session: managing contamination north carolina dot’s experience with uv fluorescence for measuring...

SESSION: MANAGING CONTAMINATION North Carolina DOT’s Experience with UV Fluorescence for Measuring Petroleum Contamination in Soil

Cyrus Parker, LG P.E., NCDOT

The North Carolina Department of Transportation (NCDOT) has started using Ultra Violet Fluorescence (UVF) to analyze soil samples for petroleum compounds instead of the traditional USEPA Method 8015. This presentation will discuss the 3 ways NCDOT has used the UVF test, the test results and potential cost and time savings associated with using the UVF test instead of Method 8015.

Cyrus is the GeoEnvironmental Supervisor for the North Carolina Department of Transportation. He has over 18 years of experience with geoenvironmental engineering as both a consultant and with the Department of Transportation. Mr. Parker has a bachelor’s degree from North Carolina State University and licenses to practice Geology and Engineering in the state of North Carolina.

Ultra Violet Fluorescence Soil Analysis

Cyrus Parker, LG, PE

North Carolina Department of Transportation

The Green Box

OverviewUltra Violet Fluorescence (UVF)

• Introduction to UVF • Data Comparison with EPA Method 8015• User Feedback• Cost Comparison with EPA Method 8015

Weigh 10 Grams Soil

Add Methanol to soil. Shake. Wait.

Extract Sample and Transfer to Cuvette

Place Cuvette into analyzer, Enter Sample ID and Click Analyze

Diesel Fuel

Heavy Fuel Oil

Regulatory ApprovalSuspected Contaminant Analytical Methods for

Preliminary Investigation Samples

Analytical Methods for Samples Collected after Preliminary Investigation

1a. Low Boiling Point Fuels: gasoline, aviation gasoline, etc. a

EPA 8015C for TPH-GRO (or UVF for TPH)b

EPA 8260B and MADEP VPH

1b. Ethanol-Gasoline Blends EPA 8015C for TPH-GRO (or UVF for TPH)b and EPA 8260B

2. Medium/High Boiling Point Fuels: jet fuels, kerosene, diesel, fuel oil #2, biodiesel (containing diesel), etc. Varsol, mineral spirits, naphtha.

EPA 8015C for TPH-GRO and EPA 8015C for TPH-DRO (or UVF for TPH)b

EPA 8260B, EPA 8270D, MADEP VPH, and MADEP EPH

3. Heavy Fuels: #4, #5, #6 fuel oils, motor oil, hydraulic fluid, etc. Mineral oilc

EPA 8015C for TPH-DRO (or UVF for TPH)b

EPA 8270D and MADEP EPH

4. Used / Waste Oil EPA 8260B, EPA 8270D, MADEP VPH, MADEP EPH, (or UVF for TPH and PAH)b and EPA 3050B or 3051A Prep: Total Metals (Cr and Pb), EPA 8081B (pesticides),and EPA 8082A (PCBs)d

EPA 8260B, EPA 8270D, MADEP VPH, MADEP EPH, EPA 3050B or 3051A Prep: Total Metals (Cr and Pb), EPA 8081B (pesticides), and EPA 8082A (PCBs)e

a

Rev. 0412

c d

NOTE:This summary represents a review of soil samples collected as grab samples on-site, analyzed immediately in the field, followed by submitting a separate container to the laboratory for 8015 analysis. Some samples noted were submitted for UVF testing for 24 or 48 hour TAT.

Thorough Homogenization was not applied. It is important to note that the Lab and the UVF did not test the same 10g sample or extract in this correlation study.

Key Notes:

UVF and EPA Method 8015Data Comparision

  UVF/DRO 8015/DRO1) HA-1 503 2642) HA-2 68.1 46.23) HA-3 1322 10604) HA-4 0 05) HA-5 2.4 06) HA-7 2.5 07) HA-8 3.3 08) HA-9 3.8 0

• In the last 4 samples the Lab results a Non Detect and the UVF results in below the action limit. The UVF results show that there are still trace amounts in the sample. Note the fingerprint example on next slide.

• ONSITE RENTAL

0 1 2 3 4 5 6 7 8 90

200

400

600

800

1000

1200

1400Lincoln DRO Samples

QED/DRO

8015/DRO

Sample Number

DRO (

mg/kg)

UVF Fingerprint Sample HA-5 (F&R, Lincoln)

UVF fingerprint trace clearly shows the presence of a degraded petroleum hydrocarbon. This is

consistent with all samples where the Lab reports 0…

UVF/DRO 8015/DRO5) HA-5 2.4 0

• Values are very close for the DRO range.

• A 30% error bar is incorporated into this graph to show that the UVF/8015 values fall within the 30% error range.

