A presentation given to Michigan Association of Environmental Professionals last spring. Heavy focus on heterogeneity and difficulty of determining NAPL with monitoring wells and traditional analytical chemistry of dissolved phase.

1. Optical Screening Tools for Characterizing NAPL Source Zones Randy St. Germain Dakota Technologies, Inc.

6. Dakota Technologies’ LIF History Optical Screening Tools (and yours truly) have existed for > 15 yrs

7. Today’s Optical Screening Tools Soil Color TarGOST – Tar-specific Green Optical Screening Tool UVOST - Ultra-Violet Optical Screening Tool ROST - Rapid Optical Screening Tool FFD – Fuel Fluorescence Detector NA Model fuels/oils (poor jet fuel response) nitrogen laser-337 nm OMA detector CPT only SCAPS (Army/Navy/AF) gov’t use coal tars/creosotes containing moderate to heavy PAH Nd:YAG laser - 532nm spectral/temporal Percussion & CPT Dakota Dakota exclusively Munsell soil color, soil class, ??? broadband white light reflectance Percussion & CPT Dakota mfct’d offered by Dakota and available to providers fuels/oils containing low to moderate PAH XeCl laser - 308nm spectral/temporal Percussion & CPT Dakota offered by numerous field service providers fuels/oils containing low to moderate PAH dye laser - 290nm spectral/temporal hybrid CPT only Dakota Fugro exclusively fuels/oils containing low to moderate PAH CW Hg Lamp - 254.7 nm PMT CPT only Vertek mfct’d offered by numerous field service providers Target Technology / Deployment Manufacturer / Providers

9. real time “NAPL hunt” Real-Time In-Situ Characterization Detailed Conceptual Model higher quality information for higher quality engineering/decisions Optical Screening Tools

10. Fluorescence Spectroscopy of Optical Screening Tools (the “mysterious magic” behind the technology) spectroscopy = the study the interaction between light and matter fancy quantum level physics rule the behavior molecules first absorb light – then might rid themselves of that energy by emitting light aromatic (ring-shaped) molecules excel at this especially poly cyclic aromatic hydrocarbons (PAHs) For details - see Joseph R. Lakowicz’ “ Principles of Fluorescence Spectroscopy ”, 3 rd Edition

11. PAH aromatic rings

12. PAH Properties fuels/oils are “soups” made up of various PAHs “PAH-16” lab analysis only analyzes for 40% of coal tar PAHs and 1% of petroleum PAHs! for instance – look what you get if you analyze just for naphthalene 31 1.4 2.8 Triphenylene 196 2.2 6.9 Chrysene 90 1.2 2.3 Benz[a]anthracene 23 41 4.5 Pyrene 240 37 2.9 Fluoranthene 828 7677 89 2-Methylphenanthrene 43 173 - 1-Methylphenanthrene 482 429 26 Phenanthrene 2400 3600 <100 Fluorenes 8800 18400 1900 Trimethylnaphthalenes 12300 31100 2000 Dimethylnaphthalenes 4700 18900 700 2-Methylnaphthalene 2800 8200 500 1-Methylnaphthalene 1000 4000 400 Naphthalene Bunker C residual oil (µg/g) No. 2 fuel oil (µg/g) Kuwait Crude (µg/g) Compound PAH concentrations in a crude oil and two distillate fuel oils (From Neff, 1979)

13. PAHs prefer NAPL that’s why they call it “source term” 1.3 x 10-5 164 0.00053 6.4 276 2 indeno[1,2,3-cd]pyrene (193-39-5) 2.8 x 10-9 217 0.0043 6.06 252.32 2 benzo[k]fluoranthene (207-08-9) 166 252.32 2 benzo[j]fluoranthene (205-82-3) 0.13 x 10-5 to 0.133 at 20°C 168 0.014 6.06 252.32 2 benzo[b]fluoranthene (205-99-2) 0.37 x 10-6 179 0.0038 6.0 252.32 1,2 benz[a]pyrene (50-32-8) 14.7 x 10-3 162 0.0057 5.6 228 1 benz[a]anthracene (56-66-3) 1328 111 0.26 5.1 202.26 1 fluoranthene (206-44-0) 91.3 x 10-6 156 0.135 4.9 202.26 1 pyrene (129-00-0) 25 216 0.045 4.5 178.24 1 anthracene (120-12-7) 90.7 101 1.29 4.5 178.24 1 phenanthrene (85-01-8) 94.7 116.5 1.98 4.18 166 1 fluorene (86-73-7) 594 95 3.42 4.33 154.21 1 acenaphthene (83-32-9) 11 960 80.5 31.7 3.5 128.16 1 naphthalene (91-20-3) Vapor pressure at 25 °C (mPa) Melting point (°C) Water solubility at 25°C (mg/L) log Kow Molecular weight Compound (C.A.S.N°)

