SPE Colum for Pesticides Analysis

• Ideal to concentrate hydrophobic trace substances in water samples.
• High recovery rate in pesticides even in polar metal coordinating compounds such as Ashram and oxine copper.
• Rapid processing with vacuum concentrators and pressurized flow pump for collection and concentration.
• A combination of Wakopak^® Wakosil^® Agri-9 and special eluent enables a easy and quick HPLC analysis of various pesticides.
• GC analysis can be carried out in high selectivity using Trajan (SGE) capillary columns.

• Column：Presep^®-C Agri (Short)
  pre-conditioning for column
  ① CH₃CN 10 mL
  ② CH₃OH 10mL
  ③ H₂O　10mL
  1) flow sample water: 500 mL^*1
  2) washing: H₂O 5 mL
  3) extraction by CH₃CN 2 mL
  4) concentrate (to 0.2〜0.3 mL) under N₂
  5) dissolve into 1mL of H₂O
  6) analysis by HPLC (10 μL injection)

  *1 500 mL of sample: add 10 mL of 0.2 mol/L EDTA・2Na, pH3.5 by diluted HNO₃ (conc.HNO₃/H₂O=1/10)

• HPLC conditions

  Column	： Wakopak® MS-Agri-9 GT (2.0 mmφ x 150 mm)
  Eluent	： A）10 mM CH3COONH4 (pH3.7) 　 B）CH3CN 　　　 0-10min.: B=12-70 % 　　　10-13min.: B=100 % 　　　13-23min.: B=12 %
  Flow Rate	：0.2 mL/min. at 40 ℃
  Injection Vol.	：each 1 ppm、2 μL

  MS/MS conditions

  ESI, MRM

  Ion Spray Voltage：	5500V (pos)	-4500V (neg)
  Temperature：	700 ℃	300 ℃
  Curtain Gas：	40	20
  Collision Gas：	5	3
  Ion Source Gas1：	80	40
  Ion Source Gas2：	70	80
  System：	3200Q TRAP(ABI)

• 

• 

18 components at positive mode

No.*1	Chemical Name	Q1/Q3	RT (min)	Recovery Rate (%)
74	Methomyl	163.1/88.1 amu	4.4	50.8 (85.2)*2
71	MPP oxon sulfoxide	279.0/104.2 amu	5.8	101.6
87	Tricyclazole	190.0/163.2 amu	6.9	99.1
71	MPP oxon sulfone	295.0/217.1 amu	7.2	99.7
18	Carbofuran (metabolite of Carbosulfan)	222.1/165.2 amu	8.5	103.1
96	Thiodicarb	355.1/88.1 amu	8.6	99.6
71	MPP sulfoxide	294.9/109.0 amu	9.0	100.1
1	Thiuram	240.9/88.1 amu	9.5	94.3
82	Probenazole	224.0/130.2 amu	9.5	98.6
71	MPP oxon	263.0/231.1 amu	9.6	99.5
86	Bensulfuron-methyl	411.0/149.2 amu	10.0	100.7
95	Flazasulfuron	408.2/182.1 amu	10.1	98.6
71	MPP sulfone	310.9/124.9 amu	10.4	99.2
98	Siduron peak1	233.1/137.2 amu	10.4	99.7
98	Siduron peak2	－	10.6	98.3
90	Azoxystrobin	404.1/372.1 amu	10.8	99.6
84	Dymron	269.1/151.1 amu	11.1	99.6
71	MPP	279.0/169.0 amu	12.1	104.3
58	Carpropamid	336.0/139.2 amu	12.2	101.8

*1 same number as Japanese Waterworks Act, Appendix.
*2 figure in parentheses is recovery rate when Presep^® Agri was employed.

10 components at negative mode

No.*1	Chemical Name	Q1/Q3	RT (min)	Recovery Rate (%)
36	Asulam	228.9/196.7 amu	5.7	99.6
17	Bentazone	239.1/131.6 amu	6.8	99.3
19	2,4-PA	219.9/161.7 amu	7.5	99.1
20	Triclopyr	255.9/198.1 amu	8.0	101.2
45	MCPP(Mecoprop)	213.0/140.9 amu	8.8	99.9
94	Halosulfuron-methyl	433.6/252.2 amu	9.6	99.1
68	DCMU(Diuron)	232.0/186.9 amu	9.7	100.4
26	Iprodione	329.9/245.1 amu	11.4	98.9
42	Bensulide(SAP)	395.9/212.7 amu	12.3	96.7
102	Fipronil	436.8/330.1 amu	12.4	97.3

*1 same number as Japanese Waterworks Act, Appendix.

Other 3 components without mixing^*3

No.*1	Chemical Name	Recovery Rate (%)
28	Oxine-copper	96.2
48	Carbary (l NAC)	101.0
75	MBC (decomposition product of Benomyl)	97.5

*1 same number as Japanese Waterworks Act, Appendix.
*3 due to stability in mixture solution.

• SPE Conditions

  Column	：Presep®-C Agri (Short)
  Pre-conditioning	：dichloromethane (5 mL), methanol (5 mL), DI water (5 mL)
  Sample	：add 100 µL of standard solution into DI 200 mL of water
  SPE treatment	：flow=10-20 mL/min.
  Draining	：air flow for 10 min.
  Extraction and dryness	：Attach two of Presep®-C Na2SO4 at the outlet and charge 2.5 mL of dichloromethane to extract. Then, remove Presep®-C Agri (Short) and Charge 6 mL of dichloromethane into Na2SO4 column. Combine crude solution.
  Concentration	：add 2 mL of hexane and concentrate crude solution under N2 to ca. 0.8 mL (don't completely dryness).
  analytical sample	：add 100 μL of internal standard solution and add 1 mL of hexane (sample solution should be in freezer to keep concentration due to vapolize).
  Standard	：10 μg/mL acetone solution
  Internal standard solution	：2 μg/mL of hexane solution with acenaphthene and chrysene (for adjusting agent for sensitivity of GC/MS analysis)

  GC conditions

  GC	： HP5890 PACKARD SERIESE GC/MS
  GC/MS	： AUTO mass JMS-AM150 (JEOL)
  Column	： 100 ％ dimethylpolysiloxane, 0.25 mmφ x 30 m, thickness=0.25 μm
  Injector	： 250 ℃
  Temp.	： 60℃ (2min)-120℃ (20℃/min)-300℃(10℃/min)-300℃(5min)
  injection	： 2.0 μL

• No.	Chemical name	Recovery rate (%)
  27	etridiazole	92.3
  30	chloroneb	91.8
  33	pencycuron	90.8
  43	benfluralin	82.3
  2	simazine	101.5
  10	propyzamide	95.8
  9	TPN	95.8
  6	diazinon	97.7
  38	MBPMC	106.3
  31	tolclofos-methyl	89.7
  34	metalaxyl	100.7
  7	MEP	97.3
  37	dithiopyr	89.4
  23	chlorpyrifos	88.9
  29	captan	103.9
  44	pendimethalin	85.7
  46	methyldymron	84.6
  22	isofenphos	91.3
  8	isoprothiolane	96.6
  41	butamifos	84.1
  32	flutolanil	100.3
  39	napropamide	99.7
  5	isoxathion	91.8
  	triclopyr-2-butoxyethyl	94.1
  35	mepronil	116.6
  40	pyributicarb	93.5
  26	iprodione	98.0
  25	pyridaphenthion	106.5
  11	DDVP(Dichlorvos)	108.9
  12	BPMC	107.5
  3	Thiobencarb	101.0
  15	IBP	115.1
  13	CNP	112.0
  16	EPN	115.4