CETAC Technologies High Throughput Analysis of … Notes...High Throughput Analysis of Hydraulic...
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High Throughput Analysis of Hydraulic Fracturing Waste Water CETAC Technologies 14306 Industrial Rd. Omaha, NE 68144 USA PHONE 402.733.2829 FAX 402.733.5292 www CETAC.com Michael Sgroi (Technical Sales Manager), Matt Nigro and David Clarke - CETAC Technologies, Omaha, NE, (402) 738-5415, [email protected] Fig.2: CETAC‘s ASXpress Plus rapid sample introduction system coupled to a Thermo iCAP dual 6000 series ICP-OES system. Introduction There are important organic and inorganic components to the testing of fracking related samples. Besides EPA methods such as SW-84622 and 200.733, the focus here is the inorganic elemental analysis associated with fracking samples and how the volume of those samples that will surely rise in the coming years can be better and more efficiently be dealt with by using the CETAC ASXpress Plus rapid sample introduction system. Background on Fracking Technique and Analytical Challenges • Hydraulic fracturing (fracking) is a relatively new method of extracting natural gas from dense shale deposits situated deep under low-permeable rock layers miles below the surface • Huge volumes of hydraulic fluids need to be pumped into wells to fracture the shale deposit and free up the gas • Although about 90% of this fluid is water, a variety of additives are used, including: • Propants like sand or bauxite • Gelling agents like cellulose polymers and cross-linkers • Foam additives • Scale inhibitors like ammonium chloride and phosphonates • Corrosion inhibitors like methyl and isopropyl alcohol • Biocides • Friction reducers like light crude oil distillates • Surfactants • Acids like HCl • This process leads to environmental concerns about drinking water quality in the surrounding area and the tremendous amount of waste water produced • Many samples are generated that need to be tested, e.g. towards the content of trace and ultra trace metals and metalloids Political Background and Progress on Legal Framework • Critics of fracking have pointed the finger at former Vice President Dick Cheney, who largely authored the 2005 Energy Bill (the so-called Halliburton Loophole), which explicitly exempted fracking from federal review under the Safe Drinking Water Act (SDWA) • Under this provision, drilling companies are under no obligation to make public which chemicals they use, although many of them are recognized or suspected carcinogens • The U.S. Environmental Protection Agency (USEPA) is currently investigating cases of suspected contamination in towns located near fracking activities . • This current state of legislation is sure to change as time moves forward and the political climate evolves Conclusion ASXpress Plus – Function Principle Fig.3: Function principle of the ASXpress Plus system and connections for sample load (upper part) and sample injection and simultaneous rinsing (lower part). Fig.1: Schematic diagram of the fracking process. Advantages and Features • Robust coupling to any ICP-OES or ICP-MS system due universal setup and GUI controlled software running without any need for an user intervention after installation • Increased efficiency due to shortened sample uptake / stabilization time • Minimized carryover and memory effects due to air bubble wash step and no exposition of the sample to peristaltic pump tubing • Constant flow to nebulizer (no fast uptake) to ensure plasma stability and easy in-line addition of internal standards • Original method total analysis time: 4 min 27 s could be reduced to 2 min 45 s using the newly develop method → efficiency increase of 38.2% without changes to the original method (0 s plasma stabilization time, 0 s rinse time, only 20 s flush time) • Combined with the total integration time a duty cycle of only 25.5% could be achieved without effecting the figures of merit more than sufficient for fracking samples Results Analytical Method ICP-OES Conditions: • RF Power: 1150 W • Nebulizer Gas Flow: 0.7 L/min • Purge gas mode: Boost, pump rate: 45 rpm • Humidified argon supply and GE SeaSpray nebulizer for high TDS matrices Sample Matrix: • 5 mL HCl + 2 mL HNO3 for 50 mL sample • ISTDs: Y @ 1.000 mg/L and In @ 10.000 mg/L • CCB & CCV every 10 samples • USEPA 6010B / 200.7 / fracking combined ASXpress Plus Configuration: • 5 mL 2 mm I.D. aqueous loop and 1.5 mm I.D. port sized aqueous valve • Extra loop rinse: • Loop rinse delay: 4.0 s • Loop evacuation delay: 3.0 s • Loop load: 10 s • Equalization time: 2.0 s • Time to evacuate probe: 2.0 s • Rinse station fill: 11 s • Pump timeout: 60 s • ASXpress Firmware: 2.50 0 6000 12000 0 2 4 6 8 10 Analyte concentration (μg/L) CCV sample number Ag Al As B Ba Be Ca Cd Co Cr Cu Fe K Li Mg Mn Mo Na Ni P Pb S Sb Se Si Sn Sr Ti Tl V Fig.4: Found concentrations in 10 CCV samples recorded during analysis of fracking waste water showing the figures of merit of the developed system and method. • Precision was less than 1% RSD and accuracy was within 5% across 10 measurements of the same CCV sample containing 32 elements of interest e.g. in fracking waste water samples • Carryover was undetectable for most elements and those that could be measured were on the maximum of 5% or well below y = 0.9826x - 24899 R² = 0.9953 0 500000 1000000 1500000 2000000 2500000 0 500000 1000000 1500000 2000000 2500000 ASXpress data (μg/L) Original data (μg/L) Na y = 1.0184x - 13.82 R² = 0.9993 0 500 1000 1500 2000 2500 3000 0 500 1000 1500 2000 2500 3000 ASXpress data (μg/L) Original data (μg/L) P Fig.5: Validation of the original and the ASXpress accelerated method for selected elements of interest.
