Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer, Equipped with Novel Sample IntroductionSanja Asendorf, Matthew Cassap, Elena Chernetsova Thermo Fisher Scientific, Bremen, Germany
2 Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer,Equipped with Novel Sample Introduction
Waste waters: As there are no European wide guidelines regulating disposal or cleaning of waste water in general, each member state’s agency is responsible for legislation, regulation and governance of domestic, commercial and industrial waste waters. Due to the wide range of these regulations, the elements selected for this analysis are those covered in the German “Abwasserverordnung - AbwV” (waste water regulation).
Sample Preparation
A high matrix concentration sample, containing Na, Ca, Mg, K, Sr, Ba, Si, Li, at a total of 4.3 % total dissolved solids was prepared in 2 % HNO3 to simulate an average fracking solution. For analysis, the sample was diluted five times in 2 % HNO3.
The method was calibrated with a 3-point calibration for all analyzed elements (see Table 2). The calibration comprised a blank, a 2.5 mg·L-1 and a 5 mg·L-1 standard in 2 % HNO3.
Instrumentation
An iCAP 7600 ICP-OES Duo with a standard sample introduction kit and a Burgener PEEK Mira Mist® high salts nebulizer was used. The instrument was equipped with a CETAC ASX-520 autosampler and a Sprint Valve for fast analysis. Method and Sprint Valve parameters, listed in Table 1 and Figure 2, were applied for all analyses.
Results Calibration
In Figure 3, calibration curves are exemplary shown for different data acquisition views of the instrument: Radial visible, axial visible and axial UV. Correlation coefficients better than 0.9999 were obtained for most analytes (see Table 2).
FIGURE 2. Sprint Valve parameters.
Stability
A Continuing Calibration Blank (CCB) and CCV sample were analyzed for trace and major components every 10 samples over a timespan of multiple hours. The recoveries of the CCV sample are shown in Figure 4.
For most elements the recoveries lie within ± 10 % of the desired value throughout the whole run. Only the last sample, obtained after 3 hours of constant analysis, shows values slightly below 90 % for most analytes. Mercury is not displayed because of it‘s high deviation (132 – 201 %) and Na shows a depression of the signal with values in the range of 62 – 71 %.
Detection Limits
Detection limits were obtained by analyzing the analysis blank 3 times with 10 repeats, multiplying the standard deviation by 3 and taking the average. Except for Na (31 µg·L-1) and Ni (12 µg·L-1), the detection limits were in the single ppb range or lower (Table 2). When comparing these detection limits with the regulatory limits, this method is appropriate for all elements, except Cd, Cr and Hg. For these elements, an alternative method should be used, such as ICP-MS, as provided by the Thermo Scientific™ iCAP™ Q ICP-MS.
Driven by the Thermo Scientific Qtegra Intelligent Scientific Data Solution (ISDS) In analytical service laboratories where the highest flexibility is required, the use of a single software package on multiple instruments (support of iCAP 6000 and 7000 Series ICP-OES and iCAP Q ICP-MS) as the Thermo Scientific™ Qtegra™ Intelligent Data Solution™ (ISDS) Software allows operators to easily move between hardware platforms, minimizing training time.
Conclusion The stability of the CCV between high concentrated samples is very high and can certainly be enhancend by using an internal standard like yttrium. As fracking is becoming a more and more popular way of natural gas extraction, the developed method for determination of trace contaminants will be an ideal solution for this analysis.
Overview Purpose: To demonstrate the use of Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) as a key solution for examining fracking flowback waters.
Methods: A Thermo Scientific™ iCAP™ 7600 ICP-OES Duo equipped with a Sprint Valve was used in conjunction with a Teledyne™ CETAC™ ASX-520 autosampler. A Continuing Calibration Verification (CCV) sample was analyzed over a timespan of multiple hours in between high matrix samples simulating fracking flowback waters.
Results: During 2.5 hours of analysis, stability of the CCV was within ± 10% of the desired value for almost all elements. The detection limits of the method are in accordance with those regulatory limits that affect surface, ground and drinking water. Only for some elements, where very low detection limits are required (Cd, Cr, Hg), another method like Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) should be used.
Introduction The recent rapid increase in natural gas production in the USA has been propelled by the extensive use of hydraulic fracturing gas extraction (also known as fracking). While in the U.S. the method is deployed readily, in Europe the topic has been of some debate. Keeping pace with the global energy market and securing energy resources is being weighed against potential environmental risks. The process of fracking extracts natural gas by drilling into bedrock (primarily shale) and then injecting fluid under high pressure causing cracks in bedrock, thereby releasing trapped gas which is then captured. Fracking fluid contains proppants like sand but also chemical additives such as friction reducers, anti-bacterial agents, and corrosion inhibitors. While fracking provides financial benefits to both local and national economies, it has not been without controversy. Inadvertent spills or the storage of fracking flowback solutions (fracking solution that returns to the surface via the well bore) into unlined collection ponds can contaminate ground water. Additionally, high levels of minerals found in fracking wastewater can impact drinking water sources prior to disinfection at downstream drinking water utilities. A challenge with analyzing fracking flowback solutions is the high levels of dissolved solids, salts are typically leached from bedrock into solution. Direct analysis of these solutions can often suppress key analytes, and cause the user to need to dilute the sample so that accurate measurement for trace analytes can take place. Additionally, high concentrations may exceed the linear calibration range for a particular analyte. The need for a robust RF generator and full wavelength selection are key to getting accurate results.
Methods
Fracking fluids might influence water bodies from surface to ground and drinking waters. In addition, contaminated flowback waters have to be stored or treated to be returned to the water cycle. Therefore a combination of different directives and guidelines are deployed for this analysis.
Drinking waters: The European drinking water guideline 98/83/EC provides Maximum Contaminant Levels (MCL) for 10 elements, defined as chemical parameters which are deemed toxic or hazardous to health. Five further indicator parameters affect the taste, smell or quality of water.
Natural waters: The analysis of natural water bodies falls under the EU Water Framework Directive 2000/60/EC. For classification of the water bodies, the directive lists Maximum Allowable Concentrations (MAC) or annual averages of specific pollutants and priority substances of which 10 are suitable for trace elemental analysis by ICP-OES.
Burgener Mira Mist is a trademark of John Burgener of Burgener Research Inc. CETAC is a registered trademark of Teledyne CETAC Technologies. Tygon is a registered trade mark of Saint-Gobain Corporation. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
Presented at the European Winter Conference on Plasma Spectrochemistry 02/2015, Muenster, Germany
Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer, Equipped with Novel Sample Introduction Sanja Asendorf, Matthew Cassap, Elena Chernetsova Thermo Fisher Scientific, Bremen, Germany
FIGURE 1. A typical fracking site.
TABLE 2. Correlation coefficients (R2), method detection limits (MDL) and regulatory limits.
TABLE 1. Method parameters.
