eph specific silica gel cartridges: in-house...
TRANSCRIPT
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EPH Specific Silica Gel Cartridges: In-House
Manufacturing
Alexandria Pavkovich
Jason Thomas
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What is EPH?
•Extractable Petroleum Hydrocarbons
•Means to separate Aliphatic and Aromatic compounds
•Clean up step for environmental samples
•Typical cartridge format for MA and NJ methods: 5g irregular silica gel fritted in 25 mL syringe tube
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Importance of EPH:
•Multiple states follow EPH Methods• MA, NJDEP, Texas, WA, Atlantic RBCA
•Used to assess impact of environmental samples• Separates target aliphatic components from target
aromatic components
•Allows separation of EPA priority 16 PAHs• Higher proportion of aromatics have more hazardous
designation relative to samples consisting of primarily aliphatic hydrocarbons
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How does a EPH cartridge work?
•Normal Phase
•Dried Silica Gel (Activated) is Polar• Non-polar compounds will elute first
•Hexane pulls off non-polar aliphatic compounds
•Dichloromethane pulls off more polar aromatic compounds• Compared to Hexane, DCM is moderately polar
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EPH Method Requirements:
•MA EPH Method• 40 – 140% Recovery for Analytes and Surrogates• < 5% Breakthrough for Naphthalene and 2-
Methylnaphthalene
•NJ EPH Method• Based off MA EPH Method• Requires monitoring of additional analytes
•Texas EPH Method• Uses Pentane instead of Hexane• 60 – 140% Recovery for Analytes, 70 – 130% Recovery
for Surrogates• < 10 – 20% Crossover
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Background – MA and NJDEP
•< 30 ng of background contamination on-column
8.2 ppm 11.5 ppm
1-Chlorooctadecane @ 5ppm
min5 7.5 10 12.5 15 17.5 20 22.5 25
14.2 ppm 13.1 ppm
o-Terphenyl @ 5ppm
min5 7.5 10 12.5 15 17.5 20 22.5 25
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Background – Texas
•< __ng of background contamination on-column
8.2 ppm 11.5 ppm
1-Chlorooctadecane @ 5ppm
min5 7.5 10 12.5 15 17.5 20 22.5 25
14.2 ppm 13.1 ppm
o-Terphenyl @ 5ppm
min5 7.5 10 12.5 15 17.5 20 22.5 25
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Typical EPH Extraction:Condition/Rinse Cartridge with
Hexane, hold for 5 min.
Elute 20 mL Dichloromethane –Collect Eluate
Concentrate Eluate to 1 mL final volume
Elute 20 mL Hexane – Collect Eluate
Load 1 mL Sample
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MA / NJDEP Separation
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Texas Separation
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Recovery – MA and NJDEP
Lot 1 Lot 2 Lot 3
Nonane (C9) 101.8 103.0 110.2
1-Chlorooctadecane 97.0 98.1 108.4
Octacosane 102.3 102.7 110.8
Tetracontane (C40) 99.4 99.9 108.9
Lot 1 Lot 2 Lot 3
1,2,3-Trimethylbenzene 89.5 89.9 93.6
Naphthalene 90.5 91.7 95.5
2-Methylnaphthalene 90.7 92.0 95.8
2-Fluorobiphenyl 90.6 92.0 95.8
2-Bromonaphthalene 88.9 89.1 89.5
Phenanthrene 90.6 92.3 96.0
o-Terphenyl 90.7 92.4 96.2
Dibenzo[a,h]anthracene 86.7 88.7 93.0
Aliphatic Fraction
Aromatic Fraction
Percent Recovery (%)
Percent Recovery (%)
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Lot 1 Lot 2 Lot 3
Nonane (C9) 101.8 103.0 110.2
1-Chlorooctadecane 97.0 98.1 108.4
Octacosane 102.3 102.7 110.8
Tetracontane (C40) 99.4 99.9 108.9
Lot 1 Lot 2 Lot 3
1,2,3-Trimethylbenzene 89.5 89.9 93.6
Naphthalene 90.5 91.7 95.5
2-Methylnaphthalene 90.7 92.0 95.8
2-Fluorobiphenyl 90.6 92.0 95.8
2-Bromonaphthalene 88.9 89.1 89.5
Phenanthrene 90.6 92.3 96.0
o-Terphenyl 90.7 92.4 96.2
Dibenzo[a,h]anthracene 86.7 88.7 93.0
Aliphatic Fraction
Aromatic Fraction
Percent Recovery (%)
Percent Recovery (%)
Recovery – Texas
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Breakthrough – MA and NJDEP:
Lot 1 Lot 2 Lot 3
Naphthalene 0.0 0.0 0.0
2-Methylnaphthalene 0.0 0.0 0.0
Breakthrough:Percent Breakthrough (5)
Breakthrough – Texas:
Lot 1 Lot 2 Lot 3
Naphthalene 0.0 0.0 0.0
2-Methylnaphthalene 0.0 0.0 0.0
Breakthrough:Percent Breakthrough (5)
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Samples with Matrix
•Standards fractionate well but what about real samples?
