Ion Analysis of Hydraulic Fluids in Fracking Process -...
Transcript of Ion Analysis of Hydraulic Fluids in Fracking Process -...
Ion Analysis of Hydraulic Fluids in Fracking Process
Presented by
Jay Gandhi*, PhD
Metrohm USA
NEMC-2013 1
NEMC-2013 2
What we will cover today
• Background – Hydraulic Fracking
• Ion Analysis Applications • Wet Chemistry methods
• Anions
• Cations
• Organic Acids
• Summary
NEMC-2013 3
Hydraulic Fracking Water Cycle
NEMC-2013 4
60
00
to
80
00
fe
et
1 to 2 miles
NEMC-2013 5
Types of Water Matrices
• Fresh Feed water
• Flowback water (Produced Water) High Ionic Water (up to 30% Salt Concentration)
• Characterization of “Retention Pond”
• Recycling water
• Discharge water (for WTP)
6 NEMC-2013
List of Chemicals from various sources
7 NEMC-2013
Hydraulic Fracking – pre-drilling tests
Ion Analysis
NEMC-2013 8
Water Matrix needs to be considered • In any industry, there is no such thing as “accident or
incident” free!!!!
• Hence in an accident of well casing break, damage or leak……there will be a possibility of contaminating
• Source of Ground water
• Ground water tables depending of chemical mobility
• Surface water (rivers and lakes)
• So for next 1.5 years USEPA is very active to establish baseline of water sources in every state where fracking is involved or potential of fracking is possible
9 NEMC-2013
So at every Fracking sites there will be following regulatory methods apply
• Under safe Drinking Water Act
• USEPA method 300
• USEPA method 552
• USEPA method 557
• ASTM method 6919 (MUR)
• All applicable methods for organics and wet chemistry
• Under OSW
• Modified USEPA method 300
• Modified ASTM method 6919
• Method for Low molecular OA
• Method for Glycols
• Methods for gas detection
• Other Methods under development
10 NEMC-2013
Ion Analysis
Hydraulic Fracking
Fluids
NEMC-2013 11
12
Titration
Ion Chromatography
Voltammetry
TitrIC
NEMC-2013
Wet Chemistry Methods
• pH
• Conductivity
• Alkalinity
NEMC-2013 13
14
TitrIC - the principle One Sample Changer – One Datbase for all systems
Ion Chromatography
Titration
Sample Changer
Report – Database
Direct Measurements
NEMC-2013
TitrIC pro – the basic setup
IC
Tit
NEMC-2013 15
15
16
tiamoTM & MagIC Net
MagIC Net is the Master – tiamoTM is Slave tiamoTM does conductivity, pH, m, p, Ca, Mg upon
request
Titration data is transfered to MagIC Net database
TitrIC pro – a step forward
NEMC-2013
TitrIC pro – the basic setup
IC
Tit
NEMC-2013 17
17
TitrIC pro - titration equipment
• 905 Titrando
• iAquatrode plus
• 856 Conductivity module
• Conductivity flow trough cell
• External vessel
Additionally for TitrIC pro I:
• Combined polymembrane electrode Ca
NEMC-2013 18
NEMC-2013 19
All TitrIC pro systems come with a T connector
Separate liquid handling
for Titration and Ion Chromatography (except for the needle part)
TitrIC pro How are Combo Kits added?
TitrIC pro II
Analysis of: conductivity, temperature, pH m p AnCat
TitrIC pro
NEMC-2013 20
Analysis of: conductivity, temperature, pH m p AnCat + MiPT
TitrIC pro TitrIC pro II
NEMC-2013 21
Analysis of: conductivity, temperature, pH m p AnCat +
Dilution
TitrIC pro TitrIC pro II
NEMC-2013 22
TitrIC pro - Time management
NEMC-2013 23
Start det.
loop
Start
HW
Rinsing
IC liquid handling and chromatography
Conductivity
pH m- & p- values
combined
report
TitrIC pro - Time management - Dilution
NEMC-2013 24
Start det.
loop
Start
HW
Rinsing
IC liquid handling and chromatography
Conductivity
pH m- & p- values
combined
report
Ion Chromatography - Anions - Cations - Organic Acids
NEMC-2013 25
Suppression
Eluent:
- Na+
+ H+
Sample:
all cations are replaced by H+
MSM CO2
Suppressor
CO2 is removed
Reduction of the background conductivity and
increase of analyte conductivity.