Element Wavelength
(nm) Plasma
View R2 MDL (µg·L-1)
Regulatory Limits
(µg·L-1) Ag 328.068 Axial 1.0000 0.8 30c
Al 167.079 Axial 0.9935 0.2 200a
As 189.042 Axial 1.0000 2.1 10a,b
B 208.959 Axial 0.9998 0.6 1 000a
Ba 455.403 Radial 0.9999 0.5 2 000c
Cd 226.502 Axial 0.9999 0.12 0.08a,b
Co 230.786 Axial 1.0000 0.3 100c
Cr 267.716 Axial 1.0000 0.7 0.6a,b
Cu 224.700 Axial 1.0000 0.7 1a,b
Fe 259.940 Radial 0.9999 4.9 200a,b
Hg 194.227 Axial 0.9958 0.58 0.07a,b
Mn 257.610 Radial 0.9997 0.1 50a
Na 589.592 Radial 0.9960 31 200 000a
Ni 231.604 Axial 0.9999 12 20a,b
Pb 220.353 Axial 0.9999 1.6 10a,b
S as SO4 182.034 Axial 0.9999 3.6 250 000a
Sb 206.833 Axial 1.0000 2.7 5a
Se 196.090 Axial 0.9998 3.2 10a
Sn 189.989 Axial 0.9999 0.7 200c
Ti 323.452 Axial 0.9998 0.3 - Tl 190.856 Axial 0.9999 1.4 50c
V 311.071 Radial 1.0000 0.8 4 000c
Zn 213.856 Axial 1.0000 0.1 8b
Parameter Setting
Pump Tubing Sample Tygon™ White/White Drain Tygon™ Yellow/Blue
Pump Speed 40 rpm Spray Chamber Glass Cyclonic Nebulizer Burgener PEEK Mira Mist© Center Tuber 2 mm Nebulizer Gas Flow 0.5 L·min-1
Auxiliay Gas Flow 0.5 L·min-1
Coolant Gas Flow 12 L·min-1 RF Power 1150 W Number of Replicates 3 Exposure Time Axial Radial UV 15 - Vis 5 5
As 189.042 nm (axial UV) Cr 267.716 nm (axial visible)
Ag 328.068 nm (radial visible)
FIGURE 3. Calibration curves for different data acquisition views.
0
20
40
60
80
100
120
140
1 2 3 4 5
Rec
over
y (%
)
CCV Number
CCV Samples
Ag 328.068 Al 167.079
As 189.042 B 208.959
Ba 455.403 Cd 226.502
Co 230.786 Cr 267.716
Cu 224.700 Fe 259.940
Mg 279.553 Mn 257.610
Mo 202.030 Ni 231.604
Pb 220.353 S 182.034
Sb 206.833 Se 196.090
Sn 189.989 Ti 323.452
Tl 190.856 V 311.071
Zn 213.856
FIGURE 4. Recoveries for CCV sample in %.
a: EU drinking water directive 98/83/EC. b: EU natural waters WDF 2000/60/EC. c: German waste water regulation.
3Thermo Scientific Poster Note • eWPC • PN43235-EN 0315S
Waste waters: As there are no European wide guidelines regulating disposal or cleaning of waste water in general, each member state’s agency is responsible for legislation, regulation and governance of domestic, commercial and industrial waste waters. Due to the wide range of these regulations, the elements selected for this analysis are those covered in the German “Abwasserverordnung - AbwV” (waste water regulation).
Sample Preparation
A high matrix concentration sample, containing Na, Ca, Mg, K, Sr, Ba, Si, Li, at a total of 4.3 % total dissolved solids was prepared in 2 % HNO3 to simulate an average fracking solution. For analysis, the sample was diluted five times in 2 % HNO3.
The method was calibrated with a 3-point calibration for all analyzed elements (see Table 2). The calibration comprised a blank, a 2.5 mg·L-1 and a 5 mg·L-1 standard in 2 % HNO3.
Instrumentation
An iCAP 7600 ICP-OES Duo with a standard sample introduction kit and a Burgener PEEK Mira Mist® high salts nebulizer was used. The instrument was equipped with a CETAC ASX-520 autosampler and a Sprint Valve for fast analysis. Method and Sprint Valve parameters, listed in Table 1 and Figure 2, were applied for all analyses.
Results Calibration
In Figure 3, calibration curves are exemplary shown for different data acquisition views of the instrument: Radial visible, axial visible and axial UV. Correlation coefficients better than 0.9999 were obtained for most analytes (see Table 2).
FIGURE 2. Sprint Valve parameters.
Stability
A Continuing Calibration Blank (CCB) and CCV sample were analyzed for trace and major components every 10 samples over a timespan of multiple hours. The recoveries of the CCV sample are shown in Figure 4.
For most elements the recoveries lie within ± 10 % of the desired value throughout the whole run. Only the last sample, obtained after 3 hours of constant analysis, shows values slightly below 90 % for most analytes. Mercury is not displayed because of it‘s high deviation (132 – 201 %) and Na shows a depression of the signal with values in the range of 62 – 71 %.
Detection Limits
Detection limits were obtained by analyzing the analysis blank 3 times with 10 repeats, multiplying the standard deviation by 3 and taking the average. Except for Na (31 µg·L-1) and Ni (12 µg·L-1), the detection limits were in the single ppb range or lower (Table 2). When comparing these detection limits with the regulatory limits, this method is appropriate for all elements, except Cd, Cr and Hg. For these elements, an alternative method should be used, such as ICP-MS, as provided by the Thermo Scientific™ iCAP™ Q ICP-MS.
Driven by the Thermo Scientific Qtegra Intelligent Scientific Data Solution (ISDS) In analytical service laboratories where the highest flexibility is required, the use of a single software package on multiple instruments (support of iCAP 6000 and 7000 Series ICP-OES and iCAP Q ICP-MS) as the Thermo Scientific™ Qtegra™ Intelligent Data Solution™ (ISDS) Software allows operators to easily move between hardware platforms, minimizing training time.
Conclusion The stability of the CCV between high concentrated samples is very high and can certainly be enhancend by using an internal standard like yttrium. As fracking is becoming a more and more popular way of natural gas extraction, the developed method for determination of trace contaminants will be an ideal solution for this analysis.
Overview Purpose: To demonstrate the use of Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) as a key solution for examining fracking flowback waters.
Methods: A Thermo Scientific™ iCAP™ 7600 ICP-OES Duo equipped with a Sprint Valve was used in conjunction with a Teledyne™ CETAC™ ASX-520 autosampler. A Continuing Calibration Verification (CCV) sample was analyzed over a timespan of multiple hours in between high matrix samples simulating fracking flowback waters.
Results: During 2.5 hours of analysis, stability of the CCV was within ± 10% of the desired value for almost all elements. The detection limits of the method are in accordance with those regulatory limits that affect surface, ground and drinking water. Only for some elements, where very low detection limits are required (Cd, Cr, Hg), another method like Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) should be used.
Introduction The recent rapid increase in natural gas production in the USA has been propelled by the extensive use of hydraulic fracturing gas extraction (also known as fracking). While in the U.S. the method is deployed readily, in Europe the topic has been of some debate. Keeping pace with the global energy market and securing energy resources is being weighed against potential environmental risks. The process of fracking extracts natural gas by drilling into bedrock (primarily shale) and then injecting fluid under high pressure causing cracks in bedrock, thereby releasing trapped gas which is then captured. Fracking fluid contains proppants like sand but also chemical additives such as friction reducers, anti-bacterial agents, and corrosion inhibitors. While fracking provides financial benefits to both local and national economies, it has not been without controversy. Inadvertent spills or the storage of fracking flowback solutions (fracking solution that returns to the surface via the well bore) into unlined collection ponds can contaminate ground water. Additionally, high levels of minerals found in fracking wastewater can impact drinking water sources prior to disinfection at downstream drinking water utilities. A challenge with analyzing fracking flowback solutions is the high levels of dissolved solids, salts are typically leached from bedrock into solution. Direct analysis of these solutions can often suppress key analytes, and cause the user to need to dilute the sample so that accurate measurement for trace analytes can take place. Additionally, high concentrations may exceed the linear calibration range for a particular analyte. The need for a robust RF generator and full wavelength selection are key to getting accurate results.
