DR. DONALD SIEGEL: SYRACUSE UNIVERSITY DR. CHARLIE CARTER: TESTAMERICA LABORATORIES INC. CHUCK NESLUND: EUROFINSLANCASTER LABORATORIES INC. BERT SMITH, PG: CHESAPEAKE ENERGY

Common Organic Contaminants in Cement and Bentonite Used For

Water and Monitoring Well Construction

EPA ANALYTICAL METHOD DEVELOPMENT HYDRAULIC FRACTURING STUDY

EPA2: glycols and 2-BE “…..may serve as reliable indicators of contamination of ground water from hydraulic fracturing activities.”

EPA3 new glycol analytical method: LC-MS low ppb levels 2,3The Potential Impacts of Hydraulic Fracturing on Drinking Water Resources: Progress Report (December 2012), EPA 601/R-12/011 (page 118)

2

WELL CONSTRUCTION MATERIALS

4Florida DEP, Bureau of Water Facilities Regulation, 2008; Monitoring Well Design And Construction Manual (page 26)

4

What is in Cement?

Grinding aids5: glycols, phenolic, alkanoamines, and other products

5Ervanne and Hakanen, Analysis of Cement Superplasticizers and Grinding Aids, A Literature Survey, Working Report 2007-15; April , 2007 (page 29)

BATCH REACTOR EXPERIMENTS GLYCOLS

• Diethylene Glycol • Ethylene Glycol • Propylene Glycol • Tetraethylene Glycol • Triethylene Glycol

2-BUTOXYETHANOL ETHANOL ISOPROPANOL N-PROPANOL TERT-BUTYL ALCOHOL

PHENOLS • Phenol • 2-Methylphenol • 2,4-Dimethylphenol • 3&4 Methylphenol

ACETONE 2-BUTANONE

BENZOIC ACID

5 CEMENTS

10 BENTONITE PRODUCTS (solids, pellets, etc.)

PORTLAND CEMENT AND BENTONITE PRODUCTS

6

1:1 Mass: Water Variable Mass to Water Ratio

TYPE I PORTLAND CEMENT, AFTER SAMPLING

SUMMARY OF GLYCOL, PHENOL, AND 2-BE ANALYSES (1:1 EXTRACTION) OF CEMENTS Parameter, µg/L or ppb

LAB Cement A Type I/II

Cement B Type I

Cement C Type I/II

Cement D Type I/II

Cement E Type I

Cement F (Dup A) Type I/II

Container Blank

Lab Blank

2-Butoxyethanol (ppb)

TA LAN

33J

12

<12

<5

<12

<5

<12

<5

51J

36 <12

13 <12

<5

<12

<5

Benzoic Acid (ppb)

TA LAN

61

17 18J

<16

<2.1

19 <2.1

22 <2.1

19 74

18 <2

<15

<1.5

<15

Diethylene Glycol (ppb)

TA LAN

37,000

34,000 <150

50 33,000

31,000 <150

230 14,000

10,000 37,000

28,000 3.7J

<25

<3.7

<25

Ethylene Glycol (ppb)

TA LAN

7,500J

5,500 <1,100

<500

<5,400

1,000 <1,100

<500

2,800J

1,600

8,900J

8,000 <27

<500

<27

<500

Propylene Glycol (ppb)

TA LAN

<900

<100

<180

<100

<900

<100

<180

130 <450

110 <900

<100

<4.5

<100

<4.5

<100

Tetraethylene Glycol (ppb)

TA LAN

11,000

9,400 <80

<25

<400

360 <80

<25

2,500

2,300 11,000

9,800 <2.0

<25

<2

<25

Triethylene Glycol (ppb)

TA LAN

79,000

71,000 <120

<25

5,200

4,200 <120

<25

20,000

20,000 76,000

66,000 <3.1

<25

<3.1

<25

Phenol (ppb)

TA LAN

<0.35

<1.0

56

29 140

71 210

120 <0.44

<1.0

<0.43

<1.0

<0.42

<1.0

<0.34

<1.0

8 No confirmed detections of isopropanol, tert-butyl alcohol, acetone, 2-butanone, n-propanol, ethanol, and phenolic isomers

(PHASE II) CEMENT CYLINDERS CURED IN VIALS FOR 72 HOURS.

