Synthetically induced Arabidopsis thaliana autotetraploids provide insights into the analysis of meiotic mutants with altered crossover frequency.

Mutations affecting crossover (CO) frequency and distribution lead to the presence of univalents during meiosis, giving rise to aneuploid gametes and sterility. These mutations may have a different effect after chromosome doubling. The combination of altered ploidy and mutations could be potentially useful to gain new insights into the mechanisms and regulation of meiotic recombination; however, studies using autopolyploid meiotic mutants are scarce. Here, we have analyzed the cytogenetic consequences in colchicine-induced autotetraploids (colchiploids) from different Arabidopsis mutants with an altered CO frequency. We have found that there are three types of mutants: mutants in which chiasma frequency is doubled after chromosome duplication (zip4, mus81), as in the control; mutants in which polyploidy leads to a higher-than-expected increase in chiasma frequency (asy1, mer3, hei10, and mlh3); and mutants in which the rise in chiasma frequency produced by the presence of two extrachromosomal sets is less than doubled (msh5, fancm). In addition, the proportion of class I/class II COs varies after chromosome duplication in the control. The results obtained reveal the potential of colchiploid meiotic mutants for better understanding of the function of key proteins during plant meiosis. This is especially relevant considering that most crops are polyploids.

Multiresidue method for the determination of critically and highly important classes of antibiotics and their metabolites in agricultural soils and sewage sludge.

In this paper, a method is proposed for the determination of antibiotics classified by the World Health Organization as critically important (four macrolides and three quinolones) and highly important (one tetracycline, one diaminopyridine, and three sulfonamides) and eight of their metabolites. The method is based on ultrasound-assisted extraction, dispersive solid-phase extraction clean-up, and analytical determination by liquid chromatography-tandem mass spectrometry. Variables affecting each stage of the analytical method were thoroughly optimised. The method was validated for its application to sewage sludge from different treatment stages (non-treated sludge: primary and secondary sludge; and treated sludge: digested sludge and compost) and to agricultural soil. Limits of quantification were in the range of 0.03-7.50 ng g-1 dry weight (dw) for most of the compounds. Accuracy values were in the range of 70-102%. Precision was below 17%. The application of the method to real samples revealed that macrolides and fluoroquinolones were the antibiotic classes at the highest concentrations in all types of samples. The lowest concentrations of antibiotics were measured in compost (highest concentration: 27 ng g-1 dw, corresponding to norfloxacin) and soil samples (highest concentration: 93 ng g-1 dw, corresponding to a metabolite of clarithromycin). The proposed method is the first developed to date for the determination of multiclass antibiotics and their main metabolites in sludge from different treatment stages. The method can provide a useful tool for obtaining information about antibiotics in sewage sludge prior to its application to agricultural soils and in agricultural soils.

Adsorption of perfluoroalkyl substances on polyamide microplastics: Effect of sorbent and influence of environmental factors.

Microplastics (MPs) and perfluoroalkyl substances (PFASs) are two types of pollutants coexisting in the environment. Their co-exposure is a source of increasing concern. MPs present in the natural environment suppose an ideal surface for the sorption of hazardous contaminants. This study investigates the adsorption behaviour of six PFASs on polyamide (PA) MPs. Adsorption experiments under various internal (PA and PFASs dosage, PA particle size) and environmental (pH, ionic strength, dissolved organic matter) factors were carried out. Isotherm results (from 0.1 to 25 mg/L of PFASs) showed that the maximum adsorption capacity of the selected PFASs on the PA was as follows: perfluorooctanesulfonic acid (PFOS, 0.873 mg/g) > perfluorooctanoic acid (0.235 mg/g) > perfluoroheptanoic acid (0.231 mg/g) > perfluorohexanoic acid (0.201 mg/g) > perfluoropentanoic acid (0.192 mg/g) > perfluorobutanoic acid (0.188 mg/g) (pH 5.88, 0% salinity and 0% of dissolved organic matter). The PFOS has more tendency to be sorbed onto PA than perfluorocarboxilic acids. The MP characterization by scanning electron microscopy, X ray diffraction and Fourier transform infrared spectroscopy showed changes in the PA surface after adsorption assays. Pore filling, hydrophobic interactions and hydrogen bonds governed sorption process. The sorption capacity of PFASs was crucially affected by the PA size (from 19.6% to 99.9% for 3 mm and 50 µm particle size, respectively). The process was not significantly influenced by salinity while the dissolved organic matter exerted a negative effect (decrease from 100% to 26% for PFOS in presence of 25 mg/L of humic acid). Finally, adsorption rates of PFASs were quantified in real water matrices (influent and effluent wastewater, surface and tap water samples). The results revealed interactions between PA and PFASs and evidenced the role of PA as a vector to transport PFASs in the aquatic environment.

