Article • J. Braz. Chem. Soc. 32
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• Apr 2021 • https://doi.org/10.21577/0103-5053.20200235 linkcopy
Alternative Approaches Applied to Inductively Coupled Plasma Techniques: Multi-Flow and Two-Flow Calibration
Authorship
person Raquel C. Machado
schoolGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, BrazilUniversidade Federal de São CarlosBrazilSão Carlos, SP, BrazilGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, Brazil
person Ana Beatriz S. Silva
schoolGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, BrazilUniversidade Federal de São CarlosBrazilSão Carlos, SP, BrazilGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, BrazilschoolEmbrapa Pecuária Sudeste, 13560-970 São Carlos-SP, BrazilEmbrapa Pecuária SudesteBrazilSão Carlos, SP, BrazilEmbrapa Pecuária Sudeste, 13560-970 São Carlos-SP, Brazil
person Daniel F. Andrade
schoolGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, BrazilUniversidade Federal de São CarlosBrazilSão Carlos, SP, BrazilGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, Brazil
person Fernanda C. Pinheiro
schoolGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, BrazilUniversidade Federal de São CarlosBrazilSão Carlos, SP, BrazilGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, Brazil
person Charles B. Williams
person George L Donati
person Ana Rita A. Nogueira
person Edenir R. Pereira-Filho *
schoolGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, BrazilUniversidade Federal de São CarlosBrazilSão Carlos, SP, BrazilGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, Brazil
Author Contributions
Raquel C. Machado, Ana Beatriz S. Silva, Daniel F. Andrade and Fernanda C. Pinheiro were responsible for conceptualization, methodology, validation, formal analysis, investigation, writing-original draft, writing-review and editing and visualization; Charles B. Williams was responsible for conceptualization, writing-original draft and visualization; George L. Donati for conceptualization, writing-original draft, writing-review and editing and visualization; Ana Rita A. Nogueira for writing-original draft, writing-review and editing, visualization, funding acquisition, project administration and resources; Edenir R. Pereira-Filho for conceptualization, investigation, writing-original draft, writing-review and editing, visualization, funding acquisition, project administration, resources and supervision.
SCIMAGO INSTITUTIONS RANKINGS
Grupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, BrazilUniversidade Federal de São CarlosBrazilSão Carlos, SP, BrazilGrupo de Análise Instrumental Aplicada, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos-SP, Brazil
Embrapa Pecuária Sudeste, 13560-970 São Carlos-SP, BrazilEmbrapa Pecuária SudesteBrazilSão Carlos, SP, BrazilEmbrapa Pecuária Sudeste, 13560-970 São Carlos-SP, Brazil
Figures | Tables | Formulas
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imageFigure 1 Multi-flow linear models considering the analytes concentration in the calibration standard solution as sample/standard ratio 1:1 for determination of (a) As, (b) Cd and (c) Pb in polymer CRM (ERM-EC681K) using ICP OES, and (d) 114Cd, (e) 59Co and (f) 51V in spinach leaves CRM (NIST 1570a) using ICP-MS. open_in_new
imageFigure 2 Multi-flow linear models using only two nebulization gas flow rates for the analytes concentration in the calibration standard solution as sample/ standard ratio 1:1 for determination of (a) Cd in soil RM-Agro E2002a by ICP OES, and (b) V in spinach leaves CRM (NIST 1570a) by ICP-MS. open_in_new
table_chartTable 1
Operating parameters and accessories used in ICP OES and ICP-MS
| Instrument parameter | ICP OES | ICP-MS |
|---|---|---|
| RF applied power / kW | 1.15 | 1.55 |
| Plasma gas flow rate / (L min-1) | 12 | 15 |
| Auxiliary gas flow rate / (L min-1) | 0.50 | 1.00 |
| Sampling depth / mm | NA | 8.0 |
| He flow rate in collision cell / (mL min-1) |
NA | 4.5 |
| Integration time / s | 15 | 3.0 |
| Nebulizer | concentric | Mira-Mist |
| Spray chamber | cyclonic | Scott type-double pass |
| Number of replicate | 3 | 3 |
| Analyte | Emission line / nm | Isotope (m/z) |
| Al | 167.079 | NA |
| As | 189.042 | 75 |
| Cd | 228.802 | 114 |
| Co | NA | 59 |
| Cr | 267.716 | NA |
| Cu | 327.396 | 65 |
| Hg | NA | 202 |
| Mo | NA | 98 |
| Mn | 259.373 | 55 |
| Ni | NA | 58 |
| Pb | 216.999 | 208 |
| Sb | NA | 121 |
| Se | NA | 78 |
| V | NA | 51 |
| Zn | 213.856 | NA |
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RF: radiofrequency; ICP OES: inductively coupled plasma optical emission spectrometry; ICP-MS: inductively coupled plasma mass spectrometry; NA: not applicable once the element was not determined by this technique.
