Recent Advances in Trace Elemental Analysis

Recent Advances in Trace Elemental Analysis Shona McSheehy Ducos and Joachim Hinrichs Thermo Fisher Scientific, Bremen, Germany The world leader in serving science

Bremen MS Centre of Excellence 12000 m 2 of R&D, Manufacturing, Application and Administration Facilities 2

Current Product Portfolio with Focus on Innovation Orbitrap Elite Orbitrap Velos Pro LTQ Orbitrap XL Hybrid FT-MS Exactive Plus FT-MS LTQ FT Ultra Hybrid FT-MS DFS High Resolution GC-MS DELTA V Gas Isotope Ratio MS MAT 253 Gas Isotope Ratio MS Proteome Discoverer Compound Discoverer Software Q Exactive FT-MS MALDI LTQ Orbitrap XL Hybrid FT-MS Qtegra Software TRITON Plus Thermal Ionization MS NEPTUNE Plus HR MC-ICP-MS ELEMENT 2 ELEMENT XR High Resolution ICP-MS ELEMENT GD Glow Discharge MS icap Q Q-ICP-MS icap 7000 ICP ice 3300 AA HELIX MC Plus HELIX SFT Noble Gas MS ARGUS VI Noble Gas MS 3

The latest steps for trace elemental analysis ICP-OES: Element Finder software tool ICP-OES made easy ICP-MS: New Quadrupole ICP-MS icap Qnova series: icap RQ Taking complexity out of ICP-MS and gain robustness GD-MS: New GD-MS ELEMENT GD PLUS pulsed discharge for advanced applications: nanometer depth profiling and ceramics 4

ICP-OES 7000 series: Element Finder The world leader in serving science

icap 7200 ICP-OES Entry level, cost-effective analysis for low sample thru-put requirements. Perfect analytical solution for restricted budgets Powerful analyte detection & resolution Analysis-ready sample introduction for consistent performance & ease of use User selectable method templates for minimized method development Field upgradeable technology to icap 7400 ICP-OES 6

icap 7400 ICP-OES For routine analysis requirements and mid-range sample thru-put. Ideal for QA/QC laboratories that require highest sensitivity from full wavelength coverage Powerful analyte detection & resolution Choice of plasma orientation to enable enhanced application suitability Intuitive software tools for optimized liquid sample introduction Advanced gas flow control for optimized liquid sample introduction Flexible data acquisition modes for routine method development operations 7

icap 7600 ICP-OES Highest productivity and maximum sample thru-put with advanced sprint valve sample introduction, flexible accessory support Best solution for laboratories experiencing the most challenging analytical demands, such as large contract, or R&D facilities Powerful analytical detection & resolution Choice of plasma orientation to enable enhanced application suitability Intelligent software for powerful autooptimization of the sample intro system Advanced data acquisition including Sprint modes for ultimate productivity & versatility Comprehensive accessory compatibility for liquid & solid sampling 8

Typical Method Development Process for ICP-OES Wavelength Selection Step 1 Determine which elements you need to analyze Step 2 Set wavelengths for analysis Step 3 Perform initial analysis Step 4 Review data for interferences Step 5 Repeat steps 2-5 as needed 9

Typical Method Development Process for ICP-OES Plasma Optimization Step 6 Set plasma conditions Step 7 Analyze samples, spikes etc Step 8 Review data Step 9 Repeat steps 6-8 as needed 10

Spectral Interferences Example asymmetric peak for boron at 249.773 nm Clear interference on boron peak (visible at 249.780 nm and 249.790 nm) 11

Manual Identification First identify the interference Over 55,000 wavelengths in the library A number of possible elements could cause this interference Aluminum, iron, germanium 12

Manual Identification The Most Likely Candidate Most likely to be iron Need to confirm and correct for the interference or select an alternative wavelength 13

Manual Identification Confirmation Analyze three solutions: The sample A single element solution of the analyte at the concentration in the sample A single element solution of the suspected interference at the concentration in the sample If this is not the interfering analyte, further analysis might be needed to determine this Suggested workflow for the proposed USP chapters on elemental impurities Select an alternative wavelength that is interference free 14

