Steve Greason, Instructor Sitelab Corporation West Newbury, MA (978) 363-2299 LSP Course No. 1203, 4 Edu Credits Westford Regency Inn, Westford, MA Tuesday, February, 2 nd 2016 1:00-5:00 PM Hydrocarbon Analysis using Sitelab UVF for DENR UST Program Field Screening Petroleum Hydrocarbons Using Ultraviolet Fluorescence Technology Page 1 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
What is Ultraviolet Fluorescence? How Does it Work? Page 2 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
What Fluoresces Gasoline Jet Fuel Kerosene Diesel Fuel Home Heating Oil, No 2. Fuel Oil Heavy Fuel Oil, No. 6 Fuel Oil Motor Oils Waste Oils Lubricating Oils Cutting Oils Transformer Oil Hydraulic Fluid Gas Condensates Drilling Muds & Drilling Fluids Crude Oils Bitumen, Tar Sands Creosote, Coal Tars, Coal Ash And What Doesn t Fluorescence does not detect straight chain aliphatic hydrocarbons: PCE, TCE, dry cleaning solvents Other SVOC chlorinated solvents Methanol or Hexane used with test kits Popular UVF Applications Soil excavation and cleanup Site Assessments Remediation & Treatment UST Fuel Sites Oil Refineries, Pipeline Spills Power Plants, MGP Sites Military Sites, Airports Natural Disasters, Oil Spills Oil & Gas Production Page 3 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Aliphatic Hydrocarbons TPH by GC-FID H C CH Saturated, Straight Chain Compounds (Alkenes) Petroleum contaminants are split into different H 3 C CH 3 Carbon Ranges or Fractions: 3 3 Pentane C5 Octadecane C18 Volatile Compounds Aromatic Hydrocarbons Unsaturated, Ring Shaped Compounds (Arenes) HC HC CH CH CH CH Benzene 1-ring C6 BTEX: Benzene, Toluene, Ethylbenzene and Xylenes Naphthalene 2-rings C10 Benzo [a] Pyrene 5 rings C20 PAHs: Polynuclear or Polycyclic Aromatic Hydrocarbons Regulators are concerned with 16 PAHs in C10-C22 range GRO, VPH, BTEX, VOCs: C6-C10, C5-C12 or C6-C12 Semi to Non-Volatile Compounds TPH, EPH, EDRO, ETPH, TRPH: DRO: C10-C28 C12-C28 ORO or RRO: C20-C35 C25-C36 C28-C36 UV Fluorescence detects Aromatic hydrocarbons over a wide range of petroleum contaminants Page 4 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Portable Analyzers Available Manufactured for Sitelab Corporation by Turner Designs Hydrocarbon Instruments, Inc. Page 5 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
UVF-3100 Analyzer Publication No. EPA/600/R-01/080 Evaluated by U.S. EPA in 2001 Ranked highest compared to other screening devices for TPH in soil. Over 200 samples were tested. EPA spent $800,000 on project. Results were compared to split samples sent to certified lab for TPH analysis using 8015 by GC-FID. Sitelab s popular UVF-3100D instrument is fitted with 3 sets of optical filters which are sensitive to different hydrocarbon ranges. Can perform TPH Fingerprinting Lab Certification with NJ DEP Sitelab s laboratory and use of UVF certified from 2009 to 2015. NC DENR Regulators approve use of UVF for TPH analysis in UST Guidelines. Sample test kits and calibration kits are used for analysis Page 6 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
UVF-3100 Calibration Kits GRO: Gasoline Range Organics Product No. CAL-025, use with Slot B Optics Correlates to Total VPH by GC/FID 0.999 29 AUG 24, 2015 NOV 24, 2015 EDRO: Extended Diesel Range Organics Product No. CAL-042, use with Slot A Optics Correlates to Total EPH by GC/FID PAHs: Poly Aromatic Hydrocarbons Product No. CAL-060 Use with Slot A Optics for Total PAHs Correlates to EPH C11-C22 Aromatics by GC Or use with Slot D Optics for Target PAHs Correlates to sum of 16 EPA PAHs by GC/MS Each kit includes Certificate of Analysis and MSDS. Standards made in methanol. Calibration standards also