Talanta 71 (2007) 486492

Simultaneous determination of aliphatic and aromatic amines in indoor and outdoor air samples by gas chromatographymass spectrometry
Mehmet Aky z u
Zonguldak Karaelmas University, Faculty of Sciences and Letters, Department of Chemistry, 67100 Zonguldak, Turkey Received 15 June 2006; received in revised form 18 October 2006; accepted 19 October 2006 Available online 27 November 2006

Abstract A gas chromatographymass spectrometry (GCMS) method has been proposed for the simultaneous determination of aliphatic and aromatic amines in indoor and outdoor air samples. The method includes pre-concentration of the compounds by percolating the air samples through the acidic solution, ion-pair extraction with bis-2-ethylhexylphosphate (BEHPA), derivatisation of compounds with isobutyl chloroformate (IBCF) and their GCMS analysis. Aliphatic and aromatic amines were isolated from aqueous samples using BEHPA as ion-pair reagent and derivatised with IBCF for their chromatographic analysis. Aliphatic and aromatic amines were then analysed with GCMS in both electron impact (EI) and positive and negative ion chemical ionisation (PNICI) mode as their isobutyloxycarbonyl (isoBOC) derivatives. The obtained recoveries ranged from 75.6 to 96.8% and the precision of this method, as indicated by the relative standard deviations (R.S.D.) was within the range of 1.04.4%. The detection limits obtained from calculations by using GCMS results based on S/N: 3 were within the range of 0.080.01 ng/m3 . 2006 Elsevier B.V. All rights reserved.
Keywords: Ion-pair extraction; Aliphatic and aromatic amines; GCMS; Indooroutdoor air samples

1. Introduction Volatile aliphatic amines like methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine and dibutylamine are important air pollutants due to their odorous and toxic characteristics and they are found in the air as a result of their industrial commercial applications or their widespread use as intermediates in chemical and pharmaceutical industries [1,2]. In addition to their toxic characteristics most of alkylamines are sensitizers and irritants to the skin, mucous membrane and respiratory tract and it is well known that they can react with nitrite, forming carcinogenic nitrosamines [3,4]. Aromatic amines like morpholine, aniline, phenylethylamine, chloroanilines, piperazine, naphthylamines, aminophenols, toluenediamines and 4-aminobiphenyl are biologically active compounds, well known as environmental pollutants because of their toxicity and carcinogenicity as they are widely used in industry to make dyes, cosmetics, medicines, rubber,

Tel.: +90 372 257 40 10x1371; fax: +90 372 257 41 81. E-mail address: makyuz2004@yahoo.co.uk.

textiles, agrochemicals and as reagents intermediates in many chemical syntheses [5,6]. Therefore, the monitoring of levels of aliphatic and aromatic amines in indoor and outdoor air is important to protect human health and the environment because of human exposure to these compounds through diet and inhalation. The most widely used techniques for the determination of aliphatic [1,2] and/or aromatic amines [5,6] in air samples are gas chromatography (GC) coupled with different detectors [1,3,5], high-performance liquid chromatography (HPLC) [4,710], ion chromatography [11], spectrophotometry [12]. Gas chromatographymass spectrometry (GCMS) has been recognized as the method of choice for the analysis of aliphatic and aromatic amines in environmental samples, due to its superiority in selectivity and sensitivity. A pre-concentration step is necessary to obtain good sensitivity and derivatisation step is generally required to improve the gas chromatographic properties because of the polarity of the amines. Liquidliquid extraction after percolation of the air sample through the acidic solution (LLE) [6,13] and solid-phase extraction (SPE) [1,2,7,12,14] have been widely employed for the isolation of these amines from air samples. The most popular derivatisation techniques employed for gas chromatographic analysis

0039-9140/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.talanta.2006.10.028

