J. Agric. FoodChem. 1001, 39, 1658-1666
1658
Solid-Phase Extraction Cleanup of Halogenated Organic Pesticides Ruei-Ching Hsu,’ Inge Biggs, and Nirmal K. Saini Chemistry Laboratory Services, California Department of Food and Agriculture, 3292 Meadowview Road, Sacramento, California 95832 This study investigated the potential of solid-phase extraction (SPE) cartridges as replacements for Attagel in the cleanup procedure of halogenated organic pesticides in raw agricultural crops. Four commodities, broccoli, carrot, celery, and orange, were fortified with a total of 44 pesticides. Pesticides were analyzed by gas chromatography (GC) with electron capture detection (ECD). Cleanup with either Cl8 or Florisil SPE showed recoveries comparable to or better than that obtained by Attagel in most cases. Both CISand Florisil SPES showed significant differences in recoveries compared to that of Attagel.
Sincetheir introduction in the mid 1970s,SPE cartridges The current California Department of Food and Agriculture (CDFA) multiresidue method (Joe, 1988) for have been reported to separate organochlorine pesticides screening of halogenated organic pesticides in raw agriin sewage sludge samples (Anon., 1989),in seafoodsamples cultural crops includes an Attagel cleanup of the final (Kohler and SU, 19g6), in waters (Sherma, iggg), in benzene solution followed by GC-ECD and electrolytic sediment and fish (Marble and Delfino, lggg), and in conductivity detection (ELCD). Due to the nonspecific samples ( ~ ~ ~et al., ~ 1989). ~ - N~~ nature of electron capture detection and the low residue comprehensive data are available on the cleanup of raw levels involved, matrix interference was evident in some agricultural crops for the determination of halogenated of the commodities. Therefore, cleanup methods have the pesticides. This study was conducted to been sought to substitute Attagel and benzene to minimize SPE cleanup in the routine PossibilitY of matrix interference and adsorption of pesticides on Attscreening method* age1and to eliminate the usage of the suspected carcinogen Only Cl8 and Florisil SPE cartridges (J.T. Baker Chembenzene. Table I. Fortification Level and GC Retention Time ( h )of Halogenated Pesticides fortn level, ppm
tR,
fortn level, ppm
min
dichlobenil ethalfluralin lindane
0.2 0.2 0.2
Fortification 1 1.59 p,p’-DDE 2.31 p,p’-DDD 5.71
trifluralin
0.2 0.2 0.2
2.31 5.28 6.9
10.83 12.27
0.2 0.2 0.2
10.04 12.28 13.50
0.2 0.2
9.13 11.78
Fortification 4 o,p‘-DDD iprodione bifenox permethrin
0.2 0.8 0.2 0.8
fenvalerate
1.0
9.90 12.73 14.20 15.73 15.96 20.15 20.92
DCNA
heptachlor
0.2 0.2 0.2
benefin profluralin, dichlone triadimefon o,p’-DDE dieldrin
0.2 0.2 0.4 0.8 0.2 0.2
2.11 3.00 5.45 6.85 8.58 9.27
vinclozolin pronamide
Fortification 5 oxadiazon folpet ethylan methoxychlor tetradifon Fortification 6O alachlor 0.4 7.37 nitrofen ani1azine 1.0 9.41 chlorobenzilate oxyfluorfen 0.2 11.52 p,p’-DDT o,p’-DDT 0.2 13.57 @Retentiontimes were obtained from a 25-mmethyl silicone capillary column. 0021-8561/Q1/143Q-1658$02.50/0 0 1991 Amerlcen Chemlcal Society sulfallate chlorothalonil aldrin o,p’-dicofol p,p’-dicofol
0.2 0.4 0.2 0.8 0.8
4.88 6.80 7.51 8.34 8.85
min
0.2 0.2
Fortification 2 endosulfan I endosulfan I1 endosulfan I11 Fortification 3 4.93 heptachlor epoxide 5.46 endrin 6.61