• OFFSITE UVF LAB

0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.50

500

1000

1500

2000

2500

3000

3500

4000

Rowan DRO Samples

QED/DRO

8015/DRO

Sample Number

DRO (

mg/kg)

  UVF/DRO 8015/DRO1) 4-1 40.5 1232) 4-3 13.8 6.63) SB-1 3504.6 34404) SB-2 2356 32205) SB-7 579.2 528

0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.50

1000

2000

3000

4000

5000

6000

6.9 0

5170 5230 5360

4.6 0

844.7989.9

293.4

Rowan GRO Samples

QED/GRO

8015/GRO

Sample Number

GRO (

mg/kg)

• Highlighted numbers are very close to standard calibrator values for GC 8015.

• All other samples correlated

• OFFSITE LAB

  UVF/GRO 8015/GRO4-1 4.6 6.94-3 0 0

SB-1 844.7 5170SB-2 989.9 5230SB-7 293.4 5360

SB-1 Lab Result   UVF/GRO 8015/GROSB-1 844.7 5170

SB-2 Lab Result  UVF/GRO 8015/GRO

SB-2 989.9 5230

SB-7 Lab Result  UVF/GRO 8015/GRO

SB-7 293.4 5360

Background Organics

*The top 2 fingerprints represent the presence of the contaminant in high concentrations.

*The bottom 2 fingerprints represent how a negative on the Rowan site would appear with background organics.

  UVF/GRO UVF/DROSB-1 844.7 3504SB-2 989.9 2356SB-3 0 0SB-4 0 0

*Please note the dates in which the samples where collected and the dates in which they were analyzed at the lab. UVF sample data was generated within 24 hours.

The UVF fingerprints exhibit the high levels of background organics in the samples, which may account for the high recoveries and results in the lab data.

The Matrix Spike and Matrix Spike Duplicate for these samples show 133% and 155% surrogate recovery. They have a qualifier to that effect In the QA/QC data.

0 2 4 6 8 10 120

5000

10000

15000

20000

25000

30000

35000

0 22.9 308

26600

252

54604580

0 148 1712.9 2.1 30.6

31283

190915.3

4515.8

7184

21.5 13.7

Guilford DRO Samples

QED/DRO

8015/DRO

Sample Number

DRO (

mg/kg)

  UVF/DRO 8015/DRO

110-3-10 12.9 <7.0

137-7-2 2.1 22.9

137-8-15    

155-4-10 30.6 308

66-6-10 31283 26600

66-14-8 190 252

66-19-9 915.3 5460

66-25-12.5 4515.8 4580

66-26-11 7184 0

116-16-10 21.5 148

116-16-12 13.7 17

*Sample 66-26-11 is a major discrepancy. A review of S&ME field

notes indicated a positive PID reading,

odor and discoloration for this sample.

0 2 4 6 8 10 120

20406080

100120140160180200220240260280300320340360380400

012.9

0 0 7.9 0

40.1

0

63.8

120

0 0 3.7 4.2 7.6

83.1

176.2

54

25.48.8

Guilford GRO Samples

UVF/GRO

8015/GRO

Sample Number

GRO (

mg/kg)

 UVF/GRO 8015/GRO

110-3-10 0 0137-7-2 0 12.9

137-8-15 3.7 <7.2155-4-10 4.2 066-6-10 2432 69666-14-8 7.6 7.966-19-9 83.1 <6.725-12.5 176.2 40.126-11 54 0

116-16-10 25.4 63.8116-16-12 8.8 120

Sample fingerprints on the following slides exhibit background organics and

explanation of conflicts.

• ONSITE LAB

137-7-2 Exhibits background organics substantial in the low level sample. 66-6-10 Exhibits an over range sample that was not diluted or recalculated with the UVF and may have been closer to Lab result.110-3-10 Lab reports <7.0 mg/kg for DRO, UVF reports 12.9 mg/kg DRO. Product is present in sample.

  UVF/DRO 8015/DRO

137-7-2 2.1 22.9

66-6-10 31283 26600

110-3-10 12.9 <7.0

137-8-15 Normal blank subtraction was not carried out in this sample. UVF reported 3.7 mg/kg GRO and the Lab reported <7.2 mg/kg GRO.

66-19-9 High concentrations of degraded diesel would require a large dilution by GC for the DRO range and it is possible the GRO range was diluted away in the process. Lab reports 5,460 mg/kg DRO and < 6.7 GRO respectively. This product is NOT highly degraded, thus to produce such high levels of DRO and NO GRO would be atypical for Diesel fuel.