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of amines are acylation, silylation, carbamate formation, sulphonamide formation and phosphoamide formation [15]. This study focuses on the development of analytical techniques that could be applied to indoor and outdoor air samples to determine various aliphatic and aromatic amines by adapting our previous method for the analysis of amines in water and sediment samples [16]. The following paper presents an analytical procedure, proposed to enable the precise determination of low-level aliphatic and aromatic amines in indoor and outdoor air and rainwater samples. This procedure offers several signicant advantages over the other techniques available, such as higher selectivity in isolation, efcient derivatisation and higher sensitivity. In the proposed method, air samples were percolated through the 0.1 M HCl solution using constant ow air pump to trap aliphatic and aromatic amines in the aqueous acidic solution as their hydrochloric salts. The compounds of interest were extracted from aqueous solution with chloroform containing bis-2-ethylhexylphosphate (BEHPA) as ion-pair reagent and derivatised with isobutyl chloroformate. Aliphatic and aromatic amines were then analysed as their isobutyloxycarbonyl (isoBOC) derivatives by GCMS. 2. Experimental 2.1. Chemicals and reagents All the reagents were of analytical grade. Bis(2ethylhexyl)-phosphate, isobutyl chloroformate, methylamine, ethylamine, diethylamine, n-propylamine, butylamine, piperidine, morpholine, diphenylamine, aniline, N-methylaniline, benzylamine, 4-aminophenol, 4-bromoaniline, piperazine, 2,5-dichloroaniline, 3,5-dichloroaniline, 3,4-dichloroaniline, dibutylamine, pyrrolidine, 3-aminophenol, 3-chloroaniline, 4chloroaniline, 2-nitroaniline, 3-nitroaniline, m-toluidine, 4methyl-o-phenylenediamine, chloroform, toluene, di-sodium hydrogen phosphate, sodium hydrogen carbonate, sodium sulphate, hydrochloric acid and isobutylalcohol were purchased from Merck. Phenylethylamine was supplied by Aldrich. 4Aminobiphenyl was supplied by Reidel-de Haen. Pyridine was purchased from J.T. Baker. 1-Naphthylamine was supplied by Sigma. Dimethylamine, 4-ethylaniline and 2-ethylaniline were purchased from Fluka. 2,6-Diethylaniline was purchased from Alfa Aesar. 2.2. Samples extraction and derivatisation Air samples (0.51.5 m3 ) were percolated through the two Drechsel bottles, containing 100 mL of 0.1 M HCl solution using constant ow air pump to trap aliphatic aromatic amines in the aqueous acidic solution as their hydrochloric salts. The pump was regulated at a rate of 46 mL/s and it would sample 1 m3 of air in about 6 h, and then, our previous method was applied to the aqueous phase with minor modications [16]. The aqueous phases were added to a separatory funnel and the pH of the solution was adjusted to 1 by dropwise addition of 0.01 M HCl. Then it was extracted with chloroform (3 3 mL) and separated.

The pH of the aqueous phase was adjusted to 8, as it has been selected to be the extraction pH of the method [16], by dropwise addition of 1 M Na2 HPO4 and then was extracted three times using 0.1 M BEHPA in chloroform (3 3 mL). The chloroform extracts containing the compounds to be analysed were back extracted with 0.1 M HCl solution for 3 min using ultrasonic bath. Then, the pH of the aqueous layer containing these amines was again adjusted to 8 and extracted three times with chloroform containing 0.1 M BEHPA (3 3 mL). The chloroform layer was taken into a vial after drying over anhydrous sodium sulfate and then evaporated to dryness under nitrogen stream at room temperature. Acetonitrile, pyridine and isobutyl alcohol (150, 200, 10 L) and then isoBCF (300 L) were added to the residue and the vial was then closed and kept at room temperature for 10 min. Then, the mixture was evaporated under a gentle stream of nitrogen at room temperature and the derivatised compounds were diluted in toluene. The toluene layer is separated and dried over anhydrous sodium sulphate after shaking with alkaline methanol (1 mL) followed by 1.5 mL of 5 M NaOH for 34 min and centrifuging at 4000 g for 23 min. The solution was then concentrated to a volume of 100 L under a gentle stream of nitrogen and the nal solutions (12 L) were injected into GCMS in splitless mode (5 min purge off). Although they were stable when stored at 15 C, the isoBOC derivatives of the compounds of interest were analysed as soon as they were prepared. Aliphatic and aromatic amines are then analysed as their isoBOC derivatives by GCMS in both electron impact (EI) and positive and negative ion chemical ionisation (PNICI) mode and quantitative analysis was performed in SIM mode. The overall process is schematically shown in Fig. 1. 2.3. Instrumental analysis In this study, a Thermo-Finnigan MAT 4500 GC/MSMS instrument operating in the electron impact and positive and negative ion chemical ionisation mode were used. The specications of the apparatus are as followscolumn identication: ZB5 ms, column length: 30 m, ID: 0.25 mm, lm thickness: 0.25 m. Temperature programinitial temperature 80 C3 min hold at 3 C/min to 140 C3 min hold at 5 C/min to 290 C10 min hold . Flow rate: 1.3 mL/min, ion source temperature: 200 C, transfer line temperature: 200 C, scan range: 30450 m/z, scan rate: 1 scan/s, electron energy: 70 eV for EI and 30 eV for PNICI, and electron current: 350 A. 3. Results and discussion 3.1. Interpretation of mass spectra of model compounds Firstly, aliphatic and aromatic amine standards were derivatised with isobutyl chloroformate (IBCF) and their isoBOC derivatives were analysed by GCMS. Total ion chromatogram (TIC) of derivatised amine standards are shown in Fig. 2. Identication of the components was performed by interpreting their mass spectra obtained in the electron impact mode. All the other isoBOC derivatives of aliphatic and aromatic amines were interpreted in the same way and relatively similar

