Activated carbon from avocado seed as sorbent phase for microextraction technologies: activation, characterization, and analytical performance.

According to green analytical chemistry principles, the use of agricultural byproducts as sorbent phases is an interesting topic due to their lignocellulosic origin, as they are biodegradable and inexpensive. To the best of our knowledge, this is the first study in which avocado seed and avocado seed activated carbon are proposed as sustainable sorbents for solid-phase microextraction technologies, which were used to assess the proof of concept. Rotating disk sorptive extraction (RDSE) was used as a model technology and ibuprofen (Ibu) and 1-hydroxy-ibuprofen (1-OH-Ibu) as representative analytes. It was found that activated carbon (AC) prepared at 600 °C with an impregnation ratio (raw material/activating agent (ZnCl2), w/w) of 1:1.2 had better extraction efficiency than other ACs obtained at different temperatures, impregnation ratios, and activating agents (K2CO3). Characterization revealed several differences between natural avocado seed, biochar prepared at 600 °C, and selected AC since the typical functional groups of the natural starting material begin to disappear with pyrolysis and increasing the surface area and pore volume, suggesting that the main interactions between analytes and the sorbent material are pore filling and π-π stacking. By using this AC as the sorbent phase, the optimal extraction conditions in RDSE were as follows: the use of 50 mg of sorbent in the disk, 30 mL of sample volume, pH 4, 90 min of extraction time at a rotation velocity of the disk of 2000 rpm, and methanol as the elution solvent. The extracts were analyzed via gas chromatography coupled to mass spectrometry (GC-MS). The method provided limits of detection of 0.23 and 0.07 µg L-1 and recoveries of 81% and 91% for Ibu and 1-OH-Ibu, respectively. When comparing the extraction efficiency of the selected activated carbon with those provided by Oasis® HLB and C18 in RDSE, nonsignificant differences were observed, indicating that avocado seed activated carbon is a suitable alternative to these commercial materials.

Ultra-trace determination of cadmium in water and food samples by a thin-film microextraction using a supported liquid membrane combined with smartphone-based colorimetric detection.

A mixture of n-octanol and dithizone was introduced as an effective and novel extraction agent in a thin-film microextraction technique for the pre-concentration of cadmium ions. The extraction agent was immobilized on small pieces of porous polypropylene flat membrane as a supported liquid membrane. The analyte extraction was performed by immersing the modified film in the sample solution, and via a complex formation between the immobilized dithizone on the film and cadmium ions. After the thin-film microextraction process, the colored cadmium-dithizone complex was directly measured by a smartphone colorimetric analysis. Under optimized conditions, the linear dynamic range, the limit of detection, and the limit of quantification were 0.5-300.0, 0.1, and 0.4 µg L-1, respectively. The developed technique was successfully employed to quantify cadmium ions in water and food samples. The high relative recovery values (95.0-103.0%) along with relative standard deviations of less than 2.5% were obtained for the spiked samples.

A thin biofilm of chitosan as a sorptive phase in the rotating disk sorptive extraction of triclosan and methyl triclosan from water samples.

The features and nature of the sorptive phase may be the stage that determines the scope of microextraction techniques. In search of new alternatives, materials of natural origin have recently been explored to establish greener analytical strategies. Based on that search, this research proposes the use of chitosan as a sorptive phase, which was assessed in the rotating disk sorptive extraction of emerging contaminants from aqueous systems. Chitosan is a biopolymer of animal origin that is usually found in the shells of crustaceans. The main characteristic of this material is the presence of a high number of nitrogenous groups, which gives it high reactivity, but its main disadvantage is associated with its high swelling capacity. In this research, chitosan was crosslinked with a low concentration of glutaraldehyde to form thin films that were easily immobilized on the surface of the rotating disk. The main advantage of this modification is the considerable decrease in the swelling capacity, which prevents loss and rupture of the sorbent during high rotation of the disk. In addition, it not only improved the physical characteristics of chitosan but also increased its extraction capacity. With regard to its use as a sorptive phase, all the variables associated with the microextraction of the analytes were studied, and optimal variables were found to be: pH 4, 20% NaCl (salting out effect), 30-45 min as equilibrium time and elution of analytes with a mixture of methanol:ethyl acetate (1:1). Validation of the methodology for the determination of methyl triclosan and triclosan was carried out, and relative recoveries between 89 and 96% and relative standard deviations less than 14% were found. The detection limits were 0.11 and 0.20 µg L-1, respectively. Through its application in real samples (natural and residual waters), triclosan was quantified between 0.7 and 1.3 µg L-1. Finally, the "green" properties of the phase were evaluated, demonstrating that it is reusable for at least three cycles and biodegradable. Compared to its efficiency with a commercial phase (in this case, the styrene divinyl benzene phase), the proposed biosorbent provided a similar and even higher sorptive capacity (depending on the analyte).

