Bruker Gas Chromatography Products

450-GC - Flexible, Multi-channel Gas Chromatograph

This GC is the ideal choice for laboratory environments where you are never quite sure what you may be asked to do tomorrow and, as a result, need a high degree of flexibility. The 450-GC can be conveniently configured for one, two, or three channel operation and has a wide array of inlets, detectors and automated sample introduction devices from which to choose. Available Injection Ports: Isothermal split/splitless capillary (1177 S/SL) Large volume (LVI) (1079 PTV) Cold On Column Injector (1093 COC) On column/530 m capillary/packed (1041 PWOC) Flash vaporizing 530 m capillary/packed injector (1061 Flash)

Available Detectors: Flame Ionization (FID); hydrocarbon response Thermal Conductivity (TCD); universal response Electron Capture (ECD); halogen specific Thermionic Selective (TSD); selective for N and P Pulsed Flame Photometric (PFPD); selective for S and P and up to 28 other elements Pulsed Discharge Helium Ionization (PDHID); universal response high sensitivity Mass spectrometer (mass fragmentation; the ultimate selective detector) Other detectors available upon request

Key Attributes: Large easy access column 3 channels can be configured and operated simultaneously Available with Inert Steel surface deactivation for improved performance for reactive components Fast oven temperature ramping; up to 120 C/min and very rapid oven cool down for fast cycle times and high throughput Full digital pneumatic control Can accommodate up to 8 valves for simple to complex analysis needs High resolution color touch screen control interface/easy to read/very easy to use Compatible with the full line of Bruker automated samplers High pressure injection ports (up to 150 psi) to reduce analysis time Powerful CompassCDS Chromatography Software

430-GC - Single Channel Gas Chromatograph

This GC is a high throughput instrument designed to meet routine analysis requirements. It is a single channel, fixed configuration GC that incorporates all of the state of the art technology contained in the 450-GC, but in a much smaller package. It is exceptionally easy to set up and use. The 430-GC is the ideal replacement system for aging large multi-channel GCs that are only used in single channel mode.

Available Inlets: Isothermal split/splitless capillary (1177 S/SL) On column 0.53 mm/packed injector (1041 PWOC) Available Detectors: Flame Ionization (FID); hydrocarbon response Thermal Conductivity (TCD); universal response Pulsed Discharge Helium Ionization (PDHID)

Key Attributes: Small laboratory bench footprint (12.5 in/32 cm wide) Simple/intuitive icon based keypad for instrument control Conveniently sized oven; uses industry standard 7 in/17.5 cm diameter capillary columns Full digital pneumatic control pneumatics Convenient rollback style cover provides easy access for routine maintenance Can accommodate a gas or liquid sampling valve Compatible with the full line of Bruker automated samplers

Samplers for GC and GC-MS

Automation and versatile sample handling systems with a range of techniques are a pre-requisite and demanded by todays GC and GC/MS laboratories. Bruker offers a range of automated samplers and associated techniques to provide versatility, high sample throughput and reliability. We offer a choice of introduction methods. Liquid, headspace, Solid Phase MicroExtraction (SPME) and in-Tube Extraction (ITEX) are all available on and within our portfolio of autosamplers.

Autosampler Range
Regardless of your sample throughput requirements, Bruker can provide an automatic solution to meet your needs. Four samplers are available, the CP8410, CP-8400, the SHS-40, and the Combi Pal-xt. Each is tailored to meet a different need and workload.

For high throughput needs, the CP-8400 accommodates up to 100 samples using 2 mL vials. For laboratories with less demanding sample load, the CP-8410 can inject up to ten samples using 2 mL vials, six samples of 5 mL or five samples of 10 mL vials.

The SHS-40 is a dedicated automated headspace sampler providing performance with value.

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The Combi Pal-xt excels as a high throughput sampler with the capability to conduct various sample processing modes.

Versatility for Modern GC Labs

Choice of introduction methods
Liquid, headspace, SPME and ITEX are possible on all syringe based autosamplers, e.g., CP-8410, CP-8400 and Combipal-xt. Choose from pre-set injection modes, or define your own custom injection parameters for maximum flexibility. The SHS-40 is a dedicated headspace sampler that employs a sophisticated injection valve and is available in sample loop or Press and Inject mode of operation.

Syringe Based Sampling

Pre-defined liquid injection modes are available: split/splitless, on-column, volatile, neat and viscous. These pre-defined modes contain the optimized parameters for specific samples. Alternatively, you can define custom injection parameters. A wide range of syringes is compatible with the samplers, fully controlled by the GC. They range from the SPME syringe for pre-concentration of selective groups of components to large volume syringes for 100+ L injection (LVI).

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Large rinse vials Large Volume Injection To meet the growing demand for improved detection limits, large injection volumes can be performed with the samplers while minimizing sample carryover with the large waste and rinse vials. Furthermore, a waste drain can be added on the CP-8400 and CP-8410 for prolonged cycles.

Easy maintenance
Routine injector maintenance such as septum and insert replacement can be accomplished without removing the sampler.

Flexibility
Standard on the CP-8400 and CP-8410 is the capability to access two independent injectors permitting dual and duplicate sample injections. In addition, internal standards or matrix spikes can be automatically added to any injection. The dual sample injection mode increases sample throughput with no additional hardware costs. It is ideal for simultaneous conformational analysis, with the benefit of increased productivity and sensitivity.

Optimal Flexibility The CP8400 and CP-8410 can be installed without limiting other unique capabilities. In this case an optional valve oven is installed.

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Reliability
Brukers unique injector nut and syringe needle guide combined with rugged, simple carousels (8400/8410), proven XYZ robotics (Combipal) precisely align the syringe needle over the injector. This design eliminates the need for complex robotics commonly associated with sample vial transfer and ensures continuous operation.

Bruker CompassCDS Chromatography Software

CompassCDS is Brukers industry proven, networked chromatographic software solution for Petrochemical production environments, providing instrument control, data acquisition, processing and results reporting for laboratories involved in the exploration, extraction, refining and distribution of hydrocarbons.

Key Benefits: Scalable: CompassCDS operates as a standalone or client server application with all current Windows versions as well as Citrix Metaframe and Virtualized environments. This software can be scaled from a single computer/GC combination to large enterprise systems with multiple instruments and client computers, providing users with a solution that enables control of all instruments and results data processing from any PC on the network. CompassCDS also interfaces seamlessly with LIMS and SCADA applications to provide bi-directional communication.

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CompassCDS Networked software solution for Petrochemical Laboratories Centralized management: The CompassCDS Configuration Manager application centralizes administration and management of users, instruments, projects and 21 CFR Part 11 support. Unrivalled instrument control: CompassCDS controlled Bruker GC Analyzers and Custom Solution GCs are the preferred solution for most Industry standard methods. CompassCDS controls in-line, routine and R&D GCs, providing operators with a common interface for all instruments. Data can also be acquired from uncontrolled GCs via the 850 MIB analog interface. Operator friendly: CompassCDS has straightforward graphical user interfaces (GUI) that can be configured, by defining user profiles, to only show those options operators use. This eliminates user error by enforcing specific user behavior and dramatically reduces training overhead. Maximum reliability: The unique Smart Time Update (STU) feature automatically updates peak retention times and time integration events to account for shifts associated with column or system performance variation. When combined with the powerful, method-independent calibration feature, CompassCDS delivers correct results, consistently. Improved efficiency: CompassCDS come with a powerful and easy to use custom calculation module that eliminates the requirement for third party calculation tools such as Excel. This custom variable editor allows calculations to be made using component-, group- and global-variables. Global variable calculations provide results at the channel level whereas Group and Peak variable calculations give results at the component level. This editor uses logical, MS-Excel like formulas and has syntax control to eliminate calculation errors.

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CompassCDS Embedded Custom Calculation Editor Examples of predefined custom calculations sets include those associated with ASTM D 3588, ISO 6976, ASTM D 4815, ASTM D 5263, IP 391 and Mol% by reference. In order to make complex calculations possible, the calculation editor allows for user-input on both Global and component level enabling users to manually input the required information into CompassCDS when setting up analysis runs. User input variables can be made mandatory to ensure that these inputs are always added prior to each analysis. The peak table in the CompassCDS Software can display all user defined values for each peak, making it easy to maintain the correct values. Custom calculations are also immediately available in the suitability testing wizard, allowing users to create additional suitability tests. The results of such tests can be exported, together with the standard calculations, to LIMS. It is also possible to send custom designed calculations to the CompassCDS summary report feature than enables users to track trends or monitor for out-of-specification analyses. All custom calculations are also fully integrated into the CompassCDS Software report editor. Bruker is the leading provider of custom GC systems for the Petrochemical industry and continuously develops industry driven analyzer solutions using CompassCDS as the supporting software platform The Bruker PIONA+ Analyzer completely characterizes hydrocarbon sample composition in accordance with ASTM, DIN, ISO, EN and IP standard test methods. The PIONA+ software module is integrated into CompassCDS for complete instrument control, data acquisition, results generation and reporting.

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CompassCDS SimDist Software The Bruker Simulated Distillation Analyzer determines true boiling point distribution of hydrocarbon mixtures. This integrated software streamlines instrument setup, operation and reporting of Simulated Distillation results. The software incorporates all of the ASTM, DIN, IP and ISO methods associated with Simulated Distillation analysis. Other integrated CompassCDS hydrocarbon software modules include: Detailed Hydrocarbon Analysis (DHA), Natural Gas (NG), MatchCompare automated peak matching and Multi-Channel calculation & reporting. Reliability; the right answer... Every time Even the very best GC columns experience column deterioration with extended use that results in shifting peak retention times. Operators can spend a significant amount of time adjusting peak identification results to account for retention time shifts. CompassCDS Software automatically adapts the integration to the shift using the unique Smart Time Update (STU) feature. STU does not modify any instrument control settings, ensuring that validated instrument method settings are not changed by the software and method validation status is retained. Approaches that modify an instrument control setting such as varying column pressure to lock peak retention times can result in analyses where the column performance falls outside of the validated envelope. CompassCDS STU adjusts both the integration parameters and the expected peak retention times of the components in the postprocessing part of a method, to correct for the expected shift due to column deterioration or column replacement. This results in consistently reliable integration and identification of components without changing any instrument control parameters and this allows user to improve efficiency by eliminating the need to reprocess data. STU can be applied irrespective of instrument type.

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CompassCDS Smart Time Update CompassCDS easily addresses the different integration and calculation requirements associated with complex petrochemical samples. Timed integration events can be used to correctly process any chromatogram without user intervention. Slice integration has been designed especially for the analysis of Mineral oil, providing reliable identification and quantification of mineral oil fractions. While most chromatography software packages are capable of performing tangent skimming, CompassCDS also offers exponential skimming ensuring far more accurate results when analyzing shoulder peaks. Customized Reporting: The CompassCDS report editor enables single or multi page reports to be designed by simply dragging and dropping objects onto the page. These reports can be stored as templates and can range from simple QC reports highlighting specific information through to comprehensive reports showing all available data from the analysis including all user defined custom calculations. A summary report option with trend & control charts displays results over time and allows users to be automatically notified if results fall outside predefined limits. This ensures quality with minimal effort from operators. Statistical tools can be used to validate methods or to monitor production by visualizing key product analysis results.

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CompassCDS Control Chart Summary Report

Bruker GC Columns
A Selection of GC Columns to Meet Y our Needs
Bruker GC columns span a broad range of column diameters, stationary phases, and capillary column materials: Fused Silica (FS) and Inert Steel (IS). Ideal for either routine or research type analyses.

Bruker GC columns span a broad range of column diameters, stationary phases, and capillary column materials: Fused Silica (FS) and Inert Steel (IS). Ideal for either routine or research type analyses.

Bruker GC column offerings bridge across many important applications and include a number of offerings such as: Standard WCOT (Wall Coated Open Tubular) Columns with an internal diameter ranging from 0.25 mm to 0.53 mm in a variety of stationary phases (from the non-polar BR-1 and BR-1ms phase up to the wax phases) for narrow and wide analyte concentration ranges. Small Internal Diameter Columns for fast analysis that improve cycle time while maintaining high resolution.

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 Solid Stationary Phase PLOT (Porous Layer Open Tubular) Columns for the analysis of volatiles that require high selectivity. The solid stationary phase is tuned for applications commonly used for the permanent gas analysis like the BRMolsieve 5A and petro- chemical analysis like the BR-Alumina range. Inert Steel Micro-Packed and Packed Columns for composition analysis with bulk components, where a high column capacity is required.

Petrochemical and Hydrocarbon Analysis

Bruker provides the most comprehensive range of GC analysis solutions for analysts working in the Petrochemical industry. Bruker configures, produces, tests, delivers, and installs gas chromatography hardware, complete with columns, software and consumables according to widely used industry standards (e.g. ASTM, UOP, ISO, GPA, EN). This saves you time and ensures confidence in your results.

Directed Solutions for Distillation

Simulated distillation per ASTM D7169 is used for determining the boiling point range distribution of petroleum products by capillary gas chromatography of heavy distillate and residual fuel oils with initial boiling points (IBP) > 100C and final boiling point (FBP) above 720C. The stationary phase must meet rigid resolution and retention time requirements, yet be stable at high temperatures. To meet the critical criteria set forth by ASTM, Bruker is using the BR-1HT SimDist column. The BR-1HT polymer is a 100% polydimethylsiloxane (PDMS) material that requires minimal conditio ning, and is 100% crosslinked and coated onto highly deactivated stainless steel tubing that has the inertness of fused silica without the temperature limitations. The BR-1HT inert steel SimDist column has a lifetime of at least 400 injections under typical SimDist conditions.

Polywax 1000 separation on a BR-1HT SimDist column. Chromatogram was obtained under temperature programming up to 430 oC

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Excellent retention and selectivity on a BR Alumina Na2SO4 PLOT column for a complex refinery gas sample; complete separation up to Hexanes within 15 minutes.

Additional Petrochemical Applications

Apart from the inert steel SimDist columns, Bruker offers a complete column product range for the petrochemical industry including (micro-)packed for refinery gas analysis, PLOT columns for selective volatiles analysis, high resolution columns for detailed hydrocarbon analysis.

A Complete Range of High Performing Stationary Phases

Bruker offers a wide range of stationary phases for any petrochemical application from non-polar BR-1MS for high resolution, to BR-1HT for high temperature applications up to highly selective molecular sieves for permanent gas analysis. Table 1. An overview of the stationary phases. (other phases available)
Bruker Phase BR-1ms Composition 100% dimethyl polysiloxane Similar Stationary Phases HP-1ms UI, DB-1ms UI, HP-1, HP1ms, DB-1,DB-1ms, Ultra-, 1 VF1ms, CP-Sil 5, CP Sil 5 CB Low Bleed/MS, Rxi-1ms, ZB-1, ZB1ms, BP-1, Optima-1, Optima1ms, SPB-1, Equity-1 DB-1HT , Rxi-1HT , ZB-1HT HP-5ms UI, HP-5, HP-5ms, DB-5, Ultra-2, CP-Sil 8, CP Sil 8 CB, Rxi-

BR-1HT BR-5

100% dimethyl polysiloxane 5% diphenyl; 95% dimethyl polysiloxane 20

5ms, ZB-5, BP-5, Optima-5, SPB5, Equity-5 BR-5ms 5% phenyl; 95% dimethyl arylene siloxane DB-5ms UI, DB-5ms, VF-5ms, CPSil 8 CB Low Bleed/MS, Rxi-5Sil MS, ZB-5MS, BPX-5, Optima-5ms, SLB-5 DB-5HT, VF-5HT, Rxi-5HT, ZB5HT DB-XLB, VF-Xms, Rxi-XLB DB-624, HP-624, VF-624ms, Rxi624Sil MS, ZB-624, BP-624, Optima-624 DB-35ms, VF-35ms, Rxi-35, Sil MS, MR2 HP-17, DB-17, DB-608 ,CP-Sil 24 CB, Rxi-17, ZB-50 DB-17ms, VF-17ms, Rxi-17Sil MS, BPX-50 Rt-Alumina Bond, GS-Alumina, HP PLOT S, CP-Al2O3/Na2SO4, Alumina-PLOT, AT-Alumina RT-Q-BOND, CP-PoraPLOT Q, CP-PoraBond Q, Supel-Q-PLOT, AT-Q RT-QS-BOND, GS-Q RT-S-BOND, CP-PoraPLOT S, Supel-G45 HP-PLOT U, RT-U-BOND, CPPoraPLOT U, CP-PoraBond U, Supel-N PLOT RT-Molsieve 5A, GS-Molsieve, HP PLOT Molsieve, CP-Molsieve 5A, AT-Molsieve, PLT-5A

BR-5HT BR-XLB BR-624ms

5% diphenyl; 95% dimethyl polysiloxane arylene/methyl modified polysiloxane 6% cyanopropyl phenyl; 94% dimethyl arylene siloxane 35% phenyl; 65% dimethyl arylene siloxane 50% diphenyl 50% dimethyl polysiloxane 50% phenyl; 50% dimethyl arylene siloxane Alumina Na2SO4 deactivated Divinylbenzene polymer

BR-35ms BR-17 BR-17ms BR-Alumina Na2SO4 BR-Q PLOT

BR-QS PLOT BR-S PLOT BR-U PLOT

Porous divinylbenzene polymer Divinylbenzene 4vinylpyridine Divinylbenzene ethylene glycol/dimethylacrylate Molecular Sieve 5A

BRMolsieve5A

Bruker Select columns for petrochemical and chemical analysis

Application Alcohols in gasoline Biodiesel GC column type BR-TCEP for alcohols in gasoline Biodiesel for Glycerides Biodiesel for FAME Biodiesel for Methanol Hydrocarbons Light hydrocarbons Squalane BR-Alumina / KCl BR-Alumina / Na2SO4 21 C1-C6 hydrocarbons Application area C1-C6 alcohols, aromatic C6C10 Glycerides acc. to ASTM D6584, EN-14105 FAME acc. to EN-14103 Methanol acc. to EN-14110

Liquid Hydrocarbons Simulated distillation

BR-DHA BR-1HT BR-500 Simdist Inert Steel BR-1 Simdist

Paraffins, aromatics, naphthenes & olefins C4-C12 C5-C100 SimDist C5-C120 SimDist C6-C44 (ASTM D2887)

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GC Packed Chromatography
A significant number of applications still use packed columns. The columns are robust and optimal for bulk composition analysis. The number of stationary phases and supports is immense. Bruker offers Inert Steel Micro-Packed and Packed Columns with the flexibility to define yourself the stationary phase, the coating % and support material.

Recommended Capillary Columns for ASTM Methods

Within ASTM methodology you have the possibility to use high resolution capillary columns to do your analysis. Below you will find a list of recommended capillary columns for each ASTM method.
ASTM D1945 Application Natural gas Recommended capillary column 10 m x 0.53 mm BRMolsieve 5A, df = 50 m 10 m x 0.53 mm BR-Q PLOT, df = 20 m D1946 Reformed gas 10 m x 0.53 mm BRMolsieve 5A, df = 50 m 10 m x 0.53 mm BR-Q PLOT, df = 20 m D1983 D2163 FAME (fatty acid methyl esters) Analysis Liquefied petroleum gases and propylene concentrations Oils and oil acids solvent-reducible paints in Aromatics in light naphthas and aviation gasolines Analysis of n-heptane and iso-octane (high purity) Xylene isomers Butadiene and styrene in butadiene concentrates C2-C5 hydrocarbons in gasolines Polyhydric alcohols in alkyd resins Non-condensable gases in C1-C3 50 m x 0.25 mm BR-2330, df = 0.2 m 50 m x 0.53 mm BR-Alumina / KCl, df = 10 m 50 m x 0.25 mm BR-2330, df = 0.2 m 50 m x 0.25 mm BR-TCEP, df = 0.4 m 50 m x 0.2 mm BR-DHA, df = 0.5 m 60 m x 0.25 mm BR-SWax, df = 0.5 m 30 m x 0.53 mm BR-1ms, df = 1.5 m 50 m x 0.53 mm BR-Alumina / KCl, df = 10 m 30 m x 0.53 mm BR-SWax, df = 1 m 30 m x 0.53 mm BRMolsieve 5A, df = 50 m P/N BR80279-107 BR80259-107 BR80279-107 BR80259-107 BR89274-105 BR80240

D2245

BR89274-105

D2267

BR89001-105

D2268

BR89853

D2306 D2426

BR89359 BR86630

D2427 D2456 D2504

BR80240 BR89345 BR80277

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hydrocarbons D2580 Phenols in water 30 m x 0.32 mm BR-5ms, df = 0.5 m 25 m x 0.53 mm BR-SWax acids, df = 1 m D2593 Butadiene purity and hydrocarbon impurity 50 m x 0.32 mm BR-Alumina / KCl, df = 5 m 50 m x 0.53 mm BR-Alumina / KCl, df = 10 m D2600 Aromatic traces in light saturated hydrocarbons 50 m x 0.25 mm BR-TCEP, df = 0.4 m 30 m x 0.32 mm BR-SWax, df = 1 m D2743 D2800 D2804 Oil and oil acids FAME analysis Purity of methyl ethyl ketone 50 m x 0.25 mm BR-2330, df = 0.2 m 50 m x 0.25 mm BR-2330, df = 0.2 m 30 m x 0.32 mm BR-SWax, df = 0.5 m 30 m x 0.53 mm BR-SWax, df = 1 m D2820 D2887 C1-C5 hydrocarbons in the atmosphere SimDist analysis of petroleum fractions 50 m x 0.32 mm BR-Alumina / KCl, df = 5 m 5 m x 0.53 mm BR-1HT, df = 0.88 m 10 m x 0.53 mm BR-ASTM 2887, df = 2.65 m >>>>> D2908 Extended SimDist Volatile organics in water 5 m x 0.53 mm BR-1HT, df = 0.2 m 30 m x 0.32 mm BR-624ms, df = 1.8 m 75 m x 0.53 mm BR-624, df = 3 m 30 m x 0.32 mm BR-SWax, df = 0.5 m 30 m x 0.53 mm BR-SWax, df = 1 m D2998 D2999 Polyhydric alcohols in alkyd resins Monopentaerythritol in commercial pentaerythritol Composition of turpentine 30 m x 0.32 mm BR-1ms, df = 1 m 30 m x 0.53 mm BR-1ms, df = 1.5 m 30 m x 0.32 mm BR-SWax, df = 0.5 m 30 m x 0.53 mm BR-SWax, df = 1 m BR86361 BR88945-106 BR80238 BR80240 BR89001-105

BR89346 BR89274-105 BR89274-105 BR89361 BR89345 BR80238 BR29869 BR29801 BR29885 BR86130 BR29026 BR89361 BR89345 BR86646 BR86630

D3009

BR89361 BR89345

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D3054 D3168

Purity and benzene content of cyclohexane Polymers in emulsion paints

100 m x 0.25 mm Squalane, df = 0.2 m 30 m x 0.32 mm BR-1ms, df = 1 m 30 m x 0.53 mm BR-1, df = 1.5 m

BR49995 BR86646 BR89830 BR80258 BR89345 BR86374 BR89816

D3271

Solvent analysis in paints

30 m x 0.53 mm BR-Q PLOT, df = 20 m 30 m x 0.53 mm BR-SWax, df = 1 m

D3304 D3328

PCBs in environmental materials Comparison of waterborne petroleum oils

60 m x 0.25 mm BR-5ms, df = 0.25 m 30 m x 0.32 mm BR-1, df = 3 m 30 m x 0.53 mm BR-1, df = 3 m

BR89815 BR89342 BR80256-106 BR80258 BR80257-107 BR80259-107 BR80280-107 BR80279-107 BR89846

D3329 D3371

Purity of methyl isobutyl ketone Nitriles in aqueous solutions

60 m x 0.53 mm BR-SWax, df = 1 m 25 m x 0.32 mm BR-Q PLOT, df = 10 m 30 m x 0.53 mm BR-Q PLOT, df = 20 m

D3416

Total hydrocarbons, methane and CO in air

10 m x 0.32 mm BR-Q PLOT, df = 10 m 10 m x 0.53 mm BR-Q PLOT, df = 20 m 10 m x 0.32 mm BRMolsieve 5A, df = 30 m 10 m x 0.53 mm BRMolsieve 5A, df = 50 m

D3432

Toluene Diisocyanates in Urethane PrePolymers

30 m x 0.32 mm BR-1, df = 1 m 30 m x 0.53 mm BR-1, df = 1.5 m

BR89830 BR89817-105

D3447

Purity of Trichlorotrifluoroethane (CFC-113) Identification of rubber FAME (fatty acid methyl esters) Analysis Purity of monomeric plasticizers

