Surfactant Analysis in Hydraulic Fracturing Flowback Waters Using SPE, 2-D UHPLC...
Transcript of Surfactant Analysis in Hydraulic Fracturing Flowback Waters Using SPE, 2-D UHPLC...
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Surfactant Analysis in Hydraulic Fracturing Flowback Waters Using SPE, 2-D UHPLC Followed by Corona CAD, MS/MS and Orbitrap HRAM Detection
Richard Jack, Ph.D. Director – Vertical Marketing, Environmental and Industrial Lee Ferguson, Ph.D. Associate Professor - Pratt School of Engineering & Nicholas School of the Environment Duke University
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Hydraulic Fracturing Technique
• Hydraulical fracturing or fracking is a technique that consists of pumping water into a wellbore to create small fractures into which fluids can migrate and leave openings to release trapped gas
• Fracking facilitates the extraction of natural gas from shale plays in which it is unreachable with conventional technologies
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What is Shale Gas?
• Muddy sediments rich in organic matter are deposited in seas and lakes
• As these rocks are buried, organic matter is converted to gas, and porosity is generated
• These rock layers are often the source rocks for conventional oil and gas fields
Typical shale in surface outcrop
1um
Microscope view
pores
organic matter
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• With the spreading of fracking, concern is raising about its safety and sustainability for the environment, in particular for air and water quality
• Opponents say there are potential adverse effects on the environment – and perhaps surrounding communities – because of the use of chemicals and large amounts of water that are injected into the subsurface
• Growing concern among the scientific community is that the fracking technology, itself, may result in the leakage of methane into the atmosphere or into water reservoirs
Hydraulic Fracturing Technique
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Hydraulic Fracturing Site in WV
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Produced Water ��High Total Dissolved Solids (60–250,000 mg/L) �
Chloride, bromide, strontium, barium�
Gaudlip et al., 2008. SPE 119898�
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Analysis of Flowback waters – the challenge
• Extremely dirty! • 20x salt conc. Compared to
sea water • Change over time • Vary by subsurface • Additives vary due to cost,
personal preference and other factors
• Organics – validated methods are not available
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Hydraulic Fracturing Fluid Composition
• Mostly Water and Sand • <2% chemicals
Water 90%
Surfactants 0.31%
Gelling Agent 0.49%
Sand 8.22% Breakers
0.10%
Crosslinker 0.31%
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Hundreds of known Chemicals in Fracking solutions
• Hundreds of chemicals in fracking solutions – typically 10-15 used per Fracking operation.
• The EPA has narrowed the list of compounds down to less than 20.
• The EPA is in the process of developing analytical methods
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Compounds found in Hydraulic Fracturing Fluids
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5.4. Analytical Method Development
US EPA: Study of the Potential Impacts of Hydraulic Fracturing on Drinking Water Resources: Progress Report
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5.4. Analytical Method Development - 2012
http://www2.epa.gov/hfstudy
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Alkylphenol Ethoxylate analysis
• DeArmond P.D., DiGoregorio A.L. Rapid liquid chromatography-tandem mass spectrometry-based method for the analysis of alcohol ethoxylates and alkylphenol ethoxylates in environmental samples. Journal of Chromatography A, Aug 30; 1305: 154-63 (2013).
