Chinese Journal of Chromatography ›› 2024, Vol. 42 ›› Issue (3): 296-303.DOI: 10.3724/SP.J.1123.2023.06002
• Technical Notes • Previous Articles Next Articles
YANG Chao1,*(), LIU Jinglong1, XU Xiaojian2, WU Lijuan1, YIN Mingming1, DAI Wei1, HAN Qian1
Received:
2023-06-05
Online:
2024-03-08
Published:
2024-03-19
Supported by:
CLC Number:
YANG Chao, LIU Jinglong, XU Xiaojian, WU Lijuan, YIN Mingming, DAI Wei, HAN Qian. Determination of nine aromatic amines in water by cloud point extraction-gas chromatography-mass spectrometry[J]. Chinese Journal of Chromatography, 2024, 42(3): 296-303.
Add to citation manager EndNote|Ris|BibTeX
URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2023.06002
Compound | Retention time/min | Quantitative ion (m/z) | Qualitative ions (m/z) | Internal standard |
---|---|---|---|---|
2-Chloroaniline (2-氯胺) | 7.122 | 127 | 129, 65 | 4-chloroaniline-d2 |
3-Chloroaniline (3-氯胺) | 8.439 | 127 | 129, 65 | 4-chloroaniline-d2 |
4-Chloroaniline (4-氯胺) | 8.483 | 127 | 129, 65 | 4-chloroaniline-d2 |
2-Nitroaniline (2-硝基苯胺) | 11.561 | 138 | 92, 65 | 4-nitroaniline-d4 |
3-Nitroaniline (3-硝基苯胺) | 12.535 | 138 | 92, 65 | 4-nitroaniline-d4 |
1-Naphthalenamine (1-萘胺) | 12.839 | 143 | 115, 116 | 2-naphthalenamine-d7 |
2-Naphthalenamine (2-萘胺) | 13.006 | 143 | 115, 116 | 2-naphthalenamine-d7 |
4-Nitroaniline (4-硝基苯胺) | 13.964 | 138 | 105 | 4-nitroaniline-d4 |
4-Phenylaniline (4-氨基苯胺) | 15.081 | 169 | 115, 168 | 2-naphthalenamine-d7 |
4-Chloroaniline-d2(4-氯胺-d2) | 8.483 | 131 | 67 | / |
2-Naphthalenamine-d7(2-萘胺-d7) | 13.006 | 150 | 122 | / |
4-Nitroaniline-d4(4-硝基苯胺-d4) | 13.964 | 142 | 112 | / |
Table 1 Retention times and MS parameters for the nine aromatic amines and three internal standards
Compound | Retention time/min | Quantitative ion (m/z) | Qualitative ions (m/z) | Internal standard |
---|---|---|---|---|
2-Chloroaniline (2-氯胺) | 7.122 | 127 | 129, 65 | 4-chloroaniline-d2 |
3-Chloroaniline (3-氯胺) | 8.439 | 127 | 129, 65 | 4-chloroaniline-d2 |
4-Chloroaniline (4-氯胺) | 8.483 | 127 | 129, 65 | 4-chloroaniline-d2 |
2-Nitroaniline (2-硝基苯胺) | 11.561 | 138 | 92, 65 | 4-nitroaniline-d4 |
3-Nitroaniline (3-硝基苯胺) | 12.535 | 138 | 92, 65 | 4-nitroaniline-d4 |
1-Naphthalenamine (1-萘胺) | 12.839 | 143 | 115, 116 | 2-naphthalenamine-d7 |
2-Naphthalenamine (2-萘胺) | 13.006 | 143 | 115, 116 | 2-naphthalenamine-d7 |
4-Nitroaniline (4-硝基苯胺) | 13.964 | 138 | 105 | 4-nitroaniline-d4 |
4-Phenylaniline (4-氨基苯胺) | 15.081 | 169 | 115, 168 | 2-naphthalenamine-d7 |
4-Chloroaniline-d2(4-氯胺-d2) | 8.483 | 131 | 67 | / |
2-Naphthalenamine-d7(2-萘胺-d7) | 13.006 | 150 | 122 | / |
