1. Analysis in ProcESS Xuan Wang Department of Chemical Engineering Department of Metallurgy and Materials Engineering 23/01/2013

2. Table of content Introduction ICP-MS  Introduction  Principles  Influence  Sample preparation AAS FT-IR PerkinElmer GC lab Mercury Analyzer Contact Angle Analyzer 2

3. Introduction ProcESS --- Process Engineering for Sustainable Systems Research focuses on: Process intensification Solid waste treatment Surface and interphase analysis Advanced separation processes using membrane technology Various analytical equipments: ICP-MS, AAS, FT-IR, GC, Mercury Analyzer, Contact Angle Analyzer… 3

4. ICP-MS Advantages: Quantitative and semi-quantitative analysis Detection limits at or below ppt level for much of the periodic table 8 orders of magnitude analytical range High productivity Isotopic analysis 4 Inductively Coupled Plasma -Mass Spectrometry  Producer: Thermo Scientific  Type: X series  Contact: Michèle Vanroelen (michele.vanroelen@cit.kuleuven.be)michele.vanroelen@cit.kuleuven.be

5. PerkinElmer, Inc 5 Remark: Method Detection Limit (MDL) is generally 2-10 times more than Instrumental Detection Limit (IDL) (PerkinElmer)

6. Principles 6 Argon Plasma Aerosol Solid Gas Atoms Ions RF Load Coils ICP Torch Schematic representation of a quadrupole ICP- MS (PerkinElmer)  Ionization of atoms  At certain time, only ions with one certain mass-to-charge ratio can pass through and be detected. mass spectrometer Cones

7. Influence 7 Matrix effects: signal suppression or enhancement caused by overloading of plasma, cooling effects, changes of ionization, blockage of cones, change of ion sampling, etc. Remedy: internal standard (Be, Ga, In, Tl). Residual signal (rlative to the signal in 0.14 M HNO 3 ) for several elements present in 0.5 M H 2 SO 4 matrix as a function of the mass number of the nuclide. (Vanhaecke F., Vanhoe H., Dams R., Vandecasteele C., Talanta, 1992, 39)

8. Influence 8 Spectral interferences: interferences between ions with similar atomic mass. Remedy: (USGS)  Use of HNO 3  Select isotopes ( 65 Cu instead of 63 Cu (ArNa + ))  Mathematical correction  Modify sample preparation

9. Influence 9 Cone blockage The small orifice (~ 1mm) on the cones can be blocked if too much total dissolved solids (TDS) in the solution. This can cause decreased sensitivity and detection capability Remedy: diluted feeding solution (TDS no more than 0.2%) Partially blocked orifice (Kym Jarvis. Presentation for Nuclear Spectrometry Users Forum, May 2005)

10. Sample preparation 10 Preparation Sample digestion  Three acids digestion  Microwave digestion  Lithium metaborate fusion digestion Sample dilution Standard preparation

11. Sample digestion 11 Three acids digestion  0.1 g finely ground sample added in Teflon beaker with heating on the bottom and lid on the top  Three acids: -HNO 3 : oxidation, dissolving oxides and hydroxides -HClO 4 : oxidation, dissolving organics -HF: dissolving silicate are added, 5 ml each, by sequential order until the previous one boiled down.  If the sample is not completely dissolved, more cycles of the process (without HClO 4 ) are needed until the complete dissolution of sample. Caution: highly corrosive acids applied and protection needed

12. Sample digestion 12 Micro wave digestion:  Acid digestion carried out in microwave transparent inert material vessels, where pressure is introduced  High temperature (260-300 °C)  High digestion quality  Reduced acid consumption  Reduced digestion time (20-60 minutes)

13. Sample digestion 13 Lithium metaborate fusion digestion:  Thoroughly mix 0.1 g finely ground sample with 1.0 g of lithium metaborate (LiBO 2 )  Put the mixture in a graphite crucible and insert crucible into an oven at 1000 °C for 15 minutes  Pour the melt mixture into 100 ml 5 vol% nitric acid solution  Stir at least 15 minutes until all solid dissolved then filtrate the solution for dilution and measurement