• Assement … 2015 http://www2.epa.gov/hfstudy discusses the prevalence and use of alklyphenols, nonylphenols in the US
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Ethoxylates reported in FracFocus
• Ethoxylation is an industrial process in which ethylene oxide is added to alcohols and phenols to turn it into a surfactant
• 4-Nonylphenol polyethoxylate • 2-(2-Butoxyethoxy)ethanol • 2-(2-Ethoxyethoxy)ethanol • 2-(2-Ethoxyethoxy)ethyl acetate • Alcohols, C11-14-iso-, C13-rich, butoxylated ethoxylated • Alcohols, C11-14-iso-, C13-rich, ethoxylated • Alcohols, C12-13, ethoxylated • Alcohols, C12-14, ethoxylated • Alcohols, C12-14, ethoxylated propoxylated • Alcohols, C12-14-secondary • Alcohols, C12-14-secondary, ethoxylated • Alcohols, C12-15, ethoxylated ….. • ETC
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Prevalence in HF – voluntary disclosure in fracfocus.org
Name Number of disclosures % of disclosures Median Maximum
concentration in HF fluid Nonyl phenol ethoxylate
2,829 16.3 % 20%
Ethoxylated propoxylated C12-14 alcohols 2,342 13.5% 2%
Poly(oxy-1,2-ethanediyl)-nonylphenyl-hydroxy
(mixture) 1668 9.6% 5%
http://www2.epa.gov/hfstudy
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Separation
• Protototype: SEC 80 Size Exclusion Stationary Phase • Polymethacrylate-based polymer • 5-µm diameter • 80Å pore size
• Thermo Scientific Acclaim™ Surfactant Plus RP • anionic surfactants (alkylbenzenesulfonates, alkyl sulfates, alkylether sulfates)
and • cationic surfactants (alkyl quaternary ammonium salts, benzylalkylammonium
salts, pyridinium salts, and quaternary imidazolium compounds) • nonionic surfactants, and polyethylene glycols (PEGs).
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Detection - Charged Aerosol Detection
• Detection of non-volatile and many semi-volatile analytes • Consistent response independent of chemical structure • Applicable to both HPLC and UHPLC • Compatible with gradient conditions Sub-nanogram sensitivity
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Detection - MS/MS and HRAM
• Quadrupole-equipped HR/AM instruments • HR/AM analyzer permits parallel detection of all target
product ions in one concerted high resolution mass analysis
Serial monitoring
Parallel monitoring
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High-resolution mass spectrometry powered by Orbitrap technology helps contaminants “emerge”:
Target screening known contaminants
Non-target screening for unknowns Assign molecular and structural formula to chromatographic features
Target screening Know contaminants with greater sensitivity
Identification of Emerging Contaminants
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Basepeak of ww influent Acclaim SEC80 0.35ml/min 20% ACN in H2O to 30 % ACN in 60 min 60˚C
Basepeak of ww influent Hypersil Gold AQ 0.35ml/min 20% ACN in H2O to 30 % ACN in 40 min 45˚C
However: • Environmental samples are
highly complex • Limits on LC-HRMS of
complex samples: • Poor chromatographic
resolution • Matrix effects/ion
suppression
Solution: • Combine two separation
mechanisms into a single analysis
=> 2D HPLC
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Separation based on Molecular
Size
Separation based on
Hydrophobicity
Hyd
roph
obic
ity
Size
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• Higher resolution in chromatography -> takes full advantage of MS technology
• 2D retention time offers another, complementary source of analyte chemical information
• Matrix reduction due to enhance separation: Gain in signal intensity
• Higher confidence in non target analysis due to reduced co-elution
• Develop a comprehensive 2D HPLC-HRMS approach
• Optimize this technique for analysis of nonionic surfactants
• Test the quantitative ability of this method
Advantages and Objectives
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How does a 2D HPLC system work?
Sample Valve 2nd Separation
- Short, max 2 min - Fast gradient - 2 short columns - used alternating
For effective separation: - Separation mechanisms have to be orthogonal. - Example: Size and Hydrophobicity or Hydrophilic interaction and Hydrophobicity. - While eluting from the first column – requires strong retention on the second column
3D plot Analysis 1st Separation
- Slow separation - isocratic
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cut every 2 minutes 90 ̊flip
Data in Matrix format
3D plot
Long chromatogram containing 45x2 minute gradients
For effective separation: - Separation mechanisms have to be orthogonal. - Example: Size and Hydrophobicity or Hydrophilic interaction and Hydrophobicity. - While eluting from the first column – requires strong retention on the second column
How does a 2D HPLC system work?