50 m x 0.53 mm BR-1, df = 5 m 30 m x 0.53 mm BR-1ms, df = 1 m 50 m x 0.25 mm BR-2330, df = 0.2 m 30 m x 0.32 mm BR-1ms, df = 0.5 m 30 m x 0.53 mm BR-1ms, df = 1.5 m

D3452 D3457 D3465

BR86645 BR89274-105 BR86661 BR86630 BR80256-106

D3476

Bis (chloromethyl)

25 m x 0.32 mm BR-Q

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Ether in air

PLOT, df = 10 m 30 m x 0.53 mm BR-Q PLOT, df = 20 m BR80258 BR86630 BR86630

D3524 D3525

Diesel fuel diluent in used diesel engine oils Gasoline diluent in used gasoline engine oils Alcohol content and purity of acetate esters Benzene and toluene in finished motor and aviation fuel

30 m x 0.53 mm BR-1ms, df = 1.5 m 30 m x 0.53 mm BR-1ms, df = 1.5 m 30 m x 0.53 mm BR-624ms, df = 3 m 50 m x 0.25 mm BR-TCEP, df = 0.4 m 15 m x 0.25 mm BR-1ms, df = 0.25 m

D3545 D3606

BR86129 BR89001-105

BR86680 BR86129 BR89345

D3687 D3695

Analysis of organic compound vapors Volatile alcohols in water by direct aqueous injection Boiling range distribution of gasoline and gasoline fractions Fatty acids in drying oils Vinyl Chloride in PVC

30 m x 0.53 mm BR-624ms, df = 3 m 30 m x 0.53 mm BR-SWax, df = 1 m 10 m x 0.53 mm BR-ASTM 2887, df = 2.65 m 30 m x 0.53 mm BR-SWax acids, df = 0.5 m 10 m x 0.32 mm BR-Q PLOT, df = 10 m 10 m x 0.53 mm BR-Q PLOT, df = 20 m

D3710

BR29801

D3725 D3749

BR88960 BR80257-107 BR80259-107 BR89373 BR80256-106 BR80258 BR89358 BR89358 BR29026

D3760 D3792

Analysis of cumene Water in water reducible paints

60 m x 0.32 mm BR-SWax, df = 0.25 m 25 m x 0.32 mm BR-Q PLOT, df = 10 m 30 m x 0.53 mm BR-Q PLOT, df = 20 m

D3797 D3798 D3871

Analysis of o-xylene Analysis of p-xylene Purgeable organic compounds in water using headspace Methoxyl and hydroxypropyl substitution in cellulose ether products

60 m x 0.32 mm BR-SWax, df = 0.5 m 60 m x 0.32 mm BR-SWax, df = 0.5 m 75 m x 0.53 mm BR-624, df = 3 m 30 m x 0.32 mm BR-1, df = 1 m

D3876

BR89846

30 m x 0.53 mm BR-1, df = 1.5 m

BR89830

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D3893

Purity of methyl amyl ketone and methyl isoamyl ketone Impurities in styrene Low-molecular weight halogenated hydrocarbons in water PCBs in insulating oil Butylated hydroxy toluene in ethylene and ethylene vinyl acetate polymers Acrylonitrile in styrene acrylonitrilecopolymers and nitrile rubber Benzene in hydrocarbon solvent

30 m x 0.53 mm BR-624ms, df = 3 m 25 m x 0.53 mm BR-SWax acids, df = 1 m 30 m x 0.53 mm BR-624ms, df = 3 m 60 m x 0.25 mm BR-5ms, df = 0.25 m 30 m x 0.32 mm BR-1, df = 3 m

BR86129

D3962 D3973

BR88945-106 BR86129

D4059 D4275

BR86374 BR89816

D4322

30 m x 0.53 mm BR-Q PLOT, df = 20 m

BR80258

D4367

15 m x 0.25 mm BR-1ms, df = 0.25 m 50 m x 0.25 mm BR-TCEP, df = 0.4 m

BR86680 BR89001-105 BR80254 BR89376 BR89895 BR89001-105 BR80245 BR86129

D4384 D4415 D4420

Acrylonitrile monomer (residual) Determination of dimer in acrylic acid Aromatics in gasoline

30 m x 0.53 mm BR-S PLOT, df = 20 m 30 m x 0.32 mm BR-SWax, df = 0.25 m 15 m x 0.25 mm BR-1, df = 0.1 m 50 m x 0.25 mm BR-TCEP, df = 0.4 m

D4424 D4443

Butylene Analysis Residual vinyl chloride monomer content in ppb range in vinylchloride homoand co-polymers by headspace Analysis of benzene Acetaldehyde contents of PET bottles

30 m x 0.53 mm BR-Alumina / Na2SO4, df = 10 m 30 m x 0.53 mm BR-624ms, df = 3 m

D4492 D4509

50 m x 0.25 mm BR-TCEP, df = 0.4 m 25 m x 0.32 mm BR-Q PLOT, df = 10 m 30 m x 0.53 mm BR-Q PLOT, df = 20 m

BR89001-105 BR80256-106 BR80258 BR89001-105 BR89345

D4534 D4735

Benzene content of cyclic products Determination of trace thiophene in refined benzene

50 m x 0.25 mm BR-TCEP, df = 0.4 m 30 m x 0.53 mm BR-SWax, df = 1 m

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D4768

Phenol and cresol inhibitors in insulating oils Test method for propylene glycol monomethyl ether, Dipropylene glycol monomethyl ether and Propylene glycol monomethyl ether acetate Determination of MTBE, ETBE, TAME, DIPE, tert-amyl alcohol and C1 to C4 alcohols Traces of methanol in propylene Impurities in high purity ethylbenzene Nicotine in indoor air Detailed analysis of petroleum naphthas through n-C9 Analysis of styrene Boiling point distribution of hydrocarbon solvents Sulfur compounds in natural gas and gaseous fuels by GC and SCD (sulfur chemiluminescence) Aromatics in Finished Gasoline

25 m x 0.53 mm BR-SWax acids, df = 1 m 30 m x 0.53 mm BR-5, df = 5 m

BR88945-106

D4773

BR89721

D4815

30 m x 0.53 mm BR-1, df = 5 m

BR89821

D4864 D5060 D5075 D5134

30 m x 0.53 mm BR-SWax, df = 1 m 60 m x 0.32 mm BR-SWax, df = 0.5 m 30 m x 0.32 mm BR-5ms, df = 1 m 50 m x 0.2 mm BR-DHA, df = 0.5 m 60 m x 0.32 mm BR-SWax, df = 0.5 m 10 m x 0.53 mm BR-ASTM 2887, df = 2.65 m 30 m x 0.32 mm BR-1, df = 0.4 m

BR89345 BR89358 BR86346 BR89853

D5135 D5399

BR89358 BR29801

D5504

BR99116

D5580

15 m x 0.25 mm BR-1ms, df = 0.25 m 50 m x 0.25 mm BR-TCEP, df = 0.4 m

BR86680 BR89001-105 BR29710

D6584

Biodiesel/glycerides analysis (includes preconnected 2 m x 0.53 mm retention gap Analysis of ethylene glycols and propylene glycols Assay of di-tert-bytyl peroxide Analysis of denatured ethanol

10 m x 0.32 mm BRBiodiesel, df = 0.1 m, with 2m x 0.53 mm guard column 30 m x 0.53 mm BR-624ms, df = 3 m 30 m x 0.53 mm BR-5, df = 5 m 60 m x 0.53 mm BR-SWax, df = 0.5 m 30 m x 0.53 mm BR-Q PLOT, df = 20 m 28

E202

BR86129

E475 E1100

BR89721 BR89357 BR80258

E1616 E1863

Analysis of acetic anhydride Analysis of acrylonitrile

50 m x 0.25 mm BR-1, df = 0.4 m 60 m x 0.32 mm BR-SWax, df = 0.5 m

BR45073 BR89358

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31

32

33

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Bruker GC Analysis Solutions

Bruker Standard Method Summary Table
Analyzer Type Standard Methods Natural Gas GPA 2177, GPA 2186, GPA 2261, GPA 2286, ASTM D1945, IP 345, ISO 6974 Refinery Gas ASTM D1945, ASTM D1946, ASTM D2597, UOP 539, DIN 51666 PIONA+ ASTM D1319, ASTM D4815, ASTM D5443, ASTM D6293, ASTM D6839, DIN 51448-1, DIN 51448-2, EN 14517, IP 382, UOP 870

Natural Gas Refinery Gas Light Naphtha Naphtha Heavy Naphtha Reformate FCC (Light) FCC (Middle) FCC (Heavy) Visbreaker Alkylate Gasoline Oxygenated Gasoline Jet Fuel Diesel Fuel Residual Fuel Oils Lubricants Crude Oil Greases Waxes

X X X X X X X X X X X X

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Analyzer Type Standard Methods

Detailed Hydrocarbon ASTM D5134, ASTM D6623, ASTM D6729, ASTM D6730, ASTM D6733, IP 344-88 (95), Fast DHA, DHA Front End

Oxygenates ASTM D4815, ASTM D7059, EN 13132, UOP 569, LOWOX, Gasohol

Simulated Distillation ASTM D2887 Extended D6417, ASTM D3710/D7096, ASTM D5307, ASTM D5442, ASTM D6352, ASTM D6417, ASTM D7096, ASTM D7169, ASTM D7213, ASTM D7500 (proposed), DIN 51435, DIN-51581 MOV, EN-15199-1 (2,3), IP 406, IP 480, IP 507, IP 545, ISO 3924

Natural Gas Refinery Gas Light Naphtha Naphtha Heavy Naphtha Reformate FCC (Light) FCC (Middle) FCC (Heavy) Visbreaker Alkylate Gasoline Oxygenated Gasoline Jet Fuel Diesel Fuel Residual Fuel Oils Lubricants Crude Oil Greases Waxes X X X X X X X X X X X X X X X X X X

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Bruker Standard Analyzers for Hydrocarbon Processing

Crude Oil and Distillates Simulated Distillation ASTM D2887 ASTM D2887 Extended ASTM D3710 ASTM D5307 ASTM D5442 ASTM D6352 ASTM D6417 ASTM D7096 DIN 51435 IP 406 IP 507 IP 545 ISO 3924 Fast Simulated Distillation ASTM D2887 Natural Gas ASTM D1945 GPA 2186 GPA 2261 GPA 2286 IP 345 ISO 6974 Hydrogen ASTM D2504 Trace Sulfur ASTM D5504 ASTM D6228 Gases Refinery Gas UOP 539 and 709 ASTM D1945 ASTM D1946 ASTM D2597 Rapid Refinery Gas UOP 539 and 709 ASTM D1945 ASTM D1946 ASTM D2597 Light Hydrocarbons ASTM D2502 ASTM D2712 ASTM D6159 Permanent Gases O2/N2 ASTM D2504 Hydrocarbon Group Characterization (PIONA+) ASTM D1319 ASTM D4815 ASTM D5443 ASTM D6293 ASTM D6839 DIN 51448-1 DIN 51448-2 EN 14517 IP 382 UOP 870 Simulated Distillation ASTM D3710 Oxygenates ASTM D4815 ASTM D7059 EN 13132 UOP 569 LOWOX Gasohol Aromatics ASTM D3606 ASTM D5580 EN 12177 CO/CO2 ASTM D2505 Naphtha and Gasoline Detailed Hydrocarbons ASTM D5134 ASTM D6729 ASTM D6730 ASTM D6733 IP 344-88 (95) FAST DHA

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Refinery Gas Analyzers

A Family of Optimized GC Analysis Solutions

The source and composition of refinery gases varies considerably. Measuring gas composition precisely and accurately is a significant challenge in todays refinery operations. Bruker refinery gas analyzers are designed to deliver superior, reliable results for a wide range of sources and analysis throughput requirements. Key Analyzer Capabilities: A complete range of refinery gas analysis (RGA) solutions. Bruker offers two RGA solutions to meet the broadest range of stream sample types and throughput requirements. A powerful, easy to use GC solution. Bruker 450-GC and CompassCDS Chromatography Software is a very powerful combination designed to achieve the best possible results. In addition, these powerful systems do not require a high degree of operator skill to be used. A highly flexible solution for analysis. All Bruker RGA solutions can be configured to analyze gas and pressurized liquids (LPG) through the use of a fully integrated Micro-Gasifier, giving the flexibility to accommodate a wide range of stream types. Operational procedures are fully documented.

All Bruker RGA analyzers not only incorporate proven GC hardware and software but also arrive pre-loaded with analysis methods and include documentation specific to the application required. A comprehensive, single vendor solution. Bruker provides complete solutions without the use of third parties. The hardware, software, application optimization, documentation, installation and performance verification are all provided by Bruker, offering an all-inclusive, convenient analysis solution.

Typical sources for refinery gases include atmospheric or FCC overheads, ethylene, propylene production, fuel gas, stack gas and off gas from desulfurization. The physical stream types range from gas to highly pressurized
41

gas or liquid. Bruker refinery gas analyzers (RGA) are turnkey systems preconfigured and tuned at the factory to conform to industry standard methods including: UOP 539, DIN-51666 and ASTM D2163. The RGA systems are based on the Bruker 450-GC. All analyzers employ a proven and optimized multi- channel approach to determine the concentration of individual saturated and unsaturated hydrocarbon components up to and including C5 (C6 and higher components as a composite peak) and all permanent gases, including hydrogen and hydrogen sulfide in a single analysis. Included in every system is Brukers powerful CompassCDS Software to provide complete analyzer control, data acquisition and flexible report generation. Since the micro-packed columns are installed in a separate heated zone, the capillary columns located in the GC oven can be temperature programmed in a more aggressive manner. This provides a substantial reduction in overall analysis time from up to 25 minutes to 5 minutes (or 7 minutes with H2S) for high sample analysis demand. However, because micro-packed columns have reduced sample capacity, streams containing a high concentration of some components (e.g. propylene steam) may require some hardware tuning by Bruker. Bruker offers three RGA systems to meet the widest range of analysis requirements: Standard RGA: A two channel 450-GC with a multi-valve design using both capillary and packed columns. The first channel is optimized for the analysis of permanent gases, the second is designed for light hydrocarbons, and the third specifically for hydrogen. The system is configured and fully tested in accordance with industry standard methods. Total analysis time for all components is less than 25 minutes. Rapid RGA: A three channel 450-GC that utilizes a multi-valve design in which the packed columns used in the Standard RGA have been replaced by micro-packed columns in both the hydrogen and permanent gas channels.

42

The separation of light hydrocarbons using the Standard RGA analyzer.

Analysis of the permanent gases using a Rapid RGA. (Refer to the Peak Identification key on page 45.)

43

The analysis of light hydrocarbons using the Rapid RGA. Note: Complete separation in less than five minutes.

Left photo shows a traditional RGA with all columns mounted in oven. Right photo shows the micro-packed columns mounted in the separate heated zone in the Rapid RGA.

44

Table 1. Bruker RGA Analyzer Characteristics

Analyzer Characteristics No. of Channels/Detectors used No. of Column Ovens Analysis Time Repeatability Linear Bench Space Required Minimum Component Detection Level Standard RGA 3 Rapid RGA 3

1 25 min. <1 % 66 cm / 26 in. 0.01% all components except H2S = 0.05% Excellent Excellent Excellent Good

2 5 min. (7 with H2S) <1 % 66 cm / 26 in. 0.01 % all components except H2S = 0.05 % Excellent Excellent Excellent Good

Suitability for following stream types: Typical Refinery Gas Impurities in Bulk Ethylene Impurities in Bulk Propylene Impurities in Bulk C4

Multiple channels of data are conveniently combined into a single analysis report.
Peak No. 1 2 3 4 5 6 7 8 9 10 Peak Name CO2 C2H4 C2H6 C2H2 O2 N2 CH4 CO H2 C5+ Channel Front (TCD) Front (TCD) Front (TCD) Front (TCD) Front (TCD) Front (TCD) Front (TCD) Front (TCD) Middle (TCD) Rear (FID) RT (min.) 2.6000 2.9550 3.5367 5.0283 9.9200 10.3267 11.1917 0.0000 1.6967 2.9217 Result (g/l) 0.1000 29.9800 17.9900 0.5020 0.0000 1.1990 11.9900 0.0000 36.0300 0.1000 Norm. (%) 0.0632 18.9449 11.3682 0.3172 0.0000 0.7577 7.5767 0.0000 22.7681 0.0632 Area (V/Sec) 13376 4139442 2867688 49786 37325 2122071 1394584 0 390257 58164

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11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

Methane Ethane Ethylene Propane Propylene i-Butane n-Butane Propadiene Aceylene t-2-Butene 1-Butene i-Butene cis-2-Butene 1,3Butadiene Methyl actylene Totals

Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID) Rear (FID)

3.7350 4.1283 4.7217 6.1933 0.0000 0.0000 0.0000 0.0000 0.0000 18.5050 0.0000 19.5167 0.0000 22.1367 0.0000

11.9900 17.9900 29.9800 0.1990 0.0000 0.0000 0.0000 0.0000 0.0000 0.0990 0.0000 0.0990 0.0000 0.0000 0.0000 158.2480

7.5767 11.3682 18.9449 0.1258 0.0000 0.0000 0.0000 0.0000 0.0000 0.0626 0.0000 0.0626 0.0000 0.0000 0.0000 100.0000

1492388 4480322 7411134 71402 0 0 0 0 0 138647 0 44492 0 16165 0 22817242

Simulated Distillation

A Full Range of Simulated Distillation Solutions

Brukers range of Simulated Distillation Analyzers provide boiling point distribution up to 750 C. Designed to meet all industry standard methods, Brukers analyzer software includes both ASTM D86 and ASTM D1160 correlations.

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A gas chromatographic (GC) technique, Simulated Distillation (SimDist) reproduces the physical distillation of petroleum materials and products by determining boiling point distribution. Used for controlling refinery operations, Brukers range of SimDist analyzers delivers fast, accurate standard test method results. The Bruker highly automated 450-GC, CompassCDS software, and integrated SimDist software are designed to meet worldwide industry standard test methods. Key Benefits: Accurate boiling point distribution up to 750 C. The Bruker SimDist Analyzer range tests a variety of distillates, blends, fuels, residues and crude oil, ranging from carbon number C1 to C120 and higher. This enables refinery processes to be monitored and controls product quality with fast, accurate boiling points versus mass distributions up to 750 C. Integrated standard test methods. Bruker, Inc. offers SimDist analyzers with built-in applications to help monitor refinery processes and control product quality. These applications fully comply with ASTM, IP, DIN and ISO standard test methods used globally. New methods will be added to Bruker SimDist software as they are approved and released. Complete, single vendor solution. Brukers single vendor approach includes the latest hardware, software and column technologies. Our solutions maximize uptime and increase the speed of data generation. Complete control from initial setup to final report. The SimDist analyzers are controlled by Brukers advanced CompassCDS Data Handling Software package. The SimDist software is fully integrated into CompassCDS for system operation, automation, calibration and report generation. ASTM D86 and ASTM D1160 correlation. SimDist software includes both ASTM D86 and ASTM D1160 correlations. Dedicated to a sample type, these correlations are crude independent. With the fully automated Bruker SimDist Analyzer, data is generated rapidly and with increased precision, making ASTM D86 and ASTM D1160 correlations faster and easier.

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Operational Simplicity for All SimDist Methods

Bruker CompassCDS Software has pre-programmed settings which streamline instrument setup, analysis and reporting to ensure outstanding data precision and reproducibility. Once the preferred industry standard method is selected, Bruker SimDist software automatically corrects any offset to the baseline signal and removes the blank analysis to provide a corrected net area and precise boiling point data. In addition, users may choose to modify individual settings to suit their specific requirements.

Easy-to-use Industry standard test methods are fully integrated into Brukers SimDist software

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ASTM D86 and ASTM D1160 Correlation Editor As the composition of raw materials and intermediates changes, the ability to modify the ASTM D86 or ASTM D1160 variables to improve correlation results is required. The Correlation Editor also allows new correlation data at the 40 %, 60 % and 95 % cut-off points to be generated for additional information between the two methods.

ASTM D86 and ASTM D1160 Correlation Editor to customize and add correlation data

Built-in Reports
Bruker SimDist software provides a wide variety of report options to meet specific lab requirements including: Chromatogram with merged corrected blank analysis and IBP/FBP marks versus retention time. Table with boiling point versus percentage of sample. Table and plot with retention time versus boiling point. Table with D86 and D1160 correlations. DIN Noak and motor oil volatility reports. Table with cutpoints and fractions. Residue analysis with recovery calculation up to C120.

Simplified, Accurate Analysis

To obtain accurate results: Run a blank to obtain an accurate baseline signal. Run a standard configuration to obtain retention time versus boiling point calibration. Run the reference sample to validate system performance and to determine the response factor. Analyze samples.
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The integrated CompassCDS SimDist software

SimDist Analyzer Specifications

Hardware Gas Chromatograph: Bruker 450-GC (single or dual channel). Injector: temperature controlled cool on-column injector (1093 COC) for capillary columns with full Electronic Flow Control (EFC). Column oven: with CO2 sub ambient cooling. Detector: FID with EFC control. Computer: with monitor. Autosampler: CP-8400 or CP-8410 autosampler with carousel heating and cooling plate. Bruker CompassCDS system control, data acquisition and report generation software. Bruker CompassCDS SimDist application software (fully integrated).

Software

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Diesel fuel analysis with fast 2887 SimDist method reduces analysis time by a factor of five compared to ASTM D2887 (6 rather than 30 minutes).

Bruker SimDist Analyzer Configurations Applicability

Seven standard configurations are available for the test methods listed in Table 1. Optional mode kits are also available to facilitate the change from one standard configuration to another. Each mode kit contains all the necessary components, including column and standard samples for a given configuration.
Configuration 1 2 3 4 5 6 7 Method ASTM D3710, ASTM D5399 ASTM D5399 ASTM D2887, ISO 3924, IP 406 Fast ASTM D2887 Extended ASTM D2887, DIN 51.435 ASTM D6352, IP 480, IP 507, IP MP CF ASTM D5307 Sample Type Gasoline Solvents Petroleum Fractions Petroleum Fractions Petroleum Fractions Petroleum distillates, residuals, crude oil Crude petroleum

ASTM D2887, D2887 Extended, ASTM D3710, ASTM D5307, ASTM D5442, ASTM D6352, ASTM D7096, ASTM D7169, ASTM D7213, ASTM D7500 (proposed), ASTM D6417, DIN 51435, DIN-51581 MOV, EN-15199-1 (2,3), IP 406, IP 480, IP 489, IP 507, IP 545, IP PM CF/98, ISO 545 and ISO 3924

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Detailed Hydrocarbon Analysis (DHA)

Optimized Solutions for Detailed Hydrocarbon Analysis

The Bruker DHA Analyzer is a complete high resolution gas chromatography solution for the analysis of hydrocarbons in petroleum streams. It is capable of performing all of the standard methods including the analysis of light petroleum streams and crude oil light end. Key Benefits: Compliant with all industry standard methods. Be confident using Bruker DHA Analyzers, which are configured in accordance with all the established standard methods including ASTM D6729, D6730, D6733, D5134, D6623, IP 344/DHA Front End and Fast DHA. Complete and fully integrated solution. Bruker DHA Analyzers come complete with everything you need to be up and running quickly. Powerful and easy-to-use analyzer. With relatively little training, operators can generate outstanding analysis results day after day. Save time. Easily generate reports with a few mouse clicks and reduce analysis time using Fast DHA, increasing laboratory productivity. Single vendor solution. Bruker GC analyzers are built and tested at the Bruker factory, as well as installed and performance-verified on-site by Bruker trained and certified engineers. Rest assured that our analyzers can meet or exceed your needs throughout the lifetime of the instrument.

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Detailed hydrocarbon analysis is often the preferred technique to fully characterize petroleum streams. The technique is based on the identification of individual components using high performance, high resolution capillary gas chromatography. Software Ensures Accurate Identification To successfully apply gas chromatography to detailed hydrocarbon analysis (DHA), the analyzer must be able to correctly identify a large number of component peaks (many eluting very closely to one another) in a complex chromatogram. The identification is based on a comparison of their individual retention index values to those in a pre-established database. Therefore, it is extremely important that the analyzer functions in a highly repeatable manner. As the concentration of some of the individual components can vary considerably from stream to stream, the retention times for those peaks can shift slightly. This shift can lead to component misidentification, particularly with peaks that elute extremely closely together or those that may partially co-elute.

