Preparation of a sustainable magnetic sorbent for the extraction and preconcentration of progestogens in natural water samples.

A film composed of agarose and graphene (G) and magnetic nanoparticles (G-MNPs) is proposed as a sorbent for the extraction and determination of medroxyprogesterone (MED), levonorgestrel (LEV), norethisterone (NOR) and progesterone (PRO) in natural water samples. Both the preparation of the film and the extraction procedure were optimized. The optimal extraction parameters were as follows: isopropyl alcohol as activation solvent, sample pH value of 3.0, extraction time of 30 min, 1.00 mL of acetonitrile as eluent, elution time of 5 min and sample volume of 100.00 mL. HPLC with photodiode array detector was used for the separation and determination. The method presented a linear range between 2.50 and 75.0 µg L-1 for all analytes, and the LODs were between 1.40 and 1.80 µg L-1. The method was applied to natural water samples, obtaining satisfactory recovery values (75-111 %). In conclusion, for the immobilization of the G-MNPs, agarose was used, which is a non-toxic, renewable and biodegradable material. The G-MNPs-agarose film was reused up to 70 times, without losing its extraction capacity significantly and presenting excellent sorbent properties, which allow the extraction and preconcentration of the progestogens under study.

3D-printed device for the kinetic determination of As(III) in groundwater samples by digital movie analysis.

High concentrations of inorganic arsenic in groundwater for human consumption is a worldwide common problem. Particularly, the determination of As(III) becomes important, since this species is more toxic than organic, pentavalent and elemental arsenic forms. In this work, a 3D-printed device that included a 24-well microplate was developed to perform the colourimetric kinetic determination of arsenic (III) by digital movie analysis. A smartphone camera attached to the device was used to take the movie during the process where As(III) inhibited the decolourization of methyl orange. The movie images were subsequently transformed from RGB to YIQ space to obtain a new analytical parameter called "d", which was related to the chrominance of the image. Then, this parameter allowed the determination of the inhibition time of reaction (tin), which was linearly correlated with the concentration of As(III). A linear calibration curve (R = 0.9995) in the range from 5 µg L-1 to 200 µg L-1 was obtained. The method was precise (RSD = 1.2%), and the limits of detection (LOD) and quantification (LOQ) were 1.47 µg L-1 and 4.44 µg L-1, respectively. These values were lower than the limit established by the World Health Organization for total arsenic in drinking water (10 µg L-1). The accuracy of the method was assessed by a recovery study with optimal results (94.3%-104.0%). Additionally, the Analytical GREEnness metric approach was applied, obtaining a score 1.7 times higher than previously published works. The method is simple, portable and low-cost, being in compliance with various principles of green analytical chemistry.

Multi-year monitoring of atmospheric dust fall as a sink for lead in an agro-industrial and petrochemical city of Argentina. Geo-accumulation and ecological risk assessment.

A multi-year monitoring data set of potentially harmful elements (PHEs), which are present in the chemical composition of atmospheric settleable particulate matter (SPM) in the urban, industrial and port areas in Bahía Blanca, was studied in order to assess potential ecological risk. The selected PHEs were metal elements of local and regional environmental importance (Cd, Cr, Cu, Ni, Pb, and Zn). Seventeen sampling campaigns were carried out between April 2013 and September 2019. After the microwave-assisted acid digestion of samples, the total contents of the PHEs were determined by ICP-OES. The annual dry deposition rate, the indexes associated with the potential ecological risk (RI) and the degree of geo-accumulation (Igeo) of each PHE were calculated. The results indicated that: (a) there are 3 groups (I, II, III) of PHEs with differentiated concentration levels, ranked I (Pb > Zn > Cu) > II (Cr ≈ Ni) > III (Cd) (p < 0.01) in all the studied areas; (b) the median of the total deposition rate was 1 mg cm-2. month-1 with a significant relative contribution of Pb; (c) a considerable increase in geo-accumulation of Pb indicated that SPM was functioning as a sink for Pb, and also reflected a significant progressive increase in the potential ecological risk in all sites (p < 0.01); and (d) there were chemometrically identified potential sources of Pb, Cu and Zn emissions that would be associated mainly to the resuspension of dust from geogenic, industrial and urban origin, and to a lesser extent, to other gaseous emissions of the industrial sector. This work highlights three major aspects of environmental assessment: (a) the value of continuous monitoring as an important tool to detect long-term trends; (b) the importance of the role of dust fall as a useful environmental indicator of lead geo-accumulation; and (c) the great utility of geo-accumulation and potential ecological risk indices as rapid quantitative assessment tools of environmental pollution.