Uptake and depuration of three common antibiotics in benthic organisms: Sea cucumber (Holothuria tubulosa), snakelocks anemone (Anemonia sulcata) and beadlet anemone (Actinia equina).

Antibiotics are widely used drugs in human and veterinary medicine, which has attracted great attention in relation to the development of bacterial resistance, currently a problem of great concern for governments and states, as it is related to the resurgence of infectious diseases already eradicated. Understanding the bioaccumulation of antibiotics in aquatic organisms is an important key to understanding their risk assessment. The present study was designed to study the bioaccumulation of target antibiotics in relevant organisms inhabiting benthic marine environments. The uptake and elimination of ciprofloxacin (CIP), sulfamethoxazole (SMX) and trimethoprim (TMP) were investigated in sea cucumbers (Holothuria tubulosa), snakelock anemone (Anemonia sulcata) and beadlet anemone (Actinia equina) under controlled laboratory conditions. The results show that antibiotics have a particular trend over time during all periods of absorption and depuration. The tissue distribution of antibiotics in sea cucumber is strongly influenced by the structure of the compounds, while CIP is concentrated in the body wall; TMP is concentrated in the digestive tract. Two different approaches were used to estimate bioconcentration factors (BCFs) in different animal models, based on toxicokinetic data and measured steady-state concentrations. The BCF ranges were 456-2731 L/kg, 6-511 L/kg and 9-100 L/kg for TMP, CIP and SMX, respectively. The estimated BCF values obtained classify TMP as cumulative in A. equina and H. tubulosa, underlining the potential bioconcentration in these marine organisms. A correlation was observed between the BCFs of the target antibiotics and the octanol-water distribution coefficient (Dow) (r2 > 0.7). The animal-specific BCF followed the order of beadlet anemone > sea cucumber > snakelock anemone.

Thermodynamic and Kinetic Investigation of the Adsorption and Desorption of Trimethoprim and Its Main Metabolites in Mediterranean Crop Soils.

The adsorption-desorption processes of organic pollutants into the soil are one of the main factors influencing their potential environmental risks and distribution in the environment. In the present work, the adsorption-desorption behavior of an antibiotic, trimethoprim (TMP), and two of its main metabolites, 3-desmethyltrimethoprim (DM-TMP) and 4-hydroxytrimethoprim (OH-TMP), were assessed in three Mediterranean agricultural soils with different physicochemical characteristics. Results showed that the adsorption kinetic is performed in two steps: external sorption and intraparticle diffusion. The adsorptions of the studied compounds in soils were similar and fitted to the three models but were better fitted to a linear model. In the case of DM-TMP and OH-TMP, their adsorptions were positively correlated with the soil organic matter. In addition, desorption was higher in less organic matter soil (from 1.3 to 30.9%). Furthermore, the desorptions measured for the TMP metabolites were lower than those measured in the case of TMP (from 2.0 and 4.0% for OH-TMP and DM-TMP, respectively, to 9.0% for TMP).

Development and validation of a highly effective analytical method for the evaluation of the exposure of migratory birds to antibiotics and their metabolites by faeces analysis.