PCNB
tR,
0.4 1.6 0.8 0.8 0.4
10.66 11.25 11.71 15.25 15.55
0.2 1.0 0.2
12.18 12.84 15.19
~
i
l
J. Agric. FoodChem., Vol.
SPE Cleanup of Halogenated Pestlcldes
39,No. 9, 1991 1859
D A
3
20
19
4
I
I 5
1
!1
22
J[
21
(Time 29 minutes) (Time 29 minutes) 7
B 9
34
11
E
29 37
6
L
33
(Time 29 minutes)
20
C
J
d (Time 29 minutes)
20
14
_1
15
42 44 40 4 3 4 1
I
(Time 29 minutes)
(Time 29 minutes)
Figure 1. GC profiles of fortification standards. Column: 50% phenyl/methyl silicone, 30 m X 0.25 mm, 0.25-rm film thickneea. Oven: 160 OC for 1 min, 160-270 OC at 6 OC/min, hold 10 min. Injector: 220 OC. Detector: ECD 350 OC. Peaks: 1, dichlobenil; 2, ethalfluralin; 3, lindane; 4, p,p‘-DDE 5, p,p’-DDD; 6, trifluralin; 7, PCNB; 8, vinclozolin; 9, endosulfan I; 10, endosulfan 11; 11, endosulfan 111; 12, pronamide; 13, DCNA; 14, heptachlor; 15, heptachlor epoxide; 16, endrin; 17, benefin; 18, profluralin; 19, dichlone; 20, triadimefon; 21, o,p’-DDE; 22, dieldrin; 23, o,p’-DDD; 24, iprodione; 25, bifenox; 26, permethrin; 27, fenvalerate; 28, sulfallate; 29, chlorothalonil; 30, aldrin; 31, o,p’-dicofol; 32, p,p’-dicofol; 33, oxadiazon; 34, folpet; 35, ethylan; 36, methoxychlor; 37, tetradifon; 38, alachlor; 39, anilazine; 40, oxyfluorfen; 41, o,p’-DDT; 42, nitrofen; 43, chlorobenzilate; 44, p,p’-DDT.
Hsu et al.
1660 J. Agrtc. FoodChsm., Vol. 39, No. 9, 1991
I B
A
I
(Time 29 minutes)
(Time 29 minutes)
C
I
(Time 29 minutes)
D
I
(Time 29 minutes)
Figure 2. GC profiles of broccoli: (A) matrix blank; (B) with Attagel; (C)with Florisil SPE;(D)with Cl8 SPE. Asterisks indicate an extraneous peak, which appeared in one batch of cartridges only. Table 11. Recoveries of Pesticides and CV in Broccoli Cl8 Florisil Attagel x CV.% x CV.% x CV.% 1.7 62 8.2 108 59 16.0 dichlobenil 5.8 124 1.9 112 108 0.2 ethalfluralin 2.5 118 2.3 108 111 1.5 lindane 1.5 122 1.6 4.4 103 117 p,p’-DDE 2.3 129 3.1 111 122 4.4 p,p’-DDD 27.3 60 65 10.3 121 7.4 trifluralin 21.6 66 59 10.2 113 7.7 PCNB 110 4.9 77 11.1 124 5.4 vinclozolin 4.7 112 94 4.9 124 5.5 endosulfan I 123 2.6 90 4.8 125 7.0 endosulfan I1 125 2.3 77 8.3 130 5.6 endosulfan 111 2.6 97 96 1.3 118 2.4 pronamide 93 3.4 92 3.1 113 4.5 DCNA 12.2 72 81 18.3 115 0.9 heptachlor 2.1 95 3.6 115 0.4 heptachlor epoxide 104 1.0 104 111 1.7 121 0.2 endrin 0.9 99 91 4.7 119 1.0 benefin 0.6 98 105 3.3 108 1.5 profluralin 0 0 0 dichlone 4.2 0.6 97 97 7.7 135 triadimefon 1.1 102 1.3 100 104 1.0 o,p’-DDE 0.5 0.4 100 108 1.7 108 dieldrin
o,p’-DDD iprodione bifenox permethrin fenvalerate sulfallate chlorothalonil aldrin o,p’-dicofol p,p’-dicofol oxadiazon folpet ethylan methoxychlor tetradifon alachlor anilazine oxytluorfen o,p’-DDT nitrofen chlorobenzilate p,p’-DDT
ical Co., 1982;1984;Zief and Kiser, 1990)were evaluated for the cleanup of crop matrices extracted according to the CDFA method. Cleanup with Attagel was also included for comparison. Four commodities and 44
pesticides were tested for this study (see Table I). The commodities were carrot, broccoli, celery, and orange, which represent a root/tuber crop, a leafy brassica, a stem vegetable, and a citrus fruit, respectively.