14. fortunately all PAH NAPLs fluoresce PAH fluorescence is a way to detect them by their “glow” short UV long UV kerosene gasoline diesel oil

15. Laser-Induced Fluorescence (LIF) it’s the poly-cyclic aromatic hydrocarbons (PAHs) found in all petroleum, oils, lubricants (POLs) that are responsible for their innate fluorescence emission spectrum is unique for each PAH – does not change with excitation wavelength

16. Laser-Induced Fluorescence (LIF) Concepts in fuels there is a mix of many PAHs their spectra overlap and you lose ability to identify any one PAH – just classes at best emission spectrum is still unique for each PAH BUT… the effect of different excitation spectra for each PAH DOES cause a change in overall emission spectrum

17. UVOST emission spectra for typical fuels naphthalene phenanthrene pyrene benzo[e] pyrene size/substitution

18. Laser-Induced Fluorescence (LIF) Concepts there is a 3 rd dimension to fluorescence that most people don’t know (or care) about it involves time over which a population of excited PAHs fluoresce

19. Laser-Induced Fluorescence (LIF) Concepts each mix of PAHs (along with the aliphatic solvent, oxygen concentration, matrix, etc.) yield a fairly unique wavelength/time matrix or “WTM” all “classes” of fuels/oils have a characteristic WTM

20. Laser-Induced Fluorescence (LIF) Concepts WTMS are powerful – but they couldn’t be obtained “on the move” and folks wanted them every foot or so (back in ROST’s early days – mid 90’s) so we were forced to get “clever” and design a solution… time delayed fluorescence “channels” solve this

21. Laser-Induced Fluorescence (LIF) Concepts with time delay you combine spectral (wavelength/color) and temporal (lifetime) fluorescence info that’s being emitted by the NAPL for fast simultaneous quantitative and qualitative information – a multi-wavelength waveform is “tough to beat”

22. Colorization of UVOST Waveforms

26. The Basics of Optical Screening Tool and Direct Push

29. UVOST response to various common PAH-containing NAPLs these logs demonstrate quantitative and qualitative response note the variable waveform shapes and varying intensity (%RE on x-scale) (similar to how a PID has variable response to VOCs)

30. UVOST Response of Various NAPLs

31. UVOST Response of Various NAPLs note poor response to coal tar, creosote, bunker (bottom 3) due to energy transfer ( too much PAH) TarGOST (discussed later) provides solution to these problematic compounds some bunkers/coal tars/creosotes have no fluorescence at all these three are “exceptional” and do fluoresce somewhat

32. lab study – demonstration of “semi-quantitative” performance of UVOST

33. UVOST logs contain both semi-quantitative and qualitative data

36. in-situ vs lab or “homogenized” samples natural heterogeneity often allows “easier” detection of NAPL vs homogenized lab samples so lab-based LODs are typically conservative

38. Example Field UVOST Logs JPGs and .txt files - the OST service “deliverable” MN – Service Station - 2 NAPLS (oil top.... gasoline bottom) MN - bus garage/terminal No. 1 Fuel Oil (kerosene)

39. Example Field UVOST Logs IA – railroad yard diesel WI – plastic plant - plasticizer cut w/diesel fuel previoulsy remediated (dug out) to 10 feet later, free product in a well – LIF shows flawed CSM

44. TarGOST versus…

45. TarGOST (good) versus… note that recording “maximum” and correlating vs lab is a bad idea integrate the same zone depth as soil sample came from average across this lower NAPL zone is 150% vs 100%

46. UVOST versus…

47. UVOST (good) versus…

48. UVOST versus…

49. UVOST (bad) versus… This also happens all the time with sampling/coring but nobody recognizes/realizes it due to expense/time of doing twins. reaction of young consultant who was “hornswoggled” into using new-fangled UVOST – duplicate is terrible!

50. 3D UVOST Field Data CSMs

52. remember the poor performance of UVOST on “heavies”? here is typical MGP coal tar on UVOST

53. PAHs, Excitation Wavelength, and Energy Transfer 308 – UV – high energy 308 – UV – high energy dilute PAHs (fuels and light oils) strong absorbance by smaller PAHs low chance of energy transfer few neighboring large PAHs strong fluorescence conc’d “close packed” PAHs (tars, creosotes, heavy crude) strong absorbance by smaller PAHs high chance of energy transfer many neighboring large PAHs weak if any fluorescence 532nm – visible - low energy conc’d “close packed” PAHs (tars, creosotes, heavy crude) no absorbance by smaller PAHs direct excitation of large PAHs low chance of energy transfer moderate fluorescence excited state energy “ cloud”

