Microbial Management to Improve OBW Discharge, H2O Injection and H2O Reuse

1. Real World Surveillance, LLC 22nd Annual Produced Water Society Seminar January 17, 18, 19th, 2012 Microbial Management to Improve OBW Discharge, H2O Injection and H2O Reuse Real World Surveillance, LLC Telephone: 601.250.6256 Johnny D. Richard, Owner/Operator Cell: 601.551.0395 Certified Minority/Veteran Business Enterprise Email: rws-llc@att.net Website: www.realworldeye.com Email: contactrws@realworldeye.com “A Hands On, Eyes Open Company” “A Real Eye in the Real World”

2. “Microbial Management” • It’s a battle of the seen and the unseen. • Microbial contamination affects: • People (diseases) • Wells, Vessels, Piping and Pipelines (Plugging, Souring, MIC) • Higher Total Suspended Solids in the Produced H2O & Oil

3. “Microbial Management” Sessile -- Biomass Planktonic -- Floaters

4. Scientific Picture of Active Biomass

5. “Microbial Management” If You Don’t Measure It, You Can’t Control It! • Mechanical Microbial Control Methods: • UV (Ultraviolent) Light – DNA Structure Damage • Magnets – Ionization of bacteria environment • Chemical Treatment: Biocides • Microbiocides - chemicals that kill microorganisms, • Biostats - chemicals that limit bacterial growth and/or activity, • Chemical solvents used to clean up and dissolve solids.

6. Mechanical Bacteria TreatmentHalliburton’s “CleanStream® Service - Ultraviolet Light Bacteria Control Process for Fracturing Fluid” The cellular DNA of microorganisms like bacteria absorbs the energy from the UV light, causing damage to their DNA structure this damage interferes with many cellular processes including protein synthesis then the replication of the chromosome prior to reproduction is impaired, leaving the bacteria unable to produce proteins or replicate.

7. Mechanical Bacteria Treatment The Eco1st Separation Enhancer "separates oil & water" by causing the water molecules to lose their ability to bond with one another and any foreign contaminates contained therein. The Separation Enhancer does this by breaking dipole bonds and stripping electrons from the water and the foreign contaminates which ionizes the water into a positively charged state. When ionized the molecules repel one another and make it easy for separation of these materials to occur. Reduce need for chemicals and biocides. *Information pulled directly from ECO1ST website.

8. Microbial Test Methods Traditional Test Methods: • Culture Test: Primarily Serial Dilution or BART Testers Serial Dilution & Biological Activity Reaction Test (BART): • Sulfate Reducing Bacteria - SRB, • Acid Producing Bacteria – APB • Heterotrophic Aerobic Bacteria – HAB • Denitrifying Bacteria – DN • Nitrifying Bacteria – N • Iron Related Bacteria – IRB • Rapid Bacterial Detection and Counting Methods • Microscopic Examination • ATP Photometry • Physical and/or fluid process changes: • Biomass Coupons • Inspection Spools, etc. Note: If our goal is to improve OBW quality, then we should use a method that fits that purpose.

9. Microbial Test Method Comparison Table

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11. “Microbial Management” • ATP stands for Adenosine • Triphosphate. • ATP is the primary energy carrier • for all life (measures all cells). • 1st Generation ATP test have • existed for 30+ years. • LuminUltra has perfected the ability to measure ATP in water, • Wastewater, and organics via superior chemistry and methods. • These 2nd Generation test kits are the only products • on the market that function in all energy sector applications

12. “Microbial Management” Real World Test Methods for: Water, Fuel, Oily-based-fluid, Deposits and Surface • QGA cATP(Quench-Gone Aqueous Cellular ATP) analysis measures only intra-cellular ATP from living cells not dead ones • QGO-M (Quench-Gone Organic Modified) provides a rapid interference-free determination of microbial concentration in filterable organic fluids • DSA (Deposit and Surface Analysis) measures biological activity in deposits, biofilm collection devices, in solid products, and on surfaces. • Use all indicators: Physical Observations, Biological Activity Reaction Testers(BARTs) and 2nd Generation ATP Test Methods

