Analysis Of Primary Aromatic Amines Research Articles

GC-MS Analysis of Primary Aromatic Amines Originated From Azo Dyes in Commercial Textile or Leather Products Using Helium Alternative Carrier Gases.

In recent years, due to the global shortage of helium gas, the development of gas chromatography (GC) analytical methods using alternatives to helium carrier gases is necessary. The objective of this study was to examine the applicability of hydrogen and nitrogen as alternative carrier gases using the test method for azo compounds in the Act on Control of Household Products Containing Harmful Substances of Japan. The gas chromatograph mass spectrometer (GC-MS) analytical method using hydrogen and nitrogen as alternative carrier gases was compared with a method using helium for 26 primary aromatic amines (PAAs) originated from azo dyes. When hydrogen and nitrogen were used as carrier gases under the same conditions used during analysis using helium (same column, gas flow rate, oven temperature conditions, etc.), sufficient peak separation of 26 PAAs was obtained. The sensitivities of the methods using helium and hydrogen were comparable, whereas the sensitivity was lower when nitrogen was used, with the detection limits ranging from 1/220 to 1/25. However, all carrier gases achieved quantification at concentrations below the standard value (30 μg/g) of the Act on Control of Household Products Containing Harmful Substances, and the results were in agreement with the standard value for the target product. Our results indicated that hydrogen or nitrogen can be used as alternative carrier gases to helium for GC-MS analysis of azo compounds producing specific aromatic amines. Using hydrogen or nitrogen as an alternative carrier gas to helium, azo compounds could be quantified with excellent accuracy.

A liquid chromatography–tandem mass spectrometry method for the analysis of primary aromatic amines in human urine

Aromatic amines are widely used in personal care products and human exposure to this class of chemicals is widespread. Bioanalytical methods to determine trace levels of aromatic amines in human urine are scarce. In this study, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed to determine 39 primary aromatic amines (AAs) along with nicotine and cotinine in human urine. Chromatographic separation of the 41 analytes was achieved on an Ultra Biphenyl (100 mm × 2.1 mm, 5 µm) column. Mass spectrometry was operated in electrospray ionization positive ion multiple reaction monitoring (MRM) mode. The method exhibited excellent linear dynamic range (0.1–50 ng/mL) with correlation coefficients (r) > 0.999 for all analytes. Urine samples (2 mL) were hydrolyzed using 10 M NaOH at 95 °C for 15 h and target analytes were extracted using methyl-tert-butyl ether (MTBE). Addition of 15 µL of 0.25 M HCl to the sample extracts improved the recoveries of several target analytes. The method was validated through the analysis of fortified quality control (QC) samples and a certified standard reference material (SRM). Relative recoveries (%) of target analytes fortified in QC samples were in the range of 75–114% for 37 of the 41 analytes while the other analytes exhibited lower recoveries (16–74%). The limits of detection (LOD) and limits of quantification (LOQ) of target analytes were in the range of 0.025–0.20 ng/mL and 0.1–1.0 ng/mL, respectively. Intra-day and inter-day precision of the method assessed through the analysis of fortified urine QC samples at three different concentrations were < 11.7% and < 15.9% (measured as RSD), respectively. The method was applied in the analysis of urine samples from the general population and known smokers; aniline, para-anisidine, para-toluidine, ortho/meta-toluidine, 3-chloroaniline, 4-chloroaniline, 3,4-dichloroaniline, and 4,4′-methylenedianiline were found in all smoker’s urine at sum concentrations ranging from 0.04 to 9.16 ng/mL.

Analysis of Primary Aromatic Amines Derived from Azo Colorants in Textile Products and Determination of Their Source Colorant.

Twenty-four primary aromatic amines (PAAs) derived from azo colorants, which are controlled by the Act on Control of Household Products Containing Harmful Substances by the Japan Ministry of Health, Labour and Welfare, aniline and 1,4-phenylendiamine were analyzed in 86 samples of 40 textile products by GC-MS. Even though these PAAs detected in the samples did not exceed the regulation value (30 μg/g), 14 kinds of PAAs were detected that exceeded the limit of quantification. 4,4'-Methylenedianiline, in amounts that exceeded the limit of quantification, was detected in 20 textile samples containing synthesis fiber (16 samples made from polyurethane, two samples made from polyester, and two samples made from acryl); however, it was not detected in natural fiber textile samples. Of these samples, 4,4'-methylenedianiline was detected in 16 out of 19 samples (84%) made from polyurethane fiber. This suggests that 4,4'-methylenedianiline is formed from polyurethane. The origin of 3,3'-dichlorobenzidine was investigated in three samples releasing more than 3 μg/g (3.9-15 μg/g) of 3,3'-dichlorobenzidine using atmospheric pressure solids analysis probe-mass spectrometry and Pigment Orange 13 was identified as the orange colorant in the textile printing parts. This result suggests that 3,3'-dichlorobenzidine detected in these three samples was generated by the reduction of Pigment Orange 13.

