Allergenic Fragrances Analysis in Brazilian Perfumes by Headspace Solid Phase Microextraction and Gas Chromatography-Mass Detector (HS-SPME-GC-MS)

Gomes, Clêrton L.; Lima, Ari C. A. de; Barbosa, Pablo G. A.; Costa, Rouse S.; Melo, Diego Q.; Nascimento, Ronaldo F.

doi:10.21577/0103-5053.20170062

Clêrton L. Gomes

Departamento de Química Analítica e Físico-Química, bloco 940, Centro de Ciências, Universidade Federal do Ceará, Campus do Pici, 60440-900 Fortaleza-CE, Brazil

Instituto Federal de Educação, Ciência e Tecnologia do Ceará, Campus Aracati, 62800-000 Aracati-CE, Brazil

Ari C. A. de Lima

Departamento de Engenharia Hidráulica e Ambiental, Bloco 713, Centro de Tecnologia, Universidade Federal do Ceará, Campus do Pici, 60440-900 Fortaleza-CE, Brazil

Pablo G. A. Barbosa

Departamento de Química Analítica e Físico-Química, bloco 940, Centro de Ciências, Universidade Federal do Ceará, Campus do Pici, 60440-900 Fortaleza-CE, Brazil

Rouse S. Costa

Departamento de Química Analítica e Físico-Química, bloco 940, Centro de Ciências, Universidade Federal do Ceará, Campus do Pici, 60440-900 Fortaleza-CE, Brazil

Diego Q. Melo

Instituto Federal de Educação, Ciência e Tecnologia do Sertão Pernambucano, Campus Petrolina, 56314-520 Petrolina-PE, Brazil

Ronaldo F. Nascimento ^** e-mail: ronaldo@ufc.br

Departamento de Química Analítica e Físico-Química, bloco 940, Centro de Ciências, Universidade Federal do Ceará, Campus do Pici, 60440-900 Fortaleza-CE, Brazil

* e-mail: ronaldo@ufc.br

Perfume	Type	Brand
PA 1-10	original	A
PB 1-5	original	B
PSA 1-10	similar	A

Compound	Retention time / min	Identification (m/z)	Quantification (m/z)
Linalool	10.75	41; 43; 71	41; 43; 71
Methyl 2-octynoate	12.25	67; 95	95
Citrolellol	12.59	41; 67; 69	41; 67; 69
Citral	12.8	84; 94	84; 94
	13.1	84; 94	84; 94
Geraniol	12.9	41; 69	41; 69
Cinnamaldehyde	13.15	77; 131	131
Hydroxycitronellal	12.75	59; 95	59
Anisyl alcohol	12.6	138; 109	138
Cinnamic alcohol	15.25	91; 92	91
Eugenol	13.2	103	103
Isoeuegenol	14.09	164	164
Coumarin	15.6	89; 118; 146	89; 118; 146
α-Isomethylioneno	15.25	107; 135; 150	107; 135; 150
Lilial®	15.64	131; 189	131; 189
Amylcinnamaldehyde	16.67	91; 115; 117	91; 115; 117
Lyral®	15.25	59; 79	79
Amylcinnamic alcohol	16.98	91; 115; 133	133
Farnesol	17.1	69; 93	69; 93
	17.25
Hexylcinnamic aldehyde	17.55	129	129
Benzyl salicylate	18.75	65; 91	91
Benzyl cinnamate	21.00	77; 91; 131	77; 91; 131

