Assessment of urinary aromatic amines in Brazilian pregnant women and association with DNA damage: Influence of genetic diversity, lifestyle, and environmental and socioeconomic factors.

Aromatic amines (AAs) are polar organic chemicals with a wide environmental distribution originating from various sources, such as tobacco smoke, diesel exhaust, and dermal absorption from textile products with azo dyes. The toxicity profile of AAs is directly related to the amino group's metabolic activation and the generation of the reactive intermediate, forming DNA adducts and potential carcinogenicity. Urinary levels of 8-hydroxy-2'-deoxyguanosine (8OHdG) are an important biomarker of DNA damage. Since AAs have been shown to cross the placental barrier, being a risk factor for adverse birth outcomes, prenatal exposure is a great public health concern. The present study aimed to measure the urinary levels of 58 AAs in Brazilian pregnant women (n = 300) and investigated the impact of this exposure on DNA damage by quantifying 8OHdG levels. The influence of tobacco smoke exposure and dermal absorption of AAs by clothes on urinary levels was also assessed. The results showed a 100% detection rate for eight AAs, two of them regulated by the European Union (2,6-dimethylaniline and 2,4-diaminotolune). Hundreds of AAs may be derived from aniline, which here showed a median of 1.38 ng/mL. Aniline also correlated positively with 2,6-dimethylaniline, p-aminophenol, and other AAs, suggesting exposure to multiple sources. The present findings suggest that both tobacco smoke and dermal contact with clothes containing azo dyes are potential sources that might strongly influence urinary levels of AAs in Brazilian pregnant women. A multiple regression linear model (R2 = 0.772) suggested that some regulated AAs (i.e., 2-naphthylamine and 4-aminobiphenyl), nicotine, smoke habit, age, and Brazilian region could induce DNA damage occurrence, increasing the levels of 8OHdG. Given the limited available data on human exposure to carcinogenic AAs, as well as the lack of toxicological information on those non-regulated, further studies focused on measuring their levels in human fluids and the potential exposure sources are clearly essential.

Determination of primary aromatic amines from cooking utensils by capillary electrophoresis-tandem mass spectrometry.

This paper describes a fast, sensitive, environment-friendly method for the determination of 19 primary aromatic amines (PAAs) in cooking utensils by capillary zone electrophoresis coupled with tandem mass spectrometry. The best electrophoretic separation of PAAs was obtained in 0.1 mol l-1 formic acid (pH 2.4) as the background electrolyte, fused silica capillary (67 cm) with a run time below 6 min. The proposed method presented a linear calibration with correlation coefficients higher than 0.99 and reproducibility in a range of 1-25%. Limits of detection were in the range of 0.2-1.3 µg kg-1 and recoveries were in a range of 85-120% for all the PAAs. The validated method was employed to determine PAAs on 36 samples of cooking utensils using acetic simulant. The results showed that 4,4'-diaminodiphenylmethane and aniline being the most frequently found PAAs in these samples and 28% of cooking utensils were not compliant.

A non-mercury electrode for the voltammetric determination of butralin in foods.

A modified electrode was developed with Co-Ag bimetallic nanoparticles stabilized in poly(vinylpyrrolidone) for butralin monitoring. This is the first non-mercury electrode proposed for the quantification of butralin. The bimetallic nanoparticles were characterized by spectroscopic and microscopic techniques, which showed that they are composed of a cobalt core partially covered with silver. The modified electrode was characterized by field emission gun scanning electron microscopy, energy dispersive X-ray spectroscopy and electrochemical impedance spectroscopy. The experimental parameters (pH, supporting electrolyte, accumulation step, pulse technique) were optimized. The calibration plot for butralin obtained by square wave voltammetry was linear in the range of 0.1-1.0 µmol L-1 with limits of detection and quantification of 32 and 106 nmol L-1, respectively. Lastly, the modified electrode was effectively implemented in the quantification of butralin in honey and apple jam samples. The results were in agreement with those furnished by UV-vis spectrometry and endorsed by statistical tests.

Occurrence and partitioning of antifouling booster biocides in sediments and porewaters from Brazilian Northeast.

