ICP - ICP/MS comparison

Comparison bet. ICP and ICP/MS

1. ICP – ICP/MS Comparison Gamal A. Hamid

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3. Contents Introduction ICP Fundamental parts of ICP Introduction ICP/MS Fundamental parts of ICP/MS Analysis Comparison Applications

4. Important criteria Selecting a technique requires the consideration of a variety of important criteria, including: Detection limits Analytical working range Sample throughput Data quality Cost Interferences Ease-of-use Availability of proven methodology

5. ICP Introduction

6. Emission Electrons in the element are excited. They jump to higher energy levels (excited state). As the electrons fall back down (ground state). Emitted(photon), the wavelength of which refers to the discrete lines of the emission spectrum.

7. ICP / AES Inductively Coupled Plasma – Atomic Emission Spectroscopy (ICP-AES ) It is a multi-element analysis technique that will dissociate a sample into its constituent atoms and ions and exciting them to a higher energy level. Cause them to emit light at a characteristic wavelength , which will be analyzing.

8. Sequence The sample is nebulized and entrained in the flow of plasma support gas, which is typically Ar. The plasma torch consists of concentric quartz tubes. The inner tube contains the sample aerosol and Ar support gas and the outer tube contains flowing gas to keep the tubes cool. A Radiofrequency (RF) generator produces an oscillating current in an induction coil that wraps around the tubes. The induction coil creates an oscillating magnetic field, which produces an oscillating magnetic field, The magnetic field in turn sets up an oscillating current in the ions and electrons of the support gas (argon). As the ions and electrons collide with other atoms in the support gas and temp increase.

9. Plasma Gas in which a significant number of atoms are ionized (significant being >1%) Will interact with a magnetic field Inductive coupling between varying field and the plasma .

10. ICP Fundamental parts

11. The functional parts of ICP The iCAP 6000 spectrometer consists of several major components: Sample introduction parts. Plasma torch. Gas control. Radio frequency power generator. Optical system; Polychromator. CID detector with thermoelectric cooling.

12. 1. Sample introduction parts Pump. Nebulizer. Spray chamber. Centre tube. Torch.

13. a. Peristaltic pump 4-channel 12-roller pump, with its unique drain sensor. The pump speed shall be computer controlled to provide programmable sample flows both during and between sample measurements . Included for the pump to be automatically switched into a standby mode upon instrument shutdown.

14. b. Nebulizer The sample solution after being sprayed by the nebulizer. Entrained in argon as a fine mist. Passes through the center channel of the torch and into the plasma. Control of the nebulizer pressure, or flow, is either through the control software or via a manual adjustment.

15. c. Cyclone spray chamber Most samples are liquids that are pumped through a nebulizer to produce a fine spray. The large droplets are removed by a spray chamber and the small droplets then pass through to the plasma.

16. d. Centre tube Types of Centre tube 1.5mm quartz for aqueous solutions (single red ring). 1.0mm quartz for organic solutions (double red ring). 2.0mm quartz for high dissolved solids solutions (single blue ring, standard on Duo configurations). 2.0mm Ceramic for HF solutions.

17. e. Plasma torch The quartz torch surrounded by the copper induction coil. The copper coil is made from copper tubing and is kept cool by circulating water. RF energy is supplied to the coil which inductively heats the argon gas to approximately 10,000oC. At this temperature the gas turns into a plasma of positively charged atoms and electrons. The plasma is kept off the sides of the quartz torch by a separate flow of argon supplied tangentially to the inside torch.

18. 2. Gas control iCAP 7200 The nebulizer gas flow is manually controlled from 0 to 0.4 MPa. The auxiliary gas is controlled with precision restrictors with flows of 0, 0.5, 1.0 and 1.5 L/min. The coolant flow is fixed at 12 L/min. iCAP 7400 The nebulizer gas is computer controlled through an MFC with options from 0 - 1.5 L/min with increments of 0.1 L/min. The auxiliary gas is computer controlled through an MFC with options from 0 - 2 L/min in 0.1 L/min increments. The coolant flow is computer controlled through an MFC from 0 - 20 L/min.

19. 3. Radio frequency RF power generator Swing frequency impedance control. Frequency changes to match plasma load. Fast response, no complex matching networks. >78% Efficiency Ability to run even difficult organics e.g. methanol. Nominal Frequency: 27.12 M Hz. Full range of power control. 750-1600w Radial, 750-1350w Duo Optimum performance for all sample types.

20. 4. Optical system Wavelength Range The instrument shall be able to operate over the range of 166.250 to 847.000 nm All elements must be represented by at least 3 sensitive and 3 secondary lines to satisfy the requirements of a wide range of sample types. An optical resolution of better than 0.007nm at 200nm, 0.014nm at 400nm and 0.021nm at 600nm.