available in hexane solvent for crude oil in water applications. Page 7 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Test Procedure is Fast and Easy 1. Weigh 5 grams of Soil 2. Add 10 ml of Solvent 3. Shake & Filter Extract 4. Dilute Extract using 2 nd Test Tube and Micropipette 5. Pour into Glass Cuvette for measurement 6. Place into UVF-3100. Concentration (ppm) is displayed in just a few seconds. Page 8 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Record and Report Test Results Soil ID UVF Reading Dilution Tested Final Concentration 1 0.550 100X Report as 55 ppm 2 OVER 100X Retest a bigger dilution 1.250 1,000X Report as 1,250 ppm 3 0.011 100X Low < 0.1 ppm Detlimit 0.077 Quality Control Tests to Perform 0.1 ppm EDRO Cal Std 5 ppm EDRO Cal Std Methanol Blank 2X Extract UVF Reading 0.109 5.122 0.001 Report as ND <0.2 ppm (2X x 0.1 ppm DetLimit) Comments Close to 0.1 ppm Close to 5.0 ppm Solvent clean, zero 5-point calibration curve and sample results can be downloaded to a computer using UVF-3100 software Page 9 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Case Studies Highlighting UVF Accuracy & Performance Page 10 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Sitelab Corporation Visit: site-lab.com USA: 978-363-2299 No. 6 Fuel EPH C11-C22 Oil Sites Aromatics Using CAL-060 on UVF-3100 Slot A Optics Results in ppm (mg/kg) Soil 1 Soil 2 Soil 3 Soil 4 Soil 5 Soil 6 Wire Factory Site in Connecticut with No. 6 Fuel Oil Lab EPH C9-C18 Aliphatics 5,100 7,700 5,600 9,600 11,000 14,000 Lab EPH C19-C36 Aliphatics 2,600 3,700 6,400 9,600 9,300 20,000 Lab EPH C11-C22 Aromatics 4,600 4,800 11,000 14,000 14,000 21,000 UVF-3100 C11-C22 Aromatics 5,300 5,250 9,100 11,800 14,400 23,600 Accuracy Y = 0.97x R 2 = 0.92 Paper Mill Site in Massachusetts with No. 6 Fuel Oil 25,000 Samples take 5 minutes to prepare and analyze. Test results directly correlate to the Mass DEP s EPH aromatic hydrocarbon fraction. Sitelab s PAH calibration kit contains same compounds used for Lab GC EPH analysis. Visible NAPL in Soil Boring Lab GC EPH C11-C22 Aromatics (ppm) 20,000 15,000 10,000 5,000 - Accuracy Y = 1.33x R 2 = 0.98-5,000 10,000 15,000 20,000 Sitelab EPH C11-C22 Aromatics (ppm) Page 11 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Sitelab Corporation Visit: site-lab.com USA: 978-363-2299 Examples testing Polycyclic Aromatic Hydrocarbons Concentrations in ppm (mg/kg) Manufactured Gas Plant UVF Results vs. Lab PAHs Target PAHs Coal Tar, Sediment Site Colorado 1,500 600 110 0.3 1,200 666 113 ND <1 Using CAL-060 on UVF-3100 Slot D Optics Naphthalene 2-Methylnaphthalene Phenanthrene Acenaphthene Acenaphthylene Fluorene Anthracene Fluoranthene Pyrene Benzo[a]Anthracene Chrysene Benzo[b]Fluoranthene Benzo[k]Fluoranthene Benzo[a]Pyrene Indeno[1,2,3)]Pyrene Dibenzo[ah]Anthracene Benzo[ghi]Perylene 14 55 11 12 ND <3 6.0 ND <3 3.6 ND <3 ND <3 ND <3 ND <3 ND <3 ND <3 ND <3 ND <3 ND <3 Concentrations in ppm (mg/kg) Soil from Wharf Site Lab PAHs = 102 ppm Sum of PAH Compounds Sitelab PAHs = 105 ppm Power Plant Petroleum Tank Farm Wharf Site Coal Ash Site North Carolina Diesel & No. 6 Fuel Oil Site Massachusetts Heating Oil & Gasoline Site Massachusetts UVF Results 30 16 9 8 UVF Results 455 370 180 75 UVF Results 213 105 70 12 vs. Lab PAHs 21 13 10 10 vs. Lab PAHs 682 350 130 80 vs. Lab PAHs 220 102 72 11 Page 12 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Gasoline Range Organics & VPH Using CAL-025 on UVF-3100 Slot B Optics Samples collected from six soil borings were split and sent to a certified lab. Results correlate well to GRO and VPH methods. Mobile lab tested 113 samples during 2-day site investigation. Data used to delineate