Assessment of pesticides in water using time-weighted average calibration of passive sampling device manufactured with carbon nanomaterial coating on stainless steel wire.

The continued contamination of water sources by pesticides is a problem that involves the life of aquatic organisms and human health, especially in countries whose economy is based on agriculture. The need to know the quality of drinking water under these circumstances is a priority for the public health of any community. Passive sampling methods allow the determination of long-term environmental pollutants through a single sample collection, reducing time and cost of analyses. One advantage of passive sampling is that it is possible to calculate a time-weighted average (TWA) concentration value or an equilibrium concentration value, depending on the type of device used and the exposure time. Passive sampling techniques using carbon nanomaterials (CNMs) have a high potential for pesticide sampling in aquatic systems. A device for passive sampling manufactured with CNMs in a microextraction system and recyclable materials was calibrated in laboratory exposure conditions over 15 days. The calibration results showed linear accumulation periods between 5 and 10 days. Sampling rates were between 0.014 and 0.146 mL day-1. The sampler was field-tested in the San Francisco river basin in the state of Minas Gerais in Brazil for 7 days. This research allowed for the detection and calculation of TWA concentrations for organochlorine pesticides such as α-HCH, 4,4-DDE, and 4,4-DD in water sources. The manufactured device demonstrated greater sensitivity than the grab sampling processes for the detection of pesticides. The performed passive sampling system using gas chromatography/mass spectrometry (GC/MS) technique allowed for the collection, detection, identification, and quantification of 26 pesticides.

Metabolomic studies of amino acid analysis in Saccharomyces cells exposed to selenium and gamma irradiation.

Metabolomic studies are essential to identify and quantify key metabolites in biological systems. Analysis of amino acids (AA) is very important in target metabolomics studies. Chromatographic methods are used to support metabolite determinations. Therefore, this work presents analysis of 17 AA in Saccharomyces cerevisiae cells (a useful model in the study of cancer metabolism) exposed to sodium selenite and gamma radiation. An improved GC/MS method using propyl chloroformate/propanol as derivatizing reagent was applied to AA determinations. The method exhibited good linearity in the range of 0.08-600.00 mg L-1; limits of determination from 0.04 to 1.60 mg L-1; limits of quantification from 0.08 to 2.76 mg L-1; repeatability ranging from 1.9 to 11.4 %; and precision ranging from 2.8 to 13.8 %. The correlations between selenite/gamma radiation with AA profile was investigated to establish candidates for cancer biomarkers. The analyses of yeast cultures found high concentrations of amino acids, such as Alanine, Serine, Glutamate, and Lysine, which might be associated with the development of metabolic adaptations of cancer based on its high demand for biomass and energy, found both in this model and neoplastic cells.

Environmental and biological determination of acrolein using new cold fiber solid phase microextraction with gas chromatography mass spectrometry.

Acrolein is a pollutant released daily to the indoor environment from different sources. The present study reports the development of a simple and sensitive cold fiber solid phase microextraction sampling method for the determination of acrolein in exhaled air and indoor air by gas chromatography mass spectrometry. O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine was used as derivatizing agent supported on a 65-µm polydimethylsiloxane-divinylbenzene SPME fiber. An acrolein permeation tube at 326.25 ng min-1 rate was used to generate gaseous standards. The method shows good results for main validation parameters. The limits of detection and quantification were 2.88 and 5.08 µg m-3, respectively, for indoor analysis; and 2.40 and 3.79 µg m-3, respectively, for exhaled air analysis. The precision showed standard deviation ranges from 6.00 to 8.00% for intra-assay analyses and from 8.00 to 10.00% for inter-assay analyses. After optimizing the conditions, analyses of real samples were performed on indoor environments contaminated by cigarette smoke, or heated oil, including pastry shops, restaurants, churros stands, and closed parking cars located in the city of Belo Horizonte, Brazil. Acrolein breaths of exposed people were also determined. A good Pearson correlation coefficient (r = 0.901) was observed between the concentration of acrolein in indoor air and exhaled air, allowing to propose acrolein breath as environmental exposure biomarker. Graphical Abstract Cold fiber solid phase microextraction gas chromatography/mass spectrometry.