Methods
Fracking fluids might influence water bodies from surface to ground and drinking waters. In addition, contaminated flowback waters have to be stored or treated to be returned to the water cycle. Therefore a combination of different directives and guidelines are deployed for this analysis.
Drinking waters: The European drinking water guideline 98/83/EC provides Maximum Contaminant Levels (MCL) for 10 elements, defined as chemical parameters which are deemed toxic or hazardous to health. Five further indicator parameters affect the taste, smell or quality of water.
Natural waters: The analysis of natural water bodies falls under the EU Water Framework Directive 2000/60/EC. For classification of the water bodies, the directive lists Maximum Allowable Concentrations (MAC) or annual averages of specific pollutants and priority substances of which 10 are suitable for trace elemental analysis by ICP-OES.
Burgener Mira Mist is a trademark of John Burgener of Burgener Research Inc. CETAC is a registered trademark of Teledyne CETAC Technologies. Tygon is a registered trade mark of Saint-Gobain Corporation. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
Presented at the European Winter Conference on Plasma Spectrochemistry 02/2015, Muenster, Germany
Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer, Equipped with Novel Sample Introduction Sanja Asendorf, Matthew Cassap, Elena Chernetsova Thermo Fisher Scientific, Bremen, Germany
FIGURE 1. A typical fracking site.
TABLE 2. Correlation coefficients (R2), method detection limits (MDL) and regulatory limits.
TABLE 1. Method parameters.
Element Wavelength
(nm) Plasma
View R2 MDL (µg·L-1)
Regulatory Limits
(µg·L-1) Ag 328.068 Axial 1.0000 0.8 30c
Al 167.079 Axial 0.9935 0.2 200a
As 189.042 Axial 1.0000 2.1 10a,b
B 208.959 Axial 0.9998 0.6 1 000a
Ba 455.403 Radial 0.9999 0.5 2 000c
Cd 226.502 Axial 0.9999 0.12 0.08a,b
Co 230.786 Axial 1.0000 0.3 100c
Cr 267.716 Axial 1.0000 0.7 0.6a,b
Cu 224.700 Axial 1.0000 0.7 1a,b
Fe 259.940 Radial 0.9999 4.9 200a,b
Hg 194.227 Axial 0.9958 0.58 0.07a,b
Mn 257.610 Radial 0.9997 0.1 50a
Na 589.592 Radial 0.9960 31 200 000a
Ni 231.604 Axial 0.9999 12 20a,b
Pb 220.353 Axial 0.9999 1.6 10a,b
S as SO4 182.034 Axial 0.9999 3.6 250 000a
Sb 206.833 Axial 1.0000 2.7 5a
Se 196.090 Axial 0.9998 3.2 10a
Sn 189.989 Axial 0.9999 0.7 200c
Ti 323.452 Axial 0.9998 0.3 - Tl 190.856 Axial 0.9999 1.4 50c
V 311.071 Radial 1.0000 0.8 4 000c
Zn 213.856 Axial 1.0000 0.1 8b
Parameter Setting
Pump Tubing Sample Tygon™ White/White Drain Tygon™ Yellow/Blue
Pump Speed 40 rpm Spray Chamber Glass Cyclonic Nebulizer Burgener PEEK Mira Mist© Center Tuber 2 mm Nebulizer Gas Flow 0.5 L·min-1
Auxiliay Gas Flow 0.5 L·min-1
Coolant Gas Flow 12 L·min-1 RF Power 1150 W Number of Replicates 3 Exposure Time Axial Radial UV 15 - Vis 5 5
As 189.042 nm (axial UV) Cr 267.716 nm (axial visible)
Ag 328.068 nm (radial visible)
FIGURE 3. Calibration curves for different data acquisition views.
0
20
40
60
80
100
120
140
1 2 3 4 5
Rec
over
y (%
)
CCV Number
CCV Samples
Ag 328.068 Al 167.079
As 189.042 B 208.959
Ba 455.403 Cd 226.502
Co 230.786 Cr 267.716
Cu 224.700 Fe 259.940
Mg 279.553 Mn 257.610
Mo 202.030 Ni 231.604
Pb 220.353 S 182.034
Sb 206.833 Se 196.090
Sn 189.989 Ti 323.452
Tl 190.856 V 311.071
Zn 213.856
FIGURE 4. Recoveries for CCV sample in %.
a: EU drinking water directive 98/83/EC. b: EU natural waters WDF 2000/60/EC. c: German waste water regulation.
4 Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer,Equipped with Novel Sample Introduction
Waste waters: As there are no European wide guidelines regulating disposal or cleaning of waste water in general, each member state’s agency is responsible for legislation, regulation and governance of domestic, commercial and industrial waste waters. Due to the wide range of these regulations, the elements selected for this analysis are those covered in the German “Abwasserverordnung - AbwV” (waste water regulation).
Sample Preparation
A high matrix concentration sample, containing Na, Ca, Mg, K, Sr, Ba, Si, Li, at a total of 4.3 % total dissolved solids was prepared in 2 % HNO3 to simulate an average fracking solution. For analysis, the sample was diluted five times in 2 % HNO3.
The method was calibrated with a 3-point calibration for all analyzed elements (see Table 2). The calibration comprised a blank, a 2.5 mg·L-1 and a 5 mg·L-1 standard in 2 % HNO3.
Instrumentation
An iCAP 7600 ICP-OES Duo with a standard sample introduction kit and a Burgener PEEK Mira Mist® high salts nebulizer was used. The instrument was equipped with a CETAC ASX-520 autosampler and a Sprint Valve for fast analysis. Method and Sprint Valve parameters, listed in Table 1 and Figure 2, were applied for all analyses.
Results Calibration
In Figure 3, calibration curves are exemplary shown for different data acquisition views of the instrument: Radial visible, axial visible and axial UV. Correlation coefficients better than 0.9999 were obtained for most analytes (see Table 2).
FIGURE 2. Sprint Valve parameters.
Stability
A Continuing Calibration Blank (CCB) and CCV sample were analyzed for trace and major components every 10 samples over a timespan of multiple hours. The recoveries of the CCV sample are shown in Figure 4.
For most elements the recoveries lie within ± 10 % of the desired value throughout the whole run. Only the last sample, obtained after 3 hours of constant analysis, shows values slightly below 90 % for most analytes. Mercury is not displayed because of it‘s high deviation (132 – 201 %) and Na shows a depression of the signal with values in the range of 62 – 71 %.
Detection Limits
Detection limits were obtained by analyzing the analysis blank 3 times with 10 repeats, multiplying the standard deviation by 3 and taking the average. Except for Na (31 µg·L-1) and Ni (12 µg·L-1), the detection limits were in the single ppb range or lower (Table 2). When comparing these detection limits with the regulatory limits, this method is appropriate for all elements, except Cd, Cr and Hg. For these elements, an alternative method should be used, such as ICP-MS, as provided by the Thermo Scientific™ iCAP™ Q ICP-MS.
