Agilent Technologies GPSD Analyzer Solutions

Transcription

1 Agilent Technologies GPSD Analyzer Solutions Agilent Science and Technology Symposium 1

2 What is an Analyzer An Analyzer is a factory-configured GC or GC/MSD system configured, tuned and tested for the application prior to delivery to the customer s laboratory. Valves Capillary Flow Technology Retention Time Locking Multichannel Customized Configurations App. Specific Supplies Deconvolution Reporting Software Capillary Flow Technology MRM Database Specialized Columns and Accessories RTL Database Retention Time Locking Sample Prep WorkBench Sample Prep WorkBench Synchronous SIM/SCAN 2

3 Intrinsic Value for Analyzer Solutions Order Placement Sample Ready Agilent Method Development Configured with Market Leading Hardware, Standard and Order Installation & Leveraging Fulfillment Technology Familiarization Innovation Analyzer Order Application Methods Developed Installation by & Fulfillment checkout Familiarization Agilent s Top Application Experts and Collaborators Databases and Libraries developed and maintained by Agilent Technologies Receive systems optimized for a particular analysis and Obtain Verificationaccurate and reliable results Save time and reduce cost for system configuration and method Agilent Analyzers development Chromatography guarantee Sample Quicker start to system calibration and Readyvalidation Time Savings Customer Method Development Customer Method Verification End User Configured Faster Application Startup with a Guaranteed Method 3

4 GPD Analyzers The Solution Approach w/o Analyzer Configured for a specific analysis with factory setup, chemical test, I&F, and field verified performance Data CD App. optimized consumables System with application setup FSS (specialist) I&F Report follows Standard Method Std. HW, SW Analyzer Delivery Point Factory FSS Individual Components produced Individual Components Tested (OFN) System assembled App. method developed on cust. system System checkout on App. mix Run 1 st customer sample customization or optimization method On-going maintains/service Factory FSE Box Delivery Point 4

5 Intrinsic Value for Analyzer Solutions Configured with Market Leading Hardware, and Leveraging Technology Innovation Methods Developed by Agilent s Top Application Experts and Collaborators Receive systems optimized for your particular analysis Obtain accurate and reliable results Save time and reduce cost for system configuration and method development Chromatography Guarantee Quicker start to system calibration and validation Databases and Libraries developed and maintained by Agilent Technologies 5

6 Typical Analyst Requirements Agilent Analyzer Solutions Sample Prep Sample Introduction Separation Detection Validated Reports Customer s Responsibility Agilent s Analyzers Provide Customer s Responsibility 6

7 Selected Agilent GPSD Analyzers Application based Solutions Food Safety Pesticides - Sensitivity (TQ) Pesticides Sens., Op. Ease (TQ) Pesticides Economical (SQ) Enhanced PAHs Sensitivity (TQ)* Enhanced PAHs Economic. (SQ)* Environmental Pesticides - Sensitivity (TQ) Pesticides Sens., Op. Ease (TQ) Pesticides Economical (SQ) Enhanced PAHs Sensitivity (TQ)* Enhanced PAHs Economic. (SQ)* Semi-Volatiles Economical (SQ) Greenhouse Gases (GC) * - New for 2014 * - New for

8 Selected Agilent GPSD Analyzers Application based Solutions Energy and Chemical LVO High Capacity RGA* LVO Fast RGA* LVO Fuels (D4815, D5580, D3606)* Fast RGA with He or H2 Carrier Extended Natural Gas Analyzer Natural Gas Analyzer Transformer Oil Gas Analyzer (TOGA) Forensics and Toxicology Controlled Substances He (SQ)* Controlled Substances H2 (SQ) * Blood Alcohol (GC) Blood Alcohol MS Confirmation (SQ)* Toxicology Screening (SQ) * - New for 2014 * - New for

9 Selected Agilent GPSD Analyzers Application based Solutions Pharmaceutical (USP 467) Residual Solvents (GC) Residual Solvents (MS) 9 February 19,

10 Agilent Technologies GPSD Analyzer Solutions Select GC/MSD Analyzers 10

11 P&EP 3.0 GC/MS/MS Pesticides Analyzer Get Customers on the Analytical FAST TRACK 11

12 Feature Elements for P&EP 3.0 Analyzer GC/MS/MS Pesticides and Environmental Pollutants Analyzer MRM database with ~1100 compounds and ~8500 optimized transitions including 710+ pesticides and breakdown products GUI that facilitates building MRM acquisition and quantitation methods based on customer s compound list Retention Time Locked separation for reliable peak identification and quantitation for CF and CP BF methods Multimode inlet for large volume injection helps optimize detection limit performance Opt 114 UI S/SL for when there is no requirement for optimal LOD performance Capillary Flow Technology Backflush for faster cycle time and reduced system maintenance Pesticide & Environmental Pollutant Analyzer