4-Nitroaniline-d4(4-硝基苯胺-d4) | 13.964 | 142 | 112 | / |
Fig. 1 Effects of (a) Triton X-114 mass fraction, (b)inorganic salt type, (c) Na2SO3 amount, (d) equilibration temperature, (e) equilibration time, and (f) type of reverse extractants on the extraction efficiencies of the nine aromatic amines (n=5)
Compound | Linear range/(μg/L) | Linear equation | R2 | LOD/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|
2-Chloroaniline | 5-1000 | y=0.952x+0.205 | 0.9987 | 0.15 | 0.50 |
3-Chloroaniline | 5-1000 | y=0.771x-0.049 | 0.9998 | 0.18 | 0.60 |
4-Chloroaniline | 5-1000 | y=0.673x+0.077 | 0.9982 | 0.17 | 0.57 |
2-Nitroaniline | 10-1000 | y=1.872x+0.342 | 0.9991 | 0.43 | 1.43 |
3-Nitroaniline | 10-1000 | y=1.306x-0.094 | 0.9988 | 0.48 | 1.60 |
4-Nitroaniline | 10-1000 | y=1.163x-0.013 | 0.9984 | 0.47 | 1.57 |
1-Naphthalenamine | 5-1000 | y=0.749x+0.270 | 0.9996 | 0.12 | 0.40 |
2-Naphthalenamine | 5-1000 | y=1.661x+0.193 | 0.9998 | 0.13 | 0.43 |
4-Phenylaniline | 10-1000 | y=0.738x+0.126 | 0.9996 | 0.22 | 0.73 |
Table 2 Linear ranges, linear equations, correlation coefficients (R2), LODs and LOQs of the nine aromatic amines
Compound | Linear range/(μg/L) | Linear equation | R2 | LOD/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|
2-Chloroaniline | 5-1000 | y=0.952x+0.205 | 0.9987 | 0.15 | 0.50 |
3-Chloroaniline | 5-1000 | y=0.771x-0.049 | 0.9998 | 0.18 | 0.60 |
4-Chloroaniline | 5-1000 | y=0.673x+0.077 | 0.9982 | 0.17 | 0.57 |
2-Nitroaniline | 10-1000 | y=1.872x+0.342 | 0.9991 | 0.43 | 1.43 |
3-Nitroaniline | 10-1000 | y=1.306x-0.094 | 0.9988 | 0.48 | 1.60 |
4-Nitroaniline | 10-1000 | y=1.163x-0.013 | 0.9984 | 0.47 | 1.57 |
1-Naphthalenamine | 5-1000 | y=0.749x+0.270 | 0.9996 | 0.12 | 0.40 |
2-Naphthalenamine | 5-1000 | y=1.661x+0.193 | 0.9998 | 0.13 | 0.43 |
4-Phenylaniline | 10-1000 | y=0.738x+0.126 | 0.9996 | 0.22 | 0.73 |
Compound | Spiked level/ (μg/L) | Surface water of drinking water sources | Offshore seawater | Wastewater of the typical printing and dyeing industry | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Recovery/ % | Intra-day RSD/% | Inter-day RSD*/% | Recovery/ % | Intra-day RSD/% | Inter-day RSD*/% | Recovery/ % | Intra-day RSD/% | Inter-day RSD*/% | ||||
2-Chloroaniline | 2.0 | 81.6 | 5.2 | 4.8 | 89.2 | 5.5 | 4.1 | 97.2 | 4.2 | 5.7 | ||
10.0 | 92.0 | 3.1 | 4.7 | 107.9 | 1.5 | 6.4 | 91.0 | 4.7 | 5.2 | |||
3-Chloroaniline | 2.0 | 83.0 | 3.2 | 4.8 | 95.6 | 3.2 | 3.5 | 106.4 | 7.5 | 6.6 | ||
10.0 | 103.9 | 2.1 | 2.6 | 115.8 | 3.7 | 4.9 | 118.2 | 7.7 | 11.3 | |||
4-Chloroaniline | 2.0 | 81.1 | 2.2 | 2.5 | 90.1 | 4.4 | 5.5 | 105.8 | 5.6 | 4.9 | ||