•Motor oil loading at a range of concentrations
•Check for breakthrough of naphthalene and 2-Methylnaphthalene
•Check for breakthrough of used motor oil samples at 20 mg/mL
•Check for PAH levels to tell a story
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Loading Capacity Check
•MADEP recommends maximum of 25 mg/mL
•Saturation of silica could lead to breakthrough of early eluting aromatics
•The separation is typically one of a delicate balance as it is without additional encumbrances• Complex matrices
•A range of concentrations of motor oil were prepared
•Breakthrough of naphthalene and 2-methylnaphthalene monitored in hexane fraction
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Sample Preparation
•5W/20 conventional motor oil was diluted into hexane to produce each target concentration
•Each sample was spiked with naphthalene and 2-methylnaphthalene at 10 ppm
•Surrogates 1-chlorooctane, o-Terphenyl and fractionation surrogates 2-bromonaphthlene, and 2-fluorobiphenyl were spiked at 20 ppm
•6 levels of motor oil were prepared in hexane• 5 mg/mL to 100 mg/mL
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Sample Preparation
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Chromatographic Results (100 mg/mL)
naphthalene
2-methylnaphthalene
naphthalene
Blue trace – aromatic fraction
Red trace – aliphatic fraction
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PAHs in Used Motor Oil
•PAH is a result of incomplete combustion produced by internal combustion engines
•Can accumulate in motor oil through blow-by
•Would be expected in higher concentrations with increasing engine age and mileage• Older technology and declining engine performance
produce more PAH• Deterioration of compression rings due to age and wear
from high mileage increases blow-by
•Diesel vehicles produce more PAH during combustion
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PAHs in Used Motor Oil
•Because of PAH content (as well as metals and other contaminants) used motor oil is more of a concern than new oil
•Wrecking yards, storage tanks
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PAHs in Used Motor Oil
•Samples were collected from vehicles with a range of ages and mileage
1B 2B 4B 6B 7B 8B
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PAHs in Used Motor Oil
•Samples were collected from vehicles with a range of ages and mileage
Sample ID # VehicleYear
Mileage Oil mileage oil wt comments
1B Ford Taurus Limited2013
41,862 9,756 5w/20
2B Honda Pilot EX2008
73,000 5,000 5w/20
3B Ford Taurus Limited2013
53,500 6,000 5w/20
4B Chevy Camaro IROC-Z1986
172,659 2 - 3,000 20w/50
5B Ford F-250 Ranger XLT1971
103,000 2,000 20w/50
6B Ford F-250 XLT2005
95,418 3,200 15w/40 diesel
7B Chevy Camaro Z-281994
105,464 728 5w/30
8B Chevy Camaro1980
178,000 N/A 20w/50 sludge from oil pan
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PAHs in Used Motor Oil
•Extent of migration of color band during elution
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PAHs in Used Motor Oil (Breakthrough)
naphthalene 2-methylnaphthalene
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PAHs in Used Motor Oil (Breakthrough)
Naphthalene 2-Methylnaphthalene
10 ppm std.
Sample 2B
Sample 4B
5 ppm std.
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PAHs in Used Motor Oil (Breakthrough)
Naphthalene 2-Methylnaphthalene
Sample 2B DCM
Sample 4B DCM
Sample 2B hex
Sample 4B hex
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PAHs in Used Motor Oil (Heavier PAHs)
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PAHs in Used Motor Oil (Diesel)
surrogates
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PAHs in Used Motor Oil (Gas Standard)
Naphthalene
2-methylnaphthalene
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Conclusions
•EPH Silica Gel is a normal phase application for separating aliphatic and aromatic compounds in environmental samples
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Questions?
Resprep EPH Fractionation SPE Cartridge
Cat # 25859