Determination of 5-hydroxymethylfurfural using an electropolymerized molecularly imprinted polymer in combination with Salle.

Coffee, a beverage with a complex chemical composition, is appreciated for the sensory experience of its taste and aroma. The compound 5-(hydroxymethyl)-2-furfural (HMF) is essential for sensory characterization of the beverage, and is also used in the traceability of its production. In this work, a procedure combining salting-out assisted liquid-liquid extraction (SALLE) and an electropolymerized molecularly imprinted polymer (e-MIP) was developed for the detection and quantification of HMF in coffee samples. The sample preparation step using SALLE employed a combination of acetonitrile and phosphate-buffered saline, in a proportion of 70:30 (ACN:PBS), with addition of 0.02 g of NaCl. The new sensor (e-MIP) was prepared by electropolymerization of p-aminobenzoic acid onto a glassy carbon electrode (GCE) using cyclic voltammetry (CV). Analytical determinations were performed by differential pulse voltammetry (DPV). The linear regression correlation coefficient (r2) for the response was 0.9986. The limits of detection and quantification were 0.372 mg L-1 and 1.240 mg L-1, respectively. The repeatability and reproducibility values obtained were 6 and 10%, respectively. The recoveries for three concentration levels were between 97 and 101%. Analyses of different coffee samples showed that the HMF concentrations varied from 261.0 ± 41.0 to 770.2 ± 55.9 mg kg-1 in powdered coffee samples, and from 1510 ± 50 to 4445 ± 278 mg kg-1 in instant coffee samples. The advantages of this procedure, compared to other methods described in the literature, are its simplicity, easy operation, good selectivity and sensitivity, low cost, and minimal use of organic solvents.

Similar polycyclic aromatic hydrocarbon and genotoxicity profiles of atmospheric particulate matter from cities on three different continents.

The extractable organic material (EOM) from atmospheric total suspended particles (TSP) contains several organic compounds including non-substituted polycyclic aromatic hydrocarbons (PAHs), alkyl-PAHs, and nitro-PAHs. These chemicals seem to be among the key drivers of TSP genotoxicity. We have shown previously that the mutagenic potencies of the EOM from Limeira, Stockholm, and Kyoto, cities with markedly different meteorological conditions and pollution sources are similar. Here we compare the profiles of non-substituted PAHs (27 congeners), alkyl-PAHs (15 congeners), and nitro-PAHs (7 congeners) from the same EOM samples from these cities. We also compared the genotoxicity profiles using comet and micronucleus assays in human bronchial epithelial cells. The profiles of PAHs, as well as the cytotoxic and genotoxic potencies when expressed in EOM, were quite similar among the studied cities. It seems that despite the differences in meteorological conditions and pollution sources of the cities, removal, mixing, and different atmospheric transformation processes may be contributing to the similarity of the PAHs composition and genotoxicity profiles. More studies are required to verify if this would be a general rule applicable to other cities. Although these profiles were similar for all three cities, the EOM concentration in the atmospheres is markedly different. Thus, the population of Limeira (∼10-fold more EOM/m3 than Stockholm and ∼6-fold more than Kyoto) is exposed to higher concentrations of genotoxic pollutants, and Kyoto's population is 1.5-fold more exposed than Stockholm's. Therefore, to reduce the risk of human exposure to TSP genotoxins, the volume of emissions needs to be reduced.

Comparative mutagenic activity of atmospheric particulate matter from limeira, stockholm, and kyoto.

Atmospheric particulate matter (PM) organic fractions from urban centers are frequently mutagenic for the Salmonella/microsome assay. This mutagenicity is related to both primary and secondary pollutants, and meteorological conditions have great influence on the secondary pollutant's formation. Our objective was to compare the mutagenicity of atmospheric total suspended particulates (TSP) from three cities with marked different meteorological conditions and TSP concentrations: Limeira (Brazil) with 99.0 µg/m3 , Stockholm (Sweden) with 6.2 µg/m3 , and Kyoto (Japan) with 28.0 µg/m3 . For comparison, we used the same batch of filters, sample extraction method, and Salmonella/microsome testing protocol with 11 strains of Salmonella with and without metabolic activation. Samples were collected during winter and pooled into one single extract representing each city. All samples were mutagenic for all tested strains, except for TA102. Based on the strain's selectivity, nitroarenes, polycyclic aromatic hydrocarbons, and aromatic amines play a predominant role in the mutagenicity of these samples. The mutagenic potencies expressed by mass of extracted organic material (EOM; revertants/µg EOM) were similar (~twofold difference) among the cities, despite differences in meteorological conditions and pollution sources. In contrast, the mutagenic potencies expressed by air volume (rev/m3 ) varied ~20-fold, with Limeira > Kyoto ≈ Stockholm. These results are the first systematic assessment of air mutagenicity from cities on three continents using the same protocols. The results confirm that the mutagenic potency expressed by EOM mass is similar regardless of continent of origin, whereas the mutagenic potency expressed by air volume can vary by orders of magnitude. Environ. Mol. Mutagen. 2019. © 2019 Wiley Periodicals, Inc.