13 Acquire RTLock Calibration Data Now available for both CP & CF methods! Note: In this example, the acquisition is in full-scan mode. 13

14 Home Screen of the MRM Database Sure it s an Excel file, but No More vlookup! New GUI thanks to the efforts of Pascal Vattaire and Laurent Pascaud! 14

15 View of Target Compound List 15

16 Build MRM Table Step 1 Select Method of Choice Step 2 Select Quant & Qualifier ions 16

17 Two Methods Can be developed: 1) MRM Acquisition Method (qqqacqmethod.xml) via the Compound List Assistant (CLA ) 2) Quant Method (quantmethod.xml) via the MRM database 17

18 Column Backflush - Benefits Elimination of long baked out at a high temperature to remove less volatile, late eluting matrix components Reduced analysis time Increased column life time Prevention of the MS source contamination Less frequent MS source maintenance Increased sample throughput C.-K. Meng, Agilent Application Brief EN 18

19 Column Backflush - Benefits Improved Ruggedness Reduced Maintenance M. Mezcua, M.A. Martinez-Uroz, P.L. Wylie, A.R. Fernandez-Alba, J. AOAC Int. 92 (2009)

20 Column Backflushing - Benefits Overlays of GC-MS/MS chromatograms for selected analytes (at 50 ng/g ) obtained within a 2.5-day sequence of 125 dietary supplement sample injections Dichlorvos m/z 185>93 Malathion m/z 173>99 Ethion m/z 231>129 Phosalone m/z 367>182 Deltamethrin m/z 253>174 Ginseng Root Powder Saw Palmetto Berry Powder x x Counts vs. Acquisition Time (min) Counts vs. Acquisition Time (min) x x Counts vs. Acquisition Time (min) Counts vs. Acquisition Time (min) Accurate x DB 3Match Counts vs. Acquisition Time (min) x Counts vs. Acquisition Time (min) x x Counts vs. Acquisition Time (min) Counts vs. Acquisition Time (min) x x Counts vs. Acquisition Time (min) Counts vs. Acquisition Time (min) Scutellaria Powdered Extract x Counts vs. Acquisition Time (min) x Counts vs. Acquisition Time (min) x Counts vs. Acquisition Time (min) x Counts vs. Acquisition Time (min) x Counts vs. Acquisition Time (min) K. Mastovska and P.L. Wylie, J. Chromatogr. A 1265 (2012)

21 Retention Time Locking (RTL) Improve Confidence with Retention Time Locking MRM Spectrum Unchanged Troubleshooting Repeatability - Run-to-run - Operator-to-operator - Instrument-to-instrument Accurate DB Match min min. Initial run 4.72 psi Trim 1 meter 4.72 psi min. Relock 4.42 psi 21

22 Importance of MRM Transitions Malathion Identification Confident Identification 22

23 Why are MRM Transitions Important? Endosulfan Sulfate (?) in Tea Extract Two (2) Transitions Std 5 ppb Rerun of data Ion Ratio within % confidence band CONFIRMED!! Organic Tea A Organic Tea A Accurate Confirmation 3.3 ppb, Equiv : mg/kg in Tea Tea EU MRL : Sum Endo a+b+sulfate = 30 mg/kg Reagent Blank Demonstrates the value of multiple optimized transitions in the MRM Database. Not just to avoid matrix interferences but also for additional confirmation! Single Qualifier Transition Ion Ratio outside % confidence band Unconfirmed 23

24 GC/MS/MS Pesticide Analyzer Value Overview Powerful MRM Database The Most Comprehensive and Flexible MRM database! New User Interface that streamlines the creation of custom MRM acquisition and quant methods. MultiMode Inlet (MMI) Large volume injection helps optimize LOD performance Opt 114 UI S/SL for customers that do not require for optimal LOD performance Industry Leading Technology Includes New Analytical Methods Expands analysis options: Constant Pressure methods: #411 & #415 Constant Flow methods: #412 & #414 Auto RTL for CFT BF Methods Auto RTL for CF and CP BF method Facilitates relocking methods In Situ Source Cleaning Keeps source clean continuously Improves quantitative performance for many analyses Accurately confirm target pesticides while reducing the time required from start-up to results 24

25 Enhanced PAH Analyzers Get Customers on the Analytical FAST TRACK 25

26 PAH Analysis Using GC/MS and GC/MS/MS 1. GC/MSD in SIM mode 2. GC/MS/MS in MRM mode 3. Typical calibration range from pg 4. Typical method acceptable linearity, R 2 > Typical method ISTD reproducibility a) +/- 20% with calibration b) +/- 30% to 50% with samples 26

27 PAH Properties and Issues with PAH Analysis 1. Properties a) Span wide molecular weight and BP ranges b) They are sticky, not active c) Subject to desublimation (deposition) 2. Analysis Issues a) Difficult to vaporize and keep from depositing b) High temperatures are important c) Minimize surface contact d) Tailing peaks need manual integration e) ISTD inconsistent response across cal range f) ESTD linearity 27