 UVF/DRO

8015/DRO

UVF/GRO

8015/GRO

137-8-15 <1.3  <6.1 3.7 <7.266-19-9 915.3 5460 83.1 <6.7

*PLEASE NOTE background and particulate present in the samples from this site.

• The Fingerprints clearly show the presence of petroleum product.

0 1 2 3 4 5 6 70

50

100

150

200

250

300

350

400

450

19.6

391

17.10 0 0

4.8

37.315.3 12.1 4.8 1.9

Pitt DRO Samples

QED/DRO

8015/DRO

Sample Number

DRO (

mg/kg)

  UVF/DRO 8015/DRO

101_SS-1 4.8 19.6

96_SS-7 37.3 391

071_2-2 15.3 17.1

075_3 12.1 0

079-1 4.8 0

085_1 1.9 0

• 100% Correlation

0 1 2 3 4 5 6 70

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0 0 0 0 00 0 0 0 0 0

Pitt GRO Samples

QED/GRO

8015/GRO

Sample Number

GRO (

mg/kg)

  UVF/GRO 8015/GRO

101_SS-1 0 0

96_SS-7 0 0071_2-2 <0.6 0075_3 <07 0079-1 <0.6 0085_1 <0.6 0

71-2(0-2) Lab reports 17.1 mg/kg DRO and UVF reports 15.3 mg/kg DRO, which shows almost a perfect correlation.

75-3(0-2) Lab reports 0 mg/kg for DRO and UVF reports 12.1 mg/kg DRO. A very clear fluorescent fingerprint of fuel product.

  UVF/DRO 8015/DRO

071_2-2 15.3 17.1

075_3 12.1 0

79-1(0-2) Lab reports 0 mg/kg DRO and the UVF reports 4.8 mg/kg DRO. A very clear fingerprint of fuel product is shown in the fingerprint. Perhaps it was detected below the lab PQL?

85-1(0-2) Lab reports 0 mg/kg DRO and UVF reports 1.9 mg/kg. Perhaps it was detected below the lab PQL? 

  UVF/DRO 8015/DRO

079-1 4.8 0

085_1 1.9 0

  UVF/DRO 8015/DRO

96_SS-7 37.3 391

Batch SS-7 QC Data

  UVF/DRO 8015/DRO

96_SS-7 37.3 391

?

SS-7 Chromatogram

User Feedback

Extremely poor Poor Satisfactory Good Excellent0

1

2

3

4

5

6

7

8

9

0

1

7

8

0

Overall experience using rapid UVF analysis.

Would you recommend replacing traditional TPH/GRO/DRO chemistry with rapid UVF analysis for soil site assessments?

No

Yes

Would you recommend replacing traditional TPH/GRO/DRO chemistry with rapid UVF analysis for soil site assessments?

No33%

Yes67%

Are You Confident in Rapid UVF Analysis?

Cost Analysis

UVF Options

• Onsite UVF Equipment Rental for Immediate Results• ~$800 per day

• Rental• Shipping• Supplies• Additional Labor

• Onsite Laboratory for Immediate Results• ~$1100 per day (all inclusive)

• Ship to Offsite Laboratory for 24 or 48 hour Results• 24 hour $55 per sample• 48 hour $45 per sample

Actual 8015 2 week Turnaround Price if UVF 48 HR Turnaround Price if 8015 48 HR Turnaround $-

$10,000.00

$20,000.00

$30,000.00

$40,000.00

$50,000.00

$60,000.00

$70,000.00

$80,000.00

$90,000.00

$100,000.00

Method 8015 vs UVF Cost Analysis

Laboratory Cost

Price if 8015 48 HR Turnaround Price if UVF 48 HR Turnaround $-

$50,000.00

$100,000.00

$150,000.00

$200,000.00

$250,000.00

$300,000.00

$350,000.00

$314,874.00

$51,682.50

8015 vs UVF Cost Analysis

Laboratory Cost

The Real Question

Would the regulatory decision change if UVF was used instead of Method 8015?

No90%

Yes10%

Change recommendations as a result of using UVF for GRO samples?

No80%

Yes20%

Change recommendations as a result of using UVF for DRO samples?

No84%

Yes16%

Change Site Recommendation as a result of using UVFBased on 49 sites

Conclusions

• Flexibility for onsite or laboratory analysis• Potential cost and time savings• Experienced users like the system• Less Experienced users can ship samples to laboratory

for analysis similar to their current process• Using UVF would not have change our

recommendations, most of the time

Felecia Owen

QROS, LLC

fowen@qros.us

919-278-8926

http://qros.us/

More Information?

Cyrus ParkerNCDOTcfparker@ncdot.gov919-707-6868