Driven by the Thermo Scientific Qtegra Intelligent Scientific Data Solution (ISDS) In analytical service laboratories where the highest flexibility is required, the use of a single software package on multiple instruments (support of iCAP 6000 and 7000 Series ICP-OES and iCAP Q ICP-MS) as the Thermo Scientific™ Qtegra™ Intelligent Data Solution™ (ISDS) Software allows operators to easily move between hardware platforms, minimizing training time.
Conclusion The stability of the CCV between high concentrated samples is very high and can certainly be enhancend by using an internal standard like yttrium. As fracking is becoming a more and more popular way of natural gas extraction, the developed method for determination of trace contaminants will be an ideal solution for this analysis.
Overview Purpose: To demonstrate the use of Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) as a key solution for examining fracking flowback waters.
Methods: A Thermo Scientific™ iCAP™ 7600 ICP-OES Duo equipped with a Sprint Valve was used in conjunction with a Teledyne™ CETAC™ ASX-520 autosampler. A Continuing Calibration Verification (CCV) sample was analyzed over a timespan of multiple hours in between high matrix samples simulating fracking flowback waters.
Results: During 2.5 hours of analysis, stability of the CCV was within ± 10% of the desired value for almost all elements. The detection limits of the method are in accordance with those regulatory limits that affect surface, ground and drinking water. Only for some elements, where very low detection limits are required (Cd, Cr, Hg), another method like Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) should be used.
Introduction The recent rapid increase in natural gas production in the USA has been propelled by the extensive use of hydraulic fracturing gas extraction (also known as fracking). While in the U.S. the method is deployed readily, in Europe the topic has been of some debate. Keeping pace with the global energy market and securing energy resources is being weighed against potential environmental risks. The process of fracking extracts natural gas by drilling into bedrock (primarily shale) and then injecting fluid under high pressure causing cracks in bedrock, thereby releasing trapped gas which is then captured. Fracking fluid contains proppants like sand but also chemical additives such as friction reducers, anti-bacterial agents, and corrosion inhibitors. While fracking provides financial benefits to both local and national economies, it has not been without controversy. Inadvertent spills or the storage of fracking flowback solutions (fracking solution that returns to the surface via the well bore) into unlined collection ponds can contaminate ground water. Additionally, high levels of minerals found in fracking wastewater can impact drinking water sources prior to disinfection at downstream drinking water utilities. A challenge with analyzing fracking flowback solutions is the high levels of dissolved solids, salts are typically leached from bedrock into solution. Direct analysis of these solutions can often suppress key analytes, and cause the user to need to dilute the sample so that accurate measurement for trace analytes can take place. Additionally, high concentrations may exceed the linear calibration range for a particular analyte. The need for a robust RF generator and full wavelength selection are key to getting accurate results.
Methods
Fracking fluids might influence water bodies from surface to ground and drinking waters. In addition, contaminated flowback waters have to be stored or treated to be returned to the water cycle. Therefore a combination of different directives and guidelines are deployed for this analysis.
Drinking waters: The European drinking water guideline 98/83/EC provides Maximum Contaminant Levels (MCL) for 10 elements, defined as chemical parameters which are deemed toxic or hazardous to health. Five further indicator parameters affect the taste, smell or quality of water.
Natural waters: The analysis of natural water bodies falls under the EU Water Framework Directive 2000/60/EC. For classification of the water bodies, the directive lists Maximum Allowable Concentrations (MAC) or annual averages of specific pollutants and priority substances of which 10 are suitable for trace elemental analysis by ICP-OES.
Burgener Mira Mist is a trademark of John Burgener of Burgener Research Inc. CETAC is a registered trademark of Teledyne CETAC Technologies. Tygon is a registered trade mark of Saint-Gobain Corporation. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
Presented at the European Winter Conference on Plasma Spectrochemistry 02/2015, Muenster, Germany
Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer, Equipped with Novel Sample Introduction Sanja Asendorf, Matthew Cassap, Elena Chernetsova Thermo Fisher Scientific, Bremen, Germany
FIGURE 1. A typical fracking site.
TABLE 2. Correlation coefficients (R2), method detection limits (MDL) and regulatory limits.
TABLE 1. Method parameters.
Element Wavelength
(nm) Plasma
View R2 MDL (µg·L-1)
Regulatory Limits
(µg·L-1) Ag 328.068 Axial 1.0000 0.8 30c
Al 167.079 Axial 0.9935 0.2 200a
As 189.042 Axial 1.0000 2.1 10a,b
B 208.959 Axial 0.9998 0.6 1 000a
Ba 455.403 Radial 0.9999 0.5 2 000c
Cd 226.502 Axial 0.9999 0.12 0.08a,b
Co 230.786 Axial 1.0000 0.3 100c
Cr 267.716 Axial 1.0000 0.7 0.6a,b
Cu 224.700 Axial 1.0000 0.7 1a,b
Fe 259.940 Radial 0.9999 4.9 200a,b
Hg 194.227 Axial 0.9958 0.58 0.07a,b
Mn 257.610 Radial 0.9997 0.1 50a
Na 589.592 Radial 0.9960 31 200 000a
Ni 231.604 Axial 0.9999 12 20a,b
Pb 220.353 Axial 0.9999 1.6 10a,b
S as SO4 182.034 Axial 0.9999 3.6 250 000a
Sb 206.833 Axial 1.0000 2.7 5a
Se 196.090 Axial 0.9998 3.2 10a
Sn 189.989 Axial 0.9999 0.7 200c
Ti 323.452 Axial 0.9998 0.3 - Tl 190.856 Axial 0.9999 1.4 50c
V 311.071 Radial 1.0000 0.8 4 000c
Zn 213.856 Axial 1.0000 0.1 8b
Parameter Setting
Pump Tubing Sample Tygon™ White/White Drain Tygon™ Yellow/Blue
Pump Speed 40 rpm Spray Chamber Glass Cyclonic Nebulizer Burgener PEEK Mira Mist© Center Tuber 2 mm Nebulizer Gas Flow 0.5 L·min-1
Auxiliay Gas Flow 0.5 L·min-1
Coolant Gas Flow 12 L·min-1 RF Power 1150 W Number of Replicates 3 Exposure Time Axial Radial UV 15 - Vis 5 5
As 189.042 nm (axial UV) Cr 267.716 nm (axial visible)
Ag 328.068 nm (radial visible)
FIGURE 3. Calibration curves for different data acquisition views.
0
20
40
60
80
100
120
140
1 2 3 4 5
Rec
over
y (%
)
CCV Number
CCV Samples
Ag 328.068 Al 167.079
As 189.042 B 208.959
Ba 455.403 Cd 226.502
Co 230.786 Cr 267.716
Cu 224.700 Fe 259.940
Mg 279.553 Mn 257.610
Mo 202.030 Ni 231.604
Pb 220.353 S 182.034
Sb 206.833 Se 196.090
Sn 189.989 Ti 323.452
Tl 190.856 V 311.071
Zn 213.856
FIGURE 4. Recoveries for CCV sample in %.
a: EU drinking water directive 98/83/EC. b: EU natural waters WDF 2000/60/EC. c: German waste water regulation.