28 Optimized PAH Analyzer 1. Inlet temperature of o C 2. Inlet liner, 4mm, with glass wool, Agilent p/n Pulsed injection of 50 psi, Purge time of min 4. PAH specific column, Agilent p/n Post-column backflushing 6. Constant column flow between 1 and 2 ml/min 7. Source temp o C, Quad temp >= 180 o C 8. 9mm drawout or extractor lens 9. Self-Cleaning Ion Source 28

29 Add Hydrogen Through Transfer Line Use CI transfer line on EI MSD. Hydrogen flows concentrically around end of column into ion volume, the same path used for CI reagent addition Hydrogen In 29 Page 29

30 Add Hydrogen to the Source (top view) Use CI transfer line on EI MSD. Hydrogen flows concentrically around end of column into ion volume, the same path used for CI reagent addition Repeller Drawout (or extractor) lens Hydrogen in via CI transfer line 30

31 PAHs on 2 different 7000B MS/MS systems, MRM Dibenzo(a,l)pyrene, a late eluter stock configuration Counts Counts Optimized PAH Analyzer 31

32 PAH 1000 pg Standard With ISTDs Abundance TIC: 1000_34_2.D\data.ms Time-->

33 500 fg Dibenzo(a,l)pyrene : 3 Runs Each Each Run Separated By 6 Injections 75 ul/min H 2 added No H 2 added 33

34 GC/MS PAH Analysis PAH ISTDs, Cal Range pg 30 Mix PAH ISTDs, 9 mm DO With 75 ul/min H 2 on SQ Continuous H 2 addition No H 2 addition normalized response Naphthalene D8 Acenaphthene-d10 Phenanthrene D10 Chrysene-D12 Perylene-d pg inj 34

35 GC/MS/MS PAH Analysis PAH ISTDs, Cal Range pg Initial data CCM Day 1 CCM Day 3 CCM Day 12 35

36 Calibration Issues Standard PAHs Dibenzo(a,l)pyrene ( pg, R2 = ) Relative Responses Relative Responses Trying to fit the data to a straight line 36

37 Calibration in Continuous Clean Mode Dibenzo(a,l)pyrene (1-1000pg, R 2 = ) Enhanced PAH Relative Responses Std PAH 37

38 GC/MS/MS PAH Analysis R 2 values for calibration pg, Cont. Cleaning Mode Continuous Continuous Initial Data Clean Initial Data Clean R 2 R 2 R 2 R 2 Naphthalene ,3-Dimethyl anthracene Methyl naphthalene Fluoranthene Methyl naphthalene ,10 Dimethyl anthracene ,2-Dimethyl naphthalene Pyrene ,6-Dimethyl naphthalene Methyl pyrene Acenaphthylene Benz (a) anthracene Acenaphthene Chrysene Fluorene Methyl chrysene Phenanthrene Benzo (k) fluoranthene Anthracene Benzo (a) pyrene Methyl phenanthrene Dibenz (a,h) anthracene Methyl anthracene Indeno (1,2,3-c,d) pyrene Methyl phenanthrene Benzo (ghi) perylene ,6-Dimethyl phenanthrene Dibenzo (a,l) pyrene R 2 values for 5977A SIM with Continuous Cleaning are nearly identical to 7000B, across the same pg calibration range 38

39 Optimized PAH Analyzer Summary Overview 1. System and Method Improvements: a) Liner b) Appropriate Temperatures c) Backflushing d) 9mm drawout or extractor lens e) Self Cleaning Ion Source 2. Analyzer Performance Results: a) Improved peak shapes, less tailing b) Consistent ISTD responses c) Linearity improved to d) Sensitivity maintained e) Source stays clean indefinitely 39

40 Controlled Substances Analyzers Get Customers on the Analytical FAST TRACK 40

41 Analysis of Controlled Substances: Challenges Routine Seized Drug Analysis Multiple sample types: Pharmaceuticals: oxycodone, alprazolam, acetaminophen Traditional drugs of abuse: heroin, cocaine, PCP Botanical materials: marijuana, mushrooms Syringe residues: heroin, morphine, fentanyl Charred pipe residues: crack cocaine, hashish, methamphetamine Analyte list constantly growing including novel psychoactive substances: Synthetic cannabinoids: JWH-018, PB-22, AB-FUBINACA, XLR-11 Designer stimulants: MDPV, BZP, NBOMe compounds 41

42 Analysis of Controlled Substances: Challenges Routine Seized Drug Analysis Laboratory Needs: Analyze complex mixtures by GC/MS Efficiency of testing Speed of analysis High quality results Time efficient data processing Simple sample prep Analytical Challenges Samples of varying nature Identify closely related analytes: isomers, analogs, etc. Variable concentrations: column overload to trace concentrations Complex matrix: botanicals, cutting agents, adulterants, non-volatile compounds 42