4-hydrazinobenzoic acid as a derivatizing agent for aldehyde analysis by HPLC-UV and CE-DAD.

Aldehydes are relevant analytes in a wide range of samples, in particular, food and beverages but also body fluids. Hydrazines can undergo nucleophilic addition with aldehydes or ketones giving origin to hydrazones (a group of stable imines) that can be suitably used in the identification of aldehydes. Herein, 4-hydrazinobenzoic acid (HBA) was, for the first time, used as the derivatizing agent in analytical methodologies using liquid chromatography aiming the determination of low-molecular aldehydes. The derivatization reaction was simultaneously performed along with the extraction process, using gas-diffusion microextraction (GDME), which resulted in a clean extract containing the HBA-aldehyde derivates. The corresponding formed imines were determined by both high-performance liquid chromatography (LC) with UV spectrophotometric detection (HPLC-UV) and capillary electrophoresis with diode array detection (CE-DAD). HBA showed to be a rather advantageous derivatization reagent due to its stability, relatively high solubility in water and other solvents, high selectivity and sensibility, reduced impurities, simple preparation steps and applicability to different separation and/or different detection techniques. Limits of detections (LODs) of the optimized methodologies (in terms of time and pH among other experimental variables) were all below 0.5 mg L-1, using both instrumental techniques. Furthermore, for the first time, the HBA-aldehyde derivatives were analyzed by LC with mass spectrometry (LC-MS), demonstrating the possibility of identification by MS of each compound. The developed methodologies were also successfully applied in the analysis of formaldehyde and acetaldehyde in several alcoholic beverages. This was also the first time GDME was combined with CE, showing that it can be a valuable sample preparation tool for electrophoresis, in particular by eliminating the interference of ions and inorganic constituents present in the samples.

Capillary electrophoresis to approach sorbate usage in processed meat products in Brazil.

Sorbate is a highly used preservative in a wide range of processed foods, including meat products. In this work sorbate usage in commercial processed meat products from the Brazilian market was evaluated. A capillary electrophoresis method for sorbate analysis using ethanol:water extraction solution (1:2, v/v) and sodium tetraborate (20 mmol L-1) electrolyte solution was validated. Low limits of detection (0.4 mg L-1) and quantification (1.0 mg L-1), good precision (RSD = 3.6%) and suitable accuracy (70.2%, RSD = 1.8%) were attained. Linearity was observed from 1.0 to 15.8 mg L-1, with r ≥ 0.999. The proposed method was applied to Brazilian pork and hot dog sausages, salami, ham and mortadella. A peak of sorbate between 4 and 6 min was found in pork and hot dog sausages, poultry and pork mortadella, but not in ham and salami. The sorbate levels ranged from 54.0 to 976.4 mg kg-1. Sorbate concentration exceeded the 200 mg kg-1 limit of the Brazilian legislation in all sorts of products in the majority of the brands despite there being no information regarding sorbate on the label. These results indicated the widespread use of sorbate, turning this into food for thought.

Mutagenicity profile of atmospheric particulate matter in a small urban center subjected to airborne emission from vehicle traffic and sugar cane burning.

Atmospheric particulate matter (PM) is genotoxic and recently was classified as carcinogenic to humans by the International Agency for Research on Cancer. PM chemical composition varies depending on source and atmospheric conditions. The Salmonella/microsome assay is the most used mutagenicity test and can identify the major chemical classes responsible for observed mutagenicity. The objective of this work was to characterize the mutagenicity of PM samples from a countryside city, Limeira, Brazil, which is influenced by heavy traffic and sugar cane biomass burning. Six samples of total PM were collected. Air mass backward trajectories were calculated. Organic extracts were assayed using the Salmonella/microsome microsuspension mutagenicity assay using TA98, YG1041, and TA1538, with and without metabolic activation (S9). YG1041 was the most sensitive strain and mutagenicity reached 9,700 revertants per m(3) without metabolic activation. Potency for TA1538 was higher than TA98, indicating that this strain should be considered in air mutagenicity studies. The increased response to YG1041 relative to TA98, and the decreased response with S9, suggests that nitroaromatics are the major contributors. Limeira is among the most mutagenic cities in the world. High mutagenicity in Limeira seems to occur when the air mass from the area of sugarcane production is mixed with air from the region impacted by anthropogenic activities such as traffic. An increase in the formation of nitro-polycyclic aromatic hydrocarbons may result from longer contact time between the aromatic compounds and the atmosphere with high NOx and ozone concentration, although more studies are required to confirm this hypothesis.