54. typical MGP coal tar on TarGOST

55. Tar-Specific Green Optical Screening Tool (TarGOST  ) designed specifically for MGP and Creosote LNAPL and DNAPL visible excitation defeats the energy transfer trap by “skipping over” the absorbance of the excitation source by the smaller PAHs who “love” to absorb UV but then transfer their energy to larger PAHs… which ultimately “quenches” fluorescence basically the visible light zips through smaller PAHs and is only absorbed by the very large PAHs which are much more likely to fluoresce due to lack of suitable “neighbors” to which they can transfer their absorbed energy instead of fluorescing especially effective for “near shore” coal tar in rivers/bays/lake sediments – where drilling is difficult rainbow sheen/blebs often indicate that “something’s amiss”

56. Typical MGP Coal Tar on UVOST vs. TarGOST TarGOST UVOST

59. Example TarGOST Field Logs NY – former MGP near river done from a barge in > 20 ft. of water Oregon 150ft – mobile NAPL at 100ft (first 30 ft were in open hole)

60. Example TarGOST Field Logs WI - 2 layers of MGP NAPL separation into LNAPL/DNAPL? CA crude oil TarGOST response >>> than UVOST

61. Do TG logs “jive” with reality? Red MGP oil

62. 2D and 3D Visualization of TarGOST Data

63. 3D Visualization of TarGOST Data

64. 3D Visualization of TarGOST Data MGP NAPL pooling on clay feature (ivory color)

65. 3D Visualization of TarGOST Data Superior WI – MGP (now water treatment plant)

66. Potential Sites/NAPLs Compatible with TarGOST no one wants to get ‘burned’ by recommending an innovative technology that fails (snake oil) neither does Dakota want to end up at a site where we don’t deliver what client needs so we typically discuss the site at length, learn what’s needing to be accomplished (drivers) and fully examine all the “what ifs” and only do projects we’re confident in Dakota provides examination of target NAPL samples, samples of potential false positives/negatives (lamp black, pitch, spent lime, wood purifier waste, etc.) at no charge example client sample logs

74. some TarGOST publications Publications R. St. Germain, B. J. Fagan, S. M. Carroll, W. R. Fisher; A Continuous In-situ Dart Profiling System for Characterization MGP Coal Tar and PAH Impacts in Sediments: A Technology Using Laser Induced Fluorescence in Sediments. EPRI, Palo Alto, CA, Alliant Energy, Madison, WI, and Ameren, St. Louis, MO: 2007. 1014749 D. Bessingpas, N. Gensky, R. St. Germain, J. Clock, A. Coleman; Deep Water Sediment Application of the TAR-Specific Green Optical Screening Tool (TarGOST) at a Manufacturing Gas Plant (MGP) Site in New York Proc: EPRI Manufactured Gas Plants 2007 Symposium , (2007). R. St. Germain; New Generation of In-Situ Sensors for Contamination Detection and Characterization. Proc. Groundwater Resources Association Symposium “High Resolution Site Characterization and Monitoring”, (2006) R. St. Germain, S. Adamek and T. Rudolph, “In situ Characterization of NAPL with TarGOST® at MGP Sites, &quot; Land Contamination & Reclamation , 14(2), 573-578(6) (2006). M. B. Okin, S. M. Carroll, W. R. Fisher, and R. W. St. Germain, &quot; Case study: confirmation of TarGOST laser-induced fluorescence DNAPL delineation with soil boring data, &quot; Land Contamination & Reclamation , 14(2), 502-507(6) (2006). C. F. Ferland, R. W. St. Germain, P. Haederle, D. Ostrye, and J. Perlow, &quot;Rapid Delineation of OLM/TLM in Soil using the Tar-Specific Green Optical Screening Tool (TarGOST),&quot; Proc: Natural Gas Technologies II: Ingenuity & Innovation , (2004). R. W. St. Germain, G. D. Gillispie, S. D. Adamek, and T. J. Rudolph, &quot;Rapid MGP Site Characterization with Tar-Specific Green Optical Screening Tool (TarGOST ) ,&quot; Proc: EPRI Manufactured Gas Plants 2003 Forum , (2004).

78. Simultaneous EC, Soil Color, and Hammer Rate key feature is EC/Soil Color “ collaboration” a peek at our brand new tools… EC – TarGOST EC- UVOST EC – SCOST Hammer Rate other combinations to come…

79. OST Data more information = better CSM

80. What will OSTs do next? they will advance…

81. Thank you! Randy St. Germain, President [email_address] Dakota Technologies, Inc. 2201-A 12th St. N. Fargo, ND 58102 Phone: 701-237-4908 www.dakotatechnologies.com