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Method Abstract for Post-column Liquid Chromatography 112

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Carbamate pesticides are widely used around the world to protect crops. In addition, they are used as biocides for industrial or other applications and in household products. Though carbamates are biodegradable compounds and bioaccumulation usually happens only to a low extend it is important to monitor produce to make sure enough time has elapsed between harvest and applying pesticides. Also, because of their high solubility, carbamates can leach into ground waters in porous soils and consequently find their way into drinking water supplies.

As part of FDA’s pesticide monitoring program individual lots of domestic and imported foods and feeds are sampled and tested for pesticide residues to enforce the tolerances set by EPA. There are 11 compounds mandated by USEPA Method 531.2 for drinking water but they represent only a fraction of the carbamates that require monitoring in domestic and imported products. Methyl carbamates are separated using a reversedphase column and then readily react with o-phthalaldehyde and a mercaptan after hydrolysis to form highly fluorescence compounds. This post-column reaction is the basis for official EPA Method 531.2 and AOAC Method 985.23.

This new expanded method is suitable for detecting a wide range of carbamates; post-column derivatization with fluorescence detection is a sensitive and selective method for residue analysis in water, food and feed samples. This method employs the same HPLC and post-column equipment and chemicals as USEPA Method 531.2 and will allow laboratories to increase the range of tested compounds.

ACKNOWLEDGEMENTS:
Pickering Laboratories would like to thank John Casanova and Frank Schenck (FDA) for their help with this project.

METHODS

Analytical Conditions

COLUMN:

Expanded resolution C8 analytical column 4x250 mm,
P/N 0840250 Guard column P/N 18ECG001

FLOW RATE:

0.8 mL/min

COLUMN TEMPERATURE:

45° C

MOBILE PHASE:

Water/Methanol

Post-Column Conditions

 

POST-COLUMN SYSTEM:

Pinnacle PCX or Vector PCX

REACTOR VOLUME:

0.5 mL

REACTOR TEMPERATURE:

100° C

REAGENT 1:

CB130

REAGENT 2:

100 mg of OPA and 2 g of Thiofluor in 950 mL of CB910 Diluent

REAGENTS FLOW RATE:

0.3 mL/min

DETECTION:

Fluorescence detector

λEX = 330 nm

λEM = 465 nm

HPLC GRADIENT:

 

Time
Water
Methanol
0
85
15
2
85
15
42
30
70
46
30
70
46.1
0
100
50
0
100

EQUILIBRATION:

10 min

Separation of the carbamates standard mixtures provided by FDA

Separation of the carbamates standard mixtures provided by FDA.

1 Aldicarb sulfoxide (Standak) 13 3-Hydroxycarbofuran 25 Banol
2 Butoxycarboxim 14 Butocarboxim 26 Isoprocarb (MIPC)
3 Aldicarb sulfone 15 Aldicarb 27 2,3,5-Trimethacarb
4 Oxamyl) 16 Metolcarb 28 3,4,5-Trimethacarb
5 Methomyl 17 Cloethacarb 29 Fenobucarb (BPMC)
6 Ethiofencarb sulfone 18 Bendiocarb 30 Methiocarb
7 Ethidimuron 19 Carbetamide 31 BDMC
8 Thiofanox sulfoxide 12 Propoxur 32 Bufencarb
9 Thiofanox sulfone 21 Carbofuran 33 Promecarb
10 Formetanate HCl 22 Carbaryl 34 Zectran
11 Ethiofencarb sulfoxide 23 Ethiofencarb 35 Aminocarb
12 Dioxacarb 24 Thiofanox    
 

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