Fouling organisms attach and grow on submerged surfaces causing several economic losses. Thus, biocides have been introduced in antifouling paints in order to avoid this phenomenon, but their widespread use became a global problem, mainly in ports, leisure and fishing boat harbors, since these substances can be highly toxic to non-target organisms. The occurrence and environmental behavior of antifouling biocides are especially unknown in some peculiar regions, such as Amazon areas. Thus, the aim of this work was to evaluate, for the first time, levels and the partitioning behavior of the antifouling organic biocides irgarol, diuron and also stable degradation products of dichlofluanid and diuron (DMSA and DCPMU, respectively) in sediments and porewaters from a high boat traffic area located in the Northeast of Brazil, a pre-Amazon region. Our results showed high concentrations of irgarol (<1.0-89.7 µg kg-1) and diuron (<5.0-55.2 µg kg-1) in sediments. In porewater, DCPMU (<0.03-0.67 µg L-1) and DMSA (<0.008-0.263 µg L-1) were the mainly substances detected. High Kd and Koc obtained for both irgarol and diuron showed a partitioning preference in the solid phase. This work represents one of the few registers of contamination by antifouling substances in Amazonian areas, despite their environmental relevance.

Primary aromatic amines in kitchenware: Determination by liquid chromatography-tandem mass spectrometry.

The aim of this paper is to develop and validate a methodology with potential for routine analysis that allows a fast and easy quantification of 19 primary aromatic amines (PAAs) in acid simulant (3% (w/v) acetic acid aqueous) in food contact materials (FCM). The main reason for studying these amines was the fact that some of them have a carcinogenic factor according to toxicological studies. To validate the method, the parameters linearity, limit of detection (LOD) and limit of quantification (LOQ), precision and accuracy using an UPLC-MS/MS were evaluated. This study also analyzed 36 samples of kitchenware obtained from retail markets: 16 were made of polyamide (PA), one was made of polypropylene (PP) and 19 were made of silicone. The origins of samples were Brazil, China and Turkey. Eleven samples had levels of 4,4´-diaminodiphenylmethane higher than permitted by legislation and five samples showed values of aniline above the limit. Considering the Mood test for polyamides, there were significant differences between the samples from Brazil and China, as well as between the colors in the silicone samples. Regarding the polyamides, the Chinese samples showed higher amounts of PAAs than the Brazilian ones, being above that allowed by legislation. Three Chinese silicone samples presented values above the legislation limit. These were all from the same importer.

Determination of residual parachloroaniline produced by endodontic treatment after the use of 5% sodium hypochlorite and 2% chlorhexidine combined: an ex-vivo study

ABSTRACT: Aim: The objective of this work was to determine the concentrations of irrigating solutions and the residual content of parachloroaniline (PCA) formed after endodontic irrigation, using 5% NaOCl, 0.9% NaCl, 10% EDTA and 2% CHX 2%. Methodology Twenty premolars were used and 13 samples were collected per tooth from each of the treatment phases. Samples of: NaOCl, EDTA, CHX and PCA were quantified by UV and visible spectrophotometry. Results: Sodium hypochlorite decreased its concentration from 3.8% to 3.4% in phases 1 to 4. In phases 5, 6 and 7, residual NaOCl was measured with concentrations of 0.007%, 0.003% and 0.001% %. The concentration of EDTA decreased to 8.85% in phase 8. In phases 9, 10 and 11, irrigated with serum, EDTA was quantified with concentrations of 0.013% to 0.002% and NaOCl values of 0.0011% to 0, 0006%. In phases 12 and 13, CHX concentrations were 1.850% and 1.812% and PCA values were 0.0005% and 0.0007%. PCA formation occurred in presence of 2% CHX and residual NaClO and was detected colorimetrically in phases 12 and 13. Conclusions. During endodontic irrigation the concentration of 5% NaOCl decreases significantly in the first four phases and the concentrations of EDTA and CHX also decrease. There is PCA training in the last stages of the procedure.

Validation of a liquid chromatography ultraviolet method for determination of herbicide diuron and its metabolites in soil samples.

Diuron is one of the most widely herbicide used worldwide, which can undergo degradation producing three primary metabolites: 3,4-dichlorophenylurea, 3-(3,4-dichlorophenyl)-1-methylurea, and 3,4-dichloroaniline. Since the persistence of diuron and its by-products in ecosystems involves risk of toxicity to environment and human health, a reliable quantitative method for simultaneous monitoring of these compounds is required. Hence, a simple method without preconcentration step was validated for quantitation of diuron and its main metabolites by high performance liquid chromatography with ultraviolet detection. Separation was achieved in less than 11 minutes using a C18 column, mobile phase composed of acetonitrile and water (45:55 v/v) at 0.86 mL min-1 and detection at 254 nm. The validated method using solid-liquid extraction followed by an isocratic chromatographic elution proved to be specific, precise and linear (R2 ˃ 0.99), presenting more than 90% of recovery. The method was successfully applied to quantify diuron and their by-products in soil samples collected in a sugarcane cultivation area, focusing on the environmental control.

