esaimen analytical
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Automated Gel PermeationChromatography (GPC) Clean-up of Soil
Extracts Prior to Analysis for
Semivolatile Organic Compounds byGC/MS
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Agilent 6890 GC with 7683 Autosampler
and 5973 MSD
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SAMPLE PREPARATION
• Standardize materials-- All reagents were pesticide grade or higher.
-- All chemicals were ACS grade quality.
-- GPC calibration standards were prepared accordingto USEPA Method 3640A and contained corn oil, bis(2-ethylhexyl) phthalate, methoxychlor, perylene andsulfur.
--Dilutions were prepared in dichloromethane ormethanol
* USEPA Method (United States Environmental Protection Agency)
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-- Soil extraction was carried out utilizing pressurizedsolvent or accelerated solvent extraction (ASE) perUSEPA Method 3545.
-- Ten grams of soil was placed in a beaker and 2.5 mL ofdiatomaceous earth were added to the sample and thentransferred to an extraction cell.
-- Appropriate matrix spikes and matrix spike duplicate wasadded to each sample batch.
Soil Extraction
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The samples were then extracted using a Dionex ASE 200with the
following conditions:
Oven temperature = 100 degrees C; Pressure = 1500psi Static Time = 5 minutes; Heat = 5 minutes
Flush Volume = 60%; Solvent A = 100% Nitrogen purge = 60 seconds at 150psi Extraction fluid = 1:1 dichloromethane:acetone
The sample extracts were then concentrated usingKuderna-Danish (K-D) apparatus and then reconstituted
in dichloromethane prior to GPC clean-up.
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• GPC Clean-up
-- GPC clean-up was achieved using a Gilson (Middleton, WI)
Automated GX-271 GPC Clean-up System equipped with aPhenomenex (Torrance, CA) EnviroSep- ABC™GPC.
-- Sample Clean-up column with guard column. The system used a 5mL sample loop and a flow rate of 5 mL/min with dichloromethane asthe mobile phase.
-- Column calibration profiles were recorded using TRILUTION LCsoftware and a Gilson Model 112 UV Detector set at 254nm. The GPCclean-up column was calibrated using the method outlined in USEPAMethod 3640A.-- The column flow rate was verified by collected the eluate in agraduated cylinder for 10 minutes and measuring the volume. Theelution times for the corn oil, bis (2-ethylhexyl) phthalate, methoxychlor,perylene and sulfur were determined.
** (See Figure 2)
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GC/MS Analysis
• Semivolatile organic compounds were analyzed byGC/MS using an Agilent 6890 GC with 7683Autosampler and 5973 MSD.
• Separation was achieved using a J&W Scientific DB5.625 , 30mm x 0.25mm x 0.25um column. The carrier
gas was Helium at a flow rate of 1.2 mL/minute. 0.5 uLof sample was injected in pulsed splitless mode withan injector temperature of 250 degrees C.
The MS conditions were as follows:
• MS Interface = 280 degrees C• MS Source = 230 degrees C• Mass Range = 35 – 500 amu• Scan Time = .317 sec/scan
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Chromatogram (GC/MSD) of a soil sample that has been spiked with thesemivolatile organic compounds listed in Table 1. No GPC clean-up was
performed. Note the fronting and tailing of peaks between 8 and 12 minutes.
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Chromatogram (GC/MSD) of a soil sample that has been spiked withsemivolatile organic compounds listed in Table 1.
GPC clean-up was performed. Note the improved resolution of peaks between8 to 12 minutes compared to the chromatogram in which no GPC had been
performed
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CONCLUSION • The use of GPC post-extraction clean-up
improved peak resolution and reduced thepresence of fronting and tailing for the analysis ofsemivolatiles from soils.
• Recovery data was adequate for semivolatileanalysis and all compounds were withinacceptable recovery limits.
• The use of GPC clean-up also reducedmaintenance costs for the GC/MS systems sinceless contaminants were able to accumulate in theinjection port area or on the front end of thecolumn
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Sample Retention Time ,(tR)(minutes)
Corn oil 10.9771
Phthalate 13.0603
Methoxychlor 14.6066Perylene 19.8885
Sulfur 23.6771
Based on the chromatography obtained, it shows thatthe soil contained 5 different samples as below :
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1. Determine the Retention Factor, k for
each samples.
2.Find the Effective Plate Number, Neff
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Retention factor, k = tR – tMtM
1) k corn oil = 10.9771 – 9.67919.671
= 0.134
2) k phthalate = 0.349
3) k metoxychlor = 0.509
4) k perylene = 1.055
5) k sulfur = 1.446
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GRAPH ofRetention factor, k against Retention Time, T R
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Given N = 7, find the value of Neff
Neff = N (k/k+1)2
1) Corn oilNeff = 7 (0.134/0.134+1)2
= 0.0977
2) PhthalateNeff = 0.469
3) MetoxychlorNeff = 0.796
4) PeryleneNeff = 1.845
5) SulfurNeff =2.446