10.0 | 109.8 | 1.9 | 3.3 | 113.0 | 2.0 | 2.7 | 120.0 | 4.8 | 5.3 | |||
2-Nitroaniline | 2.0 | 84.9 | 0.7 | 1.6 | 95.2 | 7.2 | 6.4 | 104.1 | 12.3 | 13.1 | ||
10.0 | 104.8 | 4.7 | 4.7 | 103.1 | 2.7 | 4.7 | 109.6 | 5.1 | 7.5 | |||
3-Nitroaniline | 2.0 | 83.4 | 4.5 | 6.2 | 85.6 | 8.6 | 12.2 | 111.5 | 8.5 | 8.1 | ||
10.0 | 93.4 | 3.8 | 3.5 | 83.0 | 4.2 | 5.5 | 104.2 | 3.0 | 4.0 | |||
4-Nitroaniline | 2.0 | 83.1 | 2.7 | 3.3 | 85.5 | 8.1 | 10.4 | 114.4 | 12.9 | 11.1 | ||
10.0 | 97.0 | 1.2 | 1.8 | 94.0 | 3.6 | 8.6 | 117.3 | 2.9 | 2.5 | |||
1-Naphthalenamine | 2.0 | 93.6 | 1.5 | 2.9 | 94.2 | 2.0 | 3.8 | 99.1 | 9.4 | 10.3 | ||
10.0 | 102.8 | 2.1 | 2.8 | 103.5 | 3.1 | 2.6 | 111.6 | 3.1 | 3.6 | |||
2-Naphthalenamine | 2.0 | 92.7 | 2.2 | 3.5 | 95.1 | 4.2 | 11.6 | 105.6 | 9.5 | 7.7 | ||
10.0 | 89.6 | 3.5 | 6.1 | 86.2 | 3.3 | 2.4 | 98.5 | 4.3 | 5.1 | |||
4-Phenylaniline | 2.0 | 95.9 | 3.3 | 5.0 | 92.3 | 5.1 | 4.7 | 117.3 | 4.6 | 5.2 | ||
10.0 | 91.4 | 1.0 | 3.5 | 91.5 | 4.0 | 7.3 | 99.0 | 4.8 | 2.7 |
Table 3 Spiked recoveries, intra-day and inter-day precisions of the nine aromatic amines in three samples (n=6)
Compound | Spiked level/ (μg/L) | Surface water of drinking water sources | Offshore seawater | Wastewater of the typical printing and dyeing industry | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Recovery/ % | Intra-day RSD/% | Inter-day RSD*/% | Recovery/ % | Intra-day RSD/% | Inter-day RSD*/% | Recovery/ % | Intra-day RSD/% | Inter-day RSD*/% | ||||
2-Chloroaniline | 2.0 | 81.6 | 5.2 | 4.8 | 89.2 | 5.5 | 4.1 | 97.2 | 4.2 | 5.7 | ||
10.0 | 92.0 | 3.1 | 4.7 | 107.9 | 1.5 | 6.4 | 91.0 | 4.7 | 5.2 | |||
3-Chloroaniline | 2.0 | 83.0 | 3.2 | 4.8 | 95.6 | 3.2 | 3.5 | 106.4 | 7.5 | 6.6 | ||
10.0 | 103.9 | 2.1 | 2.6 | 115.8 | 3.7 | 4.9 | 118.2 | 7.7 | 11.3 | |||
4-Chloroaniline | 2.0 | 81.1 | 2.2 | 2.5 | 90.1 | 4.4 | 5.5 | 105.8 | 5.6 | 4.9 | ||
10.0 | 109.8 | 1.9 | 3.3 | 113.0 | 2.0 | 2.7 | 120.0 | 4.8 | 5.3 | |||
2-Nitroaniline | 2.0 | 84.9 | 0.7 | 1.6 | 95.2 | 7.2 | 6.4 | 104.1 | 12.3 | 13.1 | ||
10.0 | 104.8 | 4.7 | 4.7 | 103.1 | 2.7 | 4.7 | 109.6 | 5.1 | 7.5 | |||
3-Nitroaniline | 2.0 | 83.4 | 4.5 | 6.2 | 85.6 | 8.6 | 12.2 | 111.5 | 8.5 | 8.1 | ||
10.0 | 93.4 | 3.8 | 3.5 | 83.0 | 4.2 | 5.5 | 104.2 | 3.0 | 4.0 | |||
4-Nitroaniline | 2.0 | 83.1 | 2.7 | 3.3 | 85.5 | 8.1 | 10.4 | 114.4 | 12.9 | 11.1 | ||
10.0 | 97.0 | 1.2 | 1.8 | 94.0 | 3.6 | 8.6 | 117.3 | 2.9 | 2.5 | |||
1-Naphthalenamine | 2.0 | 93.6 | 1.5 | 2.9 | 94.2 | 2.0 | 3.8 | 99.1 | 9.4 | 10.3 | ||
10.0 | 102.8 | 2.1 | 2.8 | 103.5 | 3.1 | 2.6 | 111.6 | 3.1 | 3.6 | |||
2-Naphthalenamine | 2.0 | 92.7 | 2.2 | 3.5 | 95.1 | 4.2 | 11.6 | 105.6 | 9.5 | 7.7 | ||