Compound	Linear equation	Correlation coefficient	Number of points of curve
Linalool	y = 20630x + 146779	0.995	5
Methyl 2-octynoate	y = 70166x - 67715	0.993	5
Citronellol	y = 67374x + 123450	0.995	5
Citral	y = 49185x - 67703	0.996	6
Geraniol	y = 3064.5x - 6021.9	0.996	5
Cinnamaldehyde	y = 966.41x + 1917.2	0.995	5
Hydroxycitronellal	y = 1577.1x - 1289.7	0.995	5
Anisyl alcohol	y = 18865x - 56292	0.999	5
Cinnamic alcohol	y = 1628x - 2761.9	0.997	5
Eugenol	y = 2702.7x - 2161.7	0.997	6
Isoeugenol	y = 50028x - 111773	0.996	5
Coumarin	y = 142109x - 358103	0.995	7
α-Isomethylioneno	y = 4379.2x - 7989.7	0.995	5
Lilial®	y = 128994x - 251554	0.995	5
Amylcinnamaldehyde	y = 5565x - 14563	0.995	5
Lyral®	y = 2172.9x - 947.43	0.995	5
Amylcinnamic alcohol	y = 4608.5x - 3574.6	0.996	7
Farnesol	y = 11347x - 26483	0.997	5
Hexylcinnamic aldehyde	y = 14622x - 21988	0.996	5
Benzyl salicylate	y = 70670x - 28904	0.999	6
Benzyl cinnamate	y = 1787.8x - 2566.9	0.995	5

Compound	S_a	t _calc,A	S_b	t _calc,B	Df	t _Df;95%	t test	Corrected calibration curve
Linalool	1167.4	17.67	35984.3	4.08	3	3.18	t_calc,A > t_crit t_calc,B > t_crit	y = 20630x +146779
Methyl 2-octynoate	737.3	14.40	22904.9	2.27	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 70166x
Citrolellol	3848.9	18.23	102211.3	0.66	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 67374x
Citral	6.6 × 10-7	4513155	1.4	1.17	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 49185x
Geraniol	1997.1	24.63	56743.10	1.19	5	2.57	t_calc,A > t_crit t_calc,B < t_crit	y = 3064.5x
Cinnamaldehyde	1.6 × 10^-5	193689.8	1.3	1.62	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 966.41x
Hydroxycitronellal	53.0	18.20	1564.9	1.22	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 1577.1x
Anisyl alcohol	7.9	198.57	256.6	2.03	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 18865x
Cinnamic alcohol	849.0	22.22	21646.7	2.60	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 1628x
Eugenol	76.1	21.39	2055.7	1.34	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 2702.7x
Isoeuegenol	1.6 × 10^-5	183659.1	2.00	0.77	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 50028x
Coumarin	3478.0	14.38	93984.1	1.19	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 142109x
α-Isomethylioneno	4.2 × 10^-7	7163847	1.4	1.95	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 4379.2x
Lilial®	271.8	16.10	6929.9	1.15	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 128994x
Amylcinnamaldehyde	7364.2	17.52	198996.5	1.26	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 5565x
Lyral®	1.3 × 10^-5	290242.3	1.37	2.08	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 2172.9x
Amylcinnamic alcohol	81.6	26.61	2399.2	0.39	5	2.57	t_calc,A > t_crit t_calc,B > t_crit	y = 4608.5x
Farnesol	7.6 × 10^-6	391873.2	1.04	0.86	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 11347x
Hexylcinnamic aldehyde	4.0 × 10^-6	758154.8	1.27	1.98	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 14622x
Benzyl salicylate	3.4 × 10^-6	891759.7	1.33	1.47	4	2.78	t_calc,A > t_crit t_calc,B < t_crit	y = 70670x
Benzyl cinnamate	101.7	17.57	2812.3	0.91	3	3.18	t_calc,A > t_crit t_calc,B < t_crit	y = 1787.8x

Compound	LOD / (µg L^-1)	LOQ / (µg L^-1)
Linalool	0.074	0.247
Methyl 2-octynoate	0.043	0.142
Citronellol	0.008	0.027
Citral	0.017	0.057
Geraniol	0.040	0.135
Cinnamaldehyde	0.245	0.878
Hydroxycitronellal	0.239	0.797
Anisyl alcohol	0.712	0.234
Cinnamic alcohol	0.043	0.143
Eugenol	0.270	0.900
Isoeugenol	0.064	0.215
Coumarin	0.202	0.674
α-Isomethylioneno	0.201	0.670
Lilial®	0.101	0.338
Amylcinnamaldehyde	0.005	0.017
Lyral®	0.243	0.810
Amylcinnamic alcohol	0.252	0.840
Farnesol	0.074	0.248
Hexylcinnamic aldehyde	0.211	0.702
Benzyl salicylate	0.271	0.904
Benzyl cinnamate	0.210	0.701