Preparation of a single and reusable biopolymer-based film for the extraction and preconcentration of anti-inflammatory drugs from environmental water samples.

One of the main goals of green chemistry is to reduce the use of toxic materials and the generation of hazardous waste, both during method development and in the synthesis of the materials used. Thus, a biodegradable, single and reusable material composed of agarose and multi-walled carbon nanotubes was proposed. The film preparation was carefully optimized in order to obtain a one-piece sorbent, with high extraction efficiency and the possibility of reuse. The film was tested in the simultaneous extraction and preconcentration of three non-steroidal anti-inflammatory drugs (ketorolac, ketoprofen and piroxicam) from environmental water samples. The optimal extraction parameters were as follows: isopropyl alcohol as the activation solvent, a sample pH value of 3.0, extraction time of 30 min, 2.00 mL of acetonitrile as the eluent, an elution time of 5 minutes, and a sample volume of 250.00 mL. Under these conditions, the film was reusable 50 times without losing its extraction capacity significantly. HPLC with a photodiode array detector was used for the separation and determination. The method presented a linear range between 0.10 and 1.2 µg L-1, good sensitivity with limits of detection between 0.0075 and 0.0089 µg L-1, and quantification between 0.025 and 0.030 µg L-1. In addition, low RSD values (0.46-3.13%) were obtained demonstrating satisfactory precision. Stream water samples were analyzed, and recoveries between 82.0 and 109.0% were obtained.

The use of ultrasound in the South Cone region. Advances in organic and inorganic synthesis and in analytical methods.

In organic and inorganic synthesis and in analytical methods, an external conventional heat source is usually applied to carry out a chemical reaction at a high temperature, or an extraction procedure. In the last decades, the use of ultrasound as an alternative energy source has become an interesting field of research in these topics in the South Cone region (Argentina, Chile, Uruguay, Southern Brazil and Paraguay). For this reason, the present review, covering the period 2009 to mid-2021, is a compilation of ultrasound-assisted synthetic and analytical methodologies.

Brand new Dual Absorption and Emission Smartphone-Based Spectrophotometer (DAESS) for the study of the role of water in the preparation of Natural Deep Eutectic Solvents.

Natural Deep Eutectic Solvents (NADES) are highly important for Green Chemistry principles and can be used instead of harmful organic solvents. Indeed, nowadays smartphone-based analytical devices can replace some traditional laboratory equipment. In the present work, a smartphone based dual spectrophotometer and spectrofluorometer device was designed, 3D manufactured, and validated. A resolution of 0.241 ± 0.010 pixel.nm-1 and a stability comparable with commercial instruments were obtained. Using the proposed device it was possible, for the first time, to study the role of water in NADES (fructose:urea:water) preparation, by testing the influence of structural and dilution water. In this sense, it was observed that when water was added before NADES preparation (integrated into the superstructure of the solvent), fluorescence and absorbance intensities sharply decayed (up to 90% and 95%, respectively). In contrast, dilution water had minor effects on spectroscopic features of the eutectic system, which was expressed as 29% and 23% of diminution of signal intensities for both techniques. The obtained results suggest that the moment the water is added plays a significant role in NADES properties.

Distribution of Butyltin Compounds in the Coastal Environment of the Bahía Blanca Estuary, Argentina.

This study evaluates for the first time the distribution and accumulation of butyltin compounds (BTs) in different compartments such as seawater, sediments, suspended particulate matter (SPM), and mussels (Brachidontes rodriguezii) in the Bahía Blanca estuary. The samples were collected from six sampling sites with different anthropogenic impacts. A better visualization and interpretation of data was achieved using chemometric tools (Tucker4 model), which made it possible to reveal the main relationships among the variables. This analysis showed the presence of BTs in all the estuarine environmental compartments, even in sites with low human intervention. The relationships found among BTs levels, seasons, and environmental matrices show the importance of biological processes such as phytoplankton blooms and remobilization of sediments (by tidal dynamics and/or periodic dredging) in BTs distribution and degradation. In addition, partition coefficients showed that mussels mainly bioaccumulate tributyltin from sediment, water and, to a lesser extent, SPM.

