Early screening of suspected microplastics in bottled water in the Santiago Metropolitan Region of Chile.

Bottled water has emerged as a possible healthier alternative due to concerns about the quality of drinking water sources. However, recent studies have detected worrying concentrations of environmental contaminants in bottled water, including microplastics. Therefore, it is an emerging need to quantify their concentrations in local suppliers which could differ among countries and regions. In this work, we used fluorescence microscopy with Nile Red for the identification and quantification of potential microplastics in twelve brands of bottled water distributed in the Santiago Metropolitan Region of Chile. The average concentration of microplastics was 391 ± 125 p L-1, while the highest concentration observed was 633 ± 33 p L-1. Microplastics between 5 and 20 µm were the major contributors, a size fraction that has been reported to be susceptible to accumulate in the digestive tract or generate potential alterations in the lymphatic and circulatory systems. The estimated daily intake value for per capita was estimated to be 229 p kg-1 year-1 for people weighing 65 kg and 198 p kg-1 year-1 for those weighing 75 kg.

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.

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.

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.

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.

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.

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.

Ultra-high-performance liquid chromatography-Time-of-flight high resolution mass spectrometry to quantify acidic drugs in wastewater.

A novel analytical approach involving an improved rotating-disk sorptive extraction (RDSE) procedure and ultra-high-performance liquid chromatography (UHPLC) coupled to an ultraspray electrospray ionization source (UESI) and time-of-flight mass spectrometry (TOF/MS), in trap mode, was developed to identify and quantify four non-steroidal anti-inflammatory drugs (NSAIDs) (naproxen, ibuprofen, ketoprofen and diclofenac) and two anti-cholesterol drugs (ACDs) (clofibric acid and gemfibrozil) that are widely used and typically found in water samples. The method reduced the amount of both sample and reagents used and also the time required for the whole analysis, resulting in a reliable and green analytical strategy. The analytical eco-scale was calculated, showing that this methodology is an excellent green analysis, increasing its ecological worth. The detection limits (LOD) and precision (%RSD) were lower than 90ng/L and 10%, respectively. Matrix effects and recoveries were studied using samples from the influent of a wastewater treatment plant (WWTP). All the compounds exhibited suppression of their signals due to matrix effects, and the recoveries were approximately 100%. The applicability and reliability of this methodology were confirmed through the analysis of influent and effluent samples from a WWTP in Santiago, Chile, obtaining concentrations ranging from 1.1 to 20.5µg/L and from 0.5 to 8.6µg/L, respectively.