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