O8 provides an interesting combination to remove pesticides in water.

This study aims to demonstrate a technically feasible alternative to remove pesticide residues from agro-waste water produced in farms from remnants in containers and treatment tanks, rinse in tanks after treatments, and cleaning of machines and equipment. For this, the photocatalyzed degradation of 12 pesticides commonly used on vegetables, vines, citrus and fruit crops was investigated in aqueous suspensions of TiO2 in tandem with Na2S2O8 at pilot plant scale under natural sunlight in Murcia (SE of Spain) during summer and winter seasons. Previously, preliminary experiments were carried out at laboratory scale using a photoreactor to optimize the photocatalyst (200 mg L−1) and oxidant (250 mg L−1) concentrations on the rate constants of the studied pesticides. The photodegradation of all pesticides can be modelled assuming a pseudo-first-order kinetics. The time needed for disappearance of 90% (DT90) of the studied pesticides, was lower than 4 h in summer in all cases with the exception of cyproconazole (4.9 h), while, cyproconazole (8.9 h), metalaxil (6.1 h) and propyzamide (7.9 h) showed DT90 higher than 6 h in winter. The reaction rate was enhanced 3-fold in summer season, which is directly correlated to the higher accumulated fluence per time received during this season (about a factor of 2.9 higher than in winter). In both cases, the higher and lower degradation rates were obtained for cyprodinil and cyproconazole, respectively. The total fluence to get a 90% reduction (H90) ranged from 4.6 to 5.2 J cm−2 (cyprodinil) to 71.5–76 J cm−2 (cyproconazole).

Investigations of anthropogenic contaminants in fresh- and wastewater have shown a wide variety of undesirable organic compounds such as Endocrine Disruptors (EDs). As a result, wastewater treatments using innovative technologies to remove those organic compounds are required. In this paper, the photodegradation of six EDs in wastewater at pilot plant scale is reported. The EDs were bisphenol A, bisphenol B, diamyl phthalate, butyl benzylphthalate, methylparaben and ethylparaben. Commercial TiO2 nanopowders (P25, Alfa Aesar and Kronos vlp 7000) were used as photocatalysts. The operating variables (type and loading catalyst, effect of electron acceptor and pH) were previously optimized under laboratory conditions. The results show that the use of TiO2 alongside an electron acceptor like Na2S2O8 strongly enhances the degradation rate of the studied compounds compared with photolytic tests, especially P25. The oxidation rates of the EDs at pilot plant scale were calculated following the disappearance of the target compound as a function of fluence (H). The ED degradation followed a pseudo-first order kinetics in all cases. In our experimental conditions, the half-fluence (H50) varied from 79 to 173 J cm−2 (photolytic test), 10–117 J cm−2 (TiO2 vlp 7000) and 3–58 J cm−2 (TiO2 P25), for bisphenol B and butyl benzylphthalate, respectively. It is concluded that solar photocatalysis using the tandem TiO2/Na2S2O8 can be considered as an environmental-friendly tool for water detoxification and a sustainable technology for environmental remediation, especially in the Mediterranean Basin, where many places receive more than 3000 h of sunshine per year. Although the cost depends on the nature of the pollutant, the treatment cost was estimate to be about 150 € m−3 for photocatalytic treatment with TiO2 P25.

Pesticides have been used extensively in agriculture to control pests and soil-borne diseases. Most of these pesticides can persist in soil in harmful concentrations due to their intrinsic characteristics and their interactions with soil. Soil solarization has been demonstrated to enhance pesticide degradation under field conditions. Recently, ozonation has been suggested as a feasible method for reducing the pesticide load in agricultural fields. However, the effects of ozonation in the soil microbial community have not been studied so far. Here, we evaluate the combined effects of solarization and ozonation on the microbial community of a Mediterranean soil. For this purpose, soil physico-chemical characteristics and enzyme activities and the biomass (through analysis of microbial fatty acids) and diversity (through 16S rRNA and ITS amplicon sequencing) of soil microbial communities were analyzed in a 50-day greenhouse experiment. The degradation of the pesticides was increased by 20%, 28%, and 33% in solarized soil (S), solarized soil with surface ozonation (SOS), and solarized soil with deep ozonation (SOD), respectively, in comparison to control (untreated) soil. Solarization and its combination with ozonation (SOS and SOD) increased the ammonium content as well as the electrical conductivity, while enzyme activities and soil microbial biomass were negatively affected. Despite the biocidal character of ozone, several microbial populations with demonstrated pesticide-degradation capacity showed increases in their relative abundance. Overall, the combination of solarization plus ozone did not exacerbate the effects of solarization on the soil chemistry and microbial communities, but did improve pesticide degradation., The authors acknowledge the financial support received from the European Commission through the LIFE+ Program (LIFE17 ENV/ES/000203 - LIFE AGREMSO3IL). The authors are also grateful to the Agencia Estatal de Investigación (AEI) and the Fondo Europeo de Desarrollo Regional (FEDER) for the project AGL2017-85755-R, the CSIC for the I-LINK+2018 (LINKA20069) project, and the Fundación Séneca (19896/GERM/15)