Use of exhaled air as an improved biomonitoring method to assess perchloroethylene short-term exposure.

This paper shows the use of exhaled air as a biomonitoring method to assess perchloroethylene (PERC) environmental and occupational exposure. A sensitive, fast, and solvent free analytical method was developed to determine PERC in ambient and exhaled air of individuals occupationally exposed. The developed method used cold fiber solid phase microextraction (CF-SPME) as the sampling technique, and a standard permeation method to simulation of air matrix. The analysis were conducted by gas chromatography coupled to mass spectrometry (GC/MS). The methods were validated and were found to be precise, linear and sensitive for environmental and biological monitoring. The developed methods were applied to twenty-seven sampling points spread across Belo Horizonte city, Brazil, twenty four dry cleaners, an electroplating industry, a research laboratory, and an automotive paint preparation shop. The results of ambient air analyses ranging from 14.0 to 3205.0µgm-3 with median concentration of 599.0µgm-3. Furthermore, sampling of exhaled air of individuals occupationally exposed presented results ranging from 6.0 to 2635.0µgm-3 with median concentration of 325.0µgm-3. The strong correlation observed between ambient and exhaled air (r =0.930) demonstrates that exhaled air is a suitable biomarker for evaluating occupational exposure to PERC.

Evaluation of amino acid profile by targeted metabolomics in the eukaryotic model under exposure of benzo[a]pyrene as the exclusive stressor.

Amino acids (AAs) are a class of important metabolites in metabolomics methodology that investigates metabolite changes in a cell, tissue, or organism for early diagnosis of diseases. Benzo[a]pyrene (BaP) is considered a priority contaminant by different environmental control agencies because it is a proven carcinogenic compound for humans. Therefore, it is important to evaluate the BaP interference in the metabolism of amino acids. In this work, a new amino acid extraction procedure (derivatized with propyl chloroformate/propanol) using functionalized magnetic carbon nanotubes was developed and optimized. A hybrid nanotube was used followed by desorption without heating, and excellent extraction of analytes was obtained. After exposure of Saccharomyces cerevisiae, the BaP concentration of 25.0 µmol L-1 caused changes in cell viability, indicating metabolic changes. A fast and efficient GC/MS method using a Phenomenex ZB-AAA column was optimized, enabling the determination of 16 AAs in yeasts exposed or not to BaP. A comparison of AA concentrations obtained in the two experimental groups showed that glycine (Gly), serine (Ser), phenylalanine (Phe), proline (Pro), asparagine (Asn), aspartic acid (Asp), glutamic acid (Glu), tyrosine (Tyr), and leucine (Leu) statistically differentiated, after subsequent application of ANOVA with Bonferroni post-hoc test, with a confidence level of 95%. This amino acid pathway analysis confirmed previous studies that revealed the potential of these AAs as toxicity biomarker candidates.

Novel miniaturized passive sampling devices based on liquid phase microextraction equipped with cellulose-grafted membranes for the environmental monitoring of phthalic acid esters in natural waters.