21. 5. Charge injection device CID New CID86 chip (Charge Injection Device). Allows free choice of wavelengths from 166 to 847 nm. More stable, lower noise. With the ability to measure transient signals. Thermoelectric cooling by a triple stage peltier. Reduce dark current and background noise resulting in enhanced detection limits.

22. ICP/MS Introduction

23. ICP/MS It is a multi-element analysis technique where The ICP source converts the atoms of the elements in the sample to ions. The ions positive are then separated and detected by the mass spectrometer.

24. Sequence Generating an aerosol of the sample Ionizing sample in the ICP source Extracting ions in the sampling interface Separating ions by mass Detecting ions, calculating the concentrations Using ICP-MS, all kinds of materials can be measured. Solutions are vaporized using a nebulizer, while solids can be sampled using laser ablation. Gasses can be sampled directly.

25. Plasma Three plasma gas flows pass through the torch High voltage spark acts as initial ion generator. RF power supplied to the load coil generates oscillating magnetic field. Initial ions move with the field, and collide with other Ar atoms. Collisions produce more ions which then also move with the field, Collisions also generate heat. Result is a self-sustaining plasma with a temperature of > 6000ºC

26. Processes in the plasma

27. Isotopes separation All isotopes of one element have identical chemical properties, which only involve the electrons surrounding the nucleus. It is difficult to separate isotopes from each other by chemical processes. The physical properties of the isotopes, such as their masses, boiling points, and freezing points, are different. Isotopes can be most easily separated from each other using physical processes.

28. Mass-to-charge ratio m/z The mass-to-charge ratio (m/Q) is a physical quantity that is most widely used in the electrodynamics of charged particles. The importance of the mass-to-charge ratio, according to classical electrodynamics, is that two particles with the same mass-to-charge ratio move in the same path in a vacuum when subjected to the same electric and magnetic fields. The m/z notation is used for the independent variable in a mass spectrum.

29. ICP/MS Fundamental parts

30. The functional parts of ICP/MS The iCAP/MS instrument can be divided into four main components, Sample introduction Interface (ion generation) Ion Optics (ion focusing) Mass Analyzer

31. Sample introduction system The sample introduction system of the iCAP MS comprises the :- Peristaltic pump, The nebulizer, The peltier-cooled spray chamber The torch with the injector.

32. Interface (ion generation) The interface is the region where ions generated in the plasma are transferred from atmospheric pressure to the vacuum region and introduced to the mass spectrometer as an ion beam. The interface comprises The sample cone, The skimmer cone, The extraction lens. The interface region is water-cooled because of the intense heat of the plasma.

33. Ion Optics (ion focusing) Positive ions sampled from the plasma focused and steered toward the mass spectrometer using electrostatic plates (lenses) held at specific voltages. The ion optics region comprises:- The RAPID lens, The QCell, The DA assembly. Ion optics and mass spectrometer both under high vacuum (< 10-6 mbar)

34. Mass Analyzer Ions then pass into the mass spectrometer where they are separated according to their mass to charge ratio Ion optics and mass spectrometer both under high vacuum (< 10-6 mbar). Quadrupole detector

35. Vacuum system

36. Analysis ICP & ICP/MS

37. Sample preparation Short digestion times. Minutes, not hours No loss of volatile elements. Complete recovery of Hg, As, Cd etc. No acid fumes. Improved laboratory working conditions. No sample contamination from the environment. No cross contamination. Low blanks, as minimal quantities of acids are used. Microwave digestion is the best solution for samples preparation.

38. Standards preparation ICP , Multi-element primary standards, And/or a combination of single-element and multi-element primary standards. It is a widely accepted practice to use NIST SRMs (standard reference materials) to validate various kinds of laboratory operations

39. Water & chemicals All acids , water and other used chemicals should be free of the required elements.

40. Calibration ICP and ICP/MS Are a comparative techniques in which the counts by solutions of known concentrations used to generate a calibration curve is compared to the counts of unknown samples to generate results.