Use of universal 3D-Printed smartphone spectrophotometer to develop a time-based analysis for hypochlorite.

A fully-functional smartphone-based spectrophotometer was designed and built using 3D printing. The major advantage of this approach is its capacity to be interfaced with a variety of smartphones, allowing the use of the smartphone's camera and display, and regardless of the relative position of the camera. The analytical performance of the device was analyzed using a model dye (crystal violet), leading to a proportional response for concentrations in the 0.06-15.0 mg L-1 range, with a variability of 1.0% (intra-day) and 2.6% (inter-day). To demonstrate the functionality of the device, the degradation process of the dye by sodium hypochlorite was studied. The results obtained were applied to develop a paper-based test for NaClO in sanitation solutions, in which the time required to bleach the dye was used to estimate the concentration of the solution. This device represents a simple and inexpensive tool for everyday laboratory use and could address important analytical challenges in low-income communities and features a versatile arrangement, that is compatible with a wide variety of smartphones and software platforms.

Fast and easily obtained information about mobilizable metals from sediment samples. Extraction assisted by benzothiophene-based ionic liquids.

A fast and easy method for trace metal extraction on sediments was developed in our laboratories. Three new stable S-metylbenzothiophenium salts were employed along with microwaves to modify the BCR protocol to obtain the concentration of metals of the first two fractions in only one step. The optimum conditions were obtained with 0.125 g of sediment irradiated at 250 W for 30 s at 120 °C, in 5 ml of an aqueous mixture of 10 mM of 1,2-dimethylbenzothiophenium tetrafluoroborate and 0.5 M of hydroxylamine chlorhydrate at pH 2. The method validation was carried out employing BCR 701. The extracted metals were determined by ICP OES. A student's paired t-test was applied with the reference method, giving satisfactory results.

Oxidized carbon nanotubes as sorbent for miniaturized solid-phase extraction of progestins from environmental water samples prior to their determination by HPLC-UV.

A solid-phase extraction method is presented for micro-extraction of three progestins (levonorgestrel, 19-norethisterone acetate and medroxyprogesterone acetate) from water samples. A mini-column was packed with 60 mg of oxidized multiwalled carbon nanotubes and coupled to a flow injection assembly. The extraction parameters, such as washing solution, eluent type, eluent volume, flow rate and sample volume, were optimized. Separation and determination were performed by HPLC with UV detection. The method has a good linear range (0.90-9.0 µg L-1), acceptable limits of detection (0.05-0.14 µg L-1) and low RSDs (0.8-4.6%). Attractive features of the method include low consumption of organic solvents and preconcentration factors of up to 100. The method was applied to analyze stream, underground and effluent water samples, and recoveries between 74 and 121% were obtained. Graphical abstractSchematic representation of the flow injection assembly couples to an ox-MWCNTs extraction column used to perform the solid phase extraction procedure of progestins in environmental water samples.

New, inexpensive and simple 3D printable device for nephelometric and fluorimetric determination based on smartphone sensing.

A new, inexpensive and easy to use 3D printable device was developed for nephelometric and fluorimetric determination. Its applicability was tested for the quantification of quinine in tonic drinks and sulfate in natural water with good analytical accuracy. In this way, sulfate determination was carried out by nephelometry using a red LED, while quinine was determined using a blue LED by fluorimetry. A smartphone camera was used to take the pictures and afterwards transform them into the RGB color space using the software ImageJ by a personal computer. The linear range was 2.0-50.0 mg L-1 for sulfate with a LOD of 0.13 mg L-1, and the corresponding quantification limit (LOQ) was 0.43 mg L-1. The linear range for quinine was from 0.42 to 3.10 mg L-1. The LOD and LOQ were 0.11 mg L-1 and 0.38 mg L-1, respectively.

Electrochemically Reduced Graphene Oxide-Based Screen-Printed Electrodes for Total Tetracycline Determination by Adsorptive Transfer Stripping Differential Pulse Voltammetry.

Disposable electrochemically reduced graphene oxide-based (ERGO) screen-printed electrodes (SPE) were developed for the determination of total tetracyclines as a sample screening approach. To this end, a selective adsorption-detection approach relied on adsorptive transfer stripping differential pulse voltammetry (AdTDPV) was devised, where the high adsorption capacity and the electrochemical properties of ERGO were simultaneously exploited. The approach was very simple, fast (6 min.), highly selective by combining the adsorptive and the electrochemical features of tetracyclines, and it used just 10 µL of the sample. The electrochemical sensor applicability was demonstrated in the analysis of environmental and food samples. The not-fully explored AdTDPV analytical possibilities on disposable nanostructured transducers become a new tool in food and environmental fields; drawing new horizons for "in-situ" analysis.