Effect of triclosan exposure on ovarian hormones, trace elements and growth in female rats.

Triclosan (TCS) is an antibacterial compound used mainly in personal care products. Its widespread use for decades has made it one of the most widely detected compounds in environmental matrices and in biological fluids. Although it has been shown to be an endocrine disruptor in rats and aquatic species, its safe use by humans is unclear. The aim of the present study was to evaluate the effects of exposure to TCS in female rats. To this end, 14 rats were divided into two groups and fed daily as follows: the control group with sesame oil and the TCS group at a dose of 50 mg/kg/day for 28 days. Any signs of toxicity in the rats were observed daily, and the weight and phase of the estrous cycle were recorded. At the end, the rats were decapitated, the serum and ovaries were collected. The levels of testosterone and progesterone in serum were determined by immunoassay and mass spectrometry. Estradiol (in serum) and kisspeptin-10 (in serum and ovary) were measured only by immunoassays. Trace elements were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The weight gain study of the rats showed a significant decrease by exposure to TCS, while the estrous cycle was not significantly affected compared to the control. The optimized methods based on mass spectrometry showed a significant decrease in the levels of progesterone and testosterone due to exposure to TCS. In addition, elements determined by ICP-MS in rat serum showed significant changes in calcium, lithium and aluminum due to TCS treatment. Finally, the kisspeptin-10 levels did not show a negative effect due to the treatment by TCS. The results suggest that medium-term exposure to TCS did not significantly alter estrous cyclicity but caused alterations in growth, sex hormone levels and some elements in the rat serum.

Initial phthalates fingerprint and hydrochemical signature as key factors controlling phthalates concentration trends in PET-bottled waters during long storage times.

Phthalateacid esters (PAEs) concentration in bottled water and different factors (water pH, storage time, sunlight exposure, and temperature) that affect/control them have become hot topics during recent years. Nevertheless, quite contradictory results and disagreements on the effects of these factors have been published. In an attempt to find some consensus on this topic, a comprehensive study considering the combined effect of long storage times (longer than a year) and the water hydrochemical signature (including water pH, elemental composition and the presence/absence of dissolved CO2)was performedusing the four most commonly consumed bottled water brands on the Chilean market. Each water brand was analyzed between 10 or 14 different times, depending on the brand (in total 97 samples were studied). Following the concept ofthe hydrochemical signature typically used in hydrogeology to classify types of waters, the notion of a water phthalate fingerprint was proposed. Finally, concerning the effect of long storage times, this study demonstrates that all the trends (increase, decrease or steady) of the Total PAEs concentration are possible; and these trends are controlled by the specific hydrochemical signatureandphthalate fingerprint of the bottled water.

Rapid Determination of Parabens in Water Samples by Ultra-high Performance Liquid Chromatography Coupled to Time of Flight Mass Spectrometry.

An analytical methodology has been developed and validated for the purpose of identifying and quantifying four parabens (methylparaben, ethylparaben, propylparaben and n-butylparaben) in water samples. The combination of rotating disk sorptive extraction (RDSE) technology with ultra-high performance liquid chromatography (UHPLC), along with electrospray ionization source (ESI) and time of flight mass spectrometry (TOF/MS) in trap mode, allowed for eliminating derivatization processes and a reduction of the chromatographic time required, achieving a greener analytical method. In this method, detection limits and precision (%RSD) were lower than 0.018 µg L-1 and lower than 9.7% for all the parabens, respectively, being better than similar works. Matrix effect and absolute recoveries were studied in tap and sewage water samples to observe suppressions of the signals for all analytes, and absolute recoveries were around 60%. This methodology was applied to the analysis of two sewage samples (punctual and composite) obtained from locations in Santiago, Chile.

