Amplifying ICPMS Productivity Using Discrete Sampling Technology

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Amplifying ICPMS Productivity Using Discrete Sampling Technology Continuing the discussion on high throughput ICP-MS Steve Wilbur Agilent Technologies March 26, 2009

Previously, in Tripling the Productivity of ICP-MS * We discussed various options to reduce the run time in conventional ICP-MS by systematically optimizing each component of the analysis. We were able to reduce a typical 30 element analysis from around 7 minutes to less than 3 minutes with little or no compromises in performance. We touched on Discrete Sampling as the final way to further improve throughput and showed some preliminary data. Today, we will expand on the mechanisms of discrete sampling and explore significant benefits in addition to high throughput. *Recorded version available on SpectroscopyNOW.com Link from www.chem.agilent.com Go to ICP-MS then click on e-seminars

Hardware Overview All discrete sampling systems use the same general hardware configuration. The hardware consists of: sample uptake pump carrier (nebulizer) pump 6 port valve with sample loop control hardware and software

Hardware basic configuration valve in load position (valve flow path indicated in red) sample loop 6-port valve sample uptake pump to nebulizer carrier pump carrier waste sample Sample uptake pump draws sample through valve, filling loop. Excess goes to waste, rinsing the loop in the process Simultaneously, carrier pump is pumping clean carrier (dilute acid blank) through the valve to the nebulizer During the load operation, no sample reaches the nebulizer, only clean carrier

Hardware basic configuration valve in inject position (valve flow path indicated in blue) 6-port valve sample uptake pump to nebulizer carrier pump carrier waste sample Valve rotates (switches), changing flow path. Loop is now in the carrier flow path. Sample uptake pump switches off. Carrier pump pushes sample through the loop to the nebulizer Sample never contacts carrier pump directly

Hardware basic configuration addition of online internal standards 6-port valve sample uptake pump to nebulizer carrier pump ISTD mixing tee carrier waste sample ISTD Online internal standard addition is achieved in the normal way. 2 nd channel of carrier pump pumps internal standard solution which is mixed with sample just prior to nebulization

Two types of discrete sampling 1. Time resolved mode (left) 2. Spectrum (steady state) mode (right) log y scale 180000 1000000 150000 100000 120000 10000 90000 1000 60000 100 30000 10 0 0 5 10 15 20 25 30 1 0 10 20 30 40 50 60 In time resolved mode, a small sample loop creates a peak which is integrated over its entire width, concentration ti is proportional to the area under the peak In Spectrum mode, a larger loop is used to create a period of steady state signal, which is analyzed in the same way as conventional ICP-MS

Time Resolved Discrete Sampling Time resolved discrete sampling is very fast and lends itself to analyses where a single replicate is sufficient (EPA methods require 3 replicates), and/or only a few elements need to be measured. Quantification is based on the total area under the extracted ion peak for each ion of interest, exactly in the way that a chromatographic peak would be quantified. 180000 150000 120000 90000 60000 30000 0 0 5 10 15 20 25 30

Steady State, Spectrum Mode Discrete Sampling Spectrum mode discrete sampling has the advantage of a constant signal during sample measurement. Integration times, number of isotopes and number of replicates are only limited by the size of the loop. This seminar will discuss the throughput and performance advantages of spectrum mode discrete sampling. 1000000 100000 10000 1000 100 10 1 0 10 20 30 40 50 60

Process of Spectrum Mode Discrete Sampling -load loop, inject, wait, acquire data, rinse, load next sample 10000000 Rep 1 Rep 2 Rep 3 1000000 ISTD Signal 100000 Analyte Signal Signal Intensity [CPS] 10000 1000 Delay Acquire data Rinse Go to Next Co59 In115 100 10 Load Inject Load 1 0 20 40 60 80 100 Time [sec]

Process is Fast Because High speed uptake fills the loop in ~ 10 seconds (load). carrier waste to nebulizer sample 10000000 1000000 Rep 1 Rep 2 Rep 3 ISTD Signal 100000 Signal Intensity [CPS] 10000 1000 100 Delay Acquire data Analyte Signal Rinse Go to Next Co59 In115 10 Load Inject Load 1 0 20 40 Time [sec] 60 80 100 11 Agilent Restricted

