Application of Stable Isotopes In Environmental Investigations

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Presentation illustrates the utility of using stable isotopes in environmental investigations. Examples include groundwater supply investigation, natural and artificial recharge, contaminant source evaluation, and salinity impact studies.

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Application of Stable Isotopes In Environmental Investigations

  1. 1. Application of Isotopes in Environmental Investigations Thomas Butler PG, CHG, CEG Senior Hydrogeologist/Geochemist butler@ecologic-eng.com El Dorado Hills, CA Nevada City, CA Rocklin, CA San Andreas, CA Stockton, CA Reno, NV
  2. 2. Why Isotopes? Potential Utility at Land Disposal Facilities Spatial Variability Adapted from Training Handbook for Disposal of Non- Non- Designated Waste to Land Systems: Design, Operation, and Monitoring. Water Board Training Academy, July 2004 Thomas Butler PG, CHG, CEG 2 butler@ecologic-eng.com
  3. 3. Why Isotopes? Potential Utility at Land Disposal Facilities Spatial Variability WWTF Not Present When GW Samples Taken Adapted from Training Handbook for Disposal of Non- Non- Designated Waste to Land Systems: Design, Operation, and Monitoring. Water Board Training Academy, July 2004 Thomas Butler PG, CHG, CEG 3 butler@ecologic-eng.com
  4. 4. Why Isotopes? Potential Utility at Land Disposal Facilities Spatial Variability Thomas Butler PG, CHG, CEG 4 butler@ecologic-eng.com
  5. 5. Why Isotopes? Potential Utility at Land Disposal Facilities Spatial Variability Thomas Butler PG, CHG, CEG 5 butler@ecologic-eng.com
  6. 6. Outline What is an isotope? Why is isotope geochemistry a useful tool in investigating environmental phenomena? Practical examples…. Thomas Butler PG, CHG, CEG 6 butler@ecologic-eng.com
  7. 7. Fundamentals Isotope – One of two or more forms of an element that have the same number of protons (atomic number) however a different number of neutrons, and thus a different atomic mass. May be stable or radioactive Thomas Butler PG, CHG, CEG 7 butler@ecologic-eng.com
  8. 8. Fundamentals Isotope Ratio: (R) = Heavy/Light Stable Isotopes Expressed as: δR = (Rsample/Rref. – 1)*1000 permil (‰) From Kendall and McDonnnell, 1998 Thomas Butler PG, CHG, CEG 8 butler@ecologic-eng.com
  9. 9. Fundamentals From Clark and Fritz, 1997 Thomas Butler PG, CHG, CEG 9 butler@ecologic-eng.com
  10. 10. Fundamentals Why are stable isotope useful? – Fingerprinting (source) and Fractionation (changes in the isotopic values) Fractionation Examples: H2O – Evaporation NO3 – Denitrification Hydrocarbons – Degradation From Clark and Fritz, 1997 Thomas Butler PG, CHG, CEG 10 butler@ecologic-eng.com
  11. 11. Fundamentals of Isotope Geochemistry from Clark and Fritz, 1997 Thomas Butler PG, CHG, CEG 11 butler@ecologic-eng.com
  12. 12. Stable Isotopes of Water Thomas Butler PG, CHG, CEG 12 butler@ecologic-eng.com
  13. 13. Stable Isotopes of Water *from Kendall and McDonnell, 1998 Thomas Butler PG, CHG, CEG 13 butler@ecologic-eng.com
  14. 14. Stable Isotopes of Water from Clark and Fritz, 1997 Thomas Butler PG, CHG, CEG 14 butler@ecologic-eng.com
  15. 15. Stable Isotopes of Water Thomas Butler PG, CHG, CEG 15 butler@ecologic-eng.com
  16. 16. Stable Isotopes of Water Thomas Butler PG, CHG, CEG 16 butler@ecologic-eng.com