Automated Method Development and Plasma Optimization! Element Finder plug-in for Thermo Scientific Qtegra ISDS Software Simplifies method development Automatically selects appropriate wavelengths and eliminates interferences before you know they exist Automatically sets plasma conditions to optimize the instrument s performance 15

What Does Element Finder Do? An intuitive user-friendly method development tool Automated selection of analytical wavelengths, free from potential interferences Automated plasma optimization, based on the elements of interest and the elements present in the sample matrix The software intelligently selects wavelengths and plasma conditions based on full frame images, collected in just seconds 16

Element Finder Work Flow Analyte Selection 17

Element Finder Work Flow Matrix Selection 18

Element Finder Work Flow Results Boron analyte Iron matrix element B at 249.773 nm and 249.678 nm automatically excluded interferences from iron Wavelengths for Fe added to allow the matrix element to be quantified 19

Element Finder Work Flow Unknown Samples What if your sample is a complete unknown? Run a full frame using Element Finder one for the UV region, one for the visible region All elements in the sample will be identified, just select the wavelengths you wish to use for measuring the elements of interest Takes less than 5 minutes and uses just 8mL of sample! 20

Full Frame Images With few exceptions, emission wavelengths for all known elements are known with a high degree of accuracy The map of the spectrum is compared to a database of 50,000 lines (NIST and MIT databases). Elements can be positively identified from their positions on the chip Verification using multiple wavelengths from the same element 21

Plasma Optimization Plasma conditions can be optimized automatically, following wavelength selection The optimization will take place based on a multi-component analysis Complete optimization process takes approximately ten minutes 22

Element Finder Plug-in for Thermo Scientific Qtegra ISDS Software A method development tool to automatically select analytical wavelengths that are free from spectral interferences and automatically select plasma conditions that are optimal for the application Based on full frame images (captured in seconds), the software intelligently calculates potential interferences from the sample matrix and selects analyte wavelengths that are interference free Wavelength selection and plasma optimization are fully automated optimal conditions chosen, regardless of operator skill Automatic ICP-OES method development in 20 minutes or less! 23

New Quadrupole ICP-MS: icap RQ The world leader in serving science

Challenges to Simplicity and Productivity in ICP-MS Taking the complexity out of ICP-MS Clever hardware design and software solutions How to handle interferences Which measurement mode to use for which analyte Measuring high matrix samples How to calibrate to a higher concentration How to automatically handle varying samples Running large batches of samples How to reduce operator time needed How to run for longer with less cleaning 25

icap RQ ICP-MS Taking the Complexity out of ICP-MS All new electronics maximize uptime and stability Qtegra ISDS software v2.7 Qcell CRC - Proprietary flatapole technology New robust interface for reliable long-term analysis of dirty samples Increased capacity interface pumping for higher sensitivity New robust RF generator maximum uptime Simplified power connections to facilitate installation further Quick connect sample introduction system/drop down door 26

Simplicity, Productivity and Robustness through Design Unique drop down door Quick connect Sample Introduction System Simple torch assembly Front Easy Access Right Open Geometry Left Service Connections Back No Connections 27

Robust & reliable NEW RF generator Robustness by design, tested for longevity and speed 10,000 plasma ignitions equivalent to 27 years of everyday operation! Cycling different matrices (organic solvents, high matrix samples) Instrument Control readbacks of Plasma power and Turbo pump current Every instrument is tested for cold plasma operation at less than 500W 28

Handling Interferences What Are Interferences? Ar, Air (O, N) H 2 O, Ca, Na, K, Mg, Cl, etc Reactants 29

Handling Interferences What Are Interferences? Ar, Air (O, N) ArAr, ArO, ArN, ArC, ArH, ArCa, ArNa, ArK, ArMg, ArCl, ClO, NO, CO, CaO, NaO, etc H 2 O, Ca, Na, K, Mg, Cl, etc Products Reaction Interferences Reactants 30