Potential mobility assessment of metals in salt marsh sediments from San Antonio Bay.

The BCR method was applied on sediments from the salt marsh of San Antonio Bay (SAB). It presents several channels among which the Encerrado is the most important and is impacted by abandoned mining wastes. The pseudototal concentrations of metals measured within this channel were relatively higher than in outer sites, and according to the Igeo index, its contamination level was low. The metal distribution in the different phases of sediment particles showed that the residual component, considered the safest from the environmental point of view, accounted for most of the Fe, Cd, Cu, and Zn contents. Conversely, Pb was mainly in the non-residual component as part of the reducible fraction, thus constituting the main environmental hazard among the studied elements. The predominance of residual and reducible fractions indicated a historic contamination of metal such as Pb, Cu, and Zn from the mining wastes. The low exchangeable and oxidizable fractions would indicate no actual input of metals.

Formation of S-alkyl thiophenium ionic liquids: mechanistic rationale and structural relationships.

The quaternization of thiophenes through S-alkylation reactions with iodoalkanes in the presence of silver salts opens the door to a new family of room-temperature ionic liquids, yet relatively unexplored in terms of chemical reactivity and applications. This computational study provides a mechanistic rationale that accounts for their formation. The results are consistent with the calculated energy barriers of the corresponding transition structures. Calculations indicate that the geometry at the sulfur atom goes from flat to tetrahedral during salt formation, and the electron delocalization of thiophene is greatly reduced, if not lost, as inferred from aromaticity indexes. Moreover, the rationale explains the influence of polarizable anions on S-alkylation and why alkyl substitution at the α-position of thiophenes gives rise to more stable species than unsubstituted derivatives.

A soft material for chromium speciation in water samples using a chemiluminescence automatic system.

A soft material formed by multiwall carbon nanotubes and 1-butyl-3-methyl imidazolium chloride was used as sorbent material to perform the chromium speciation in natural waters. This soft material was not yet used for the speciation of metals as chromium. Thus, a multicommutated flow system containing a minicolumn packed with the soft material was designed. The procedure was based on the capacity of the sorbent to retain Cr(VI) as Cr2O7= and allow to pass Cr(III) through the column. Then, a fully automated flow-batch analysis system was developed to quantify both species using chemiluminescence detection. Thus, Cr(III) was determined as catalyst of the luminol and hydrogen peroxide reaction and Cr(VI) as oxidant of luminol reaction. This represents a new approach because the oxidation of luminol using Cr2O7= has not been reported in literature. The variables of the two systems were optimized. The limits of detection were 1.4 µg L-1 for Cr(VI) and 4.0 µg L-1 for Cr(III). The precision of the method was 3.8% and 7.0% for Cr(VI) and Cr(III), respectively. The present method was applied to real water samples with recoveries between 95% and 107%. Besides, these results were in accordance with those obtained using inductive coupled plasma-optical emission spectrometry technique.

Fast and Feasible Ultrasound-Assisted Pretreatment for the Determination of Organotin Compounds in Environmental Samples.

The goal of this study was to improve an already established reference method, such as the one devoted to organotin compounds determination (Reference Method for Marine Pollution Studies, No. 59, UNEP). The proposed upgrade consists of replacing the mechanical shaking by ultrasound energy and applying low temperature throughout the whole procedure. The optimization of the new operational conditions was performed by using a factorial design. Quality control was performed using a certified sediment reference material (PACS-2) for sediments (82.5-97% of recovery) and recoveries on spiked samples for suspended particulate matter (SPM) and mussels (94-100%). The proposed procedure was applied to surface sediment samples, SPM, and native bivalve mollusks (Brachidontes rodriguezii) collected in Bahia Blanca estuary, a very industrialized zone. The relative standard deviation (RSD %) of the environmental samples were less than 7.9%. It is important to note that the proposed procedure reduced the sample pretreatment time about seven times.

A simple and new reverse liquid-liquid microextraction for the automated spectrometric determination of doxycycline in chicken fat.

