Safety Issues of Shale Gas Extraction Waste Water Marine Chemist Association Seminar August 3, 2015

1. Safety issues ofShale gas extraction waste watermarine chemist association seminaraugust 3, 2015 Cynthia A. Znati, Ph.D. CG-ENG-5 U.S. Coast Guard Headquarters Hazardous Materials Division Washington, DC

2. USCG Headquarters Staff (CG-5PS)

3. Hazardous Materials Division (CG-ENG-5) • Division Chief • CDR Evan Hudspeth • Bulk Solids & Packaged Hazardous Materials • Amy Parker • LT Andrew Murphy • Tom Gleave • Bulk Liquids • Patrick Keffler • Chris McKenna • Liquefied Gases and Vapor Control Systems • Dr. Cynthia Znati • LT Cristina Nelson

4. Bulk Liquid Regulations • 46 CFR Subchapter D and/or O • List of tables • 46 CFR 30.25-1 • 46 CFR Table 151.05 • 46 CFR 153 Table 1 • 46 CFR 153 Table 2 • 46 CFR 154 Table 4 • 33 CFR 151.47 • 33 CFR 151.49

5. Unlisted Bulk Liquid Cargoes • 46 CFR 151.01-15(a) Any liquid or liquefied gas, which meets the definitions referred to in §151.01-1 and is not named in Table 151.05 or Table 30.25-1 of this chapter shall not be transported in bulk in a manned or unmanned tank barge without the prior specific approval of the Commandant. • 46 CFR 153.900(c) No ship may carry any bulk liquid cargo not listed in §30.25-1 of this chapter, Table 151.05 of Part 151 of this chapter, Table 1 or Table 2 of this part, Table 4 of Part 154 of this chapter, 33 CFR 151.47, or 33 CFR 151.49 unless the cargo name is endorsed on the Certificate of Inspection or contained in a letter issued under paragraph (d) of this section. • NVIC 7-87 Guidance on Waterborne Transport of Oil Field Wastes

6. Shipping Unlisted Bulk Liquid Cargoes • Shipper: • Makes written request to Coast Guard to carry the cargo • Supplies any information needed by the CG to make determination for carriage requirements • Responsible for transporting liquid in accordance with Coast Guard requirements • CG: • Specifies appropriate requirements for shipment • Provides written endorsement for shipment • Verifies compliance during standard inspections

7. Shale Gas Extraction Waste Water • Waste water by-product of hydraulic fracturing of shale formations to produce natural gas • Includes • Flowback • Production water • Formation water

8. U.S. Shale Plays

9. Hydraulic Fracturing Illustration of a horizontal well showing the water life cycle of hydraulic fracturing (U.S. EPA, 2011)

10. Transportation/Disposal of Shale Gas Extraction Waste Water Multiple options: Local storage; evaporation; truck; rail; deepwell injection. Barging is a feasible alternative for moving large quantities, over longer distances

11. Into the Well Mixture of water, sand, and chemicals • Can be reused, but not indefinitely

12. What is in the Water: Additives

13. Out of the Well • How much? • Average 4.3 millions of water used per well • Approximately 60-70% resurfaces • What? • Additives injected • Constituents in the formation • Reactions underground?

14. Heavy Metals in Marcellus Shale Production Water • Pb • 35 ppb* • As • 90 ppb* • Ba • 1450 ppm* • Cr (VI) • 539 ppb* • Mg • 177 ppm • Mg (dissolved) • 2170 ppm • Mn • 1890 ppb • Mn (dissolved) • 2975 ppb • Sr • 1115 ppm • Sr (dissolved) • 629 ppm Paleontological Research Institute, Marcellus Shale, Issue Number 8, 2011 * Exceeds EPA limit for drinking water

15. Constituents in SGEWW • TSS: 10.8-3220 mg/l • Turbidity: 2.3-1540 NTU • TDS: 3010-261,000 mg/l • COD:228-21,900 mg/l • Cl: 1670-181,000 mg/l • Br: 15.8-1600 mg/l • Na:10,700-95,500 mg/l • Sulfate: 2.4-106 mg/l • Oil & grease: 4.6-655 mg/l • BTEX: up to 5460 mg/l • VOC: up to 7260 mg/l • NORM: up to 18,000 pCi/l, median: 2460 pCi/l • Ba: 21.4-13,900 mg/l • Sr: 163-4830 mg/l • Pb: up to 0.606 mg/l • Fe: 13.8-242 mg/l • Mn: 0.881-18.6 mg/l Hammer, et al., NRDC Document May 2012 D:12-05-A

16. NORM and TENORM in SGEWW • Naturally Occurring Radioactive Materials • Ra-226 • Ra-228 • Concentrations in Marcellus Shale Formation Water • Total Ra • Range: 8 - 18,045 pCi/l • Median: 5490 pCi/l • EPA limits • Drinking water: 5 pCi/l • Industrial Effluent: 60 pCi/l Rowan, et al., USGS Scientific Investigations Report 2011-5135