43 Current Situation Routine Seized Drug Analysis Expanding list of new drug targets Long Cycle Times (23.0 Min) Carry-over interferences between samples PBM Based Searching Subjective Manual Data Review Manual Baseline Review and Spectral Subtraction Variability of Results Through Different Reviewers (Data Bias) Methods vary from lab-to-lab Limited standardization of method Inconsistent spectral libraries and retention times Cost of Analysis with Helium Carrier 43

44 Need for New Method Rapid Identification of Seized Drug Samples Reduce Operating Expense Improve Sample Throughput Reliable and Robust Analytical Performance Consistent Identification Operator-to-Operator and System-to-System Up-to-Date Target List including Novel Psychoactive Substances 44

45 Objective: Create a New Configuration Rapid Identification of Seized Drug Samples Reduce operating expense: Use hydrogen carrier gas High speed analysis: Reduce cycle time Ultra Inert Flow Path: Minimizes sample decomposition Backflushing: Minimize column trimming and eliminate sample carry-over Retention Time Locking (RTL): Precise RT matching column-to-column, instrument-to-instrument, and lab-to-lab Deconvolution Reporting Software: Rapid reliable compound identification Expand compound database: Comprehensive list of controlled substances including new psycho active substances (synthetic cannabinoid, and Bath Salt compounds) 45

46 Test Mix using Helium and Hydrogen Systems Analyzer Checkout Sample 1 Amphetamine 2 Phentermine 3 Methamphetamine 4 N-Propylamphetamine 5 Pentobarbital 6 10,11-Dihydrodibenz(b,f)(1,4)oxazepin-11-one Cocaine 8 Oxycodone 9 Alprazolam 10 Strychnine 6 7 Original Helium Method TIC: BCP45.D\data.ms New Analyzer Method TIC: [BSB2]SAK10.D\data.ms 46

47 Deconvolution Training Standard Deconvolution Reporting Software (DRS) Familiarization What is this peak? First, use conventional approach of average spectrum and PBM search to identify it

48 Probability Based Matching Identifies THC Conventional Approach 299 Average Spectrum THC, 96 Match First hit is THC with 96 PBM match. Second hit is hydrocodone with only 35 match 48

49 Peak Is THC, Right? How confident are you? Average Spectrum Hit 1:THC, 96 Match PBM Hit 2: Hydrocodone, 35 Match PBM

50 Overlap of THC and Hydrocodone As viewed in AMDIS THC min Hydrocodone min THC 314 THC 271 Hydrocodone 185 Hydrocodone 96 Deconvolution finds 2 compounds closely merged together. Peaks are separated by only min. (Less than 1 scan) 50

51 First Peak Found By AMDIS THC 299 Deconvoluted Spectrum at min THC, 95 Net Match AMDIS deconvolution confirms that the first peak is THC 51

52 Second Peak Found By AMDIS Hydrocodone 299 Deconvoluted Spectrum at min Hydrocodone, 95 Net Match This peak would probably have been missed without AMDIS deconvolution 52

53 DRS Report For Training Sample Automated Deconvolution and Reporting Retention Time (R.T.) MSD Deconvolution Report Sample Name: THC/HC Data File: D:\MassHunter\GCMS\1\data\HCOD_THC.D Date/Time: 17:18 Wednesday, Oct Adjacent Peak Subtraction = 1 Resolution = High Sensitivity = Medium Shape Requirements = Medium The NIST library was searched for the components that were found in the AMDIS target library. Amount (ng) AMDIS NIST Cas # Compound Name Chemstation AMDIS Match R.T. Diff Reverse Match N-Propylamphetamine ,11-Dihydrodibenz(b,f)(1,4)oxazepin-11-one Cannabidiol Delta-9-tetrahydrocannabinol (THC) Hydrocodone Hydromorphone Cannabinol Hit Number Automated report generation takes about ~ 60 sec! 53

54 Confirming Presence of Drugs of Abuse GC/MS DRS Controlled Substances Analyzer Retention Time Locked method ensuring reliable database matching Video training tutorials for easy learning about DRS and other advanced Analyzer features Quick-start guide and Application Note that guide you through operation of the screening method CD-ROM with analysis methods, data files, and reports Toxicology DRS Screening GC/MS Analyzer 54

55 Confirming Presence of Drugs of Abuse GC/MS DRS Controlled Substances Analyzer Order an Agilent 5977A Series GC/MSD along with the following system option: G3445B#472 Controlled Substances Analyzer Helium Carrier Gas G3445B#476 Controlled Substances Analyzer Hydrogen Carrier Gas Marijuana Sample with Synthetic Cannabinoids from Real World Forensics Lab Sample Amount (ng) Retention Time (R.T.) Cas # Compound Name Chemstation AMDIS Match R.T. Diff (sec) Reverse Match Hit Num N Propylamphetamine ,11 Dihydrodibenz(b,f)(1,4)oxazepin 11 one Delta 9 tetrahydrocannabinol (THC) Cannabinol JWH JWH AMDIS NIST Synthetic Cannabinoids 55