A high throughput approach to rotating-disk sorptive extraction (RDSE) using laminar cork for the simultaneous determination of multiclass organic micro-pollutants in aqueous sample by GC-MS.

In this study, a high throughput approach to rotating-disk sorptive extraction (RDSE) using laminar cork as extraction phase is demonstrated for the first time in the determination of 20 multiclass organic micro-pollutants including pesticides, PAHs and UV filters compounds from aqueous samples with gas chromatography mass spectrometry (GC-MS). The influencing parameters (desorption solvent, volume and time, extraction time and sample pH and ionic strength) were carefully optimized using multivariate designs. The optimal conditions were 10 min for extraction using 35 mL of water samples and a liquid desorption using 1 mL of MeOH:AcOEt (50:50% v/v) for 20 min. A low-cost apparatus that allows six extractions simultaneously, providing a high throughput of 5 min per sample turnaround times, considering the sample preparation step was used for the first time in this modified RDSE methodology. Satisfactory analytical performance was achieved with limits of detection (LOD) between 0.08 and 1.5 µg L-1 and limits of quantification (LOQ) between 0.3 and 4.8 µg L-1. The relative recoveries for the analytes were determined using river and lake water samples spiked at different concentrations and ranging from 80% to 119% for all analytes, with relative standard deviations (RSD) lower than 20%. The extraction efficiency obtained for the proposed configuration with laminar cork was significantly superior to powdered cork, demonstrating an interesting new configuration for new applications.

Cork sheet as a sorptive phase to extract hormones from water by rotating-disk sorptive extraction (RDSE).

This work reports for the first time the use of laminar cork as a sorptive phase in a microextraction technique, rotating-disk sorptive extraction (RDSE). Typical hormones (estrone, estradiol, estriol and ethinyl estradiol) were selected as analyte models and extracted from wastewater samples on laminar cork with statistically equivalent extraction efficiency to that provided by Oasis HLB. The cork characterization was performed by confocal fluorescence microscopy (CLSM), Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), allowing the identification of lignin, suberin and polysaccharides (cellulose and hemicellulose) as the main components of the cork. The best conditions for extraction were as follows: rotation velocity of the disk, 2000 rpm; extraction time, 45 min; and sample volume, 20 mL. The analytical features of the developed method show that calibration curves for all analytes have R2 values higher than 0.99. The absolute recoveries were higher than 63%, and the precision, expressed as relative standard deviation, ranged from 2 to 16%. The LOD and LOQ ranges were 3-19 and 10-62 ng L-1, respectively. The proposed method was applied to the analysis of wastewater, and the concentrations of hormones in a wastewater treatment plant in Santiago, Chile, ranged from

Simultaneous determination of multiresidue and multiclass emerging contaminants in waters by rotating-disk sorptive extraction-derivatization-gas chromatography/mass spectrometry.

An efficient method has been developed for the multiresidue and multiclass determination of 16 emerging contaminants (parabens, hormones, anti-inflammatory drugs, triclosan and bisphenol A) in water samples using rotating-disk sorptive extraction (RDSE) and gas chromatography coupled to mass spectrometry (GC-MS). Silylation of the compounds prior to GC-MS analysis was optimized using a factorial experimental design; the optimal derivatization conditions to maximize the response of the set of analytes included 70 µL of N-methyl-N-(trimethylsilyl)trifluoroacetamide at 80 °C for 35 min. RDSE was implemented using Oasis® HLB as a sorptive phase and an extraction time of 60 min. The method was applied to Chilean environmental samples. In tap water, none of the analytes under study were detected. In the river and well waters, the concentrations of the four detected contaminants were below 0.38 µg L-1. In the effluent and influent of the wastewater treatment plant, the maximum concentrations of contaminants were 3.1 and 4.2 µg L-1, respectively. The proposed analytical strategy suggests clear improvements with respect to other methods reported in the literature, considering not only the different steps involved in the analytical process (extraction, derivatization and chromatography) but also taking into account that this method involves the determination of different families of analytes with different physicochemical and structural properties.

A green and simple sample preparation method to determine pesticides in rice using a combination of SPME and rotating disk sorption devices.