Antifouling booster biocides in coastal waters of Panama: First appraisal in one of the busiest shipping zones.

A baseline study for antifouling booster biocides in coastal waters of Panama is presented. Solid Phase Extraction (SPE) was used for extraction and Liquid Chromatography tandem Mass Spectrometry (LC-MS/MS) was applied for the quantification of irgarol 1051, diuron, (2-thiocyanomethylthio)benzothiazole (TCMTB), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) and dichlofluanid. TCMTB, DCOIT and dichlofluanid were not detected in any seawater sample, while irgarol 1051 and diuron were found in four out of thirteen areas (<0.3 to 5.0ngL-1 and <2.7 to 70ngL-1, respectively). Although the hotspots were identified in areas influenced by marinas and in one of the ports, diuron and irgarol 1051 levels were all lower than the threshold levels set by the Environmental Quality Standard of United Kingdom. However, this is only a snapshot of the status of costal water contamination by antifouling booster biocides and a more comprehensive assessment is needed to assess risks associated to long term exposure.

Silver nanoparticle-modified electrode for the determination of nitro compound-containing pesticides.

This paper reports the electroanalytical determination of pendimethalin and ethyl parathion by square-wave adsorptive stripping voltammetry using a material comprised of chitosan-stabilized silver nanoparticles to modify a glassy carbon electrode. Under optimized experimental conditions, the peak current was found to vary linearly with the concentration of pendimethalin in the range of 70 to 2000 nmol L(-1) and with concentration of ethyl parathion in the range of 40 to 8000 nmol L(-1). Detection limits of 36 and 40 nmol L(-1) were obtained for pendimethalin and ethyl parathion, respectively. The silver - nanoparticle-modified electrode was successfully employed for the analysis of pesticides in tap and mineral water (pendimethalin) and in lettuce and honey (ethyl parathion) samples. Pendimethalin recovery was between 94 and 100 %, and ethyl parathion recovery was between 97 and 101 %, indicating no significant matrix interference effects on the analytical results. The accuracy of the electroanalytical methodology using the proposed modified electrode was also compared to that of the UV-vis spectrophotometric method.

Degradation of 2,4,6-trinitrotoluene by P. aeruginosa and characterization of some metabolites.

Degradation of 2,4,6-trinitrotoluene (TNT), a nitroaromatic explosive found in the soil and ground water, was investigated using Pseudomonas aeruginosa in in vitro experiments . Biodegradable abilitiy of this bacteria was performed with 50 and 75 mg L (-1) TNT concentrations in a defined liquid medium for 96 h time period. Treatment of TNT in supernatant samples taken at 0, 6, 12, 24, 48, 72 and 96 h from agitated vessels was followed by reverse-phase high-performance liquid chromatography (HPLC). In cultures supplemented with 50 and 75 mgL (-1) TNT, after 96 h of incubation 46% and 59% reduction were detected respectively. Two metabolites as degradation intermediates with nitrite release into the medium, 2,4-dinitrotoluene (2,4-DNT) and 4-aminodinitrotoluene (4-ADNT), were elucidated by thin layer chromatography (TLC) and gas chromatography-mass spectrometry (GC-MS). These findings clearly indicate that Pseudomonas aeruginosa can be used in bioremediation of TNT contaminated sites.

Degradation of 2,4,6-trinitrotoluene by P. aeruginosa and characterization of some metabolites

Degradation of 2,4,6-trinitrotoluene (TNT), a nitroaromatic explosive found in the soil and ground water, was investigated using Pseudomonas aeruginosa in in vitro experiments. Biodegradable abilitiy of this bacteria was performed with 50 and 75 mg L−1 TNT concentrations in a defined liquid medium for 96 h time period. Treatment of TNT in supernatant samples taken at 0, 6, 12, 24, 48, 72 and 96 h from agitated vessels was followed by reverse-phase high-performance liquid chromatography (HPLC). In cultures supplemented with 50 and 75 mgL−1 TNT, after 96 h of incubation 46% and 59% reduction were detected respectively. Two metabolites as degradation intermediates with nitrite release into the medium, 2,4-dinitrotoluene (2,4-DNT) and 4-aminodinitrotoluene (4-ADNT), were elucidated by thin layer chromatography (TLC) and gas chromatography-mass spectrometry (GC-MS). These findings clearly indicate that Pseudomonas aeruginosa can be used in bioremediation of TNT contaminated sites.