Compound	Intermediate precision			Repeatability
Compound	1 µg L^-1 (n = 3)	10 µg L^-1 (n = 3)	30 µg L^-1 (n = 3)	30 µg L^-1 (n = 6)
Linalool	4.4 (6.4)^a a Intermediate precision 5 µg L-1 (N = 5);17	2.6 (12)^b b intermediate precision 10 µg L-1 (N = 5);17	19.3 (4.6)^c c intermediate precision 20 µg L-1 (N = 5);17	16.3 (1)^d d repeatability 20 µg L-1 (N = 3).17
Methyl 2-octynoate	9.7 (8.6)^a a Intermediate precision 5 µg L-1 (N = 5);17	6.9 (12)^b b intermediate precision 10 µg L-1 (N = 5);17	13.6 (8.6)^c c intermediate precision 20 µg L-1 (N = 5);17	8.6 (1)^d d repeatability 20 µg L-1 (N = 3).17
Citronellol	1.6 (8.7)^a a Intermediate precision 5 µg L-1 (N = 5);17	3.1 (7.9)^b b intermediate precision 10 µg L-1 (N = 5);17	10.2 (6.5)^c c intermediate precision 20 µg L-1 (N = 5);17	14.0 (9.6)^d d repeatability 20 µg L-1 (N = 3).17
Citral	8.2 (1.2)^a a Intermediate precision 5 µg L-1 (N = 5);17	6.2 (3.4)^b b intermediate precision 10 µg L-1 (N = 5);17	10.9 (2.9)^c c intermediate precision 20 µg L-1 (N = 5);17	15.6 (0.8)^d d repeatability 20 µg L-1 (N = 3).17
Geraniol	14.9 (6.6)^a a Intermediate precision 5 µg L-1 (N = 5);17	8.3 (5.3)^b b intermediate precision 10 µg L-1 (N = 5);17	13.3 (2.5)^c c intermediate precision 20 µg L-1 (N = 5);17	13.9 (0.6)^d d repeatability 20 µg L-1 (N = 3).17
Cinnamaldehyde	13.3 (7.7)^a a Intermediate precision 5 µg L-1 (N = 5);17	5.6 (12)^b b intermediate precision 10 µg L-1 (N = 5);17	7.5 (4.3)^c c intermediate precision 20 µg L-1 (N = 5);17	13.0 (1)^d d repeatability 20 µg L-1 (N = 3).17
Hydroxycitronellal	15.3 (4.3)^a a Intermediate precision 5 µg L-1 (N = 5);17	4.1 (11)^b b intermediate precision 10 µg L-1 (N = 5);17	16.4 (3.7)^c c intermediate precision 20 µg L-1 (N = 5);17	15.2 (3.6)^d d repeatability 20 µg L-1 (N = 3).17
Anisyl alcohol	15.8 (3.6)^a a Intermediate precision 5 µg L-1 (N = 5);17	11.9 (11)^b b intermediate precision 10 µg L-1 (N = 5);17	18.4 (6.0)^c c intermediate precision 20 µg L-1 (N = 5);17	15.4 (7.1)^d d repeatability 20 µg L-1 (N = 3).17
Cinnamic alcohol	4.4 (5.3)^a a Intermediate precision 5 µg L-1 (N = 5);17	5.7 (5.4)^b b intermediate precision 10 µg L-1 (N = 5);17	10.9 (7.5)^c c intermediate precision 20 µg L-1 (N = 5);17	16.2 (5.9)^d d repeatability 20 µg L-1 (N = 3).17
Eugenol	15.4 (6.5)^a a Intermediate precision 5 µg L-1 (N = 5);17	10.7 (6.6)^b b intermediate precision 10 µg L-1 (N = 5);17	4.8 (3.9)^c c intermediate precision 20 µg L-1 (N = 5);17	15.7 (2.8)^d d repeatability 20 µg L-1 (N = 3).17