5Thermo Scientific Poster Note • eWPC • PN43235-EN 0315S
Waste waters: As there are no European wide guidelines regulating disposal or cleaning of waste water in general, each member state’s agency is responsible for legislation, regulation and governance of domestic, commercial and industrial waste waters. Due to the wide range of these regulations, the elements selected for this analysis are those covered in the German “Abwasserverordnung - AbwV” (waste water regulation).
Sample Preparation
A high matrix concentration sample, containing Na, Ca, Mg, K, Sr, Ba, Si, Li, at a total of 4.3 % total dissolved solids was prepared in 2 % HNO3 to simulate an average fracking solution. For analysis, the sample was diluted five times in 2 % HNO3.
The method was calibrated with a 3-point calibration for all analyzed elements (see Table 2). The calibration comprised a blank, a 2.5 mg·L-1 and a 5 mg·L-1 standard in 2 % HNO3.
Instrumentation
An iCAP 7600 ICP-OES Duo with a standard sample introduction kit and a Burgener PEEK Mira Mist® high salts nebulizer was used. The instrument was equipped with a CETAC ASX-520 autosampler and a Sprint Valve for fast analysis. Method and Sprint Valve parameters, listed in Table 1 and Figure 2, were applied for all analyses.
Results Calibration
In Figure 3, calibration curves are exemplary shown for different data acquisition views of the instrument: Radial visible, axial visible and axial UV. Correlation coefficients better than 0.9999 were obtained for most analytes (see Table 2).
FIGURE 2. Sprint Valve parameters.
Stability
A Continuing Calibration Blank (CCB) and CCV sample were analyzed for trace and major components every 10 samples over a timespan of multiple hours. The recoveries of the CCV sample are shown in Figure 4.
For most elements the recoveries lie within ± 10 % of the desired value throughout the whole run. Only the last sample, obtained after 3 hours of constant analysis, shows values slightly below 90 % for most analytes. Mercury is not displayed because of it‘s high deviation (132 – 201 %) and Na shows a depression of the signal with values in the range of 62 – 71 %.
Detection Limits
Detection limits were obtained by analyzing the analysis blank 3 times with 10 repeats, multiplying the standard deviation by 3 and taking the average. Except for Na (31 µg·L-1) and Ni (12 µg·L-1), the detection limits were in the single ppb range or lower (Table 2). When comparing these detection limits with the regulatory limits, this method is appropriate for all elements, except Cd, Cr and Hg. For these elements, an alternative method should be used, such as ICP-MS, as provided by the Thermo Scientific™ iCAP™ Q ICP-MS.
Driven by the Thermo Scientific Qtegra Intelligent Scientific Data Solution (ISDS) In analytical service laboratories where the highest flexibility is required, the use of a single software package on multiple instruments (support of iCAP 6000 and 7000 Series ICP-OES and iCAP Q ICP-MS) as the Thermo Scientific™ Qtegra™ Intelligent Data Solution™ (ISDS) Software allows operators to easily move between hardware platforms, minimizing training time.
Conclusion The stability of the CCV between high concentrated samples is very high and can certainly be enhancend by using an internal standard like yttrium. As fracking is becoming a more and more popular way of natural gas extraction, the developed method for determination of trace contaminants will be an ideal solution for this analysis.
Overview Purpose: To demonstrate the use of Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) as a key solution for examining fracking flowback waters.
Methods: A Thermo Scientific™ iCAP™ 7600 ICP-OES Duo equipped with a Sprint Valve was used in conjunction with a Teledyne™ CETAC™ ASX-520 autosampler. A Continuing Calibration Verification (CCV) sample was analyzed over a timespan of multiple hours in between high matrix samples simulating fracking flowback waters.
Results: During 2.5 hours of analysis, stability of the CCV was within ± 10% of the desired value for almost all elements. The detection limits of the method are in accordance with those regulatory limits that affect surface, ground and drinking water. Only for some elements, where very low detection limits are required (Cd, Cr, Hg), another method like Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) should be used.
Introduction The recent rapid increase in natural gas production in the USA has been propelled by the extensive use of hydraulic fracturing gas extraction (also known as fracking). While in the U.S. the method is deployed readily, in Europe the topic has been of some debate. Keeping pace with the global energy market and securing energy resources is being weighed against potential environmental risks. The process of fracking extracts natural gas by drilling into bedrock (primarily shale) and then injecting fluid under high pressure causing cracks in bedrock, thereby releasing trapped gas which is then captured. Fracking fluid contains proppants like sand but also chemical additives such as friction reducers, anti-bacterial agents, and corrosion inhibitors. While fracking provides financial benefits to both local and national economies, it has not been without controversy. Inadvertent spills or the storage of fracking flowback solutions (fracking solution that returns to the surface via the well bore) into unlined collection ponds can contaminate ground water. Additionally, high levels of minerals found in fracking wastewater can impact drinking water sources prior to disinfection at downstream drinking water utilities. A challenge with analyzing fracking flowback solutions is the high levels of dissolved solids, salts are typically leached from bedrock into solution. Direct analysis of these solutions can often suppress key analytes, and cause the user to need to dilute the sample so that accurate measurement for trace analytes can take place. Additionally, high concentrations may exceed the linear calibration range for a particular analyte. The need for a robust RF generator and full wavelength selection are key to getting accurate results.
Methods
Fracking fluids might influence water bodies from surface to ground and drinking waters. In addition, contaminated flowback waters have to be stored or treated to be returned to the water cycle. Therefore a combination of different directives and guidelines are deployed for this analysis.
Drinking waters: The European drinking water guideline 98/83/EC provides Maximum Contaminant Levels (MCL) for 10 elements, defined as chemical parameters which are deemed toxic or hazardous to health. Five further indicator parameters affect the taste, smell or quality of water.
Natural waters: The analysis of natural water bodies falls under the EU Water Framework Directive 2000/60/EC. For classification of the water bodies, the directive lists Maximum Allowable Concentrations (MAC) or annual averages of specific pollutants and priority substances of which 10 are suitable for trace elemental analysis by ICP-OES.
Burgener Mira Mist is a trademark of John Burgener of Burgener Research Inc. CETAC is a registered trademark of Teledyne CETAC Technologies. Tygon is a registered trade mark of Saint-Gobain Corporation. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
Presented at the European Winter Conference on Plasma Spectrochemistry 02/2015, Muenster, Germany
Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer, Equipped with Novel Sample Introduction Sanja Asendorf, Matthew Cassap, Elena Chernetsova Thermo Fisher Scientific, Bremen, Germany
FIGURE 1. A typical fracking site.
TABLE 2. Correlation coefficients (R2), method detection limits (MDL) and regulatory limits.
TABLE 1. Method parameters.