Phthalic acid esters (PAEs) are considered endocrine disruptors and potential carcinogens. Consequently, efficient and accurate environmental monitoring of trace levels of these organic pollutants is necessary to protect the population against their hazardous effects. Passive sampling techniques have gained notoriety for environmental monitoring and have been proven highly sensitive to temporal variations. This study developed a miniaturized passive sampling device (MPSD) based on hollow fiber liquid-phase microextraction (HF-LPME). The devices were calibrated in the laboratory using an automated calibration system. The results demonstrated the first-order uptake ranges for Diethyl phthalate (DEP), Diisobutyl phthalate (DiBP), Dibutyl phthalate (DBP), Benzyl butyl phthalate (BBP) and Bis(2-ethylhexyl phthalate) (DEHP) between 30 min and 24 h with sampling rates equivalent to 0.009; 0.021; 0.033; 0.085 and 0.003 mL h-1 respectively (R2 between 0.88 and 0.99). The calibrated devices were deployed in 12 marginal lagoons, stretching approximately 330 km along the main river. The extracts recovered from the devices were analyzed by gas chromatography (GC), resulting in the identification and quantification of DEP (0.697-13.7 ng L-1), DiBP (0.100-4.43 ng L-1), DBP (0.014-1.21 ng L-1), BBP (0.218-5.67 ng L-1), and DEHP (0.002-2.24 ng L-1). Despite being frequently identified, DEHP concentrations were well below the maximum established limits, revealing a good water quality in terms of the target PAEs. In contrast, screening the extracts using GCxGC was possible to detect other hazardous pollutants such as pesticides, drugs, and their metabolites. The described device was effective and reliable, providing accurate PAE measurements following short exposure periods. In this sense, its deployment during emergency operations, such as accidental discharges of industrial effluents into natural waters, could continuously and cost-effectively monitor water quality.

A new carbon nanomaterial solid-phase microextraction to pre-concentrate and extract pesticides in environmental water.

This research describes a solid-phase microextraction device using carbon nanomaterials supported on steel threads. The device was used to pre-concentrate and extract 24 pesticides in water. The carbon nanomaterials were obtained by a chemical vapor deposition (CVD) process, using methane and acetonitrile as carbon source. The different pesticides were separated, detected, and quantified using gas chromatography coupled to mass spectrometry (GC-MS). The system, optimized and validated in the laboratory, presented good results. Linearity was between 0.0007 and 50.00 µg L-1, with determination coefficients greater than 0.9. The detection and quantification limits were in the range of 0.0002-1.1309 µg L-1 and 0.0007-3.7320 µg L-1, respectively. The studied pesticides presented recovery values in the range of 70 ± 8 to 123 ± 18%. Carbon nanomaterials exhibited high thermal and mechanical resistance, as the same fiber could be used for approximately 300 extractions. The device was applied to analyze environmental water samples collected from the São Francisco river basin in Brazil and in the Chinampas in Mexico City.

Sampling of benzene in environmental and exhaled air by solid-phase microextraction and analysis by gas chromatography-mass spectrometry.

Benzene is classified as a Group I carcinogen by the International Agency for Research on Cancer (IARC). The risk assessment for benzene can be performed by monitoring environmental and occupational air, as well as biological monitoring through biomarkers. The present work developed and validated methods for benzene analysis by GC/MS using SPME as the sampling technique for ambient air and breath. The results of the analysis of air in parks and avenues demonstrated a significant difference, with average values of 4.05 and 18.26 microg m(-3), respectively, for benzene. Sampling of air in the occupational environment furnished an average of 3.41 and 39.81 microg m(-3). Moreover, the correlations between ambient air and expired air showed a significant tendency to linearity (R (2) = 0.850 and R (2) = 0.879). The results obtained for two groups of employees (31.91 and 72.62 microg m(-3)) presented the same trend as that from the analysis of environmental air.

New passive sampling device for effective monitoring of pesticides in water.

The extensive use of pesticides promotes environmental contamination, mainly in surface and ground waters. However, they remain at very low concentration and present wide degradation level requiring the use of efficient devices for pesticides passive sampling. In this study, a new in situ passive sampling device was developed for monitoring and estimating time-weighted average (TWA) of pesticides in waters. The device was made with simple, recyclable and cheap materials. The sampling system involves the liquid phase microextraction technique with hollow fiber in two-phases mode. Pesticides determination was done by gas chromatography coupled to mass spectrometry. The method was optimized and validated for the determination of 29 pesticides in water, showing good linearity in the range between 0.012 and 40.00 µg L-1 with determination coefficients of R2 > 0,9649. Limit of detection (LOD) ranged from 0.009 to 0.557 µg L-1 and limit of quantification (LOQ) from 0.012 to 0.802 µg L-1. The recoveries of spiked pesticides in water samples were in the range from 96 to 130%. The method was applied to forty environmental water samples collected at São Francisco river basin, Brazil. The highest detection frequency was found for the pesticides 4,4-DDE, 4,4-DDD and propazine. They were detected in more than 20 percent of the samples.