This work presents a new, simple and inexpensive reverse liquid-liquid microextraction of doxycycline (DOC) from chicken fat. In this just 13min extraction methodology, acidulated water, as extraction solvent (400µL), was used. A monochannel flow injection system was designed for the spectrometric determination of the analyte (ʎ=344nm). The extracted solution containing DOC was loaded into the injection valve of the continuous flow manifold. A lineal range between 100 and 700µgDOCkg-1 sample was obtained. The LOD and LOQ were 33µgkg-1 and 100µgkg-1 respectively. The relative standard deviation was 4.87% and the sample throughput for the entire process was 4.5h-1. As recovery values when the method was applied to real samples showed variability, the expanded uncertainties were calculated. Their values indicated that the new method is independent of the concentration of the analyte and the origin of the sample.

Organotin compounds in Brachidontes rodriguezii mussels from the Bahía Blanca Estuary, Argentina.

Levels of tributyltin and its breakdown compounds, including the first record of monobutyltin (MBT) in history for Latin America, were determined in native mussels (Brachidontes rodriguezii) by means of CG-MS, after extraction/derivatization assisted by ultrasound. The samples were collected in 2013 in Bahía Blanca Estuary (Argentina) at 6 sites, which reflect different levels of maritime activities. Total butyltins (TBts = TBT+ DBT+ MBT) levels ranged from 19.64 to 180.57ng Sn g-1 dry weight. According to the Oslo-Paris commission, the results indicated that 73.9% of mussels could be under biological effects risks associated with TBT pollution. In accordance with the calculated bioaccumulation factors, approximately 56% of samples appeared to have accumulated TBT through the sediments. All sampling sites were shown to be impacted by organotin compounds (OTCs) showing variable levels through seasons, which could be related with the variation of the water temperature. Degradation index analyses suggested aged inputs of TBT possibly under a general degradation process at the area of study. In addition, the occurrence of DBT and MBT could not be uniquely attributed to the degradation pathway of the TBT; in fact, results outlined the possible contribution of some punctual and diffuse sources at the area such as proximity to plastic industries, industrial effluents, sewage outlets and domestic wastewaters.

Ionic liquid mediated extraction, assisted by ultrasound energy, of available/mobilizable metals from sediment samples.

A new extraction method for metals from sediment samples was developed. In this procedure, the chelating agent EDTA was combined with a minimal amount of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (Bmim[BF4]), assisted by ultrasound energy. The available analytes -Cd, Cr, Cu, Ni, Pb and Zn- were extracted under optimal conditions for a 12.5 ratio (extractant volume/sample mass) with 0.005molL-1 EDTA solution, 0.1molL-1 NaHCO3, 5.0mmolL-1 Bmim[BF4] and 7.0min of sonication time, using an ultrasonic bath (output power of 160W). The best extractions were obtained with 100W (power dissipated in the liquid). These conditions were obtained applying the univariate method. It is important to highlight that the conventional method (extraction with 0.05molL-1 EDTA solution only) consumes 6h to extract available metals from sediment samples selectively, and with the proposed procedure the extraction time is noticeable reduced to 7.0min. Extractable metal concentrations obtained were measured by flame atomic absorption spectrometry. The results showed good agreement with those obtained by the conventional method using a Student's paired t-test.

Chemometric approach to visualize and easily interpret data from sequential extraction procedures applied to sediment samples.

The aim of this study was to assess metal mobility/availability in coastal surface (oxic) sediment samples from the Bahía Blanca estuary. Particularly, two sequential extraction procedures able to discriminate metals associated to amorphous Fe and Mn oxides and those associated with crystalline oxides of Fe were applied. Sequential procedures differ in the number of steps, type of reagents used, and in the order in which metals associated to organic matter are extracted. The studied metals were Cd, Cr, Cu, Pb, Ni and Zn because of their hazardous potential and relative abundance in the estuary. Tucker4 model with three factors describes appropriately the data sets (explained variance of 64.05%). This model made it possible to visualize and explain the information underlying in the data set. From the multivariate analysis, it was possible to evaluate the metal behaviour and their availability. In this way, Cd and Zn are associated to the more available fractions whereas Ni, Cr, Cu and Pb are mainly associated to the unavailable fractions. On the other hand, Zn and Cu are associated to organic matter fraction. Despite the fact that the two-fractionation schemes are quite different, the results obtained with both schemes are comparable.