10.0 | 89.6 | 3.5 | 6.1 | 86.2 | 3.3 | 2.4 | 98.5 | 4.3 | 5.1 | |||
4-Phenylaniline | 2.0 | 95.9 | 3.3 | 5.0 | 92.3 | 5.1 | 4.7 | 117.3 | 4.6 | 5.2 | ||
10.0 | 91.4 | 1.0 | 3.5 | 91.5 | 4.0 | 7.3 | 99.0 | 4.8 | 2.7 |
Method | Sample volume/ mL | LODs/(μg/L) | Recoveries/ % | Ref. | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
2-Chloro- aniline | 3-Chloro- aniline | 4-Chloro- aniline | 2-Nitro- aniline | 3-Nitro- aniline | 4-Nitro- aniline | 1-Naphth- alenamine | 2-Naphth- alenamine | 4-Phenyl- aniline | ||||
CPE-GC-MS | 10 | 0.15 | 0.18 | 0.17 | 0.43 | 0.48 | 0.47 | 0.12 | 0.13 | 0.22 | 81.1-120.0 | this work |
CPE-UV-Vis | 10 | / | / | / | 50 | 80 | 60 | / | / | / | 98.6-115.0 | [ |
CPE-LC | 15 | / | / | / | 2 | 5 | 13 | / | / | / | 80.5-109.3 | [ |
DLLME-LC | 2 | / | / | / | 0.3 | / | 0.5 | / | / | / | 87.6-101.8 | [ |
SPE-LC | 1000 | / | / | / | / | / | 0.5 | / | / | / | 72.2-96.1 | [ |
LLE-GC-MS | 1000 | 0.045 | 0.022 | 0.035 | 0.013 | 0.046 | 0.035 | / | / | / | 80.44-98.79 | [ |
DLLME-LLE-GC-MS | 150 | / | / | 0.05 | / | / | / | / | 0.05 | / | 75.6-115.1 | [ |
DLLME-GC-MS | 5 | 0.3 | / | / | 1.5 | / | / | / | / | / | 94.7-106 | [ |
Table 4 Comparison of analytical methods for aromatic amines in water
Method | Sample volume/ mL | LODs/(μg/L) | Recoveries/ % | Ref. | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
2-Chloro- aniline | 3-Chloro- aniline | 4-Chloro- aniline | 2-Nitro- aniline | 3-Nitro- aniline | 4-Nitro- aniline | 1-Naphth- alenamine | 2-Naphth- alenamine | 4-Phenyl- aniline | ||||
CPE-GC-MS | 10 | 0.15 | 0.18 | 0.17 | 0.43 | 0.48 | 0.47 | 0.12 | 0.13 | 0.22 | 81.1-120.0 | this work |
CPE-UV-Vis | 10 | / | / | / | 50 | 80 | 60 | / | / | / | 98.6-115.0 | [ |
CPE-LC | 15 | / | / | / | 2 | 5 | 13 | / | / | / | 80.5-109.3 | [ |
DLLME-LC | 2 | / | / | / | 0.3 | / | 0.5 | / | / | / | 87.6-101.8 | [ |
SPE-LC | 1000 | / | / | / | / | / | 0.5 | / | / | / | 72.2-96.1 | [ |
LLE-GC-MS | 1000 | 0.045 | 0.022 | 0.035 | 0.013 | 0.046 | 0.035 | / | / | / | 80.44-98.79 | [ |
DLLME-LLE-GC-MS | 150 | / | / | 0.05 | / | / | / | / | 0.05 | / | 75.6-115.1 | [ |
DLLME-GC-MS | 5 | 0.3 | / | / | 1.5 | / | / | / | / | / | 94.7-106 | [ |
Fig. 2 Chromatograms of wastewater of the printing and dyeing industry (a)before and (b) after spiking (100 μg/L) Peak identifications: 1. 2-chloroaniline; 2. 3-chloroaniline; 3. 4-chloroaniline-d2; 4. 4-chloroaniline; 5. 2-nitroaniline; 6. 3-nitroaniline; 7. 1-naphthalenamine; 8. 2-naphthalenamine-d7; 9. 2-naphthalenamine; 10. 4-nitroaniline-d4; 11.4-nitroaniline; 12. 4-phenylaniline.
|
Viewed | ||||||
Full text |
|
|||||
Abstract |
|
|||||