Degradation of 2, 4, 6-trinitrotoluene by P aeruginosa and characterization of some metabolites

Degradation of 2,4,6-trinitrotoluene (TNT), a nitroaromatic explosive found in the soil and ground water, was investigated using Pseudomonas aeruginosa in in vitro experiments. Biodegradable abilitiy of this bacteria was performed with 50 and 75 mg L−1 TNT concentrations in a defined liquid medium for 96 h time period. Treatment of TNT in supernatant samples taken at 0, 6, 12, 24, 48, 72 and 96 h from agitated vessels was followed by reverse-phase high-performance liquid chromatography (HPLC). In cultures supplemented with 50 and 75 mgL−1 TNT, after 96 h of incubation 46% and 59% reduction were detected respectively. Two metabolites as degradation intermediates with nitrite release into the medium, 2,4-dinitrotoluene (2,4-DNT) and 4-aminodinitrotoluene (4-ADNT), were elucidated by thin layer chromatography (TLC) and gas chromatography-mass spectrometry (GC-MS). These findings clearly indicate that Pseudomonas aeruginosa can be used in bioremediation of TNT contaminated sites.(AU)

Determination of chemical components derived from 2% chlorhexidine gel degradation using gas chromatography-mass spectrometry.

OBJECTIVE: This study determined the chemical components derived from degradation of 2% chlorhexidine (CHX) gel and solution by using gas chromatography-mass spectrometry. MATERIALS AND METHODS: Three 2% CHX gels were used to identify the products of CHX gel degradation using gas chromatography-mass spectrometry. A solution of CHX was also evaluated to compare the degradation between gel and solution. Degradation was evaluated in four storage situations (on the worktable with light: on the worktable without light; in the Pasteur oven at 36.5°C without light; and in the refrigerator at 8°C without light). Measurements were made at four time points: initial analysis and 1, 3 and 6 months after. The conversion of CHX into para-chloroaniline in storage situations and in different periods was analyzed statistically using chi-square test (α = 5%). RESULTS: The 2% CHX gel or solution had already degraded vial found within the period of validity, at all time points and for all storage conditions. The amount of para-chloroaniline (pCA) was directly proportional to time in the case of CHX solution, but not in CHX gel due to lack of homogeneity. CHX homogeneity in hydroxyethylcellulose gel was directly dependent on compounding mode. CONCLUSIONS: Degradation products, such as para-chloroaniline (pCA), orto- chloroaniline (oCA), meta-chloroaniline (mCA), reactive oxygen species (ROS) and organochlorines (ortho-chlorophenyl isocyanate and 2-amino-5-clorobenzonitrila) were found in 2% CHX gel and solution, regardless of storage conditions or time. In relationship to gel homogenization an alternative to produce 2% CHX gel and a new homogenization method have been developed.

Detection of para-chloroaniline, reactive oxygen species, and 1-chloro-4-nitrobenzene in high concentrations of chlorhexidine and in a mixture of chlorhexidine and calcium hydroxide.

INTRODUCTION: Chlorhexidine (CHX) is likely to decompose into reactive by-products. This study evaluated the generation of 4-chloroaniline (pCA), reactive oxygen species (ROS), and 1-chloro-4-nitrobenzene in high concentrations of CHX and in a mixture of CHX and calcium hydroxide at different time points. METHODS: A gas chromatography method was developed to detect pCA and CHX by-products. Mass spectroscopy was used to elucidate the structure of compounds. The samples, which were kept at 36.5°C and 95% relative humidity during the study, were analyzed immediately and 7 days after preparation. RESULTS: pCA was detected in the 2% CHX solution and in the mixture of CHX and calcium hydroxide at all time points. pCA concentrations increased after storing under those conditions. The 2% CHX solution alone and the mixture of CHX and calcium hydroxide released ROS at all time points, but 1-chloro-4-nitrobenzene was not found. CONCLUSIONS: pCA and ROS were identified as by-products of the 2% CHX aqueous solution alone and as ointment base of calcium hydroxide paste.

Low-cost gas sensors produced by the graphite line-patterning technique applied to monitoring banana ripeness.

A low-cost sensor array system for banana ripeness monitoring is presented. The sensors are constructed by employing a graphite line-patterning technique (LPT) to print interdigitated graphite electrodes on tracing paper and then coating the printed area with a thin film of polyaniline (PANI) by in-situ polymerization as the gas-sensitive layer. The PANI layers were used for the detection of volatile organic compounds (VOCs), including ethylene, emitted during ripening. The influence of the various acid dopants, hydrochloric acid (HCl), methanesulfonic acid (MSA), p-toluenesulfonic acid (TSA) and camphorsulfonic acid (CSA), on the electrical properties of the thin film of PANI adsorbed on the electrodes was also studied. The extent of doping of the films was investigated by UV-Vis absorption spectroscopy and tests showed that the type of dopant plays an important role in the performance of these low-cost sensors. The array of three sensors, without the PANI-HCl sensor, was able to produce a distinct pattern of signals, taken as a signature (fingerprint) that can be used to characterize bananas ripeness.

