Pete the penguin says… “Before “Before the show begins, don’t forget to visit the snack bar”

Pete the penguin says…Pete the penguin says…

““Before the show Before the show begins, don’t forget to begins, don’t forget to visit the snack bar”visit the snack bar”

MDEQ DRO/ORO AnalysisMDEQ DRO/ORO Analysis

8015 – GC/FID8015 – GC/FID

EPA 8015 and Wisconsin EPA 8015 and Wisconsin 80158015

These methods define Diesel Range These methods define Diesel Range Organics, DRO, as anything eluting Organics, DRO, as anything eluting between Cbetween C1010 and C and C2828

No other carbon ranges includedNo other carbon ranges included

An example chromatogram of diesel An example chromatogram of diesel fuel using Cfuel using C1010-C-C2828

Why change? Why change?

This chromatogram looks OK, doesn’t it?This chromatogram looks OK, doesn’t it?

2000 ppm 10W30 Oil “old” method2000 ppm 10W30 Oil “old” method

Much of this material is included in the CMuch of this material is included in the C1010--CC2828 range range

Why change? Why change?

Maybe this chromatogram doesn’t look so Maybe this chromatogram doesn’t look so good, a lot of oil is being defined as Diesel good, a lot of oil is being defined as Diesel Range Organics.Range Organics.

Why change? Why change? ((What are the current problems?)What are the current problems?)

There’s still space left on the runThere’s still space left on the run The diesel is gone before CThe diesel is gone before C2828

The motor oil is half included in the The motor oil is half included in the diesel range diesel range

Why change? Why change? ((What are some solutions?)What are some solutions?)

Define DRO as CDefine DRO as C1010-C-C2020

Add Add OOil il RRange ange OOrganics as Crganics as C2020-C-C3434

1000 ppm Diesel Fuel “new” 1000 ppm Diesel Fuel “new” methodmethod

Most of the diesel (>90%) is contained Most of the diesel (>90%) is contained within the rangewithin the range

2000 ppm 10W30 Oil “new” 2000 ppm 10W30 Oil “new” methodmethod

Much of this material would be included in the Much of this material would be included in the CC1010-C-C2828 range, but now has a place of its own range, but now has a place of its own

Why change? Why change? (What are some outcomes)(What are some outcomes)

Better description of contaminantBetter description of contaminant There are no regulatory criteria, so There are no regulatory criteria, so

its all about aestheticsits all about aesthetics

Technical DetailsTechnical Details OverviewOverview

This analysis has some specific This analysis has some specific differences from normal differences from normal chromatographic analyseschromatographic analyses

Have an open mind Have an open mind The quantitative results are going to The quantitative results are going to

be used for guidance, not necessarily be used for guidance, not necessarily for regulatory compliancefor regulatory compliance

Technical DetailsTechnical Details Integration/CalibrationIntegration/Calibration

Baseline is drawn horizontallyBaseline is drawn horizontally All material under the signal is includedAll material under the signal is included Do not integrate valley to valleyDo not integrate valley to valley 8015 allows for baseline subtraction to 8015 allows for baseline subtraction to

account for column bleed but… account for column bleed but… Calibration by linear regression accounts Calibration by linear regression accounts

for bleed without need for subtractionfor bleed without need for subtraction

Technical DetailsTechnical Details Surrogate: n-Eicosane (CSurrogate: n-Eicosane (C2020))

Why CWhy C2020?? CC2020 is the dividing point between the is the dividing point between the

two analyte fractions two analyte fractions CC2020 is in a good range to determine is in a good range to determine

accurate extraction recoveryaccurate extraction recovery Easier to use area summing feature Easier to use area summing feature

on software on software (pragmatic, not lazy)(pragmatic, not lazy)

Technical DetailsTechnical Details Surrogate: n-Eicosane (CSurrogate: n-Eicosane (C2020))

Technical Details Technical Details Surrogate RecoverySurrogate Recovery

Surrogate recoveries for high Surrogate recoveries for high concentration samples, or samples concentration samples, or samples containing unknown or degraded containing unknown or degraded

hydrocarbons should be considered hydrocarbons should be considered estimated.estimated.