In this study, a novel environmentally-friendly approach was developed to overcome certain limitations in the analysis of solid food samples. An experimental setup based on solid-phase microextraction apparatus coupled to a rotating disk device is proposed for the determination of polar and slightly-polar pesticides including carbofuran, molinate, atrazine, simazine and tebuconazole in rice samples. In this innovative procedure, a rice sample is inserted into the cavity of the rotating disk device which is then immersed in an aqueous solution followed by high-speed agitation. In this case, water is employed as a green solvent for leaching the analytes from the sample matrix. Simultaneously, a solid-phase microextraction fiber comprised of divinylbenzene/carboxen/polydimethylsiloxane (2 cm length and 50/30 µm film thickness) was immersed in the aqueous solution to extract the slightly polar analytes from the aqueous matrix with subsequent thermal desorption in the injector of a gas chromatograph-mass spectrometer instrument. The optimal extraction conditions were obtained using an extraction temperature of 80 °C for 40 min, with 125 mg of rice inserted in the rotating disk. Using the previously optimized extraction conditions, the analytical performance was satisfactory with correlation coefficients higher than 0.9881 for all analytes, limits of detection ranging from 0.46 to 5.9 ng g-1, limits of quantification from 1.5 to 19.7 ng g-1, relative recoveries from 76 to 109%, intra-day precision (n = 3) from 1.3 to 19%, and inter-day precision (n = 9) from 3.5 to 6.5%. The proposed method represents a promising alternative for the analysis of complex solid food samples using SPME, since the SPME fiber damage is substantially decreased when the contact with the solid matrix is avoided.

Detection and assignment of inorganic aqueous polymers relevant to environmental nanogeoscience by direct infusion electrospray ionization mass spectrometry.

Inorganic polymers in aqueous solutions are being proposed as essential components in new theories concerning nonclassical nucleation and growth of nanominerals relevant to environmental nanogeosciences. The study of those complex natural processes requires multi-technique analytical approaches able to characterize the solutions and their constituents (solutes, oligomers, polymers, clusters and nanominerals) from atomic to micrometric scales. A novel analytical approach involving an electrospray ionization source (ESI) coupled to time-of-flight mass spectrometry (TOF/MS) was developed to identify inorganic polymers in aqueous solution. To this end, the presence of initial Al oligomers and their polymerization processes was studied during a nanomineral aqueous synthesis (hydrobasaluminte, Al4 SO4 (OH)10 ·12-36H2 O). Ensuring the feasibility and robustness of the methodology as well as the stability of the polymers under study (avoiding undesirable fragmentation), a meticulous study of the ESI-TOF MS working conditions was performed. Precision of the methodology was evaluated obtaining relative standard deviations below 3.3%. For the first time in the study of inorganic polymers in the earth sciences, the mass accuracy error (ppm) has been reported and the use of significant decimal figures of the m/z signal has been taken into account. Complementary to this, a four-step polymer assignment methodology and a database with the Al- and Al-SO4 2- polymers assigned were created. Several polymers have been assigned for the first time, including Al (SO4 )+ ·H2 O, Al2 O(SO4 )2+ ·H2 O, Al5 O4 (OH)5 2+ ·2H2 O, and Al3 O5 (OH)2- ·4H2 O, among others. The results obtained in the present study help create a foundation to include mass spectrometry as a routine analytical technique to study mineral formation in aqueous solution.

Liquid chromatography-time-of-flight high-resolution mass spectrometry study and determination of the dansylated products of estrogens and their hydroxylated metabolites in water and wastewater.