56 Controlled Substances Analyzer Value Overview for Customers Retention Time Locking (RTL) RT stability column-tocolumn, instrument-toinstrument and lab-tolab Helium or Hydrogen Carrier Gas Quantitation and confirmation from three signals Scan, SIM, and NPD collected in a single run CFT Post Column Backflush Improved throughput through shorter reduced cycle times, cleaner baselines and reduced system maintenance Deconvolution Reporting Software (DRS) Improved data quality using fewer QA resources New 460 compound data base including new Psychoactive Substances incl. Synthetic Cannabinoids and Bath Salts 56

57 Blood Alcohol Analysis Get Customers on the Analytical FAST TRACK 57

58 Blood Alcohol Analyzer System Overview Headspace Sampler coupled to S/SL inlet Reproducible sampling across a wide calibration range Dual Column-Dual FID configuration or Single Column GC/FID/MS Provides differentiation of ethanol peak from potential contaminants Provides confirmation of ethanol presence with a single injection - MSD provide spectral confirmation Retention gap with deactivated fused silica Serves as guard column to protect analytical columns Easily replaced to facilitate maintenance Un-purged splitter for dual column analysis Replaces problematic two hole ferrules or Y splitters - Eliminates leaks common to Y splitter - Overcomes uncertainty of two hole ferrules Precise reproducible split of sample between columns Provides reliable split of flow between columns 58

59 Model 7697A Vial Sampling Pneumatics Designed to minimize carryover 59

60 GC/FID/MS Configuration for Blood Alcohol Helium carrier gas HS Trsfr Line 5977 MSD FID Aux EPC S/Sl DB-ALC1 Restrictor 7890B GC 60

61 Capillary Flow Technology (CFT) 2-Way Splitter Reproducible flow to both detectors Effluent Splitter (2 Way) DB-ALC1 Column in Aux EPC in MSD out FID out Competitive Advantage 61

62 Split/Splitless Connections Reproducible transfer from the headspace sampler Deactivated fused silica transfer line (0.53 mm ID) Uses G3521A Weldment Liner (1 mm): Ultra Inert # Split/Splitless Fused silica inserted through septum Transfer line (0.53 mm): Inert, #G Competitive Advantage 62

63 TIC and FID Retention Time Alignment 2-propanol Acetone MS Methanol Ethanol n-propanol FID 63

64 Ethanol Linearity FID and MS Performance Real world data from Domestic Toxicology Laboratory (USA) FID R MS R

65 Carry Over Testing Potential for Cross Contamination between Samples? TIC FID Multicomponent mix at 0.4% w/v ISTD Blank after 0.4% Multicomponent mix No carry over following challenge with a high concentration! 65

66 Blood Alcohol Analysis GC/FID/MS Blood Alcohol Analyzer Benefits Rapid Cycle time to maximize sample throughput: less than three (<3) minute run time Agilent proven EPC and CFT provides reproducible split between FID and MSD Defensible data through MS confirmation of ethanol presence with spectral comparison reporting No carry over following challenge of the system with a 0.50% EtOH concentration sample Blood Alcohol Analyzer GC/FID/MS 66

67 Blood Alcohol Analysis Dual Channel Blood Alcohol Analyzer (GC/FID/MS) Calibration Curve for GC/FID/MS Real World Toxicology Laboratory FID for Quantitation Collected Spectra Order an Agilent G3440B GC system with 5977A MS and the following SP1 Option: GC/MS/FID Blood Alcohol Analyzer NIST Spectral Confirmation Link to Solution Portal Information Custom Report: FID Quant, MS Confirmation 67

68 GC/FID/MS Blood Alcohol Analyzer Value Overview ( ) Headspace Sampler Coupled to S/SL Inlet Reproducible sampling across a wide calibration range CFT Purged Dual Column Splitter Single column analysis Precise reproducible split of flow between FID and MS Detection with FID and Single Quad MS Quantitation of Alcohol content with the FID Simultaneous Spectral confirmation of ethanol presence Custom Reporting with MS Spectra Comparison Less than three minute run time. Spectral confirmation of ethanol presence. 68

69 Dual Channel GC/FID/FID Blood Alcohol Analyzer Value Overview Analyzer, G3445B #683 Headspace Sampler Coupled to S/SL Inlet Reproducible sampling across a wide calibration range Retention Gap Serves as guard column to protect analytical columns Easily replaced to facilitate maintenance CFT Splitter Replaces problematic two hole ferrules or Y splitters Precise reproducible split of sample between columns Dual Column-Dual FID Configuration Serves as guard column to protect analytical columns Easily replaced to facilitate maintenance Four minute runtime and no carry over with a 0.50% EtOH sample challenge 69