The widespread occurrence of antibiotics in the environment may exert a negative impact on wild organisms. In addition, they can become environmental reservoirs, through the ingestion of food or contaminated water, and vectors for antibiotic-resistant bacteria. This fact is even more important in migratory birds that can promote their dissemination across continents. In this work, a multiresidue analytical method suitable for the determination of five families of antibiotics and their main metabolites in waterbird faeces has been developed and validated. The target compounds include environmentally significant sulfonamides, macrolides, fluoroquinolones, tetracyclines and antifolates. Sample treatment involves ultrasound-assisted extraction with methanol and dispersive solid-phase extraction clean-up with C18. Analytical determination was carried out by liquid chromatography-tandem mass spectrometry. The most significant parameters affecting sample extraction and extract clean-up were optimised by means of experimental designs. Good linearity (R2 > 0.994), accuracy (from 41 to 127%), precision (relative standard deviation lower than 24%) and limits of quantification (lower than 2 ng g-1 (dry weight, dw)) were obtained for most of the compounds. The method was applied to the determination of the selected compounds in 27 faeces samples from three common migratory waterbird species. Nine antibiotics and three of their metabolites were detected in the analysed samples. Fluoroquinolones and macrolides were the antibiotics most frequently detected. The highest concentrations corresponded to norfloxacin (up to 199 ng g-1 dw).

Ultrasound-assisted extraction as an easy-to-perform analytical methodology for monitoring ibuprofen and its main metabolites in mussels.

Non-steroidal anti-inflammatory drugs (NSAIDs) have been reported to be the main pharmaceutical class accumulated in seafood. Among them, ibuprofen (IBU) is of special concern as it is used worldwide to treat common pain, does not require a medical prescription, it is often taken in a high daily dose, and has been reported to cause potential adverse effects on aquatic organisms. IBU is highly transformed into hydroxy- and carboxy-metabolites and/or degradation products generated not only after its administration but also during wastewater treatment or in the environment. These compounds can be present in the environment at higher concentrations than IBU and present higher toxicity. In this work, a low-cost and affordable routine analytical method was developed and validated for the first-time determination of IBU and its main metabolites in mussels. The method is based on ultrasound-assisted extraction (UAE), clean-up by dispersive solid-phase extraction (d-SPE) and analytical determination by liquid chromatography-tandem mass spectrometry. Box-Behnken experimental design was used for method optimisation to better evaluate the influence and interactions of UAE and d-SPE variables. Extraction recoveries were in the range from 81 to 115%. Precision, expressed as relative standard deviation, was lower than 7%. Method detection limits were in the range from 0.1 to 1.9 ng g-1 dry weight. The method was successfully applied to wild mussels.

Antibiotic adsorption by natural and modified clay minerals as designer adsorbents for wastewater treatment: A comprehensive review.

Increased antibiotic use worldwide has become a major concern because of their health and environmental impacts. Since most antibiotic residues can hardly be removed from wastewater using conventional treatments, alternative methods receive great attention. Adsorption is one of the most efficient and cost-effective treatment methods for antibiotics. Among the adsorbents, clay minerals have garnered increasing attention due to their unique properties including availability, high specific surface area, low cost, cation exchange capacity, and good removal efficiency. This paper reviews the recent progress made in the use of natural and modified clay minerals for the removal of antibiotics from water. First, the sources, occurrence, removal and health effects of the antibiotics commonly encountered in water bodies are described. Antibiotic concentration levels and average removal efficiencies measured in conventional activated sludge treatment systems worldwide are also provided to better address the problem. Second, the review explores the characteristics of clay minerals as adsorbent of antibiotics and the factors affecting the adsorption. The review identifies and discusses the future trends and strategies used to increase the adsorption capacity of clay minerals by modification and combination techniques (intercalation of novel functional groups such as organocations, biopolymers and metal pillared-clay minerals, combination with biochar or thermal activation). The quantitative comparisons of clay minerals' ability for antibiotic removal are given. Some natural clay minerals have good removal potential for antibiotics, with maximum adsorption capacities over 100 mg/g. For most other adsorbents, surface modifications and combination techniques resulted in improved adsorption properties (including higher surface area, enhanced adsorption capacity, increased stability and mechanical strength). Finally, the application of these adsorbents at pilot scale, using real wastewater samples, their reuse, economic analysis and life cycle assessment are other issues that have been considered.

Comparison of Different Techniques for the Determination of Platinized Cytostatic Drugs in Urine Samples.