table_chartTable 2
Elements determined by ICP OES and ICP-MS in the CRMs and RMs analyzed
| Material | ICP OES | ICP-MS |
|---|---|---|
| ERM-EC680K (polyethylene, low level) | NA | As, Cd, Hg, Pb, Sb |
| ERM-EC681K (polyethylene, high level) | As, Cd, Hg, Pb | NA |
| NIST 1570a (spinach leaves) | Al, Mn, Zn | As, Cd, Co, Cu, Ni, Se, V |
| RM-Agro E3001a (bovine liver) | NA | Cd, Co, Mn, Mo, Se |
| RM-Agro E2002a (soil) | As, Cd, Cr, Cu, Pb | NA |
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ICP OES: inductively coupled plasma optical emission spectrometry; ICP-MS: inductively coupled plasma mass spectrometry; NA: not applicable once the RM/CRMs were not analyzed by this technique.
table_chartTable 3
Analytical performance parameters for the elements determined in the CRMs/RMs spinach leaves, soil, and polymer digests by ICP OES and in the CRMs/RMs spinach leaves, bovine liver, and polymer by ICP-MS using EC and MFC
| Analyte | ICP OES | ICP-MS | ||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| EC | MFC | Acquisition mode |
EC | MFC | ||||||||
| LOQ / (mg kg-1) |
R2 | LOQ / (mg kg-1) |
R2 range | LOQ / (mg kg-1) |
R2 | LOQ / (mg kg-1) |
R2 range | |||||
| Al | 0.4 | 0.9989 | 2 | 0.9968-0.9998 | NA | NA | NA | NA | NA | |||
| Cd | 0.08 | 0.9999 | 0.1 | 0.9936-0.9998 | no gas | 0.02 | 0.9995 | 0.01 | 0.9814-0.9999 | |||
| Co | NA | NA | NA | NA | no gas | 0.01 | 0.9994 | 0.005 | 0.9909-0.9998 | |||
| Cr | 0.2 | 0.9999 | 0.4 | 0.9996-0.9998 | NA | NA | NA | NA | NA | |||
| Cu | 0.04 | 0.9999 | 2 | 0.9998 | no gas | 0.1 | 0.9996 | 0.08 | 0.9920-0.9998 | |||
| Hg | NA | NA | NA | NA | no gas | 1.5 | 0.9996 | 0.3 | 0.9953-0.9989 | |||
| Mo | NA | NA | NA | NA | no gas | 0.09 | 0.9995 | 0.04 | 0.9984-0.9999 | |||
| Mn | 0.02 | 0.9999 | 0.2 | 0.9968-0.9970 | no gas | 0.04 | 0.9994 | 0.04 | 0.9989-0.9995 | |||
| Ni | NA | NA | NA | NA | He | 0.09 | 0.9998 | 0.05 | 0.9964-0.9991 | |||
| Pb | 2.0 | 0.9999 | 5 | 0.9778-0.9815 | no gas | 0.2 | 0.9994 | 0.09 | 0.9955-0.9995 | |||
| Sb | NA | NA | NA | NA | no gas | 0.03 | 0.9997 | 0.04 | 0.9979-0.9990 | |||
| V | NA | NA | NA | NA | no gas | 0.02 | 0.9995 | 0.01 | 0.9968-0.9992 | |||
| Zn | 0.06 | 0.9999 | 0.3 | 0.9957-9968 | NA | NA | NA | NA | NA | |||
| Asa | 4 | 0.9999 | 3 | 0.9911-0.9985 | He | 0.07 | 0.9996 | 0.3 | 0.9809-0.9978 | |||
| He/HMI | 0.005 | 0.9990 | 0.009 | 0.9889-0.9988 | ||||||||
| Sea | NA | NA | NA | NA | no gas | 0.3 | 0.9991 | 0.2 | 0.9883-0.9960 | |||
| no gas/HMI | 0.06 | 0.9990 | 0.05 | 0.9881-0.9981 | ||||||||
-
a
Analytes where He and He/HMI were used. ICP OES: inductively coupled plasma optical emission spectrometry; ICP-MS: inductively coupled plasma mass spectrometry; EC: external standard calibration; MFC: multi-flow calibration; LOQ: limit of quantification; R2: determination coefficient; HMI: high matrix introduction; NA: not applicable once the element was not determined by this technique as shown in Table 2.