70 Agilent Technologies GPSD Analyzer Solutions Select GC Analyzers 70

71 Refinery Gas Analyzers with External Valve Oven Get Customers on the Analytical FAST TRACK 71

72 Importance of Refinery Gases and RGA Process Characterization Quickly and Reliably Produced from hydrocarbon cracking and distillation Typically contains saturated and unsaturated HCs (C 1- C 5 ) H 2, O 2, N 2, CO, and CO 2. C 1 -C 6 or higher hydrocarbons Sulfur contaminants, e.g., H 2 S Challenging analysis due to variable source and composition Producers require quick accurate analysis to monitor process Typically complex mixtures from a broad range of samples 72

73 Introducing the 7890B Large Valve Oven Isothermal Zone for Valves and Columns Temperature control: - Independent control of LVO and GC oven zones Temperature Limit: - Max 330 C (valve and column dependent) Valve configurations: - Accommodates 4/6/10/14 port valves including Hastelloy valves Column Compatibility: - Large Mandrel: Accommodates 15 feet of 1/8 inch OD metal column - Small Mandrel: Accommodates 7 Ft of 1/8 OD metal column 73

74 Introducing the 7890B Large Valve Oven Isothermal Zone for Valves and Columns Column Mandrel Valve or Mandrel Position 6 Internal Positions: Valves or Columns Variable Restrictor - Up to six (6) heated valve positions - Four (4) needle valve positions - Uses 1 heated zone 6-port Valve 12-port Valves 74

75 Large Valve Oven Features/Benefits Feature 6 position isothermal valve oven for actuated valves, microgasifiers, needle valves, and columns (including 1/8 in packed columns) with access to valves connections without removing actuators Benefit Open configuration that allows for easy maintenance; maximizing up-time. Also allows for multiple configurations for method development as well as set SP1 and configured Feature Use only one 7890B heated zone Benefit Current multi-valve configurations may quickly consume 6 heated zones, LVO uses 5 leaving 1 for future applications Feature Dual thermal zones allow for thermal isolation between column oven and LVO Benefit Ability to configure analyses that require multiple thermal zones. Can run isothermal temperatures in the LVO while temperature ramping the GC oven 7809B with Large Valve Oven 75

76 Fast RGA with Micropacked Columns GC/FID/TCD/TCD Micropack LVO Plumbing Micropack System Flow Diagram 76

77 Performance Features LVO RGA Analyzers Fast RGA Analyzer Total run time is 8 minutes - LVO at 70 C Hydrocarbons to C 5 (C 6+ backflush) Permanent Gases O 2 and H 2 S Compounds Limit Hydrocarbons 0.01 Mol% Hydrogen Sulfide 500 ppm Carbonyl Sulfide 300 ppm Hydrogen 0.01 Mol% O2, N2, CO, CO Mol% Fast RGA with Large Valve Oven G3445B #532 77

78 Fast RGA with Micropacked Columns Analytical Performance Hydrocarbon Channel (FID), LVO 70 C 78

79 Fast RGA with Micropacked Columns Analytical Performance Perm. Gas Channel (TCD), LVO 70 C

80 Fast RGA with Micropacked Columns Helium Carrier Analytical Performance Compound Concentration RT Area C Methane (FID) Ethane (FID) n butane t 2 butane butene n pentane Hydrogen Oxygen Nitrogen balance Carbon Monoxide Carbon Dioxide Methane (TCD) Ethane (TCD) Hydrogen Sulfide Repeatability of Select Refinery Gas Components (% RSD s for retention times and areas with the large valve oven at 70 C) 80

81 High Capacity RGA with Micropacked Columns Application Note Packed Column Refinery Gas Analysis System Based on the Agilent 7890B GC System and G3507A Large Valve Oven Publication Number: EN 81

82 Fast RGA LVO Analyzer Value Overview Analyzer, G3445B #532 Large Valve Oven External Thermal Zone Isothermal Operation Up to 6 valves or columns Expands capability of 7890 Micropacked Columns Built for speed Rapid 8 minute cycle time Isothermal Zone Protect temperature sensitive columns Simultaneous analysis of hydrogen disulfide (H 2 S) and oxygen (O 2 ) Stable response for oxygen (O 2 ) Three Channel Analytical Method Simultaneous analysis of hydrogen hydrocarbons and permanent gases Simultaneous analysis of O 2 and H 2 S <8 Minutes 82

83 Performance Features LVO High Capacity RGA Analyzer High Capacity RGA Analyzer Total run time is 16 minutes. Hydrocarbons to C 5 (C 6+ backflush) Permanent Gases O 2 and H 2 S Compounds Limit Hydrocarbons 0.01 Mol% Hydrogen Sulfide 500 ppm Carbonyl Sulfide 300 ppm Hydrogen 0.01 Mol% O2, N2, CO, CO Mol% High Capacity RGA with Large Valve Oven G3445B #531 83

