COMMON ORGANIC CONTAMINANTS FOUND IN CEMENT AND BENTONITE PRODUCTS USED IN WATER AND MONITORING WELL CONSTRUCTION AND DRILLING DR. DONALD SIEGEL: SYRACUSE UNIVERSITY DR. CHARLIE CARTER: TESTAMERICA LABORATORIES INC. CHUCK NESLUND: EUROFINSLANCASTER LABORATORIES INC. BERT SMITH, PG: CHESAPEAKE ENERGY JULY 10, 2013

STUDY QUESTION AND SCOPE Are organic compounds present and do they leach from

annular sealants used in monitoring and water wells? • Tested 5 Type I/II Portland cement products • Tested 10 bentonite annular sealants and viscosifying

bentonite products • Cured cement samples and then conducted leaching tests

National laboratories (separate replicate analysis) • EurofinsLancaster Laboratories Inc. • TestAmerica Laboratories Inc. Project Overseen by Academic Partner (Syracuse University,

Dr. Donald Siegel) 2

WHY ANALYZE CEMENT AND BENTONITE?

EPA1 considers selected organics to be related to hydraulic fracturing (HF) fluids (e.g.):

But-- materials used in monitoring/water well completions not tested for, and may contain, these organic compounds.

EPA samples collected from monitoring and water wells being analyzed for these organic compounds –Detections allegedly linked to HF

Need to identify potential false-positive contamination sources 1 The Potential Impacts of Hydraulic Fracturing on Drinking Water Resources: Progress Report (December 2012), EPA 601/R-12/011 (Appendix A) 3

o Glycols o 2-butoxyethanol (2-BE)

o Benzoic acid o Phenols

EPA ANALYTICAL METHOD DEVELOPMENT HF STUDY

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

Commercial glycol analytical method: 8015b has 5 to 20 ppm method detection limit

EPA3 Region 3 new glycol analytical method: Liquid Chromatography-

Tandem Mass Spectrometry achieves low ppb levels TestAmerica and EurofinsLancaster Laboratories used similar EPA

glycol test method (LC/MS/MS) for cement/bentonite study

2,3The Potential Impacts of Hydraulic Fracturing on Drinking Water Resources: Progress Report (December 2012), EPA 601/R-12/011 (page 118)

4

MONITORING WELL CONSTRUCTION MATERIALS

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

4

PARAMETER LIST

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

CEMENT CHEMISTRY

Grinding aids5: glycols, phenolic, alkanoamines, and other products. They are added to cements for increased efficiency in grinding.

Google Search Glycols in Portland Cements 2,270,000 results

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

REPRESENTATIVE CEMENT GRINDING AIDS

6Ervanne and Hakanen, Analysis of Cement Superplasticizers and Grinding Aids, A Literature Survey, Working Report 2007-15; April , 2007 (page 29)

6

5 CEMENT PRODUCTS • Product A: Type I/II • Product B: Type I • Product C: Type I/II • Product D: Type I/II • Product E: Type I • Product F: (Duplicate A)

10 BENTONITE PRODUCTS • Product 1: 20% solids grout • Product 2: 30% solid grout • Product 3: *Uncoated pellets

• Product 4: *Coated pellets • Product 5: Drilling viscosifier • Product 6: Chips • Product 7: Drilling viscosifier • Product 8: 30% solid grout • Product 9: Chips • Product 10: Drilling viscosifier • Product 11: Duplicate 10

*In plastic bucket

SUMMARY OF PORTLAND CEMENT AND BENTONITE PRODUCTS TESTED (BAGGED)

9

Cement Ratios (wtp/wtw) • Product A: 1:1 • Product B: 1:1 • Product C: 1:1 • Product D: 1:1 • Product E: 1:1 • Product F: 1:1

Bentonite Ratios (wtp/wtw) • Product 1: 1:6 (20% solids grout) • Product 2: 1:4 (30% solid grout) • Product 3: 1:1 (Uncoated pellets) • Product 4: 1:1 (Coated pellets) • Product 5: 1:30 (Drilling viscosifier) • Product 6: 1:1 (Chips) • Product 7: 1:50 (Drilling viscosifier) • Product 8: 1:4 (30% solid grout) • Product 9: 1:1 (Chips) • Product 10: 1:50 (Drilling viscosifier) • Product 11: 1:50 (Drilling viscosifier)

MULTIPLE EXTRACTION RATIOS

10

TYPE I PORTLAND CEMENT, BEFORE SAMPLING

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

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

(PHASE II) CEMENT CYLINDERS CURED IN 40 ML VOA VIALS FOR 72 HOURS. GLASS THEN REMOVED

14

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

15

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 FOR 5 DAYS (REPLACE LEACHATE WATER AND GLASSWARE EACH DAY)

16

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

17

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

18

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)

19

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)

20

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)

21

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

20% SOLIDS BENTONITE GROUT GRANULARS, AFTER SAMPLING

VISCOSIFYING BENTONITE DRILLING ADDITIVE, AFTER SAMPLING

BENTONITE 3/8” MEDIUM CHIPS

BENTONITE 1/4” PELLETS (UNCOATED)

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

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

MONITORING/WATER WELL DRILLING AND COMPLETION MATERIALS MAY NEED ADDITIONAL TESTING

Materials that require further analytical testing may include: • 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 soaps and liquids • Compressor oils • Sand pack materials (processed sands) • Preservation acids, bottle ware, and filters

27

SUMMARY AND CONCLUSIONS Common Type I/II Portland Cements contain relatively high

and leachable concentrations of glycols (ppm levels) Other compounds potentially present in Portland Cements

include 2-BE, phenols, and benzoic acid (ppb levels) Some bentonite products may contain ppb levels of glycols;

more testing needed Most, if not all, of the materials used in monitoring/water

well completions and sampling have not been tested for chemicals of interest in hydraulic fracturing studies (or to the low ppb levels now achievable)

To avoid false positives, all materials should be tested prior to use down hole in monitoring/water well completions

Glycols and 2-BE are not diagnostic to HF chemical impact 28

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