A method combining liquid chromatography with a dual-probe ultraspray electrospray ionization (ESI) source and time-of-flight high-resolution mass spectrometry (LC-ESI-TOF/MS) was developed for the simultaneous determination of four steroidal sex hormones, estrone (E1), 17ß-estradiol (E2), 17α-ethinyl estradiol (EE2), and estriol (E3), as well as five of their hydroxylated metabolites, 2-hydroxyestrone (2-OHE1), 4-hydroxyestrone (4-OHE1), 16α-hydroxyestrone (16-OHE1), 2-hydroxyestradiol (2-OHE2), and 4-hydroxyestradiol (4-OHE2), in water samples in a short chromatographic run of 10 min. Derivatization of the analytes was optimized using dansyl chloride as the derivatizing agent. Under optimal positive ionization conditions, the following signals, which had not been previously reported, were observed (with theoretical values of m/z 377.1373 for 2- and 4-OHE1 and 378.1452 for 2- and 4-OHE2), corresponding to doubly derivatized catechol estrogens in the form of [M+2H]2+. These mass spectrometric signals were more abundant than those reported previously for the [M+H]+ forms of these hydroxylated metabolites. Solid-phase extraction (SPE) with an octadecyl-endcapped sorbent was used to pretreat tap water and effluent from a wastewater treatment plant (WWTP) in Santiago, Chile. The method achieved the simple, fast, and sensitive measurement of nine estrogens with quantitative recoveries (higher than 85.4%). Detection and quantification limits were between 1 and 17 ng L-1 and between 3 and 58 ng L-1, respectively, for all compounds in water. The estrogens E1 and E2 were found in WWTP effluent at concentrations of 7 ± 1 and 41 ± 1 ng L-1, respectively, and EE2 was detected at a concentration below the limit of quantitation. This study shows that the proposed method is suitable for the accurate, rapid, and selective determination of all these analytes at trace levels. Graphical abstract ᅟ.

Exploiting green sorbents in rotating-disk sorptive extraction for the determination of parabens by high-performance liquid chromatography with tandem electrospray ionization triple quadrupole mass spectrometry.

In this study, the viability of applying cork and montmorillonite clay modified with ionic liquid as biosorbents in the rotating-disk sorptive extraction technique was investigated. Specifically, this was aimed at the determination of methyl paraben, ethyl paraben, propyl paraben, and isobutyl paraben, with separation/determination by high-performance liquid chromatography coupled with mass spectrometry. The optimization of the method for both biosorbents was performed using multivariate procedures. The extraction efficiencies for the target compounds in aqueous matrices were compared to those obtained using the commercial sorbent Octadecil Silano-C18. The optimum extraction conditions for both natural sorbents were the use of an ammonia solution (pH 10) as desorption solvent and an extraction time of 30 min. The proposed methods show limits of quantification of 0.8 µg/L for cork, 3.0 µg/L for montmorillonite clay and 6.0 µg/L for Octadecil Silano-C18. The relative recoveries from river water and tap water samples ranged from 80.3 to 118.7% and 80.0 to 119.9% for cork and montmorillonite clay modified with ionic liquid, respectively. Relative standard deviations were obtained for intra- and interday precisions of <15% and <19% for cork and <19% and <17% for montmorillonite clay modified with ionic liquid.

Uncertainty in the measurement of toxic metals mobility in mining/mineral wastes by standardized BCR®SEP.

Mining residues management is one of the greatest challenges for mining companies around the world. The increasing consciousness of the general public and governments about the potential threat that those residues can pose to the environment is demanding consistent and precise methodologies for assessing the potential release of toxic metals. On this regard, the modified BCR® sequential extraction procedure (SEP) is frequently the chosen assessing protocol. However, this protocol was designed to study soils and sediments with low to moderate metal pollution, and validation of its applicability to mining residues is missing. The present research covers this gap of knowledge by subjecting selected highly polluted mining residues to the modified BCR®SEP. On the light of these results, it was confirmed that most of the metal bearing minerals in the mining residues were not completely dissolved in the corresponding SEP and, therefore, the application of BCR®SEP to mining residues systematically leads to an underestimation of metals mobility. The necessary changes to optimize the BCR®SEP to study mining residues would set a extraction procedure distinctively different from the original; thus it is strongly recommended to use alternative approaches to assess toxic metals mobility in highly polluted mining residues.

Chemometric optimization of the extraction and derivatization of parabens for their determination in water samples by rotating-disk sorptive extraction and gas chromatography mass spectrometry.