Analysis
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Sample
Ultimate 3000 - LPG pump, 350 ul mixer - HPG pump, 10 ul mixer
6 port Valve with 25 µl injection loop
10 port valve With 2 Reversed phase columns
(2.1 *50mm, 2µm)
2D HPLC-HRMS Setup
Analyzers: - UV detector - Charged aerosol detector - Orbitrap Velos pro (>100’000 Res, <2 ppm accuracy)
First Separation HILIC/SEC
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First Separation HILIC/SEC Analyzers:
- UV detector - Charged aerosol detector - Orbitrap Velos pro (>100’000 Res, <2 ppm accuracy)
Sample
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6 port Valve with 25 µl injection loop
10 port valve With 2 Reversed phase columns
(2.1 *50mm, 2µm)
2D HPLC-HRMS Setup
Accucore C18, 50x2.1 mm, 2.6 um Low back pressure High chromatographic resolution High reproducibility
Ultimate 3000 - LPG pump, 350 ul mixer - HPG pump, 10 ul mixer
?
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Two candidates for the first separation
HILIC Hydrophilic Interaction Chromatography
• Dionex Acclaim HILIC, 1.0 x 15 cm
Flow rate: 50 µl/min 99.5 % ACN in H2O
• Separation based on polarity – apolar elute first
• High organic mobile phase
SEC Size Exclusion
• prototype Acclaim SEC80, 4.6 x
300mm Flow rate: 350 µl/min
20% ACN in H2O • Separation based on size – large
molecules elute first
flow Silica Gel
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SEC of OPEO
Advantages for SEC • Longer run => more RP time • Compatible moble phase: No
make-up flow required for RP 2nd dimension
• Cut off/early elution of matrix
OPEO
Compounds of interest
Large Molecules – early cut off
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Qualitative and qualitative analysis of nonionic surfactants
• Nonionic surfactants are complex, polymeric series consisting of alcohol- or alkylphenol hydrophobes that are polyethoylated
• They are applied ubiquitously in consumer, industrial, and commercial applications
• Some nonionic surfactants (alkylphenol ethoxylates) are precursors of known endocrine disruptors
• Analysis of these species by HPLC-MS is very challenging due to difficulty in separations, problems with matrix effects
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• 4 Surfactant standards for optimization:
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Separating Surfactants by 1D-HPLC
Hydrophobicity
2
4
3
5
6
7
8 9
10
11 12
number of ethoxylates (OPEO)
Separation on SEC:
Separation on RP:
OPEO
NPEO
LAOE CetOE
Octylphenol ethoxylate (OPEO)
Nonyl phenol ethoxylate (OPEO)
Lauryl alcohol ethoxylate (LaOE)
Cetyl alcohol ethoxylate (CetOE)
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LAOE B
LAOE A NPEO
OPEO
CetOE
OPEO
NPEO
CetOE
LAOE LAOE LAOE
1D SEC
Separating Surfactants by 2D-HPLC
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Resolving and quantifying mixtures of nonionic surfactants using the Charged Aerosol Detector
Blank
0.1 mg/ml
0.5 mg/ml
1.0 mg/ml
5.0 mg/ml
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Hydrofracking flowback wastewater sample • Fracking waters often contain nonionic surfactants as
emulsifiers • To date these surfactants have not been well-characterized in
wastewaters discharged from fracking operations
Sample
Wastewater from hydrofracking flowback
Work up
Extraction with Dionex Autotrace (200 mg HRHPS)
2D Analysis
Application to environmental samples
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Fracking Fluid Sample - Basepeak
XIC
• Environmental sample gives comparable surfactant bands
• Retention times in standard and sample the same
Hydrofracking wastewater- Results Surfactant Standards NPEO
LAOE
OPEO
LAOE A NPEO
OPEO
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• Two dimensional HPLC combined with HRMS is a powerful tool for resolving micropollutants in complex mixtures
• Size exclusion chromatography combined with reverse phase HPLC provides excellent orthogonality for nonionic surfactant analysis
• Nonionic surfactants can be resolved and identified in hydrofracking wastewaters by 2D-HPLC-HRMS.
• 2D-HPLC-HRMS spectra show lower noise, fewer matrix effects, and less co-elution than 1D HPLC-HRMS analysis
• The developed method can be applied for both target analysis as well as suspect screening of micropollutants in complex environmental samples.
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Conclusions
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Questions?
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