Green sample preparation strategies for organic/inorganic compounds in environmental samples

A rigorous evaluation of environmental contamination requires constant innovation in analytical approaches to gain early identification and accurate quantification of every substance able to compromise health and well-being. Particularly, when trace analysis of organic and inorganic contaminants, and their species, in complex environmental samples is required. The analytical process comprises several steps, above all sample treatment, involving isolation of analytes, purification of extracts and preconcentration, often constitute the most time and labor consuming part. This review provides an overview in sample-treatment procedures applied for the analysis of organic and inorganic compoundsin environmental samples in recent years. The current state of the art is emphasized on those techniques and approaches that have already demonstrated their sufficient analytical performance.Fil: Cerutti, Estela Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Pacheco, Pablo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Gil, Raul Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Determination of nitrated and oxygenated polycyclic aromatic hydrocarbons in water samples by a liquid–liquid phase microextraction procedure based on the solidification of a floating organic drop followed by solvent assisted back-extraction and liquid chromatography–tandem mass spectrometry

A methodology was optimized for the determination of nitrated-PAHs (nitro-PAHs) and oxygenated-PAHs (oxy-PAHs) in natural waters. The extraction/preconcentration procedure was performed by liquid–liquid phase microextraction based on the solidification of a floating organic drop followed by a novel solvent assisted back-extraction (DLLME-SFO-SBE) combined with liquid chromatography-tandem mass spectrometry. The solvent assisted back extraction into a suitable solvent enabled the direct injection of nitro and oxy-PAHs into the UHPLC-(+)APCI-MS/MS system. Parameters affecting the efficiency of the back-extraction procedure were evaluated and optimized, including the nature of the back-extractant volume, temperature and agitation effect. Additionally, various strategies related to the emulsion formation process were assayed. Detection and quantification limits were in the range of 0.02–0.85 ng mL−1 and 0.15–1.10 ng mL−1. Acceptable extraction recoveries between 95.1 and 100% and enrichment factors between 192 and 200-fold, with relative standard deviations <7.6%, were obtained. The method was successfully applied to the analysis of different types of water samples. In addition, concentration levels of nitro-PAHs and oxy-PAHs ranging from 0.97 to 7.16 ng mL−1 and from 0.69 to 2.36 ng mL−1; respectively, were detected in lake water. The proposed methodology is an easy, sensitive, and accurate analytical approach for determining nitrated and oxygenated PAHs of environmental concern in water samples.Fil: Guiñez, María Evangelina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Bazan, Cristian Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Cerutti, Estela Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentina; Argentin

CD/CV: Blockchain-based schemes for continuous verifiability and traceability of IoT data for edge-fog-cloud

This paper presents a continuous delivery/continuous verifiability (CD/CV) method for IoT dataflows in edge¿fog¿cloud. A CD model based on extraction, transformation, and load (ETL) mechanism as well as a directed acyclic graph (DAG) construction, enable end-users to create efficient schemes for the continuous verification and validation of the execution of applications in edge¿fog¿cloud infrastructures. This scheme also verifies and validates established execution sequences and the integrity of digital assets. CV model converts ETL and DAG into business model, smart contracts in a private blockchain for the automatic and transparent registration of transactions performed by each application in workflows/pipelines created by CD model without altering applications nor edge¿fog¿cloud workflows. This model ensures that IoT dataflows delivers verifiable information for organizations to conduct critical decision-making processes with certainty. A containerized parallelism model solves portability issues and reduces/compensates the overhead produced by CD/CV operations. We developed and implemented a prototype to create CD/CV schemes, which were evaluated in a case study where user mobility information is used to identify interest points, patterns, and maps. The experimental evaluation revealed the efficiency of CD/CV to register the transactions performed in IoT dataflows through edge¿fog¿cloud in a private blockchain network in comparison with state-of-art solutions.This work has been partially supported by the project “CABAHLA-CM: Convergencia Big data-Hpc: de los sensores a las Aplicaciones” S2018/TCS-4423 from Madrid Regional Government, Spain and by the Spanish Ministry of Science and Innovation Project “New Data Intensive Computing Methods for High-End and Edge Computing Platforms (DECIDE)”. Ref. PID2019-107858GB-I00; and by the project 41756 “Plataforma tecnológica para la gestión, aseguramiento, intercambio preservación de grandes volúmenes de datos en salud construcción de un repositorio nacional de servicios de análisis de datos de salud” by the PRONACES-CONACYT, Mexic