Platinum-based cytostatic drugs are one of the most widely used cancer treatments. They are excreted via the urinary tract and can reach the environment through wastewater, posing a risk to human health due to their side effects. Four identification and quantification techniques, including liquid chromatography (LC) separation coupled to (i) a diode array ultraviolet (UV(DAD)) (ii), mass spectrometer in single ion monitoring mode (LC-MS) and (iii) multiple reaction monitoring mode (LC-MS/MS) and (iv) derivatization with diethyldithiocarbamate prior to LC-MS/MS analysis, have been optimized and compared for the multiresidue determination of main platinized cytostatic drugs (cisplatin, carboplatin, and oxaliplatin) in urine samples. Parameters that affect the efficiency of the chromatographic separation and analytical determination of different methods (column, mobile phase, wavelength, precursor ions, fragmentor, and product ions) were optimized. Analytical features, such as matrix effect, sensitivity, precision, selectivity, and linearity, were calculated. In terms of selectivity, the derivatization technique was discarded since it was only applicable to the platinated sum. A high dilution of the sample with LC-UV(DAD) was needed to reduce the matrix effect. Overall, the LC-MS/MS method presented the best analytical features (% RSD ≤ 12.8%, R2 ≥ 0.991, or method-detection limits between 0.01-1 µg mL-1). The selected method was applied to the quantification of platinized cytostatic drugs in hospital urine samples from oncologic patients.

An Overview of Analytical Methods to Determine Pharmaceutical Active Compounds in Aquatic Organisms.

There is increasing scientific evidence that some pharmaceuticals are present in the marine ecosystems at concentrations that may cause adverse effects on the organisms that inhabit them. At present, there is still very little scientific literature on the (bio)accumulation of these compounds in different species, let alone on the relationship between the presence of these compounds and the adverse effects they produce. However, attempts have been made to optimize and validate analytical methods for the determination of residues of pharmaceuticals in marine biota by studying the stages of sample treatment, sample clean-up and subsequent analysis. The proposed bibliographic review includes a summary of the most commonly techniques, and its analytical features, proposed to determine pharmaceutical compounds in aquatic organisms at different levels of the trophic chain in the last 10 years.

Occurrence of the main metabolites of the most recurrent pharmaceuticals and personal care products in Mediterranean soils.

The use of sewage sludge and wastewater in agricultural lands provide contaminants to soils. As a result, a large number of contaminants can be present in soils. Among others, pharmaceuticals and personal care products (PPCPs) are two of the most studied families of emerging contaminants in wastewater. However, there is scarce information about their behaviour in soils. Occurrence, fate and behaviour in soils of metabolites are even less known. In this work, the degradation of most recurrent PPCPs in the environment and their main metabolites has been evaluated using batch experiments in three typical Mediterranean soils. Batch experiments were carried out in a climatic chamber using spiked soils under Mediterranean climatic conditions. The studied compounds were five pharmaceutically active compounds (carbamazepine, ibuprofen, caffeine, sulfamethoxazole and diclofenac), two parabens (methylparaben and propylparaben) and twelve of their main metabolites. Studied PPCPs and metabolites showed different adsorption capacity onto the studied soils. As results, despite of the compounds were spiked at the same concentrations, different contents were measured at the beginning of the batch experiments. The soil 3 showed the lowest degradation rate for all studied compounds what could be related with the higher adsorption capacity of this soil. A decrease of the measured contents was observed for all studied compounds, except in the case of CBZ and EP-CBZ. No transformations of parent compounds into their metabolites or vice versa were observed, except in the case of Ibuprofen and its metabolites. Although the results showed overall short degradation times for the most of the compounds studied, the evaluation of the environmental risks of the PPCPs and their metabolites should not be underestimated.

Pharmaceuticals and Their Main Metabolites in Treated Sewage Sludge and Sludge-Amended Soil: Availability and Sorption Behaviour.