table_chartTable 4
Evaluation of MFC used for Al, As, Cd, Cr, Cu, Mn, Pb, and Zn determination by ICP OES considering the analytes concentration in the calibration standard solution as sample/standard ratios 1:0.5, 1:1, and 1:2. Determined values (mean ± standard deviation, n = 3) and recoveries from the certified values in spinach leaves, soil and polymer
| Analyte | Determined value (recovery / %) / (mg kg-1) | ||||
|---|---|---|---|---|---|
| Certified value | EC | MFC 0.5 | MFC 1.0 | MFC 2.0 | |
| Spinach leaves (NIST 1570a) | |||||
| Al | 310 ± 11 | 222 ± 1 (72) | 241 ± 8 (78) | 245 ± 8 (79) | 254 ± 4 (82) |
| Mn | 76 ± 2 | 62.1 ± 0.9 (82) | 66.2 ± 0.6 (87) | 69.4 ± 0.6 (91) | 65.3 ± 0.9 (86) |
| Zn | 82 ± 3 | 65.9 ± 0.5 (80) | 74.2 ± 0.3 (90) | 77.8 ± 0.4 (95) | 74.6 ± 0.1 (91) |
| Soil (RM-Agro E2002a) | |||||
| As | 59 ± 7 | 47 ± 23 (79) | 64 ± 6 (109) | 56 ± 5 (96) | 58 ± 6 (98) |
| Cd | 94 ± 11 | 65 ± 6 (70) | 75 ± 7 (80) | 73 ± 7 (78) | 75± 7 (80) |
| Cr | 120 ± 30 | 104 ± 8 (86) | 109 ± 8 (91) | 106 ± 8 (88) | 107 ± 8 (89) |
| Cu | 9 ± 4 | 5 ± 1 (54) | 7 ± 1 (84) | 7 ± 1 (81) | 7 ± 1 (84) |
| Pb | 174 ± 19 | 166 ± 15 (96) | 178 ± 16 (102) | 169 ± 15 (97) | 173 ± 16 (100) |
| Polymer (ERM-EC681K) | |||||
| As | 29 ± 2 | 23.9 ± 0.5 (82) | 30 ± 1 (104) | 24.4 ± 0.9 (84) | 32 ± 1 (110) |
| Cd | 137 ± 4 | 127.3 ± 0.01 (93) | 134.5 ± 0.2 (98) | 131.4 ± 0.3 (96) | 138.5 ± 0.3 (101) |
| Pb | 98 ± 6 | 90.4 ± 0.1 (92) | 94 ± 4 (96) | 91 ± 3 (93) | 101 ± 4 (103) |
-
EC: external standard calibration; MFC: multi-flow calibration.