A combination of rotating disk sorptive extraction (RDSE) using Oasis® HLB as the sorbent phase and gas chromatography mass spectrometry (GC-MS) has been performed for the determination of four of the most widely used parabens: methylparaben, ethylparaben, propylparaben and n-butylparaben. The extraction and derivatization of the analytes in water samples were optimized by using factorial (screening) and Doehlert designs, thus reducing the number of analyses with the concomitant reduction of time, reagents, waste, samples and cost. Thus, a RDSE method using 20mL of sample was performed. The disk was rotated at 2900rpm for 70min at room temperature. After a desorption step and evaporation of solvent, a derivatization method using 5µL of N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) for 15min at room temperature was used previously to inject the final extract into GC-MS. The detection limits and precision (%RSD) were lower than 0.05µgL- 1 and 9.7% for the studied compounds, respectively. Recoveries were studied using effluent samples of a wastewater treatment plant (WWTP), with values higher than 80% being obtained. The applicability and reliability of this methodology were confirmed through the analysis of tap water and influents from Santiago, Chile, with concentration values ranging from 0.57 to 0.83µgL- 1 in influents. The main advantage of the present RDSE method is that it is significantly faster than its counterpart by SBSE and requires a considerable lower volume of derivatizing agent.

Characterization and evaluation of phenolic profiles and color as potential discriminating features among Spanish extra virgin olive oils with protected designation of origin.

Changes in phenolic profiles and color parameters can help to differentiate between extra virgin olive oils (EVOOs) with protected designation of origin (PDO). Phenolic profile characterization and CIELAB parameters determination of 9 PDO EVOOs from Spain were developed. Both properties of EVOOs are very relevant to their commercialization and increase the product value. The Serrana de Espadán olive cultivar was characterized for the first time and showed the highest pinoresinol concentrations and clarities in these olive oils, which are important values for the product image. To detect fraudulent instrumental work and implement quality control, principal component analysis (PCA) and linear discriminant analysis (LDA) were performed. EVOO geographical origin and cultivar distributions were achieved with cumulative variances of 93.4% and 92.4%, respectively. A categorization of PDO EVOOs was proposed using the following 7 phenolic compounds: phenolic alcohols (tyrosol and hydroxytyrosol), 3,4-DHPEA-EDA, 3,4-DHPEA-EA, p-HPEA-EDA, pinoresinol and total phenolic compounds.

Released fraction of polychlorinated biphenyls from soil-biosolid system using a leaching procedure and its comparison with bioavailable fraction determined by wheat plant uptake.

The bioavailability of polychlorinated biphenyls (PCBs) in soils amended with biosolids was estimated using an aqueous leaching process of the compounds combined with rotating disk sorptive extraction (RDSE), and compared with bioavailability determined through of PCB absorption in wheat plants growing in the same soil-biosolid matrix. The matrices consisted of soil amended with biosolids at doses of 30, 90, and 200 Mg/ha, which increase concomitantly the organic matter content of the matrix. Considering that PCBs were natively absent in both the biosolids and soil used, the compounds were spiked in the biosolids and aged for 10 days. For each biosolid dose, the aqueous leaching profile was studied and equilibrium time was calculated to be 33 h. The leaching fractions determined by RDSE, considering total PCBs studied, were 12, 7, and 6% and the bioavailable fractions absorbed by the wheat root were found to be 0.5, 0.3, and 0.2% for 30, 90, and 200 Mg/ha doses, respectively. Both fractions leachable and bioavailable decrease with both increasing hydrophobicity of the compound (Kow) and increasing in the biosolid dose. It was found that both fractions (leaching and bioavailable) correlated according to the bivariate least squares regression, represented by a coefficient of correlation of 0.86. Therefore, the application of the chemical method involving a leaching procedure is an alternative to estimate the bioavailable fraction of PCBs in wheat plants in a simpler and in a shorter time.

Effects of applying biosolids to soils on the adsorption and bioavailability of 17α-ethinylestradiol and triclosan in wheat plants.

Biosolids contain inorganic and organic contaminants, including pharmaceutical and personal care products (PPCPs) that have accounted for a series of emerging contaminants, such as triclosan (TCS) and the hormone 17α-ethinylestradiol (EE2). The general aim of this study was to evaluate the effects of biosolid application on EE2 and TCS adsorption and bioavailability in soils through testing with wheat plants. For the bioavailability study, sand and two soils, Lampa and Lo Prado, were used. The sand and soils were treated using two biosolid application rates (0 and 90 mg ha-1), and the EE2 and TCS concentrations in the biosolids were determined as 0.54 ± 0.06 and 8.31 ± 0.19 mg kg-1, respectively. The concentration observed in wheat plants indicated that EE2 and TCS are mainly concentrated in the roots rather than in the shoots. Furthermore, the bioavailability of the compounds in plants depends on the properties of the contaminants and the soil. Adsorption studies showed that increasing the soil organic matter content increases the adsorption of TCS and EE2 on these substrates and that both compounds follow the Freundlich adsorption model. The desorption procedure indicated that availability for both TCS and EE2 depended on the soil type because TCS and EE2 were small in the Lampa soil with and without biosolid application and TCS increased by nearly 50% in the Lo Prado soil. The Lo Prado soil had an acidic pH (5.9) and the Lampa soil had a neutral pH of 7.3, and the organic carbon content was smaller.