  17. 17. Stable Isotopes of Water Thomas Butler PG, CHG, CEG 17 butler@ecologic-eng.com
  18. 18. Application Water Rights Appropriation, Washoe County, Nevada Thomas Butler PG, CHG, CEG 18 butler@ecologic-eng.com
  19. 19. Water Rights Appropriation Washoe County, Nevada -15.8/-122 Thomas Butler PG, CHG, CEG 19 butler@ecologic-eng.com
  20. 20. Water Rights Appropriation Washoe County, Nevada -60 WF-1 W3B W-36 W5 Coyote -70 Biddleman Well Biddleman Spring WG WS USGS Ave Truckee River USGS Ave. Truckee River USGS 19 -80 USGS 20 Water Recharge USGS 21 USGS 22 USGS 23 δ H (PERMIL, VSMOW) USGS 24 USGS 26 -90 USGS 29 USGS 30 USGS 38 USGS 47 USGS 51 USGS 53 -100 Average Local Recharge TRCC-1 TRCC-2 2 TRCC-3 -110 -120 Typical of Groundwater Dominated by Precipitation Recharge -130 -18 -17 -16 -15 -14 -13 -12 -11 -10 -9 -8 -7 -6 δ O (PERMIL, VSMOW) 18 Thomas Butler PG, CHG, CEG 20 butler@ecologic-eng.com
  21. 21. Water Rights Appropriation Washoe County, Nevada Thomas Butler PG, CHG, CEG 21 butler@ecologic-eng.com
  22. 22. Water Rights Appropriation Washoe County, Nevada Thomas Butler PG, CHG, CEG 22 butler@ecologic-eng.com
  23. 23. Application Salinity Impacts at a Land Disposal Facility, Solano County, California Thomas Butler PG, CHG, CEG 23 butler@ecologic-eng.com
  24. 24. Application – Solano County Sub-Regional Thomas Butler PG, CHG, CEG 24 butler@ecologic-eng.com
  25. 25. Application – Solano County Sub-Regional Thomas Butler PG, CHG, CEG 25 butler@ecologic-eng.com
  26. 26. Application – Solano County Sub-Regional Thomas Butler PG, CHG, CEG 26 butler@ecologic-eng.com
  27. 27. Application – Solano County Butler, 2007 Sub-Regional Thomas Butler PG, CHG, CEG 27 butler@ecologic-eng.com
  28. 28. Application – Solano County Sub- Regional Thomas Butler PG, CHG, CEG 28 butler@ecologic-eng.com
  29. 29. Application – Solano County Local Thomas Butler PG, CHG, CEG 29 butler@ecologic-eng.com
  30. 30. Application – Solano County Thomas Butler PG, CHG, CEG 30 butler@ecologic-eng.com
  31. 31. Application – Solano County PP-3 Thomas Butler PG, CHG, CEG 31 butler@ecologic-eng.com
  32. 32. Application – Solano County Combined Solute and Water Isotope Data Valuable for: Identifying Regional Mixing Related to Agricultural Water Sources Fingerprinting Salinity Sources (wastewater vs. non- wastewater) Quantification of Regional Salinity trends Identification of processes/source influencing compliance wells Thomas Butler PG, CHG, CEG 32 butler@ecologic-eng.com
  33. 33. Application Salinity Impacts at a Land Disposal Facility, Yolo County, California Thomas Butler PG, CHG, CEG 33 butler@ecologic-eng.com
  34. 34. Application – Yolo County Thomas Butler PG, CHG, CEG 34 butler@ecologic-eng.com
  35. 35. Application – Yolo County Thomas Butler PG, CHG, CEG 35 butler@ecologic-eng.com
  36. 36. Application – Yolo County Thomas Butler PG, CHG, CEG 36 butler@ecologic-eng.com
  37. 37. Application – Yolo County Thomas Butler PG, CHG, CEG 37 butler@ecologic-eng.com
  38. 38. Application – Yolo County Combined Solute and Water Isotope Data Valuable for: Fingerprinting Salinity Sources at Compliance Wells (percolated pond water vs. background source) Identification of Groundwater/Surface Water Mixing relationships Quantification of Chemical Changes in Effluent during Evaporation Thomas Butler PG, CHG, CEG 38 butler@ecologic-eng.com