Determination of total sulfur in agricultural samples by high-resolution continuum source flame molecular absorption spectrometry.

The usefulness of molecular absorption was investigated for the determination of total sulfur (S) in agricultural samples by high-resolution continuum source flame molecular absorption spectrometry. The lines for CS at 257.595, 257.958, and 258.056 nm and for SH at 323.658, 324.064, and 327.990 nm were evaluated. Figures of merit, such as linear dynamic range, sensitivity, linear correlation, characteristic concentration, limit of detection, and precision, were established. For selected CS lines, wavelength-integrated absorbance equivalent to 3 pixels, analytical curves in the 100-2500 mg L(-1) (257.595 nm), 250-2000 mg L(-1) (257.958 nm), and 250-5000 mg L(-1) (258.056 nm) ranges with a linear correlation coefficient better than 0.9980 were obtained. Results were in agreement at a 95% confidence level (paired t test) with those obtained by gravimetry. Recoveries of S in fungicide and fertilizer samples were within the 84-109% range, and the relative standard deviation (n=12) was typically <5%.

Atmospheric emission of reactive nitrogen during biofuel ethanol production.

This paper evaluates emissions to the atmosphere of biologically available nitrogen compounds in a region characterized by intensive sugar cane biofuel ethanol production. Large emissions of NH3 and NOx, as well as particulate nitrate and ammonium, occur at the harvest when the crop is burned, with the amount of nitrogen released equivalent to approximately 35% of annual fertilizer-N application. Nitrogen oxides concentrations show a positive association with fire frequency, indicating that biomass burning is a major emission source, with mean concentrations of NOx doubling in the dry season relative to the wetseason. During the dry season biomass burning is a source of NH3, with other sources (wastes, soil, biogenic) predominant during the wet season. Estimated NO2-N, NH3-N, NO3- -N and NH4+ -N emission fluxes from sugar cane burning in a planted area of ca. 2.2 x 10(6) ha are 11.0, 1.1, 0.2, and 1.2 Gg N yr(-1), respectively.

Measurements of ambient ozone using indigo blue-coated filters.

Ozone monitoring techniques utilize expensive instruments that are often large and heavy. These instruments are not easy to handle in the field, and their size also limits some sampling schemes, principally for indoor ozone determination. We have developed a lightweight, inexpensive, and sensitive method that offers flexibility to undertake measurements of ambient ozone in many environments, both indoor and outdoor. The method is based on the reaction of ozone with indigo blue dye. The indigo molecule contains 1 carbon double bond (C = C) that reacts with ozone and results in nearly colorless reaction products. During sample collection, 2 cellulose filters coated with 40 micro of 1.0 x 10(-3) M indigo blue were used. The determinations were done spectrophotometrically at 250 and 600 nm. The analytical parameters studied were sampling time and flow rate. Analytical curves were constructed with concentrations ranging from 37 to 123 parts per billion by volume (ppbv) of standard ozone, at 0.4 L/min and 15 min sampling time. The detection limits achieved were 6 and 9 ppbv, respectively, at 250 and 600 nm. Considering interferences, measurements made at 250 nm gave more reliable and specific values for ozone.

Influence of agricultural biomass burning on aerosol size distribution and dry deposition in southeastern Brazil.

The size distributed composition of ambient aerosols is used to explore seasonal differences in particle chemistry and to show that dry deposition fluxes of soluble species, including important plant nutrients, increase during periods of biomass (sugar cane trash) burning in São Paulo State, Brazil. Measurements were made at a single site centrally located in the State's sugar cane growing region but away from the immediate vicinity of burns, so that the airsampled was representative of the regional background. Calculation of ion equivalent balances showed that during burning periods smaller particles (Aitken and accumulation modes) were more acidic, containing higher concentrations of SO4(2-), oxalate, NO3-, HCOO-, CH3COO-, and CI-, but insufficient NH4+ and K+ to achieve neutrality. Larger particles showed an anion deficit due to the presence of unmeasured ions and comprised resuspended dusts modified by accumulation of nitrate, chloride, and organic anions. Increases of resuspended particles during the burning season were attributed to release of earlier deposits from the surfaces of burning vegetation as well as increased vehicle movement on unsurfaced roads. During winter months the relative contribution of combined emissions from road transport and industry diminished due to increased emissions from biomass combustion and other activities specifically associated with the harvest period. Positive increments in annual particulate dry deposition fluxes due to higher fluxes during the sugar cane harvest were 44.3% (NH4+), 42.1% (K+), 31.8% (Mg2+), 30.4% (HCOO-), 12.8% (CI-), 6.6% (CH3COO-), 5.2% (Ca2+), 3.8% (SO4(2-)), and 2.3% (NO3-). Na+ and oxalate fluxes were seasonally invariant. Annual aerosol dry deposition fluxes (kg ha(-1)) were 0.5 (Na+), 0.25 (NH4+), 0.39 (K+), 0.51 (Mg2+), 3.19 (Ca2+), 1.34 (Cl-), 4.47 (NO3-), 3.59 (SO4(2-)), 0.58 (oxalate), 0.71 (HCOO-), and 1.38 (CH3COO-). Contributions of this mechanism to combined aerosol dry deposition and precipitation scavenging (inorganic species, excluding gaseous dry deposition) were 31% (Na+), 8% (NH4+), 26% (K+), 63% (Mg2+), 66% (Ca2+), 32% (Cl-), 33% (NO3-), and 36% (SO4(2-)).