Isoeugenol	6.6 (6.3)^a a Intermediate precision 5 µg L-1 (N = 5);17	13.9 (0.6)^b b intermediate precision 10 µg L-1 (N = 5);17	3.7 (2.4)^c c intermediate precision 20 µg L-1 (N = 5);17	6.7 (3)^d d repeatability 20 µg L-1 (N = 3).17
Coumarin	6.5 (7.1)^a a Intermediate precision 5 µg L-1 (N = 5);17	13.5 (7.7)^b b intermediate precision 10 µg L-1 (N = 5);17	9.8 (3.7)^c c intermediate precision 20 µg L-1 (N = 5);17	17.5 (4.3)^d d repeatability 20 µg L-1 (N = 3).17
α-Isomethylioneno	3.1 (7.0)^a a Intermediate precision 5 µg L-1 (N = 5);17	5.4 (2.5)^b b intermediate precision 10 µg L-1 (N = 5);17	11.2 (0.8)^c c intermediate precision 20 µg L-1 (N = 5);17	13.8 (0.9)^d d repeatability 20 µg L-1 (N = 3).17
Lilial®	3.0 (4.8)^a a Intermediate precision 5 µg L-1 (N = 5);17	11.3 (4.8)^b b intermediate precision 10 µg L-1 (N = 5);17	8.7 (3.0)^c c intermediate precision 20 µg L-1 (N = 5);17	16.3 (1.6)^d d repeatability 20 µg L-1 (N = 3).17
Amylcinnamaldehyde	9.5 (4.6)^a a Intermediate precision 5 µg L-1 (N = 5);17	16.9 (8.9)^b b intermediate precision 10 µg L-1 (N = 5);17	6.3 (3.7)^c c intermediate precision 20 µg L-1 (N = 5);17	19.7 (2.5)^d d repeatability 20 µg L-1 (N = 3).17
Lyral®	18.0 (11)^a a Intermediate precision 5 µg L-1 (N = 5);17	7.4 (17)^b b intermediate precision 10 µg L-1 (N = 5);17	12.5 (3.2)^c c intermediate precision 20 µg L-1 (N = 5);17	8.9 (1.4)^d d repeatability 20 µg L-1 (N = 3).17
Amylcinnamic alcohol	14.3 (5.9)^a a Intermediate precision 5 µg L-1 (N = 5);17	11.4 (5.5)^b b intermediate precision 10 µg L-1 (N = 5);17	15.5 (4.3)^c c intermediate precision 20 µg L-1 (N = 5);17	14.4 (0.8)^d d repeatability 20 µg L-1 (N = 3).17
Farnesol	10.2 (7.1)^a a Intermediate precision 5 µg L-1 (N = 5);17	11.2 (6.3)^b b intermediate precision 10 µg L-1 (N = 5);17	13.9 (1.9)^c c intermediate precision 20 µg L-1 (N = 5);17	16.8 (1.4)^d d repeatability 20 µg L-1 (N = 3).17
Hexylcinnamic aldehyde	3.6 (4.0)^a a Intermediate precision 5 µg L-1 (N = 5);17	5.9 (8.8)^b b intermediate precision 10 µg L-1 (N = 5);17	13.2 (3.3)^c c intermediate precision 20 µg L-1 (N = 5);17	16.1 (2.5)^d d repeatability 20 µg L-1 (N = 3).17
Benzyl salicylate	16.8 (11)^a a Intermediate precision 5 µg L-1 (N = 5);17	17.9 (3.2)^b b intermediate precision 10 µg L-1 (N = 5);17	7.3 (9.2)^c c intermediate precision 20 µg L-1 (N = 5);17	15.6 (7.6)^d d repeatability 20 µg L-1 (N = 3).17
Benzyl cinnamate	13.6 (12)^a a Intermediate precision 5 µg L-1 (N = 5);17	12.0 (15)^b b intermediate precision 10 µg L-1 (N = 5);17	12.8 (5.3)^c c intermediate precision 20 µg L-1 (N = 5);17	19.2 (6.8)^d d repeatability 20 µg L-1 (N = 3).17