extent of NAPL below ground. Gasoline Station UST Site in Dracut, Massachusetts: Concentrations in ppm units (mg/kg) Lab GRO (ppm) UVF-3100 GRO Results 176 666 1,481 3,037 5,704 5,570 UVF Accuracy vs. Lab GC GRO R 2 = 0.90 y = 1.18x UVF GRO (ppm) Lab GC EPA 8015-GRO 260 1,500 1,500 2,300 6,000 8,000 UVF Accuracy vs. Lab GC Total VPH Lab VPH (ppm) R 2 = 0.95 y = 1.27x UVF GRO (ppm) Lab GRO (ppm) Lab GC Total VPH 292 886 1,526 2,665 7,025 8,103 Lab GC Methods GRO vs. Total VPH R 2 = 0.98, y = 1.06x Lab VPH (ppm) EPA Method 8015 reports All hydrocarbons in the C6-C10 range. Mass DEP VPH Method reports hydrocarbon fractions SEPARATELY: C5-C8 Aliphatic Hydrocarbons C8-C12 Aliphatic Hydrocarbons C9-C10 Aromatic Hydrocarbons + Target BTEX Compounds & MtBE Page 13 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Sitelab Corporation Visit: site-lab.com USA: 978-363-2299 Contaminated Wharf Site, Massachusetts UVF-3100 EDRO Performance vs. Total EPH Method Soil # C9-C18 Aliphatics C19-C36 Aliphatics C11-C22 Aromatics Sum of 17 PAHs Lab GC Total EPH UVF-3100 EDRO Extended Diesel Range Organics Using CAL-042 on UVF-3100 Slot A Optics Samples collected from ten borings were split and sent to a certified laboratory. Sitelab EDRO correlates well to TPH & EPH Methods. GRO VPH Range Extended Diesel & Oil Range C6 C10 C36 Total Petroleum Hydrocarbons Sitelab EDRO calibration kit is specially formulated to account for aliphatics not detectable by UVF. 1 2 3 4 5 6 7 8 9 10 67 270 1,600 1,600 1,700 3,200 2,700 3,600 8,800 12,000 78 57 120 170 150 280 220 290 750 1,100 96 140 750 650 630 1,700 1,100 1,700 2,400 3,400 Concentrations in ppm units (mg/kg) ND 11 21 45 49 72 83 102 220 182 241 478 2,491 2,465 2,529 5,252 4,103 5,692 12,170 16,682 350 390 1,300 1,750 2,450 3,500 5,050 6,872 12,800 16,420 UVF Accuracy vs. Lab GC R 2 = 0.97, y = 0.95x Good! Mass DEP EPH Method reports hydrocarbon fractions SEPARATELY as illustrated above States using EPA Method 8015M or similar TPH GC Methods report SAMErange of hydrocarbons but not in fractions. Page 14 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Sitelab Corporation Visit: site-lab.com USA: 978-363-2299 Tank Battery Storage Site UVF-3100 EDRO Results 22 ppm 1,891 ppm 2,452 ppm 3,706 ppm Lab GC TPH TX 1005 Results ND <33 ppm 1,860 ppm 2,180 ppm 2,350 ppm Texas Crude Oil Sites Pipeline Spill Site 2,782 ppm 5,190 ppm 1,900 ppm 4,590 ppm Tank Battery Spill, West Texas Contractor uses their UVF-3100D analyzer to help excavate and remediate soils contaminated by produced water and crude oil. Laboratories in Texas test TPH using the TX 1005 GC-FID Method. This method is similar to U.S. EPA Method 8015M, but reports the GRO, DRO and ORO fractions separately. Texas 1005 Reports TPH in GRO, DRO and ORO Ranges: C6-C12 Gasoline Range Hydrocarbons 356 ppm C12-C28 Diesel Range Hydrocarbons 3,920 ppm C28-C35 Oil Range Hydrocarbons 314 ppm Total Petroleum Hydrocarbons (TPH) Response/Voltage + = 4,590 ppm Chromatogram shows TPH fractions. The peaks are surrogates used for quality control UVF equipment is set up in a field trailer. Customer tests soils using Sitelab EDRO, C5 C12 C28 C35 Product No. CAL-042. GRO DRO ORO Retention Time in Minutes Page 15 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