Element Wavelength
(nm) Plasma
View R2 MDL (µg·L-1)
Regulatory Limits
(µg·L-1) Ag 328.068 Axial 1.0000 0.8 30c
Al 167.079 Axial 0.9935 0.2 200a
As 189.042 Axial 1.0000 2.1 10a,b
B 208.959 Axial 0.9998 0.6 1 000a
Ba 455.403 Radial 0.9999 0.5 2 000c
Cd 226.502 Axial 0.9999 0.12 0.08a,b
Co 230.786 Axial 1.0000 0.3 100c
Cr 267.716 Axial 1.0000 0.7 0.6a,b
Cu 224.700 Axial 1.0000 0.7 1a,b
Fe 259.940 Radial 0.9999 4.9 200a,b
Hg 194.227 Axial 0.9958 0.58 0.07a,b
Mn 257.610 Radial 0.9997 0.1 50a
Na 589.592 Radial 0.9960 31 200 000a
Ni 231.604 Axial 0.9999 12 20a,b
Pb 220.353 Axial 0.9999 1.6 10a,b
S as SO4 182.034 Axial 0.9999 3.6 250 000a
Sb 206.833 Axial 1.0000 2.7 5a
Se 196.090 Axial 0.9998 3.2 10a
Sn 189.989 Axial 0.9999 0.7 200c
Ti 323.452 Axial 0.9998 0.3 - Tl 190.856 Axial 0.9999 1.4 50c
V 311.071 Radial 1.0000 0.8 4 000c
Zn 213.856 Axial 1.0000 0.1 8b
Parameter Setting
Pump Tubing Sample Tygon™ White/White Drain Tygon™ Yellow/Blue
Pump Speed 40 rpm Spray Chamber Glass Cyclonic Nebulizer Burgener PEEK Mira Mist© Center Tuber 2 mm Nebulizer Gas Flow 0.5 L·min-1
Auxiliay Gas Flow 0.5 L·min-1
Coolant Gas Flow 12 L·min-1 RF Power 1150 W Number of Replicates 3 Exposure Time Axial Radial UV 15 - Vis 5 5
As 189.042 nm (axial UV) Cr 267.716 nm (axial visible)
Ag 328.068 nm (radial visible)
FIGURE 3. Calibration curves for different data acquisition views.
0
20
40
60
80
100
120
140
1 2 3 4 5
Rec
over
y (%
)
CCV Number
CCV Samples
Ag 328.068 Al 167.079
As 189.042 B 208.959
Ba 455.403 Cd 226.502
Co 230.786 Cr 267.716
Cu 224.700 Fe 259.940
Mg 279.553 Mn 257.610
Mo 202.030 Ni 231.604
Pb 220.353 S 182.034
Sb 206.833 Se 196.090
Sn 189.989 Ti 323.452
Tl 190.856 V 311.071
Zn 213.856
FIGURE 4. Recoveries for CCV sample in %.
a: EU drinking water directive 98/83/EC. b: EU natural waters WDF 2000/60/EC. c: German waste water regulation.
6 Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer,Equipped with Novel Sample Introduction
Waste waters: As there are no European wide guidelines regulating disposal or cleaning of waste water in general, each member state’s agency is responsible for legislation, regulation and governance of domestic, commercial and industrial waste waters. Due to the wide range of these regulations, the elements selected for this analysis are those covered in the German “Abwasserverordnung - AbwV” (waste water regulation).
Sample Preparation
A high matrix concentration sample, containing Na, Ca, Mg, K, Sr, Ba, Si, Li, at a total of 4.3 % total dissolved solids was prepared in 2 % HNO3 to simulate an average fracking solution. For analysis, the sample was diluted five times in 2 % HNO3.
The method was calibrated with a 3-point calibration for all analyzed elements (see Table 2). The calibration comprised a blank, a 2.5 mg·L-1 and a 5 mg·L-1 standard in 2 % HNO3.
Instrumentation
An iCAP 7600 ICP-OES Duo with a standard sample introduction kit and a Burgener PEEK Mira Mist® high salts nebulizer was used. The instrument was equipped with a CETAC ASX-520 autosampler and a Sprint Valve for fast analysis. Method and Sprint Valve parameters, listed in Table 1 and Figure 2, were applied for all analyses.
Results Calibration
In Figure 3, calibration curves are exemplary shown for different data acquisition views of the instrument: Radial visible, axial visible and axial UV. Correlation coefficients better than 0.9999 were obtained for most analytes (see Table 2).
FIGURE 2. Sprint Valve parameters.
Stability
A Continuing Calibration Blank (CCB) and CCV sample were analyzed for trace and major components every 10 samples over a timespan of multiple hours. The recoveries of the CCV sample are shown in Figure 4.
For most elements the recoveries lie within ± 10 % of the desired value throughout the whole run. Only the last sample, obtained after 3 hours of constant analysis, shows values slightly below 90 % for most analytes. Mercury is not displayed because of it‘s high deviation (132 – 201 %) and Na shows a depression of the signal with values in the range of 62 – 71 %.
Detection Limits
Detection limits were obtained by analyzing the analysis blank 3 times with 10 repeats, multiplying the standard deviation by 3 and taking the average. Except for Na (31 µg·L-1) and Ni (12 µg·L-1), the detection limits were in the single ppb range or lower (Table 2). When comparing these detection limits with the regulatory limits, this method is appropriate for all elements, except Cd, Cr and Hg. For these elements, an alternative method should be used, such as ICP-MS, as provided by the Thermo Scientific™ iCAP™ Q ICP-MS.
Driven by the Thermo Scientific Qtegra Intelligent Scientific Data Solution (ISDS) In analytical service laboratories where the highest flexibility is required, the use of a single software package on multiple instruments (support of iCAP 6000 and 7000 Series ICP-OES and iCAP Q ICP-MS) as the Thermo Scientific™ Qtegra™ Intelligent Data Solution™ (ISDS) Software allows operators to easily move between hardware platforms, minimizing training time.
Conclusion The stability of the CCV between high concentrated samples is very high and can certainly be enhancend by using an internal standard like yttrium. As fracking is becoming a more and more popular way of natural gas extraction, the developed method for determination of trace contaminants will be an ideal solution for this analysis.
Overview Purpose: To demonstrate the use of Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) as a key solution for examining fracking flowback waters.
Methods: A Thermo Scientific™ iCAP™ 7600 ICP-OES Duo equipped with a Sprint Valve was used in conjunction with a Teledyne™ CETAC™ ASX-520 autosampler. A Continuing Calibration Verification (CCV) sample was analyzed over a timespan of multiple hours in between high matrix samples simulating fracking flowback waters.
Results: During 2.5 hours of analysis, stability of the CCV was within ± 10% of the desired value for almost all elements. The detection limits of the method are in accordance with those regulatory limits that affect surface, ground and drinking water. Only for some elements, where very low detection limits are required (Cd, Cr, Hg), another method like Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) should be used.
Introduction The recent rapid increase in natural gas production in the USA has been propelled by the extensive use of hydraulic fracturing gas extraction (also known as fracking). While in the U.S. the method is deployed readily, in Europe the topic has been of some debate. Keeping pace with the global energy market and securing energy resources is being weighed against potential environmental risks. The process of fracking extracts natural gas by drilling into bedrock (primarily shale) and then injecting fluid under high pressure causing cracks in bedrock, thereby releasing trapped gas which is then captured. Fracking fluid contains proppants like sand but also chemical additives such as friction reducers, anti-bacterial agents, and corrosion inhibitors. While fracking provides financial benefits to both local and national economies, it has not been without controversy. Inadvertent spills or the storage of fracking flowback solutions (fracking solution that returns to the surface via the well bore) into unlined collection ponds can contaminate ground water. Additionally, high levels of minerals found in fracking wastewater can impact drinking water sources prior to disinfection at downstream drinking water utilities. A challenge with analyzing fracking flowback solutions is the high levels of dissolved solids, salts are typically leached from bedrock into solution. Direct analysis of these solutions can often suppress key analytes, and cause the user to need to dilute the sample so that accurate measurement for trace analytes can take place. Additionally, high concentrations may exceed the linear calibration range for a particular analyte. The need for a robust RF generator and full wavelength selection are key to getting accurate results.
