Graphene oxide functionalized with N-methyl-d-glucamine as a novel sorbent for boron removal from produced and formation waters.

This work describes the synthesis of a novel material based on graphene oxide (GO) for the selective removal of boron in an aqueous medium. The material was obtained by functionalizing graphene oxide with N-methyl-d-glucamine (NMDG). This material, named NMDG@GO, was successfully characterized using Fourier-transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, atomic force microscopy, and elemental analysis. The adsorption process was studied from a kinetic perspective using pseudo-first-order and pseudo-second-order models, with the pseudo-second-order model presenting a better fit. The adsorption process was studied using Langmuir and Freundlich isotherms, with the Freundlich model providing a better fit and an r2 value of 0.9368. This result indicates that the adsorption process occurred in multilayers, considering a heterogeneous distribution of adsorption sites. The levels of the factor's adsorbent mass, pH, and time were optimized using a central composite design, with the optimal values achieved at 120 mg of material, pH = 2.0, and an agitation time of 40 min. Under these optimized conditions, it was possible to remove 22 to 35% of the boron present in saline waters from oil production (production and formation waters) using the developed adsorbent.

Disruption of a three-component solution as a novel strategy for Cu and Ni extraction from vegetable oils for their determination by GF AAS.

In this work, we propose a novel approach for extracting Cu and Ni from vegetable oils (which can be expanded to other metals). The method is based on the transference of the analytes to an aqueous acid phase due to the disruption of a three-component solution. The extraction was carried out in two steps. In the first step, a three-component solution was prepared comprising the sample, 1-octanol, and HNO3 solution. Next, the homogeneous system was disrupted by adding 1.0 mL of deionized water, and two phases were formed. The aqueous extract deposited in the bottom of the flask was collected with a micropipette, and Cu and Ni were determined by graphite furnace atomic absorption spectrometry (GF AAS). The developed method presented limits of quantification (LOQ) of 0.25 and 0.17 ng g-1 for Cu and Ni, respectively, and was successfully applied in the analysis of eleven oil samples from different origins.

Single-vial preconcentration and cold vapor generation for the determination of Hg(II) in water samples of different salinities.

In this work, a single-vial methodology for the extraction and cold vapor generation of mercury(II) was developed, followed by the determination of the analyte by atomic absorption spectrometry, with application in water samples of different salinities. L-cystine-modified Fe3O4 nanoparticles (2LcysMNP) were used as sorbent material in the magnetic solid phase extraction (MSPE) in the same flask in which the mercury vapor generation step was performed using a handmade gas-liquid separator developed in our laboratory. The main conditions for extraction, pre-concentration, and cold vapor generation of mercury were optimized. Under the optimized conditions, detection and quantification limits of 0.04 and 0.12 µg L-1, respectively, were achieved with a relative standard deviation of 7.5%. The single-vial system allowed for a preconcentration factor of 30 and an enrichment factor of 24. The accuracy of the method was evaluated by applying it to certified reference materials, and the obtained values were not significantly different from the expected values according to the Student's t-test. Verification of non-specific interferences was assessed by recovery tests, resulting in recoveries ranging from 81 to 111% for water samples of different salinities.

Microwave-Assisted Digestion of Polyurethane Foam as an Alternative to Elution: Solid Phase Extraction of Cd(II) and Pb(II) for Their Determination in Swimming Pool Waters.

In this work, a separation/preconcentration method is proposed for the determination of Cd(II) and Pb(II) in swimming pool waters, using ammonium pyrrolidine dithiocarbamate (APDC) as a complexing agent and unloaded polyurethane foam (PUF) as a sorbent. The proposed method was optimized, and the defined optimal conditions were a pH of 7, 30 min of shaking time, 400 mg of PUF, and 0.5% (m/v) of the APDC solution. The release of Cd(II) and Pb(II) from the solid phase was achieved through the total digestion of PUF using a microwave-assisted acid approach with a 10.5 mol·L-1 HNO3 solution. The methodology was applied to four samples of swimming pool water for the determination of Cd(II) and Pb(II) using graphite furnace atomic absorption spectrometry (GF AAS). The limits of detection and quantification obtained were 0.02 and 0.06 µg·L-1 for Cd(II) and 0.5 e 1.8 µg·L-1 for Pb(II), respectively. We analyzed four samples of swimming pool waters, finding Cd concentrations between 0.22 and 1.37 µg·L-1. On the other hand, only one sample presented Pb concentration above the limit of quantification (11.4 µg·L-1). Recovery tests were performed by spiking the samples with known concentrations of the analytes, and recovery percentages between 82% and 105% were obtained.