Determination of primary aromatic amines in cold water extract of coloured paper napkin samples by liquid chromatography-tandem mass spectrometry

ABSTRACTThe aim of this study was the optimisation of a multi-analyte method for the analysis of primary aromatic amines (PAAs) from napkins in order to support official controls and food safety. We developed a UHPLC-MS/MS method for the simultaneous determination of 36 toxicologically relevant PAAs for paper and board. Good regression coefficients of the calibration curves in a range of 0.992–0.999 and reproducibilities in a range of 2.3–15% were obtained. Limits of detections (LODs) were in the range of 0.03–1.4 µg l–1 and recoveries were in a range of 21–110% for all the amines. A total of 93 coloured paper napkin samples from different European countries were bought and extracted with water to determine the PAAs. The results showed that 42 of 93 samples contained at least one PAA. More than half of the detected PAAs are considered as toxic, carcinogenic or probably carcinogenic to humans by the International Agency for Research on Cancer (IARC), or are classified as such in the European Union legislation on chemicals. Summed concentrations of PAAs in seven samples were higher than 10 µg l–1, the limit of summed PAA in the European Union plastic food contact material regulation. Also, eight PAAs, classified as Category 1A and 1B carcinogen in the European Union legislation of chemicals, were detected at concentrations higher than 2 µg l–1, exceeding the limit proposed by the Federal Institute for Risk Assessment in Germany. Aniline (n = 14) was most frequently present in higher concentrations followed by o-toluidine, o-anisidine, 2,4-dimethylaniline and 4-aminoazobenzene. Red, orange, yellow and multicoloured paper napkins contained the highest concentrations of total PAAs (> 10 µg l–1). Although the European Union has not harmonised the legislation of paper and board materials and, thus, there is no specific migration limit for PAAs from paper napkins, the present study showed that coloured paper napkins can contain toxic and carcinogenic PAAs at concentrations that are relevant for monitoring.

Inter-laboratory comparison study on the determination of primary aromatic amines in cold water extracts of coloured paper napkins

To evaluate the competence in the analysis of primary aromatic amines (PAAs) in cold water extracts from napkins, an inter-laboratory comparison study was conducted with 19 participating laboratories. Two cold water extracts spiked at two different PAA concentration levels, each containing four different PAAs (aniline, o-toluidine, 2,4-dimethylaniline and o-anisidine) and, additionally, four different napkins containing one of the PAAs each were distributed between the laboratories. In this exercise, the influence of different parameters in the preparation of cold water extracts from napkins according to the European Norm (EN) 645 was also investigated. For the already spiked cold water extracts and the napkins, 88% and 77% of the results were satisfactory with zU-scores of ≤ |2|. The Horwitz ratio (HorRat) values for the spiked cold water extracts were in the range of 0.48–1.25. For the napkins, HorRat values were in the range of 1.261.91, whereas the lowest assigned value was 0.97 µg l−1 (o-toluidine). Thus, the results show that preparation and instrumental analysis of PAAs in cold water extracts from napkins according to EN 645 has been well established.

Target analysis of primary aromatic amines combined with a comprehensive screening of migrating substances in kitchen utensils by liquid chromatography–high resolution mass spectrometry

An analytical strategy including both the quantitative target analysis of 8 regulated primary aromatic amines (PAAs), as well as a comprehensive post-run target screening of 77 migrating substances, was developed for nylon utensils, using liquid chromatography–orbitrap-high resolution mass spectrometry (LC–HRMS) operating in full scan mode. The accurate mass data were acquired with a resolving power of 50,000 FWHM (scan speed, 2Hz), and by alternating two acquisition events, ESI+ with and without fragmentation. The target method was validated after statistical optimization of the main ionization and fragmentation parameters. The quantitative method presented appropriate performance to be used in official monitoring with recoveries ranging from 78% to 112%, precision in terms of Relative Standard Deviation (RSD) was less than 15%, and the limits of quantification were between 2 and 2.5µgkg−1. For post-target screening, a customized theoretical database was built for food contact material migrants, including bisphenols, phthalates, and other amines. For identification purposes, accurate exact mass (<5ppm) and some diagnostic ions including fragments were used. The strategy was applied to 10 real samples collected from different retailers in the Valencian Region (Spain) during 2014. Six out of eight target PAAs were detected in at least one sample in the target analysis. The most frequently detected compounds were 4,4′-methylenedianiline and aniline, with concentrations ranging from 2.4 to 19,715µgkg−1 and 2.5 to 283µgkg−1, respectively. Two phthalates were identified and confirmed in the post-run target screening analysis.