TPH Fingerprinting Applications Test for GRO and PAHs Compare Signatures to Other Contaminants Page 16 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Sitelab Corporation Visit: site-lab.com USA: 978-363-2299 Photo of Solvent Extracts at 10,000 ppm Oklahoma Crude Oil CHESTER Ref Oil 41 API Well 1 Well 2 Well 3 Well 4 MISS. Ref Oil 34 API Oil company tests crude oils from different well sites to determine the percentage of oil content from two formations. The wells tap into these zones at different depths. Knowing what type of oil being pumped is important. ppm (or%) 60 50 40 30 20 10 0 CHESTER Fluorescence Response at 100 ppm Well 1 Well 2 Well 3 Well 4 MISSISSIPPI GRO Total PAHs Target PAHs Heavy PAHs UVF-3100D TD-500D CHESTER FORMATION %? MISSISSIPPI FORMATION Use UVF Data to Calculate % Content Oils at 5 ppm Chester Well 1 Well 2 Well 3 Well 4 Mississippi Total PAHs 0.45 ppm 0.76 ppm 0.96 ppm 1.32 ppm 1.43 ppm 1.80 ppm % Content Chester 77% 62% 36% 27% % Content Mississippi 23% 38% 64% 73% Page 17 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
MW-35 Outlier? Former naphtha tank location MW-30 Weathered fuel oil and crude oil NAPL Plume at Former Refinery Site Examples at 10 ppm GRO Response DRO Response DRO/GRO Ratios MW-22 MW-30 1.52 ppm 0.73 ppm 1.80 ppm 12.5 ppm 1.2 17 MW-22 Contains mostly gasoline MW-35 0.32 ppm 0.18 ppm 0.6 NAPL samples collected from 35 monitoring wells Page 18 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Field Screening PAHs in Sediments: West Branch Grand Calumet River U.S. EPA post-dredge site in Hammond, Indiana, located near Lake Michigan. Client collected 100 sediment samples by boat using push cores. GPS used to locate samples. Sitelab s test equipment was setup in back of U-Haul truck on-site during 4-day site investigation. Dredge Site Data used by client to determine which areas would require further attention as part of cap monitoring plan. Page 19 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Sediment Contamination in River Map showing Target PAH Concentrations from 100 Sample Locations Field Trailer & Dredging Facility Hot Spots Sediments collected over a 1-mile stretch of river Fingerprinting Map showing Total PAH to Heavy PAH Signatures Older, more weathered crude oil Fresher, less weathered crude oil Hot Spots Field Trailer & Dredging Facility Page 20 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Close up of Hot Spots LAF-038 LAF-040 LAF-070 LAF- 071 LAF-073 Examples showing PAH Concentrations and Ratios Exhibited: Sample ID LAF 038 LAF 040 LAF 070 LAF 071 LAF 073 Total PAHs 75,900 ppm 5,940 ppm 19,840 ppm 17,000 ppm 42,600 ppm Target PAHs 6,240 ppm 590 ppm 1,860 ppm 1,420 ppm 4,000 ppm Heavy PAHs 2,260 ppm 696 ppm 500 ppm 426 ppm 1,700 ppm Total PAH to Target PAHs: 12x 10x 11x 12x 11x Total PAH to Heavy PAHs: 34x 9x 40x 40x 25x Page 21 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Costs & Benefits using UVF? Section of Grand Calumet River Showing Two Hot Spot Locations 400 test results in 4 days. Cost $9,500. Hot Spots Contamination identified as crude oil using fingerprinting data. Page 22 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Challenges and Limitations using UVF Technology Page 23 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Sitelab Corporation Visit: site-lab.com USA: 978-363-2299 Soils from Pipeline Spill Soil Sample 1 Soil Sample 2 Customer EDRO Results 15,150 ppm 7,160 ppm Sitelab s EDRO Results Nigeria Crude Oil Nigerian Lab GC-FID 15,000 ppm 6,829 ppm 15,430 ppm 7,800 ppm Safic Technologies, Ltd. - Port Harcourt For QA/QC, sample extracts were sent to Sitelab for EDRO analysis and results were the same. Samples were split and sent to a Nigerian lab and a highly reputable lab in the United States for confirmation. Using EPA 8015M: C9-C40 American Lab GC-FID Using EPA 8015M: C10-C36 46,000 ppm 13,000 ppm Results high! Samples retested! American Lab GC-FID 24,800 ppm 10,200 ppm Lower/better results! Remember, labs don t always get it right. Chromatograms Can Look Different Too American Lab GC Sample 1 = 24,800 ppm After testing the samples a second