This work evaluated the availability and sorption behaviour of four pharmaceuticals and eight of their metabolites in sewage sludge and sludge-amended soil. Digested sludge and compost were evaluated. The highest levels found in digested sludge corresponded to caffeine (up to 115 ng g-1 dm), ibuprofen (45 ng g-1 dm) and carbamazepine (9.3 ng g-1 dm). The concentrations measured in compost were even lower than in digested sludge. No compound was detected in sludge-amended soils. This fact could be due to the dilution effect after sludge application to soil. Different adsorption capacities in sludge-soil mixtures were measured for the studied compounds at the same spike concentration. In general, except for paraxanthine and 3-hydroxycarbamazepine, the metabolite concentrations measured in the mixtures were almost two-fold lower than those of their parent compounds, which can be explained by their mobility and lixiviation tendency. The log Kd ranged from -1.55 to 1.71 in sludge samples and from -0.29 to 1.18 in soil-sludge mixtures. The log Kd values calculated for compost were higher than those calculated for digested sludge. The obtained results implied that the higher organic carbon content of compost could influence soil contamination when it is applied to soil.

Selective pressurized extraction as single-step extraction and clean-up for the determination of organophosphate ester flame retardant in Citrus aurantium leaves by gas chromatography-tandem mass spectrometry.

In this work, an analytical method has been developed and validated for the determination of organophosphate esters (OPEs) in urban ornamental tree leaves. OPEs are flame retardants and plasticizers which are classified as health and environmental hazards substances. Their presence in urban air has been previously described. The method proposed in this work would allow the use of urban tree leaves as simple, cheap, and widely distributed in urban areas alternative to the existing active and passive sampler for sample collection. The method was based on sample treatment by selective pressurized liquid extraction (SPLE) and determination by gas chromatography with triple quadrupole mass spectrometry detector. After the optimization of the extraction solvent, the key parameters applied to SPLE (clean sorbent and sorbent amount applied for the sample clean-up, temperature, extraction cycles, and time) were optimized using a Box-Behnken response surface design. The method achieves high recoveries (higher than 60% for most of the target compounds), accuracies between 70 and 109%, and method detection and quantification limits ranged 0.05-4.96 ng/g dw (dry weight) and 0.15-14.4 ng/g dw, respectively. The method allowed the proper biomonitoring of OPE in tree leaves. Concentrations measured in analyzed samples were from 47.5 to 5477 ng/g dw (TEP). The most frequently detected compounds were triethyl phosphate tri-n-butyl phosphate, triphenyl phosphate, and tris(1-chloro-2-propyl)phosphate, while tris(2-ethylhexyl)phosphate was not detected in the analyzed samples. The proposed analytical method constitutes a starting point for the use of ornamental urban trees as passive sampler for the evaluation of OPE as air pollutants. Graphical Abstract.

Distribution of metals in sediments of the Guadiamar river basin 20 years after the Aznalcóllar mine spill: Bioavailability and risk assessment.

In April 1998, 6 million m3 of acid water and sludge were accidently spilled on to the Guadiamar riverbed (South of Spain). In this study, the long term distribution of Al, Cd, Cu, Fe, Mn, Pb, and Zn in the sediments of the Guadiamar river basin is described using fractionation analysis. Changes in the availability of metals from 2002 to 2018, covering a period of 20 years after the dam collapse, have been evaluated and their potential environmental risks have been examined. A substantial decrease in the concentrations of all the metals studied was observed, except Pb. However, the concentrations of Cu, Zn, and Pb remained higher than the background concentrations, which indicates a high influence of the mining activity, even in 2018. An increase of the residual fraction was observed from 2002 (47%) to 2018 (67%), which was mainly due to the mobilisation of metals from their oxidisable fraction to their residual fraction. Environmental risk assessment revealed a significant decrease in the risk associated with metals from 2002 to 2018, mainly due to the decrease of the metals concentration in the sediments over the year and to the lower availability of these metals in 2018. In 2002, the most challenging metals were Pb and Zn, whereas in 2018, Zn and Cd were the most problematic due to their toxicity and availability.

Approach to the Dynamic of Carbamazepine and its Main Metabolites in Soil Contamination through the Reuse of Wastewater and Sewage Sludge.