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Fig. 2. Total ion chromatogram (TIC) of isobutyloxycarbonyl derivatives of aliphatic and aromatic amine standards. The concentrations of derivatised amines are within the range of 0.010.08 ng/ L (1 L injection). (1) Methylamine, (2) dimethylamine, (3) ethylamine, (4) diethylamine, (5) propylamine, (6) butylamine, (7) pyrrolidine, (8) morpholine, (9) piperidine, (10) dibutylamine, (11) N-methylaniline, (12) aniline, (13) diphenylamine, (14) m-toluidine, (15) benzylamine, (16) phenylethylamine, (17) 2ethylaniline, (18) 2,6-diethylaniline, (19) 3-chloroaniline, (20) 4-ethylaniline, (21) 4-chloroaniline, (22) 2,5-dichloroaniline, (23) 3,5-dichloroaniline, (24) 4bromoaniline, (25) 2-nitroaniline, (26) 3-nitroaniline, (27) 3,4-dichloroaniline, (28) piperazine, (29) -naphthylamine, (30) 3-aminophenol, (31) 4aminophenol, (32) 4-methyl-o-phenylenediamine and (33) 4-aminobiphenyl.

Fig. 1. Flow chart showing the isolation and preparation of the compounds of interest for GCMS analysis.

fragmentations were obtained. For example, interpretation of mass spectrum of isoBOC derivative of aniline was carried out in the following way; the ions observed at m/z 137, 120 and 93 are formed by the loss of C(CH3 )3 , OC(CH3 )3 and OCOC(CH3 )3 groups from the molecular ion observed at m/z 193. The loss of the butyl groups gives the ion at m/z 57 when using IBCF. These peaks are characteristic for the isobutyloxycarbonyl derivatives. The molecular ion of aniline at m/z 93 observed as the base peak is formed by the loss of isobutyloxycarbonyl group from the molecular ion of isoBOC derivatives of aniline observed at m/z 193. Identication of the compounds was also conrmed by GCMS in PNICI mode using methane as reagent gas. 3.2. Recovery of the compounds of interest from samples Firstly, a standard solution containing 10 mg/L of each of the amines was prepared in acetone and diluted to give a nal con-