14. Sample preparation 14 Sample dilution:  The digested solution normally need to be dilute  Concentration not larger than 1000 ppb  Concentration not lower than detection limit  Normally 2 vol% HNO 3 is added Standard preparation:  Chose concentration of elements according the element concentration in diluted sample  Addition of internal standards (e.g. Be, Ga, In and Tl)  3 or 5 calibration points, including one blank

15. Atomic Absorption Spectroscopy AAS 15 (http://web.vscht.cz/poustkaj) Principle: absorption of EM-radiation characteristic for electron transition in the outer shell of an atom of an element.

16. AAS 16 Measurement of almost all metals, metalloids and some non-metals (B, Si, P) Sample: - Solution in diluted acids - Diluted biological fluids - Suspensions of solid samples (slurries) Flame AAS (in CIT): measurement of higher concentration (10-100 ppm) – high temperature flame (N2O) Measurement time 3-10 seconds Contact: Michèle Vanroelen (michele.vanroelen@cit.kuleuven.be)michele.vanroelen@cit.kuleuven.be

17. FT-IR Fourier Transform InfraRed (with diamond ATR) 17 (Thermo Nicolet, co.) Principle: absorption of IR-radiation results in changes of vibrational energy of molecules.

18. FT-IR 18 Identification of unknown pure (organic) compounds Identification of functional groups Sample: liquid, solid (in solution), solid. Fast measurement, in a matter of seconds Less suited for quantitative analysis, detection limits around 2 % Contact: Christine Wouters (christine.wouters@cit.kuleuven.be )christine.wouters@cit.kuleuven.be

19. PerkinElmer GC lab 19 GC-MS GasChromatograph Mass Spectrometry Analysis of PCBs, phenols, trizaines, organophosphorus and organochlorine pesticides, PAHs, mono-aromatic hydrocarbons. GC-FID/ECD GasChromatograph Flame Ionization Detector and Electron Capture Detector Analysis of PCBs, phenols, organochlorine pesticides, mono-aromatic hydrocarbons, aspecific solvents, mineral oil, volatile organic acids.

20. PerkinElmer GC lab 20 GC-FID GasChromatograph Flame Ionization Detector Analysis of phenols, mono-aromatic hydrocarbons, aspecific solvents, mineral oil, volatile organic acids. GC-FID/NPD GasChromatograph Flame Ionization Detector and Nitrogen Phosphorus Detector Analysis of phenols, triazines, organophosphorus pesticides, mono-aromatic hydrocarbons, aspecific solvents, mineral oil, volatile organic acids. Contact: Christine Wouters (christine.wouters@cit.kuleuven.be )christine.wouters@cit.kuleuven.be

21. Mercury analyzer 21 Design for all types of sample: -Environmental samples (water, soil, plants, etc) -Human samples (hair, blood, urine, etc) Vapour generation technique (remove most chemical interferences) Atomic fluorescence spectrometry (mercury analysis down to ppt level) Contact: Tom Van Gerven (thomas.vangerven@cit.kuleuven.be(thomas.vangerven@cit.kuleuven.be ) (not operational yet by the moment, part of RARE 3 project)

22. Contact Angle Analyzer 22 KRÜSS Dsa10-MK2 Contact: Bart Van der Bruggen (bart.vanderbruggen@cit.kuleuven.be )

23. Contact 23 ICP-MS AAS FT-IR PerkinElmer GC lab Mercury Analyzer Contact Angle Analyzer Michèle Vanroelen (michele.vanroelen@cit.kuleuven.be)michele.vanroelen@cit.kuleuven.be Christine Wouters (christine.wouters@cit.kuleuven.be )christine.wouters@cit.kuleuven.be Tom Van Gerven (thomas.vangerven@cit.kuleuven.be(thomas.vangerven@cit.kuleuven.be ) Bart Van der Bruggen (bart.vanderbruggen@cit.kuleuven.be )

24. 24 Many thanks!