table_chartTable 5
Evaluation of MFC used for As, Cd, Co, Cu, Hg, Mo, Mn, Ni, Se, Sb, Pb, and V determination by ICP-MS considering the analytes concentration in the calibration standard solution as sample/standard ratios 1:0.5, 1:1, and 1:2. Determined values (mean ± standard deviation, n = 3) and recoveries from the certified values in spinach leaves, bovine liver and polymer
| Isotope | Determined value (recovery / %) / (mg kg-1) | ||||
|---|---|---|---|---|---|
| Certified value | EC | MFC 0.5 | MFC 1.0 | MFC 2.0 | |
| Spinach leaves (NIST 1570a) | |||||
| 51V | 0.57 ± 0.03 | 0.50 ± 0.02 (87) | 0.57 ± 0.02 (101) | 0.61 ± 0.02 (107) | 0.62 ± 0.02 (110) |
| 58Ni | 2.4 ± 0.1 | 2.5 ± 0.1 (116) | 2.50 ± 0.05 (91) | 3.10 ± 0.06 (108) | 3.49 ± 0.07 (118) |
| 59Co | 0.39 ± 0.05 | 0.22 ± 0.02 (55) | 0.37 ± 0.01 (95) | 0.40 ± 0.01 (102) | 0.40 ± 0.01 (103) |
| 65Cu | 12.2 ± 0.6 | 10.3 ± 0.4 (85) | 11.3 ± 0.2 (92) | 11.7 ± 0.3 (96) | 12.1 ± 0.3 (99) |
| 75As | 0.07 ± 0.01 | 0.09 ± 0.03 (127) | < LOQ | < LOQ | < LOQ |
| 78Se | 0.117 ± 0.009 | < LOQ | < LOQ | < LOQ | < LOQ |
| 114Cd | 2.89 ± 0.07 | 2.32 ± 0.08 (81) | 2.62 ± 0.05 (91) | 2.71 ± 0.05 (94) | 2.78 ± 0.05 (97) |
| Bovine liver (RM-Agro E3001a) | |||||
| 55Mn | 8 ± 1 | 6.9 ± 0.06 (92) | 7.75 ± 0.09 (102) | 7.93 ± 0.09 (104) | 8.04 ± 0.09 (105) |
| 59Co | 0.32 ± 0.05 | 0.26 ± 0.01 (81) | 0.340 ± 0.006 (87) | 0.352 ± 0.006 (98) | 0.340 ± 0.006 (91) |
| 78Se | 0.7 ± 0.1 | 0.5 ± 0.2 (75) | 0.64 ± 0.04 (95) | 0.75 ± 0.06 (112) | 0.76 ± 0.06 (113) |
| 98Mo | 4.1 ± 0.1 | 3.13 ± 0.09 (77) | 3.32 ± 0.08 (81) | 3.6 ± 0.09 (88) | 3.49 ± 0.09 (90) |
| 114Cd | 0.104 ± 0.02 | 0.059 ± 0.003 (57) | 0.092 ± 0.005 (106) | 0.103 ± 0.006 (110) | 0.096 ± 0.005 (106) |
| Polymer (ERM-EC680K) | |||||
| 75As | 4.1 ± 0.5 | 3.6 ± 0.6 (89) | 3.1 ± 0.2 (76) | 3.3 ± 0.23 (82) | 3.3 ± 0.3 (81) |
| 114Cd | 20 ± 1 | 24.2 ± 0.1 (121) | 20.8 ± 0.6 (104) | 21 ± 1 (105) | 20.8 ± 0.8 (104) |
| 123Sb | 10 ± 2 | 15 ± 3 (149) | 9.9 ± 0.5 (99) | 11.2 ± 0.7 (111) | 10.6 ± 0.6 (105) |
| 202Hg | 4.6 ± 0.2 | 4 ± 3 (99) | 4.4 ± 0.08 (96) | 5.1 ± 0.2 (110) | 5.4 ± 0.4 (117) |
| 208Pb | 13.6 ± 0.5 | 13 ± 9 (99) | 10.2 ± 0.6 (75) | 12.9 ± 0.5 (95) | 12.9 ± 0.6 (95) |
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EC: external standard calibration; MFC: multi-flow calibration; LOQ: limit of quantification.
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