Attagel CV,% 110 3.6 124 7.2 3.3 123 120 2.2 123 2.8 79 1.4 77 2.6 94 1.3 101 1.0 2.9 65 114 0.8 101 1.2 116 1.0 118 2.6 116 3.0 7.5 88 102 3.0 125 1.7 58 1.6 127 1.9 111 2.5 117 1.2 x
Cl8 x
Florisil
cv, % ~~
110 160 134 111 125 49 108 88 110 42 113 121 95 115 115 124 143 132 131 137 117 135
0.4 0.6 2.8 1.4 3.6 27.1 0.9 6.9 0.7 4.3 1.6 1.9 2.1 0.4 0.8 2.3 4.5 0.8 2.7 1.7 1.2 1.2
cv. %
x ~~~
99 133 123 112 115 92 92 98 105 99 106 92 116 109 111 115 101 127 125 117 117 126
0.2 10.6 1.0 1.1 1.2 1.6 0.5 2.7 3.6 6.1 4.1 2.4 3.3 4.0 2.4 1.3 3.7 2.2 2.2 3.6 1.1
0.3
SPE Cleanup of Halogenated Peeticks
Table 111. Recoveries of Pesticides and CV in Carrot cu Florisil Attagel x CV,% x CV,% x CV,% 38 12.9 81 2.1 dichlobenil 40 7.4 111 2.9 108 4.9 ethalfluralin 102 3.3 lindane 107 2.9 107 2.0 107 2.9 118 3.8 p,p’-DDE 113 1.3 106 1.9 117 2.1 p,P’-DDD 115 0.2 109 2.7 trifluralin 2.9 115 88 19.5 71 3.2 PCNB 3.8 108 84 19.1 69 3.6 vinclozolin 80 2.1 116 1.9 111 5.2 1.1 112 3.0 109 4.1 endosulfan I 90 114 1.4 120 endosulfan I1 89 1.2 2.5 endosulfan I11 79 0.5 116 1.6 122 0.7 pronamide 104 2.7 91 10.1 95 3.5 DCNA 91 6.4 109 3.0 86 6.7 2.6 112 2.3 73 heptachlor 97 17.8 5.7 heptachlor epoxide 105 1.7 113 3.1 92 endrin 4.3 116 103 1.7 106 1.6 benefin 94 8.8 103 3.5 101 1.5 113 3.6 102 profluralin 98 12.6 1.8 dichlone 5.3 50 45 1.6 41 1.7 triadimefon 27 19.1 123 5.4 117 7.7 o,p’-DDE 104 11.3 105 108 1.4 3.2 dieldrin 74 25.1 110 0.4 112 1.7 Table IV. Recoveries of Pesticides and CV in Celery Cl8 Florisil Attagel x CV,% x CV,% x CV,% 6.9 118 43 16.8 dichlobenil 51 2.8 22.8 113 47 57.4 ethalfluralin 71 1.0 37.4 lindane 87 11.4 109 1.3 65 2.3 105 106 7.1 p,p’-DDE 120 1.4 110 3.5 p,p’-DDD 117 2.0 109 1.7 trifluralin 83 7.4 116 3.3 98 8.8 PCNB 7.0 117 109 9.9 88 7.3 9.0 121 2.5 112 1.0 vinclozolin 99 5.3 114 1.6 109 1.6 endosulfan I 101 endosulfan I1 103 9.0 118 1.3 118 0.5 12.2 120 1.0 121 1.2 endosulfan I11 98 4.2 100 84 0.7 pronamide 94 6.8 DCNA 71 10.6 101 8.4 113 0.6 19.3 113 0.7 36 34.0 heptachlor 78 7.9 115 0.2 76 9.3 heptachlor epoxide 103 endrin 5.5 112 99 5.2 112 1.8 1.5 benefin 97 2.6 116 3.9 101 1.0 117 101 0.8 profluralin 104 4.6 142 1.1 dichlone 108 3.2 160 1.6 3.2 triadimefon 92 6.3 107 6.9 102 o!p’-DDE 108 1.9 91 5.3 102 0.8 101 0.2 dieldrin 108 1.9 98 4.0 Table V. Recoveries of Pesticides and CV in Orange Attagel ClS Florisil x CV,% x CV,% x CV,% 2.0 132 dichlobenil 83 1.7 100 8.3 ethalfluralin 42 10.6 118 1.5 55 9.1 111 1.7 57 lindane 33 13.5 5.6 8.2 111 2.0 p,p’-DDE 49 79 9.4 p,P’-DDD 42 7.2 113 1.5 75 6.9 trifluralin 43 13.4 116 2.1 59 16.8 PCNB 35 14.4 9.9 104 3.0 62 vinclozolin 32 12.2 119 75 13.1 2.6 endosulfan I 41 10.8 110 2.0 66 15.0 endosulfan I1 37 9.2 116 1.9 73 14.3 11.5 122 endosulfan I11 29 1.4 72 13.0 pronamide 14 93 29.4 5.6 48 10.9 DCNA 13 29.3 109 0.7 59 8.5 heptachlor 20 25.0 111 0.9 47 17.5 heptachlor epoxide 20 30.6 110 0.7 50 12.6 endrin 22 30.3 113 50 14.2 1.0 benefin 95 2.7 136 0.7 3.3 97 profluralin 102 1.2 118 94 0.7 9.7 dichlone 10.3 46 6.0 90 51 3.6 triadimefon 92 9.6 131 95 9.9 4.3 o,p’-DDE 106 0.2 106 3.5 98 2.2 dieldrin 104 1.7 108 3.2 95 3.1