The release of pharmaceutically active compounds to the soils through the application of sewage sludge and the irrigation with wastewater, or even with surface water, is constant. The adsorption of these compounds onto the soil is one of the key factors affecting their fate in the environment and their potential environmental risks. In this work, the adsorption of carbamazepine (CBZ) and its metabolites, 3-hydroxy-carbamazepine (3OH-CBZ), carbamazepine-10,11-dihydro-10,11-epoxide (EP-CBZ), and 10,11-dihydro-10-hydroxycarbamazepine (10OH-CBZ), in three Mediterranean soils was evaluated using single-solute and four-solute experiments. The highest adsorptions were measured for 3OH-CBZ, followed by CBZ, EP-CBZ, and 10OH-CBZ, in that order. A high influence of the physicochemical characteristics of the compounds, pH, and soil characteristics in the adsorption of the studied compounds was observed and corroborated by the statistical analysis of the results. Moreover, a good fit was observed in the three isotherm models evaluated (linear, Freundlich, and Langmuir) in single-solute experiments (R2 > 0.90). However, a decrease of the measured adsorptions and a worse fit to the isotherm models were observed in the case of multiple-solute experiments. This could be mainly due to the competition established between the studied compounds for the active sites of the soils.

Routine analytical method for monitoring the main metabolites for a recurrent group of parabens and pharmaceuticals in wastewater and tap water.

The presence of parabens and pharmaceuticals on the aquatic environment has been widely evaluated in the last years. Nevertheless, there is scarce information about the occurrence of their metabolites and/or degradation products in spite of the fact that they can be more toxic or more concentrated than their parent compounds. One of the main drawbacks for their monitoring is the lack of simple and reliable analytical methods for their routine determination. In this work, an analytical method has been developed and validated for the simultaneous extraction and determination of the main metabolites of the pharmaceuticals diclofenac, ibuprofen, sulfamethoxazole, carbamazepine and caffeine and of the parabens methylparaben and propylparaben and their parent compounds in wastewater and tap water samples. Sample extraction was carried out by conventional solid-phase extraction with OASIS HLB cartridges. Analytical determination was carried out by liquid chromatography-tandem mass spectrometry with electrospray ionization. Average accuracy was in the range from 66 to 120% in wastewater and from 86 to 120% in tap water. Precision, expressed as relative standard deviation, was lower than 17% for all the compounds. Method quantification limits were in the range from 1.0 to 33 ng L-1 in wastewater and from 0.5 to 28 ng L-1 in tap water. The method was applied to wastewater and tap water samples. None of the target compounds was detected in tap water whereas all of them were detected in wastewater. Concentrations of the metabolites were similar or higher than those of the parent compounds. Graphical abstract.

Dispersive liquid-liquid microextraction as a new clean-up procedure for the determination of parabens, perfluorinated compounds, UV filters, biocides, surfactants, and plasticizers in root vegetables.

An analytical method based on ultrasound-assisted extraction and dispersive liquid-liquid microextraction (DLLME) clean-up has been developed and validated for the determination of 31 emerging pollutants in root vegetables. The target compounds were four preservatives, six perfluoroalkyl compounds, six UV filters, two biocides, eight anionic surfactants, three nonionic surfactants, and two plasticizers. The type and volume of the extraction solvent, those of the disperser solvent, the pH and NaCl content of the DLLME aqueous phase, the amount of sample, and the sonication time were optimized. Box-Behnken experimental design was applied to select the best extraction conditions. Matrix-matched calibration curves were used for quantification. Four internal standards were used to compensate for residual matrix effects. Good linearity (R2 > 0.990), accuracies (expressed as the relative recovery) of >82%, and precisions (expressed as the relative standard deviation) of <18% were achieved. Method quantification limits (MQLs), calculated from spiked samples as the concentrations corresponding to signal-to-noise ratios of 10, were in the range 0.1-25 ng g-1 dry weight (d.w.). MQL values for 26 of the 31 target compounds were lower than 5 ng g-1 d.w. The method was successfully applied to determine the target pollutants in carrots, potatoes, and turnips from a local market. To the best of our knowledge, the proposed method constitutes the first application of DLLME as a clean-up procedure for the multiresidue determination of emerging pollutants in vegetables. The method affords similar recoveries and method detection limits to previously reported methods but requires smaller solvent volumes and sample amounts and is less expensive.