Detailed hydrocarbon analysis of a reformate sample.

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Selecting Individual Peaks and Updating the Database CompassCDS DHA includes a Peak Select and Database Update function to make identification of unknown peaks as straightforward as possible. The system automatically provides the operator with detailed comparative retention index information for each unknown peak including a highlighted best fit indicator, making it easy for the operator to determine the ID.

CompassCDS provides an easy-to-use graphical means to select peaks and update the database. Integrated Standard Test Methods Bruker DHA Analyzers are compliant with the following methods: - ASTM D6623 - ASTM D6729 - ASTM D6730 - Fast DHA - ASTM D6733 - IP 344 Front end - ASTM D5134 Although each DHA analyzer is configured, tested and certified at the factory for a standard method specified by the customer, CompassCDS DHA software permits the operator to utilize any of the other popular standard methods as well. And, because of the outstanding performance and flexibility of the 450-GC and CompassCDS software design, Bruker is able to quickly modify the existing methods or add new ones if required as a result of the on-going dynamic industry standard processes.

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Powerful reporting built into Bruker DHA software includes several report options to accommodate the standard methods and/or to meet the customers special needs. These include: Carbon number distribution PIONA report; (weight and volume percentage by hydrocarbon group) Physical properties calculations; specific gravity and molecular weight True distillation profile RON/MON specification

Choosing report options is simple. DHA Analyzer Includes These Key Components: Bruker 450-GC high performance gas chromatograph equipped with: - Split/splitless capillary injection port - High performance capillary column (dependent on specified method on order) - Flame ionization detector (FID) - Full electronic flow control (EFC) of all gases CP-8400 or CP-8410 automatic liquid sampler CompassCDS Software for system control, data acquisition and report generation CompassCDS DHA application software Computer/monitor Pre-loaded standard methods Factory test Reference chromatogram Reference standard for use in conducting on-site performance verification

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Detailed hydrocarbon report.

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Reduce Sample Analysis Time with Fast DHA These chromatograms illustrate the decreased analysis time using theFast DHAmethod.

Chromatogram of a naphtha sample run on a 40 m x 0.10 mm x 0.2 m film non-polar column using theFast DHAmethod (above).

Chromatogram of the same sample, but run on a 100 m x 0.25 mm ID x 0.5 m film non-polar column using standard method D6729 (under). Note reduced analysis time from ~80 minutes to ~20 minutes; almost four-fold.

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Hydrocarbon Analysis by Group (PIONA+)

Characterization of Engine Fuels by Hydrocarbon Group Type

Brukers innovative PIONA+ Analyzer provides a highly flexible GC analysis platform to obtain comprehensive characterization and quantitative information, including hydrocarbon group types, oxygenates and carbon number distribution for spark emission fuels.

Key Analyzer Capabilities: Unparalleled operational flexibility. The inherent flexibility of the analyzer design allows the operator to conduct analyses in any one of a number of different operational modes including PNA, PONA, PIONA, O-PONA and O-PIONA. Compliant with industry standard methods. Due to the outstanding operational flexibility of the analyzer, it can be utilized for any of the following established standard methods: ASTM D6839, ASTM D6293, ASTM D5443, ASTM D1319, IP-382, IP-526, EN 14157, UOP 870 and DIN-51448. A complete and fully integrated solution. Bruker PIONA+ Analyzer is based on the powerful 450-GC gas chromatograph and comes complete with ultra high performance columns and traps, CompassCDS chromatography software, dedicated PIONA+ data analysis and report generation software, factory test/certification, calibration/reference standards, PIONA+ manual and on-site installation/performance verification. A single vendor solution. All Bruker GC analyzers are built and tested at our factory using all Bruker components. On-site installation and performance verification is then performed by Bruker trained and certified engineers. A powerful analyzer yet very easy to use. Brukers high performance 450-GC, ultra-stable columns and traps and powerful CompassCDS chromatography software with built-in PIONA+ software all contribute to the analyzers ability to generate outstanding analysis results day after day. However, a powerful system does not necessarily have to mean that only highly skilled operators are able to use it.

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PIONA is the preferred technique today to characterize petroleum streams by hydrocarbon group type. The technique is based on the separation of individual hydrocarbon groups by utilizing a complex yet fully automated multi-dimensional gas chromatography approach. Analysis Challenge Since the first description of PNA (hydrocarbon type) group analysis in the 1980s, the multi-dimensional gas chromatography based technique has gone through continuous improvement and change. Although the technique has evolved and is now commonly used to obtain hydrocarbon group-type information for paraffins, iso-paraffins, naphthenes, olefins, aromatics and oxygenated components (see Tables 1a & 1b) by refinery laboratories worldwide, the basic chromatographic selectivity required to do so has remained fundamentally unchanged. From a gas chromatography hardware standpoint, several different approaches have been used in the past, but the exchange of columns and traps within the multi-dimensional system has always been the most problematic aspect of the analysis. Recent developments in thermal management techniques and mechanical interconnection devices by Bruker have enabled the development of a new class of hydrocarbon group analyzer based on the 450-GC. The analyzer is not only fully capable of performing a complete analysis as described in ASTM D6839 (and similar methods) but provides unprecedented analysis flexibility and simplified operation through the use of a novel approach to column/trap heating and exchange (see Figure 1).

Traps are easily accessible and do not require any tools to install or replace.

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Table 1a: Example of a Mass% Report.

Group Carbon Number 1 2 3 4 5 6 7 8 9 10 Total BP>185 C Oxygenates MTBE Total Oxygen 7.24 1.32 Paraffins 0.00 0.00 0.03 0.91 16.84 9.85 7.14 6.94 1.17 0.28 43.16 1.01 O-content 1.32 0.00 0.00 0.43 2.18 3.59 0.49 0.15 0.03 6.87 0.00 0.00 0.09 0.46 1.09 0.66 0.67 0.17 0.00 3.14 0.00 0.00 0.15 0.24 0.30 0.13 0.10 0.00 0.92 0.84 6.37 15.45 11.26 3.74 37.66 Naphthenes Olefins Cyclic Olefins Aromatics

Table 1b: Example of Volume% Report.

Group Carbon Number 1 2 3 4 5 6 7 8 9 10 Total BP>185 C Oxygenates MTBE 7.24 Paraffins 0.00 0.00 0.05 1.17 20.00 11.07 7.72 7.30 1.20 0.29 48.80 0.89 0.00 0.00 0.43 2.13 3.51 0.47 0.14 0.02 6.70 0.00 0.00 0.11 0.52 1.19 0.69 0.69 0.17 0.00 3.37 0.00 0.00 0.17 0.26 0.32 0.14 0.10 0.00 0.99 0.70 5.44 13.19 9.55 3.12 32.00 Naphthenes Olefins Cyclic Olefins Aromatics

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Reduced Analysis Time and Increased Sample Throughput Efficiency through the Use of Concurrent Heating A unique aspect of the design of the Bruker 450 PIONA+ system is the ability to independently heat the individual traps. As shown in Figure 2, when the PIONA+ system is operated in the normal mode, a total analysis time of 180 minutes is required to elute all of the component groups. However, as shown in Figure 3, a reduction in total analysis time from 180 minutes to 95 minutes can be obtained. Such a reduction in analysis time is achieved by carefully optimizing the temperature settings of the various traps and columns, and independently heating the Molsieve traps. This is referred to as concurrent heating. This approach enables a fast PIONA mode, which results in the elution of the paraffins immediately after their naphthene and iso-paraffin counterparts. However, the elution integrity of the component groups remains intact with no negative influence on either naphthene or iso-paraffin groups, (see Figure 3 inset for a close up view of the resulting elution sequence). By employing this technique, sample throughput can be nearly doubled compared to systems that do not offer this unique capability.

Figure 2. Chromatogram of a calibration mix in conventional PIONA+ mode.

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Figure 3. Chromatogram of a calibration mix using concurrent heating in fast PIONA+ mode.
PNA EN 14517 ASTM D6839 ASTM D6293 DIN 5148-2 ASTM D1319 (FIA) DIN 5148-1 ASTM D5443 UOP 870 IP 382 x = X X X X Compliant with Method X X X X X x X X X X X X = X X X X X X X X Reports PONA PIONA O-PONA O-PIONA X X X X X X X X X

Determining Total Olefin Content is Now Practical The stability, sample loading and lifetime for all of the critical chromatographic components have been improved and thoroughly optimized in the Bruker 450 PIONA+ Analyzer. However, the most noteworthy improvement has been increasing the sample loading capacity of the olefin trap. As a result, it is now possible to analyze streams with olefin content as high as 35-40 % or more. This makes it quite practical to employ a single analytical method to obtain total olefin content (see example report in Table 2).

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The Bruker 450-GC PIONA+ Analyzer includes: Bruker 450-GC high performance gas chromatograph equipped with: o o o o o o Flash direct injection port (1061 flash) Bruker high performance capillary column(s) (dependent on method specified at the time of order) PIONA+ column/trap/valve cabinet Flame ionization detector (FID) Full electronic flow control (EFC) of all gases CP-8400 or CP-8410 automatic liquid sampler

CompassCDS chromatography software for system control, data acquisition and report generation CompassCDS PIONA+ application software Computer/monitor Pre-loaded standard methods Factory test Reference chromatogram Reference standard for use in conducting onsite performance verification

Table 2. Example weight % report for a gasoline sample with very high olefinic content; in this case 46 % (highlighted in red).
Saturates Carbon 3 4 5 6 7 8 9 10 11 Total Cyclic 0.00 0.00 0.31 3.17 4.31 1.42 0.01 0.01 0.00 9.23 Iso 0.00 0.00 11.33 9.95 6.77 3.12 0.00 0.00 0.00 31.17 Normal 0.00 0.06 2.98 1.40 0.00 0.00 0.00 0.00 0.00 4.43 Unsaturates Cyclic 0.00 0.00 0.87 2.40 2.14 0.39 0.04 0.09 0.00 5.93 Iso 0.00 0.03 9.91 8.58 4.76 2.06 0.02 0.00 0.00 25.36 Normal 0.00 0.54 7.57 4.40 1.91 0.00 0.00 0.03 0.00 14.46 Aromatics 0.00 0.00 0.00 1.72 7.46 0.07 0.03 0.01 0.00 9.29 Oxygenates 0.00 0.00 0.03 0.04 0.00 0.00 0.00 0.00 0.00 0.07 Total 0.00 0.64 32.99 31.67 27.35 7.05 0.10 0.13 0.00 99.93

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Oxygenates
Gasoline - ASTM D4815
The Bruker ASTM D4815 GC Analyzer provides a highly cost effective solution for the analysis of oxygenates in gasoline, according to the widely used industry standard method ASTM D4815. The combination of Brukers extremely reliable GC hardware, powerful software and industry leading pre- and post-sales support teams make this analyzer package the most comprehensive solution available today.

Key Benefits: Optimized for analysis of oxygenated compounds in gasoline by ASTM D4815. The system is configured and fully tested at the factory to ensure data provided is in compliance with the requirements of the standard method. Bruker will install the system and check its performance in the laboratory. An easy to use, sophisticated solution. Bruker 450-GC and CompassCDS Chromatography Software are a powerful combination and key to generating reliable results. The Bruker ASTM Analyzer yields excellent results, regardless of the operators skill level. An efficient, cost-effective and time-saving solution. All Bruker GC analyzers not only include proven GC hardware and software but are also pre- loaded with analysis methods and documentation specific to the method required. Operational procedures are fully documented. Complete, comprehensive single vendor solution. Bruker provides complete solutions without relying on third parties. The hardware, software, application optimization, documentation, installation and support services are all supplied by Bruker. This solution allows analyses to be carried out quickly and efficiently, delivers effective troubleshooting and gives peace of mind from one complete, dependable, professional supplier.

Oxygenated compounds can be present in various hydrocarbon matrices either because they were purposely added (e.g., gasoline) or because they are naturally present or formed during catalytic processes, such as polymer production. In gasoline, oxygenated compounds are added as anti-knock agents to increase the octane number and decrease emissions by replacing organo-lead compounds.

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The type and concentration of oxygenated compounds must be measured in reformulated gasolines as part of ongoing product quality assessment, and to confirm the oxygenated components have been added in the correct amounts according to regulatory requirements (e.g. California Air Resources Board). ASTM D4815 is frequently chosen as the standard method for the determination of oxygenated compounds. Individual ethers and alcohols are quantified in gasoline including: MTBE, ETBE, TAME, DIPE, C1-C4 alcohol and tert-amyl alcohol. Individual ether components are measured from 0.1 to 20.0 mass %. The individual alcohols are measured from 0.1 to 12.0 mass %. The analysis works as follows: The sample is introduced to the system via the split/ splitless capillary inlet, vaporized and transferred to the first column (TCEP; micro-packed) where the lower boiling/non-polar components are separated from higher boiling/polar components. The lower boiling components (those eluting prior to methyl-cyclopentane) are then flushed to the vent. At a pre-determined time, the valve is switched and the higher boiling/polar components retained on the first column are back-flushed onto the second (capillary) column (non-polar) which is placed in the analysis path. The components of interest are then eluted by the second column and separated based on individual boiling point and detected via the flame ionization detector (FID).

Once benzene and TAME have fully eluted, the second column is back-flushed and the remaining components are vented. Electronic flow control is used to increase the column pressure to accelerate elution of the remaining components as a composite peak, helping to reduce the overall sample analysis time.

4815 - Typical Chromatogram Calibration is performed using several concentrations of a multi-component standard mixture with varying measured amounts of each of the oxygenated compound. DME (1,2-dimethoxyethane) is added to each of the calibration mixtures as an internal standard. The system automatically generates a calibration curve for each analyte and computes linearity data. The samples are
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analyzed, each of the oxygenates are automatically quantified and a results report is printed at the end of each analysis cycle. Reference: ASTM D4815, Standard Test Method for the Determination of MTBE, ETBE, TAME, DIPE, tertiary- Amyl Alcohol and C1 to C3 Alcohols in Gasoline by Gas Chromatography; American Society for Testing and Materials, Philadelphia, PA.

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Typical repeatability for analysis of 15 consecutive samples. Total mass % oxygen report generated using Bruker CompassCDS custom calculation and reporting function.
Peak Area Counts per Target Analyte Analysis Run Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Mean Area Count Std. Dev. RSD (%) ETBE 1091607 1092548 1089694 1075404 1094391 1082492 1081258 1086955 1078448 1078209 1097805 1095479 1074047 1070283 1074517 1084209 8971 0.83 MTBE 1055853 1056604 1053480 1040368 1057769 1047466 1046027 1051162 1043422 1043115 1058447 1058130 1039164 1035161 1035223 1048092 8435 0.80 DIPE 1006944 1006333 1003985 989958 1008441 994728 995978 1001150 992506 992645 1011330 1009374 989716 984098 988866 998403 8833 0.88 TAME 2723971 2729622 2722182 2689793 2737793 2710139 2706787 2721315 2701805 2703248 2745709 2741334 2691657 2677596 2695103 2713203 20479 0.75 Methanol 2314775 2314607 2311682 2288325 2327095 2302127 2306457 2321677 2302820 2310069 2361642 2344727 2292032 2294149 2292921 2312340 20227 0.87 Ethanol 4502637 4508744 4504657 4457518 4521321 4488649 4489523 4505866 4485725 4485939 4548321 4540612 4450770 4452828 4452076 4493012 30748 0.68

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The ASTM D 4815 Analyzer utilizes the Bruker 450-GC System

CompassCDS Hydrocarbon Report ASTM D4815 System: 103241 User: Acquired: 21/9/2006 09:08:36 Processed: 10/10/2007 09:54:31 Printed: 10/10/2007 09:57:49 Method: 103241_astm4815 Operator 1 Sample Description: N/A Chromatogram: 141_channel1 103241_astm4815_21-9-2006 9_07_01_

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Peak Report
Index 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Total Time (Min) 2.88 3.39 3.91 4.40 5.02 5.65 6.24 6.72 7.22 7.46 7.87 8.38 8.93 9.25 10.36 Name Methanol Ethanol Isopropanol tert-Butanol n-Propanol MTBE Sec-Butanol DIPE i-Butanol ETBE tert-Pentano DME n-Butanol Benzene TAME Area (V/Sec) 13281183.2 21207159.1 23693528.8 33903279.7 28492571.8 15176064.0 29684299.4 16193644.0 33914281.2 16477060.7 36553240.2 2192221.0 31759056.6 32670524.5 31550613.7 376748727.8 Quantity (g/L) 7.30 7.30 7.30 7.20 7.30 4.00 7.30 4.00 7.30 3.90 7.20 5.99 7.29 5.00 7.30 95.67 Volume (%) 7.76 7.79 7.83 7.70 7.65 4.54 7.62 4.65 7.67 4.43 7.46 5.82 7.59 3.53 7.97 100.00

Total mass % oxygen report generated using Bruker CompassCDS custom calculation and reporting function.

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Gasoline - Alcohol and Ethers (Gasohol)

Bruker offers a range of GC analyzers to measure oxygenates in various hydrocarbon streams. The Bruker Gasohol Analyzer provides refineries with the ability to optimize gasoline production by measuring alcohol and ether content more rapidly and with increased confidence. Key Benefits: The ideal choice for the analysis of oxygenated additives in gasoline. The Bruker Gasohol Analyzer is a turnkey solution for the analysis of oxygenated additives in gasoline. All operational parameters including gas flows are tuned and set at the factory and the system is shipped with the actual method. The analyzer is suited to the analysis of ethers and alcohols in gasolines and light naphtha. A comprehensive, single vendor solution. Bruker provides complete solutions without the use of third parties. The hardware, software, application optimization, documentation, installation and performance verification are all provided by Bruker, offering an all-inclusive and convenient analysis solution. Based on outstanding hardware, software and column technology. The Gasohol Analyzer incorporates Brukers popular 450-GC, CompassCDS chromatography software and its advanced capillary column technology in a system that is very powerful but extremely easy to use. Dual mode operation. Brukers Gasohol Analyzer has two modes of operation. The wide range mode measures ethers (MTBE, TAME) and all C1 to C4 alcohols with BP up to 100 C and is most suitable for gasoline with low olefinic content. The MTBE mode is more suitable for highly olefinic gasoline with optimized separation of MTBE and low boiling oxygenates. Unrivalled repeatability and retention times. By using either the CP-8400 or CP-8410 automatic liquid samplers, not only is a high degree of run-torun repeatability obtained but also high sample analysis throughput to keep up with the demands placed on todays refinery laboratory.

Figure 1 depicts a separation of alcohols and ethers in high olefinic gasoline. By operating the Gasohol Analyzer in wide range mode, the ethers (MTBE, TAME) and all C1-C4 alcohols are determined. However, when using the MTBE mode, MTBE and lower boiling point oxygenates (with the exception of TAME and 1butanol) can be determined. Specifications:
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Analysis Time: Up to 20 minutes. Minimum Detectability: Typically 100 ppm per component. Dynamic Range: >104. Please note, due to the possibility of column overload, the maximum concentration for individual oxygenated components is limited to 30 %. For critical separations at extremely high levels, some loss in peak resolution can be expected. Accuracy: The methods either use external or internal standard calibration. Internal standard is recommended (1,4 dioxane or MEK may be used as internal standard). Therefore, analytical accuracy is related to the accuracy and quality of the calibration standard sample and the repeatability of the analyzer. Repeatability: Retention time repeatability is typically better than 0.03 mins. RSD (using an automatic liquid sampler) and peak area count repeatability typically 2 % RSD or better at 1 % concentration level. Hardware Configuration: Single channel, multi-dimensional, capillary column configuration, based on the 450-GC chromatograph Injector: split/splitless capillary injector Detection: Flame Ionization Detector (FID) Full Electronic Flow Control (EFC) CP-8400 or CP-8410 Autosampler (highly recommended)

Figure 1. Separation of alcohols and ethers in high olefinic gasoline.

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Low Level Oxygenates (Lowox)

The determination of sub to high ppm levels of ethers, alcohols, aldehydes and ketones in different hydrocarbon matrices is a recurring challenge in the petroleum refining and petrochemical industry. The Bruker Low Level Oxygenates Analyzer is an easy to use turnkey solution to meet this analysis challenge. The Lowox analyzers conform to ASTM D7423: Determination of Oxygenates in C2, C3, C4, and C5 Hydrocarbon Matrices. Key Benefits: Factory optimized to ensure excellent analysis results. The system is configured, optimized and tested at the factory to analyze oxygenated components at concentrations as low as 100 ppb in streams with a final boiling point of up to 250 C and no interference from the hydrocarbon matrix. An optimized system for the analysis of oxygenates at trace level. A powerful GC solution, yet extremely easy to operate. The 450-GC and CompassCDS Chromatography Software from Bruker, is a very powerful combination and is key to the systems ability to generate reliable results. The system can be used successfully without a high level of operator skill. A flexible, economical analysis solution. The analysis system is configured to accommodate gas, liquid and liquefied petroleum gas (LPG) streams. With both a gas and a liquid sampling valve, both substances can be analyzed by any hardware reconfiguration. A cost effective, time-saving solution. All Bruker GC analyzers not only include proven GC hardware and software but are also pre-loaded with analysis methods and documentation specific to the method required. All operational procedures are fully documented. A comprehensive, single vendor solution. Bruker is the only GC supplier to provide complete solutions without relying on third parties. The hardware, software, application optimization, documentation, installation and support services are all provided by Bruker, allowing analysis to be carried out quickly and efficiently by one dependable supplier.

Oxygenated compounds can be present in hydrocarbon streams for a variety of reasons. For example, methanol is added to crude oil to reduce the formation of hydrates during transportation and storage. Unfortunately, the presence of methanol in downstream operations is highly problematic. Clean-up processes like hydro-treating are used in an attempt to remove oxygenated compounds. However, even at trace levels (sub ppm), oxygenates quickly degrade or destroy expensive process catalysts (e.g. polymer production).
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Analyzer Overview The Bruker Low Level Oxygenates Analyzer is designed and optimized to quantify ppm and sub ppm levels of ethers (e.g. DME, MTBE, ETBE, DIPE), alcohols (e.g. methanol, ethanol, propanol), ketones (e.g. acetone, MEK) and aldehydes in various hydrocarbon matrices. In general, all oxygenated components with a boiling point of up to 100 C can be analyzed. The sample can be a gas, LPG, or liquid under ambient conditions with a final boiling point up to 250 C. The system comprises a Bruker 450-GC configured with gas and liquid sampling valves, two high performance capillary analysis columns, digitally controlled pneumatics including a fluidic switch and Flame Ionization Detector (FID). An optional pressure station can be added to eliminate the possibility of losing sample due to evaporation when analyzing LPG. The 450-GC is controlled via the CompassCDSTM Chromatography Software from Bruker, which acquires data, processes it and generates analyses reports. The gas or liquid sample is injected via a gas or liquid sampling valve onto the first of two columns (non-polar and Lowox). A fluidic switch is positioned between the two columns. The lighter fraction (containing the oxygenates) is separated from the rest of the stream components on the non-polar column. The heavier components are then back-flushed to vent. The fraction containing the lighter components is transferred onto the second column (Lowox) using the fluidic switch. The Lowox column is used to separate the individual oxygenated components from the bulk hydrocarbons. Due to its high selectivity, large amounts of sample can be introduced onto the Lowox column which, through the use of the sensitive FID, enables the system to achieve the required low detection levels for oxygenated compounds. The analyzer includes both gas and liquid samples for maximum flexibility. Calibration is performed using several concentrations of a multi-component standard mixture with varying known/measured amounts of each oxygenated compound. The system automatically generates a calibration curve for each analyte. The samples are analyzed, each of the oxygenates are automatically quantified and a report of the results is printed at the end of each analysis cycle. Typical performance results are depicted in the following tables.

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A typical chromatogram showing a wide range analysis of a liquid sample stream Peak Idenfication
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Diethylether Acetaldehyde Ethyl tert. Butyl ether Methyl pert. Butyl ether Diisopropylether Propanal Tert. amyl methyl ether Propylether Isobutyraldehyde Butyraldehyde 19. 11. 12. 13. 14. 15. 16. 17. 18. Methanol Acetone Isovaleraldehyde Valeraldehyde 2-Butanone Ethanol 1-Propanol Tert. butanol 2-Methyl 1-propa 1-Butanol

A typical chromatogram showing an MTBE range analysis of a gas stream

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Typical repeatability in the analysis of oxygenates in a gas stream.