NO2 emissions from agricultural burning in São Paulo, Brazil.

We report here on the application of a compact ultraviolet spectrometer to measurement of NO2 emissions from sugar cane field burns in São Paulo, Brazil. The time-resolved NO2 emission from a 10 ha plot peaked at about 240 g (NO2) s(-1), and amounted to a total yield of approximately 50 kg of N, or about 0.5 g (N) m(-2). Emission of N as NOx (i.e., NO + NO2) was estimated at 2.5 g (N) m(-2), equivalent to 30% of applied fertilizer nitrogen. The corresponding annual emission of NOx nitrogen from São Paulo State sugar cane burning was >45 Gg N. In contrast to mechanized harvesting, which does not require prior burning of the crop, manual harvesting with burning acts to recycle nitrogen into surface soils and ecosystems.

Indirect determination of chloride and sulfate ions in alcohol fuel by capillary electrophoresis.

A capillary zone electrophoresis method using indirect UV detection for the analysis of chloride and sulfate in alcohol fuel samples was developed. The anions were analyzed in less than 3 min using an electrolyte containing 10 mmol l(-1) chromate and 0.75 mmol l(-1) hexamethonium bromide (HMB) as electroosmotic flow modifier. Coefficients of variation were better than 0.6% for migration time ( n=10) and between 2.05 and 2.82% for peak area repeatabilities. Analytical curves of peak area versus concentration in the range of 0.065-0.65 mg kg(-1) for chloride and 0.25-4.0 mg kg(-1) for sulfate were linear with coefficients of correlation higher than 0.9996. The limits of detection for sulfate and chloride were 0.033 and 0.041 mg kg(-1), respectively. Recovery values ranged from 85 to 103%. The method was successfully applied for the quantification of sulfate and chloride in five alcohol fuel samples. The concentration of sulfate varied from 0.45 to 3.12 mg kg(-1). Chloride concentrations were below the method's LOD.

Determination of low-aliphatic aldehydes indoors by micellar electrokinetic chromatography using sample dissolution manipulation for signal enhancement.

This work describes a novel approach for the analysis of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and acrolein) and acetone in environmental samples using micellar electrokinetic chromatography (MEKC). The method is based on the reaction of carbonyl compounds with 3-methyl-2-benzothiazoline hydrazone (MBTH) that gives an azine intermediate with maximum absorbance at 216 nm. A systematic evaluation of sample dissolution medium was conducted as a means to enhancing sensitivity. In the best condition, samples were dissolved in 0.030 mol.L(-1) tetraborate solution. This condition presented enhancement factors in the range of 35-54 for the aldehydes under investigation, computed as the improvement of the concentration limits of detection (LODs) with reference to the sample dissolved in pure water. The running buffer was 0.020 mol.L(-1) tetraborate, pH 9.3, containing 0.050 mol.L(-1) sodium dodecyly sulfate (SDS). The overall methodology presented several advantages over established methods for aldehydes. Worthy mentioning that MBTH is available in high purity degree, dispensing laborious reagent purification procedures. A few method validation parameters were determined revealing good migration time repeatability (< 2.5% coefficient of variation, CV) and area repeatability (< 4% CV), excellent linearity (20-120 micro g/L, r > 0.995) and adequate sensitivity for environmental applications. The LODs with respect to each single aldehyde were in the range of 0.54-4.0 micro g.L(-1) and 11 micro g.L(-1) for acetone. The methodology was applied to the determination of aldehydes indoors. Samples were collected in an impinger flask containing 0.05% MBTH solution, at a flow rate of 0.80 L.min(-1), during 2.5 h, at different times during the day. The most abundant carbonyls in the samples were acetone, followed by formaldehyde and acetaldehyde, with estimate peak concentrations of 452, 5.2 and 2.2 ppbv, respectively.