17. Radium residues • Ra is chemically similar to Ca • Ra co-precipitates with Ba • Ra will deposit on surfaces

18. Radium-226 Decay Chain

19. TENORM in Shale Gas Extraction Waste • Fracturing fluid: 64-21,000 pCi/l • Flowback fluid: 551-25,500 pCi/l • Produced water: 40.5- 26,600 pCi/l • No direct measurements of scale in tanks from SGEWW • Filter cakes from POTWs • Mean: 20 pCi/g • Max: 55.6 pCi/g • Native rock: 2.4 pCi/g PADEP TENORM Study Report, Jan 2015

20. PA DEP TENORM Study • Evaluated entire natural gas production chain • Well sites • Waste water treatment plants • Publicly Owned Treatment Works • Centralized Waste Water Treatment Plants • Zero Liquid Discharge Plants • Landfills • Gas Distribution and End Use • Oil and Gas Brine-Treated Roads

21. PA DEP TENORM Conclusions • Well sites • There is little potential for internal radiation exposure to workers and members of the public from and  surface radioactivity from natural gas well site development drilling operations. • There is little potential for exceeding public dose limits from external gamma radiation during the drilling phase of natural gas wells. • There is little potential for additional Rn exposure to workers and members of the public • during the flowback phase of unconventional natural gas wells. • on or near natural gas well sites.

22. PA DEP TENORM Conclusions • Well sites • There is little potential for radiological exposure to workers and members of the public from • the handling, hauling, and temporary storage of vertical drill cuttings on natural gas well sites. • handling, hauling, and temporary storage of horizontal drill cuttings on natural gas well sites. • hydraulic fracturing proppant sand. • drilling mud. • handling and temporary storage of hydraulic fracturing fluid on natural gas well sites. • handling and temporary storage of flowback fluid on natural gas well sites. • handling and temporary storage of produced water on natural gas well sites.

23. PA DEP TENORM Conclusions • Well sites • However, there is a potential for radiological environmental impacts from spills of • hydraulic fracturing fluid on natural gas well sites and from spills that could occur from the transportation and delivery of this fluid. • flowback fluid on natural gas well sites and from spills that could occur from the transportation and delivery of this fluid. • produced water from unconventional natural gas well sites and from spills that could occur from the transportation and delivery of this fluid.

24. PA DEP TENORM Conclusions • Landfills • There is little potential for radiological exposure to workers and members of the public • from leachate at landfills. • from handling and temporary storage of filter cake at landfills that accept O&G waste for disposal. • from sediment-impacted soil at landfills that accepted O&G waste for disposal. • There is little difference in the radium detected in the leachate from the nine landfills selected based on the volume of O&G industry waste accepted and from the 42 other landfills.

25. PA DEP TENORM Conclusions • Landfills • There is little potential for • additional Rn exposure to workers and the members of the public at or from landfills that accept O&G waste for disposal. • internal and  surface radioactivity exposure to workers and members of the public at landfills that accept O&G waste for disposal. • exceeding public dose limits from external gamma radiation for workers and members of the public at landfills that accept O&G waste for disposal.

26. PA DEP TENORM Conclusions • Landfills • There is limited potential for radiological environmental impacts from spills or discharges of effluent or influent leachate at landfills that accept O&G waste for disposal. • However, there is a potential for radiological environmental impacts • from spills and the long-term disposal of landfill filter cake from landfills that accept O&G waste for disposal. • to soil from the sediments from landfill leachate treatment facilities that treat leachate from landfills that accept O&G waste for disposal.

27. PA DEP TENORM Conclusions • Gas Distribution and End Use • Radon concentrations in natural gas • are lower after underground storage. • are consistent with the Rn in natural gas concentrations in samples collected at well sites when • sampled entering power plants • sampled at compressor stations • entering the natural gas processing plant • The potential radiation dose received by home residents is a small fraction of the allowable general public dose limit of 100 mrem/yr.

28. PA DEP TENORM Conclusions • Gas Distribution and End Use • There is little potential for • exceeding public dose limits from external gamma radiation for workers and members of the public at natural gas-fired power plants. • additional Rn exposure to workers and the members of the public at or from natural gas-fired power plants. • additional Rn exposure to workers and the members of the public at or from natural gas compressor stations. • for additional Rn exposure to members of the public in homes using natural gas from Marcellus Shale wells. • There is potential for • exceeding public dose limits from external gamma radiation for workers at the natural gas processing plant. • internal and  surface radioactivity exposure to workers at the natural gas processing plant when a filter housing is opened.

29. PA DEP TENORM Conclusions • Oil and Gas Brine-Treated Roads • Radium activity measured in O&G brine-treated road samples is greater than typical surface soil concentrations. • There is little potential for members of the public exceeding the public dose limit from exposure to Ra in O&G brine-treated roads.