Handling Interferences with Collision/Reaction Cell Technology Collision/Reaction Cell (CRC) technology can be used to remove interferences - QCell Several measurement modes are available Method development can be quite complex Measurement Mode CRC Gas When STD - Standard NONE Analytes with no interferences KED - Kinetic Energy Discrimination CCT - Collision Cell Technology He Analytes with interferences comprehensive interference removal O 2, H 2 /He, NH 3/ He Analytes with interferences targeted interference removal for ultra low LODs 31

QCell He KED Interference Removal with LMCO He KED filters out unwanted polyatomic interferences Target Analyte 75 As + Comprehensive Interference Removal Quadrupole set to filter out exact mass of target analyte e.g. 75 As + Δ E 75 [ArCl] +, 75 [Ca(OH) 2 H] + He KED energy barrier rejects polyatomic interferences Complex Matrix 32

QCell He KED Interference Removal with LMCO Target Analyte 75 As + Comprehensive Interference Removal QCell flatapole dynamically applies Low Mass Cut Off (LMCO) relative to target analyte Mass LMCO Interferences Precursors Quadrupole set to filter out exact mass of target analyte e.g. 75 As + 51 V 35 35 Cl 16 O, 37 Cl 14 N, 34 S 16 OH H, N, O, S, Cl 63 Cu 45 40 Ar 23 Na, 12 C 16 O 35 Cl, 31 P 32 S 75 As 47 40 Ar 35 Cl, 40 Ca 35 Cl, C, N, O, Na, P, S, Cl, Ar H, S, Cl, Ca, Ar 40 Ar +, 40 Ca +, 35 Cl +, 16 O +, 1 H + Low mass cut off filters out unwanted precursor ions Complex Matrix 33

QCell He KED Interference Removal with LMCO Target Analyte 75 As + Comprehensive Interference Removal QCell flatapole dynamically applies Low Mass Cut Off (LMCO) relative to target analyte Mass LMCO Interferences Precursors Quadrupole set to filter out exact mass of target analyte e.g. 75 As + 51 V 35 35 Cl 16 O, 37 Cl 14 N, 34 S 16 OH H, N, O, S, Cl 63 Cu 45 40 Ar 23 Na, 12 C 16 O 35 Cl, 31 P 32 S 75 As 47 40 Ar 35 Cl, 40 Ca 35 Cl, C, N, O, Na, P, S, Cl, Ar H, S, Cl, Ca, Ar 40 Ar +, 40 Ca +, 35 Cl +, 16 O +, 1 H + Low mass cut off filters out unwanted precursor ions Complex Matrix 34

QCell He KED Interference Removal with LMCO Target Analyte 75 As + Comprehensive Interference Removal Comprehensive Easy Powerful Quadrupole set to filter out exact mass of target analyte e.g. 75 As + 75 [ArCl] +, 75 [Ca(OH) 2 H] + He KED filters out unwanted polyatomic interferences Interference Removal Complex Matrix 40 Ar +, 40 Ca +, 35 Cl +, 16 O +, 1 H + Low mass cut off filters out unwanted precursor ions 35

Handling Interferences Superior Interference Suppression Calibration curve for 75 As in a solution containing 1.2% v/v HCl STD mode: Polyatomic interference leads to poor IDL and elevated BEC KED mode: Polyatomic interference removed - IDL below 5 ppt 36

Simplicity and Productivity - Single Measurement Mode High sensitivity He KED mode Li, Be up to Pb, U can be analyzed Single measurement mode for all analytes in analytical method: Gas switching is eliminated - that s a saving of 10-20 s per sample! Selection of 1 measurement mode effectively eliminates method development! 37

Environmental Samples and the Challenges for ICP-MS Ar, Air (O, N) Matrix suppression Instrumental drift Signal loss H 2 O, Ca, Na, K, Mg, Cl, etc 38

Handling Matrix Customized Interfaces for Maximum Flexibility Unique interface designed for maximum coverage of sensitivity and dynamic range: Robust 4.5 mm High Matrix 3.5 mm High Sensitivity 2.8 mm STDR KEDR CCTR STD KED CCT STDS KEDS CCTS Easily implemented through dedicated grouping and autotunes in the software 39