En este artículo se presenta un vaso cerámico calado descubierto en las excavaciones de la puerta oriental del poblado ibérico contestano de Coimbra del Barranco Ancho (Jumilla, Murcia). La pieza, que por contexto arqueológico se data en el siglo III a. C., se cataloga como un «vaso singular» por su excelente factura y sobre todo por mostrar en cada una de sus patas un prótomo de lobo modelado, representado con gran detalle. Esta circunstancia se da en otras tipologías cerámicas, pero hasta la fecha no se había documentado en un vaso calado. Considerando el papel simbólico de este animal en la cultura íbera y su relación con la aristocracia y sus ritos de tránsito e iniciación, se propone una función ritual para el recipiente, que por sus características pudo servir como brasero o quemaperfumes en esas ceremonias. In this paper we present a fretworked ceramic vase which was discovered in the excavations of the Eastern gate at the Contestanian-Iberian site of Coimbra del Barranco Ancho (Jumilla, Murcia). This piece of pottery, which can be dated back to the 3rd century BC, is catalogued as «singular vase» due to its excellent manufacture and, especially, for presenting on each of its feet a modeled wolf head with great detail. This fact can be found in other typologies, but has never been documented on fretworked vases. Considering the symbolic role of this animal in the Iberian culture and its relation with aristocratic initiation and passage rites, a ritual function is proposed for this vessel which, according to its features, could have been used as a brazier or incense-burner in these ceremonies. Trabajo realizado en el marco del Grupo de Investigación E041-08 Arqueología Histórica y Patrimonio del Mediterráneo Occidental de la Universidad de Murcia y del Proyecto de I+D+i HAR-2017-82806-P: Ciudades y complejos aristocráticos ibéricos en la conquista romana de la Alta Andalucía. Nuevas perspectivas y programa de puesta en valor (Cerro de la Cruz y Cerro de la Merced, Córdoba), financiado por Proyectos de Excelencia del MINECO. Programa estatal de Fomento de la Investigación Científica y Técnica de Excelencia. También en el marco de una ayuda Formación Profesorado Universitario (FPU18-00735) del Ministerio de Ciencia, Innovación y Universidades.

El presente estudio analiza una crátera griega de campana realizada con la técnica de figuras rojas que Sorolla representó varias veces durante su estancia de pensionado en Roma. El nivel de detalle con el que este vaso se representa y la metodología pictórica de Sorolla parecen indicar que se trata de una pieza real. La búsqueda del correlato arqueológico, empleando para ello corpora y bases de datos de cerámica, ha permitido saber de qué vaso se trata y en qué colección se encontraba, lo que arroja nuevos datos sobre la estancia y el trabajo de Sorolla en Roma.

This work assesses the behavior (adsorption, degradation and leaching) of four insecticides (chlorantraniliprole, thiametoxam, imidacloprid and pirimicarb) and their main reaction intermediates in a clay-loam textured soil (1.6% OM). Following the batch equilibrium method, the KOC (as log values) ranged from 1.2 to 3.9 (thiametoxam and pirimicarb, respectively). All the insecticides were moderately persistent (t½ = 39–100 days) in the following order: thiametoxam > imidacloprid > pirimicarb > chlorantraniliprole. Two major transformation products, desmethyl-formamido pirimicarb and desmethyl pirimicarb, were formed as consequence of dealkylation of the parent compound. Using disturbed soil columns only thiametoxam (93% of the initial amount) and imidacloprid (42% of the initial amount) were recovered from leachates. In the case of pirimicarb and chlorantraniliprole, 74% and 30%, respectively, were recovered from the soil. Thiametoxam and imidacloprid can be catalogued as mobile compounds, while pirimicarb and chlorantraniliprole are classified as immobile according to the screening indices used (GUS and ELI). Leachates containing thiametoxam and imidacloprid were subjected to photocatalytic treatment for 240 min using TiO2/Na2S2O8 with the help of a photochemical reactor equipped with LED lamp. Both compounds had a very fast degradation rate (half-lives ≤ 0.5 min) in deionized water, while their half-lives were 112 min and 178 min, respectively, in leaching water. This implies a strong effect of the water matrix composition, mainly due to organic matter dissolved (quenching). Only traces of thiametoxam urea and hydroxy imidacloprid were detected during the photocatalytic experiment.