In-syringe dispersive liquid-liquid microextraction.

Dispersive liquid-liquid microextraction (DLLME) has recently been widely used in the separation and preconcentration of various chemical species. Among the various approaches using DLLME are systems that use a syringe as an extraction environment. In this review, details of some methods that use this approach are presented. The ways to promote dispersion, analytical characteristics, and the advantages and disadvantages of the methods, among other aspects, are discussed critically. Finally, some trends in the use of in-syringe microextraction systems are described.

Extraction of permethrin from impregnated fabrics for determination by ultra-high performance liquid chromatography with diode array detection.

Permethrin is a synthetic pyrethroid insecticide that is largely used in the impregnation of fabrics employed for different purposes. This paper reports a detailed study on the conditions for its extraction from fabrics and for its determination by ultra-high performance liquid chromatography with diode array detection (UHPLC-DAD). Several parameters that could affect the extraction efficiency of permethrin were evaluated, such as the extraction time, agitating mode (mechanical or ultrasound-assisted), solvent type (methanol or acetonitrile), concentration, and volume. Under optimized conditions, the extraction was performed for 10 min using a 2 × 2 cm piece of impregnated fabric and 5 mL of pure methanol. The flask containing the sample and the solvent was shaken mechanically using a horizontal roller mixer. The accuracy of the method was assessed by a recovery test, which presented satisfactory results ranging from 86.8% to 95.2%. The method was employed in the analysis of nine samples of commercial fabrics of different colors and grammages that were impregnated with permethrin. The concentration of permethrin found in these samples varied between 25.6 ± 4.2 and 934 ± 119 mg m-2.

Passive sampling of toluene (and benzene) in indoor air using a semipermeable membrane device.

The distribution and concentration of organic compounds in the environment have attracted great interest mainly due to their capability of bioaccumulation, dispersion, and danger to living organisms. Factors such as urbanization, population growth, and the emergence of new technologies contribute to the increase in pollutant emissions, especially volatile organic compounds (VOCs), such as benzene, toluene, ethylbenzene, and xylenes (BTEX). These compounds are emitted by several sources, becoming more common in work environments, influencing indoor air quality (IAQ), which can cause health damage, in addition to increasing the likelihood of cancer development. In this context, we developed a semipermeable membrane device (SPMD), consisting of low density polyethylene membrane (8 cm long × 3 cm wide), filled with 3 mL of acetonitrile, for passive sampling of toluene (and benzene) in gas phase. With this configuration, the SPMD needed 24 h exposure to the indoor air in order to achieve equilibrium. The target compounds were quantified in the acceptor phase by HPLC-DAD. The optimized SPMD was tested for the collection of toluene and benzene in six chemistry laboratories at Fluminense Federal University and in five nail salons in the city of Niterói, in the state of Rio de Janeiro, Brazil. The developed sampling method was able to identify the analytes in the indoor air of the studied environments, and was easy to operate, with no need to clean up the extracts, allowing their direct injection into the chromatographic system.

Renewable column on-line magnetic preconcentration of Cd(II) using Fe3O4 nanoparticles functionalized with l-glutamine for determination by flame atomic absorption spectrometry.

This work reports the development of a flow injection analysis (FIA) system for online magnetic preconcentration and determination of Cd(II) in water by flame atomic absorption spectrometry (F AAS). Magnetic nanoparticles of Fe3O4, functionalized with l-glutamine (GlnMNP), were synthesized and used as a support for Cd(II) retention and preconcentration. Each measurement cycle was performed through online complexation of Cd(II) by l-glutamine attached to Fe3O4 magnetic nanoparticles at pH 10.5, followed by their retention in a coil due to the action of a cylindrical permanent magnet. Subsequently, the retained magnetic nanoparticles containing Cd(II) were dissolved with an acid solution (4 mol L-1 HCl solution), releasing Cd(II) for transportation to the detector. The main chemical and flow parameters that affected the performance of the system were optimized. Under optimum experimental conditions, the limits of detection and quantification were 2 and 5 µg L-1, respectively, and a relative standard deviation of 6.5% (at 50 µg L-1, n = 10) was observed. The FIA system allowed the injection of 24 samples per hour and presented an enrichment factor of four. The method was applied in the analysis of river and pond water samples. The pond water sample was irradiated with ultraviolet light prior to the analysis, in order to eliminate the organic matter. Accuracy of the method was assessed by recovery tests, which provided recovery percentages between 82 and 111%. The developed method was also compared to the direct determination by graphite furnace atomic absorption spectrometry (GF AAS). In this case, the results were not statistical different at 95% confidence level when the Student's t-test was applied.