Optimization of methods to assess levels of As, Bi, Sb and Se in airborne particulate matter by FI-HG-ICP OES

A study was undertaken to assess the level of selected trace elements namely, As, Bi, Sb and Se in airborne particulate matter collected on ash-free glass-fibre filters from urban and industrial areas of Argentina. For sample digestion, a simple acid treatment with HCl + HF is proposed with the aim to minimize contamination and reduce sample treatment steps. A flow injection-hydride generation system in combination with inductively coupled plasma optical emission spectrometry was used. While, Se and Bi could be determined directly from the digest, As and Sb needed a pre-reduction with KI, and H3BO3 to avoid the interference of F- ions that may cause losses via volatile compounds such as AsF3 and Sb(v) complexes. Limits of detection (3σ) of 0.3 ng m-3 for As; 0.09 ng m-3 for Bi, and 0.1 ng m-3 for Sb and Se were achieved. Precision resulted in better than 6.1% accuracy for all the elements determined. Accuracy test was assessed by means of the certified reference material, NIST 1648 (urban particulate matter).Fil: Savio, Marianela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Pacheco, Pablo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Smichowski, Patricia Nora. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Gil, Raul Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Ultratrace arsenic determination through hydride trapping on oxidized multiwall carbon nanotubes coupled to electrothermal atomic absorption spectrometry

Arsenic determination in natural waters is an issue of current research. This article reports a novel hydride generation (HG) approach developed for As determination with electrothermal atomic absorption spectrometry (ETAAS) detection. The HG process was interfaced with ETAAS through hydride trapping onto a carbon nanotubes microcolumn. To this end a homemade gas-liquid separator was used, allowing arsine formation and its flow throughout the CNT microcolumn. The retention process involved thus a solid phase extraction from the gas phase to the solid support. Once arsine generation was completed, the elution was carried out with nitric acid directly onto the dosing hole of the graphite furnace. Outstanding sensitivity with detection limit of 1 ng L-1, quantification limit of 5 ng L-1 and the characteristic mass, 5.8 ± 0.4 pg could be achieved. A satisfactory correlation between concentration of As and absorbance (R = 0.9993) from the limit of quantification up to 500 ng L-1, with a relative standard deviation of 6.3% were obtained. A sensitive enhancement factor of 38 was reached when 2 mL of sample were processed and 50 μL of HNO3 were used as eluent. The system was successfully applied to the analysis of a standard reference material, QC LL2 metals in natural waters. In addition tap water analysis provided an As concentration of 0.29±0.03 μg L-1.Fil: Maratta Martínez, Sergio Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Química de San Luis; ArgentinaFil: Acosta, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Química de San Luis; ArgentinaFil: Pacheco, Pablo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Química de San Luis; ArgentinaFil: Gil, Raul Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Química de San Luis; Argentin

Handling spectral interferences and matrix effects in DRC-ICPMS to assess the elemental profile in human serum samples after dissolution with formic acid

Inductively coupled plasma mass spectrometry instrumentation along with the dynamic reaction cell (DRC) technology has been increasingly used in the last decade for multielemental analysis of biological samples. This work reports the development of a method to assess concentrations of Li, Be, B, Sc, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Cd, Sr, Mo, Pd, Ag, Sb, Te, Cs, Ba, Os, Tl, Pb, and Bi in human serum samples treated with formic acid. This is a single-step procedure that minimizes sample handling and avoids contamination risks and analyte losses. Towards this aim, several experimental conditions such as sample pretreatment with formic acid and instrumental operating parameters were optimized. Interferences due to polyatomic ions were eliminated using DRC with oxygen as reaction gas through the formation of MO+ ions. Our method involved low dilution factors, and appropriate limits of detection in the low μg L-1 range for all elements. The accuracy was evaluated through the analysis of a standard reference material (Inorganic Constituents in Animal Serum, NIST 1598a) and spiked samples, with satisfactory recoveries.Fil: Verni, Ernesto Ricardo. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Moyano, Mario Franco. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; ArgentinaFil: Lapierre, Alicia Viviana. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Gil, Raul Andres. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Slurry sampling in serum blood for mercury determination by CV-AFS