Process is Fast Because High speed uptake fills the loop in ~ 10 seconds (load). Acquisition delay is ~ 15 seconds from inject to reaching steady state signal. Acquisition can be optimized to ~ 30 45 seconds or less 10000000 1000000 sample Rep 1 Rep 2 carrier Rep 3 waste ISTD Signal to nebulizer Signal Intensity [CPS] 100000 10000 1000 100 Delay Acquire data Analyte Signal Rinse Go to Next Co59 In115 10 Inject Load 1 0 20 40 Time [sec] 60 80 100 12 Agilent Restricted

Process is Fast Because High speed uptake fills the loop in ~ 10 seconds (load). Acquisition delay is ~ 15 seconds from inject to reaching steady state signal. Acquisition can be optimized to ~ 30 45 seconds or less After inject, ALS probe can be moved to rinse position to begin rinsing during acquisition. Loop is rinsed by next sample or optional post-acquisition rinse can be added. Total run time: 1.25 3 min depending on element list and sample type 2-3x faster than normal (continuous) sample introduction Signal Intensity [CPS] 10000000 1000000 100000 10000 1000 100 10 1 rinse port Inject Delay sample Rep 1 Rep 2 Acquire data carrier Rep 3 Analyte Signal Rinse waste ISTD Signal normal (continuous) sample 0 20 40 60 80 100 Go to Next 0 20 40 Time [sec] 60 80 100 Load to nebulizer Co59 In115 13 Agilent Restricted

Integrated Sample Introduction System (ISIS) configured for spectrum mode discrete sampling ISIS-DS Uptake pump 6-port valve Second ISIS pump and optional second valve are not used Sample loop Nebulizer pump Carrier reservoir ISTD reservoir

Significantly Reduced Matrix Loading Conventional sample introduction system (Entire sample consumption goes to the nebulizer ~2.5 ml) Sample Uptake (~0.5 ml) Stabilization (~0.5 ml) Analysis (~0.5 ml) Rinseout (~1 ml) Discrete sampling introduction system (Sample is nebulized only during analysis ~0.1-0.5 ml depending on acquisition method which determines the necessary loop size) Sample uptake (0 ml) Analysis (~0.1-0.5 ml) Rinseout (0 ml) Discrete sampling achieves the same actual measurement time with Only 10-20% of the matrix load on the interface* *actual sample consumption is higher, closer to 2-2.5 ml, but most of the sample does not reach the p p g,, p nebulizer and is used to rinse the sample uptake system including the loop.

Performance Advantages of Discrete Sampling (in addition to much faster run times) Significantly reduced exposure of ICP-MS to high TDS samples Constant nebulization speed Reduced signal drift Reduced cleaning and maintenance Ability to run much higher matrix samples routinely Longer peripump tube life Improved precision Elimination of peristaltic pump tubing from sample path Absolutely l constant t internal standard addition Reduced contamination Better rinseout Improved internal standard correction

Internal Standard Stability During Sample Uptake and Washout - monitored in tune screen Analytes, Be, Co and U Sc and In internal standards <2% RSD

Example Internal Standard Stability Over Calibration Range (7 level calibration shown) Ge Rh Lu These are 7 overlaid points Level CPS RSD 1 204394.0 0.64 2 204935.9 0.44 Level CPS RSD 1 387493.0 0.58 2 392238.7 1.18 Level CPS RSD 1 314976.7 1.16 2 314170.0 0.73 3 205970.6 105 1.05 3 390889.4 052 0.52 3 309012.4 011 0.11 4 204983.0 0.89 5 205443.0 0.53 6 195918.1 1.23 4 386144.9 1.75 5 386485.6 0.33 6 379757.9 1.60 4 310652.0 1.25 5 311939.6 1.57 6 311161.3 0.25 7 191928.7 070 0.70 7 372980.22 060 0.60 7 309836.5 120 1.20

Analytical Conditions for 75 second analysis Plasma Robust mode 1550 Watts Nebulizer Glass concentric (standard) Number of elements (including internal 31 standards) d ORS Mode He - 4 ml/min (single mode) Integration time per point 0.1 seconds (all elements) Points per peak 1 Replicates 3 Total acquisition time (3 reps) 26 seconds Loop volume 300µL Loop rinse and fill time 8-10 seconds Acquisition delay (after valve rotation to inject) 15 seconds Steady state signal time (before valve rotation 30 seconds to fill again)

Sample Sequence Using ISIS-DS 1. Initial Calibration (0.1, 1, 10 and 100 ppb all elements) 2. Sample block repeated 26 times 50 ppb calibration check (CCV) NIST 1643e water CCB (blank) USEPA Interference Check Solution A (ICS-A) USEPA ICS-AB (spiked with all analytes at 100 ppb to monitor carryover) 216 Samples analyzed in 4 hours 29 minutes (He only mode) 75.6 seconds per sample, run to run Sample consumed - 22mlpersample 2.2