84 High Capacity Refinery Gas Analysis with Std Columns GC/FID/TCD/TCD Standard Column LVO Plumbing Std Column LVO Flow Diagram 84

85 High Capacity RGA with Standard Columns Analytical Performance - LVO at 70 C Hydrocarbon Channel Permanent Gas Channel Hydrogen Channel 85

86 High Capacity RGA with Standard Columns Application Note Packed Column Refinery Gas Analysis System Based on the Agilent 7890B GC System and G3507A Large Valve Oven Publication Number: EN 86

87 High Capacity RGA LVO Analyzer Value Overview Analyzer, G3445B #531 Large Valve Oven External Thermal Zone Isothermal Operation Up to 6 valves or columns Expands capability of 7890 Standard 1/8 Packed Columns High capacity Rapid 17 minute cycle time Isothermal Zone Protect temperature sensitive columns Simultaneous analysis of hydrogen disulfide (H 2 S) and oxygen (O 2 ) Stable response for oxygen (O 2 ) Three Channel Analytical Method Simultaneous analysis of hydrogen hydrocarbons and permanent gases Simultaneous analysis of O 2 and H 2 S. Capacity for higher concentration samples. 87

88 3-in-1 Reformulated Fuels Analyzers ASTM D5580, D4815 and D3606 Get Customers on the Analytical FAST TRACK

89 Analysis of Oxygenates and Aromatics in Gasoline ASTM D3606 Benzene and Toluene in Gasoline - official EPA method for benzene ( vol%) and toluene (2 to 20 vol%) in gasoline ASTM Method D4815 Oxygenated Additives - 14 different ethers and alcohols from 0.1 to 15 wt% - usually only one or two oxygenates found in a sample ASTM Method D5580 Aromatics in Gasoline - measures benzene (0.1 to 5%), toluene (1 to 15%), C 8 aromatics (0.5 to 10%) C 9 plus aromatics (5 to 30%), and total aromatics (10 to 80%) - requires two injections per sample for complete analysis 89

90 3-in-1 Gasoline Solution 7890B GC with Large Valve Oven (LVO) LVO Larger capacity for valves, packed columns and micro-packed columns Flexibility for method using complex valve/column configurations Enables multiple methods to reside on a single GC - reduce instrument costs - run more samples in less lab space - 3-in-1 Gasoline Solution D3606 D4815 D

91 3-in-1 Gasoline Solution Detailed LVO Configuration TCEP Micro-packed Column on Heated Mandrel Variable Restrictor D port Valve D4815 & D port Valves 91

92 GC Configuration for D4815 and D5580 Similarities between each method Same GC hardware requirements - Inlets, detectors, plumbing and valve configuration Same separation scheme 2-D separation using polar TCEP micro-packed primary column 20% TCEP on 80/100 Chromosorb PAW, 22 x 1/16 stainless Only one difference in instrument requirements Non-polar capillary column - D m methyl silicone, 30m x 0.53mm - D m methyl silicone, 30m x 0.53mm 92

93 3-in-1 Gasoline Solution Main Column Oven D3606 Packed Columns D4815 and D5580 Capillary Columns PDMS packed pre-column Polar packed analytical column D4815 HP-1 (30 m x 0.53 mm x 2.65 m) D5580 HP-1 (30 m x 0.53 mm x 5.0 m 93

94 7890 Instrument Conditions for D3606 carrier gas Inlet Inlet temperature Inlet total flow Septum purge flow Column flow Aux pressure TCD temperature LVO Temperature Main oven temperature Backflush time helium Purge 59.4 psi 200 Deg C 23 ml/min 3 ml/min 20 ml/min 35.5 psi 250 deg C 60 deg C 135 deg C isothermal 2.5 min LVO temperature remains stable with high main oven temperature 94

95 LVO Fuels Analyzer Summary Overview New Large Valve Oven for the 7890B GC: Provides greater capacity and flexibility for GC methods using complex valve configurations Allows multiple ASTM methods to be configured on a single GC reduces costs and saves lab space 95

96 D3606 Precision and Accuracy for Work Bench Prepared Samples Commercial Gasoline Sample Volume % run benzene toluene avg stddev RSD 0.938% 0.668% r (exp) r (ASTM Spec) Meets ASTM repeatability specifications D3606 Check Sample vol%* Run Benzene Toluene *benzene = 1.00 vol% (+/- 0.02) *toluene = 5.00 vol% (+/- 0.08) Analysis results match known quantities in sample 96

97 D Precision for WorkBench Samples Meets ASTM Repeatability (r) Specifications wt% Found in Gasoline Sample 1 benzene toluene ethylbenzene m,p-xylene o-xylene C9 plus Total Run Run r (calc) r (ASTM spec) wt% Found in Gasoline Sample 2 benzene toluene ethylbenzene m,p-xylene o-xylene C9 plus Total Run Run r (calc) r (ASTM spec) wt% Found in Gasoline Sample 3 benzene toluene ethylbenzene m,p-xylene o-xylene C9 plus Total Run Run r (calc) r (ASTM spec)