Run Run Run Run Run Run Run Run Run Run N Mean Std. RSD ETBE 579554 578838 585890 579313 578500 577796 579844 580253 580592 578693 10 579927 2142.60 0.37 MTBE 490771 491908 481217 491673 492449 493989 490743 487207 484805 487272 10 489203 3775.30 0.77 Methanol 59388 59310 60135 59663 59897 59766 59879 59800 59856 59946 10 59764 238.60 0.40 Acetone 224339 224407 225063 224583 224743 224583 224593 224570 224539 224530 10 224595 187.10 0.08 MEK 338840 339195 340116 339338 339606 339482 339622 339470 339556 339893 10 339512 334.20 0.10 Ethanol 129250 129779 131457 130075 131011 130628 130645 130874 130808 131131 10 130566 637.80 0.49 1224083 225111 227596 225695 227058 226651 226309 226918 226284 226630 10 226234 975.60 0.43

Typical analyzer performance.

Minimum Detection Level System Linearity Typical RSD % 100 ppb/Weight 100 ppb to 500 ppm For gas streams; < 2 % for MTBE, methanol and ethanol. For liquid streams; < 2.5 % for MTBE, methanol and ethanol.

Natural Gas Analysis

A Family of Optimized GC Solutions
Natural gas is bought and sold as a bulk commodity with price based on its energy content. It is very important for all stakeholders in the natural gas supply and consumer chain to accurately determine the heating value of their streams.

Bruker offers a full range of GC based solutions for the analysis of natural gas. The analyzer family is designed to offer superior results through the use of industry proven hardware, software, optimized columns and consumables, and is backed by a team of global sales and support specialists.

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Key Benefits A complete range of natural gas analysis (NGA) solutions. Bruker offers many different NGA gas chromatography analyzers to meet the broadest range of stream sample types and throughput needs, whether the analysis is conducted in a laboratory, at-line or in the field. Easy to operate, powerful GC solutions. The Bruker 450-GC with CompassCDSTM Chromatography Software form a powerful analysis combination and do not require a high degree of skill to be used successfully. Complete, comprehensive single vendor solution. Bruker provides complete solutions without relying on third parties. The hardware, software, columns, application optimization, documentation, installation and support services are all supplied by Bruker. This solution allows analyses to be carried out quickly and efficiently, delivers effective troubleshooting and gives peace of mind from one complete, dependable, professional supplier. Operational procedures are fully documented. All Bruker NGA analyzers not only incorporate proven GC hardware and software, but arrive with the pre-loaded analysis method(s) and documentation specific to the application. Flexibility to analyze natural gas, liquefied petroleum gas or natural gas liquids (NGL). Brukers 450-GC based NGA analyzers can be configured to measure the composition of LPG or NGL streams through the use of specialized sample conditioners, ensuring sample integrity is consistently maintained.

The Bruker 450-GC based Natural Gas Analyzer Gas chromatography offers a proven means to determine the composition and heating value of natural gas and related streams quickly and cost effectively. Brukers natural gas analyzers (NGAs) are standard turnkey systems preconfigured and tuned at the factory to ensure their compliance with standard methods used to determine the heating value of natural gases and related streams. They can also be specially configured to determine other components of
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interest (e.g. sulfur compounds), to ensure the suitability for use in downstream processes. The analyzers are based on the Bruker 450-GC and Brukers CompassCDS Chromatography Software. All systems employ a proven and optimized multi-channel/multi-dimensional approach to determine the heating/calorific value of natural gas, as well as quantify individual components. Bruker offers several NGA systems to meet the widest range of analysis needs. Basic NGA (System A): This is the simplest of all available natural gas analysis systemsThe system employs a single valve column designed for simplicity, a Thermal Conductivity Detector (TCD) and Flame Ionization Detector (FID). The TCD is used for the determination of O2, N2, CH4, CO2 and hydrocarbons, while the FID, connected in series, determines hydrocarbons in low concentrations, i.e. C4 C9 or a C4-C5 with a C6 + back-flushed grouping peak. A single unheated 4 port Liquid Sampling Valve (LSV) is available for LPG type samples.

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NGA/Natural Gas Liquids (System B) This system is optimized to analyze natural gas or de-methanized hydrocarbon matrices. For natural gas, the components of interest are typically: oxygen, nitrogen, carbon dioxide, methane, ethane, propane, butane, iso- butane, pentane, hydrogen sulfide, and C6+ as a composite peak. For de-menthanized streams (natural gas liquids), the components of interest are typically carbon dioxide, ethane, propane, butane, iso-pentane, hexane and C7+ as a composite peak. The system is configured with a 10 and 12 port valve (third; liquid sampling valve is added if liquid streams are to be analyzed) and three analysis columns connected to TCD and FID detectors (see diagram on next page). The system simultaneously injects the stream on to two column systems: MolSieve column for the determination of O2 and N2 without the use of coolants, and short/long DC200/500 for the analysis of hydrocarbons and CO2. The DC 200/500 columns are set up for early back-flush, which optimizes sensitivity while reducing run time(from 25 minutes using the A configuration, to less than 15 minutes). An example chromatogram is shown on the next page. An automated 4 port LSV is available for LPG samples. 7

Chromatogram of natural gas sample from System A TCD Channel.

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System configuration schematic diagram for Natural Gas Analyzer A.

System configuration schematic for Natural Gas Analyzer B.

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Chromatogram of natural gas samples from System B TCD channel. Note separation of oxygen and nitrogen. NGA/Natural Gas Liquids - Extended Analysis (System C) This system is specifically designed to analyze rich natural gas or natural gas liquid streams by offering the ability to separate all hydrocarbon components up to C16. Like System B, it is able to separate and quantify oxygen and nitrogen, as well as measure hydrogen sulfide down to ~100 ppm. The system is configured with a 14 port valve and 6 port valve. The 14 port valve enables the system to introduce the sample stream simultaneously to three independent columns with automated detector switching which provides high sensitivity detection of all components of interest. The valves are installed in the multi-valve oven for flexible operation of the conventional column oven. Two of the sample paths flow onto MolSieve and porous polymer columns to separate oxygen, nitrogen and carbon dioxide, ethane, methane, ethane and H2S and the other via a splitter onto a high resolution non-polar capillary column to separate the hydrocarbon components up through C16. The 6 port valve is used to direct the separated components fraction to the TCD detector while components remaining on the MolSieve column are flushed to vent. If natural gas liquids are to be analyzed, a third valve, (liquid sampling) is added to the configuration described above. An automated dual unheated LSV is available for injection of LPG samples.

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Chromatogram showing natural gas sample from System C FID channel. Note individual separation of C6+ components.

System schematic for Natural Gas Analyzer C.

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Natural Gas Report -System C generated using Bruker CompassCDS Chromatography Data Software. Bruker Base Natural Gas Analysis Systems
Analyzer Characteristic O2, N2, CO2, CH4 Ethane, Propane, Butane, Iso-butane, Neo-pentane, Pentane, Iso-pentane C6+ as a composite peak C7+ as a composite peak O /N Separation He/H Separation Max. hydrocarbon number speciated LPG De-methanized natural gas / natural gas liquids Typical analysis to analysis repeatability % RSD Analysis time Standard Gas Methods IP-345 YES 450-GC System A YES YES YES YES YES(1) NO C6 YES(3) NO <1.0 30 min 450-GC System B YES YES YES YES YES YES C7 YES(3) YES <1.0 14 min
(2)

450-GC System C YES YES YES YES YES YES(2) C16 YES(3) YES <1.0 15-20 min

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GPA 2172 GPA 2177 GPA 2261 GPA 2286 GPA 2186 ISO 6974 ISO 6976 ASTM D5504 ASTM D6228 Notes:
(1) (2) (3) (4)

YES YES YES YES YES YES

Contact Bruker, several configuration possibilities Contact Bruker, several configuration possibilities YES(5) YES(5)

Requires liquid nitrogen or liquid CO oven cooling Requires additional channel including valve, columns and TCD Requires LSV to be additionally installed

This method is specifically for sulfur components in natural gas, therefore, a sulfur selective detector must be used.

Biodiesel Analysis
A Family of Comprehensive Solutions
Biodiesel is one of the most promising alternative fuel sources available today. Unlike conventional diesel fuel derived from crude oil, biodiesel comes from vegetable oils and animal fats. Compared to its fossil fuel based counterpart, biodiesel is safe, renewable, biodegradable, cleaner burning and is compatible with todays diesel engines. However, like its petroleum based counterpart, biodiesel can present a significant analysis challenge.

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Key Benefits Extremely powerful, easy to use analysis solutions. Brukers flexible 450GC or single channel 430-GC and CompassCDS Chromatography Software, combined with a broad range of application optimized columns and consumables, provides the analytical power needed to perform all biodiesel analysis methods and ensures that conducting them is simple and straightforward. A complete range of GC based biodiesel solutions. Bruker offers comprehensive solutions for the analysis of biodiesel by gas chromatography based on standard methods. These include: EN-14105 (free and total glycerol, mono, di and tri-glycerides content), EN-14103 (total FAME and linolenic acid methyl esters), EN14106 (free glycerol), EN-14110 (residual methanol) and ASTM-6584 (free and total glycerin). Outstanding multi-channel flexibility of the 450-GC. Depending on your analysis and throughput requirements, two or more standard methods can be accommodated with a single 450-GC system. Both an automated liquid and headspace sampler can be installed on a single 450-GC. It is therefore possible to conduct more than one standard GC analysis method, on a single system without the need for any hardware reconfiguration or lengthy startup/equilibration times. A broad range of application optimized consumables columns specifically designed for biodiesel analysis and long life time. All consumables included in these biodiesel analysis solutions have been carefully selected to ensure both high performance and reliability. Furthermore, a range of high performance capillary columns has been developed specifically for biodiesel applications, including the unique Bruker Biodiesel Glycerides Inert Steel column, which provides superior separation performance, extremely low phase bleed performance and unequalled column lifetime. Complete, comprehensive single vendor solution. Bruker provides complete solutions without relying on third parties. The hardware, software, columns, application optimization, documentation, installation and support services are all supplied by Bruker. This solution allows analysis to be carried out quickly and efficiently, delivers effective troubleshooting and gives peace of mind from one complete, dependable, professional supplier.

There are a variety of ways to determine biodiesel composition and quality. Both ASTM (American Standard and Testing Methods) and CEN (Comite Europeen de Normalisation) have implemented methods to characterize biodiesel and ensure it conforms to their standard specifications: EN-14214 or ASTM D6751. Of all biodiesel standard methods in use today, those employing GC are the most commonly used. These methods are listed and summarized below. Analysis of Free Glycerine and Total Glycerol; EN-14105, ASTM D6584 The analysis of glycerine in biodiesel is extremely important because excessive amounts can make long term storage problematic, or cause the formation of unwanted deposits, leading to injector fouling and accelerated engine wear. The analysis of free glycerine and total glycerol requires the use of on-column injection with a high resolution capillary column operated at a very high temperature (> 350
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C). Although there are several factors which can negatively impact the performance of a GC, the most significant associated with these particular methods is stress placed on the capillary column as it is subjected to repetitive high temperature thermal cycling of the oven. If conventional fused silica capillary columns are used for either of these methods, a severe reduction in useful column lifetime occurs as a result. This is due to structural failure of the fused silica column coating itself, leading to shattering. To combat this problem, the column is constructed using high tensile strength metal to eliminate the possibility of column failure. The metal column is treated and converted to Inert Steel to ensure maximum inertness. Like all Brukers line of high performance capillary columns, phase bleed is extremely low and separation efficiency is maximized. Furthermore, the column is extremely easy to install because it has the retention gap pre-coupled and is thoroughly leak tested at the factory.

The Bruker 450-GC and CompassCDS Chromatography software provide a powerful analysis platform for biodiesel analysis by GC.

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Summary of Bruker GC based biodiesel analysis solutions.

Standard Method ASTM D 6584 EN-14103 EN-14105 Analytes Free & total Glycerine Ester & linoleic acid methyl esters Free and total Glycerine & Mono, Di & Tri-glycerides Free Glycerol Methanol Injector Type On-Column Split / Splitless On-Column Recommended Bruker GC 450-GC 450-GC or 430GC 450-GC Time per Analysis 32 mins 30 mins 35 mins

EN-14106 EN-14110

Split / Splitless Headspace with Split / Splitless

450-GC or 430GC 450-GC or 430GC

10 mins 10 mins

Fatty Acid Methyl Esters (FAME) are created from feedstock, e.g. vegetable oils, animal fat and palm oil, via the transesterifcation process.

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Chromatogram of B-100 biodiesel obtained via EN-14105 method

Chromatogram of B-100 biodiesel using Bruker Biodiesel for FAME column according to EN-14103.

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450-GC and 430-GC with automated headspace sampler for the analysis of methanol via EN 14110.

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Pre-Defined Hardware Configurations

Over the years we have designed, tested and delivered a very wide range of specially requested hardware configurations to address the specific needs of customers. These configurations typically include special plumbing to properly connect individual GC components like injectors, valves and detectors. Many of these configurations require special testing to ensure desired performance. All of these special hardware configurations have been documented and assigned a unique part number to simplify the ability of a customer and his/her sales representative to quickly pick and choose the appropriate combination to meet specific analytical needs. We have listed the most popular configurations below. Please contact your Bruker sales representative or approved dealer for part number and pricing information.
Straight system for capillary columns with injector and detector Straight system for packed/wide columns with injector and detector Gas sampling valve with injector for capillary columns Gas sampling valve with injector for packed/wide bore columns Gas sampling valve for packed/wide bore columns Gas sampling valve with injector for heavy samples for packed/wide bore columns Gas and liquid sampling valve with injector for capillary columns Liquid sampling valve with injector for capillary columns Liquid sampling valve with injector for packed/wide bore columns Liquid sampling valve for packed/wide bore columns Liquid sampling valve for heavy samples for packed/wide bore columns Backflush to detector for packed/wide bore columns Backflush of stripper column to vent for packed columns Sequence reversal without backflush for packed columns Sequence reversal with backflush of column 1 to detector for packed columns Backflush to vent with same carrier to column for packed columns Backflush to vent with same carrier to detector for packed columns Capillary injector with backflush of pre-column to vent Capillary injector with backflush of pre-column to second detector Capillary injector with pre-column to vent and backflush to second column Gas and liquid sample valve with sequence reversal and backflush of column 1 to

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detector for packed columns Injector with sequence reversal with backflush of column 1 to vent for packed/wide bore columns Alternate injection into two packed columns, both columns with backflush to vent Packed injector with backflush of pre-column to analytical column Gas sampling valve with backflush to detector for packed columns Gas sampling with backflush of pre-column to vent for packed columns Gas sampling with backflush to vent for packed columns Gas sampling valve with backflush to vent for packed/wide bore columns Gas sampling valve with backflush to vent for packed/wide bore columns including injector Gas sampling valve with series/bypass column isolation option for packed/wide bore columns Gas sampling valve with sequence reversal and backflush of column 1 to detector for packed columns Gas sampling valve with sequence reversal and fore flush of column 1 to detector for packed columns Gas sampling valve with series/bypass column isolation option for packed/wide bore columns including injector Injector with backflush to vent for packed/wide bore columns Gas sampling valve with backflush to series/bypass valve for packed/wide bore columns Gas sampling valve to series/bypass and backflush to vent for packed/wide bore columns including injector Gas sampling valve with backflush to vent with series/bypass valve for packed/wide bore columns Gas sampling valve and injector for capillary columns with backflush to detector Gas sampling valve with capillary injector and backflush of pre-column to vent Gas sampling valve for packed/wide bore columns to vent or detector selection valve Alternate injection for two streams into the same packed/wide bore column Alternate injection for one stream into two packed/wide bore columns including two injectors Alternate injection for one stream into a packed/wide bore column and capillary column including two injectors Alternate injection for one stream into two capillary columns including two injectors Gas sampling valve for one stream into two packed/wide bore columns including two detectors Gas sampling valve for one stream into two packed/wide bore columns Gas sampling valve for one stream into two capillary columns including two injectors Gas sampling valve for one stream into one capillary and one packed/wide bore column including two injectors Alternate injection for two streams into the same packed/wide bore column including one injector Gas sampling valve for one stream into a capillary injector to detector and one stream into a packed/wide bore injector in series with a series/bypass column to detector

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Series/bypass valve with column isolation option for packed/wide bore columns Gas sample flush option Series/bypass valve for methanizer column Methanizer with serial connection to FID detector TCD detector with serial connection to methanizer/FID detector Methanizer with serial connection to FID and series/bypass valve for the methanizer TCD detector with serial connection to methanizer/FID and series/bypass valve for methanizer Two detectors connected in parallel TCD detector serially connected to a second detector Single injector to a selection valve between two detectors for packed/wide columns Gas sampling valve with injector to a selection valve between detector and vent for capillary columns Deans switching for capillary columns with injector and two detectors Deans switching for capillary columns with gas injection valve, injector and two detectors

Custom Analyzers
As noted, Bruker offers a broad array of standard analyzers (configured and tested systems to meet industry standard protocols), as well as pre- defined systems (GC hardware configurations that have been repeatedly implemented in the past for particular analytical needs).

However, we recognize that in some cases that is not enough. We know from much experience that there will be times when you have a very specific application need and a standard analyzer or pre-defined hardware system may not be able to meet or exceed it. Or, perhaps you need to have the system tested with your specific sample or stream, then validated to meet or exceed special requirements prior to shipment.

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An example of a GC solution where Multistream selection valves are mounted on top of the 450-GC to allow maximum automation of similar sample streams that require the same analysis.

In order to meet such needs, we established a Custom Solutions Group at our factory in Goes, The Netherlands, with over 25 years of experience. The sole purpose of this group is to work with our sales representatives and customers worldwide to identify the best way to meet specific GC analysis needs. Once a special configuration has been defined, the system is assembled and rigorously tested at our factory to meet the specific requirements. Complete documentation is then provided and, if necessary, special installation instructions provided to service personnel and special training (if required) to install and support custom solutions. The bottom line is that Bruker is fully committed to meet or exceed your GC analysis requirements regardless of how simple or complex they might be. If you are unsure whether a GC can do the job, all you have to do is ask us. Rest assured Bruker is prepared to do whatever we can to ensure your success. Please contact your local sales representative or authorized dealer for more details regarding Bruker Custom GC Solutions.

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SCION SQ and TQ GC-MS Systems

Figure 1. SCION TQ with 451-GC and 8400 Autosampler The GC-MS has been applied in all phases of the petroleum industry from crude oils to refinery products. With GC-MS, the full scan mass spectra allow for compound identification with high specificity by searching libraries containing thousands of known spectra. The combination of the GC retention time index and identification power of MS has made GC-MS an obvious choice for analyzing complex petroleum samples. GC-MS has also been responsible for the rapid growth of petroleum organic geochemistry for analyzing biomarkers to characterize the history and future of the oil fields. The biomarkers are hydrocarbons that retain the basic carbon skeletons of the once living organism that underwent physicochemical transformation to form the petroleum. The biomarkers are used as fingerprints to revel the correlation of oils with each other and oils with their source rocks. More recently, GC-MS based biomarker fingerprint technique has also been used for environmental forensic investigation of oil spills. Petroleum biomarkers are very complex and their analysis by conventional GCMS are often compromised by co-eluting components and matrix interferences. The problem can be resolved by coupling a GC to a tandem mass spectrometer (MS/MS) such as a triple quadrupole mass spectrometer operated in the Multiple Reaction Monitoring (MRM) mode. In MRM, as shown, the first quadrupole Q1 is a mass filter to allow only the selected m/z ion (precursor ion) through; Q2 is an collision cell filled with Ar gas, the selected m/z ion entering Q2 collides with Ar molecules and gets fragmented; Q3 is a mass filter like the Q1 but only allows the
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selected fragment ions (product ions) to pass to the detector. The MRM based GC-MS/MS greatly improved the sensitivity over the GC-MS by eliminating much of the interferences and co-elution problem, and to provide unambiguous identification and accurate quantitation of the trace biomarkers. Figure 3 is an example of MRM chromatograms showing cleanly resolved hopane and norhopane biomarkers from the black shale from Taoudeni Basin of Northwestern 1 Africa . The information allows for reconstruction of local weather conditions (limited nitrogen) as well as the favored bacteria under such environment 1.2 billion years ago. The Bruker SCION series GC-MS systems are revolutionary mass spectrometers designed for ease of use and maintenance and with superior sensitivity and robustness. Two SCION models are available: single quadrupole SCION SQ and triple quadrupole SCION TQ. Three key features of SCION are: A lens-free design that greatly simplifies operation and increases the robustness; Compound-based scanning (CBS) software that simplifies full-scan/SIM and MRM method developments; The smallest footprint in the industry that can easily fit into a lab with limited bench space.

The SCION SQ and TQ are equipped with the purposely built 451-GC that shares the same versatility and reliability as the Bruker 450-GC. SCION GC-MS systems can be used with Bruker SHS-40 headspace autosampler for headspace VOC analysis. The Atomx Purage and Trap (P&T) system coupled with SCION GC-MS system will provide a convenient and automated ways to analyze volatile and semi-volatile hydrocarbons from crude oils and environmental sedimentary samples.

Figure 2. Illustration of Multiple Reaction Monitoring (MRM) process in a triple quadruple mass spectrometer from precursor ion to product ion (precursor ion-product ion)

Martin Blumenberg, et al., Precambrian Research, 196-197 (2012), pp 113-127.

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Figure 3. MRM GC-MS/MS Chromatograms of hopanes and norhopanes biomarker from black shale from Taoudeni Basin of Northwestern Africa. [Ref: Martin Blumenberg, et al., Precambrian Research, 196-197 (2012), pp 113-127]

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Inductively Coupled Plasma Mass Spectrometry (ICP-MS)

Bruker aurora M90 ICP-MS System
Inductively Coupled Plasma Mass Spectrometry is the trace elemental analysis technique of choice when the lowest possible detection levels are required. If youve ever wished that ICPMS could be simpler, wish no more. The aurora M90 makes light work of it. No matter what your requirements, with a Bruker ICP-MS, you can tackle any application with ease.

Key benefits of aurora M90 include: Brukers patented high-efficiency 90 degree ion optics and double offaxis quadrupole delivers exceptionally low background noise and unmatched sensitivity at more than 1 million counts per second for 1 g/L. Tunable from normal to high sensitivity, the aurora M90 is perfect for both routine and research-grade applications Flexibility at your fingertips. The aurora M90 delivers industry leading detection limit performance. Collision/reaction interface (CRI) technology makes setup of complex cell systems a thing of the past. Simply turn on the gas flow to remove interferences. Its that simple. Featuring the only all-digital ICP-MS detector, covering more than nine decades of dynamic range in pulse counting mode, the aurora M90 delivers fast and accurate multi-element analysis from ultra-trace to major levels in a single measurement.

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Fast, Flexible, Interference-Free Analysis Bruker is proud to bring you CRI II, now even simpler to use and more effective at removing troublesome interferences from your sample analysis. The CRI injects helium (He) and hydrogen (H2) collision and reaction gasses directly into the plasma as it passes through the orifice of the skimmer cone. This innovative approach suppresses interferences before the analytes are extracted into the ion optics. Its that simple! No need for expensive or corrosive gasses such as ammonia or methane, so laboratory costs are reduced. No additional cleaning as CRI forms part of the cone interface, making this interference management system maintenance-free.

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Choose your analysis mode CRI II universal analysis mode provides fast and accurate results for samples routinely encountered across the wide range of environmental and industrial monitoring processes. While multi-mode delivers the ultimate in performance and flexibility for any sample type including those less routine in nature. So if you need absolute confidence in your results, no matter what the sample, CRI II is the answer. Sample Introduction Kits Along with the peltier cooled spraychamber that is standard on the aurora M90, optional sample Introduction kits are available for specialized applications including the analysis of organic solvents. These kits are designed to improve performance and reliability when running organic solvents, and the kits include a torch with optimized injector bore sizes for different solvent types. Part number 99-200 005-00: Organics kit, used for the analysis of common organic samples and solvents, such as alcohols and kerosene based solvents commonly used in the analysis of bio-fuels and oils. Part number 99-200004-00: Volatile Organics kit, used for the analysis of volatile organic samples and solvents, such as naphtha and gasoline.