Methods
Fracking fluids might influence water bodies from surface to ground and drinking waters. In addition, contaminated flowback waters have to be stored or treated to be returned to the water cycle. Therefore a combination of different directives and guidelines are deployed for this analysis.
Drinking waters: The European drinking water guideline 98/83/EC provides Maximum Contaminant Levels (MCL) for 10 elements, defined as chemical parameters which are deemed toxic or hazardous to health. Five further indicator parameters affect the taste, smell or quality of water.
Natural waters: The analysis of natural water bodies falls under the EU Water Framework Directive 2000/60/EC. For classification of the water bodies, the directive lists Maximum Allowable Concentrations (MAC) or annual averages of specific pollutants and priority substances of which 10 are suitable for trace elemental analysis by ICP-OES.
Burgener Mira Mist is a trademark of John Burgener of Burgener Research Inc. CETAC is a registered trademark of Teledyne CETAC Technologies. Tygon is a registered trade mark of Saint-Gobain Corporation. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
Presented at the European Winter Conference on Plasma Spectrochemistry 02/2015, Muenster, Germany
Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer, Equipped with Novel Sample Introduction Sanja Asendorf, Matthew Cassap, Elena Chernetsova Thermo Fisher Scientific, Bremen, Germany
FIGURE 1. A typical fracking site.
TABLE 2. Correlation coefficients (R2), method detection limits (MDL) and regulatory limits.
TABLE 1. Method parameters.
Element Wavelength
(nm) Plasma
View R2 MDL (µg·L-1)
Regulatory Limits
(µg·L-1) Ag 328.068 Axial 1.0000 0.8 30c
Al 167.079 Axial 0.9935 0.2 200a
As 189.042 Axial 1.0000 2.1 10a,b
B 208.959 Axial 0.9998 0.6 1 000a
Ba 455.403 Radial 0.9999 0.5 2 000c
Cd 226.502 Axial 0.9999 0.12 0.08a,b
Co 230.786 Axial 1.0000 0.3 100c
Cr 267.716 Axial 1.0000 0.7 0.6a,b
Cu 224.700 Axial 1.0000 0.7 1a,b
Fe 259.940 Radial 0.9999 4.9 200a,b
Hg 194.227 Axial 0.9958 0.58 0.07a,b
Mn 257.610 Radial 0.9997 0.1 50a
Na 589.592 Radial 0.9960 31 200 000a
Ni 231.604 Axial 0.9999 12 20a,b
Pb 220.353 Axial 0.9999 1.6 10a,b
S as SO4 182.034 Axial 0.9999 3.6 250 000a
Sb 206.833 Axial 1.0000 2.7 5a
Se 196.090 Axial 0.9998 3.2 10a
Sn 189.989 Axial 0.9999 0.7 200c
Ti 323.452 Axial 0.9998 0.3 - Tl 190.856 Axial 0.9999 1.4 50c
V 311.071 Radial 1.0000 0.8 4 000c
Zn 213.856 Axial 1.0000 0.1 8b
Parameter Setting
Pump Tubing Sample Tygon™ White/White Drain Tygon™ Yellow/Blue
Pump Speed 40 rpm Spray Chamber Glass Cyclonic Nebulizer Burgener PEEK Mira Mist© Center Tuber 2 mm Nebulizer Gas Flow 0.5 L·min-1
Auxiliay Gas Flow 0.5 L·min-1
Coolant Gas Flow 12 L·min-1 RF Power 1150 W Number of Replicates 3 Exposure Time Axial Radial UV 15 - Vis 5 5
As 189.042 nm (axial UV) Cr 267.716 nm (axial visible)
Ag 328.068 nm (radial visible)
FIGURE 3. Calibration curves for different data acquisition views.
0
20
40
60
80
100
120
140
1 2 3 4 5
Rec
over
y (%
)
CCV Number
CCV Samples
Ag 328.068 Al 167.079
As 189.042 B 208.959
Ba 455.403 Cd 226.502
Co 230.786 Cr 267.716
Cu 224.700 Fe 259.940
Mg 279.553 Mn 257.610
Mo 202.030 Ni 231.604
Pb 220.353 S 182.034
Sb 206.833 Se 196.090
Sn 189.989 Ti 323.452
Tl 190.856 V 311.071
Zn 213.856
FIGURE 4. Recoveries for CCV sample in %.
a: EU drinking water directive 98/83/EC. b: EU natural waters WDF 2000/60/EC. c: German waste water regulation.
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www.thermoscientific.com©2015 Thermo Fisher Scientific Inc. All rights reserved. ISO is a trademark of the International Standards Organization. Burgener Mira Mist is a trademark of John Burgener of Burgener Research Inc. CETAC is a registered trademark of Teledyne CETAC Technologies. Tygon is a registered trade mark of Saint-Gobain Corporation. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scientific products. It is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others. Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.
Thermo Fisher Scientific (Bremen) GmbHManagement System Registered to ISO 9001:2008
Waste waters: As there are no European wide guidelines regulating disposal or cleaning of waste water in general, each member state’s agency is responsible for legislation, regulation and governance of domestic, commercial and industrial waste waters. Due to the wide range of these regulations, the elements selected for this analysis are those covered in the German “Abwasserverordnung - AbwV” (waste water regulation).
Sample Preparation
A high matrix concentration sample, containing Na, Ca, Mg, K, Sr, Ba, Si, Li, at a total of 4.3 % total dissolved solids was prepared in 2 % HNO3 to simulate an average fracking solution. For analysis, the sample was diluted five times in 2 % HNO3.
The method was calibrated with a 3-point calibration for all analyzed elements (see Table 2). The calibration comprised a blank, a 2.5 mg·L-1 and a 5 mg·L-1 standard in 2 % HNO3.
Instrumentation
An iCAP 7600 ICP-OES Duo with a standard sample introduction kit and a Burgener PEEK Mira Mist® high salts nebulizer was used. The instrument was equipped with a CETAC ASX-520 autosampler and a Sprint Valve for fast analysis. Method and Sprint Valve parameters, listed in Table 1 and Figure 2, were applied for all analyses.
Results Calibration
In Figure 3, calibration curves are exemplary shown for different data acquisition views of the instrument: Radial visible, axial visible and axial UV. Correlation coefficients better than 0.9999 were obtained for most analytes (see Table 2).
FIGURE 2. Sprint Valve parameters.
Stability
A Continuing Calibration Blank (CCB) and CCV sample were analyzed for trace and major components every 10 samples over a timespan of multiple hours. The recoveries of the CCV sample are shown in Figure 4.
For most elements the recoveries lie within ± 10 % of the desired value throughout the whole run. Only the last sample, obtained after 3 hours of constant analysis, shows values slightly below 90 % for most analytes. Mercury is not displayed because of it‘s high deviation (132 – 201 %) and Na shows a depression of the signal with values in the range of 62 – 71 %.
Detection Limits
Detection limits were obtained by analyzing the analysis blank 3 times with 10 repeats, multiplying the standard deviation by 3 and taking the average. Except for Na (31 µg·L-1) and Ni (12 µg·L-1), the detection limits were in the single ppb range or lower (Table 2). When comparing these detection limits with the regulatory limits, this method is appropriate for all elements, except Cd, Cr and Hg. For these elements, an alternative method should be used, such as ICP-MS, as provided by the Thermo Scientific™ iCAP™ Q ICP-MS.