centration of 100 ng/L and then derivatised with IBCF. Seven calibration standards with the concentrations in the range from 0.01 to 25 ng/L were prepared by diluting the derivatised standard solution (100 ng/L) and used for the calibration. Calibration standards of aliphatic and aromatic amines were analysed as their isoBOC derivatives by GCMS in SIM mode in triplicate. Calibrations were performed by calculating the peak areas of the compounds and the calibration graphs were linear for the concentration ranges stated. The linearity of the proposed method was calculated in the investigated concentration range, as the determination coefcients, R2 , shown in Table 1. The limit of detection (LOD) of each of the amines was estimated to be seven replicate runs by comparing the signal-to-noise ratio (S/N) of the lowest detectable concentration to a S/N: 3. In order to evaluate recoveries of amines from aqueous solution, a solution of a known concentration (50 ng/L) of amines mixture was prepared by diluting the standard solution and known volumes (10, 20 and 50 mL) of this solution was spiked into the distilled water that had previously been shown to contain no amines to give nal concentrations around 0.5, 1.0 and 5.0 ng/L of each of the amines, respectively. Spiking the known volumes (25, 50 and 100 mL) of amines solution (50 ng/L) with water samples (250 and 500 mL) which were analysed for the compounds of interest were also performed to evaluate absolute recovery (plus the blank value). Quantitative analyses of the

M. Aky z / Talanta 71 (2007) 486492 u Table 1 The absolute recoveries of amines for overall procedure with R.S.D.s at selected pH, R2 , LOD and QI Standard amines Methylamine Dimethylamine Ethylamine Diethylamine n-Propylamine Butylamine Pyrrolidine Morpholine Piperidine Dibuthylamine N-Methylaniline Aniline Diphenylamine m-Toluidine Benzylamine Phenylethylamine 2-Ethylaniline 2,6-Diethylaniline 3-Chloroaniline 4-Ethylaniline 4-Chloroaniline 2,4-Dichloroaniline 2,5-Dichloroaniline 3,5-Dichloroaniline 4-Bromoaniline 2-Nitroaniline Piperazine -Naphthylamine 3-Aminophenol 4-Aminophenol 4-Methyl-o-phenylenediamine 4-Aminobiphenyl Optimum extraction pH 8.88 7.50 8.08 8.15 8.18 8.00 7.50 7.92 8.12 8.50 7.78 8.01 8.93 8.50 9.21 9.01 8.50 8.00 8.50 8.00 8.50 8.90 9.00 9.00 8.33 9.00 8.11 7.90 8.00 8.06 8.50 8.21 Absolute recoveries (%) with R.S.D.s at selected pH 8 75.6 (2.6) 86.0 (2.8) 89.4 (2.4) 90.6 (2.2) 90.7 (1.8) 89.6 (1.7) 89.8 (2.5) 93.1 (2.3) 94.9 (1.7) 92.8 (2.2) 96.4 (1.0) 95.5 (1.5) 96.8 (2.4) 95.3 (1.4) 92.3 (3.8) 95.7 (2.0) 95.5 (1.8) 96.5 (1.4) 94.8 (1.6) 96.2 (1.7) 94.9 (1.9) 94.7 (2.0) 94.8 (1.8) 94.8 (1.3) 93.8 (4.2) 92.3 (4.4) 95.8 (2.2) 94.3 (1.8) 93.8 (1.6) 93.9 (1.8) 92.6 (2.1) 95.3 (2.3) R2 0.9926 0.9956 0.9945 0.9922 0.9928 0.9940 0.9976 0.9979 0.9976 0.9978 0.9994 0.9993 0.9988 0.9982 0.9924 0.9994 0.9994 0.9995 0.9983 0.9996 0.9978 0.9976 0.9976 0.9976 0.9954 0.9920 0.9978 0.9989 0.9984 0.9984 0.9988 0.9982 LOD (ng/m3 ) 0.08 0.07 0.07 0.06 0.05 0.04 0.03 0.03 0.04 0.03 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.02 0.02 0.02 0.05 0.07 0.01 0.01 0.03 0.03 0.01 0.01

489

QI1,2,3 m/z 76, 58, 132 90, 72, 146 106, 79, 146 118, 102, 72 104, 130, 160 118, 130, 174 116, 70, 172 116, 88, 188 128, 84, 186 130, 186, 230 151, 107, 207 93, 137, 193 169, 141, 66 150, 106, 207 150, 106, 207 164, 106, 221 106, 121, 221 148, 175, 249 127, 171, 227 165, 106, 221 172, 152, 227 161, 205, 261 161, 205, 261 205, 161, 261 171, 215, 271 135, 106, 235 187, 87, 287 143, 187, 243 153, 209, 309 153, 209, 309 121, 221, 322 213, 169, 269

n = 7; quantiers ions: QI1 , QI2 and QI3 .