The heavy metal mercury (Hg) is a neurotoxin known to have a serious health impact even at relatively low concentrations. A slurry method was developed for the sensitive and precise determination of mercury in human serum blood samples by cold vapor generation coupled to atomic fluorescence spectrometry (CV-AFS). All variables related to the slurry formation were studied. The optimal hydrochloric concentration and tin(II) chloride concentration for CV generation were evaluated. Calibration within the range 0.1-10 μg L-1 Hg was performed with the standard addition method, and compared with an external calibration. Additionally, the reliability of the results obtained was evaluated by analyzing mercury in the same samples, but submitted to microwave-assisted digestion method. The limit of detection was calculated as 25 ng L-1 and the relative standard deviation was 3.9% at levels around of 0.4 μg L-1 Hg.Fil: Aranda, Pedro Rodolfo. Universidad Nacional de San Luis; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Gil, Raul Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Moyano, Susana. Universidad Nacional de San Luis; ArgentinaFil: de Vito, Irma Esther. Universidad Nacional de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Luis; Argentin

Risk Assessment on Irrigation of Vitis vinifera L. cv Malbec with Hg Contaminated Waters

Concerns regard watering crops with Hg contaminated waters have arisen worldwide recently. In these sense Hg uptake by Vitis vinifera L. cv. Malbec was evaluated under greenhouse conditions by the administration of Hg2+ for 4 days through irrigation water (short-term administration). Vines uptake Hg translocating it from roots through stems to leaves. Roots accumulated the higher Hg concentration. Hg in stems and leaves was accumulated mostly as organic Hg, bind to different moieties. Size exclusion chromatography (SEC) and ion pair chromatography (IPC) were employed to reach insights into these ligands. Hg is distributed mainly in high molecular weight fractions of 669 kDa in vine plants. In stems and leaves, Hg-S associations were found in 669 and 66 kDa fractions. Hg-S association at 66 kDa suggests a possible protein or peptide binding affecting vines normal physiology. Since Hg contamination through organomercurials is more harmful than Hg2+ itself, methyl mercury, dimethyl mercury, and phenyl mercury, more toxic Hg species were evaluated with negative results.Fil: Spisso, Adrián Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; ArgentinaFil: Pacheco, Pablo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Gomez, Federico Jose Vicente. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; ArgentinaFil: Silva, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

Determination of Metal Content in Valerian Root Phytopharmaceutical Derivatives by Atomic Spectrometry

Phytopharmaceuticals containing Valerian are used as mild sleep-inducing agents. The elemental composition of 3 different marks of Valeriana officinalis roots commercially available in the Argentinian market, their teas, and a commercial tincture have been studied. The content of Al, Ca, Cd, Co, Cr, Cu, Fe, Li, Mn, Ni, Pb, V, and Zn was determined in phytopharmaceuticals by flame atomic emission/absorption spectrometry, electrothermal atomic absorption spectrometry, and ultrasonic nebulization coupled to inductively coupled plasma-optical emission spectrometry. Prior to analyses of the samples, a digestion procedure was optimized. The analytical results obtained for Fe, Al, Ca, and V in the solid sample study were within the range 100-1000 mg/kg, and for Mn, Zn, and Pb within the range 10-100 mg/kg. Cadmium was found at levels up to 0.0125 mg/kg.Fil: Arce, Silvia Lilia. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; ArgentinaFil: Cerutti, Estela Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Olsina, Roberto Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Gomez, Maria Roxana Anabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin

A novel on-line preconcentration method for trace molybdenum determination by USN-ICP OES with biosorption on immobilized yeasts

A new system for on-line preconcentration of molybdenum by sorption on a minicolumn associated to inductively coupled plasma - optical emission spectrometry with ultrasonic nebulization was studied. It is based on the sorption of molybdenum on a column packed with immobilized baker's yeasts on controlled pore glass without further complexing reagent. The molybdenum preconcentrated by biosorption was subsequently eluted with hydrochloric acid. Considering a sample flow rate of 5.0 mL min- 1, 10 mL of sample was preconcentrated in 2 min achieving a sensitive total enhancement factor of 480-fold, and the detection limit (3 s) obtained was 21 ng L- 1. Additionally, the calculated precisions expressed as percent relative standard deviation (RSD%) was 1.9%. Satisfactory results were obtained for the determination of molybdenum in standard reference material NIST 1643e Trace Elements in Water and real water samples.Fil: Gil, Raul Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Pasini Cabello, Sergio David. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Takara, Eduardo Andres. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Analítica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Smichowski, Patricia Nora. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica; ArgentinaFil: Olsina, Roberto Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Martinez, Luis Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentin