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MDEQ DRO/ORO Analysis 8015 – GC/FID

EPA 8015 and Wisconsin 8015 EPA 8015 and Wisconsin 8015 These methods define Diesel Range Organics, DRO, as anything eluting between C 10 and C 28 These methods define Diesel Range Organics, DRO, as anything eluting between C 10 and C 28 No other carbon ranges included No other carbon ranges included

An example chromatogram of diesel fuel using C 10 -C 28

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

2000 ppm 10W30 Oil “old” method Much of this material is included in the C 10 -C 28 range Much of this material is included in the C 10 -C 28 range

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

Why change? (What are the current problems?) There’s still space left on the run There’s still space left on the run The diesel is gone before C 28 The diesel is gone before C 28 The motor oil is half included in the diesel range The motor oil is half included in the diesel range

Why change? (What are some solutions?) Define DRO as C 10 -C 20 Define DRO as C 10 -C 20 Add Oil Range Organics as C 20 -C 34 Add Oil Range Organics as C 20 -C 34

1000 ppm Diesel Fuel “new” method Most of the diesel (>90%) is contained within the range Most of the diesel (>90%) is contained within the range

2000 ppm 10W30 Oil “new” method Much of this material would be included in the C 10 -C 28 range, but now has a place of its own Much of this material would be included in the C 10 -C 28 range, but now has a place of its own

Why change? (What are some outcomes) Better description of contaminant Better description of contaminant There are no regulatory criteria, so its all about aesthetics There are no regulatory criteria, so its all about aesthetics

Technical Details Overview This analysis has some specific differences from normal chromatographic analyses This analysis has some specific differences from normal chromatographic analyses Have an open mind Have an open mind The quantitative results are going to be used for guidance, not necessarily for regulatory compliance The quantitative results are going to be used for guidance, not necessarily for regulatory compliance

Technical Details Integration/Calibration Baseline is drawn horizontally Baseline is drawn horizontally All material under the signal is included All material under the signal is included Do not integrate valley to valley Do not integrate valley to valley 8015 allows for baseline subtraction to account for column bleed but… 8015 allows for baseline subtraction to account for column bleed but… Calibration by linear regression accounts for bleed without need for subtraction Calibration by linear regression accounts for bleed without need for subtraction

Technical Details Surrogate: n-Eicosane (C 20 ) Why C 20 ? Why C 20 ? C 20 is the dividing point between the two analyte fractions C 20 is the dividing point between the two analyte fractions C 20 is in a good range to determine accurate extraction recovery C 20 is in a good range to determine accurate extraction recovery Easier to use area summing feature on software (pragmatic, not lazy) Easier to use area summing feature on software (pragmatic, not lazy)

Technical Details Surrogate: n-Eicosane (C 20 )

Technical Details Surrogate Recovery Surrogate recoveries for high concentration samples, or samples containing unknown or degraded hydrocarbons should be considered estimated. Surrogate recoveries for high concentration samples, or samples containing unknown or degraded hydrocarbons should be considered estimated.

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

Technical Details Surrogate Recovery A known amount of surrogate, n-eicosane, is added by the laboratory before extraction. A known amount of surrogate, n-eicosane, is added by the laboratory before extraction.

Technical Details Surrogate Recovery N-Eicosane is also present in many petroleum products. N-Eicosane is also present in many petroleum products. If the product is a known material, the presence and quantity of n-eicosane can be accounted for. If the product is a known material, the presence and quantity of n-eicosane can be accounted for. Diesel fuel in our method has a 1.0% contribution from C 20. Diesel fuel in our method has a 1.0% contribution from C W30 Motor Oil has a 0.22% contribution from C W30 Motor Oil has a 0.22% contribution from C 20. Our method has calculations to make corrections for surrogate recovery based on concentrations of diesel fuel and motor oil in samples. Our method has calculations to make corrections for surrogate recovery based on concentrations of diesel fuel and motor oil in samples.

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

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

Technical Details Surrogate Recovery If the surrogate recovery is so estimated, why bother to use it? If the surrogate recovery is so estimated, why bother to use it? Surrogate works OK if sample contains diesel or 10W30 and even better as the analyte levels decrease. If you have no analyte, the surrogate will give you a good measure of extraction recovery. Surrogate works OK if sample contains diesel or 10W30 and even better as the analyte levels decrease. If you have no analyte, the surrogate will give you a good measure of extraction recovery.

Technical Details FID vs MSD Why can’t we use GC/MS? Why can’t we use GC/MS? You can! Just make sure to scan to a high enough mass to get signal from all the high molecular weight compounds. You can! Just make sure to scan to a high enough mass to get signal from all the high molecular weight compounds.

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

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