A known amount of surrogate, n-eicosane, is A known amount of surrogate, n-eicosane, is added by the laboratory before extraction. N-added by the laboratory before extraction. N-Eicosane is also present in many petroleum Eicosane is also present in many petroleum products. If the product is a known material, the products. If the product is a known material, the presence and quantity of n-eicosane can be presence and quantity of n-eicosane can be accounted for. Our method includes calculations accounted for. Our method includes calculations to make corrections for surrogate recovery based to make corrections for surrogate recovery based on concentrations of diesel fuel and motor oil in on concentrations of diesel fuel and motor oil in samples. In samples containing unknown or samples. In samples containing unknown or degraded materials the concentration on n-degraded materials the concentration on n-eicosane cannot be accounted for, therefore the eicosane cannot be accounted for, therefore the calculation of surrogate recovery is and estimate.calculation of surrogate recovery is and estimate.


A known amount of surrogate, n-eicosane, is A known amount of surrogate, n-eicosane, is

added by the laboratory before extraction.added by the laboratory before extraction.


N-Eicosane is also present in many petroleum N-Eicosane is also present in many petroleum products. products.

If the product is a known material, the presence If the product is a known material, the presence and quantity of n-eicosane can be accounted for.and quantity of n-eicosane can be accounted for.

Diesel fuel in our method has a 1.0% contribution Diesel fuel in our method has a 1.0% contribution from Cfrom C2020..

10W30 Motor Oil has a 0.22% contribution from 10W30 Motor Oil has a 0.22% contribution from CC2020..

Our method has calculations to make corrections Our method has calculations to make corrections for surrogate recovery based on concentrations of for surrogate recovery based on concentrations of diesel fuel and motor oil in samples.diesel fuel and motor oil in samples.


In samples containing unknown or degraded In samples containing unknown or degraded materials the concentration on n-eicosane cannot materials the concentration on n-eicosane cannot be accounted for, therefore the calculation of be accounted for, therefore the calculation of surrogate recovery is and estimate.surrogate recovery is and estimate.


A known amount of surrogate, n-eicosane, is A known amount of surrogate, n-eicosane, is added by the laboratory before extraction. N-added by the laboratory before extraction. N-Eicosane is also present in many petroleum Eicosane is also present in many petroleum products. If the product is a known material, the products. If the product is a known material, the presence and quantity of n-eicosane can be presence and quantity of n-eicosane can be accounted for. Our method includes calculations accounted for. Our method includes calculations to make corrections for surrogate recovery based to make corrections for surrogate recovery based on concentrations of diesel fuel and motor oil in on concentrations of diesel fuel and motor oil in samples. In samples containing unknown or samples. In samples containing unknown or degraded materials the concentration on n-degraded materials the concentration on n-eicosane cannot be accounted for, therefore the eicosane cannot be accounted for, therefore the calculation of surrogate recovery is and estimate.calculation of surrogate recovery is and estimate.


If the surrogate If the surrogate recovery is so recovery is so estimated, why bother estimated, why bother to use it?to use it?

Surrogate works OK if Surrogate works OK if sample contains diesel sample contains diesel or 10W30 and even or 10W30 and even better as the analyte better as the analyte levels decrease. If levels decrease. If you have no analyte, you have no analyte, the surrogate will give the surrogate will give you a good measure you a good measure of extraction recovery.of extraction recovery.

Technical Details Technical Details FID vs MSDFID vs MSD

Why can’t we use Why can’t we use GC/MS?GC/MS?

You can! Just make You can! Just make sure to scan to a sure to scan to a high enough mass high enough mass to get signal from to get signal from all the high all the high molecular weight molecular weight compounds.compounds.

Technical Details Technical Details DisclaimerDisclaimer

This method defines only the carbon This method defines only the carbon range of analytes. For example, a range of analytes. For example, a positive result for DRO does not positive result for DRO does not indicate diesel fuel, only the indicate diesel fuel, only the presence of hydrocarbons in a boiling presence of hydrocarbons in a boiling point range similar to, or point range similar to, or encompassed by, diesel fuel.encompassed by, diesel fuel.

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2000 ppm 5W30 Oil “new” method2000 ppm 5W30 Oil “new” method

2000 ppm 20W50 Oil “new” 2000 ppm 20W50 Oil “new” methodmethod

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Pete the penguin says… “Before “Before the show begins, don’t forget to visit the snack bar”