  39. 39. Application Water Supply Investigation, San Joaquin County, California Thomas Butler PG, CHG, CEG 39 butler@ecologic-eng.com
  40. 40. Supply Well, San Joaquin County Thomas Butler PG, CHG, CEG 40 butler@ecologic-eng.com
  41. 41. Supply Well, San Joaquin County Thomas Butler PG, CHG, CEG 41 butler@ecologic-eng.com
  42. 42. Supply Well, San Joaquin County δ18O δ2H Well/Water Source Chloride (mg/l) (permil, VSMOW) (permil, VSMOW) Seawater 19400 0 0 Park Supply Well 36 -10.62 -77.4 ND-72M (Shallow) 12 -10.67 -77.6 ND-72M (Deep) 2160 -8.93 -69.2 This info was then used to model a theoretical Isotope dataconcentration = 2140 mg/l at the Cl indicates that 89% of water (Very similar Deep is river water ND-72M to the measured value) Thomas Butler PG, CHG, CEG 42 butler@ecologic-eng.com
  43. 43. Supply Well, San Joaquin County Thomas Butler PG, CHG, CEG 43 butler@ecologic-eng.com
  44. 44. Application Land Disposal Facility, Stanislaus County, California Thomas Butler PG, CHG, CEG 44 butler@ecologic-eng.com
  45. 45. Wastewater Treatment Plant – Conventional Aerated Pond Treatment, San Joaquin County, CA Thomas Butler PG, CHG, CEG 45 butler@ecologic-eng.com
  46. 46. Wastewater Treatment Plant – Conventional Aerated Pond Treatment, San Joaquin County, CA ‐20 MW‐1 MW‐2 MW‐3 MW‐4 MW‐5 A‐Line Irrigation Ditch Effluent Reservoir Influent (composite) Water Supply ‐30 ‐40 δ H (permil, VSMOW) ‐50 2 ‐60 ‐70 ‐80 0 500 1000 1500 2000 2500 3000 3500 4000 Chloride (mg/L) Thomas Butler PG, CHG, CEG 46 butler@ecologic-eng.com
  47. 47. Wastewater Treatment Plant – Conventional Aerated Pond Treatment, San Joaquin County, CA ‐20 MW‐1 MW‐2 MW‐3 MW‐4 MW‐5 A‐Line Irrigation Ditch Effluent Reservoir Influent (composite) Water Supply Evaporation Model (Closed) ‐30 Transpiration of Crops  Irrigated with Effluent Groundwater ‐40 δ H (permil, VSMOW) ‐50 2 ‐60 Transpiration of Crops  Irrigated with Local Groundwater ‐70 ‐80 0 500 1000 1500 2000 2500 3000 3500 4000 Chloride (mg/L) Thomas Butler PG, CHG, CEG 47 butler@ecologic-eng.com
  48. 48. Wastewater Treatment Plant – Conventional Aerated Pond Treatment, San Joaquin County, CA ‐20 MW‐1 MW‐2 MW‐3 MW‐4 MW‐5 A‐Line Irrigation Ditch Effluent Reservoir Influent (composite) Water Supply Transpiration/Mixing Model Evaporation Model (Closed) ‐30 Transpiration of Crops  Irrigated with Effluent Groundwater 100% ‐40 80% δ H (permil, VSMOW) 60% ‐50 40% 2 ‐60 20% 0% Transpiration of Crops  Irrigated with Local Groundwater ‐70 ‐80 0 500 1000 1500 2000 2500 3000 3500 4000 Chloride (mg/L) Thomas Butler PG, CHG, CEG 48 butler@ecologic-eng.com
  49. 49. Application Water Supply Investigation, Mono County, California Thomas Butler PG, CHG, CEG 49 butler@ecologic-eng.com
  50. 50. Hydraulic Connectivity of Well Supply and Surface Water – Mono County, California Gull Lake Reversed Creek - Upstream of Ski Area Ski Area Well Spring Across from Ski Area Test Well 1 Test Well 2 Thomas Butler PG, CHG, CEG 50 butler@ecologic-eng.com
  51. 51. Hydraulic Connectivity of Well Supply and Surface Water – Mono County, California Gull Lake hydraulically up gradient of supply wells and springs. Spring Potential Are the springs and/or supply wells in Production hydraulic communication with the Lake? Wells Will production from the well likely have an impact on lake levels? What are the sources (or other sources) of water to the supply wells? Surface Water Location GWE Monitoring Well 1 7,556 feet Well 2 7,566 feet Existing Production Gull Lake 7,602 feet Well Thomas Butler PG, CHG, CEG 51 butler@ecologic-eng.com