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Application Note # CA-270388 Simulated Distillation of Crude Oil According to ASTM D 5307
Introduction This note describes the determination of the boiling range distribution of water-free crude petroleum through 538 C (1000 F). Material boiling above 538 C is reported as residue. Instrumentation Technique: Bruker Simulated Distillation Analyzer for ASTM D 5307, based on the 450-GC Gas Chromatograph Injector: 1093 COC Cold On-Column injector with full EFC control Detection: FID with full EFC control Autosampler: Bruker CP-8400 AutoSampler Software: GC Control and Data Handling: CompassCDS Chromatography Software Simulated Distillation Calculations: SimDist plug-in software fully integrated into CompassCDS Materials and reagents Sample: Crude oil Calibration: Mixture of n-paraffins (approx 1 %) dissolved in carbon disulfide Internal Standard: ASTM D 5307 Crude Oil Int. St. Sample preparation Weigh at least 10 g of a water-free crude oil to the nearest 0.1 mg into a 25 mL vial. Add approximately 1 g of internal standard mixture to the same vial. Determine the weight to the nearest 0.1 mg. Dilute the mixture with an approximately equal volume of carbon disulfide. Cap the vial tightly and shake vigorously for 2 min or until the mixture is solubilized completely. In a second vial, dissolve approximately the same amount of dried sample with an approximately equal volume of carbon disulfide. Use this solution for the separate crude oil without internal standard analysis.

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Conditions Injector: On-column, 100 C @ 15 C/min to 350 C Carrier Gas: Helium, 20 mL/min Temperature: 35 C @ 10 C/min to 350 C Detection: FID, 350 C Results and discussion The column specified for use with ASTM D 5307 is a packed column. The method, however, permits the use of other columns. For the Simdist Analyzer for ASTM D 5307, wide bore capillary column is used. In order to achieve the proper settings for boiling point distribution calculations, a calibration mixture containing nparaffins is analyzed. From this calibration mixture a calibration curve is derived (Figure 4). The boiling points of the n-paraffins are plotted against the elution time. A smooth line is drawn through the various data points indicating that the system is properly calibrated. Since the recovery of crude oil will be less than 100 %, two sample injections are made (Figures 1 and 2).

Figure 1. Crude oil. Figure 2 shows the chromatogram with an added internal standard to calculate the actual sample recovery, and corrected for the results shown in Figure 1. The CompassCDS SimDist software produces a summary report (Table 1). The SimDist report shows the initial boiling point (IBP), the % off temperatures as well as the D1160 C profile. The % recovery value is also listed.

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Figure 3: Calibration mixture.

Figure 4: Calibration curve.

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Table 1: SimDist analysis report of crude oil.

Conclusion The Bruker Simulated Distillation Analyzer for ASTM D5307 is well suited to determining the boiling point distribution of crude oil according to ASTM D 5307. All facets of this analyzer, including the 450-GC Gas Chromatograph, the SimDist column and the CompassCDS GC control and data handling software, extended with a SimDist plug-in, are fully integrated. This approach ensures trouble free operation, easy data handling and reporting, all according the method. Keywords ASTM D 5307, Crude petroleum, boiling range distribution Instrumentation and Software Bruker 450-GC Bruker CP-8400 AutoSampler CompassCDS Chromatography Software Bruker SimDist Analyzer References ASTM D 5307-97(2007), Determination of Boiling Range Distribution of Crude Petroleum by Gas Chromatography ASTM International, West Conshohocken, PA, www.astm.org
Bruker Daltonics Inc. Billerica, MA USA Phone +1 (978) 663-3660 Fax +1 (978) 667-5993 ms-sales@bdal.com www.bruker.com Fremont, CA USA Phone +1 (510) 683-4300 Fax +1 (510) 687-1217 ms-sales@bdal.com Bruker Daltonik GmbH Bremen Germany Phone +49 (0)421-2205-0 Fax +49 (0)421-2205-103 sales@bdal.de

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Application Note # CA-270389 Simulated Distillation of a Heavy Gasoil and FCC Feed according to IP 480
Introduction The IP 480 standard specifies a method for the determination of the boiling range distribution of petroleum products by capillary gas chromatography using flame ionization detection. The standard is applicable to materials having a vapor pressure low enough to permit sampling at ambient temperature and a boiling range of at least 100 C. The standard is applicable to distillates with initial boiling points (IBP) above 100 C and final boiling points (FBP) below 750 C, for example, middle distillates and lubricating base stocks. Instrumentation: GC: Bruker Simulated Distillation Analyzer for IP 480 based on the 450-GC Gas Chromatograph Injector: 1093 COC Cool On-Column with full EFC control Detection: FID with full EFC control Autosampler: Bruker CP-8410 AutoSampler Software: GC Control and Data Handling: CompassCDS Software Simulated Distillation Calculations: SimDist plug-in software fully integrated into CompassCDS Chromatography Software Materials and Reagents Sample: Heavy Gasoil, FCC Feed Column: SimDist column, 5 m x 0.53 mm x 0.09 m Calibration: Mixture of n-paraffins (approx 1 %) dissolved in carbon disulfide

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Figure 1: Polywax 1000 spiked with n-alkanes, calibration mix.

Figure 2: Heavy gasoil and CS2 blank.

Figure 3: FCC feed and CS2 blank.

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Sample Preparation The calibration mix is prepared by dissolving 0.1 g polywax 1000 in 7 mL CS2 and adding 10 L of an equal volume mixture of n-alkanes, all according to the method. The samples are obtained by making a 2 to 3 % (m/v) solution in CS2. Conditions Sample Size: 1 L Carrier Gas: Helium, 19 mL/min Oven Program: 35 C @ 10 C/min to 430 C Injector Program: 100 C @ 15 C/min to 430 C Detection: 450 C Results and discussion The software relates boiling point to the retention time using the n-alkane calibration mix. Baseline and solvent signal correction is done using an analysis of the pure solvent (CS2). The solvent analysis is subtracted from the sample analysis resulting in a net signal of the fully eluting sample. Area normalization is used to calculate the percentage eluted sample versus boiling point. The results of both samples are illustrated in table 1 and 2 including sequential analyses of both samples. This shows the good repeatability of the SimDist analyzer for IP 480. Table 1: Reproducibility values of heavy gasoil analysis.

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Table 2: Reproducibility values of FCC feed analysis.

Conclusion The chromatograms from the calibration mix for both heavy gasoil and FCC feed provide firm evidence of the solid performance of the Bruker Simulated Distillation Analyzer. The reproducibility values shown are consistent with those prescribed in the IP 480 method. Keywords IP-480, Simulated Distillation, heavy gasoil Instrumentation and Software Bruker CP-8410 AutoSampler Bruker 450-GC Gas Chromatograph CompassCDS Chromatography Software Bruker Simdist Analyzer for IP 480 Reference IP 480, 2007 Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils, Energy Institute, London, UK.

Bruker Daltonics Inc. Billerica, MA USA Phone +1 (978) 663-3660 Fax +1 (978) 667-5993 ms-sales@bdal.com www.bruker.com

Fremont, CA USA Phone +1 (510) 683-4300 Fax +1 (510) 687-1217 ms-sales@bdal.com

Bruker Daltonik GmbH Bremen Germany Phone +49 (0)421-2205-0 Fax +49 (0)421-2205-103 sales@bdal.de

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Application Note # CA-270390 High Temperature SimDist Analysis According to IP 507/07

Introduction The IP 507/07 standard specifies a method for the determination of the boiling range distribution of petroleum products by capillary gas chromatography using flame ionization detection. The standard is applicable to materials having a vapor pressure low enough to permit sampling at ambient temperature and a boiling range of at least 100 C. The standard is applicable to materials with initial boiling points (IBP) above 100 C and final boiling points (FBP) above 750 C, for example, heavy distillate fuels and residuals. The method is not applicable to bituminous samples. Instrumentation: GC: Bruker Simulated Distillation Analyzer for IP 507/07 based on the 450-GC Gas Chromatograph Injector: 1093 COC Cold On-Column injector with full EFC control Column oven: With cryogenic (CO2) cooling Detector: FID with EFC control Autosampler: CP-8400 Software: GC control and data handling: CompassCDS Chromatography Software SimDist calculations: SimDist plug-in software fully integrated into CompassCDS Materials Column: SimDist column, 5 m x 0.53 mm x 0.1 m Calibration mix for determination of TBP range Motor oil for 100% recovery determination

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Figure 1: Typical chromatogram of a calibration mix.

Figure 2: Typical calibration curve.

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Figure 3: Chromatogram of a motor oil sample. Recovery is 100%. Sample preparation All samples and calibration mixtures are dissolved in CS2 at 2%. Conditions Oven: 35C, @ 10C/min to 430C Injector: 100C, @ 15C/min to 430C Detector: 450 C Carrier gas: Helium, 19 mL/min Sample size: 1 L

Figure 4: Result plot of the motor oil sample.

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Figure 5: Chromatogram of a residue sample. Recovery is 88.7%. Conclusion The Bruker SimDist Analyzer and its CompassCDS based software provide the solution for high temperature simulated distillation applications as specified in SimDist method IP 507/07. Table 1: Results from the residue sample.

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Keywords
IP 507/07, petroleum products, heavy distillate fuels

Instrumentation and Software

Bruker CP-8400 Bruker 450 -GC Gas Chromatograph CompassCDS Chromatography Software SimDist Analyzer

Reference IP 507/07, Determination of boiling range distribution by gas chromatography method - Part 2: Heavy distillates and residual fuels. Energy Institute, London.
Bruker Daltonics Inc. Billerica, MA USA Phone +1 (978) 663-3660 Fax +1 (978) 667-5993 ms-sales@bdal.com www.bruker.com Fremont, CA USA Phone +1 (510) 683-4300 Fax +1 (510) 687-1217 ms-sales@bdal.com Bruker Daltonik GmbH Bremen Germany Phone +49 (0)421-2205-0 Fax +49 (0)421-2205-103 sales@bdal.de

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Application Note #Application Note # CA-270365 Determination of light hydrocarbons in stabilized crude oils according to IP 344
Introduction

Detailed hydrocarbon analysis (DHA) of crude oils is highly regulated. One of the methods, IP 344, was originally a packed GC column method but has been translated to a capillary column method. This note describes the use of such a capillary method that covers the quantitative determination of the individual hydrocarbons in stabilized crude oil, up to and including dodecane.
Instrumentation Bruker 450-GC Gas Chromatograph Bruker CP-8400 Autosampler CompassCDS Chromatography Software for data handling and GC control DHA plug-in software fully integrated in CompassCDS Software Materials and reagents Columns: non-polar, 25 m x 0.25 mm, df=0.12 m Internal Standard: 3,3-Dimethyl-1-butene The system configuration is shown in Figure 2. Sample preparation A known amount of internal standard (3,3-dimethyl-1-butene) was added to an aliquot of the crude oil. The samples were then injected into the system. Upon elution of dodecane, the pre-column was back-flushed to vent the higher boiling components. Samples used: Standard Gippsland crude Cossack crude

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Figure 1: Gippsland crude oil with internal standard. Conditions Injector: Split ratio 1:100 Carrier Gas: Helium, 60 psi FID Detector: 275 C Column temperature: 35 C (30 min) @ 2.0 C/min to 250 C (5 min) Results and discussion To calibrate the system and optimize the DHA database a calibration standard was analyzed. See Figure 3 for a quantitative PIONA standard. Figure 1 shows the chromatogram of a Gippsland crude oil. It is clearly evident that the fraction above dodecane was back-flushed and did not appear on the chromatogram. Figure 4 depicts a chromatogram of the analysis of a Cossack crude oil. The DHA software calculated, per component, the weight percent and volume percent content. This is reported in a Detailed Hydrocarbon Analysis report (Table 2). The information can be reported in a volume percent profile or a weight percent profile. Table 3 shows the weight percent profile of the Cossack crude of Figure 4. Conclusion The front end DHA analysis standard IP344, originally a packed GC method, was slightly modified to a capillary version. The Bruker 450-GC gas chromatograph-based Detailed Hydrocarbon Analyzer, together with CompassCDS GC control and data handling software, and DHA plug-in software, delivered excellent results for DHA analysis according to the IP 334 or front end standard.

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Table 1. Peak identification for the PIONA standard in Figure 3.

Figure 2: System configuration.

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Figure 3: Quantitative PIONA standard + Internal standard.

Figure 4. Cossack crude oil and internal standard.

Quantitative PIONA standard Analysis of Cossack crude oil

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Table 2. Detailed Hydrocarbon Analysis report of Cossack crude oil.

Table 3. Weight percent profile report of Cossack crude oil.

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Keywords IP 334, Front end analysis, Crude oil Instrumentation and Software Bruker 450 -GC Bruker CP-8400 Autosampler CompassCDS Chromatography Software References IP 344: Determination of light hydrocarbons in stabilized crude oils Gas chromatography method. Energy Institute, London.

Bruker Daltonics Inc. Billerica, MA USA Phone +1 (978) 663-3660 Fax +1 (978) 667-5993 ms-sales@bdal.com www.bruker.com

Fremont, CA USA Phone +1 (510) 683-4300 Fax +1 (510) 687-1217 ms-sales@bdal.com

Bruker Daltonik GmbH Bremen Germany Phone +49 (0)421-2205-0 Fax +49 (0)421-2205-103 sales@bdal.de

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Application Note # CA-270367 Detailed Hydrocarbon Analysis of Spark Ignition Engine Fuels by GC using ASTM D6729
Introduction This application note covers the determination of individual hydrocarbon components of spark ignition engine fuels. The method is commonly referred to as detailed hydrocarbon analysis, or DHA. It is also applicable to mixtures containing oxygenate blends (MTBE, ETBE, TAME, ethanol, etc) with boiling ranges up to 225 C and other light liquid hydrocarbon mixtures typically encountered in petroleum refining operations, such as blending stocks (naphthas, reformates, alkylates, etc). Individual component concentrations and precision are determined in the range of 0.01 to approximately 30 mass%. Interfering co-elution of olefins above C7 is possible, especially for samples containing significant amounts of olefins. Therefore, samples that contain an olefin concentration greater than 25% are not well suited to this analysis. Instrumentation Technique: Bruker Detailed Hydrocarbon Analyzer for ASTM D6729 based on the 450-GC Injector: 1177 S/SL, split/splitless, full EFC control Column Oven: With cryogenic (CO2) cooling Detection: FID with full EFC control Autosampler: Bruker CP-8400 AutoSampler Software: GC Control and Data Handling: CompassCDS Chromatography Software DHA Calculations: DHA software fully integrated into CompassCDS Materials and reagents Column: PONA 100 m x 0.25 mm x 0.5 m

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Figure 1: Chromatogram of a EURO95 gasoline. Conditions Sample Size: 1 L Carrier Gas: Helium, 45 psi Injector: 1177 S/SL, 250 C, split 200 mL/min Detection: FID, 300 C Oven: 0 C (15 min), @ 1C/min to 50 C, @ 2C/min to 130 C, @ 4C/min to 270 C (10 min) Results and discussion A calibration mixture containing n-alkanes was used to calculate the Kovats indices of all components in the sample. These indices are compared with known indices in the database and peaks assigned accordingly. A more detailed view of a part of the chromatogram is shown in Figure 2. This results in a detailed hydrocarbon analysis report shown in Table 1. All components are reported with retention time, peak area, peak area%, weight% and volume%. To ensure accurate results, the DHA software calculates peak symmetry. Depending on the peak skewing, a corrected retention time is calculated, as well as the corresponding Kovats indices. This is also shown in table 1 in the CRT (corrected retention time) column. The DHA software is capable of grouping individual components by hydrocarbon type. These groups include cyclic-, isoand normal saturates and unsaturates, aromatics and oxygenates. Each group is reported based on carbon number in a weight and volume percent profile (Table 2). The database contains all the physical properties of the different sample components. The DHA software uses these properties and combines them with volume% and weight% values in the sample. These combined calculations enable the properties of the sample to be reported in the physical properties report, as shown in Table 3.
Detailed hydrocarbon analysis

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Figure 2: Detailed view of the gasoline chromatogram of Figure 1.

Table 1: Detailed hydrocarbon analysis report.

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Table 2: Weight percent profile report.

Figure 3: Repeatability values of mass% benzene. In Figure 4, the mass% of benzene, toluene and total aromatics is shown compared to the average, the achieved standard deviation and the method specified standard deviation.

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Table 3: Physical properties report.

Figure 4: Repeatability figures of mass% toluene and total aromatics.

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Table 4: Repeatability values of a EURO95 gasoline analysis.

Conclusion The Bruker Detailed Hydrocarbon Analyzer for ASTM D6729 including the DHA software generate excellent results in accordance with the performance requirements of ASTM D6729. Mass (m/m) results within 0.001 % are produced as required by the method. By using the density properties of each component, its volume% is calculated and reported. The DHA software also groups the components by type (normal, cyclic, iso saturated and unsaturated hydrocarbons, aromatics and oxygenates) and can be represented in either mass% or volume%. The repeatability of the system is determined by analyzing a reference sample multiple times (Table 4). The table depicts a selection of test results. Individual analysis data includes average and standard deviation (including the ASTM method specified standard deviation/average value) as well as physical properties such as MON (Motor Octane Number), RON (Research Octane Number), density, mass% for selected components such as TAME, benzene and toluene, total aromatics and total olefins. Table 4 indicates the excellent repeatability obtained. The ASTM D6729 method requires that the standard deviation/average value be less than or equal to 0.1. The Bruker Detailed Hydrocarbon Analyzer for ASTM D6729 performs well within ASTM specifications. Figures 3 and 4 depict the repeatability and confidence windows as specified in the ASTM method.

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Keywords ASTM D6729, DHA, Spark ignition engine fuels Instrumentation and Software Bruker Detailed Hydrocarbon Analyzer for ASTM D6729 Bruker CP-8400 AutoSampler CompassCDS Chromatography Software Bruker 450 -GC Gas Chromatograph References ASTM Standard D6729-04, Determination of Individual Components in Spark Ignition Engine Fuels by 100 Meter Capillary High Resolution Gas Chromatography, ASTM International, West Conshohocken, PA, www.astm.org.

Bruker Daltonics Inc. Billerica, MA USA Phone +1 (978) 663-3660 Fax +1 (978) 667-5993 ms-sales@bdal.com www.bruker.com

Fremont, CA USA Phone +1 (510) 683-4300 Fax +1 (510) 687-1217 ms-sales@bdal.com

Bruker Daltonik GmbH Bremen Germany Phone +49 (0)421-2205-0 Fax +49 (0)421-2205-103 sales@bdal.de

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Application Note # CA-270367 Paraffins, Naphthenes and Aromatics (PNA) in Hydrocarbon Streams with the Bruker PIONA+ Analyzer
Introduction This application note describes the quantitative determination of paraffins, naphthenes and aromatics (PNA) in spark ignition fuels by the multi dimensional gas chromatography separation approach utilized in the Bruker PIONA+TM analyzer. The Bruker PIONA+ Analyzer is a comprehensive GC system and offers the ability to characterize and quantify the components in a variety of spark ignition fuels according to an array of industry standard method protocols. The system is very flexible and can be operated in multiple method modes depending on the analysis requirement of a given stream type. For this particular application, the system was set up to characterize the PNA content of spark ignition fuel. Instrumentation: Bruker PIONA+ Analyzer Software: CompassCDS Chromatography Software with PIONA+ plug-in software Conditions The analysis/separation is achieved through the use of carefully chosen columns and traps. All analysis parameters are set by Bruker at the factory to achieve optimal separation for the specified analysis mode, in this case, PNA. The analysis scheme used to determine the samples PNA composition is detailed in Table 1. Table 1: Elution scheme for PNA.

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Figure 1: Chromatogram of test sample 1. Results and discussion A test sample was analyzed on the PIONA+ Analyzer in PNA mode. A representative chromatogram is shown in Figure 1. The Bruker PIONA+ Analyzer includes a number of report/type options. For this application, the summary by weight% and summary by volume% options were selected and examples are shown in Tables 2 and 3. The results are well within the requirements of methods, such as DIN 5148, ASTM D 5443, UOP 870 and IP 382. In the next example, a naphtha sample is analyzed in PNA mode. A representative chromatogram is shown in Figure 2. It is apparent that, as with the first example, there is very clear group separation making identification and quantification straightforward. The weight% and volume% results by carbon number and total reports are shown in Tables 4 and 5. Weight and volume% profile reports were generated as before. In these reports, grouping of naphthenes, paraffins and aromatics is shown per carbon number as well as thetotals of the different groups and the totals per carbon number.

Figure 2: Chromatogram of a naphtha sample.

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Table 2: Mass% results of the calibration sample.

Table 3: Volume% results of the calibration sample.

Table 4: Weight% results of the naphtha sample.

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Table 5: Volume% results of the naphtha sample.

Conclusion The Bruker PIONA+ Analyzer provides the required mass% and volume% reports fully in accordance with DIN 5148-1, ASTM D 5443, UOP 870 and IP 382. Keywords
DIN 5148, ASTM D 5443, UOP 870, IP 382, Naphtha, PNA mode

Instrumentation and Software Bruker PIONA+ Analyzer CompassCDS Chromatography software PIONA+ plug-in software References ASTM D 5443-04, Paraffin, Naphthene and Aromatic Hydrocarbon Type Analysis in Petroleum Distillates Through 200C by Multi Dimensional Gas Chromatography, ASTM International, West Conshohocken, PA, www.astm.org.

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Application Note # CA-270380 Paraffins, Iso-Paraffins, Naphthenes and Aromatics (PINA) in Hydrocarbon Streams
Introduction This application note describes the quantitative determination of paraffins, isoparaffins, naphthenes and aromatics (PINA) in spark ignition fuels by the multidimensional gas chromatography separation approach utilized in the Bruker PIONA+ Analyzer. The Bruker PIONA+ Analyzer is a comprehensive GC system that offers the ability to characterize and quantify the components in a variety of spark ignition fuels according to an array of industry standard method protocols. The system is highly flexible and can be operated in one of multiple method modes depending on the analysis requirements for a given stream type. For this application, the system was set up to characterize the PINA content of spark ignition fuels. Table 1: Elution scheme for PINA.

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Figure 1: Chromatogram of test sample 1. Instrumentation: Bruker PIONA+ Analyzer CompassCDS Chromatography Software with PIONA+ plug-in software Conditions All conditions for the different columns and traps are set in order to obtain the elution pattern outlined in Table 1. Results and discussion The chromatogram in Figure 1 shows the analysis of test sample 1. This sample is used to calibrate the analyzer. The component grouping is very clear, making identification and quantification easy and accurate. From the chromatogram the PIONA+ software generates reports. Weight% and volume% profile reports are shown in Tables 2 and 3. The paraffins, iso-paraffins, naphthenes and aromatics are grouped and reported per carbon number and as totals. Furthermore, totals per carbon number are reported. Another example of a PINA analysis is shown in Figure 2. This chromatogram shows a reformer feed, a fairly simple sample containing hydrocarbons from C6 to C11. From this chromatogram, CompassCDS software with the PIONA+ plug-in generate weight% and volume% profile reports as shown in table 4 and 5. Thus, in one overview, the amounts of the different groups, naphthenes, iso-paraffins, paraffins and aromatics, are reported. In addition, the totals per group and per carbon number are displayed.

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Table 2: Weight% report of the test sample.

Table 3: Volume% report of the test sample.

Table 4: Weight% report of the reformer feed.

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Table 5: Volume% report of the reformer feed.

Figure 2: Chromatogram of a reformer feed. Keywords spark ignition fuels, Quantitation, paraffins, iso-paraffins, naphthenes, aromatics Instrumentation and Software Bruker PIONA+ Analyzer CompassCDS Software with PIONA+ plug-in software Conclusion The Bruker PIONA+ Analyzer successfully analyzed paraffins, iso-paraffins, naphthenes and aromatics in a calibration sample and a reformer feed. The PIONA+ Analyzer provided comprehensive mass% and volume% reports.

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Application Note # CA-270379 Paraffins, Olefins, iso-Paraffins, iso-Olefins, Naphthenes and Aromatics (PIONA) in Hydrocarbon Streams
Introduction This application note describes the quantitative analysis of n- and iso-saturates, nand iso-olefins, and aromatics in spark-ignition engine fuels by multi-dimensional gas chromatography using the Bruker PIONA+ Analyzer. Through the use of this system, hydrocarbon types (paraffins, iso-paraffins, olefins, iso-olefins, naphthenes and aromatics) are analyzed and reported, based on carbon number or as a total. Instrumentation: Bruker PIONA+ Analyzer Bruker 450 -GC Gas Chromatograph PIONA+ multi column module Software: CompassCDS Chromatography Software with PIONA+ plug-in software Conditions All conditions (temperatures, valve/switch timings) for the different columns and traps are set and tuned at the Bruker factory per method/mode to obtain an optimized chromatographic separation. In this application, the PIONA mode for the analyzer has been selected. In the PIONA mode of operation, the MolSieve 5A trap is not only used to separate the n-paraffins from the iso-paraffins but also the n-olefins from the iso-olefins as well. An example is shown in Figure 1.