high
conductivity
- Na+
+ H+
low
conductivity
high
conductivity
low
conductivity
Na+ + Cl- H+ + Cl-
lowest
conductivity
Na+ + HCO3- H2CO3 H2O + CO2
NEMC-2013 26
Anions
– Fracking Fluids
NEMC-2013 27
Anions of Interest
• Matrix ranging from 1% Salt up to 30% Salt
Analytes of interest and ranges
Nitrite-N 0 to 1ppm
Bromide 0 to 1ppm
Nitrate-N 0 to 1ppm
Sulfate 0 to 1ppm
28 NEMC-2013
Instrument set-up
NEMC-2013 29
Metrohm Inline Dilution with filtration
30 NEMC-2013
Sample Sample preparation IC-System – suppressed cond
31 NEMC-2013
Ion Chromatography (USEPA Region-6)
• Anions with in-line filtration
NEMC-2013 32
Anions IC Conditions
• Column: Metrosep ASUPP7-250 (4mm x 250mm)
• Sample Loop: 10uL
• Eluent: 3.2mM Na2CO3 + 1.0mM NaHCO3 + 2% Acetonitrile
• Eluent Flow: 0.7mls per minute
• Suppressor Solutions
• Regen: 100mM Sulfuric Acid + 10% Acetonitrile
• Rinse: UHP DI water + 10% Acetonitrile
• Detection: Suppressed Conductivity with
Tandem UV
NEMC-2013 33
Anions – Fracking Solutions
Up to 3% Brine Solution
– direct inject NO DILUTION!!!!!
0.1ppm Analytes
Chloride to Analyte
Ratio = 30000:0.1
NEMC-2013 34
Suppressed
Conductivity
Tandem UV
Applications
35
IC-MS
NEMC-2013
Anions
Metrosep A Supp 5 – 150
1; 2 Bromide 79; 81
3 Nitrate 62
4; 5 Phosphate 79; 97
6; 7 Sulfate 97;99
8 Oxalate 89
9 Thiosulfate 113
m/z
3.2/1.0 mmol/L Na2CO3/ NaHCO3; 0.7 mL/min; 10 ppm Standard
ESI: 13 L/min; 60 psig; 350°C; 3 kV MS: SIM neg.; Frag. 70V
36 NEMC-2013
IC-MS
Anions – Oxyhalides
ESI: 13 L/min; 60 psig; 350°C; 3 kV MS: SIM neg.; Frag. 70V
Metrosep A Supp 5 – 250
1 Chlorite 67
2 Bromate 127
4 Chlorate 83
5 Bromide 79
6 Nitrate 62
7 Phosphate 79
8 Phosphate 97
9 Sulfate 97
m/z
3.2/1.0 mmol/L Na2CO3/ NaHCO3; 0.7 mL/min; 10 ppm Standard
37
IC-MS
NEMC-2013
Anions – Halo Acetic Acids: Standard
A Supp 5 – 100 + A Supp 1
1 Fluoride 7 DBAA
2 MCAA 8 Nitrate
3 MBAA 9 Bromide
4 Chloride 10 Phosphat
e
5 DCAA 11 TCAA
6 Nitrite + BCAA
12 Sulfate
3.2/1.0 mmol/L Na2CO3/ NaHCO3; 0.7 mL/min; 10 ppm Standard
1
38
IC-MS
Conductivity
NEMC-2013
Anions – Halo Acetic Acids: Standard
A Supp 5 – 100 + A Supp 1
1 MCAA 93
2 MBAA 137
3 DCAA 127
4 BCAA 171
5 DBAA 217
6 TCAA – CO2 117
m/z
10 ppm Cl-, NO3-, SO4
2-
3.2/1.0 mmol/L Na2CO3/ NaHCO3; 0.7 mL/min; Standard 10 ppb HAAs
MS
ESI: 13 L/min; 60 psig; 350°C; 5 kV MS: SIM neg.; Frag. 70 V
39
IC-MS
NEMC-2013
Cation Analysis Suppressed or Non-Suppressed?