Stability: Internal Standard Recoveries (n = 216) 6Li 150 45 Sc 140 72 Ge 115 In 130 159 Tb 120 175 Lu 110 100 90 80 70 60 50 Lowest values are EPA ICS-A and ICS-AB samples (still ~90% recovery) 1ppb 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e ICS- 50ppb CCV ICS-A NIST1643e - - - - - - - - Typical suppression is ~40% with conventional systems

Precision: 50 ppb CCV recoveries (n=26) EPA limits (+/- 10%) shown in red 120.00% 115.00% 110.00% 105.00% 100.00% 95.00% 90.00% 85.00% 80.00% 9Be 51 V 53 Cr 55 Mn 59 Co 60 Ni 63 Cu 66 Zn 75 As 78 Se 95 Mo 107 Ag 111 Cd 121 Sb 205 Tl 208 Pb CCV #2 CCV #3 CCV #4 CCV #5 CCV #6 CCV #7 CCV #8 CCV #9 CCV #10 CCV #11 CCV #12 CCV #13 CCV #14 CCV #15 CCV #16 CCV #17 CCV #18 CCV #19 CCV #20 CCV #21 CCV #22 CCV #23 CCV #24 CCV #25 CCV #26

Accuracy and Precision: NIST 1643e (trace metals in water) Mass/Element Mean (n = 26) RSD Certified Recovery measured value (µg/l) (%) value (µg/l) (%) 9 Be 13.8 2.5 14.0 101.0% 23 Na 22689.2 2.0 20740.0 109.4% 24 Mg 7300.33 21 2.1 8037.00 90.8% 27 Al 142.3 3.3 141.8 100.4% 39 K 1837.8 1.1 2034.0 90.4% 43 Ca 32170.1 0.7 32300.0 99.6% 51 V 37.8 1.1 37.9 99.8% 53 Cr 19.2 1.7 20.4 93.9% 55 Mn 38.0 0.9 39.0 97.6% 56 Fe 98.1 3.9 98.1 100.0% 59 Co 28.8 0.7 27.1 106.4% 60 Ni 59.2 08 0.8 62.4 94.9% 9% 63 Cu 23.2 0.8 22.8 101.9% 66 Zn 70.0 0.5 78.5 89.2% 75 As 54.3 0.9 60.5 89.8% 78 Se 10.0 3.4 12.0 83.2% 95 Mo 121.7 1.1 121.4 100.3% 107 Ag 1.1 1.4 1.1 101.1% 111 Cd 6.2 0.8 6.6 94.3% 121 Sb 59.5 0.9 58.3 102.0% 205 Tl 74 7.4 08 0.8 74 7.4 100.0% 0% 208 Pb 19.6 0.9 19.6 99.7% %RSD for 26 separate analyses over 216 samples

Washout 3-4 orders of magnitude or better reduction Element ICS-AB spike % reduction mean mean mean 9 Be 94.9315 0.0199 99.979% 23 Na 96707.6923 19.6032 99.980% 24 Mg 79238.8462 14.2332 99.982% 27 Al 75758.0769 11.7913 99.984% 984% 39 K 82694.2308 17.6441 99.979% 43 Ca 9092.8462 1.4105 99.984% 51 V 100.3408 0.0105 99.990% 53 Cr 95.7327 0.0419 99.956% 55 Mn 94.8977 0.0132 99.986% 56 Fe 77021.9231 12.5122 99.984% 57 Fe 75266.5385 12.0863 99.984% 59 Co 106.8577 0.0140 99.987% 60 Ni 101.3692-0.01610161 100.016% 016% 63 Cu 98.5700 0.0163 99.984% 66 Zn 99.9350 0.0055 99.994% 75 As 95.8615 0.0290 99.970% 78 Se 94.0162 0.0841 99.911% 95 Mo 1862.3077 1.4281 99.923% 107 Ag 96.8769 0.0181 99.981% 111 Cd 104.0538 0.0134 99.987% 121 Sb 109.1346 0.2629 99.759% 205 Tl 93.4731 0.0339 99.964% 208 Pb 92.4704-0.0175 100.019% Washout is equivalent to or better than traditional peristaltic pumped p sample introduction systems in a fraction of the run time. Intelligent sequencing can automatically add additional blanks after high samples to prevent possible carryover if necessary.