Physical vapor deposited thin films of lignins extracted from sugar cane bagasse: morphology, electrical properties, and sensing applications.

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 × 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan δ of 3.9 × 10(-3), and conductivity of 1.75 × 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Experimental poisoning of guinea pig (Cavia porcellus) with Indigofera suffruticosa.

Indigofera suffruticosa causes hemolytic anemia and hemoglobinuria in cattle. The plant was administered to six groups of two guinea pigs each, at the daily dose of 10 g/kg body weight, for periods of 2, 4, 6, 8, 10 and 15 days. The guinea pigs progressively developed reduced hematocrits and hemoglobin concentrations, and finally presented anemia, without hemoglobinuria. Urine passed by guinea pigs that had ingested the plant for more than 24 h acquired a turquoise blue pigmentation 8-10 h after urination. It is suggested that the anemia is caused by the aniline contained in I. suffruticosa.

Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS.

The coordination polymer [Zn(BDC)(H(2)O)(2)](n) was tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoxim-methyl and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using gas chromatography-mass spectrometry in selected ion monitoring mode (GC/MS, SIM). Experiments carried out at different fortification levels (0.1, 0.5 and 1.0 µg g(-1)) resulted in recoveries in the range 73-97%, and RSD values were between 5 and 12% for the [Zn(BDC)(H(2)O)(2)](n) sorbent. Detection and quantification limits ranged from 0.02 to 0.07 µg g(-1) and from 0.05 to 0.1 µg g(-1), respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-14.0 µg g(-1)), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison between [Zn(BDC)(H(2)O)(2)](n) and the commercial phase C(18)-bonded silica showed good performance of the [Zn(BDC)(H(2)O)(2)](n) polymeric sorbent for the pesticides tested.

Effect of storage on chemical and sensory profiles of peanut pastes prepared with high-oleic and normal peanuts.

BACKGROUND: Peanut paste and peanut butter have high oil contents and are thus susceptible to developing rancidity and off-flavours through lipid oxidation. Preservation of the chemical and sensory quality of these products is one of the main problems in the peanut industry. The purpose of this study was to compare the chemical and sensory stability of peanut paste prepared with high-oleic peanuts (cv. Granoleico, GO-P) with that of peanut paste prepared with normal peanuts (cv. Tegua, T-P) from Argentina. RESULTS: Chemical (peroxide and p-anisidine values and conjugated dienes) and sensory (roasted peanutty, oxidised and cardboard flavours) indicators of lipid oxidation were measured in peanut pastes stored at 4, 23 and 40 °C. Chemical indicator values and oxidised and cardboard flavours showed lower increments in GO-P than in T-P during storage. T-P had significantly higher peroxide value than GO-P. Roasted peanutty flavour showed a lower decrease in GO-P. Peanut paste prepared with high-oleic peanuts had four (at 4 °C), two (at 23 °C) and three (at 40 °C) times longer shelf-life than peanut paste prepared with normal peanuts. CONCLUSION: These results indicate that high-oleic Granoleico kernels provide peanut paste with higher protection against lipid oxidation.

Inocula from activated sludge for ready biodegradability testing: homogenization by preconditioning.

The use of activated sludge as inoculum source in ready biodegradability tests (RBT) suffers from several drawbacks related to the heterogeneity of these communities. In this work, the ability of a 7-day aeration period in a mineral medium to homogenize the characteristics of various activated sludges, as suggested by some RBT, was studied. The biodegradation potential of three activated sludge supernatants obtained from different wastewater treatment plants was assessed in terms of cultivable cell density, dehydrogenasic activity and a profile of hydrolytic enzymes. After the preconditioning, the homogenization of these characteristics in the supernatants was observed, as well as a decrease. When preconditioned inocula were used in acetate RBT, the biodegradation kinetics were homogenized. However, some preconditioned supernatants lost their ability to degrade an easily-assimilable xenobiotic compound (aniline) during the observation period, showing the effect of inoculum preconditioning on the behavior of complex bacterial communities, specialist populations (e.g. aniline degraders) being more sensitive than generalist populations (e.g. acetate degraders). These results show that preconditioning cannot be an optional inoculum pretreatment in RBT, and emphasize the importance of further studies focusing on inoculum homogenization.