Evaluation of Copper and Manganese Concentrations in Commercial Fruit Juices and Nectars Consumed in Brazil by GF AAS.

The present work proposes a simple method for direct determination of Cu and Mn in commercial fruit juices and nectars by graphite furnace atomic absorption spectrometry (GF AAS). We analyzed samples of different flavors (orange, mango, passion fruit, peach, and grape) and brands of Brazilian commercial fruit juices and nectars. We also carried out a study to define a suitable temperature program and to optimize the calibration conditions. It was possible to determine Cu and Mn in the samples just after a simple dilution of samples with a 0.70 mol L-1 HNO3 solution, except in the case of grape juice. We compared the results obtained with the proposed method to those obtained after a traditional treatment based on acid digestion in a microwave oven, and no significant differences were observed (except for grape juice). The accuracy of the method was assessed through a recovery test, which provided recovery percentages in the range of 81-117%. Precision was always better than 8%, and the limits of quantification for Cu and Mn were 6 µg L-1 and 9 µg L-1, respectively. We analyzed twenty-two samples, and the concentrations of Cu and Mn were in the range of 24.1-321 µg L-1 and 116-3296 µg L-1, respectively. Statistical analysis using a two-way analysis of variance (ANOVA) at 95% confidence level showed that flavor and brand impacted on the concentration of the analytes in the samples. Among the samples analyzed, the grape juice presented the highest concentrations of both Cu and Mn.

Extraction induced by microemulsion breaking as a novel tool for the simultaneous determination of Cd, Mn, Pb and Sb in gasoline samples by ICP-MS and discrete sample introduction.

This study reports a simple and efficient method for the simultaneous determination of Cd, Mn, Pb, and Sb at trace levels in gasoline samples by discrete sample introduction in inductively coupled plasma mass spectrometry (ICP-MS), employing the extraction induced by microemulsion breaking as a sample preparation method. In this work, a microemulsion was formed by mixing 0.7 mL of the gasoline sample with 0.28 mL of ethanol and 0.02 mL of 7 mol L-1 HNO3 solution. Afterwards, 0.1 mL of ultrapure water was added to induce microemulsion breaking. This lead to the formation of two different phases: (i) a top organic phase and (ii) a bottom aqueous phase that contained acid, ethanol and the extracted analytes. After that, 20 µL of the bottom phase (extract) was collected, and the analyte concentrations were determined by discrete sample introduction in ICP-MS. Calibration curves with 20 µg L-1 of Rh as an internal standard were set up to each analyte in the range from 1 up to 10 µg L-1, wherein the standard solutions were prepared in the matrix-matched extract (70:25:5, ethanol: deionized water: 7 mol L-1 HNO3 solution). The optimization of the EIMB conditions was carried out by analyzing the effects of the parameters that could affect the extraction efficiency, such as the relation between the nature of the alcohol and the proportion of the volumes of the microemulsion constituents (sample, HNO3 and alcohol), acid concentration, and the water volume used for the microemulsion breaking. The following limits of detection relative to the amount of sample were obtained: 0.03 (Cd), 0.49 (Mn), 0.07 (Pb) and 0.02 (Sb), all of them in µg L-1. The accuracy of the method was evaluated by the analysis of spiked samples, because no certified gasoline reference material is available. The average recoveries achieved for every analyte ranged from 96% to 114%. The developed methodology was successfully applied to the determination of these metals in five commercial gasoline samples.

Evaluation of a semi-permeable membrane device (SPMD) for passive sampling of solar filters from swimming pool waters and determination by HPLC-DAD.