98 D4815 Comparison of Manual and WorkBench Sample Prep Manual Sample Prep Add 0.5 ml DME to 10 ml volumetric flask Record DME weight to 0.1 mg Add sample to 10 ml mark Record sample weight to 0.1 mg Mix Work Bench Sample Prep Add 0.95 ml sample to an empty 2 ml vial Record sample weight to 0.01 mg Add 0.05 ml DME to sample in the 2 ml vial Record DME weight to 0.01 mg Mix Gas1 wt% MTBE Gas2 wt% Ethanol Gas3 wt% Ethanol Manual Prep WorkBench Manual Prep WorkBench Manual Prep WorkBench run run Avg r (calc) r (spec)

99 High Capacity Reformulated Fuel Analyzer Analyzer Overview, G3445B #621 Large Valve Oven External Thermal Zone Isothermal Operation Up to 6 valves or columns Expands capability of 7890 Multiple ASTM Methods on a Single GC D 4815, D5580 and D3606 Rapid change over between methods Thermal Isolation from Main Oven Protect temperature sensitive columns Higher main oven temperature (135 deg C) has no effect on lower LVO temperature (60 deg C) 7696A Sample Prep Workbench Automates sample preparation (ISTD addition) Provides reproducibility that meets or beats ASTM method requirements Simultaneous analysis of O 2 and H 2 S. Capacity Stable for response higher concentration for samples. oxygen (O 2 ) 99

100 Ultrafast Simulated Distillation Application of the Low Thermal Mass (LTM) Module Get Customers on the Analytical FAST TRACK 100

101 Fast Simulated Distillation Designed for ASTM D7798 For the determination of boiling range distribution of petroleum products and biodiesel (B5,B10,B20) Applicable to petroleum distillates having a final boiling point not greater than 538 C Difference between initial BP and final BP must be greater than 55 C Not applicable to naphthas, reformates, gasolines or full range crude oils Tested in the factory. LTM Column and LTM Transferline will ship pre-assembled as 1 module. 101

102 LTM Low Thermal Mass Technology Fast Temperature Ramps < 400 o C/min Typical <400 o C/min Temperature Range 120 V Oven Fast Ramps Insert ** ( C) ( C/min) > 200 V, 15A > 200 V, 15A 50 to to to to to * * Requires G Fast Cool-Down Temp (oc) LTM Cooldown Times (Standard Size) Time (sec) 2m LTM 5m LTM 10m LTM 7890 GC 102

103 Fast Simulated Distillation Under 3 Minutes Using LTM 6x faster compared to conventional ASTM D2887 procedure pa ASTM D2887 Reference Oil LTM Module : 45ºC to 350ºC at 150ºC/min Faster than conventional GC ( o C/min max) min pa C5 C10 C12 C14 C16 Calibration sample C5-C44 LTM Module : 45ºC to 350ºC at 150ºC/min C6 C7 C8 C 9 C11 C15 C C18 C20 C24 C28 C32 C36 C min 103

104 Repeatability: RGO with 160 C/min Temperatures in F % OFF AVG RSD %RSD ASTM DIFF F ASTM DIFF = Allowable difference (+ or -) from last column 104

105 Examples of Calibration and %Off Reports 105

106 Cracked Gas Oil Engineering Report 106

107 LTM Simulated Distillation Analyzer Analyzer Overview, G3445B #658 Low Thermal Mass (LTM) Oven Configured per Industry Standard Available with Various Inlet Options Simulated Distillation Software Rapid temperature programming, up to 1800 ºC/min Fast cooling allows for rapid cycle times Constant flow mode for very good retention time repeatability ASTM D2887 Round Robin review underway Multi-Mode Inlet Split/Splitless Inlet User defined within Analyzer configuration Intuitive Graphic User Interface (GUI) Rapid analysis and report generation Interfaces with ChemStation for report automation Simultaneous analysis of O 2 and H 2 S. Capacity for higher concentration samples. 107

108 Analyzer Information HPI Solution Guide EN Product Flyers Solution Brochure EN GC Analyzer Webpage Services/Instruments-Systems/Gas- Chromatography/Pages/default.aspx MS Analyzer Webpage Services/Instruments-Systems/Mass- Spectrometry/Pages/default.aspx 108

109 The Value of Analyzer Solutions Preconfigured and analytically tested No instrumental method development. Consistent identification of drug targets operator-tooperator and lab-to-lab 109

110 Analyzer Value to Customers Helping customers enhance their competitive advantage Alleviate Resource Pressure Guaranteed Method Optimized Performance Advanced Technologies Quicker Deployment and Return 110

111 Questions Thank you for your attention 111