amines in known volumes of these samples were performed in seven replicates using GCMS in SIM mode. The concentrations of amines were calculated by peak areas and these areas were compared with the calibration graphs of the standards. The optimum extraction pHs of each amine were investigated and most of them were found to be around 8. The extraction pH of the method was therefore selected to be 8. The recoveries of amines at selected pH were also evaluated. The absolute recoveries of amines from aqueous solution with relative standard deviations (R.S.D.s) at optimum and selected extraction pHs were reported in our previous work [16]. The absolute recoveries of amines for overall procedure described in this work was estimated considering the recoveries of amines from aqueous solution with R.S.D.s at selected extraction pH and the recoveries of amines from air samples. To evaluate recoveries of the compounds from air samples, two systems each composed of two drechsel bottles containing 100 mL of 0.1 M HCl solution were connected to constant ow air pumps separately. Another drechsel bottle containing 50 mL of standard amine solution at the concentration of 10 ng/L of each of the amines was connected in front of one of these systems and the pumps were regulated at the same ow rate of 46 mL/s. Air samples were then percolated through both systems simulta-

neously. The recovery experiments were performed in triplicate using 10, 20 and 50 mL of standard solution (10 ng/L), respectively, plus the blank value. In order to conrm the absolute recoveries from air, the recovery experiments were also performed in seven replicates using standard amines and clean air. The aqueous phases containing the compounds of interest are analysed in the same way as described in Section 2. Obtained results revealed that water soluble amines were almost 100% with R.S.D.s within the range of 0.30.9 trapped into acidic solution and these results are in agreement with the results reported by Skarping et al. [3] and Gr nberg et al. [17]. The absolute o recoveries of the compounds of interest for overall procedure with R.S.D.s at selected pH, correlation coefcients (R2 ), limits of detection and quantier ions (QI) are shown in Table 1. As it has been reported in our previous work [16], derivatisation of dry residue obtained from the chloroform extract with IBCF was carried out in this work and lower limits of detection were obtained in comparison to the two-phase derivatisation [6,13,1820]. The obtained results revealed that, the ion-pairs of amines with BEHPA in chloroform may prevent the losses due to volatilization of low-molecular weight aliphatic amines and once derivatised it becomes easier to keep volatile amines as their isoBOC derivatives probably due to their higher molecular

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mass for the simultaneous determination of low-level aliphatic and aromatic amines in air and rainwater samples. 3.3. Determination of aliphatic and aromatic amines as their isoBOC derivatives in air samples In order to conrm the viability of the proposed method, it was applied to indoor and outdoor air samples to determine various aliphatic and aromatic amines. Indoor and outdoor air samples were collected simultaneously at six points in Zonguldak province during Summer (MaySeptember) times of 20042005 and Winter (OctoberApril) times of 20052006. The indoor air samples (1 m3 ) collected from both smoking and non-smoking areas were analysed for the compounds of interest by the proposed method. Structural identication of isobutyloxycarbonyl derivatives of aliphatic and aromatic amines was carried out by interpretation of the mass spectra and possible match with reagent grade standards spectra and existing library data obtained in EI mode and also conrmed by PNICI. Quantitative analyses of the identied amines were performed in SIM mode using their peak areas and the peak areas were compared with the calibration graphs. Total ion chromatogram of isobutyloxycarbonyl derivatives of aliphatic and aromatic amines isolated from one of the indoor air samples (1 m3 ) collected from smoking area are shown in Fig. 3. The seasonal mean concentrations of amines determined in indoor air samples by using the proposed method during Summer times of 20042005 and Winter times of 20052006 are shown in Table 2. In the most of indoor air samples collected from smoking areas in Zonguldak where the number of asthma patients is known as high, piperazine was found at the highest concentrations to be up to 19.98 and 27.68 ng/m3 in Summer and Winter times, respectively, which can induce asthma and partly reacts with nitrite forming carcinogenic N-mononitrosopiperazine in stomach when transported with saliva after inhalation [3]. Piper-