Sunscreens are used to protect skin against ultraviolet radiation, avoiding the damages that can be caused by it. However, in vitro and in vivo studies report that some organic substances employed as sunscreens can alter the biological effects of several hormones. Therefore, a methodology for passive sampling using a semipermeable membrane device (SPMD) was developed for the extraction and preconcentration of some organic compounds employed in sunscreen formulations, such as benzophenone (BZP), 2-hydroxy-4-methoxybenzophenone (BZP-3), 3-(4-methylbenzylidene)-camphor (4-MBC), 2-ethylhexyl-4-methoxycinnamate (4-MCN), 2-ethylhexyl salicylate (EHS), and homomethyl salicylate (HMS), from swimming pool waters where exposure to these substances is unintended. The determination of these analytes in the acceptor phase was performed using high performance liquid chromatography with diode array detection (HPLC-DAD). The optimization of the methodology included the evaluation of several variables, such as type and volume of acceptor phase, dimensions and time of exposure of the SPMD, sample pH, and volume. The optimum conditions for the collection of the solar filters were achieved with an 8-cm device filled with 3.0 mL of acetonitrile and without adjustment of the sample pH, which was approximately 5.8. The collection time was 24 h. Afterwards, some parameters of merit of the developed method were determined. The working range for BZP, BZP-3, 4-MBC, 4-MCN, EHS, and HMS was established as 25-500 µg L-1. The methodological limits of detection and quantification for these analytes were 0.2-1.0 µg L-1 and 0.7-3.1 µg L-1, respectively. Quantification of the analytes was performed on four samples collected from different swimming pools. Recovery tests were performed with the samples spiked with 100 µg L-1 of each substance, and recovery percentages in the range of 75-116% were obtained. The performance of the SPMD was also verified through the determination of BZP-3, EHS, and HMS in a swimming pool water sample intentionally contaminated with a commercial sunscreen.

Development of an extraction method for the determination of inorganic anions (chloride, sulfate and phosphate) in edible oils from different origins by ion chromatography.

The present work reports the development of ion chromatography conductivity based detection analytical method for the determination of some inorganic anions (chloride, sulfate and phosphate) in vegetable oils. The analytes were extracted from samples prior to injection into the chromatographic system, employing a simple two-step procedure. In the first step, 4.5 g of the sample was vigorously mixed with 15 mL of deionized water and then mixed for 15 min on a horizontal roller. Afterwards, the mixture was sonicated for 15 min in an ultrasonic bath. Then, the mixture was centrifuged for 15 min at 5000 rpm and, after filtration through a 0.22 µm membrane, the aqueous phase was used for the determination of the analytes. A clean-up step was introduced in the analysis of olive oils in order to correct an increase of the baseline of the chromatograms. The limits of detection and quantification of the proposed method were, respectively, 0.005 and 0.02 µg g-1 for chloride, 0.02 and 0.06 µg g-1 for phosphate and 0.008 and 0.03 µg g-1 for sulfate. Vegetable oils from corn, canola, soybean, sunflower and olive were analyzed and recovery tests (94.8 ± 10.1% mean recovery) were performed to attest the accuracy of the proposed method.

Determination of acetate and formate in vegetable oils by ion chromatography after multivariate optimization of the extraction process using a Doehlert design.

In this work, we present the development of a method for the determination of acetate and formate in vegetable oils by ion chromatography with conductometric detection following their extraction from samples using a diluted KOH solution. The extraction procedure was optimized using a multivariate approach. The application of a 24 full factorial design showed that the mass of sample, extraction time, and KOH concentration presented significant influence on the extraction of both acetate and formate, whereas the temperature presented little influence on the process. As a result, we set the extraction temperature at 22 °C and performed the multivariate optimization of the other variables using a Doehlert design. The optimum conditions were: 4.8 g of sample, 8 mmol L-1 KOH solution and 19 min extraction time. Six samples of vegetable oils (soybean, corn, canola, sunflower and olive) were analyzed and recovery tests provided recovery percentages in the range of 82-118%.

Ultrasensitive and rapid immuno-detection of human IgE anti-therapeutic horse sera using an electrochemical immunosensor.