13. “Microbial Management” Project Description - Example • Improve & Minimize Biocide Treatment Effect on Produced H2O • Compare Rapid Biological Test Method to Traditional Methods Testing Protocol Baseline: • Baseline Data: • Days since last biocide treatment • Current treatment rates: Water sample to chemical account rep. for residuals • BS&W (Ops Shake-outs) of affected vessels • O&G of affected vessels: Field Batch Monitor & Non-protocol GR/GRS • Millipore survey (10u Teflon) or Norman Filter (if not available onsite collect 1 qt, refrigerate and send in with non-protocol samples) *Your call • ATP Baseline Survey (Oil, Water, Emulsion Pad & Solids Interface of Vessels) • Serial Dilution - SRB/APB & BART SRB/APB Testers • pH, Temperature & Visual analysis of oil and water phase • Evaluate recycle streams into vessels when pumping • Photos *Note: Any chemical suspected of having an effect on the microbial levels of the produced water should be adjusted or optimize prior to start. Measure Wemco 02 levels

14. “Microbial Management” Testing Protocol Baseline cont’d Optional Baseline Data: • Analysis of chemical and solid residue in the water sample • Temperature, pressure, pH, dissolved O2, dissolved H2S, etc • IC/ICP water analysis • Temperature profile of vessel for solids accumulation Disposal Well (if applicable) • Disposal rate/pressure Ensure all equipment are in good working order: Chemical injection system, O&G batch/online monitor, good supply of sample bottles, S.O. machine, etc.

15. Primary Contamination Sources: Formation, Vessels(Bottoms/Interface/Fluid Outlets), Wet/Bad Oil Tanks, Treaters, & Production Sumps Testing Locations

16. “Microbial Management” • Test results will be available the same day using the LuminUltra 2nd generation test method in all fluids/solid samples collected. BARTs are maximum 10 days, whereas serial dilution are 7 – 28 days. • Labeling, documentation and photos are key to the project and comparison with the serial dilution or BART’s if you decide to use them. • It is recommended to clean the production sump if possible or treat with biocide at least twice before starting the project. For heavily contaminated systems, e.g. high ATP values >100,000 pg/mL in all locations, you might want to see how effective is your biocide batch method first, after one week or one day. In such cases a continuous treatment maybe in order to establish some control. Continuous treatment rate can be controlled using the ATP method. On the other hand, if there are minimum oil and water quality issues on your platform, you may have bacteria species that are not affecting the process. Auxiliary WHRU/Steam systems that do not contain ethylene glycol should be checked also due the reality, if you lose your heat medium system, oil and water separation becomes more of a challenge. The same can be said for the drinking water and/or potable water system. Sick personnel means not much gets done.

17. “Microbial Management” Testing Protocol Biocide Treatment: • Use the recommended treatment dosage and rate at the designated location. • Estimate the time for the biocide to travel through system to the final discharge and/or re-injection point. • Collect a visual sample at the first notice of change to the water outlet or one hour after treatment. • Testing frequency is 4, 8, 16 & 24 hours on the first day of treatment and daily until ATP values stabilize at a low point and begin to climb back up again. • It is a judgment call when to collect the serial dilutions, BART’s and other comparable methods. As a minimum to this first project, I recommend daily. • Biocides sometimes damage bacteria cells and the ATP within the cells are not fully released. This is overcome by adding the “LumiSolve Wash” after steps 1-3 in the QGA protocol. LumiSolve is a buffer that is used to re-dissolve extra-cellular ATP that may have been captured on the filter from damaged cells. This has been an issue when using Gluteraldehyde. A similar test can also be done with the LumiClean product.

18. “Microbial Management” Testing Protocol Biocide Treatment cont’d: • Time biocide treatment • Date/Time of sample, location, type of sample (water, emulsion or solids) • Current treatment rates and send a water sample to the chemical account rep. for residuals of C.I., S.I., and Biocide • BS&W (Ops Shake-outs) of affected vessels • O&G of affected vessels: Field Batch Monitor & Non-protocol GR/GRS • Millipore survey (10u Teflon) or Norman Filter (if not available onsite collect 1 qt, refrigerate and send in with non-protocol samples) *Your call • ATP Survey (Oil, Water, Emulsion Pad & Solids Interface of Vessels) • Serial Dilution - SRB/APB & BART SRB/APB Testers • pH, Temperature & Visual analysis of oil and water phase • Check status of recycle streams into vessels when testing • Photos, notes or observations Note: GR = EPA 1664 HEM, GRS = EPA SGT-HEM