Compound	Recovery (RSD) / %
Compound	5 µg L^-1 (n = 3)	10 µg L^-1 (n = 3)	30 µg L^-1 (n = 3)
Linallol	70 ± 13.1	111 ± 8.3	75 ± 8.4
Methyl 2-octynoate	72 ± 11.3	88 ± 4.9	92 ± 5.7
Citronellol	90 ± 5.8	80 ± 11.5	107 ± 6.3
Citral	70 ± 6.7	88 ± 7.4	98 ± 9.7
Geraniol	86 ± 8.4	73 ± 13.6	76 ± 6.2
Cinnamaldehyde	83 ± 7.9	77 ± 10.5	94 ± 8.2
Hydroxycitronellal	69 ± 7.5	87 ± 9.1	105 ± 6.6
Anisyl alcohol	78 ± 12.1	86 ± 7.2	82 ± 12.4
Ainnamic alcohol	86 ± 8.7	59 ± 4.5	66 ± 10.3
Eugenol	78 ± 9.5	76 ±5.7	103 ± 8.1
Isoeugenol	89 ± 13.2	82 ± 4.8	110 ± 4.8
Coumarin	103 ± 7.1	94 ± 6.9	88 ± 12.9
α-Isomethylioneno	73 ± 4.9	113 ± 4.2	109 ± 8.4
Lilial®	87 ± 7.7	66 ± 11.2	89 ± 3.9
Amylcinnamaldehyde	86 ± 9.4	114 ± 8.2	101 ± 11.9
Lyral®	72 ± 6.9	115 ± 9.0	112 ± 7.9
Amylcinnamic alcohol	81 ± 4.7	90 ± 6.6	87 ± 7.4
Farnesol	80 ± 7.3	111 ± 8.9	78 ± 4.9
Hexylcinnamic aldehyde	92 ± 5.9	85 ± 5.4	98 ± 9.6
Benzyl salicylate	71 ± 8.7	93 ± 8.5	102 ± 5.3
Benzyl cinnamate	103 ± 6.8	99 ± 10.1	88 ± 8.1

