common organic contaminants in cement and bentonite … · bentonite used for ... progress report...
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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)
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WELL CONSTRUCTION MATERIALS
4Florida DEP, Bureau of Water Facilities Regulation, 2008; Monitoring Well Design And Construction Manual (page 26)
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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
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1:1 Mass: Water Variable Mass to Water Ratio
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.
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Mix ratio equivalent: 5.5 gallons reagent-grade water to 94# bag of cement
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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)
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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
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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
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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)
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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)
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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)
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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
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
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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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