We have evaluated the efficiency of silk fibroin (SF) coated with ZnO nanoparticles in the photocatalytic disappearance of one acaricide (etoxazole) and three fungicides (difenoconazole, myclobutanil and penconazole) in water exposed to sunlight irradiation. Electrospun SF/ZnO mats were successfully synthesized by electrospinning technique and characterized by XRD, FE-SEM, XPS, XDS, FTIR, and BET. The influence of catalyst loading on the degradation kinetics of the different pesticides was examined in order to gain knowledge of maximum degradation efficiency. A significant increment in degradation rates was observed with the addition of ZnO. SF mats with 25 mg of ZnO were finally selected since no significant differences (p &lt, 0.05) were detected when the loading was enlarged from 25 to 50 mg for the majority of the compounds. In the experimental conditions, the half-lives ranged from 33 min to 93 min for etoxazole and myclobutanil, respectively. The comparison of SF materials coated with similar amount of TiO2 and ZnO showed that the later was slightly more efficient to remove pesticide residues. Hence, the use of electrospun SF/ZnO nanostructures would provide an environmentally friendly approach with photocatalytic activity to be applied in the reclamation of water polluted by pesticides.

The photocatalytic properties of silk fibroin (SF) incorporating TiO

The determination of 15 pyrethroids in soil and water samples was carried out by gas chromatography with mass spectrometry. Compounds were extracted from the soil samples (4 g) using solid-liquid extraction and then salting-out assisted liquid-liquid extraction. The acetonitrile phase obtained (0.8 mL) was used as a dispersant solvent, to which 75 μL of chloroform was added as an extractant solvent, submitting the mixture to dispersive liquid-liquid microextraction. For the analysis of water samples (40 mL), magnetic solid-phase extraction was performed using nanocomposites of magnetic nanoparticles and multiwalled carbon nanotubes as sorbent material (10 mg). The mixture was shaken for 45 min at room temperature before separation with a magnet and desorption with 3 mL of acetone using ultrasounds for 5 min. The solvent was evaporated and reconstituted with 100 μL acetonitrile before injection. Matrix-matched calibration is recommended for quantification of soil samples, while water samples can be quantified by standards calibration. The limits of detection were in the range of 0.03-0.5 ng/g (soil) and 0.09-0.24 ng/mL (water), depending on the analyte. The analyzed environmental samples did not contain the studied pyrethroids, at least above the corresponding limits of detection.

There is no previous work on the determination of chlorophenoxy acid herbicides in soils. Here we analysed six chlorophenoxy acid herbicides using magnetic solid phase extraction for their preconcentration, then liquid chromatography and tandem mass spectrometry with a triple-quadrupole (LC-QqQ-MS/MS) in the multiple reaction monitoring mode. 40 mg of CoFe2O4@polypyrrole magnetic nanoparticles was added to a 30-mL sample, and vortex stirring was applied for 10 min. Analytes were desorbed using acidified methanol. The reliability of the results was validated through recovery assays, giving mean values in the 80–117 range. The intraday precision was in the 6.3–14% range, in terms of relative standard deviation.

This work studies the effect of chitosan (CH) and 2,4-epibrasinolide (BRs) on total fruit yield and the content in bioactive compounds, in tomatoes cultivated in a greenhouse under high temperature conditions. Five treatments were applied: 0.1 and 1 g L-1 CH, 10 and 30 µM BRs and a control. Treatment with BRs increased the total fruit yield as a result of an increase in fruit weight. In addition, at the highest dose (30 µM), an increase in the number of fruits compared with control plants was observed. For the CH treatment, only the highest dose (1 g L-1) led to an increase in yield that was related to an increase in the number of fruits. Regards carotenoids, BRs treatments had no significant effect on the concentration of health-related carotenoids (phytoene, phytofluene, β-carotene and lycopene) except for lutein that decreased by the treatment with 30 µM. Finally, treatments with CH had no effect on phytoene, phytofluene and lycopene but it decreased lutein and β-carotene concentrations at the highest dose. The results show that the application of bioestimulants could be considered a potential tool for increasing tomato production under high temperature conditions without decreasing the concentration of the most of the major carotenoids.