Amino Acid Biosignature in Plasma among Ischemic Stroke Subtypes.

Ischemic stroke is a neurovascular disorder caused by reduced or blockage of blood flow to the brain, which may permanently affect motor and cognitive abilities. The diagnostic of stroke is performed using imaging technologies, clinical evaluation, and neuropsychological protocols, but no blood test is available yet. In this work, we analyzed amino acid concentrations in blood plasma from poststroke patients in order to identify differences that could characterize the stroke etiology. Plasma concentrations of sixteen amino acids from patients with chronic ischemic stroke (n = 73) and the control group (n = 16) were determined using gas chromatography coupled to mass spectrometry (GC-MS). The concentration data was processed by Partial Least Squares-Discriminant Analysis (PLS-DA) to classify patients with stroke and control. The amino acid analysis generated a first model able to discriminate ischemic stroke patients from control group. Proline was the most important amino acid for classification of the stroke samples in PLS-DA, followed by lysine, phenylalanine, leucine, and glycine, and while higher levels of methionine and alanine were mostly related to the control samples. The second model was able to discriminate the stroke subtypes like atherothrombotic etiology from cardioembolic and lacunar etiologies, with lysine, leucine, and cysteine plasmatic concentrations being the most important metabolites. Our results suggest an amino acid biosignature for patients with chronic stroke in plasma samples, which can be helpful in diagnosis, prognosis, and therapeutics of these patients.

A Simple and Quick Method for the Determination of Pesticides in Environmental Water by HF-LPME-GC/MS.

This paper describes a simple and quick method for sampling and also for carrying out the preconcentration of pesticides in environmental water matrices using two-phased hollow fiber liquid phase microextraction (HF-LPME). Factors such as extraction mode, time, solvents, agitation, and salt addition were investigated in order to validate the LPME method. The following conditions were selected: 6 cm of polypropylene hollow fiber, ethyl octanoate as an acceptor phase, and extraction during 30 min under stirring at 200 rpm. The optimized method showed good linearity in the range of 0.14 to 200.00 µg L-1; the determination coefficient (R2) was in the range of 0.9807-0.9990. The LOD ranged from 0.04 µg L-1 to 0.44 µg L-1, and LOQ ranged from 0.14 µg L-1 to 1.69 µg L-1. The recovery ranged from 85.17% to 114.73%. The method was applied to the analyses of pesticides in three environmental water samples (a spring and few streams) collected in a rural area from the state of Minas Gerais, Brazil.

Magnetic amphiphilic hybrid carbon nanotubes containing N-doped and undoped sections: powerful tensioactive nanostructures.

In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen.

Study of polycyclic aromatic hydrocarbons in atmospheric particulate matter of an urban area with iron and steel mills.

Polycyclic aromatic hydrocarbons (PAHs) were analyzed from ambient air particulate matter <10 µm (PM(10) ) and the total suspended particulate (TSP) phase continuously for a period of six months (May-October 2010) at five sampling sites located in the urban area of Divinópolis (Minas Gerais), southeastern Brazil, near iron and steel mills. The carcinogenic potency of priority PAHs relative to benzo[a]pyrene was estimated for a period of six months. Benzo[a]pyrene equivalents were 7.52 ng/m(3) for the study period. The estimated risk of lifetime lung cancer was 6.5 × 10(-4) . A model based on the diagnostic ratio and principal component analysis was applied for source apportionment. Considering the entire study period, the burning of biomass and fuel oil accounted for about 70% of the PAH profile. An inventory was performed during the monitoring period, with 37 companies representing major industries located in the urban area. The observations were consistent with the distribution of sources and indicated that the iron and steel sector was the largest contributor.