9

Mix ratio equivalent: 5.5 gallons reagent-grade water to 94# bag of cement

10

Testing occurred after 1 day, 5 days, 10 days and 20 days in baths

CEMENT CYLINDERS IN WATER LEACHING BATHS (PRODUCT A) (86 ML CEMENT, ~35 GRAMS) TO 450 ML REAGENT-GRADE WATER)

Phase I Testing

Phase II Testing

Analytical Results Product A

CURED CEMENT TESTING RESULTS (PHASE I) DAILY ANALYSIS (REPLACE LEACHATE WATER AND GLASSWARE EACH DAY)

11

No 2-BE, phenol, or benzoic acid was confirmed as detected at method detection or quantitation limits

Day Diethylene Glycol, ppb

Ethylene Glycol, ppb

Propylene Glycol, ppb

Tetraethylene Glycol, ppb

Triethylene Glycol, ppb

TA LAN TA LAN TA LAN TA LAN TA LAN Day 1 540 440 <540 <500 <90 <100 160J 150 1,500 1,200 Day 2 170 200 <270 <500 <45 <100 95 74 580 520 Day 3 110 85 <540 <500 <90 <100 78 34 400 240 Day 4 88 66 <540 <500 <90 <100 62 <25 300 95 Day 5 78 97 <270 <500 <45 <100 52 28 250 220 Container Blank

<3.7 <25 <27 <500 <4.5 <100 <2.0 <25 <3.1 <25

Duplicate (Day 1)

230 550 <540 <500 <90 <100 190 130 1,400 1,000

Lab Blank <3.7 <25 <27 <500 <4.5 <100 <2.0 <25 <3.1 <25

CURED CEMENT TESTING RESULTS (PHASE I) DAILY ANALYSIS FOR 5 DAYS (PRODUCT A) (REPLACE LEACHATE WATER AND GLASSWARE EACH DAY)

EurofinsLancaster Results

12

0 100 200 300 400 500 600 700 800 900

1000 1100 1200 1300 1400 1500 1600

1 2 3 4 5

Glyc

ol C

once

ntra

tion,

ppb

Day

DEG TetEG TriEG

CURED CEMENT TESTING RESULTS (PHASE I) DAILY ANALYSIS FOR 5 DAYS (PRODUCT A) (REPLACE LEACHATE WATER AND GLASSWARE EACH DAY)

TestAmerica Results

13

0 100 200 300 400 500 600 700 800 900

1000 1100 1200 1300 1400 1500 1600

1 2 3 4 5

Glyc

ol C

once

ntra

tion,

ppb

Day

DEG TetEG TriEG

Analytical Results Product A

CURED CEMENT TESTING RESULTS (PHASE II) (ANALYSIS OF LEACHATE BATHS AFTER 1, 5, 10 AND 20 DAYS)

14

No 2-BE, phenol, or benzoic acid confirmed as detected at method detection or quantitation limits

Day Diethylene Glycol, ppb

Ethylene Glycol, ppb

Propylene Glycol, ppb

Tetraethylene Glycol, ppb

Triethylene Glycol, ppb

TA LAN TA LAN TA LAN TA LAN TA LAN Day 1 230 550 <540 <500 <90 <100 190 130 1,400 1,000 Day 5 1,200 1,500 <540 <500 <90 <100 630 360 4,200 2,900 Day 10 1,800 1,900 <1,400 <500 <230 <100 730J 680 6,100 4,400 Day 20 2,200 1,900 <1,400 560 <230 <100 900J 840 7,100 5,600 Container Blank

<3.7 <25 <27 <500 <4.5 <100 <2.0 <25 <3.1 <25

Duplicate (Day 1)

540 440 <540 <500 <90 <100 160J 150 1,500 1,200

Lab Blank <3.7 <25 <27 <500 <4.5 <100 <2.0 <25 <3.1 <25

CURED CEMENT TESTING RESULTS (PHASE II) ANALYSIS OF LEACHATE BATHS (PRODUCT A) (ANALYSIS OF LEACHATE BATHS AFTER 1, 5, 10 AND 20 DAYS)

