comparison of various extraction methods for petroleum ... · % recovery soxhletsoxtec shake tumble...
TRANSCRIPT
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Comparison of Various Extraction Methods for
Petroleum Hydrocarbons (PHC) in Soils and in
Drilling Waste
John Ashworth1 & Ron Minks2
1. Director, Soil Science; ETL
2. Director of Calgary Operations; ETL
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• Alberta’s drilling waste disposal guidelines (G-50, 1996) are currently being revised
• After drilling waste disposal, parameters must fall within scientifically determined, risk-based “end-point” soil quality values
• The end-points for petroleum hydrocarbons (PHCs) are geared to the Canada-Wide Standard Method of soil analysis (CCME)
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Upstream Petroleum Guidelines (Hydrocarbons)CCME method. Fine, surface, agricultural soil
Fraction 1 0.026 % 260 mg/kgC6-C10
Fraction 2 0.09 % 900 mg/kgC10-C16
Fraction 3 0.08 % 800 mg/kgC16-C34
Fraction 4 0.40 % 4,000 mg/kgC34-C50
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Treatability Test #2 (Fertilized) - Results to Feb. 2003
0
200
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1,000
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1,400
1,600
1,800
2,000
0 2 4 6 8 10 12
Months
Co
nce
ntr
atio
n (
mg
/kg
)
PHC F2 (mg/kg)
PHC F3 (mg/kg)
PHC F4 (mg/kg)
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Soils Used in the CCME Validation Study
Soil % sand % clay % moisture texture organic matterA 42 32 0 clay loam 1 %B 91 5 0 sand 2 % approx.C 34 25 0 loam 12 % approx.D1 38 31 0 clay loam 9 %D2 38 31 20 clay loam 9 %
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Two Extraction Studies
• CCME CWS PHC extraction of soilsü5 methodsü5 soil typesü7 spikes eachü= a lot of data!
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Two Extraction Studies
• Drilling waste comparison using CCME benchmark extraction vs cold shake extractionüUse shake method to pre-determine
hydrocarbon loading for G-50 purposes
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Soil Extraction Techniques:
Ø SoxhletØ SoxtecØ Cold shakeØ TumblerØ Sonic bath
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Soxhlet Soxhlet -- EPA 3540EPA 3540• CCME PHC benchmark • Named after Franz Soxhlet
(1848 - 1913), a German food analyst
• Series of distillations/cycles• Total extraction time: 16-24
hours
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SoxtecSoxtec -- EPA 3541EPA 3541• Rapid extraction by
Soxtec is the 21st century, automated version of Soxhlet extraction
• Total extraction time: 1-2 hours
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Cold ShakeCold Shake
• Wrist-action shaker• Total extraction time: 1 hour
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TumblerTumbler• TCLP-type
extraction (EPA 1331) using solvent
• End-over-end rotation/tumble
• Total extraction time: 2 hours
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Sonic Bath Sonic Bath -- EPA 3550EPA 3550
• Extract with ultrasonic waves in a water bath
• Total extraction time: 10 minutes
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GC/FID SystemGC/FID System• Carrier gas flows into the
injector, through the column and then into the detector
• Sample extract is injected into the heated injection port and vaporized
• Hydrocarbons are separated through a column based upon boiling points
• Each compound is detected by the FID
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Comparison to Benchmark
• Soxhlet defined as benchmark extraction for CCME PHCs
• Each soil type spiked with diesel and SAE 30 motor oil - 7 replicates
• Recoveries measured are relative to Soxhlet
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F2 (C10-C16)
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Clay Loam,9%OM
Clay Loam,9% OM 20% H2O
Clay Loam, < 2 %OM
Sand Loam
% R
eco
very
SoxhletSoxtecShakeTumbleSonic bath
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F3 (C16-C34)
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Clay Loam,9%OM
Clay Loam, 9%OM 20% H2O
Clay Loam, < 2 %OM
Sand Loam
% R
eco
very Soxhlet
SoxtecShakeTumbleSonic bath
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F4 (C34-C50)
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Clay Loam,9%OM
Clay Loam, 9%OM
20% H2O
Clay Loam, < 2 %OM
Sand Loam
% R
eco
very Soxhlet
SoxtecShakeTumbleSonic bath
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Recovery Summary -Compared to Soxhlet Recovery
• Soxtec within 10%• Cold shake method recovery ranges from
42%-111%• Tumble method recovery ranges from
66%-107%• Sonic bath method recovery ranges from
56%-100%• No data available for ASE or microwave
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Bio-availability(aging; sequestration)
• Effect of organic matter (a form of partitioning)
• Effect of texture, especially sorption on clays
• Other suggested factors: encapsulation in precipitates; pH; temperature
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Comparison Using Real-World Samples
• Random sample selection (approx. 200)• Extract duplicate sample using Soxhlet
and Soxtec• Regression of data onto chart (Lloyd
Hodgins)
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F2 (C10 to C16)
y = 1.0015x + 53.204R 2 = 0.907
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0 2000 4000 6000 8000 10000
Soxtec
Soxh
let
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F3 (C16 to C34)
y = 0.912x + 29.802R2 = 0.9859
0
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12000
0 2000 4000 6000 8000 10000 12000 14000
Soxtec
Soxh
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F4 (C34-C50)
y = 0.9406x + 13.035R2 = 0.9333
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Soxtec
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We also analyzed two drilling wastes for total extractable hydrocarbons (TEH) using the cold shake method
and compared recoveries to the CCME benchmark method
Drilling Waste % Moisture“DWA” 28%“DWB” 58%
Diesel spike ranged from 2,000 – 4,000 mg/kg
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% TEH Recovery
0%
20%
40%
60%
80%
100%
120%
140%
CCME PHC Cold shake w/hexane/acetone
Cold shake w/ hexane
% R
ecov
ery
DW-A
DW-B
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Summary - Soils
• Soxtec is equivalent to CCME benchmark Soxhlet method
• Other alternative methods have various challenges to meet equivalency
• Bioavailability of PHCs in soil an issue for recovery
• Ensure ongoing equivalency using PT samples (CAEAL) and real-world samples
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Summary - Drilling Wastes
• Cold shake extraction works well for drilling wastes compared to CCME benchmark soxhlet method
• Hexane alone works well• Drilling wastes do not display the
bioavailabiltiy issues found in soils• Receiving soils will require CCME PHC
method
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Thank you!