Figure 1: PIONA+ chromatogram of a test sample analysis in PIONA mode.

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Table 1: Elution scheme for PIONA.

Results and discussion An example of a PIONA analysis is shown in the chromatogram below. A test sample is used to calibrate the PIONA+ analyzer as shown in Figure 1. Clearly visible is the group type separation per carbon number. The high resolution allows for easy identification and thus accurate and precise quantification. CompassCDS software, together with the PIONA+ plug-in, generate weight% and volume% profile reports as shown in Tables 2 and 3. In one view, the amounts of the different groups as well as the totals per group and per carbon number can be seen. Another example is shown in Figure 2. A second test sample containing additional C5 components and Unsaturates, was analyzed using the PIONA+ system. It is noteworthy that in spite of the fact that additional components are present (compared to the example shown in Figure 1), excellent peak resolution and group separation are still produced. This enables the analyst to achieve precise identification and subsequent quantification, as shown in Table 4 (weight% report) and Table 5 (volume% report). Thus, in one overview, the saturated and unsaturated groups are reported as a total and per carbon number. In addition, the totals per carbon number are revealed. Table 2: Weight% report of calibration sample 1.

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Table 3: Volume% report of calibration sample 1.

Figure 2: Piona+ chromatogram of test sample 2 in PIONA mode. Table 4: Weight% report of calibration sample 2.

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Table 5: Volume% report of calibration sample 2.

Conclusion The data and results clearly demonstrate that the Bruker PIONA+ Analyzer is capable of providing both mass% and volume% in accordance with the DIN 51448-2 standard method. Keywords DIN 51448-2, Quantitation, engine fuels, PIONA analysis, Hydrocarbon streams Instrumentation and Software Bruker PIONA+ Analyzer PIONA plug in software CompassCDS Chromatography Software References DIN (Deutsches Institut fr Normung e. V) 51448-2, Testing of liquid petroleum hydrocarbons - Determination of hydrocarbon types Part 1: Gas chromatographic analysis by column switching procedure, Berlin, Germany. www2.din.de.

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Application Note # CA-270383 Fast Analysis of Paraffins, iso-Paraffins, Naphthenes and Aromatics in Hydrocarbon Streams
Introduction The Bruker PIONA+ Analyzer was developed to provide a high level of flexibility in determining the composition by hydrocarbon group-type of spark ignition fuels through the use of multi-dimensional gas chromatography. Through the use of different columns and specially selected and optimized traps, the hydrocarbon components in the fuel sample are separated by group according to carbon number. In this application, the PIONA+ system was set up to separate normal and iso-paraffins, naphthenes and aromatics (PINA). In conventional mode, there can be breakthrough of volatile n-paraffins from the Bruker Molsieve 5A trap, which can make quantification quite difficult. Also, co-elution is possible for high C number iso-paraffins and corresponding naphthenes. In addition, the total analysis time is approximately two hours. Temperature programming of the Bruker Molsieve 5A trap together with the Bruker Molsieve 13X trap results in two large advantages. Firstly, grouping of naphthenes, iso- paraffins and n-paraffins according to carbon number will reduce both potential sources of miscalculation. Secondly, analysis time is markedly reduced, in this application by about 40 minutes, or nearly 45 %. Instrumentation Bruker PIONA+ Analyzer Software CompassCDS Chromatography Software with PIONA+ plug-in software Results and discussion Figures 1 shows some of the quantification problems encountered using conventional PINA analysis. A calibration mix was analyzed and breakthrough is apparent. The separation per component group and per carbon number is clearly shown. However, breakthrough of the volatile n-paraffins challenges the software, for example, in the case of nP5 from 7 to 9.5 minutes as shown in Figure 1b. This effect is particularly evident around 9 minutes when the N6 (naphthenes C6) elutes. Figure 2 clearly shows the improved performance of the fast PINA system, enabling easier quantification and reduced analysis time. In the regular PINA mode analysis time is about 95 minutes. In fast PINA mode, this is reduced to 55 minutes. It is also apparent that the analysis time reduction is achieved without adaptations in hardware and without any negative effect on chromatographic separation. This means that the chromatographic specifications remain unchanged.

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Figure 1: Chromatogram of a test sample in conventional PINA mode. N = Napthenes (cyclic paraffins), iP = Iso paraffins, nP = normal paraffins, A = Aromatics

Figure 1b: Magnified section from Figure 1 that is difficult to quantify.

Figure 2: Chromatogram of a test sample in fast PINA mode. N = Napthenes (cyclic paraffins), iP = Iso paraffins,nP = normal paraffins

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Figure 2b: Magnified section from Figure 2 showing improved ease of quantification Conclusion Temperature programming the Molsieve 5A trap (concurrent heating) together with the Molsieve 13X trap in the Bruker PIONA+ Analyzer greatly extends the application range for wide samples. Quantification of volatile hydrocarbons in wide range samples is also improved. The reduction of analysis time in this example was 40 minutes, or nearly 45 %. Keywords spark ignition fuels, PINA, Concurrent heating, Multi-dimensional gas chromatography Instrumentation and Software Bruker PIONA+ Analyzer CompassCDS Chromatography Software PIONA+ plug-in software

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Application Note # CA-270382 Analysis of Oxygenates, Paraffins, Naphthenes and Aromatics (O-PNA) in Hydrocarbon Streams
Introduction This application note describes the quantitative determination of oxygenates, paraffins, naphthenes and aromatics (O-PNA) in spark ignition fuels by the multidimensional gas chromatography separation approach utilized in the Bruker PIONA+ GC analysis system. The Bruker PIONA+ Analyzer is a comprehensive GC system that offers the ability to characterize and quantify components in a variety of spark ignition fuels according to an array of industry standard method protocols. The system can be operated in one of multiple method modesdepending on the analysis requirement of a given stream type. For this particular application, the system was set up in O-PNA mode and used to characterize the oxygenate, paraffin, naphthene and aromatic content of spark ignition fuels. Instrumentation: Bruker PIONA+ Analyzer Software: CompassCDS Chromatography Software with PIONA+ plug-in software

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Figure 1: Chromatogram of test sample 1 spiked with oxygenates. Conditions All conditions for the different columns and traps were set in order to obtain the elution scheme represented in Table 1. Table 1: Elution scheme for O-PNA.

Results and discussion When all columns and traps are set in the O-PNA mode required settings, a chromatogram according to the elution scheme in Table 1 is obtained. In this
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case, a chromatogram of test sample 1 spiked with oxygenates is shown. The Bruker PIONA+ Analyzer is preset with a number of reports, as shown in Tables 2 and 3. In Figure 2, a chromatogram of a gasoline is shown. Again, a clear overview of the group type separation per carbon number and the oxygenates is revealed, in this case only MTBE. From this chromatogram volume and weight percent profile reports are generated. The reports are divided into several columns with saturated and unsaturated component groups. Furthermore, a clear overview per carbon number is produced as well as the totals per group and per carbon number. Finally, the oxygenates are reported per carbon number and as individual components (Tables 4 and 5). Table 2: Mass% results of test sample 1.

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Table 3: Volume% profile of test sample 1.

Figure 2: Chromatogram of a gasoline type sample.

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Table 4: Weight% profile of a gasoline.

Table 5: Volume% profile of a gasoline.

Conclusion This application note describes the determination of oxygenates, paraffins, olefins, naphthenes and aromatics with the Bruker PIONA+ analyzer. This analyzer provides the required mass% and volume% reports and functions fully according the ASTM methods D 6839 and D 6293. Keywords ASTM D 6839, ASTM D 6293, Spark ignition fuels, O-PNA Instrumentation and Software Bruker PIONA+ Analyzer
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CompassCDS Chromatography Software PIONA plug-in software References ASTM D 6293, (2003)e1, Standard Test Method for Oxygenates and Paraffin, Olefin, Naphthene, Aromatic (O-PONA) Hydrocarbon Types in Low-Olefin Spark Ignition Engine Fuels by Gas Chromatography, ASTM International, West Conshohocken,PA, www.astm.org. Other methods: ASTM D 6839, DIN 51448 (1 and 2), ASTM D 1319 (FIA), ASTM D 5443, UOP 870, IP 382, ASTM D 3710 (TBP), ASTM D 4815, ASTM D 6296, DIN 51413-2, DIN 51413-9, ASTM D 55

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Application Note # CA-270381 Analysis of Oxygenates, Paraffins, Olefins, Naphthenes and Aromatics (O-PONA) of Hydrocarbon Streams
Introduction This application note describes the quantitative determination of oxygenates, Paraffins, naphthenes and aromatics (O-PONA) in spark ignition fuels by the multi- dimensional gas chromatography separation approach utilized in the Bruker PIONA+ GC analysis system. The Bruker PIONA+ Analyzer is a comprehensive GC system that offers the ability to characterize and quantify components in a variety of spark ignition fuels according to an array of industry standard method protocols. The system can be operated in one of multiple method modes depending on the analysis requirement of a given stream type. For this particular application, the system was set up to characterize the O-PONA content of spark ignition fuels. Instrumentation: Bruker PIONA+ Analyzer Software: CompassCDS Chromatography Software with PIONA+ Software plug-in Conditions In the O-PONA mode, an olefin trap is used to separate the Olefins from Paraffins (Table 1).

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Figure 1: Chromatogram of test sample 1. Table 1: Elution scheme for O-PONA.

Results and discussion The chromatogram shown in Figure 1 is an example of an O-PONA analysis. In this case, a test sample is run. Clearly made visible here is the group separation making identification and quantification very easy. The oxygenates elute without
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co-elution of other sample components allowing accurate and precise quantification. All conditions for the different columns and traps are set in order to obtain the elution scheme represented in Table 1. CompassCDS Chromatography Software, together with the PIONA+ plug-in software, generate a weight% and a volume% profile report. A summary of these reports is shown in Tables 2 and 3. The amount of the different groups per carbon number is shown as well as the totals per group and per carbon number. Oxygenates are reported as a group per carbon number but also per component. In Figure 2, a chromatogram of a gasoline is shown. Again, a clear view of the group type separated by carbon number and the oxygenates is obtained, in this case only MTBE. From this chromatogram, volume and weight percent profile reports are generated. The reports are divided into several columns showing saturated and unsaturated component groups. Furthermore, a clear overview per carbon number is shown as well as the totals per group and per carbon number. Table 2: Mass% results of a test sample.

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Table 3: Volume% profile of a test sample.

Figure 2: Chromatogram of a gasoline sample.

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Table 4: Volume% profile of a gasoline.

Table 5: Weight% results of a gasoline.

Conclusion This application note describes the determination of oxygenates, Paraffins, Olefins, naphthenes and aromatics with the Bruker PIONA+ Analyzer. This analyzer provides the required mass% and volume% reports and functions fully according the ASTM methods D 6839 and D 6293.

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Keywords ASTM D 6839, ASTM D 6293, Spark ignition fuels, Oxygenates, O-PONA Instrumentation and Software Bruker PIONA+ Analyzer CompassCDS Chromatography Software PIONA+ plug-in software References ASTM D 6293-98, (2003)e1, Standard Test Method for Oxygenates and Paraffi n, Olefin, Naphthene, Aromatic (O-PONA) Hydrocarbon Types in Low-Olefin Spark Ignition Engine Fuels by Gas Chromatography, ASTM International, West Conshohocken,PA, www.astm.org. Other methods: ASTM D 6839, DIN 5148 (1 and 2), ASTM D 1319 (FIA), ASTM D 5443, UOP 870, IP 382, ASTM D 3710 (TBP), ASTM D 4815, ASTM D 6296, DIN 51413-2, DIN 51413-9, ASTM D 5580 and ASTM D 3606

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Application Note # CA-270384 Fast Analysis of Paraffins, iso-Paraffins, Olefins, isoOlefins, Naphthenes and Aromatics in Hydrocarbon Streams
Introduction The Bruker PIONA+ Analyzer is a development to characterize the complete hydrocarbon sample composition, including individual oxygenates, in a single analysis of spark ignition engine fuels by multi-dimensional gas chromatography. The sample is separated in the component groups per carbon number and in individual components through the use of multiple columns and traps. In the PIONA+ system, paraffins, iso-paraffins and iso-olefins, olefins, naphthenes and aromatics are identified. However, analysis time in the PIONA mode is about 180 minutes, which severely limits the number of samples that can be analyzed per day. A unique aspect of the design of the Bruker PIONA+ Analyzer is the ability to independently heat the individual traps (concurrent heating). This application note describes work to determine if concurrent heating could be used to significantly reduce the analysis time and improve sample throughput. Instrumentation: Bruker PIONA+ Analyzer CompassCDS Chromatography software PIONA+ plug-in software Results and discussion As shown in Figure 1, when the PIONA+ system is operated in the conventional mode, a total analysis time of 180 minutes is required to elute all of the component groups. However, as shown in Figure 2, through the use of concurrent heating of both Bruker Molsieve 5A and 13X traps, a reduction in total analysis time from 180 minutes to 95 minutes is obtained, i.e. ~50 % less.

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Figure 1: Chromatogram of a test sample 1 in conventional PIONAmode. The reduction in analysis time is achieved by carefully optimizing the temperature settings of the various traps and columns and invoking simultaneous heating of the Molsieve traps. This approach, referred to as the FastPIONA mode, results in the elution of the paraffins immediately after their naphthene and iso-paraffin counterparts. Yet the elution integrity of the component groups remains intact with no negative influence on either naphthene or iso-paraffin groups. Figure 3 shows a close-up of the resulting elution sequence. The same results occur for the olefin group separations. The cyclic and iso-olefins normally elute from 100 130 minutes and the n-olefins, in conventional PIONA mode, from 150 180 minutes. However, through the use of concurrent heating they completely elute between 55 and 70 minutes (Figure 4). In the example of Figure 5, a commercial standard was analyzed for O-PIONA (oxygenates, paraffins, iso-paraffins, olefins, iso-olefins, naphthenes and aromatics) utilizing the concurrent heating approach described above. Note that the oxygenates elute separately from the other component groups and are easily identified and calculated by the PIONA+ software.

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Figure 2: Chromatogram of the test sample in fast PIONA mode.

Figure 3: Close-up view of C8 and C9 components. Separation in both conventional and fast PIONA mode.

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Figure 4: Close-up view of olefins in conventional and fast PIONA mode.

Figure 5: Chromatogram of a commercial standard in fast O-PIONA mode.

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Conclusion Temperature programming a Molsieve 5A trap (concurrent heating) together with a Molsieve 13X trap greatly reduces the total analysis time of PIONA+ type analysis and, in some cases, can improve the performance. Total analysis time is reduced by one third in the case of O-PIONA and by as much as half for PIONA. The reduction in analysis time is possible without any hardware changes and can be achieved without any negative effect on the quality of the component class separation. In addition, the analyses remain compliant with the method EN ISO 22854:2008. Keywords EN ISO 22854, spark ignition engine fuels, hydrocarbons, oxygenates Instrumentation and Software Bruker PIONA+ Analyzer CompassCDS Chromatography Software with PIONA+ plug-in software References EN ISO 22854:2008 Liquid petroleum products. Determination of hydrocarbon types and oxygenates in automotive-motor gasoline. Multidimensional gas chromatography method.

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Application Note # CA-270356 ASTM D 4815 the Determination of Oxygenated Compounds in Gasoline
Introduction With the arrival of reformulated gasoline as mandated by the EPA and the California Air Resources Board (CARB), petroleum refiners have had to incorporate some form of oxygen containing component in the gasoline they produce. The model on which the regulations are based requires 2.0% by weight of oxygen in reformulated gasoline. Both refiners and regulators have had to insure that this requirement is met by the addition of certain compounds to the gasoline blend. Most of these compounds take the form of aliphatic alcohols or ethers, such as ethanol and t-butyl-methyl ether (MTBE). To quantify these oxygenated additives, CARB has designated ASTM D 4815 as the test method for all reformulated gasoline sold in California. The Oxygenates in Gasoline analyzer performs the analysis according to ASTM D 4815. The analyzer tests all finished motor gasolines for the oxygenated compounds as listed in the ASTM method. Instrumentation The analyzer is based on the Bruker 450 -GC equipped with two columns, an 1177 S/SL split/splitless injector, a ten-port rotary valve, and a single FID detector. The first column is highly polar and pre-separates the low boiling and non-polar components from the higher boiling and polar components. The alcohols, ethers, and high-boiling components are back flushed into the second non-polar column where they are separated by boiling point order. The system utilizes electronic control of carrier gas to decrease the total analysis time by automatically increasing the carrier pressure during the final back flush. An additional TCD detector may be added to assist in the setting of proper valve switching times. Data handing is accomplished by CompassCDS chromatography software. Experimental Samples are injected into the GC and vaporized in the 1177-S/SL split/splitless injector. The polar column pre- separates the low boiling and non-polar components from the higher boiling and polar components. The lower boiling and non-polars (those eluting before methylcyclopentane) are flushed to vent (Figure 1). At a pre-determined time, the capillary column is switched in-flow and the polar components (including all the alcohols and ethers) and higher boiling compounds are back flushed from the polar column onto the non-polar column where they are separated according to their boiling points (Figure 2). After the complete elution of benzene and TAME, the capillary column is back flushed to the detector. This composite peak is not quantified but shows when the back flush has been completed by a return of the signal to baseline. Electronic Flow Control (EFC) can be used to increase the column pressure at this time. This will speed the return of
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the signal to baseline and, thereby, decrease the overall analysis time by approximately 40%. Calibration is made with several multi-component mixtures each containing different amounts of each of the oxygenated compounds. An amount of an internal standard such as 1,2dimethoxyethane (DME) is added to each level. The system then automatically generates a calibration curve for each analyte and computes linearity data. Results and discussion Results were generated automatically and can be printed at the end of each run. Figure 3 shows the chromatogram of a qualitative oxygenates blend. Conclusion The Bruker Oxygenates in Gasoline analyzer offers the petroleum chemist a reliable, fully automated device for insuring compliance with current CARB and EPA requirements for reformulated gasoline. The instrument conforms fully to the ASTM D 4815 procedure and provides excellent separation and quantitation for all the specified oxygenates.

Figure 1: Injection mode. The sample is injected onto the polar column. The light non-polar components that elute before methyl cyclopentane are vented.

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Figure 2: Analysis mode: Valve 1 switches and sets the polar column in back flush. All remaining components elute onto the non-polar column. After elution of benzene and TAME valve 1 switches back

Figure 3: Chromatogram of an oxygenates blend. It is a mixture of approximately 1% by weight of each alcohol and 3% by weight of each ether, including the internal standard DME. (see Figure 1) and sets the non-polar column in back flush.

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Keywords ASTM D 4815, Gasoline, Oxygenates, Gas chromatography Instrumentation and Software Oxygenates in Gasoline Analyzer Bruker 450-GC CompassCDS Chromatography Software References ASTM D 4815. Standard Test Method for the Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol, and C1 to C4 Alcohols in Gasoline by Gas Chromatography. American Society for Testing and Materials, Philadelphia, PA, USA.

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Technical Note # CA-270360 Determination of Methanol Content in Biodiesel using Gas Chromatograph with Headspace Sampling According to EN-14110
Introduction The popularity and interest in biodiesel is significantly growing in many areas of the world and has become a commonly sought after alternative fuel source for use with diesel engines. Biodiesel is produced from vegetable oils or animal fats via transesterification using methanol to yield Fatty Acid Methyl Esters (FAME) and glycerine. The yield, pure FAME (once the glycerine and the residual methanol has been recovered/removed) is called B-100. In order for biodiesel to be used as a motor fuel or blended with petroleum diesel, it must conform to standard specifications (ASTM D 6751 or EN-14214). There are GC methods in use today to determine whether biodiesel conforms to the standard specifications. One of these methods, EN-14110, is used to determine the methanol content. EN-14110 is applicable for a concentration range from 0.01 % (m/m) to 0.5 % (m/m) methanol*. Instrumentation Bruker 430 -GC: Injector: 1177 S/SL Split / splitless, full EFC control Detector: FID, full EFC control Headspace sampler: SHS-40, sample loop mode GC control and data handling software: Bruker CompassCDS Chromatography Software

Materials and reagents Column: Biodiesel for Methanol,30 m x 0.32 mm x 3.0 m Fatty Acid Methyl Ester mixture (FAME) with a methanol content of <0.001 %

Sample Preparation Calibration solutions: Solution A: 0.5 % (m/m) methanol in FAME Solution B: 0.1 % (m/m) methanol in FAME Solution C: 0.01 % (m/m) methanol in FAME A 1 mL aliquot was accurately weighed, and transferred into a 20 mL vial and then immediately capped.

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Sample: A 1 mL sample was accurately weighed then transferred into a 20 mL vial and immediately capped. Conditions GC conditions: SHS-40 Sample loop: 1 mL Vial/heating: 80 C Equilibrium time: 45 min Injector: 250 C, Split rate: 50:1 Detector: 275 C, FID Oven: 80 C (0.5 min. isothermal) @ 20 C/min to 160 C (2 min) Carrier gas: 2.0 mL/min const. flow, Helium

Figure 1: Overlay traces of calibration solutions. Results and discussion All three calibration solutions were analyzed twice and a calibration curve was obtained. See Figure 1 for an overlay of the methanol peaks of the different calibration solutions. The calibration curve (Figure 2) shows excellent correlation with the method. The correlation coefficient should be > 0.95. In this case the correlation coefficient was determined to be 0.9998. A typical chromatogram of a biodiesel sample is shown in Figure 3. Since biodiesel generally does not contain volatile components, other than methanol, identification and quantification is quite straightforward. The methanol content of the biodiesel was 0.038 % (m/m) thus meeting the specifications set in EN-14214, (methanol content <0.2 %). Furthermore the repeatability figures indicated that the system was properly optimized for the analysis as seen in Figure 5, where the analyses trend line is well within the repeatability window set forth in the EN-14110 method. In Figure 5 this is visualized by adding the average line and the window of repeatability set in the EN-14110 method.

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Figure 2: Calibration curve. Conclusions The GC Headspace system (Bruker 430-GC Gas Chromatograph and an SHS-40 Headspace Sampler) was shown to be well suited for the determination of methanol content in biodiesel according to specifications outlined in EN-14110, and the biodiesel tested in this application note meets the specifications on methanol content set forth in EN-14214.

Figure 3: Overlay traces of calibration solutions. Methanol (mass %) N Average St. dev. Repeatability figures. RSD (%) 15 0.038 0.0007 1.96

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Figure 5: Repeatability values are within the specification boundaries established in EN-14214 as indicated by the red lines in the chart. Keywords Methanol, Biodiesel, EN-141110, FAME Instrumentation and Software Bruker 430-GC CompassCDS Chromatography Software References EN-14110 Fat and oil derivatives Fatty Acid Methyl Esters (FAME) Determination of methanol content.