Antivenom allergy disease mediated by patient IgE is an important public health care concern. To improve detection of hypersensitive individuals prior to passive antibody therapy, an amperometric immunosensor was developed to detect reactive human IgE. Whole horse IgG3 (hoIgG3) was immobilized onto the surface of carbon or gold screen-printed electrodes through a cross-linking solution of glutaraldehyde on a chitosan film. Sera from persons with a known allergic response to hoIgG3 or non-allergic individuals was applied to the sensor. Bound human IgE (humIgE) was detected by an anti-humIgE antibody through a quantitative amperometric determination by tracking via the electrochemical reduction of the quinone generated from the hydroquinone with the application of a potential of 25 mV. The optimal immunosensor configuration detected reactive humIgE at a dilution of 1:1800 of the human sera that represent a detection limit of 0.5 pg/mL. Stability testing demonstrated that through 20 cycles of a scan, the specificity and performance remained robust. The new immunosensor successfully detected humIgE antibodies reactive against hoIgG3, which could allow the diagnosis of potential allergenic patients needing therapeutic antivenom preparations from a horse.

Adsorption of the herbicides diquat and difenzoquat on polyurethane foam: Kinetic, equilibrium and computational studies.

This work reports a study about the adsorption of the herbicides diquat and difenzoquat from aqueous medium employing polyurethane foam (PUF) as the adsorbent and sodium dodecylsulfate (SDS) as the counter ion. The adsorption efficiency was shown to be dependent on the concentration of SDS in solution, since the formation of an ion-associate between cationic herbicides (diquat and difenzoquat) and anionic dodecylsulfate is a fundamental step of the process. A computational study was carried out to identify the possible structure of the ion-associates that are formed in solution. They are probably formed by three units of dodecylsulfate bound to one unit of diquat, and two units of dodecylsulfate bound to one unit of difenzoquat. The results obtained also showed that 95% of both herbicides present in 45mL of a solution containing 5.5mgL-1 could be retained by 300mg of PUF. The experimental data were well adjusted to the Freundlich isotherm (r2 ≥ 0.95) and to the pseudo-second-order kinetic equation. Also, the application of Morris-Weber and Reichenberg equations indicated that an intraparticle diffusion process is active in the control of adsorption kinetics.

Novel extraction induced by microemulsion breaking: a model study for Hg extraction from Brazilian gasoline.

This paper proposes a novel approach for the extraction of Hg from Brazilian gasoline samples: extraction induced by microemulsion breaking (EIMB). In this approach, a microemulsion is formed by mixing the sample with n-propanol and HCl. Afterwards, the microemulsion is destabilized by the addition of water and the two phases are separated: (i) the top phase, containing the residual gasoline and (ii) the bottom phase, containing the extracted analyte in a medium containing water, n-propanol and the ethanol originally present in the gasoline sample. The bottom phase is then collected and the Hg is measured by cold vapor atomic absorption spectrometry (CV-AAS). This model study used Brazilian gasoline samples spiked with Hg (organometallic compound) to optimize the process. Under the optimum extraction conditions, the microemulsion was prepared by mixing 8.7mL of sample with 1.2mL of n-propanol and 0.1mL of a 10molL-1 HCl solution. Emulsion breaking was induced by adding 300µL of deionized water and the bottom phase was collected for the measurement of Hg. Six samples of Brazilian gasoline were spiked with Hg in the organometallic form and recovery percentages in the range of 88-109% were observed.

Use of a versatile, easy, and rapid atmospheric monitor (VERAM) passive samplers for pesticide determination in continental waters.

The versatile, easy, and rapid atmospheric monitor (VERAM), a passive sampler device widely used for air monitoring, was evaluated as passive sampler for the determination of 23 pesticides in water. Gas chromatography with mass spectrometry detection was employed for determination of pesticides after microwave-assisted-extraction and specific clean-up of deployed samplers. The proposed methodology reached method detection levels from 2 to 10 ng pesticide per sampler. Sampling rate (Rs) was determined for every pesticide from an uptake isotherm study performed at three different concentration levels (50, 125, and 250 ng L-1). The obtained RS values ranged from 0.06 to 0.76 L d-1. The obtained limits of detection for a 24-h passive sampling were from 4 to 50 ng L-1. The effect of water parameters, such as temperature, pH, and ionic strength, were evaluated for their effect on pesticides retention using VERAMs. Pesticide RS values were independent of the water composition and increased on increasing temperature. Finally, the VERAM uptake was compared with that obtained using classic semipermeable membrane devices (SPMDs). This study is the first precedent for the use of VERAMs as passive samplers for the adsorption and concentration of pesticides in water and it confirms the satisfactory analytical figures of merit of VERAM as passive sampler of water. Graphical Abstract Scheme of water sampling of pesticides using versatile, easy, and rapid atmospheric monitor (VERAM) passive samplers.