NEMC-2013 40
List of target Cations by Ion Chromatography (ASTM D6919)
• Modification to this ASTM method is required
• Matrix 30% NaCl solution – Flowback Water
• Target analytes at 1ppm Detection level
• Potassium
• Calcium
• Magnesium
• Strontium
• Barium
41 NEMC-2013
Manganese
Copper
Nickel
Zinc
Cobalt
Also Low Molecular weight Amines
AW IC US6-0177-052013
Cation IC Conditions
• Column: Metrosep C6 (4mm x 100mm)
• Sample Loop: 15uL
• Eluent: 2mM Oxalic Acid + 2mM PDCA + 2% Acetonitrile
• Eluent Flow: 0.9mls per minute
• Detection: Non Suppressed Conductivity
AW IC US6-0177-2013
NEMC-2013 42
Cations and Amines – Fracking Solutions
43
AW IC US6-0177-2013
NEMC-2013
Low Level Ammonium Ion in presence of High Sodium Ion
NEMC-2013 44
Cation IC Conditions
• Column: Metrosep C6 (4mm x 150mm)
• Sample Loop: 10uL
• Eluent: 1.75mM Oxalic Acid
• Eluent Flow: 0.9mls per minute
• Detection: Non Suppressed Conductivity
NEMC-2013 45
NEMC-2013 46
Calibration from 0.1 ppm to 10.0 ppm
NEMC-2013 47
Cations – Ultra Trace Analysis of Amines
Metrosep C 4 - 100
1 Diethylamine 0.2
2 Triethylamine 0.2
ppb
4.0 mmol/L tartaric acid/ 10 % ACN; 0.5 mL/min; 350 µL; m/z 74 & 102
ESI: 13 L/min; 60 psig; 350°C; 3.0 kV MS: SIM pos.; Frag. 70 V
IC-MS
48 NEMC-2013
Low Molecular weight
Organic Acids
– Fracking Fluids USEPA “RSK” based method
NEMC-2013 49
AW IC US6 0176- 042013
List of target Organic Acids
• Matrix up to 30% NaCl solution –
• Target analytes at 5ppm Detection level
• Lactic Acid
• Acetic Acid
• Formic Acid
• Propionic Acid
• Iso-Butyric Acid
• Butyric Acid
50 NEMC-2013
This is equivalent of 0.5ppm detection level in 3% NaCl solution
1:10 dilution of 30% NaCl solution
AW IC US6 0176- 042013
Organic Acid IC Conditions
• Column: Metrosep OA-250 (4mm x 250mm)
(Ion Exclusion Column)
• Sample Loop: 50uL (In-line Cation removal – MISP)
• Eluent: 0.5mM H2SO4
• Eluent Flow: 0.5mls per minute
• Metrohm Suppressor Solutions
• Regenerant: 50mM LiCl
• Rinse: UHP DI water
• Detection: Inversed Suppressed Conductivity
NEMC-2013 51
AW IC US6 0176- 042013
52 NEMC-2013
Inline Automatic Dilution, filtration and cation removal setup
AW IC US6 0176- 042013
Organic Acids – Fracking Solutions
• Lactic
• Formic
• Acetic
• Propionic
• Iso-Butyric
• Butyric
NEMC-2013 53
0.1 ppm Organic Acids in Reagent Water
AW IC US6 0176- 042013
Calibration Curves
NEMC-2013 54
Calibration Range
0.1ppm to 50ppm
AW IC US6 0176- 042013
0.5 ppm OA in 3% NaCl matrix
55 NEMC-2013
AW IC US6 0176- 042013
Summary
History of Hydraulic Fracking
Ion Analysis (Combined automated systems) for
Wet Chemistry
Ion Chromatography
NEMC-2013 56
What has not been presented yet
• Electrochemistry measurement (VA) hyphenated with Ion Chromatography for Metals analysis and Ion Chromatography for Total Ion Balance
• Ethylene and Propylene glycol analysis at single digit ppb level detection using ONLY Ion Chromatography…….
57 NEMC-2013
Acknowledgements
• Mr. David Neliegh – USEPA Region – 6
• Dr. Melvin Ritter – USEPA Region – 6
• Mr. Johnson Mathew– USEPA Region – 6
• Mr. William Telliard – Retired USEPA - DC
• Ms. Marvyln Humphrey – USEPA Region – 6
• Metrohm AG applications team
especially, Dr. Katinka Ruth and Dr. Andrea Willie
• Dr. Chunlong Zhang– University of Houston – Clearlake
• Mr. Brian Wilson and Ms. Jahnavi – Graduate students
58 NEMC-2013
The many faces of Metrohm Applications
Let us help you become the expert in your lab!
Thank you for listening
59 NEMC-2013
60
? ? ?
NEMC-2013