Driven by the Thermo Scientific Qtegra Intelligent Scientific Data Solution (ISDS) In analytical service laboratories where the highest flexibility is required, the use of a single software package on multiple instruments (support of iCAP 6000 and 7000 Series ICP-OES and iCAP Q ICP-MS) as the Thermo Scientific™ Qtegra™ Intelligent Data Solution™ (ISDS) Software allows operators to easily move between hardware platforms, minimizing training time.
Conclusion The stability of the CCV between high concentrated samples is very high and can certainly be enhancend by using an internal standard like yttrium. As fracking is becoming a more and more popular way of natural gas extraction, the developed method for determination of trace contaminants will be an ideal solution for this analysis.
Overview Purpose: To demonstrate the use of Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) as a key solution for examining fracking flowback waters.
Methods: A Thermo Scientific™ iCAP™ 7600 ICP-OES Duo equipped with a Sprint Valve was used in conjunction with a Teledyne™ CETAC™ ASX-520 autosampler. A Continuing Calibration Verification (CCV) sample was analyzed over a timespan of multiple hours in between high matrix samples simulating fracking flowback waters.
Results: During 2.5 hours of analysis, stability of the CCV was within ± 10% of the desired value for almost all elements. The detection limits of the method are in accordance with those regulatory limits that affect surface, ground and drinking water. Only for some elements, where very low detection limits are required (Cd, Cr, Hg), another method like Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) should be used.
Introduction The recent rapid increase in natural gas production in the USA has been propelled by the extensive use of hydraulic fracturing gas extraction (also known as fracking). While in the U.S. the method is deployed readily, in Europe the topic has been of some debate. Keeping pace with the global energy market and securing energy resources is being weighed against potential environmental risks. The process of fracking extracts natural gas by drilling into bedrock (primarily shale) and then injecting fluid under high pressure causing cracks in bedrock, thereby releasing trapped gas which is then captured. Fracking fluid contains proppants like sand but also chemical additives such as friction reducers, anti-bacterial agents, and corrosion inhibitors. While fracking provides financial benefits to both local and national economies, it has not been without controversy. Inadvertent spills or the storage of fracking flowback solutions (fracking solution that returns to the surface via the well bore) into unlined collection ponds can contaminate ground water. Additionally, high levels of minerals found in fracking wastewater can impact drinking water sources prior to disinfection at downstream drinking water utilities. A challenge with analyzing fracking flowback solutions is the high levels of dissolved solids, salts are typically leached from bedrock into solution. Direct analysis of these solutions can often suppress key analytes, and cause the user to need to dilute the sample so that accurate measurement for trace analytes can take place. Additionally, high concentrations may exceed the linear calibration range for a particular analyte. The need for a robust RF generator and full wavelength selection are key to getting accurate results.
Methods
Fracking fluids might influence water bodies from surface to ground and drinking waters. In addition, contaminated flowback waters have to be stored or treated to be returned to the water cycle. Therefore a combination of different directives and guidelines are deployed for this analysis.
Drinking waters: The European drinking water guideline 98/83/EC provides Maximum Contaminant Levels (MCL) for 10 elements, defined as chemical parameters which are deemed toxic or hazardous to health. Five further indicator parameters affect the taste, smell or quality of water.
Natural waters: The analysis of natural water bodies falls under the EU Water Framework Directive 2000/60/EC. For classification of the water bodies, the directive lists Maximum Allowable Concentrations (MAC) or annual averages of specific pollutants and priority substances of which 10 are suitable for trace elemental analysis by ICP-OES.
Burgener Mira Mist is a trademark of John Burgener of Burgener Research Inc. CETAC is a registered trademark of Teledyne CETAC Technologies. Tygon is a registered trade mark of Saint-Gobain Corporation. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
Presented at the European Winter Conference on Plasma Spectrochemistry 02/2015, Muenster, Germany
Analysis of Fracking Related Samples by Inductively Coupled Plasma – Optical Emission Spectrometer, Equipped with Novel Sample Introduction Sanja Asendorf, Matthew Cassap, Elena Chernetsova Thermo Fisher Scientific, Bremen, Germany
FIGURE 1. A typical fracking site.
TABLE 2. Correlation coefficients (R2), method detection limits (MDL) and regulatory limits.
TABLE 1. Method parameters.
Element Wavelength
(nm) Plasma
View R2 MDL (µg·L-1)
Regulatory Limits
(µg·L-1) Ag 328.068 Axial 1.0000 0.8 30c
Al 167.079 Axial 0.9935 0.2 200a
As 189.042 Axial 1.0000 2.1 10a,b
B 208.959 Axial 0.9998 0.6 1 000a
Ba 455.403 Radial 0.9999 0.5 2 000c
Cd 226.502 Axial 0.9999 0.12 0.08a,b
Co 230.786 Axial 1.0000 0.3 100c
Cr 267.716 Axial 1.0000 0.7 0.6a,b
Cu 224.700 Axial 1.0000 0.7 1a,b
Fe 259.940 Radial 0.9999 4.9 200a,b
Hg 194.227 Axial 0.9958 0.58 0.07a,b
Mn 257.610 Radial 0.9997 0.1 50a
Na 589.592 Radial 0.9960 31 200 000a
Ni 231.604 Axial 0.9999 12 20a,b
Pb 220.353 Axial 0.9999 1.6 10a,b
S as SO4 182.034 Axial 0.9999 3.6 250 000a
Sb 206.833 Axial 1.0000 2.7 5a
Se 196.090 Axial 0.9998 3.2 10a
Sn 189.989 Axial 0.9999 0.7 200c
Ti 323.452 Axial 0.9998 0.3 - Tl 190.856 Axial 0.9999 1.4 50c
V 311.071 Radial 1.0000 0.8 4 000c
Zn 213.856 Axial 1.0000 0.1 8b
Parameter Setting
Pump Tubing Sample Tygon™ White/White Drain Tygon™ Yellow/Blue
Pump Speed 40 rpm Spray Chamber Glass Cyclonic Nebulizer Burgener PEEK Mira Mist© Center Tuber 2 mm Nebulizer Gas Flow 0.5 L·min-1
Auxiliay Gas Flow 0.5 L·min-1
Coolant Gas Flow 12 L·min-1 RF Power 1150 W Number of Replicates 3 Exposure Time Axial Radial UV 15 - Vis 5 5
As 189.042 nm (axial UV) Cr 267.716 nm (axial visible)
Ag 328.068 nm (radial visible)
FIGURE 3. Calibration curves for different data acquisition views.
0
20
40
60
80
100
120
140
1 2 3 4 5
Rec
over
y (%
)
CCV Number
CCV Samples
Ag 328.068 Al 167.079
As 189.042 B 208.959
Ba 455.403 Cd 226.502
Co 230.786 Cr 267.716
Cu 224.700 Fe 259.940
Mg 279.553 Mn 257.610
Mo 202.030 Ni 231.604
Pb 220.353 S 182.034
Sb 206.833 Se 196.090
Sn 189.989 Ti 323.452
Tl 190.856 V 311.071
Zn 213.856
FIGURE 4. Recoveries for CCV sample in %.
a: EU drinking water directive 98/83/EC. b: EU natural waters WDF 2000/60/EC. c: German waste water regulation.