Analytical method for the evaluation of the outdoor air contamination by emerging pollutants using tree leaves as bioindicators.

In this work, an analytical method, based on sonication-assisted extraction, clean-up by dispersive solid-phase extraction and determination by liquid chromatography-tandem mass spectrometry, has been developed and validated for the simultaneous determination of 15 emerging pollutants in leaves from four ornamental tree species. Target compounds include perfluorinated organic compounds, plasticizers, surfactants, brominated flame retardant, and preservatives. The method was optimized using Box-Behnken statistical experimental design with response surface methodology and validated in terms of recovery, accuracy, precision, and method detection and quantification limits. Quantification of target compounds was carried out using matrix-matched calibration curves. The highest recoveries were achieved for the perfluorinated organic compounds (mean values up to 87%) and preservatives (up to 88%). The lowest recoveries were achieved for plasticizers (51%) and brominated flame retardant (63%). Method detection and quantification limits were in the ranges 0.01-0.09 ng/g dry matter (dm) and 0.02-0.30 ng/g dm, respectively, for most of the target compounds. The method was successfully applied to the determination of the target compounds on leaves from four tree species used as urban ornamental trees (Citrus aurantium, Celtis australis, Platanus hispanica, and Jacaranda mimosifolia). Graphical abstract Analytical method for the biomonitorization of emerging pollutants in outdoor air.

Removal of priority and emerging pollutants from aqueous media by adsorption onto synthetic organo-funtionalized high-charge swelling micas.

In this work, the removal of different types of emerging pollutants (four perfluoroalkyl compounds, two preservatives, three surfactants and nine pharmaceutical compounds) from aqueous solution by adsorption onto two novel synthetic clays, a high-charge swelling mica (Na-Mica-4) and an organo-functionalized mica (C18-Mica-4), was evaluated. Na-Mica-4 and C18-Mica- 4 were prepared and characterized by X-Ray diffraction, Zeta potential, specific surface area, thermogravimetric analysis and transmission electron microscopy, before and after adsorption experiments. The influence of the aqueous sample pH, salt addition and extraction time in the removal were evaluated. The results showed the high adsorption affinity of C18-Mica-4 for most of the emerging pollutants analysed after a removal time of 24 h (14 out of 18 pollutants were effectively removed [70-100%]). A high correlation was observed between the log Kow of the selected emerging pollutants and the adsorption onto C18-Mica-4. The results also indicate that adsorption occurs in the interlayer space. While the removal rates with Na-Mica-4 were in the range 8-97% after seven days, some of the compounds, perfluorobutanoic acid and most of pharmaceutically active compounds, were not adsorbed onto the high-charge mica. C18-Mica- 4 was effectively used for the removal of contaminants from four types of water samples.

Novel synthetic clays for the adsorption of surfactants from aqueous media.

The aim of this work was to assess for the first time the use of two high-charge swelling micas (Na-Mica-4 and C18-Mica-4) for the removal of four linear alkylbenzene sulfonates (LAS) from aqueous samples. To this end, Na-Mica-4 was synthesized and organically functionalized with cations of octadecylamine to obtain C18-Mica-4. Na-Mica-4 and C18-Mica-4 were characterized by X-Ray diffraction, Zeta potential, specific surface area and thermogravimetric analysis before and after the adsorption experiments. LAS removal studies were carried out in water samples spiked with a LAS mixture (10 mg L-1). Removal rates with C18-Mica-4 were between 94% and 97% at pH = 2, and between 98% and 99% at pH = 5 after 1 h. For the same amount of Na-Mica-4, removal rates were between 54% and 81% at pH = 2, and between 24% and 66% at pH = 5 after seven days. No significant effects on the removal rates of C18-Mica-4 were observed for pH values between 0.5 and 9. The experimental equilibrium data were fitted to 30 min, with removal rates of up to 98% in all the experiments. C18-Mica-4 characterization tests indicate that LAS adsorption occurs in the interlayer space. Finally, C18-Mica-4 was applied successfully to the removal of the target compounds from influent and effluent wastewater, surface water and tap water samples.