Ionic liquids intercalated in montmorillonite as the sorptive phase for the extraction of low-polarity organic compounds from water by rotating-disk sorptive extraction.

Montmorillonite (MMT) clays were modified by the intercalation into their galleries of ionic liquids (IL) based on imidazolium quaternary ammonium salts. This new eco-materials exhibited good features for use as a sorptive phase in the extraction of low-polarity analytes from aqueous samples. Spectroscopic analyses of the modified clays were conducted and revealed an increase in the basal spacing and a shifting of the reflection plane towards lower values as a consequence of the effective intercalation of organic cations into the MMT structure. The novel sorbent developed herein was assayed as the sorptive phase in rotating-disk sorptive extraction (RDSE), using polychlorinated biphenyls (PCBs), representative of low-polarity pollutants, as model analytes. The final determination was made by gas chromatography with electron capture detection. Among the synthetized sorptive phases, the selected system for analytical purposes consisted of MMT modified with the 1-hexadecyl-3-methylimidazolium bromide (HDMIM-Br) IL. Satisfactory analytical features were achieved using a sample volume of 5 mL: the relative recoveries from a wastewater sample were higher than 80%, the detection limits were between 3 ng L-1 and 43 ng L-1, the precision (within-run precision) expressed as the relative standard deviation ranged from 2% to 24%, and the enrichment factors ranged between 18 and 28. Using RDSE, the extraction efficiency achieved for the selected MMT-HDMIM-Br phase was compared with other commercial solid phases/supports, such as polypropylene, polypropylene with 1-octanol (as a supported liquid membrane), octadecyl (C18) and octyl (C8), and showed the highest response for all the studied analytes. Under the optimized extraction conditions, this new device was applied in the analysis of the influent of a wastewater treatment plant in Santiago (Chile), demonstrating its applicability through the good recoveries and precision achieved with real samples.

Volatile-Mediated Effects Predominate in Paraburkholderia phytofirmans Growth Promotion and Salt Stress Tolerance of Arabidopsis thaliana.

Abiotic stress has a growing impact on plant growth and agricultural activity worldwide. Specific plant growth promoting rhizobacteria have been reported to stimulate growth and tolerance to abiotic stress in plants, and molecular mechanisms like phytohormone synthesis and 1-aminocyclopropane-1-carboxylate deamination are usual candidates proposed to mediate these bacterial effects. Paraburkholderia phytofirmans PsJN is able to promote growth of several plant hosts, and improve their tolerance to chilling, drought and salinity. This work investigated bacterial determinants involved in PsJN stimulation of growth and salinity tolerance in Arabidopsis thaliana, showing bacteria enable plants to survive long-term salinity treatment, accumulating less sodium within leaf tissues relative to non-inoculated controls. Inactivation of specific bacterial genes encoding ACC deaminase, auxin catabolism, N-acyl-homoserine-lactone production, and flagellin synthesis showed these functions have little influence on bacterial induction of salinity tolerance. Volatile organic compound emission from strain PsJN was shown to reproduce the effects of direct bacterial inoculation of roots, increasing plant growth rate and tolerance to salinity evaluated both in vitro and in soil. Furthermore, early exposure to VOCs from P. phytofirmans was sufficient to stimulate long-term effects observed in Arabidopsis growth in the presence and absence of salinity. Organic compounds were analyzed in the headspace of PsJN cultures, showing production of 2-undecanone, 7-hexanol, 3-methylbutanol and dimethyl disulfide. Exposure of A. thaliana to different quantities of these molecules showed that they are able to influence growth in a wide range of added amounts. Exposure to a blend of the first three compounds was found to mimic the effects of PsJN on both general growth promotion and salinity tolerance. To our knowledge, this is the first report on volatile compound-mediated induction of plant abiotic stress tolerance by a Paraburkholderia species.