Ultimate Speed Plus Ultimate Matrix Tolerance ISIS-DS plus HMI* Seamless Integration of High Speed Discrete Sampling with Online Aerosol Dilution Fully compliant EPA 6020 analysis for ultra high matrix samples in under 3 minutes per sample No sample dilution No matrix matching of standards or blanks ICP-MS sensitivity and data quality ICP-OES speed and matrix tolerance *HMI Agilent s Unique High Matrix Introduction Accessory - allows direct analysis of % level TDS samples without prior sample dilution by using a combination of very robust plasma conditions and online aerosol dilution

ISIS-DS plus HMI - Simple, Seamless & Compatible with Intelligent Sequencing Sample uptake pump 6-port valve and loop HMI Makeup Gas Port Nebulizer and Internal Standard Pump Combination of ISIS-DS and HMI is easy - simply connect HMI makeup gas port. HMI optimization software works seamlessly with ISIS-DS

Performance Evaluation Sample Analysis 4 Sample types (75 samples each + QC = 114 runs each) -waters -soil digests (undiluted) -TCLPs (undiluted) d) -sea waters (undiluted) 47 elements including ISTDS 2 cell modes - He for all elements except Se and Si (H 2 ) Total run time 2.97 minutes, sample to sample (3 reps) A single HNO 3 /HCl calibration was used for 4 sample types Elements No matrix Cal 1 matching, Cal 2 Cal no 3 optimized Cal 4 tuning Cal 5 or Cal calibration 6 Cal 7 CCV Trace 0.2ppb 1 ppb 2 ppb 20 ppb 100 ppb 200 ppb 100 ppb elements Na, K, Ca, 20 ppb 100ppb 200 ppb 2000 ppb 10,000 ppb 20,000 ppb 10,000 ppb Mg, Fe, Si B, P 1 ppb 5 ppb 10 ppb 100 ppb 500 ppb 1000 ppb 500 ppb

Measured Minimum* Linear Dynamic Range Highest Calibration Linear Range Standard Measured Element (mg/l) Conc (mg/l) value (mg/l) Recovery % Aluminum 0.2 1000 1081.0 108.1% Antimony 0.2 10 9.2 91.7% Arsenic 0.2 10 10.8 108.3% Barium 0.2 10 10.5 105.3% Beryllium 0.2 10 10.7 107.3% Boron 1 10 9.5 95.4% Cadmium 0.2 10 10.5 104.7% Calcium 20 1000 1014.0 101.4% Chromium 0.2 10 10.7 106.9% Cobalt 0.2 10 11.0 109.5% Copper 0.2 100 109.3 109.3% Iron 20 1000 977.4 97.7% Lead 0.2 200 207.9 104.0% Lithium 0.2 10 10.8 108.4% Magnesium 20 1000 1014.0 101.4% Manganese 0.2 10 10.8 108.1% Nickel 0.2 10 10.9 108.8% Phosphorus 20 500 486.4 97.3% Potassium 20 1000 982.3 98.2% Selenium 0.2 10 10.2 101.5% Silicon 1 500 462.0 92.4% Silver 0.2 10 8.4 84.0% Sodium 20 1000 956.3 95.6% Strontium 0.2 10 10.5 105.1% Thallium 0.2 10 10.3 103.1% Thorium 0.2 10 10.2 101.7% Tin 0.2 20 20.9 104.7% Titanium 0.2 10 9.8 97.7% Uranium 0.2 10 10.3 103.4% Vanadium 0.2 10 10.6 105.7% Zinc 0.2 50 52.0 103.9% Zirconium 0.2 10 10.6 105.8% *Most elements were limited by availability of high enough stock concentrations ti and solubilities of mixed standards Only silver was < 90% recovery at 10 ppm due to limited solubility in Cl containing standard mix

Internal Standard Recoveries High TDS Waters 1.2 1 0.8 0.6 0.4 NIST 1643e contains Bi, here run undiluted 0.2 0 Sc Sc Ge Ge Rh Rh Tb Tb Lu Pt Bi blank 1ppb 100ppb blank blank Water 04714-002 Water 04714-005 Water 04714-008 blank Water 04714-012 Water 04714-015 Water 04714-018 100ppb Water 04714-021 Water 04714-024 Water 04714-002 NIST 11634e Water 04714-005 Water 04714-008 Water 04714-011 Water 04714-014 blank Water 04714-017 Water 04714-020 Water 04714-023 100ppb Water 04714-001 Water 04714-004 Water 04714-007 NIST 11634e Water 04714-010 Water 04714-013 Water 04714-016 Water 04714-019 blank Water 04714-022 Water 04714-025 blank