19. “Microbial Management” Modified Testing Protocol: Baseline and Protocol Testing • Date/Time of sample, location, type of sample (Before and After Biocide Treatment) • Current treatment rates • BS&W (Ops Shake-outs) of affected vessels: In lieu of S.O.’s, collect a 1000 mL sample and allow it to stand until fluids separate. Photo immediately after taking sample and after complete fluid separation. • O&G of affected vessels: Field Batch Monitor & Non-protocol GR/GRS • Millipore data : collect 1 qt sample, refrigerate and send in with non-protocol samples) *Your call • ATP Survey: Collect samples in sterile vials (e.Coli samplers), allow sample to over flow, refrigerate and send in to specified lab for analyses. • Serial Dilution - SRB/APB & BART SRB/APB Testers : Collect and send in to lab. Modified Biocide Testing: 1) Test H2O outlet of vessel prior to biocide treatment, 2) Test H2O after treatment: Frequency: Day 1 (Hour 1, 4, 8, 16 & 24), then daily……

20. “Microbial Management” Verdict: All methods are unique! ≠ ≠ Viable sub-populations of total populations Total bacterial population Estimate of activity of total population

21. “Microbial Management” • Use all indicators: • Physical Observations, • Water Chemistry, • Biological Activity Reaction Testers(BARTs) and • 2nd Generation ATP Test Methods as your 1st Line of Defense Tool

22. Real World Surveillance, LLC Microbial Management Programs What is Your Microbial Management Plan to Improve OBW Discharge, H2O Injection and H2O Reuse? Incorporate the 2nd Generation ATP Technology as the “The First Line of Defense Tool”

23. “Microbial Management” Overview of: LuminUltra 2nd Generation ATP Test Methods With field test results. BART’s – Biological Activity Reaction Testers

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25. “Microbial Management”QGO-M: Quench-Gone Organic Modified EXTRACTION

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27. LuminUltra Quality Control

28. ATP Data from HED Chemical Free Debug Project

29. HED: Pre-Frac H2O Treatment Test

30. LuminUltra Technologies – April 2011 Newsletter ASTM Approves Method for ATP Measurement in Fuels • On April 1st, 2011, ASTM International approved the new method D7687 (Standard Test Method for Measurement of Cellular Adenosine Triphosphate in Fuel, Fuel/Water Mixtures and Fuel-Associated Water with Sample Concentration by Filtration). LuminUltra is pleased to announce that its QGO-M test kit is compliant with this new method. This new standard provides industry stakeholders with a rapid, portable and robust method for the quantification of total active biomass in a wide range of sample types that can be encountered in the liquid fuel handling sector. The QGO-M test kit is also compliant with ASTM Standard E2694 (Standard Test Method for Measurement of Adenosine Triphosphate in Water-Miscible Metalworking Fluids). QGO-M is fast becoming an industry standard for the measurement of total biomass via ATP in a myriad of organic-based sample types, ranging from metalworking fluids to fuels to organic chemicals and even water samples laden with organic contaminants. Click here to learn more about the QGO-M test kit and the applications to which it applies!

31. BART’s – Biological Reaction Tester Principal Microbial Groups Determinable Using the BART™ Biodetectors Microbial Community Selective Culture Medium* Iron Related Bacteria IRB Winogradsky’s medium Sulfate Reducing Bacteria RB Postgate’s medium Slime Forming Bacteria SLYM Glucose Peptone medium Heterotrophic Aerobic Bacteria HAB Sugar Peptone medium Algae ALGE Bold’s medium Fluorescent Pseudomonads FLOR Peptone base medium Denitrifying Bacteria DN Nitrate Peptone medium Nitrifying Bacteria N Ammonium salts medium Acid Producing Bacteria APB Modified Glucose Peptone medium Biochemical Oxygen Demand BOD Modified Sugar Peptone medium

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33. BART Tester

34. BART Tester Interpretation Guide

35. BART Result Interpretation

36. BART Bacteria Population Estimate

38. BART Results Photos

39. BART Results Photos cont’d

40. Real World Surveillance, LLC THANKS!