15

EurofinsLancaster Results

0

1000

2000

3000

4000

5000

6000

7000

8000

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Glyc

ol C

once

ntra

tion,

ppb

Days in Leaching Bath

DEG TetEG TriEG

CURED CEMENT TESTING RESULTS (PHASE II) ANALYSIS OF LEACHATE BATHS (PRODUCT A) (ANALYSIS OF LEACHATE BATHS AFTER 1, 5, 10 AND 20 DAYS)

16

TestAmerica Results

0

1000

2000

3000

4000

5000

6000

7000

8000

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Glyc

ol C

once

ntra

tion,

ppb

Days in Leaching Bath

DEG

TetEG

TriEG

BENTONITE 3/8” MEDIUM CHIPS

BENTONITE 1/4” PELLETS (UNCOATED)

SUMMARY OF GLYCOL, PHENOL, AND 2-BE EXTRACTION ANALYSES BENTONITE PRODUCTS

Parameter, µg/L or ppb

LAB Bent 1

Bent 2

Bent 3

Bent 4

Bent 5

Bent 6

Bent 7

Bent 8

Bent 9

Bent 10

Bent 11

Dup 10

Container Blank

Lab Blank

2-Butoxyethanol (ppb)

TA LAN

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

Benzoic Acid (ppb)

TA LAN

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

Diethylene Glycol (ppb)

TA LAN

<3.7 40

<37 <25

5.5J 29

49 49

<3.7 <25

<3.7 34

<3.7 51

<3.7 <25

<3.7 86

<3.7 75

<3.7 <25

<3.7 <25

<3.7 <25

Ethylene Glycol (ppb)

TA LAN

<54 <500

<270 <500

<27 <500

41J <500

<27 <500

<2.7 <500

<2.7 <500

<270 <500

<27 <500

<27 <500

<27 <500

<27 <500

<27 <500

Propylene Glycol (ppb)

TA LAN

<9.0 <100

<45 <100

<4.5 <100

25J <100

<4.5 <100

<4.5 <100

<4.5 <100

<45 <100

<4.5 <100

<4.5 <100

<4.5 <100

<4.5 <100

<4.5 <100

Tetraethylene Glycol (ppb)

TA LAN

<2.0 <25

<20 <25

2.9J <25

38 <25

<2.0 <25

<2.0 <25

<2.0 <25

<20 <25

<2.0 <25

<2.0 <25

<2.0 <25

<2.0 <25

<2.0 <25

Triethylene Glycol (ppb)

TA LAN

<3.1 <25

<31 <25

<3.1 <25

24J <25

<3.1 <25

<3.1 <25

<3.1 <25

<31 <25

<3.1 <25

<3.1 <25

<3.1 <25

<3.1 <25

<3.1 <25

Phenol (ppb)

TA LAN

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

ND ND

19 No confirmed detections of isopropanol, tert-butyl alcohol, acetone, 2-butanone, n-propanol, ethanol, phenol, 2-BE, benzoic acid and phenolic isomers

A Need to Look at Contamination from Products Used: • Casing materials • Synthetic lubricants • Annular sealants (bentonite and cements) • Pre-mix concrete (for pad completions—shallow groundwater) • Drilling additives (including polymers) • Completion additives (including polymers) • Sampling & development equipment (bailers, tubing, swabs) • Disinfectants • Decontamination liquids • Compressor oils

20

IMPLICATIONS

AND OBVIOUSLY…

Glycols and 2-BE inherently cannot indicate hydraulic fracturing contamination These compounds leach from the

cement used to construct monitoring wells.

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THANK YOU DR. DONALD SIEGEL: SYRACUSE UNIVERSITY DR. CHARLIE CARTER: TESTAMERICA LABORATORIES INC. CHUCK NESLUND: EUROFINSLANCASTER LABORATORIES INC. BERT SMITH, PG: CHESAPEAKE ENERGY JULY 10, 2013