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Application Note # CA-270361 Determination of Free Glycerol Content in Fatty Acid Methyl Esters (FAME) and Biodiesel According to EN-14106
Introduction Biodiesel is produced by transesterification of the parent oil or fat with an alcohol, usually methanol, in the presence of a catalyst, usually potassium hydroxide or sodium hydroxide, or, increasingly, alkoxides. The resulting product contains not only the desired alkyl ester product but also non or partly reacted starting material mono-, di- and triacylglycerides, residual alcohol and catalyst. Glycerol is formed as a by-product and separated from the biodiesel in the production process. However, traces of glycerol can be found in the final biodiesel product. In higher concentrations, glycerol has a negative effect on fuel behavior and performance. In order for biodiesel to be used as a motor fuel or blended with petroleum diesel, it must conform to standard specifications (ASTM D6751 or EN-14214). There are GC methods in use today to determine whether biodiesel conforms to the standard specifications. One of these methods, EN-14106, is used to determine the glycerol content. This European Standard specifies a gas chromatographic method for the determination of free glycerol content in Fatty Acid Methyl Esters (FAME) in the range of 0.005 % to 0.070 %. Instrumentation System: Bruker 450 GC Gas Chromatograph Injector: 1177 S/SL Split / Splitless (full EFC control) Detector: FID (full EFC control) Autosampler: CP-8410 Software/GC Control & Data Handling: Bruker CompassCDS Chromatography Software Materials and reagents Column: PoraPLOTQ, 10 m x 0.32 mm, Biodiesel Sample: Pure biodiesel (conforming to EN-14214 standard specification)

Sample Preparation Ethyl alcohol, water, hexane and a known amount of internal standard were added to a known quantity of sample.
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Please note that when these solvents are added together, two phases are formed. The free glycerol transferred into the lower of the two phases. Approximately 3.5 g of sample was weighed into a 10 mL test tube. 1 mL of ethyl alcohol was added and gently shaken to ensure uniform mixing. Exactly 1 mL of internal standard solution and 4 mL of hexane were added. The tube was tightly plugged and shaken vigorously for ~ 5 minutes. After an ~15 minutes centrifuge, the lower phase was used for gas chromatographic analysis. Calibration and calculation A calibration mix containing known quantities of 1,4-Butanediol and Glycerol was used to determine the response factor of Glycerol. Response Factor (Fr) = (A1/M1)/(A2/M2) A1 is the peak area of internal standard A2 is the peak area of Glycerol M1 is the mass of 1,4-Butanediol in response factor solution, expressed in mg M2 is the mass of glycerol in response factor solution, expressed in mg

The results were calculated using the following equation: Free Glycerol, % (m/m) = (((A2/A1) * Fr * m1)/m)*100 A1, A2, Fr see formula 1 m1 mass of int std in sample (mg) m mass of sample (mg)

Analysis conditions Injector: 270 C, split 75 mL/min Detector: 270 C, FID Carrier Gas: Helium, 6.5 psi Oven: 210 C, isothermal Inj. Vol.: 1 L Results and discussion The sample of biodiesel used in this application was analyzed multiple times. A chromatogram of this analysis is shown in figure 1. Table 2 shows the repeatability figures, average and standard deviation. Chart 1 shows the individual numbers compared to repeatability and reproducibility limits described in the EN-14106 method.

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Figure 1: Biodiesel chromatogram.

Chart 2: Analysis repeatability based on 13 runs. Red lines indicate the maximum and minimum variation limits of the method.

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Table 2: Analysis repeatability figures.

Conclusions This application note demonstrates the applicability of this system for the analysis of free glycerol according to the EN-14106 method. When using the 450 -GC an excellent repeatability is obtained. Keywords EN-14106, Glycerol, Biodiesel Instrumentation and Software Bruker 450-GC CompassCDS Chromatography Software References EN-14106 Fat and oil derivatives Fatty Acid Methyl Esters (FAME) Determination of free glycerol content. EN-14214 Automotive fuels Fatty Acid Methyl Esters (FAME) for diesel engines Requirements and test methods.

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Application Note # CA-273877 Ethanol Content in Denatured Fuel Ethanol According to ASTM D 5501
Introduction Biofuels have become increasingly important as alternatives to conventional fuels. Examples are biodiesel and bioethanol. Biodiesel is derived from esterification of vegetable or animal fat. Bioethanol is mainly produced by sugar fermentation.The main source of the sugar used for bioethanol production comes from specifically grown crops. These crops include corn, maize and wheat. However, waste straw, willow and poplar trees, sawdust, reed canary, cord and miscanthus grasses, Jerusalem artichokes, and sorghum are also used. Ethanol has a high octane number and was originally intended to replace lead as an octane enhancer. Nowadays, ethanol is blended with gasoline to improve combustion efficiency thereby reducing polluting emissions. The most common blend is 10 % ethanol and 90 % petrol (E10) though the latest vehicles can operate on up to 85 % ethanol and 15 % petrol blends (E85). ASTM D 5501 is the method commonly used to determine the ethanol content of denatured fuel ethanol by gas chromatography. Ethanol is determined from 93 to 97 mass%. Instrumentation: Bruker 450 -GC Gas Chromatograph Injector: 1177 S/SL split/splitless, full EFC control Detection: FID with full EFC control Autosampler: Bruker CP-8400 GC Control and Data Handling: CompassCDS Chromatography Software Materials and Reagents: Column: PONA CB, 100 m x 0.25 mm x 0.5 m Sample Preparation: A commercially available household methylated spirit or denatured ethanol was used for this application note.

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Conditions Carrier Gas: Helium, 40 psi Injector: 250 C, split 1:200 Injection Volume: 2 L Oven: 15 C (12 min) @ 30 C/min to 250 C (19 min) Detection: 300 C Table 1: Response factor according ASTM D 5501.
Component Methanol Ethanol Mass relative response factor 3.20 2.06

Results and discussion Figure 1 shows a chromatogram of denatured alcohol obtained using the conditions set out above. The calculation of the mass% of ethanol and methanol is done using a normalized area percent calculation with response factors. In order to show the suitability of the system, repeatability was tested. According to ASTM D 5501, two successive results may exceed 0.21 % only once every 20 analysis. Figure 2 shows the data set from 36 successive runs and the limits specified. The same approach was taken for the determination of the methanol content of the sample. In Figure 3, 15 successive runs are shown, again with limits specified in ASTM D 5501. Figures 2 and 3 show that the data never exceeded the levels specified in the method.

Figure 1: Chromatogram of a household methylated spirit or denatured ethanol.

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Figure 2: Repeatability of ethanol content with limits specified by the method.

Figure 3: Repeatability of methanol content with limits specified by the method. Conclusion The data presented here clearly show the suitability of the system for accurate determination of ethanol and methanol according ASTM D 5501. Keywords Ethanol, ASTM D 5501, Denatured Fuel Ethanol, Gas chromatography Instrumentation and Software 450 -GC Gas Chromatograph CP-8400 Autosampler CompassCDS Chromatography Software Authors: Arno Woltering References ASTM Standard D 5501, 1994, Determination of Ethanol Content of Denatured Fuel Ethanol by Gas Chromatography, ASTM International, West Conshohocken, PA, www.astm.org

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Application Note # CA-272646 The Analysis of Sulfur Components in Various LPGs (Liquefied Petroleum Gases)
Introduction The low level analysis of sulfur containing components such as H2S (Hydrogen Sulfide), COS (Carbonyl Sulfide) and mercaptans is challenging. First of all the system has to be inert; stainless steel adsorbs H2S and other sulfur containing components. Secondly, the column used must be able to separate the component of interest. Although a highly selective pulsed flame photometric detector is used in sulfur mode, the bulk hydrocarbon tends to quench the PFPD signal. Bruker therefore developed a two-channel configuration for this type of analysis. Both channels are equipped with a PFPD (Pulsed Flame Photometric Detector), see Figure 1. The LPG type samples are injected as a gas via two gas sampling valves in series. A Micro-Gasifier in front of the injection valves ensures a fully gaseous sample state. The complete sample path is UltiMetalTM deactivated ensuring an inert system preventing adsorption of sulfur components. The two columns/channels approach permits the LPG type analysis of all components of interest in one run. If the bulk is mainly propane, H2S is analyzed on the non-polar column from channel A. The COS is analyzed on the PoraBOND Q column from channel B. The mercaptans can be analyzed on both columns. If the bulk is mainly butane, the methyl mercaptan is analyzed on PoraBOND Q from Channel B as it co-elutes with butane on the non-polar column of channel A.

Figure 1: Plumbing scheme for the two channel system.

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Instrumentation Bruker 450 -GC gas chromatograph Channel A and B Injection: Gas sampling valve to an 1177 SL/L Split/Splitless injector Detection: PFPD (Pulsed Flame Photometric Detection)

Software: CompassCDS Chromatography Software

Materials and Reagents Column: Channel A : Non-polar 30 m x 0.32 mm, df = 5 m Channel B : PoraBOND Q, 25 m x 0.32 mm

Samples : Sulfur Calibration standard in nitrogen Propane Butane

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Conditions Channel A and B: Channel A: Channel B: Sample loop isothermal @ 100 C injector 220 C, split 1:30 injector 220 C, split 1:20

Oven: 35 C @ 12 C/min to 250 C (1.25 min) Channel A and B: Carrier Gas Helium, 2 mL/min

PFPD Detector settings: - Temperature: - Air 1: - Air 2: - H2: - Trigger level: - Tube voltage: - Sampling delay: - Sample width: 200 C 17 mL/min 10 mL/min 13 mL/min 200 mV 510 V 4 ms 10 ms

Results and Discussion Figures 2 and 3 are chromatograms of bulk propane analysis. The non-polar column from channel A shows co-elution of propane and COS. H2S and the mercaptans are very well resolved and perfectly placed for quantification. The PoraBOND Q column from channel B has no co-elution of COS with the bulk and is analyzed. Also the mercaptans can be analyzed on this channel. Figures 4 and 5 show the analysis of sulfur components in bulk butane. On the non-polar column in channel A, the bulk butane co-elutes with methylmercaptan causing quenching of the PFPD. In this case methyl mercaptan is analyzed on the PoraBOND Q of channel B. The H2S and COS are analyzed on the non-polar column of channel A. The higher mercaptans can be analyzed on both channels. To validate the performance of the system, a calibration mixture is used. The sample balance is nitrogen preventing any quenching on both channels for all sulfur components. The calibration sample is analyzed 15 times for statistical data (Tables 2 and 3, Figures 8 and 9). Chromatograms obtained for both channels are shown in Figures 6 and 7.

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Figure 2: Sulfur components in propane on a non-Polar column.

Figure 3: Sulfur components in Propane on a PoraBOND column.

Figure 4: Sulfur components in Butane on a non-Polar column.

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Figure 5: Sulfur components in Butane on a PoraBOND column.

Figure 6: Sulfur components in a Calibration standard on a non-Polar column.

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Figure 7: Sulfur components in a Calibration standard on a PoraBOND column.

Figure 8: Visualized repeatability of data from Table 2.

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Table 2: Repeatability data of Channel A

Run 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 N Average Std Dev RSD% H2S 1215606 1254247 1239701 1274378 1243905 1285376 1228259 1291766 1275770 1278718 1273792 1236414 1235316 1225871 1237259 15 1253092 24587 2.0% COS 918906 935746 943248 948168 924324 937870 964881 939709 964140 979071 970358 949312 919577 908744 926690 15 942050 20763 2.2% MeSH 327886 328676 332392 335003 339181 338153 335009 335747 341016 341823 335827 330520 329219 322353 320472 15 332885 6360 1.9% EtSH 294361 298574 300742 296093 299545 299489 298247 299883 302965 299995 305986 297651 291021 292467 289776 15 297786 4406 1.5% i-PropSH 404068 425778 419173 425080 426836 433643 424477 413521 437842 430574 432967 434679 423661 415695 416483 15 424298 9218 2.2% n-PropSH 633667 628584 646792 617068 618302 648998 623804 625520 651128 641596 638665 655549 632948 661764 662962 15 639156 15062 2.4%

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Table 3: Repeatability data of Channel B

Run 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 N Average Std Dev RSD% H2S 545462 538184 532203 544055 548043 542476 552342 538959 541759 518534 538677 525475 525827 521071 518329 15 535426 11104 2.1% COS 687805 677330 693217 703604 702749 695695 713601 702750 697077 699979 684485 702033 708639 711786 702762 15 698901 9988 1.4% MeSH 827495 824772 846290 839709 843958 847346 856817 844759 850350 844822 829601 840280 834848 830656 833949 15 839710 9223 1.1% EtSH 1594184 1583903 1612155 1596015 1588910 1601313 1665891 1629822 1633218 1617188 1574632 1613474 1573162 1615305 1605378 15 1606970 24335 1.5% i-PropSH 1424799 1439569 1463529 1466332 1433280 1494175 1532625 1461748 1489508 1494334 1430748 1498361 1491257 1457386 1446365 15 1468268 30926 2.1% n-PropSH 1628308 1642325 1634377 1658115 1641332 1672709 1706860 1667079 1678310 1665749 1651976 1691346 1648297 1634290 1633789 15 1656991 23141 1.4%

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Conclusion The custom configured 450 -GC offers a number of benefits. The micro-gasifier enables the direct coupling of an LPG stream to the GC. No sample pre-treatment is required. The UltiMetal sample path ensures a trouble free analysis of sulfur-containing components at low concentrations. The two-channel approach allows an increased flexibility with regard to the different samples that contain the sulfur component traces. The two different columns, each equipped with a PFPD detector, ensure a maximum flexibility and an excellent separation independent of the bulk component to analyze H2S, COS, methyl mercaptan, ethyl mercaptan, propyl mercaptan, iso-propyl mercaptan, tertbutyl mercaptan and tetrahydrothiophene. Repeatability data show that the system is perfectly suited for the analysis of these low level, sulfur-containing components. Keywords LPG, Sulfur traces, Propane, Butane Instrumentation and Software Bruker 450-GC CompassCDS Chromatography Software

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Fremont, CA USA Phone +1 (510) 683-4300 Fax +1 (510) 687-1217 ms-sales@bdal.com

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184

Application Note #283078 Direct Analysis of Finished Plastic Products by Heated Headspace and GC/MS
Plastic Product Volatiles Analysis A sample of raw or finished material is directly analyzed for volatile components using an automated headspace auto sampler. Little or no sample preparation is required, making it an ideal technique for high throughput quality control testing in manufacturing. When operated in a synchronous SIM/Scan mode, the Bruker SCION SQ single quadrupole mass spectrometer provides quantitative data, along with tentatively identified compounds (non-target compounds). Introduction Material testing for outgassing volatile organic chemicals is required in many industries to ensure consumers are not being exposed to harmful contaminants. This is especially important when a material such as a plastic is exposed to excess heat with little or no ventilation. A good example would be plastic materials in a car such as dash boards, which are exposed to very high temperatures in direct sunlight. Volatile chemicals are also common in carpeting and polyvinyl chloride (PVC) piping, and may pose a risk in poorly ventilated homes. Chlorinated solvents that outgas from materials are generally considered harmful, because they are classified as being carcinogenic or environmental hazards. Other compounds detected may be uncharacterized with little known about their toxicity. Phthalate esters, for example, have been linked to endocrine disruption in some animal species, and regulations are emerging to control these substances in plastic bottles (1). Experimental Samples of polypropylene from a car manufacturer and PVC pipe were cut into small pieces and placed directly into 20 mL headspace vials. About 500 mg-1g was added. The Bruker SHS-40 Auto sampler conditions used are cited in Table 1.

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Table 1. SHS-40 Sampling Conditions.

Parameter Oven Temp Valve/Loop Temp Transfer line Temp Pressure Loop Volume PC (incubation) Time GC-MS Run Time Shake option Set Point 70 C 160 C 125 C 500 psi 1 mL 30 min 20 min ON

Figure 1. Bruker SHS-40 Headspace Autosampler (left) with SCION GC-MS. Results The polypropylene dash board sample was analyzed in full scan. Figure 2 shows all compounds that were tentatively identified using an automated library search against the NIST 08 library.

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Figure 2. Full Scan Identification of Compounds in Polypropylene Sample. The SCION GC-MS column, oven program, and injector conditions: Column: Injector: BR-624ms, 20 M x 0.18 mm x 1.0 m BR-1079, PTV injector with 3.4 mm single goose-neck open split liner set at 200C 1 mL/min Initial 35 C hold 2 min; program to 170C at 10C/min; hold 0; program to 250 C at 50 C/min, hold 1 min, (total run time 17.9 min)

Injector split ratio: 1:20 Column flow: Oven program:

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Table 2. Compounds detected in polypropylene dash board sample.

RT (min) 2.581 3.066 6.216 6.766 7.333 7.455 7.919 8.16 8.279 11.732 11.821 11.921 12.482 12.565 12.657 12.775 13.634 14.128 15.271 15.321 Peak Name Pentane, 2-MethylHexane 1-Butanol, 2-EthylToluene Hexane, 2,3,5-TrimethylHexane, 2,3,4-Trimethyl2,4-Dimethyl-1-Heptene Nonane, 4-Ethyl-5-MethylHexane, 3-Ethyl1-Nonene, 4,6,8-Trimethyl1-Undecene, 4-MethylUndecane, 4,7-DimethylOctane, 2,3,6,7-TetramethylHexane, 2,3,4-TrimethylHexane, 2,3,4-TrimethylUndecane, 4-Methyl6-Methyl-2-Pyrazinylmethanol Oxalic Acid, Isobutyl Nonyl Ester 1-Lodo-2-Methylundecane Heptadecane, 2,6,10,14-TetramethylResult Type TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC Amt 450552256 43213484 10450404 10159705 139044608 1922249344 16034614 48203884 418871424 85041800 1740321664 208282336 48176440 417671808 92484168 21904856 15546811 11080139 40731856 638716608 Match 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Result 933 903 877 901 925 922 858 909 921 876 884 883 878 877 889 870 766 885 882 911 Library NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST

Table 3. Synchronous SIM/SCAN parameters.

Compound Name Vinyl Chloride 1,2-Dichloroethane Full Scan Retention Time (RT) 3.10 4.67 NA RT Window 1.0 1.0 2.0-17.9 Scan Mode, Ions monitored SIM, 62, 64 SIM, 62, 64 Full (m/z 35-300) Dwell Time (ms) 49 49 300

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Table 4. Tentatively Identified compounds in PVC sample.

RT (min) 1.184 1.283 1.389 2.159 3.116 3.583 5.659 5.705 5.807 7.752 9.732 9.848 10.159 10.348 10.421 10.516 10.657 10.763 10.787 10.885 11.25 11.409 11.543 11.802 11.88 11.919 11.983 12.224 12.554 13.033 13.282 13.367 13.63 14.874 Peak Name 1-Methyldodecylamine Hydrazinecarboxamide Ethyne, FluoroAcetone Thiirane Butane, 2-NitroPentanal 2-Propenoic Acid, 2-Methyl-, Methyl Este Acetaldehyde Hexanal Heptanal Benzene, (1-Methylethyl)2,2,7,7-Tetramethyloctane 1-Butanol, 3,3-Dimethyl2,2,7,7-Tetramethyloctane Heneicosane, 11-(2,2Dimethylpropyl)Hexanal, 2-EthylTetradecane, 1-IodoPentane, 2,3,4-TrimethylPentanoic Acid, 1,1-Dimethylpropyl Ester Heneicosane, 11-(2,2Dimethylpropyl)Pentane, 3-Ethyl-2,2-DimethylOctane, 2,4,6-RrimethylOxalic Acid, Isobutyl Nonyl Ester Pentane, 3-Ethyl-2,2-DimethylHeneicosane, 11-(2,2Dimethylpropyl)Oxalic Acid, Isobutyl Octyl Ester Hexane, 2,4-DimethylHexane, 1,1-Dichloro-3-MethylEthanone, 2,2-Dihydroxy-1-PhenylNonanal Benzenemethanol, .Alpha.,.Alpha.Dimethy 6-Methyl-2-Pyrazinylmethanol 2-Decen-1-Ol Result Type TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC TIC Area 6.79E+07 6.61E+06 546473 4.23E+06 4.68E+08 1.32E+07 5.34E+06 5.40E+06 5.83E+06 2.89E+07 6.03E+06 6.89E+06 2.41E+07 5.30E+06 1.39E+07 8.77E+06 5.78E+06 1.00E+07 5.01E+06 3.35E+06 2.04E+07 8.05E+06 4.56E+07 6.71E+06 2.68E+07 2.79E+06 2.44E+07 2.94E+07 8.90E+06 1.32E+07 2.19E+07 8.96E+06 9.97E+06 1.31E+07 Amt 67918424 6613686 546473 4234303 4.68E+08 13169822 5341163 5398963 5825911 28887902 6025094 6891179 24139264 5302461 13884072 8773806 5782036 9995009 5005334 3354330 20381632 8048495 45579500 6708442 26790618 2789403 24356798 29438408 8901146 13228981 21900612 8960782 9966499 13070243 Match 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Result 735 762 665 867 907 760 796 806 830 886 867 853 872 747 846 824 776 793 764 733 890 896 867 850 886 795 886 817 656 879 865 727 741 888 Library NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST NIST

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The PVC sample was run in SIM/Scan mode. Figure 3 shows detection of 1,2dichloroethane, a target compound with qualifier ion.

Figure 3. SIM/Scan analysis of PVC sample.

Figure 4. RIC of PVC sample.

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Conclusion The Bruker SHS-40 headspace coupled with the SCION GC/MS is an excellent tool for qualitative and quantitative identification of volatile compounds in raw materials. Using SIM, compounds can be selectively quantitated at very low concentrations. Full scan data can be interrogated for TICs and used for quality control fingerprints. The compounds were tentatively identified and are listed in Table 3. Lower display is magnification of peaks eluting between 10 and 14 min. References (1) Developmental Effects of Endocrine-disrupting Chemicals in Wildlife and Humans; T. Colborn, F. S. vom Saal, and A. M. Soto, W. Alton Jones Foundation, Washington, DC 20037. Author: Ed George

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Application Note #CA 284780 Meeting Challenging Laboratory Requirements for USEPA Method 8270 Using a Highly Sensitive, Robust, and Easy-to-Use GC-MS
Abstract The analysis of semi-volatile organic compounds (SOCs) using EPA Method 8270 presents challenges due to the wide variety of acids, bases, and neutrals that must be analyzed in extremely complex sample extracts. Laboratories are under pressure from their customers to provide lower detection limits, faster sample turn-around-time, and detailed reports that contain all the validated quality control data. In addition, these labs want a GC-MS system that is easy to set up and manage, because constant requests for new target analytes increase the overall burden of data analysis and processing when changes to the existing method are required. The Bruker SCION Single Quadrupole (SQ) Mass Spectrometer is designed to meet these new challenges and provides a total solution to laboratories for USEPA Method 8270. Introduction Traditionally, USEPA Method 8270 has been used to analyze a variety of complex sample matrices using full scan GC-MS. Most labs analyze a subset of the compounds listed in the method, typically 75 to 100, at a calibration concentration range of 1 to 200 ppm. Newer versions of the method allow for the use of selected ion monitoring (SIM), which can significantly lower detection limits. Mixed mode scan methods, such as SIM/Scan, have the benefits of lowering detection limits and simultaneously providing full scan data for library search confirmation of target compounds and tentative identification of any unknown peaks in a chromatogram. To take full advantage of this mixed mode approach the mass spectrometer must be capable of fast acquisition speed, especially if large numbers of compounds are added to the SIM component of the method. Secondly, the analytical system must have excellent sensitivity in the full scan mode, because library search results will be used for confirmation in many cases. Finally, the data acquisition and processing must be easy to maintain and manage in the mixed mode to meet the demand for the ever-increasing number of target compounds. The Bruker SCION SQ meets these challenges by providing an inert ion source and revolutionary ion optics to obtain part-per-billion sensitivity in full scan analysis. In addition, software known as Compound Based Scanning (CBS) makes it easier than ever before to set up, optimize, and maintain complex mixed
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mode methods. Additional tools such as tune-to-target and custom EPA reporting templates round out a complete solution for USEPA Method 8270. Experimental The following conditions were used for set up of the gas chromatograph and full scan mass spectrometry components of Method 8270. A pulsed-split injection was used for the analysis, which provided excellent sensitivity with a minimized amount of sample entering the column. The SCION SQ under these conditions is capable of easily detecting and quantitating concentrations of most analytes down to 75 ppb or lower in full scan, which is 10-100 times less than what is required in the method. In the mixed scan mode, all 100 components were analyzed in full scan, along with 57 compounds in SIM mode. See Table 1 for analytes and SIM ions monitored for each. Calibration standards were prepared at 0.075, 0.15, 1, 2, 5, 10, 30 ppm. Seventeen very dirty sludge extracts were provided by a local environmental laboratory, see Figure 1 showing an example extract. 451-GC Gas Chromatographic Conditions Column: Column Flow Rate: Injector: Injector Conditions: Column Temperature Program: BR-5ms, 30 m x 0.25 mm x 0.25 um 1.0 mL/min constant flow Bruker Split/Splitless injector, with 4 mm ID Siltek Fritted Liner 40 psi pulsed split set 1:50 for 0.30 min at 250 C 45 C, hold 3 min, ramp to 120 at 30 C/min, hold 1 min; ramp to 310 C at 10 C/min, hold 5 min. 1.0 L using Bruker 8400 auto sampler 45-450, unit mass resolution 200 ms, positive ion polarity 300 C 280 C 2 min 80 A

Injection: Scan Range: Scan rate: Ion Source Temperature: Transfer line Temperature: Filament Delay time: Filament Emission Current:

SCION SQ Full Scan MS Conditions

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Table 1: SIM ions monitored in mixed mode on the SCION SQ

Compound Name N-Nitrosodimethylamine 2-Fluorophenol Phenol-d5 Phenol bis(2-chloroethyl)ether 2-Chlorophenol 1,4-Dichlorobenzene-d4 N-nitroso-di-n-propylamine Nitrobenzene-d5 2,4-Dimethylphenol 2,4-Dichlorophenol Naphthalene 4-Chloro-3-methylphenol 2-Methylnaphthalene 1-Methylnaphthalene 2,6-Dimethylnaphthalene 2,4,6-Trichlorophenol 2,4,5-Trichlorophenol 2-Fluorobiphenyl 2,3,4-Trichlorophenol Biphenyl Dimethylphthalate Acenaphthylene Acenapthene 2,3,5-Trimethylnaphthalene Diethylphthalate Fluorene Azobenzene 2,4,6-Tribromophenol Hexachlobenzene Pentachlorophenol Phenanthrene-d10 Phenanthrene Anthracene Carbazole 1-Methylphenanthrene Di-n-butylphthalate Fluoroanthene Retention Time 3.639 5.177 6.106 6.119 6.212 6.290 6.542 7.071 7.312 7.892 8.237 8.524 9.597 9.867 10.071 10.248 10.491 10.563 10.673 10.698 10.885 11.633 11.841 12.242 13.139 13.278 13.444 13.853 14.023 14.731 15.240 15.658 15.714 15.834 16.281 17.188 17.195 18.555 SIM Ion 74 112 99.1 94.1 93 128 152 70 82 107 162 128 107 142.2 142.2 156 196 196 172 196 154 163 152.2 153.2 170 149.1 149.1 77 330 284 266 188.1 178.2 178.2 167 192 149.1 202.2

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Compound Name Pyrene Terphenyl-d14 Butylbenzylphthalate Chrysene Benzo(a)anthacene Bis(2-ethylhexyl)phthalate Di-n-octylphthalate Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(e)pyrene Benzo(a)pyrene Perylene-d12 Perylene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene

Retention Time 19.089 19.544 20.784 21.975 22.062 22.176 23.649 24.376 24.436 24.945 25.047 25.171 25.224 27.469 27.531 28.149

SIM Ion 202.2 244.3 149.1 228.2 228.2 149.1 149.1 252.2 252.2 252.2 252.2 264.2 252.2 276.3 278.3 276.2

Results All users of USEPA Method 8270 know that passing the DFTPP tune is critical to the validity of the sample data. The Bruker SCION SQ has built-in tune-to-target ratio in mass calibration for DFTPP, as shown in Figure 2. A tune report is easily generated using built-in report for- mats by simply selecting the data file and DFTPP peak, and then generating a pass/fail report as shown in Figure 3. System Performance Check Compounds (SPCCs) are used to check the integrity of the liner/column and the inertness/ cleanliness of the ion source region. Pentachlorophenol is a good test for active sites, as it tends to fail peak Gaussian test probes when the system becomes dirty. SPCCs can be injected and then immediately checked for degradation, Gaussian peak shape, or resolution in one easy reporting tool that is uses Microsoft Access to generate the required report. An example report for pentachlorophenol peak shape on the SCION SQ is shown in Figure 4.