Fig. 3. TIC of isobutyloxycarbonyl derivatives of aliphatic and aromatic amines isolated from one of the indoor air sample. (1) Methylamine, (2) dimethylamine, (5) propylamine, (8) morpholine, (10) dibutylamine, (11) N-methylaniline, (12) aniline, (13) diphenylamine, (17) 2-ethylaniline, (22) 2,5-dichloroaniline, (25) 2-nitroaniline, (28) piperazine, (29) -naphthylamine, (30) 3-aminophenol, (31) 4-aminophenol and (32) 3,4-toluenediamine.

azine was also found at relatively higher concentrations in indoor air samples collected from non-smoking areas up to 10.15 ng/m3 in Summer and 12.88 ng/m3 Winter times. Furthermore, n-propylamine, butylamine and dibutylamine were found at relatively higher concentrations in indoor air samples collected from smoking areas in Winter times which were up to 11.73, 22.10 and 6.72 ng/m3 and in indoor air samples collected from non-smoking areas in Winter times up to 2.05, 6.75 and 2.70 ng/m3 , respectively. -Naphthylamine, known to cause bladder cancer in humans, was found in indoor air samples collected from smoking areas at concentrations up to 4.48 ng/m3 in Winter times whereas it was not detected in the air samples collected from non-smoking area and outdoor air samples during Summer times. In addition, aniline was also found in concentrations in indoor air samples collected from smoking areas up to 25.50 ng/m3 and non-smoking areas up to 8.93 ng/m3 . Furthermore, aniline was found at relatively higher concentrations in Summer time indoor air samples collected from smoking area at up to 13.02 ng/m3 from non-smoking area up to 3.40 ng/m3 and outdoor air samples up to 2.50 ng/m3 . Aniline and its derivatives were found relatively at higher concentrations in indoor air samples than outdoor air samples. The source of aniline and its derivatives in indoor air is likely due to smoking and widespread usage of these compounds in paints, cleaning products, shoe polishing and cosmetics [5,6]. The outdoor air samples (1 m3 ) collected from six different points in Zonguldak province where pollution is very high due to mainly solid coal waste and where coal is also used for central heating between October and April were analysed by the proposed method and the seasonal mean concentrations of amines determined in outdoor air samples in Summer times of 20042005 and Winter times of 20052006 are shown in Table 2. Piperazine was found at the highest concentrations in outdoor air samples at up to 9.67 ng/m3 in Summer times and 11.86 ng/m3 in Winter times. Furthermore, dimethylamine, npropylamine, dibutylamine, aniline and p-toluidine were found in outdoor air samples at relatively higher concentrations at up to 2.52, 2.03, 0.45, 2.50 and 2.33 ng/m3 Summer times and 3.76, 3.61, 3.80, 6.90 and 5.21 ng/m3 in Winter times, respectively. The results obtained from outdoor air samples in Zonguldak showed that the concentrations of amines measured depend mainly on the air temperature and frequency of rain. To prove that rainwater sample which was taken from the rst rain after a few dry days was analysed and similar pattern in the chromatogram was found as in the outdoor air sample taken before the rain. The seasonal mean concentrations of aliphatic and aromatic amines identied in rainwater samples during Summer times of 20042005 and Winter times of 20052006 are shown in Table 2. The analyses of the air samples after the rain showed that the levels of the amines signicantly dropped as a result of removal of the compounds from the atmosphere by rain. These results indicated the fact that there are signicant correlations between the levels of amine compounds in outdoor air and rainwater samples as reported by Gr nberg et al. [17]. o The results revealed that the proposed method, as described in our previous work [16], has been successfully applied to air