  52. 52. Hydraulic Connectivity of Well Supply and Surface Water – Mono County, California Gull Lake Reversed Creek - Upstream of Ski Area Ski Area Well Spring Across from Ski Area Test Well 1 Test Well 2 Thomas Butler PG, CHG, CEG 52 butler@ecologic-eng.com
  53. 53. Hydraulic Connectivity of Well Supply and Surface Water – Mono County, California Thomas Butler PG, CHG, CEG 53 butler@ecologic-eng.com
  54. 54. Hydraulic Connectivity of Well Supply and Surface Water – Mono County, California -100 Gull Lake Reversed Creek - Upstream of Ski Area -105 Ski Area Well Spring-Across from Ski Area Test Well 1 -110 Test Well 2 δ 2 H (permil, VSMO W) -115 -120 -125 -130 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 Chloride (mg/L) Thomas Butler PG, CHG, CEG 54 butler@ecologic-eng.com
  55. 55. Hydraulic Connectivity of Well Supply and Surface Water – Mono County, California Pumping Tests (Well 1 and Well 2) No response in observation well during pumping test of either Well 1 or Well 2 7602 feet No response in Spring during Well 1 7566 feet pumping test 7556 feet There was a response in the Spring during Well 2 pumping test Thomas Butler PG, CHG, CEG 55 butler@ecologic-eng.com
  56. 56. Isotopes and Landfills San Francisco Bay Area, California Thomas Butler PG, CHG, CEG 56 butler@ecologic-eng.com
  57. 57. Isotopes and Landfills Thomas Butler PG, CHG, CEG 57 butler@ecologic-eng.com
  58. 58. Isotopes and Mines San Francisco Bay Area, California Thomas Butler PG, CHG, CEG 58 butler@ecologic-eng.com
  59. 59. Processes Influencing Acid Generation and Metals Transport – Leona Heights Sulfur Mine, Oakland, California Thomas Butler PG, CHG, CEG 59 butler@ecologic-eng.com
  60. 60. Processes Influencing Acid Generation and Metals Transport – Leona Heights Sulfur Mine, Oakland, California Exposed waste rock and acid mine drainage (Leona Heights Sulfur Mine, Oakland, Ca) Thomas Butler PG, CHG, CEG 60 butler@ecologic-eng.com
  61. 61. Processes Influencing Acid Generation and Metals Transport – Leona Heights Sulfur Mine, Oakland, California 14 12 0% 10 δ OSulfate (permil, VSMOW) 8 6 25% 4 LHSM Alameda County, Ca Pyrite Oxidation: 2 Stoichiometric Isotope-Balance Model: 50% 1. FeS2(s) + 3.5O2 + H2O = Fe2+ + 2SO42- + 2H+ (pH>4) 0 4. δ18OSO4 = XH2O(δ18Ow + εw) + (1 – XH2O)[0.875(δ18Oa + εa) + 0.125(δ18Ow + εw)] -2 Fe2+ + 0.25O2 + H+ = Fe3+ + 0.5H2O (Catalyzed by bacteria at pH <4) 18 5. XH2O = (δ18OSO4 – 0.125*δ18Ow – 11.5375)/(0.875*δ18Ow – 7.4375) PA Coal Mines -4 75% 3. FeS2(s) + 14Fe3+ + 8H2O = 15Fe2+ + 2SO42- +16H+ -6 100% -8 -10 -16 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 18 δ OWater (permil, VSMOW) Thomas Butler PG, CHG, CEG 61 butler@ecologic-eng.com
  62. 62. Processes Influencing Acid Generation and Metals Transport – Leona Heights Sulfur Mine, Oakland, California 2.50 1200 Ferrous Iron D isso lved F erro u s Iro n Mass F lu x (m m o l/m in ) Insolation 1000 2.00 800 In so latio n (W/m 2 ) 1.50 600 1.00 400 0.50 200 0.00 0 4/25/02 0:00 4/25/02 12:00 4/26/02 0:00 4/26/02 12:00 4/27/02 0:00 4/27/02 12:00 4/28/02 0:00 Date/Time Sampled (Pacific Standard Tim e) Thomas Butler PG, CHG, CEG 62 butler@ecologic-eng.com