Sample

Concentration / (mg L^-1)

Linalool

Methyl
2-octynoate

Citronellol

Citral

Geraniol

Cinnamaldehyde

Hydroxy
citronellal

Anisyl
alcohol

Cinnamic
alcohol

Eugenol

Isoeugenol

Coumarin

PA1

< LOD

58.9

< LOD

31.5

< LOD

16.2

22.2

28.2

< LOD

PA2

50.2

< LOD

8.6

19.8

60.5

< LOD

21

PA3

30.9

< LOD

12.3

82.5

< LOD

15.2

< LOD

13.7

25.6

47.9

PA4

8.8

< LOD

7.4

< LOD

11

< LOD

9.0

< LOD

19.1

< LOD

13.5

PA5

41.6

< LOD

9.9

52.1

8.9

< LOD

9.0

182.5

24.8

81.1

PA6

42.1

< LOD

42.1

77.8

< LOD

32.9

< LOD

42.9

PA7

14.1

< LOD

9.1

< LOD

1.1

2.1

25.9

< LOD

PA8

11.5

< LOD

19

42.4

1.9

13

< LOD

9.1

66.5

10.3

PA9

< LOD

4.7

1.4

22

38.7

< LOD

PA10

12.7

< LOD

5.5

7.0

22.2

1.3

34.2

< LOD

PB1

46.4

< LOD

8.7

10

77.4

1.7

11.7

< LOD

PB2

< LOD

19.8

6.0

46.5

< LOD

7.0

< LOD

12.3

< LOD

41.7

PB3

35.4

< LOD

13.7

1.1

21.3

< LOD

11

< LOD

PB4

30.0

< LOD

11.2

8.3

31

6.3

9.0

< LOD

10.4

< LOD

PB5

36.3

< LOD

17.2

86.5

1.6

14.1

< LOD

13.5

19

< LOD

34.5

PSA1

31.4

< LOD

6.7

8.2

56.5

< LOD

1.2

1.4

< LOD

PSA2

14.7

< LOD

8.0

3.5

28.2

< LOD

PSA3

< LOD

1.0

1.4

19.2

< LOD

1.3

< LOD

1.3

5.6

PSA4

< LOD

10.6

< LOD

23.4

< LOD

1.9

1.1

0.0

PSA5

17.7

< LOD

13.7

< LOD

2.0

< LOD

1.8

PSA6

2.2

< LOD

46.8

< LOD

10.6

< LOD

8.3

< LOD

PSA7

17.6

< LOD

PSA8

34.9

< LOD

7.2

34.0

< LOD

1.6

< LOD

PSA9

12.6

< LOD

19.2

< LOD

2.6

< LOD

2.3

< LOD

PSA10

8.4

< LOD

6.6

< LOD

28.8

< LOD

1.7

< LOD

Sample

Concentration / (mg L^-1)

α-Isomethyl
ioneno

Lilial®

Amylcinnamaldehyde

Lyral®

Amylcinnamic alcohol

Farnesol

Hexylcinnamic aldehyde

Benzyl
salicylate

Benzyl
cinnamate

PA1

36.1

164.7

< LOD

31.0

< LOD

30.7

< LOD

PA2

< LOD

39.1

< LOD

PA3

< LOD

128.5

< LOD

16.6

< LOD

31.1

< LOD

7.1

< LOD

PA4

< LOD

7.0

< LOD

8.2

12.6

1.3

< LOD

PA5

32.7

162.8

< LOD

29.9

< LOD

PA6

1.5

76.1

< LOD

22.1

< LOD

16.4

2.3

< LOD

PA7

< LOD

43.5

< LOD

2.4

34.6

< LOD

37.4

< LOD

PA8

< LOD

15.0

< LOD

2.6

< LOD

PA9

< LOD

9.4

< LOD

12.9

14.9

< LOD

3.2

55.7

< LOD

PA10

< LOD

PB1

13.1

106.6

< LOD

11.3

8.3

< LOD

190

< LOD

PB2

17.4

51.2

< LOD

26.5

14.1

< LOD

1.6

14.2

< LOD

PB3

9.4

48.8

< LOD

9.1

< LOD

3.3

< LOD

PB4

11.2

46.4

< LOD

12.6

7.5

< LOD

30.1

< LOD

PB5

< LOD

8.7

< LOD

12.5

< LOD

12.8

< LOD

PSA1

3.0

3.5

< LOD

PSA2

1.5

2.6

< LOD

PSA3

< LOD

8.8

< LOD

PSA4

2.3

22.7

< LOD

PSA5

< LOD

9.6

< LOD

PSA6

< LOD

6.9

< LOD

PSA7

< LOD

1.9

< LOD

PSA8

< LOD

PSA9

2.8

4.7

< LOD

PSA10

< LOD

4.7

< LOD

[1] * e-mail: ronaldo@ufc.br

Injector temperature / ºC	240
Mode	SIM
Split	1/30
Transfer line temperature / ºC	280
Ion source temperature / ºC	220
Temperature programming	45 ºC, hold 2 min; 8 ºC min-1 to 100 ºC; 15 ºC min-1 to 150 ºC; 20 ºC min-1 to 200 ºC; 8 ºC min-1 to 240 ºC, hold 5 min. Total time 24.50 min
Cutting time / min	5.5

time / min	Fragments
5.50-9.42	68; 67; 93; 79; 108 and 77
9.42-10.83	71; 43 and 41
10.83-18.97	41; 95; 67; 69; 44; 68; 84; 131; 103; 132; 59; 43; 71; 92; 91; 78; 164; 149; 118; 146; 89; 77; 135; 107; 150; 189; 147; 115; 129; 117; 104; 79; 93; 133; 105; 65; 138; 109 and 94
18.97-24.50	91; 131 and 77

Brasil

Brasil

Allergenic Fragrances Analysis in Brazilian Perfumes by Headspace Solid Phase Microextraction and Gas Chromatography-Mass Detector (HS-SPME-GC-MS)