Internal Standard Recoveries Undiluted Soil Digests 120.0% 100.0% 0% 80.0% 40.0% Bismuth Germanium 60.0% Germanium 20.0% 0.0% Standards and blanks samples Lutetium Rhodium Rhodium Scandium Scandium Terbium Terbium 0.2ppb 20ppb blank 100ppb Soils 04714-051 Soils 04714-054 Soils 04714-057 NIST 1643e Soils 04714-060 Soils 04714-063 Soils 04714-066 Soils 04714-069 blank Soils 04714-072 Soils 04714-075 Soils 04714-053 100ppb Soils 04714-056 Soils 04714-059 Soils 04714-062 NIST 1643e Soils 04714-065 Soils 04714-068 Soils 04714-071 Soils 04714-074 blank Soils 04714-052 Soils 04714-055 Soils 04714-058 100ppb Soils 04714-061 Soils 04714-064 Soils 04714-067 NIST 1643e Soils 04714-070 Soils 04714-073 NIST 1643e

Internal Standard Recoveries Undiluted, Undigested TCLP Extracts 120.00% 100.00% 80.00% 60.00% 00% TCLP EPA Method 1311. Toxicity Characteristic Leaching Procedure 40.00% 20.00% 0.00% ~25 g dry sample is added to 500 ml of water acidified with 5.7 ml glacial acetic acid and buffered with 64ml 1N NaOH (or not depends) and extracted with agitation for 18 hours (very simplified summary of method) Bismuth Germanium Germanium Lutetium Rhodium Rhodium Scandium Scandium Terbium Terbium TCLP 04714-095 TCLP 04714-098 NIST 1643e 0.2ppb 20ppb blank 100ppb TCLP 04714-076 TCLP 04714-079 TCLP 04714-082 NIST 1643e TCLP 04714-085 TCLP 04714-088 TCLP 04714-091 TCLP 04714-094 blank TCLP 04714-097 TCLP 04714-100 TCLP 04714-078 100ppb TCLP 04714-081 TCLP 04714-084 TCLP 04714-087 NIST 1643e TCLP 04714-090 TCLP 04714-093 TCLP 04714-096 TCLP 04714-099 blank TCLP 04714-077 TCLP 04714-080 TCLP 04714-083 100ppb TCLP 04714-086 TCLP 04714-089 TCLP 04714-092 NIST 1643e

Internal Standard Recoveries Undiluted* Sea Waters 140.00% 120.00% Note no downward drift due to cone clogging 100.00% 80.00% Bismuth Germanium 60.00% Germanium 40.00% 20.00% 00% 0.00% Lutetium Rhodium Rhodium Scandium Scandium Terbium Terbium 0.2ppb 20ppb CASS-4 Sea Water 04714-026 Sea Water 04714-029 Sea Water 04714-032 Sea Water 04714-035 blank Sea Water 04714-038 Sea Water 04714-041 Sea Water 04714-044 100ppb Sea Water 04714-047 Sea Water 04714-050 Sea Water 04714-028 CASS-4 Sea Water 04714-031 Sea Water 04714-034 Sea Water 04714-037 Sea Water 04714-040 blank Sea Water 04714-043 Sea Water 04714-046 Sea Water 04714-049 100ppb Sea Water 04714-027 Sea Water 04714-030 Sea Water 04714-033 CASS-4 Sea Water 04714-036 Sea Water 04714-039 Sea Water 04714-042 Sea Water 04714-045 blank Sea Water 04714-048 CASS-4 *No other ICP-MS can measure undiluted sea water All other instruments t are limited it to 10% seawater and then also require matrix matched standards to control suppression

Sample Cone after 75 undiluted sea water samples This is the reason there was no downward drift. No blockage of sampling orifice. Close up