41. Comparison ICP &ICP/MS

42. ICP & ICP/MS ICP/MS ICP

43. Analyzed samples

44. Theory of technique Liquid samples are desolvated, vaporized, atomized, and excited in an argon plasma. When the excited atoms relax back to the ground state, they emit characteristic wavelengths of light. A solid state detector collects all the emitted wavelengths of light simultaneously. For each wavelength, the amount of emitted light is directly proportional to the concentration of the element in the sample. Liquid samples are desolvated, vaporized, atomized, and ionized in an argon plasma. Each element has a different mass; once ionized, each element forms its own characteristic mass spectrum. An ion counting detector counts the number of ions at each mass-to-charge ratio , which is directly proportional to the concentration of each element in the sample. ICP ICP/MS

45. Analyte selection Wavelength selection Isotopes selection ICP ICP/MS

46. Sample introduction Same components Same + Cooling ICP ICP/MS

47. Analyte separation Optical system, axial and radial views Ions optics ICP ICP/MS

48. Detector CIDs composed of doped silicon wafers, containing a two dimensional array of light sensitive elements called pixels. light strike the surface of detector photons liberate electrons in the detector substrate which are then trapped in the pixel sites; The signal is then digitized. Ions pass into the mass spectrometer where they are separated according to their mass to charge ratio Detector change the number of ions striking the detector “counts per second (cps)” into an electrical signal that can be measured ICP ICP/MS

49. Interference Spectral Physical Chemical Spectral Physical Matrix ICP ICP/MS The interferences for ICP and ICP/MS discussed in details in the ICP presentation and ICP/MS presentation

50. Detection limits

51. Linear dynamic range extrapolation. The large linear dynamic range for ICP of about 10 5 . For example, copper can be measured at the 324.75 nm wavelength from its detection limit of about 0.002 ppm to over 200 ppm. In ICP, extrapolation of two point calibrations can be accurately used to achieve orders of magnitude above the top standard.

52. LDR 10 5 ICP-AES has a considerably wider dynamic range, up to 10 5 , making it a more suitable technique for highly concentrated samples, 10 8 ICP-MS typically operates at much lower concentration levels so that linear ranges up to 10 8 can be achieved for some analytes. ICP/MS ICP

53. Matrix tolerance ICP-OES is mainly used for samples with high total dissolved solids (TDS) or suspended solids and is, therefore, more robust for analyzing ground water, wastewater, soil, and solid waste. ICP-OES has much higher tolerance for TDS (up to 30 %). Although both ICP-OES and ICP-MS can be used for high matrix samples, sample dilution is often necessary for use on ICP-MS. ICP-MS has much lower tolerance for TDS (about 0.2%) ICP/MS ICP

54. Analysis speed

55. Costs

56. Ease of use ICP-AES systems are easy to set up and have to be adjusted relatively infrequently . If there are major spectral interferences, method development can be complicated. In general, though, method development is moderately easy, although the library of methods is less than for the AAS and GFAAS techniques . ICPs are capable of a high degree of automation , and can run unattended. ICP-MS systems are getting easier to set up for routine analysis. Some parts of the system (e.g., the interface cones) may need regular attention to preserve performance . Method development can be more involved than with the other techniques and requires a higher level of expertise. ICP-MS systems can be fully automated, and can run unattended. ICP/MS ICP

57. Regulatory methods EPA 200.5 EPA 200.7 EPA 6010 ISO 11885:2007 ISO/TC 190/SC3/WG1 N0252 NPR 6425:1995 NEN 6426:1995 EN 12506: 2003 EPA 200.8 EPA 321.8 (IC-ICP-MS) EPA 6020 ISO/DIS 17294-1:2004 ISO 17294-2:2016 NEN 6427:1999 ICP/MS ICP

58. Applications ICP & ICP/MS

59. Applications Environmental Analyses Petrochemical Analyses Metallurgical analyses Geological analyses Foodstuffs analyses Pharmaceutical analyses And more.

60. Environmental Waters – potable, natural, effluent, wastewaters, sea and coastal waters Soils – soils, sediments, foliage, biota, contaminated land, landfill sites Sludge's – solid and digested waste Air – chimney exhaust filters, air filters of contaminated sites, dusts

61. Petrochemical Specifically oils & greases, Additives, pigments, intermediates Petrochemical applications at refineries, wear metal analysis for industrial fleets, heavy industry by-products Paints and inks

62. Metallurgical Steels and Alloys Precious metals – PGMs Bulk Materials – bronzes and brasses Traces – contaminants.

63. Geological Rock samples, sediments, slags, ceramics, cements Survey work, quality control, raw material screening Robust Matrix tolerant Stability Detection limits (traces)

64. Foodstuffs Bulk materials, raw and finished products in food production Trace analysis of micronutrients Toxins - contamination of land and sea Animal feed Crop analysis

65. Pharmaceutical Comfortably meet the most demanding global pharmaceutical regulations and legislation , including; International Council on Harmonization (ICH) guideline Q3D U.S . Pharmacopoeia (USP) chapters, 232 , 233 and 2232 Comply with the most rigorous data audit and security measures. Qtegra ISDS software is fully compliant with Food and Drug Administration (FDA) 21 CFR Part 11 and is equipped with full IQ/OQ procedures for simple implementation in GMP/GLP regulated environments

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