J. Agrlc. FoodChem., Vol.
o,p’-DDD iprodione bifenox permethrin fenvalerate sulfallate chlorothalonil aldrin o,p’-dicofol p,p’-dicofol oxadiazon folpet ethylan methoxychlor tetradifon alachlor anilazine oxyfluorfen o,p’-DDT nitrofen chlorobenzilate p,p’-DDT
Attagel CV,% 89 29.3 135 1.8 126 2.6 57 30.4 55 30.5 89 2.4 93 4.1 101 0.8 109 0.6 80 1.0 119 1.4 108 4.4 0 121 2.4 121 2.1 102 4.7 149 2.4 123 3.3 54 2.2 127 2.1 119 3.1 109 2.6
o,p’-DDD iprodione bifenox permethrin fenvalerate sulfallate chlorothalonil aldrin o,p’-dicofol p,p’-dicofol oxadiazon folpet ethylan methoxychlor tetradifon alachlor anilazine oxyfluorfen o,p’-DDT nitrofen chlorobenzilate p,p’-DDT
Attagel x CV,% 109 2.7 139 1.8 112 0.4 107 1.1 109 2.6 106 2.6 94 7.8 101 3.8 105 1.8 92 3.2 122 2.8 110 2.0 116 1.5 116 3.3 122 0.3 70 1.5 142 1.4 115 0.7 50 2.7 116 2.3 107 1.0 105 2.5
o,p’-DDD iprodione bifenox permethrin fenvalerate sulfallate chlorothalonil aldrin o,p’-dicofol p,p’-dicofol oxadiazon folpet ethylan methoxychlor tetradifon alachlor anilazine oxyfluorfen o,p’-DDT nitrofen chlorobenzilate p,p’-DDT
Attagel x CV,% 108 1.0 106 11.2 93 3.1 115 2.3 119 3.8 97 3.2 85 11.2 100 2.5 98 5.1 40 4.8 108 4.2 96 10.3 114 2.5 114 6.1 103 6.1 36 11.6 89 1.1 90 3.2 36 3.1 83 2.0 84 2.7 75 2.0
x
x
113 157 135 105 115 56 128 103 121 44 122 135 0 125 127 132 167 136 134 138 125 154
x
98 151 128 92 97 85 121 81
125 49 124 123 93 120 119 117 158 129 119 135 115 132
x
112 156 116 115 123 80 122 95 110
31 115 126 86 114 116 120 137 108 122 108 107 104
30, NO. 9, 1001 1661
Cl8 CV,% 2.2 2.3 0.9 5.1 4.2 15.5 0.5 3.5 0.9 3.9 0.6 0.7 0.3 0.2 0.8 1.3 2.6 1.1 1.5 1.0 1.3
Cl8 CV,% 5.9 1.1 0.8 7.0 6.6 0 1.2 14.3 2.2 2.2 1.6 0.6 3.0 1.1
0.3 1.0 2.1 0.8 2.0 1.4 0.6 1.1
Cl8 CV,% 2.9 1.5 0.4 2.7 1.5 13.0 2.0 1.5 2.3 8.7 3.5 3.1 5.1 2.5 4.1 2.2 2.9 3.0 1.0 5.2 2.4 5.2
Florisil CV,% 110 1.4 149 2.4 130 1.0 124 0.7 120 1.0 84 0.7 99 1.3 98 1.1 102 0.7 80 0.5 101 0.5 91 3.0 x
0 98 101 107 151 126 119 124 120 128
1.6 1.0 0.8 1.2 1.2 4.1 0.7 4.5 3.0
Florisil x CV,% 103 0.2 151 2.2 124 0.2 116 0 113 0.5 112 2.3 106 1.5 101 1.9 106 1.4 96 1.1 113 1.4 90 4.6 112 1.4 105 0.9 109 1.5 116 1.2 153 0.4 127 1.0 127 1.2 129 2.2 116 0.8 125 0.2 Florisil x CV,% 94 2.0 108 0 83 11.0 110 1.1 110 2.2 86 6.6 88 12.4 93 2.6 92 6.9 79 4.8 95 3.6 74 14.1 106 5.3 89 7.5 92 6.2 94 3.8 92 7.2 88 5.7 114 0.2 84 8.3 86 6.4 91 2.3
Hsu et al.
1882 J. Agdc. Food Chem.. Vol. 39, No. 9, 1991
B
A
(Time 29 minutes)
(Time 29 minutes)
D
C
II d
(Time 29 minules)
r
(Time 29 minutes)
Figure 3. GC rofiles of carrot: (A) matrix blank; (B)with Attagel; (C) with Florisil SPE; (D) with CISSPE. Asterisks indicate an
E, which appeared in one batch of cartridges only.
extraneous pea
Table VI. Number of Halogenated Organic Pesticides with 70-190% Recovery and a CV of