CCV Recoveries, TCLPs and Seawaters TCLP Extracts Seawaters TCLP Extracts Seawaters Element undiluted undiluted Mean (n=9) %RSD Mean (n=9) %RSD Aluminum 101.90% 2.02% 94.70% 1.97% Antimony 98.84% 1.63% 98.67% 1.76% Arsenic 99.43% 2.28% 97.05% 1.55% Barium 99.46% 1.77% 97.81% 1.94% Beryllium 100.13% 0.92% 96.22% 3.12% Boron 103.93% 1.66% 119.84% 4.35% Cadmium 98.75% 1.42% 99.29% 1.79% Calcium 99.95% 1.42% 100.08% 1.56% Chromium 99.32% 1.49% 100.15% 15% 1.51% Cobalt 99.75% 1.50% 100.71% 1.71% Copper 98.85% 1.96% 95.78% 1.66% Iron 100.01% 0.96% 99.52% 1.80% Lead 99.54% 1.44% 98.85% 1.66% Lithium 99.76% 1.51% 95.22% 2.39% Magnesium 102.51% 1.52% 100.10% 1.76% Manganese 98.80% 1.33% 100.40% 1.62% Element Mean (n=9) %RSD Mean (n=9) %RSD Molybdenum 98.44% 1.39% 95.29% 1.48% Nickel 100.31% 1.26% 99.59% 2.24% Phosphorus 99.37% 1.78% 99.02% 1.44% Potassium 101.52% 1.49% 100.63% 3.08% Selenium 100.37% 1.23% 100.09% 1.99% Silicon 103.20% 1.25% 101.82% 2.30% Silver 98.64% 1.59% 96.63% 1.73% Sodium N/A N/A N/A N/A Strontium 98.24% 1.70% 96.28% 1.20% Thallium 99.25% 0.91% 98.31% 1.51% Thorium 99.66% 1.26% 92.19% 1.80% Tin 99.68% 1.77% 98.78% 1.77% Titanium 99.13% 1.44% 99.74% 1.68% Uranium 98.80% 1.06% 96.73% 1.73% Vanadium 99.10% 1.82% 100.43% 1.37% Zinc 99.52% 2.61% 95.54% 1.57% Zirconium 97.98% 1.64% 94.25% 1.26%

CCV Recoveries, Waters and Soil Digests Waters Soil Digests Waters Soil Digests undiluted Element Mean (n=9) %RSD Mean (n=9) %RSD Aluminum 101.16% 3.15% 99.74% 2.59% Antimony 101.71% 2.57% 100.54% 1.60% Arsenic 99.79% 2.15% 102.21% 1.79% Barium 100.71% 2.68% 100.79% 2.29% Beryllium 102.21% 2.73% 106.35% 5.04% Boron 99.24% 2.00% 101.06% 3.14% Cadmium 101.12% 2.15% 100.79% 2.19% Calcium 101.68% 3.26% 100.45% 2.11% Chromium 101.26% 1.93% 103.25% 2.76% Cobalt 99.85% 1.70% 103.23% 2.82% Copper 99.28% 2.62% 104.10% 2.41% Iron 101.58% 2.10% 102.04% 2.62% Lead 101.83% 2.23% 102.34% 3.15% Lithium 102.38% 2.55% 104.37% 4.33% Magnesium 102.92% 2.67% 103.90% 2.89% Manganese 100.45% 2.48% 100.62% 1.48% Element Mean (n=9) %RSD Mean (n=9) %RSD Molybdenum 100.01% 2.49% 100.22% 2.29% Nickel 100.34% 1.94% 102.42% 2.98% Phosphorus 100.55% 2.49% 97.34% 2.53% Potassium 102.01% 1.44% 102.57% 1.63% Selenium 101.24% 1.52% 103.06% 1.99% Silicon 101.59% 1.16% 94.07% 4.21% Silver 100.94% 101.91% 2.68% Sodium 101.44% 2.21% 103.59% 2.96% Strontium 100.82% 3.16% 98.37% 2.18% Thallium 101.31% 1.82% 101.83% 2.78% Thorium 100.89% 2.37% 100.15% 3.40% Tin 100.54% 2.73% 101.13% 2.28% Titanium 100.31% 2.13% 100.34% 1.87% Uranium 102.38% 2.75% 102.23% 3.36% Vanadium 99.90% 2.35% 102.09% 2.31% Zinc 99.99% 2.26% 102.20% 1.71% Zirconium 100.35% 2.19% 99.79% 2.11%

Conclusions ISIS-DS can significantly improve sample throughput with no compromise in analytical performance More samples per shift- up to 380 analyses in 8 hours Reduced interface exposure to sample matrix reduces signal drift and improves short and long term precision. Fewer recalibrations, fewer sample re-runs Less frequent need for cone cleaning and interface maintenance When coupled with Agilent s High Matrix Introduction Accessory y( (HMI), Analyze samples prepared for ICP-OES with ICP-MS Better DLs and freedom from interferences compared to ICP-OES, leading to superior data quality ISIS-DS can provide very rapid analysis of samples containing percent level TDS without special optimizations