Environmental Health Laboratories Yongtao B. Li, Ed J. George, Earl M. Hansen, and Jerry J. Thoma and Werner Martin and Peter D. Smith (LEAP Technologies)

Environmental Health Laboratories

Yongtao B. Li, Ed J. George, Earl M. Hansen, and Jerry J. Thoma

and

Werner Martin and Peter D. Smith (LEAP Technologies)

An Innovative Automated Microscale Solid Phase Extraction Technology

Coupled with GC-MS for Online Analysis of Water Samples

Pittcon 2000

March 14, 2000


Large Volume Injection (LVI) GC and GC-MS


LVI-GC Conditions

• Injection Vol.: 50 µL eluate • Injector Temp.: 80 ºC for 1 min, 80-280 ºC at 300ºC/min,

280 ºC for 34 min• Vent Valve: 0-0.6 min open, 0.6-3.5 min closed, 3.5-

37 min open• Vent Flow: 85 mL/min• Column Temp.: 45 ºC for 3 min, 45-160 ºC at 50 ºC/min,

160-260 ºC at 5 ºC/min, 260-330 ºC at 6 ºC/min, 330 ºC for 1 min

• Helium: 26 cm/s at 100 ºC


SPE Twin-PAL LVI-GC-MS


Extraction and Collection Plates


SPE Twin-PAL LVI-GC-MS Running Sequence


SPE Twin-PAL LVI-GC-MS Running Sequence


Automated SPE Conditions

• Cleaning: 500 µL 1:1 dichloromethane:ethyl acetate• Conditioning: 500 µL methanol & 500 µL reagent water• Extraction: 10 mL samples• Washing: 1 mL reagent water• Drying: 5 min nitrogen gas• Elution: 160 µL 1:1dichloromethane:ethyl acetate• Mixing: ~ 90 µL eluate + 10 µL internal standard• Injection: 50 µL


Automated Multi-Step Elution

• 160 µL 1:1 dichloromethane:ethyl acetate at 10 µL/s.

– 70 µL solvent, then soak for 60 s;– 30 µL solvent, then soak for 30 s;– 30 µL solvent, then soak for 30 s;– 30 µL solvent, then soak for 30 s.

• Flush with nitrogen gas at 15 psi for 5 s.


SPE Twin-PAL LVI-GC-MS Calibrations


0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

0 2 4 6 8 10

Heptachlor

Bromacil

Heptachlor Epoxide

gamma-Chlordane

alpha-Chlordane

trans-Nonachlor

Dieldrin

Endrin

0.05-10 ug/L, 50 uL

R2

= 0.999-1.000

Concentration, ug/L

Sam

ple

Are

a/S

tand

ard

Are

a

Method Sensitivity, Accuracy and PrecisionCompound aMDL, g/L bAbs. R% bRSD%2,6-Dinitrotoluene 0.069 119.7 15.92,4-Dinitrotoluene 0.075 94.7 25.1Propachlor 0.051 115.6 3.9Trifluralin 0.066 121.9 3.7Hexachlorobenzene 0.044 60.0 3.7Prometon 0.074 109.2 4.5Simazine 0.043 101.2 5.9Atrazine 0.030 95.8 6.4Lindane(gamma-BHC) 0.052 126.6 2.2Metribuzin 0.018 68.7 13.4Alachlor 0.043 108.5 7.2Heptachlor 0.066 90.7 5.7Bromacil 0.066 57.1 16.0Aldrin 0.037 64.6 14.8Metolachlor 0.038 108.4 2.3Cyanazine 0.054 93.2 15.7Heptachlor Epoxide 0.033 95.8 7.3gamma-Chlordane 0.027 66.8 10.2alpha-Chlordane 0.028 75.5 6.3Butachlor 0.036 95.2 1.4trans-Nonachlor 0.027 54.5 10.2Dieldrin 0.031 90.4 6.6Endrin 0.019 86.5 5.5Methoxychlor 0.044 116.9 4.9

Reagent water spikes, a : 7 replicates at 0.1 g/L and b: 4 replcates 1.0 g/L.

Online Analysis of Treated Well WaterCompound Conc. g/L %Abs. Rec. %RSD2,6-Dinitrotoluene 1.0 94.6 8.42,4-Dinitrotoluene 1.0 67.5 14.4Propachlor 1.0 50.4 7.9Trifluralin 1.0 95.4 8.7Hexachlorobenzene 1.0 70.5 12.7Prometon 1.0 116.4 6.0Simazine 1.0 97.4 3.7Atrazine 1.0 120.0 4.1Lindane(gamma-BHC) 1.0 105.8 15.6Metribuzin 1.0 86.0 6.5Alachlor 1.0 96.5 14.1Heptachlor 1.0 99.4 17.1Bromacil 1.0 108.3 6.2Aldrin 1.0 86.4 13.5Metolachlor 1.0 111.7 13.7Cyanazine 1.0 105.9 3.8Heptachlor Epoxide 1.0 82.7 9.4gamma-Chlordane 1.0 99.7 10.4alpha-Chlordane 1.0 93.9 8.7Butachlor 1.0 104.4 5.5trans-Nonachlor 1.0 98.8 11.2Dieldrin 1.0 98.8 3.4Endrin 1.0 72.1 11.2Methoxychlor 1.0 124.5 11.0

Based on four unpreserved replicated spikes.