time, the American lab got better results. Labs from different countries report TPH in different carbon ranges. Nigerian Lab GC Sample 1 = 15,000 ppm TPH Range: C9 to C40 TPH Range: C10 to C36 Page 24 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Jet Fuel TPH Sites Consultant uses Sitelab to test soils collected from borings to delineate a large plume of jet fuel below ground. TPH is used to calculate the total mass of NAPL. Split samples were sent to a lab for analysis using the VPH/EPH method. Soil 1 Soil 2 Soil 3 Soil 4 Soil 5 Soil 6 Jet Fuel Contaminated Soils, Westover Air Force Base Concentrations in ppm units (mg/kg) UVF-3100 GRO Results 6 4,760 6,270 7,800 9,760 16,380 Lab GC Total VPH Results 8 1,100 4,200 6,500 3,900 6,000 UVF is Higher UVF-3100 EDRO Results 1 680 700 950 1,175 1,800 Lab GC Total EPH Results ND 4,400 5,000 6,700 7,000 12,000 Sitelab UVF GRO+EDRO = TPH 7 5,440 6,970 8,747 10,938 18,180 Jet Fuel Chromatogram Showing C10 to C12 Hump Total VPH C5-C12 Jet Fuels are abundant with naphtha aliphatics (the Hump ) which are not detectable by UVF Lab GC VPH+EPH = TPH 8 5,500 9,200 13,200 10,900 18,000 UVF is Lower But TPH is Accurate Total EPH C10-C36 C6 C10 C12 C36 Sitelab s UVF-3100 analyzer has optical filters sensitive to GRO and EDRO range hydrocarbons GRO EDRO UVF detects higher GRO vs. VPH due to C10 break point Page 25 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
PAHs in Asphalt Sample 1 Sample 2 Sample 3 Photo showing asphalt samples used for TD-500D evaluation (granular size 2 mm) Laboratory PAH results testing different particle sized sub-samples TD-500D PAH results ESITC France Ecole Supérieure d'ingénieurs des Travaux de la Construction de Cachan New regulations across Europe are requiring laboratory analysis for PAH content in asphalt. Scientists are using the TD-500D analyzer to monitor PAH levels in new and reclaimed/recycled asphalt. In this study, samples were ground down to different particle sizes and sent to four certified laboratories for comparison. In France, they use EPA Method 8270 for PAH analysis. Sample 1 10 mm LAB 1: ESITC 600 LAB 2 340 LAB 3 555 LAB 4 246 Sample 2 LAB 1: ESITC LAB 2 LAB 3 LAB 4 Sample 3 LAB 1: ESITC LAB 2 LAB 3 LAB 4 290 172 215 109 2,033 1,685 1,310 729 0.5 mm 270 424 367 282 129 212 195 141 747 1,347 1,231 958 2 mm 349 426 356 220 182 243 162 84 1,531 1,773 1,967 1,139 356 228 1,177 Concentrations above are in ppm units (mg/kg) The TD-500D is highly sensitive to PAHs in asphalt Samples are extracted in methanol solvent PAH Calibration Kit CAL-061 used for analysis Page 26 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
Proficiency Evaluation Study Testing Water Samples vs. 83 Laboratories Gasoline Concentration 3.47 mg/l Acceptance Limit 1.34 mg/l to 6.11 mg/l UVF-3100 GRO Result 3.33 mg/l 3.60 mg/l Laboratory Lab GC-GRO Methods Used Mean Result EPA 8015 California LUFT EPA 8015B Iowa OA-1 EPA 8015M Maine 4.2.17 EPA 8020 NWTPH-GX EPA 8260B Diesel Fuel Concentration 3.62 ppm Pretty Easy To Pass! Acceptance Limit 0.90 mg/l to 4.66 mg/l UVF-3100 EDRO Result Laboratory Mean Result 3.78 mg/l 2.60 mg/l Lab GC-DRO Methods Used EPA 8015 EPA 8015B EPA 8015M Florida PRO Iowa OA-2 California LUFT Connecticut ETPH Maine 4.2.25 NWTPH-DX Oklahoma DRO Laboratories must passthese blind tests to be certified thru the National Environmental Laboratory Accreditation Program (NELAP) or similar programs several times a year. This study conducted by ERA, Inc. Page 27 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation
End of Presentation Up Next: Test Demonstration Visit: site-lab.com Call: 978-363-2299 Page 28 of 28 LSPA Training Course, Feb 2, 2016 Sitelab Corporation