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    11/4/2010 Confidential Information 2010 M-I SWACO1

    Equilibrating Water Utilization in Shale Gas

    Operations Through Water Treatment Technologies

    Scott LaRue

    Water Treatment Technologies Operations Manager

    US Land

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    11/4/2010 Confidential Information 2010 M-I SWACO2

    Emerging Shale Gas Plays in USA

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    11/4/2010 Confidential Information 2010 M-I SWACO3

    Water = Scarce Resource

    Growing Population

    Changing Environment

    Consumption

    Industrial Utilization

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    11/4/2010 Confidential Information 2010 M-I SWACO4

    Regulations

    Meet Ch. 95 discharge standards

    TDS 500 mg/L as AML; 1,000 mg/L as MDL

    Chloride 250 mg/L as AML; 500 mg/L as MDL

    Total Barium 10 mg/L as AML; 20 mg/L as MDL

    Total Strontium 10 mg/L as AML; 20 mg/L as MDL

    Monitor for NORM

    Radium

    Alpha

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    11/4/2010 Confidential Information 2010 M-I SWACO5

    Water Recycling

    Goals:

    Recycle/Reuse flow back and produced

    waters

    Reduce fresh water consumption Reduce disposal cost

    Reduce trucking cost

    Environmentally safe

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    CONFIDENTIAL INFORMATION 2009 M-I L.L.C.

    Integrated Oil Field WaterManagement

    Central Location

    M-I SWACO Water Treatment

    On Site

    M-I SWACO Water Treatment

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    11/4/2010 Confidential Information 2010 M-I SWACO7

    Water Treatment Technologies

    Filtration

    Reclamation

    Disinfection / Bacteria Control

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    11/4/2010 Confidential Information 2010 M-I SWACO8

    Aqualibrium Systems for Water Recycling

    Aqualibrium Filtration System

    Filtration of total suspended solids

    99.9% water recover for reuse

    Inexpensive with all flow back and

    produced waters

    Low energy consumption

    Highly mobile

    Aqualibrium Reclamation System

    Chemical precipitation of contaminates

    Filtration of total suspended solids

    99 to 90% water recover for reuse

    Adaptable to changes in feed water

    chemistry

    Low energy consumption

    Highly mobile

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    11/4/2010 Confidential Information 2010 M-I SWACO9

    Aqualibrium Filtration System - Dirty

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    11/4/2010 Confidential Information 2010 M-I SWACO10

    Aqualibrium Filtration System - Processed

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    11/4/2010 Confidential Information 2010 M-I SWACO11

    Contaminant Issues

    Concerns Culprits Potential Impact

    Hardness Ca, Mg, Ba, Sr Creates borate cross links, may contribute to norm

    Friction Reducer

    Effectiveness

    Multivalent Ions (Fe, Ca,

    Mg, Ba, Sr)

    Can reduce friction reducer effectiveness, drive up horspower costs

    Scaling calcium carbonate,

    calcium sulfate, barium

    sulfate, strontium

    sulfate, and iron sulfide

    Equipment fouling, can clog flow lines, form oily sludges that must be removed, and form

    emulsions that are difficult to break

    Bacterial Corrosion Bacteria and

    Microbacteria

    Can clog equipment and pipelines and accelerate corrosion and form slime. Can reduce viscosity to effectively transport

    propant. Slime s and oxides can plug formations and reduce permeabil ity. They can also form difficult- to-break emulsions and

    hydrogen sulfide, which can be corrosive.

    Metals Principal ly I ron Potential tox ici ty, can cause production problems ( iron in p rodu ced water can react wi th ox ygen in th e ai r to pro duce sol ids,

    which can interfere with processing equipment, such as hydrocyclones), and can plug formations during injection, or cause

    staining or deposits at onshore discharge sites

    Low pH Can disturb the oil/water separation process and can impact receiving waters when discharged. Many chemicals used in scale

    removal are acidic.

    Norm Sulfates, Barium,

    Strontium, Calcium,

    Chloride

    Sulfate concentration controls the solubility of several other elements in solution, particularly Barium and Calcium. Barium,

    Calcium and Strontium sulfates are larger compounds, and the smaller atoms, such as Radium 226 and Radium 228 can fit into

    the empty spaces of the compound and be carried through the flowback fluids. Radioactive ele ments may precipitate,

    endanger public water supplies. The real issue is with accumulation in equipment, which is also difficult to measure

    accurately. Typically not a problem in situ, unless concentrated. Barium / Barium Sulfate is acid insolu ble and has to be

    removed mechanically (drilled out). Barium is highly soluble in Chloride, which can precipitate quickly with sulfates.