  63. 63. Processes Influencing Acid Generation and Metals Transport – Leona Heights Sulfur Mine, Oakland, California pH Lake Aliso ORP Lake Aliso Insolation 8.10 1000 7.90 800 I n s o la tio n (W /m 2 ) O R P (m V ) a n d 7.70 600 pH 7.50 400 7.30 200 7.10 0 7/3/2002 0:00 7/3/2002 12:00 7/4/2002 0:00 7/4/2002 12:00 7/5/2002 0:00 7/5/2002 12:00 7/6/2002 0:00 Date/Time Thomas Butler PG, CHG, CEG 63 butler@ecologic-eng.com
  64. 64. Processes Influencing Acid Generation and Metals Transport – Leona Heights Sulfur Mine, Oakland, California 250 1200 Copper Manganese Zinc Insolation 198 198 1000 191 200 181 161 161 M a ss Flux (m g /m in) 800 Inso la tio n (W /m ) 2 150 600 100 72 400 66 66 49 53 53 50 200 6.6 5.6 6.9 6.3 6.9 6.3 0 0 7/3/2002 0:00 7/3/2002 12:00 7/4/2002 0:00 7/4/2002 12:00 7/5/2002 0:00 7/5/2002 12:00 7/6/2002 0:00 Date/Time Thomas Butler PG, CHG, CEG 64 butler@ecologic-eng.com
  65. 65. Solute Isotopes/Other Tools commons.wikimedia.org/wiki/File:Boric-acid-2D.png http://www.kgs.ku.edu/Publications/pic14/pic14_1.html http://etharelkatatney.blogspot.com/2008/06/bitter-pill-to-swallow.html Thomas Butler PG, CHG, CEG 65 butler@ecologic-eng.com
  66. 66. Source of Boron Wastewater Nonmarine evaporites Borax/NaBO4 (-1 to +7‰) from Hoefs, 2004 Thomas Butler PG, CHG, CEG 66 butler@ecologic-eng.com
  67. 67. Application – Solano County Local Thomas Butler PG, CHG, CEG 67 butler@ecologic-eng.com
  68. 68. Application – Solano County PP-3 Thomas Butler PG, CHG, CEG 68 butler@ecologic-eng.com
  69. 69. Nitrate Source from Clark and Fritz, 1997 Thomas Butler PG, CHG, CEG 69 butler@ecologic-eng.com
  70. 70. Application – Solano County Thomas Butler PG, CHG, CEG 70 butler@ecologic-eng.com
  71. 71. Pharmaceuticals and PCPs Thomas Butler PG, CHG, CEG 71 butler@ecologic-eng.com
  72. 72. Rare Earth Elements Anthropogenic Gadolinium Lack of Anthropogenic Gadolinium Thomas Butler PG, CHG, CEG 72 butler@ecologic-eng.com
  73. 73. Source of Recharge and Age Dating 1.00 He Percent Relative Decrease in Solubility 0.90 0.80 Ne 0.70 Typical USA 0.60 Groundwater Temperature 0.50 N O Ar 0.40 Kr 0.30 Xe 0.20 0 10 20 30 40 50 Temperature (C) Thomas Butler PG, CHG, CEG 73 butler@ecologic-eng.com
  74. 74. Source of Recharge and Age Dating Isotope/Compound Decay Product Half Life Issues/Deficiencies (yrs) Tritium (3H) Helium-3 (3He) 12.43 Accounting for excess air and crustal sources (6Li + n = 3H + α) Sulfur Hexafluoride (SF6) NA NA Accounting for excess air and potential local sources Chlorofluorocarbons (CFCs) NA NA Reduction of the CFCs has resulted in limited uses for recent GW Recharge Krypton-85 (85Kr) Krypton-85 (85Kr) Rubidum-85 (85Rb) Rubidum-85 (85Rb) 10.76 10.76 Large volume of water (~100 L) Large volume of water (~100 L) Argon-39 (39Ar) Argon-39 (39Ar) Potassium-39 (39K) Potassium-39 (39K) 256 256 Large volumes of water Large volumes of water (~1000L); specialized analysis (~1000L); specialized analysis Thomas Butler PG, CHG, CEG 74 butler@ecologic-eng.com
  75. 75. Fundamentals of Isotope Geochemistry from Clark and Fritz, 1997 from U.S. Geological Fact Sheet 134-99 Thomas Butler PG, CHG, CEG 75 butler@ecologic-eng.com
  76. 76. The End…. http://www.youtube.com/watch?v=t5ZFoU0S5iE&NR=1 Thomas Butler PG, CHG, CEG 76 butler@ecologic-eng.com

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