Handling Matrix Customized Interfaces for Maximum Flexibility 4.5 mm Minimal drift and reduced user maintenance Calibration Range (>2000ppm) Environmental Routine industrial Matrix Long term analysis Dirty samples less cleaning 3.5 mm Best balance for sensitivity and matrix tolerance Food safety, pharmaceutical and drinking water analysis 2.8 mm Best signal to noise ratio and lowest detection Sub-ppt analysis Ultra pure chemicals LODs Sensitivity Geoscience, advanced materials, research 40

Linear Dynamic Range Ultra Trace to Major Concentrations Linearity of ICP-MS, over 10 orders of magnitude (0.1 cps to 5 x 10 9 cps) 175 Lu 1 ppq 10 ppq 100 ppq 1 ppt 10 ppt 100 ppt 1 ppb 10 ppb 100 ppb 1 ppm 5 ppm 41

Extended Calibration Ranges and Matrix Tolerance Many protocols require that quantified levels in samples fall within the calibration range performed For high matrix samples, higher calibration is required Many protocols also specify Internal Standard recovery range Traditionally, ICP-MS will tolerate 0.2 % TDS (2000 ppm) 42

Extending the Calibration Range to 5000 ppm 23 Na - KED Robust interface will expand calibration range up to 5000 ppm BUT more importantly, the Internal Standard recovery of 45 Sc > 70% 75.1 % 45 Sc recovery Reduced Suppression Less Dilution icap RQ ICP-MS 4.5 mm insert; KEDR mode 43

Matrix Handling US EPA 200.8 for Water Analysis 4.5 mm insert 0 1 2 3 4 5 6 7 8 9 10 11 12 Time/hours US EPA Method 200.8 Blank & Calibration of 28 Analytes Initial QC checks: ICV, ICB, LFB, QCS Ongoing QC checks: CCB, CCV Internal Standards - 6 Li, 45 Sc, 71 Ga, 89 Y, 115 In and 159 Tb Drinking water (faucet) spiked with 100 ppm Ca (hard water) 44

Matrix Handling Auto-dilution Thermo Scientific Qtegra Intelligent Scientific Data Solution (ISDS) Software provides complete software control of the ESI prepfast: Auto-calibration calibration of the ICP-MS from one standard Automated prescriptive dilution for preparation of: Samples Standards Automated intelligent dilution: Internal standard range auto-dilution Over calibration range auto-dilution Close coupling of the discrete sampling valves to ICP for minimized uptake and washout increases throughput and reduces contamination 45

Matrix Handling - Intelligent Auto-dilution Calibration Over-Range User defines: The maximum calibration limit as a percentage of the top calibration standard, e.g. 110% The target concentration of the analyte after auto-dilution Internal Standard Recovery User defines: The range of acceptable Internal Standard Recovery, e.g. 60-125% The auto-dilution factor step and # of possible dilutions 46

Accuracy and Stability for EPA 200.8 Drinking Water Fast & Easy Minimal drift Excellent accuracy 47

Simplifying the Workflow and Accelerating Productivity Simplicity Simplest method development Intuitive sample introduction system design Easy access to sample and skimmer cone Open geometry for peripheral connection Qtegra ISDS software Less training, up and running faster Intuitive and common software Get Ready one-click set-up Integrated QC Integrated reporting and import/export to LIMs etc.. Integrated CFR compliance tools Productivity Single mode He-KED no gas switching Fully software controlled valves reducing uptake and washout Cost efficient AGD module available for direct analysis of heavy matrix samples Robustness More uptime, more productivity Robust interface - reduced drift and operator intervention (less cleaning) High Matrix tolerance Robust RF design for reliable hot and cold plasma operation 48

New GD-MS: ELEMENT GD PLUS with pulsed discharge The world leader in serving science

Element GD PLUS GD-MS Discharge voltage Ion intensity GD-MS is an ideal solution for solid sampling and bulk metal analysis But what about other sample types? Pulsed source enables new sample types and applications GD pulses Ions Time [ms] 50