    Too Sal ine (High TDS) Any salt, but principally

    Chlorides

    Can impair friction reducer and drive up costs of additives and drive up cost of horsepower for pumping. Some claim

    freshwater may dissolve reservoi r salts for better production (Highly contested and debated topic). Freshwater preferred if

    not clay content. KCL can also adversely sensitize the shale by removing calcium such that fresh water can be damaging.

    Clay Swelling - Not enough

    Salt for clay formations

    Insufficient salt Some salt preferred if formation has clay. If injected water is less saline than formation water, can cause clay swelling and

    reduce permeability. 1-3% KCL typically used as clay stabilizer to prevent swelling

    Iron f ines, scale, SRB and H2S Fe Dispersed Iron can consume the scale Inhibitor, can act as metabol ic source for Sulfate Reducing Bacteria, may combine oxygen

    to produce insolluble iron fines

    Reservoir Production Oil wetting can wet the shale, causing problems

    Gel Stabi li ty Divalent cation s To o high divalent cations can co nf li ct w ith ge l s tabi li ty to su pport proppant co nduction

    H2S Bacteria Sul fate Redu cing Bacteria (most commo n) can p rod uce H2S; Stron g env ironmental and safety concerns for H2S

    Transport Costs TDS, Chlorides Like to keep less than 3,000 so can use irrigat ion l ines for transport . Potential to seep out of irrigation l ines, could prohibit use.

    Reservoir Performance Chlorides Want to keep under 40K to not impair friction reducer effectiveness. 20J-25K ppm will adversely affect gel performance.

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    11/4/2010 Confidential Information 2010 M-I SWACO12

    Water Disinfection Technologies

    Chlorine Dioxide

    Ozonation

    Hypochlorous Acid

    Ultra Filtration (size exclusion technology)

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    11/4/2010 Confidential Information 2010 M-I SWACO13

    Types of Bacteria

    Common Types of Bacteria in flowback andfracing waters:

    a. Iron Reducing Bacteria (IRB)

    b. Slim Forming Bacteria (SLYM)

    c. Sulfate Reducing Bacteria (SRB)

    d. Acid Producing Bacteria (APB)

    e. Aerobic Bacteria

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    11/4/2010 Confidential Information 2010 M-I SWACO14

    Why is Disinfection Required?

    The presence of bacteria in fracturing fluids can cause:

    Microbial Induced Corrosion

    Reservoir Souring

    Odor Issues/Sulfide Production (QHSE Issues) Plugging

    Disinfection Level:

    o General Statement : Complete kill

    What is currently used: biocides

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    11/4/2010 Confidential Information 2010 M-I SWACO15

    Log Reduction

    1 log reduction means the number of germs is 10 times smaller

    2 log reduction means the number of germs is 100 times smaller3 log reduction means the number of germs is 1000 times smaller

    4 log reduction means the number of germs is 10,000 times smaller

    5 log reduction means the number of germs is 100,000 times smaller

    6 log reduction means the number of germs is 1,000,000 times smaller

    7 log reduction means the number of germs is 10,000,000 times smaller

    M-I SWACO Bacteria Disinfection Criteria 3 log reduction

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    11/4/2010 Confidential Information 2010 M-I SWACO16

    Chlorine Dioxide OverviewDisinfection Mechanism

    ClO2 can penetrate biofilm in a selective oxidation mode:

    - Helped by small size of the molecule, attraction to amino acids and reaction speed.

    - ClO2 can penetrate the cell walls inside the biofilm in search of these chemical functionalities.

    - Other indiscriminant oxidizers simply react with the C=O double bonds on the cell surface leaving

    the oxidized organics to form a protective layer on top of the biomass.

    From DuPont, June 2009

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    11/4/2010 Confidential Information 2010 M-I SWACO17

    Field Trial 2 Endurance TestBacteria Plate Count

    Detection Limit

    < 1.0 CFU/mL

    Detection Limit

    < 3.0 CFU/mL

    Detection Limit

    < 3.0 CFU/mL

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    11/4/2010 Confidential Information 2010 M-I SWACO18

    Ozone

    The ozone molecule is a very powerful oxidizer

    and sanitizer. It oxidizes any organic substancethat it comes in contact with, faster and more