30. PA DEP TENORM Conclusions • Waste Water Treatment Plants • POTWs • There is little potential for • internal radiation exposure to workers and members of the public from and  surface radioactivity at POTWs. • exceeding public dose limits from external gamma radiation for workers and members of the public at POTWs. • additional Rn exposure to workers and the members of the public inside POTW-I’s. • radiological exposure to workers and members of the public from • handling and temporary storage of filter cake at POTW-I’s. • handling and temporary storage of filter cake at POTW-N’s. • sediment-impacted soil at POTW-I’s. PADEP TENORM Study Report, Jan 2015

31. PA DEP TENORM Conclusions • Waste Water Treatment Plants • POTWs • There is little potential for radiological environmental impacts from spills and the long-term disposal of POTW-N filter cake. • However, there is a potential for radiological environmental impacts • from spills and the long-term disposal of POTW-I filter cake. • to soil from the sediments from POTW-I’s. PADEP TENORM Study Report, Jan 2015

32. PA DEP TENORM Conclusions • Waste Water Treatment Plants • Centralized Waste Water Treatment Plants • There is little potential for • exceeding public dose limits from external gamma radiation for workers and members of the public at CWTs that treat O&G wastewater. • radiological exposure to workers and members of the public from • handling and temporary storage of filter cake at CWTs that treat O&G wastewater. • sediment-impacted surface soil at CWTs that treat O&G wastewater. • impacted soil at CWTs that treat O&G wastewater. PADEP TENORM Study Report, Jan 2015

33. PA DEP TENORM Conclusions • Waste Water Treatment Plants • Centralized Waste Water Treatment Plants • There is potential for internal radiation exposure to workers and members of the public from and  surface radioactivity at CWTs that treat O&G wastewater. Fixed  and  surface radioactivity may present a potential inhalation and ingestion hazard if disturbed during routine system maintenance. PADEP TENORM Study Report, Jan 2015

34. PA DEP TENORM Conclusions • Waste Water Treatment Plants • Centralized Waste Water Treatment Plants • However, there is a potential for radiological environmental impacts from spills and the long-term disposal of CWT filter cake from CWTs that treat O&G wastewater. • However, there is a radiological environmental impact to • soil from the sediments from CWTs that treat O&G wastewater. • surface soil at CWTs that treat O&G wastewater. • There is little potential for additional Rn exposure to workers and the members of the public inside CWTs that treat O&G wastewater. PADEP TENORM Study Report, Jan 2015

35. PA DEP TENORM Conclusions • Waste Water Treatment Plants • Zero Liquid Discharge Plants • There is little potential for • exceeding public dose limits from external gamma radiation for workers and members of the public at ZLDs that treat O&G wastewater. • radiological exposure to workers and members of the public from • handling and temporary storage of filter cake at ZLDs that treat O&G wastewater. • influent and effluent water at ZLDs that treat O&G wastewater. • additional Rn exposure to workers and the members of the public at ZLDs that treat O&G wastewater. • exceeding public dose limits from external gamma radiation for truck drivers from hauling O&G wastewater or sludge/filter cake from facilities that treated O&G wastewater. PADEP TENORM Study Report, Jan 2015

36. PA DEP TENORM Conclusions • Waste Water Treatment Plants • Zero Liquid Discharge Plants • There is potential for internal and  surface radioactivity exposure to workers and members of the public at ZLDs that treat O&G wastewater. Fixed  and  surface radioactivity may present a potential inhalation and ingestion hazard if disturbed during future routine system maintenance. PADEP TENORM Study Report, Jan 2015

37. PA DEP TENORM Conclusions • Waste Water Treatment Plants • Zero Liquid Discharge Plants • However, there is a potential for radiological environmental impacts from • spills and the long-term disposal of filter cake from ZLDs that treat O&G wastewater. • spills of influent and effluent water at ZLDs that treat O&G wastewater. PADEP TENORM Study Report, Jan 2015

38. PA DEP TENORM Conclusions • Radiation exposure hazards • Most exposures have little potential • Possible fixed surface radioactivity • Similar to what could be found in tanks • Potential environmental impacts PADEP TENORM Study Report, Jan 2015

39. Proposed Policy Letter for Carriage of SGEWW • Pre-shipment testing • Set conditions of carriage, including limits on NORM • Procedures/testing to prevent cross-contamination prior to shipping other cargos • Procedures/testing to ensure that tank is safe for entry to allow Coast Guard marine inspectors to conduct internal surveys during structural inspections • DOT levels of fixed and non-fixed radioactive material

40. Proposed Policy Letter • Published for comment in October 2013 • Over 71,000 comments received • Developing response

41. Coast GuardContact Information • Mailing Address:Hazardous Materials Division (CG-ENG-5)U. S. Coast Guard 2703 Martin Luther King Jr. Ave. SE STOP 7509Washington, DC 20593-7509 • E-mail: HazmatStandards@uscg.mil • Liquefied Gases and Vapor Control Systems Point of Contact: Dr. Cynthia Znati Tel: 202-372-1412 E-mail: Cynthia.A.Znati@uscg.mil