Analysis of primary aromatic amines originated from azo dyes in commercial textile products in Japan

The purpose of this study was to clarify the actual condition of 26 types of carcinogenic primary aromatic amines (PAAs) originated from azo dyes in commercial textile products in Japan. In the case of textiles made of various fibers of various colors, the fibers were separated by color and analyzed. A total of 86 textile products (117 samples) were analyzed. Twenty-one kinds of PAAs were detected in the samples and almost all the PAAs were detected at low concentrations. However, the concentrations of benzidine, 3,3′-dimethoxybenzidine, and 2,4-diaminotoluene (56–440 μg g−1) in placemats made of cotton were found to exceed EU regulation limits of 30 μg g−1. Although such placemats do not always come into contact with the user's skin, it is thought that they should be handled more carefully. Finally, 7 products (8 samples) contained PAAs at concentrations that exceeded the regulation limits. Two sample preparation methods (with and without solvent extraction) were performed on the same sample in order to compare the PAAs in samples in which it is difficult to separate the component materials, such as a cotton fabric that contained polyester fibers. In a comparison of the results obtained from the two methods, it was observed that the concentrations and/or kinds of PAAs detected in the samples were different. It was therefore thought that textile products that present this particular challenge should be analyzed by both methods.

Analysis of Primary Aromatic Amines in Paper Products

A highly sensitive analytical method for 25 kinds of primary aromatic amines and azo-dyes in paper products was developed. Free amines and total amines of the samples were analyzed. The amount of each azo-dye was calculated from the amount of total amines by subtracting the amount of free amines. Amines and azo-dyes were migrated into water at 23 degrees C for 24 hours. Free amines were extracted into dichloromethane after alkalization with sodium hydroxide solution. Azo-dyes were reduced to amines with sodium dithionite, alkalized, and then extracted into dichloromethane as total amines. They were determined by GC/MS. The recoveries of 100 microg/kg amines spiked into migration solution were in the range of 69-122%, except for 4,4'-oxydianiline and 4,4'-diaminodiphenylmethane which gave recovery rates of approximately 40%. The determination limits of amines were 4-20 microg/kg in paper. Amines and azo-dyes were surveyed in 17 kinds of base paper and 16 kinds of paper products for food contact use. Aniline was detected at levels of 4-20 microg/kg from most recycled papers, whereas the other amines were not detected in any sample.

Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

New gas‐chromatographic/mass spectrometric method for the quantitative analysis of primary aromatic amines in main‐ and side‐stream cigarette smoke. I

AbstractA sensitive and accurate method to quantitate 17 primary aromatic amines in tobacco smoke has been set up. two Italian commercial brands of cigarette were smoked in a home‐made smoking machine; the amines in the smoke were trapped in dilute hudrochloric acid (containing 2H5‐aniline, 13C1‐o‐toluidine and 2H9‐4‐aminobiphenyl as internal standards) and, after extraction and purification, derivatized as pentafluoropro‐pionamides and measured by gas chromatography/mass spectrometry in the selected‐ion‐monitoring mode. Our results confirmed that side‐stream smoke contains total levels of aromatic amines about 50–60 times higher than those of main‐stream smoke of black‐tobacco cigarettes is richer in aromatic amines compared to light‐tobacco cigarettes.

Portable liquid chromatograph for analysis of primary aromatic amines in coal-derived materials

This paper presents the preliminary results of the selective detection of primary aromatic amines with the use of a portable liquid chromatography with electro-chemical detection system. The primary aromatic amines were in materials derived from coal. (13 refs.)

Analysis of primary aromatic amines and nitrite by diazotization and pyrolysis gas chromatography

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAnalysis of primary aromatic amines and nitrite by diazotization and pyrolysis gas chromatographyAnthony. Savitsky and Sidney. SiggiaCite this: Anal. Chem. 1974, 46, 1, 153–155Publication Date (Print):January 1, 1974Publication History Published online1 May 2002Published inissue 1 January 1974https://doi.org/10.1021/ac60337a040RIGHTS & PERMISSIONSArticle Views260Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (397 KB) Get e-Alerts Get e-Alerts