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Table 2 The seasonal mean concentrations of amines determined in air and rainwater samples collected during Summer times of 20042005 and Winter times of 20052006 in Zonguldak Compounds Indoor air (SummerWinter) Smoking area mean concentrations (ng/m3 ) Methylamine Dimethylamine Ethylamine Diethylamine n-Propylamine Butylamine Morpholine Piperidine Dibuthylamine N-Methylaniline Aniline Diphenylamine m-Toluidine Benzylamine Phenylethylamine 2-Ethylaniline p-Toluidine 2,6-Diethylaniline 4-Ethylaniline 4-Chloroaniline 2,4-Dichloroaniline 2,5-Dichloroaniline 3,5-Dichloroaniline 4-Bromoaniline 2-Nitroaniline Piperazine -Naphthylamine -Naphthylamine 3-Aminophenol 4-Aminophenol Methyl-o-phenylenediamine 4-Methyl-o-phenylenediamine 4-Aminobiphenyl 1.051.76 1.113.46 ND0.12 1.351.92 4.168.73 7.5014.10 2.704.28 ND0.34 1.114.72 1.343.32 6.1221.03 ND0.48 ND0.54 ND0.65 NDND ND0.45 1.1116.17 ND0.20 ND0.56 0.400.42 0.090.66 0.120.13 ND0.47 NDND 0.421.21 8.3021.62 1.322.71 1.542.38 0.62ND 1.202.23 NDND 0.441.03 0.420.98 Non-smoking area mean concentrations (ng/m3 ) 0.460.85 1.683.41 0.211.20 0.610.80 0.661.33 1.212.25 0.601.10 0.451.13 0.791.26 1.031.75 1.184.42 0.031.30 ND0.03 ND0.16 0.50ND 0.93ND 1.084.68 0.21ND 0.080.72 0.490.78 ND1.00 0.531.05 0.180.56 0.10ND 0.320.96 4.859.58 0.071.66 ND1.05 0.440.51 1.161.52 ND0.76 0.060.45 0.380.70 Outdoor air (SummerWinter) Mean concentrations (ng/m3 ) 0.261.30 2.182.96 ND0.35 0.830.62 0.683.11 0.050.36 0.300.43 ND0.04 0.152.60 0.350.67 1.644.02 ND0.06 ND0.21 ND0.36 0.060.18 NDND 0.942.85 0.230.27 0.080.49 0.080.23 0.200.25 0.120.66 0.080.32 0.24ND 0.380.62 3.419.00 0.180.67 ND0.33 0.340.45 0.410.87 0.100.34 0.060.40 ND0.05 Rainwater (SummerWinter) Mean concentrations (ng/L) 0.100.12 0.472.43 ND0.21 ND0.36 0.431.88 0.130.33 0.110.32 ND0.05 0.210.43 ND0.11 0.981.16 NDND 0.080.16 0.561.06 0.120.18 NDND 0.891.62 NDND 0.130.24 0.521.81 0.120.78 0.340.58 0.080.25 0.180.60 0.210.71 0.183.20 0.070.14 ND0.16 0.220.53 0.240.59 0.321.42 0.431.52 0.070.22

n 6; ND: not detected; Summer: MaySeptember (while central heatings off); Winter: OctoberApril (central heatings on).

and rainwater samples with some suitable modications for the simultaneous determination of aliphatic and aromatic amines. The obtained recoveries ranged from 75.6 to 96.8% and the precision of this method, as indicated by the relative standard deviations (R.S.D.s) was within the range of 1.04.4%. The limits of detection obtained from calculations by using GCMS results based on S/N: 3 were within the range from 0.08 to 0.01 ng/m3 . The detection limits differ substantially for the various amines determined, but all were below our stated limits of detection. Excellent linearity was obtained in the concentration range of 0.0125 ng/L, with correlation coefcients (R2 ) in the range of 0.99200.9996. 4. Conclusions Consequently, the method described in this study has been shown to be suitable with satisfactory accuracy and good reproducibility for the qualitative and quantitative determination of aliphatic and aromatic amines at the levels of ng/m3 in air samples.

Through the obtained results, it may be concluded that, the method developed can be proposed as a procedure in the monitoring of trace levels of aliphatic and aromatic amines in a variety of environmental samples including indoor air, outdoor air and rainwater to protect human health and the environment because of human exposure to these compounds through diet and inhalation, due to its effective selectivity in isolation, efcient derivatisation and higher sensitivity in comparison to the most of the other methods available. Acknowledgements The author wishes to thank the State Planning Organization of Turkey (2003K121120), and the Zonguldak Karaelmas University (2004-13-02-12) for the opportunity and support to carry out this research. References
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