Determination of chloride in brazilian crude oils by ion chromatography after extraction induced by emulsion breaking.

The present paper reports on the development of a novel extraction induced by emulsion breaking (EIEB) method for the determination of chloride in crude oils. The proposed method was based on the formation and breaking of oil-in-water emulsions with the samples and the consequential transference of the highly water-soluble chloride to the aqueous phase during emulsion breaking, which was achieved by centrifugation. The determination of chloride in the extracts was performed by ion chromatography (IC) with conductivity detection. Several parameters (oil phase:aqueous phase ratio, crude oil:mineral oil ratio, shaking time and type and concentration of surfactant) that could affect the performance of the method were evaluated. Total extraction of chloride from samples could be achieved when 1.0g of oil phase (0.5g of sample+0.5g of mineral oil) was emulsified in 5mL of a 2.5% (m/v) solution of Triton X-114. The obtained emulsion was shaken for 60min and broken by centrifugation for 5min at 5000rpm. The separated aqueous phase was collected, filtered and diluted before analysis by IC. Under these conditions, the limit of detection was 0.5µgg(-1) NaCl and the limit of quantification was 1.6µgg(-1) NaCl. We applied the method to the determination of chloride in six Brazilian crude oils and the results did not differ statistically from those obtained by the ASTM D6470 method when the paired Student-t-test, at 95% confidence level, was applied.

Polyurethane foam loaded with sodium dodecylsulfate for the extraction of 'quat' pesticides from aqueous medium: Optimization of loading conditions.

The cationic herbicides paraquat, diquat and difenzoquat are largely used in different cultures worldwide. With this, there is an intrinsic risk of environmental contamination when these herbicides achieve natural waters. The goal of this work was to propose a novel and low-cost sorbent for the removal of the cited herbicides from aqueous medium. The proposed sorbent was prepared by loading polyurethane foam with sodium dodecylsulfate. The influence of several parameters (SDS concentration, HCl concentration and shaking time) on the loading process was investigated. The results obtained in this work demonstrated that all studied variables influenced the loading process, having significant effect on the extraction efficiency of the resulted PUF-SDS. At optimized conditions, the PUF was loaded by shaking 200mg of crushed foam with 200mL of a solution containing 5.0×10(-3)molL(-1) SDS and 0.25molL(-1) HCl, for 30min. The obtained PUF-SDS was efficient for removing the three herbicides from aqueous medium, achieving extraction percentages higher than 90%. The sorption process followed a pseudo second-order kinetics, which presented excellent predictive capacity of the amount of herbicide retained with time.

Sorption of the herbicides diquat and difenzoquat from aqueous medium by polymeric resins in the presence of sodium dodecylsulfate: Kinetic and mechanistic study.

The goal of this work was to propose a novel method for the solid-phase extraction of the herbicides diquat (DQT(2+)) and difenzoquat (DFQT(+)) from aqueous medium using polymeric Amberlite XAD-2 and XAD-4 resins in the presence of sodium dodecylsulfate (SDS). The addition of SDS to the medium was of fundamental importance in order to allow the formation of a negatively charged surface able to sorb the cationic solutes. Several factors that could influence the sorption process, such as SDS concentration in the medium, sorbent mass, pH, ionic strength, and initial concentration of the solutes were investigated. Kinetic studies were also performed to model the system and to identify the mechanisms that operate the sorption process of the herbicides. SDS concentration in the medium presented remarkable influence on the extraction efficiency, achieving maximum values when the ratios [SDS]/[herbicide] were approximately 90, for XAD-2, and 22 and 11 for DQT(2+) and DFQT(+), respectively, for XAD-4. The sorption process followed a pseudo second-order kinetic in all cases studied. It was also found that an intraparticle diffusion process controlled exclusively the sorption of the herbicides by the Amberlite XAD-2 and XAD-4 resins in the first 15 min, becoming less active with time.