Online Analysis of Untreated Well WaterCompound Conc. g/L %Abs. Rec. %RSD2,6-Dinitrotoluene 1.0 39.0 3.92,4-Dinitrotoluene 1.0 69.2 6.6Propachlor 1.0 67.9 2.4Trifluralin* 1.0 27.5 4.0Hexachlorobenzene 1.0 43.3 2.8Prometon 1.0 83.0 4.6Simazine 1.0 68.9 8.6Atrazine 1.0 78.3 5.4Lindane(gamma-BHC) 1.0 88.7 3.2Metribuzin 1.0 57.0 3.0Alachlor 1.0 74.6 2.8Heptachlor 1.0 91.2 3.1Bromacil 1.0 60.6 13.6Aldrin 1.0 66.6 3.2Metolachlor 1.0 84.6 4.1Cyanazine 1.0 91.7 3.4Heptachlor Epoxide 1.0 77.1 5.4gamma-Chlordane 1.0 64.5 4.0alpha-Chlordane 1.0 70.5 3.2Butachlor 1.0 71.6 2.8trans-Nonachlor 1.0 54.5 10.2Dieldrin 1.0 67.0 4.0Endrin 1.0 59.1 11.5Methoxychlor 1.0 131.1 3.1

Based on four unpreserved replicated spikes.

Online Analysis of Tap WaterCompound Conc. g/L %Abs. Rec. %RSD2,6-Dinitrotoluene 1.0 80.3 15.02,4-Dinitrotoluene 1.0 82.8 11.5Propachlor 1.0 134.5 10.6Trifluralin 1.0 134.5 10.8Hexachlorobenzene 1.0 66.5 6.5Prometon* 1.0 34.1 68.8Simazine 1.0 93.5 8.1Atrazine 1.0 103.9 13.5Lindane(gamma-BHC) 1.0 186.1 8.0Metribuzin 1.0 71.4 4.9Alachlor 1.0 115.7 7.8Heptachlor 1.0 110.5 4.8Bromacil 1.0 103.0 7.2Aldrin 1.0 74.5 5.9Metolachlor 1.0 114.1 5.4Cyanazine 1.0 115.2 3.6Heptachlor Epoxide 1.0 108.3 11.2gamma-Chlordane 1.0 64.2 6.1alpha-Chlordane 1.0 70.6 8.2Butachlor 1.0 98.2 7.2trans-Nonachlor 1.0 55.9 7.0Dieldrin 1.0 97.8 7.2Endrin 1.0 75.0 16.3Methoxychlor 1.0 106.3 11.1

Based on four replicates dechlorinated with Na2SO3 and preserved with HCl.

Online Analysis of Tap WaterCompound Conc. g/L %Rel. Rec. %RSD2,6-Dinitrotoluene 1.0 92.1 3.12,4-Dinitrotoluene 1.0 87.3 12.5Propachlor 1.0 116.3 4.7Trifluralin 1.0 92.8 3.4Hexachlorobenzene 1.0 94.1 5.0Prometon 1.0 102.6 13.5Simazine 1.0 86.7 4.0Atrazine 1.0 121.9 7.4Lindane(gamma-BHC) 1.0 118.5 4.9Metribuzin 1.0 101.6 2.5Alachlor 1.0 110.2 7.8Heptachlor 1.0 91.2 3.1Bromacil 1.0 101.4 4.6Aldrin 1.0 82.5 8.6Metolachlor 1.0 110.6 10.2Cyanazine 1.0 80.2 10.6Heptachlor Epoxide 1.0 102.5 6.6gamma-Chlordane 1.0 100.1 5.5alpha-Chlordane 1.0 107.7 2.5Butachlor 1.0 102.1 5.1trans-Nonachlor 1.0 95.3 5.6Dieldrin 1.0 101.4 6.0Endrin 1.0 67.9 2.4

Based on four replicates dechlorinated with Na2SO3 and preserved with HCl.

Documents

Environmental Health Laboratories Yongtao B. Li, Ed J. George, Earl M. Hansen, and Jerry J. Thoma and Werner Martin and Peter D. Smith (LEAP Technologies)