Transcript of CETAC Technologies High Throughput Analysis of … Notes...High Throughput Analysis of Hydraulic...
High Throughput Analysis of Hydraulic Fracturing Waste Water CETAC Technologies 14306 Industrial Rd. Omaha, NE 68144
USA
PHONE 402.733.2829 FAX 402.733.5292 www CETAC.com
Michael Sgroi (Technical Sales Manager), Matt Nigro and David Clarke - CETAC Technologies, Omaha, NE, (402) 738-5415, [email protected]
Fig.2: CETAC‘s ASXpress Plus rapid sample introduction system coupled to a Thermo iCAP dual 6000 series ICP-OES system.
Introduction There are important organic and inorganic components to the testing of fracking related samples. Besides EPA methods such as SW-84622 and 200.733, the focus here is the inorganic elemental analysis associated with fracking samples and how the volume of those samples that will surely rise in the coming years can be better and more efficiently be dealt with by using the CETAC ASXpress Plus rapid sample introduction system.
Background on Fracking Technique and Analytical Challenges
• Hydraulic fracturing (fracking) is a relatively new method of extracting natural gas from dense shale deposits situated deep under low-permeable rock layers miles below the surface
• Huge volumes of hydraulic fluids need to be pumped into wells to fracture the shale deposit and free up the gas
• Although about 90% of this fluid is water, a variety of additives are used, including: • Propants like sand or bauxite • Gelling agents like cellulose polymers and cross-linkers • Foam additives • Scale inhibitors like ammonium chloride and phosphonates • Corrosion inhibitors like methyl and isopropyl alcohol • Biocides • Friction reducers like light crude oil distillates • Surfactants • Acids like HCl
• This process leads to environmental concerns about drinking water quality in the
surrounding area and the tremendous amount of waste water produced
• Many samples are generated that need to be tested, e.g. towards the content of trace and ultra trace metals and metalloids
Political Background and Progress on Legal Framework • Critics of fracking have pointed the finger at former Vice President Dick Cheney, who
largely authored the 2005 Energy Bill (the so-called Halliburton Loophole), which explicitly exempted fracking from federal review under the Safe Drinking Water Act (SDWA)
• Under this provision, drilling companies are under no obligation to make public which chemicals they use, although many of them are recognized or suspected carcinogens
• The U.S. Environmental Protection Agency (USEPA) is currently investigating cases of suspected contamination in towns located near fracking activities.
• This current state of legislation is sure to change as time moves forward and the political climate evolves
Conclusion
ASXpress Plus – Function Principle
Fig.3: Function principle of the ASXpress Plus system and connections for sample load (upper part) and sample injection and simultaneous rinsing (lower part).
Fig.1: Schematic diagram of the fracking process.
Advantages and Features
• Robust coupling to any ICP-OES or ICP-MS system due universal setup and GUI controlled software running without any need for an user intervention after installation
• Increased efficiency due to shortened sample uptake / stabilization time • Minimized carryover and memory effects due to air bubble wash step and no exposition
of the sample to peristaltic pump tubing • Constant flow to nebulizer (no fast uptake) to ensure plasma stability and easy in-line
addition of internal standards
• Original method total analysis time: 4 min 27 s could be reduced to 2 min 45 s using the newly develop method → efficiency increase of 38.2% without changes to the original method (0 s plasma stabilization time, 0 s rinse time, only 20 s flush time)
• Combined with the total integration time a duty cycle of only 25.5% could be achieved without effecting the figures of merit more than sufficient for fracking samples
Results
Analytical Method ICP-OES Conditions:
• RF Power: 1150 W • Nebulizer Gas Flow: 0.7 L/min • Purge gas mode: Boost, pump rate: 45 rpm • Humidified argon supply and GE SeaSpray
nebulizer for high TDS matrices
Sample Matrix:
• 5 mL HCl + 2 mL HNO3 for 50 mL sample • ISTDs: Y @ 1.000 mg/L and In @ 10.000 mg/L • CCB & CCV every 10 samples • USEPA 6010B / 200.7 / fracking combined
ASXpress Plus Configuration:
• 5 mL 2 mm I.D. aqueous loop and 1.5 mm I.D. port sized aqueous valve
• Extra loop rinse: • Loop rinse delay: 4.0 s • Loop evacuation delay: 3.0 s
• Loop load: 10 s • Equalization time: 2.0 s • Time to evacuate probe: 2.0 s • Rinse station fill: 11 s • Pump timeout: 60 s • ASXpress Firmware: 2.50
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g/L)
CCV sample number
Ag Al AsB Ba BeCa Cd CoCr Cu FeK Li MgMn Mo NaNi P PbS Sb SeSi Sn SrTi Tl V
Fig.4: Found concentrations in 10 CCV samples recorded during analysis of fracking waste water showing the figures of merit of the developed system and method.
• Precision was less than 1% RSD and accuracy was within 5% across 10 measurements of the same CCV sample containing 32 elements of interest e.g. in fracking waste water samples
• Carryover was undetectable for most elements and those that could be measured were on the maximum of 5% or well below
y = 0.9826x - 24899 R² = 0.9953
0
500000
1000000
1500000
2000000
2500000
0 500000 1000000 1500000 2000000 2500000A
SXp
ress
dat
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g/L
) Original data (µg/L)
Na
y = 1.0184x - 13.82 R² = 0.9993
0
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ASX
pre
ss d
ata
(µg
/L)
Original data (µg/L)
P
Fig.5: Validation of the original and the ASXpress accelerated method for selected elements of interest.