Element GD PLUS Forging into New Applications Depth profiling Single digit nm layer detection Sub-ppm semiquantitative depth profiling ELEMENT GD PLUS GD-MS Bulk Metals Better stability & Reproducibility Applicable to low melting point materials Bulk Non-conductors Use of secondary electrode Example: Al 2 O 3 powders for Sapphire production SP01 SP02 SP03 SP04 SP05 SP06 SP07 SP08 AVG STD RSD B11(MR) 309 314 319 306 303 318 292 293 307 11 3% C12(MR) 1615 1683 1656 1545 1591 1622 1484 1509 1588 70 4% Mg24(MR) 138 140 142 140 138 142 139 137 139 2 1% P31(MR) 4.0 4.0 4.1 4.0 4.0 4.1 3.9 3.9 4 0 2% S32(MR) 5 6 5 5 6 5 5 5 5 0 3% Ca44(MR) 16 16 17 17 17 16 17 16 17 0 2% Mn55(MR) 10 10 10 10 10 10 10 10 10 0 1% Fe56(MR) 429 435 429 424 430 431 431 442 431 5 1% Cu63(MR) 6 6 6 6 6 6 6 6 6 0 1% Zn66(MR) 36 37 38 37 38 38 37 38 37 1 2% Ga69(MR) 84 85 86 86 86 86 87 87 86 1 1% As75(MR) 38 39 40 40 40 41 40 40 40 1 2% Se82(MR) 6 6 6 6 6 6 6 6 6 0 4% Zr91(MR) 313 308 315 326 322 321 328 329 320 7 2% Nb93(MR) 44 44 44 45 45 44 46 46 45 1 2% Ag107(MR 71 71 72 73 73 74 74 74 73 1 2% Sn117(MR) 85 84 86 88 87 87 89 89 87 2 2% Sb121(MR) 39 39 41 41 41 42 42 43 41 1 3% Te130(MR) 9 9 9 9 10 9 10 10 9 0 4% Ta181(MR) 1 1 1 1 1 1 1 1 1 0 3% W184(MR) 5 5 5 5 6 6 6 6 5 0 3% Tl205(MR) 2 2 2 2 2 2 2 2 2 0 2% Pb208(MR 21 21 21 22 22 21 22 22 21 1 3% Bi209(MR) 12 12 13 13 13 13 13 13 13 1 4% 51

Improvements for the Standard Bulk Metal Application Semiquant. Concentration [ppm] High sample throughput Improved stability Reduced source maintenance Robust discharge: measured concentrations are stable over a wide range of instrumental settings Major benefit for semiquantitative, non-calibrated analyses due to improved long term stability 16 repeat analyses of Ni-alloy incl. sample preparation measured over several days: Excellent reproducibility with pulsed mode. 52

Pulsed GD-MS for high speed, high precision Spot 1 Spot 2 Spot 3 Spot 4 Spot 5 Spot 6 Spot 7 Spot 8 AVG STD RSD Cert STD RSD Mg24(MR) 131.1 132.8 132.0 134.1 128.7 131.3 132.7 131.6 131.80 1.59 1.2% 130 7 5.4% Zn66(MR) 28.8 29.2 29.1 28.6 28.7 29.0 28.6 28.7 28.83 0.23 0.8% 28.8 1.4 4.9% Ga69(MR) 49.3 52.0 49.5 49.5 49.5 49.4 49.5 49.9 49.82 0.92 1.8% 49.6 2 4.0% As75(MR) 51.1 51.3 50.9 51.6 50.3 50.6 50.7 51.9 51.05 0.52 1.0% 50.4 2.5 5.0% Se82(MR) 6.3 5.2 5.5 5.8 6.2 5.5 5.2 5.5 5.63 0.41 7.2% 5.7 0.8 14.0% Ag107(MR) 42.7 42.7 42.9 42.6 42.6 43.1 43.0 43.4 42.88 0.29 0.7% 42.5 0.9 2.1% Cd111(MR) 0.35 0.37 0.41 0.40 0.41 0.43 0.37 0.39 0.39 0.03 6.5% 0.37 0.04 10.8% In115(MR) 19.6 20.5 20.0 20.1 19.9 19.8 20.1 20.2 20.04 0.27 1.3% 20 (info) Sn117(MR) 92.8 92.5 92.1 92.9 92.1 93.6 93.9 94.5 93.06 0.87 0.9% 93 8 8.6% Sb121(MR) 44.1 45.0 44.7 44.8 44.4 44.4 45.5 45.0 44.75 0.43 1.0% 45 4 8.9% Te130(MR) 10.0 8.9 9.0 9.6 10.0 9.1 8.7 9.1 9.30 0.50 5.4% 9.3 0.8 8.6% Tl205(MR) 1.88 1.88 1.91 1.94 1.84 1.94 1.86 1.91 1.90 0.04 1.9% 1.9 0.3 15.8% Pb208(MR) 21.8 21.9 21.6 21.9 22.0 22.4 22.3 22.8 22.09 0.40 1.8% 22.2 1.2 5.4% Bi209(MR) 9.4 10.0 9.7 9.3 9.9 10.3 10.5 9.9 9.88 0.40 4.0% 10.3 0.6 5.8% Duration GD Power Source Mode Presputter 45 s 45 W DC Stabilization 15 s 15 W pulsed Analysis 90 s 15 W pulsed Sample throughput for most important elements in Ni alloys can be increased to >10 sample per hour, i.e. <5min per sample! 53

Repeat analysis of low level S Sulfur conc. [ppm] Spot 1 2 3 AVG STD RSD Date Mar 04 2011 Mar 18 2011 Mar 22 2011 n=3 spots n=3 spots n=3 spots Sample 1 0.060 0.058 0.065 0.061 0.003 5.7% Sample 2 0.348 0.343 0.355 0.35 0.01 1.7% Sample 3 4.03 3.93 3.90 4.0 0.1 1.7% Calibrated with NIST 1249: 6.4 ± 1.0 ppm Sulfur certified The sulfur retaining gas cartridge comes as standard on all new instruments. 54

Depth Profiling of Ultra Thin Protection Layers for Hard Disks a) 10µs pulse width, 700V Total thickness of layer stack ~ 25nm. Single nm layers detectable. Semiquant. concentrations with Standard RSF. b) 20µs pulse width, 700V Longer pulses = faster sputtering and higher signal. Pt ~ 8 Ångstrøm ~ 0.8nm Co ~ 10 Ångstrøm ~ 1nm 55

Non-conductive Powders: Example Al 2 O 3 press analyze Tantalum target (5N) with non-conductive powder pressed into orifice non-conductor sputtered along with the Tantalum electrode 56

Semiquant Results Al 2 O 3 for CRM NMIJ 8007a Great sensitivity, stability, and detection limits. Simple sample preparation, no digest. ~15 to 20 min per sample including sample preparation CRM can be used to improve accuracy. Semiquant (STD RSF) Certified conc. [ppm wt.] ELEMENT GD PLUS [ppm wt.] St. Dev (n=4) B 0.21 1.08 0.09 Mg 2.8 3.1 0.2 Si 17.1 19.5 1.3 Ca 0.92 2.4 1.0 Ti 0.26 0.35 0.06 Cr 0.84 1.15 0.09 Fe 5.01 5.0 0.3 Cu 0.92 1.25 0.06 Sr 0.022 0.025 0.007 Zr 1.8 2.5 0.6 Th - 0.010 0.003 U - 0.030 0.003 57

Poster at Winter Plasma Conference 2016: CNO analysis Ongoing development for low or sub-ppm detection limits for Carbon, Nitrogen, and Oxygen 58

Element GD PLUS GD-MS Pulsed source GD-MS enables new and exciting applications.. non conductors, nanometer depth resolution in layers, improved bulk analysis 59

Thank you for your attention! joachim.hinrichs @thermofisher.com 60