Figure 1: Clean extract (left), sludge extract (right)

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Figure 2: Tune-to-target for EPA tuning compounds are selectable in the software, and ratios can be easily edited if further optimization is required.

Figure 3: Example tune report for DFTPP

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Figure 4: Peak tailing factor and Peak Gaussian report generated for the SPCC sample in Bruker MSWS 8 Custom

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Access reports The other SPCCs are listed below in Table 2 as average RRF compared to the method 8270 criteria. Table 2: SPCC Results
Compound N-nitroso-di-n-propylamine Hexachlorocyclopentadiene 2,4-Dinitrophenol 4-Nitrophenol Method 8270 Criteria (Min RRF) 0.05 0.05 0.05 0.05 RRF on SCION SQ Cal Range 0.075-30ppm 0.109 0.138 0.149 1.03

After the system checks out a calibration series is analysed. In this case, the laboratory required a much lower concen- tration range than suggested by the method, from 0.075 ppm to 30 ppm (Method uses 5 ppm to 200 ppm). These concentrations clearly challenge the analytical system, especially for compounds that tend to be absorbed by active sites at low concentration. Figure 5 is an example section of a chromatogram in full scan mode for the cali- bration standard at 0.075 ppm. Internal standards are at a concentration of 40 ppm as recommended by the method. Note that the trichlorophenols are easily detected in scan mode.

Figure 5: Full Scan of 0.075 ppm calibration standard (Top) and extracted ion chromatogram (bottom) for the trichlorophenols Calibration curves for most analytes were linear over the calibration range, even for difficult compounds like pyridine as shown below. As seen here, the SCION SQ is a very inert system as there is no loss of the pyridine at the low end of the calibration curve. Overall Calibration Statistics: Average % RSD = 11.62 %
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Average Correlation Coeffiecient =0.9989

Figure 6: Pyridine calibration curve from 0.075 ppm to 30 ppm in full scan of the SCION SQ. In order to gain even more sensitivity for key target com- pounds in Method 8270, SIM mode is often used. Modern GC/MS systems can be set up in a mixed scan mode, in which SIM ions are monitored at the same time during a full scan acquisition. The Bruker SCION SQ has a unique software feature known as Compound Based Scanning (CBS), in which SIM ions for compounds are stored in either a factory supplied library or user created library. The scan information, compound retention times, and individual dwell times are all stored and are easily selected and loaded directly into a data acquisition method. CBS automatically optimizes scan times based upon desired number of data points to be acquired for a chromatographic peak, typically 10 points, so that accurate and precise quantitation is possible. The user does not have to manage complex time segments, because CBS automatically optimizes SIM scans throughout the chromatographic run based upon the retention time and retention time window. See Figure 7.

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Figure 7: Mixed mode data acquisition for Method 8270. CBS automatically optimizes scanning ranges for target SIM ions. The full scan segment (red and on top) occurs throughout the run. The total scan time is represented by a bar graph at the top. CBS is therefore a powerful tool to easily manage a large number of SIM ion acquisitions for a complex method like 8270. No need to worry about too many ions in a single segment, segment breaks, or whether one compound needs to be in more than one segment. CBS also automatically creates the data handling method that is associated with the acquisition method, linking the tables. Therefore, if there is a change in the acquisition method, e.g., a compound added or deleted, the change will be reflected in the data handling method table as well. This saves the operator time because only one list of method compounds and conditions needs to be managed. The mixed scan mode in CBS provides excellent sensitivity, as shown in the example chromatogram in Figure 8. Benzo(ghi)perylene is a PAH that elutes late in the chromatographic run, often with excessive column bleed. SIM monitoring provides clean baseline and enhanced signal-to-noise resulting in lower detection limits.

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Figure 8: Mixed mode acquisition using CBS of 0.075 ppm calibration standard. Ion at m/z 276 can be extracted from the full scan data (green), but SIM run (red) simultaneously give best signal-to-noise and peak shapes to be used for low-level quantitation. DFTPP can also be checked and will pass method criteria when the SCION SQ is operated in the mixed mode. Thisis because of the high speed scan rate combined with the optimal placement of the SIM scans in the acquisition. Another important aspect in the routine operation of the method is the ability to maintain good data quality while analyzing dirty sample extracts. Since the SCION SQ is very sensitive, a pulsed-split injection can be used instead of a pulsed-splitless injection. Pulsed-split decreases the total amount placed onto the column, therefore increasesthe life of the column, liner, and thus improves throughput. Laboratories that analyse sludge extracts like that shown in Figure 1 often see loss of internal standards and poor peak shape after only a few injections. Continuing calibrationchecks (CCCs) are used to monitor the recovery of internal standards before and after sample extracts are run to ensure that there is minimal loss in sensitivity. An example of internal and surrogate standard peaks monitored in theCCC before and after 17 sludge extracts is shown in Table 3.

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Table 3: Peak areas in the CCC of internal and surrogate standards before and after sludge extracts. Peak shape and response were maintained in spite of over 30 injections of the sludge extracts, as shown in Figure 9 below.
Standard Peak Area 1st CCC Peak Area Last CCC % Difference Perylened12 93230000 Phen2306000000 Terphenyld14 369600000 Phenold5 343800000 Nitrobenzened5 181700000

71140000

2409000000

365400000

369000000

201100000

23.69

4.47

1.14

7.33

10.68

Figure 9: Excellent peak shape and response for pentachlorophenol is still maintained after 30 injections of sludge extracts. (Top- PCP peak before injection of extracts, Bottom-PCP peak after injection of extracts). Reporting of the samples and quality control is the final step that must be completed by the lab. Bruker offers EnviroPro, a Microsoft Access database that will gene- rate all of the required reports for EPA Method 8270, as well as several other methods. Example reports are tune criteria, method detection limit calculations, initial calibration reports, and continuing calibration checks. There are several graphic options available for printing chromatograms and target compounds, as well as unknown peaks (non- target analytes). Qualitative interrogation of full scan data is another very important reason to run Method 8270 in the mixed mode.

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Conclusion The Bruker SCION SQ GC/MS and MSWS software has been shown to be a complete solution for USEPA Method 8270. The robust ion source and sensitivity of the instrument allow for lower reporting limits in challenging sample extracts. Compound based scanning is a novel approach allowing easy set-up and management of complex mixed mode methods. Compound scan information is loaded directly into the method by choosing them from a factory or user created library. It automatically optimizes scan times for SIM ions, and links the mass spectrometer acquisition table directly with data handling parameters, saving time and making it easier to add or delete compounds. Standard EPA templates for Method 8270 and several other EPA methods are available in EnivroPro, a Microsoft Access database reporting package.

Figure 10: The Bruker EnviroPro software package for environmental methods in Microsoft Access 2010.\ Keywords SCION SQ, GC-MS, EPA 8270, Environmental Testing Instrumentation and Software SCION SQ 451-GC 436-GC 8400 A/S Author: Ed George For research use only. Not for use in diagnostic procedures.

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Application Note # CA-274101 Evaluation of Rapid Extraction and Analysis Techniques forPolycyclic Aromatic Hydrocarbons (PAHs) in Seafood by GC/MS/MS
Rapid sample preparation methods for the analysis of Polycyclic Aromatic Hydrocarbons (PAHs) in seafood were evaluated using GC/MS/MS as the determinative technique. Three preparation techniques were studied: a) QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction followed by cleanup/concentration with stir bar sorptive extraction (SBSE), b) QuEChERS extraction followed by cleanup with dispersive solid phase extraction (dSPE), and c) QuEChERS extraction followed by direct analysis with a Chromatoprobe sample introduction device. The first two techniques provided excellent quantitative data at low to sub- 1 ng/g for most PAHs in the seafood matrices studied. The Chromatoprobe in the third technique was used as a rapid screening tool for levels in the 20 -50 ng/g range. The combined use of GC/MS/MS with these sample preparation methods was necessary to eliminate matrix interference and increase both precision and accuracy. Introduction The Gulf of Mexico oil spill in the summer of 2010 created immense anxiety over environmental and seafood safety concerns. Laboratories capable of performing sampling and analysis of seafood were inundated with requests. The presence of PAHs was determined to be a good indicator of seafood contamination. As a result, laboratories turned to an approved method of analysis developed by the NOA A (National Oceanographic and Atmospheric Administration)[1]. The NOA A method, however, was incapable of processing the large numbers of samples that needed to be analyzed from an oil spill of this magnitude. In order to meet the demand, organizations such as AOAC and others began to look for more rapid extraction techniques. The QuEChERS approach, which had been used successfully for the analysis of pesticide residues in a variety of food commodities, seemed to be a logical method to try with seafood [2]. It would allow an analyst to analyze 50 -100 samples per day with minimal solvent consumption. Currently, the AOAC is in the process of evaluating a QuEChERS-like extraction method for seafood in an inter-laboratory study. The new method uses gas chromatography-mass spectrometry for detection, allowing either single ion monitoring (SIM) mode or tandem mass spectrometry.[3] Although the AOAC method provides a more rapid analysis than the NOA A method, it still requires two laborious solvent exchange steps and clean-up with a silica gel column. Typical cleanup of QuEChERS extracts employ dispersive solid phase extraction (dSPE), followed by rapid centrifugation; no further cleanup or solvent exchange is required. Cochran et al. reported a method using QuEChERS
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with dSPE cleanup of shrimp and mussel tissue [4]. Ed Phankoch et al. reported cleanup and concentration of QuEChERS extracts using stir bar sorptive extraction (SBSE) and thermal desorption or solvent back extraction GC/MS and LC/Fluorescence techniques [5],[6]. In this work, dSPE and SBSE cleanup techniques on QuEChERS seafood extracts were evaluated. In addition, a screening analysis for seafood samples is presented. GC/MS/MS was chosen because it provided excellent quantitative results in the low to sub-ng/g range. Experimental The seafood matrices studied were shrimp, oyster, Atlantic salmon, and blue mussel tissue (ASTM Standard spiked reference material). Calibration and matrix spikes were prepared and analyzed as described below. Three sample preparation approaches were evaluated: PAHs by QuEChERS with Stir Bar Sorptive Extraction (SBSE) followed by Back Extraction (TBE) PAHs by QuEChERS with Dispersive Solid Phase Extraction (dSPE) PAHs by QuEChERS Express Extraction and Screening with the Chromatoprobe inlet

QuEChERS + SBSE The logic for this experiment was based on the idea that (SBSE), a coating of polydimethylsiloxane on a small magnetic stir bar, could be added to a diluted QuEChERS extract to absorb the PAH compounds with minimal co-extraction of matrix material. It can then be placed in a thermal desorption unit with cryotrap to remove/trap/ desorb the PAHs directly into the GC/MS. Since the thermal desorption unit and cryotrap hardware was not available for the study, an alternative method was developed to remove the PAHs from the extraction device. Back Extraction (TBE) has been reported in liquid chromatography applications [6]. This technique involves adding a small volume of solvent to the SBSE device in a micro vial to extract the analytes. The extraction process for the seafood samples using this approach is described in the flow chart (Figure 1). Figure 2 describes SBSE with back extraction.

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Figure 1: QuEChERS extraction procedure with Back Extraction. QuEChERS with Dispersive Solid Phase Extraction (dSPE) This sample preparation was designed around the original QuEChERS cleanup procedure, which uses a cocktail of salts and C18 sorbent that is vigorously mixed with a small volume of the extract and subsequently centrifuged before transferring to a collection vial. Figure 3 describes the overall extraction procedure used.

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Figure 2: Left figure is the SBSE in diluted seafood extract; Right figure is the device inside a vial containing an insert with 220 L hexane. Setting the vial on the edge of the stir plate with the magnet turned ON allows the SBSE to be gently agitated during back extraction.

Figure 3: QuEChERS extraction procedure with dSPE cleanup.

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QuEChERS Express Extraction and Screening with the Chromatoprobe Inlet The final experiment was designed to provide a rapid prep-and-screen approach for PAHs. It could be used to gain information on batches of seafood samples. A crudely prepared sample was added to a micro vial and placed into a Chromatoprobe inlet, which is coupled to the mass spectrometer source with a 2 meter narrow bore capillary column. Figures 4 and 5 describe the sample preparation method and Chrompatoprobe technique. The short capillary transfer line to the ion source enables some separation of analytes and protects it from matrix overload. Only 1-3 L of the crude extract is required to obtain good sensitivity for screening. Semi-quantitative data may be obtained by comparing to known standards.

Figure 4: Sample preparation workflow for PAH screening method. General Instrument Parameters and Consumables Bruker 300 -MS with 450 -GC, Combi-PAL Auto sampler Injector Inlets: 1177 Split/splitless, 1079 (in Programmed Temperature mode-PTV), Chromatoprobe accessory for 1079. Inlet Liners: 4 mm Restek Siltek fritted liner for 1177 splitless injections 3.4 mm SGE Focus Liner for PTV injections on 1079 Columns: Restek Rxi-5 Sil-MS, 30 M x 0.25 mm x 0.25 m; DB-1 for use with Chromatoprobe, 2 M x 0.1 mm x 0.1 m SBSE device for backextraction experiments, 0.5 mm PDMS x 10 mm length dSPE with Restek Q-sep Q251, 150 mg MgSO4/50mg PSA /50 mg C18, packaged in 2 mL centrifuge tubes

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Column and Inlet Conditions: Column Oven Program: 45C hold 1 min, 200C @ 10C/min, hold 0; 270C @ 5C/min, hold 0; 300C @ 10C, hold 0; 320C @ 20C/ min, hold 1 min. 1177 Splitless mode for 0.9 min, 270C, 40 psi pulse 1079 PTV mode; temp and vent times optimized for hexane (TBE) and Acetonitrile (dSPE) Chromatoprobe: 70C to 350C @ 200C/min; Column: 45C for 1 min; 65C @ 20C/min, hold 0; 320C @ 50/min, hold 1 min Source: 300C Collision Gas: Argon, 2 mTorr MRM dwell times: 100 ms most transitions with total scan time less than 0.6 min/segment. The s-MRM tool was used to optimize the distribution of MRM segments and sensitivity

General MS Parameters:

Figure 5: Chromatoprobe inlet. The device is inserted into a programmable injection port to allow for temperature control during analysis. A disposable micro-vial is inserted into the probe tip, which resides inside a standard GC injection liner. The column is typically a short 0.10 mm ID capillary column with a thin coating. Results QuEChERS + SBSE
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Calibration standards were prepared in pure acetonitrile solvent. One milliliter of each standard was added to 4 mL 0.1 M sodium bicarbonate solution. The SBSE unit was added and allowed to stir for 90 minutes. The SBSE device was then back extracted with 220 L of hexane in a micro vial and injected into the GC/MS/MS. These standards were injected in both standard hot splitless mode and in the PTV mode. Results are presented in Tables 1-5 and Figures 6 -8. Excellent response is seen for all calibration levels, especially when PTV is used. The higher % RSD response for naphthalene was due to laboratory background and reagent contamination seen at low ng/g levels. The actual amount of analyte injected on the column for each injection technique is summarized in Table 3. Matrix spikes and standard reference material were used to validate method performance. An example total ion current (TIC) MRM chromatogram is shown if Figure 8, followed by matrix spike data. All spiked seafood was homogenized thoroughly before the QuEChERS extraction.

Figure 6: Example Calibration Curve for Benzo(a)pyrene, 1 ng/g to 250 ng/g.

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Table 1: Calibration statistics for PAHs with SBSE and TBE, 1ng/g to 250 ng/g, 2 L splitless injection.
RRF Avg. RRF 0.737 1.068 0.846 0.690 1.403 1.049 1.806 1.771 1.483 1.467 1.683 1.620 1.436 1.422 1.608 1.538 % RSD 21.1 8.6 5.1 17.6 13.6 16.0 17.9 11.1 17.6 17.2 12.3 17.1 11.9 18.3 27.9 18.7 1 ng/g 1.017 0.979 0.842 0.931 1.769 1.215 2.445 2.127 2.005 1.939 2.088 2.175 1.779 1.942 2.513 2.112 RRF 5 ng/g 0.820 1.244 0.918 0.684 1.437 1.300 1.812 1.791 1.386 1.507 1.690 1.605 1.412 1.412 1.530 1.526 RRF 10 ng/g 0.673 1.043 0.853 0.628 1.349 0.936 1.603 1.810 1.436 1.474 1.642 1.519 1.385 1.246 1.312 1.412 RRF 50 ng/g 0.665 1.058 0.839 0.664 1.326 0.964 1.711 1.707 1.419 1.341 1.573 1.484 1.350 1.292 1.404 1.356 RRF 100 ng/g 0.612 1.019 0.782 0.594 1.237 0.887 1.579 1.595 1.278 1.252 1.537 1.458 1.323 1.298 1.442 1.390 RRF 250 ng/g 0.636 1.064 0.842 0.642 1.298 0.992 1.685 1.598 1.374 1.290 1.567 1.479 1.369 1.344 1.449 1.430

Compound Name Naphthalene Acenaphthylene Acenapthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene

Corr. 0.9996 0.9997 0.9991 0.9988 0.9995 0.9979 0.9992 0.9998 0.9990 0.9997 0.9999 1.0000 0.9998 0.9998 0.9999 0.9998

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Table 2: Calibration statistics for PAHs with SBSE and back-extraction, 0.5 ng/g to 50 ng/g, 8 L PT V injection.
RRF Compound Name Naphthalene Acenaphthylene Acenapthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene Corr. 0.99257 0.99992 0.99999 0.99998 0.99996 0.99998 1.00000 0.99998 0.99998 0.99998 1.00000 0.99997 1.00000 1.00000 1.00000 1.00000 Avg. RRF 2.0385 1.8079 1.5050 0.7279 1.6401 1.4000 1.5072 1.6158 1.5972 1.8862 2.5040 2.5244 1.2573 1.3964 1.1545 1.4017 % RSD 46.5 8.5 10.4 12.1 9.5 3.4 3.1 7.0 8.8 8.0 6.5 3.6 3.4 7.1 5.1 3.9 0.5 ng/g 2.3539 1.6020 1.6180 0.7223 1.6045 1.4386 1.5666 1.4986 1.6926 2.0244 2.6802 2.4579 1.2583 1.5249 1.2365 1.4714 RRF 1 ng/g 3.1240 1.8283 1.6593 0.8535 1.8582 1.4263 1.5153 1.7603 1.7360 1.9965 2.6000 2.6158 1.3171 1.4226 1.0995 1.4208 RRF 5 ng/g 1.8042 1.9753 1.3973 0.6758 1.6081 1.4020 1.4923 1.6419 1.5237 1.8180 2.4090 2.5885 1.2224 1.3219 1.1504 1.3547 RRF 50 ng/g 0.8719 1.8259 1.3457 0.6601 1.4896 1.3334 1.4549 1.5624 1.4366 1.7062 2.3268 2.4352 1.2314 1.3160 1.1317 1.3599

Table 3: Calibration standard theoretical amounts (assuming 100% absolute recovery) of PAHs injected into the Bruker 300-MS GC/MS/MS system. Based on 3 g seafood with sample preparation described in Figure 1. Subng/g levels are easily detected.
2 L Spike Conc (ng/g) 0.1 0.5 1 5 10 50 100 250 (ng) on Twister 0.02 0.1 0.2 1 2 10 20 50 (ng/mL) in TBE 0.091 0.46 0.91 4.6 9.1 45.5 91 228 (pg) inj on column 0.182 0.91 1.82 9.1 18.2 91 182 455 8 L (pg) inj on column 0.728 3.64 7.28 36.4 72.8 364 728 1820

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Figure 7: Example PT V calibration injection, MRM 252>250, 0.5 ng/g level for Benzo(b)fluoranthene, Benzo(k)fluoranthene, and Benzo(a)pyrene.

Figure 8: TIC-MRM chromatogram of oyster matrix spike by QuEChERSSBSE-TBE, 5 ng/g.

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Table 4: 20 ng/g seafood spikes results.

Compound Naphthalene Acenaphthylene Acenapthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene Spike Level 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Shrimp Obs Conc 24.1 21.6 21.1 22.0 20.3 18.3 18.4 25.8 19.9 19.6 15.6 16.1 15.1 14.0 15.1 14.0 Oyste Obs Conc 24.1 19.7 19.2 19.9 20.4 17.1 17.7 26.3 20.9 20.5 15.2 14.3 14.6 11.1 11.7 11.7 Salmon Obs Conc 27.3 24.3 22.1 24.0 20.9 21.3 16.5 26.0 19.8 18.9 14.4 12.6 11.4 11.2 14.0 11.8 Ave % Recovery 126 109 104 110 103 95 88 130 101 98 75 72 68 60 68 62

Results Summary SBSE can be efficiently back-extracted with a small amount of hexane instead of using more expensive and complex thermal desorption equipment. Resulting extract is very clean (no color) less matrix is always better for high-throughput robust methods. (See Figure 9) 2 L splitless injection of the back-extract gives plenty of sensitivity- use 8 L PTV for better precision and accuracy at 0.1- 0.5 ng/g. Lower recovery of late eluting PAHs was observed, could be corrected using C13 labeled internal standards. A more efficient SBSE extraction warrants further investigation. Background naphthalene and other PAHs become magnified laboratory and reagent contamination problems at low concentrations.

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Figure 9: Final oyster SBSE extract (left) compared to dSPE extract (right). Less matrix is co-extracted with SBSE. Table 5: ASTM SRM 1974b Blue Mussel tissue, 2 L splitless injection.
Compound Naphthalene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene/ Terphenylene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene Certified Value (ng/g) 2.43 0.494 2.58 0.527 17.1 18.04 4.74 10.63 6.46 3.16 2.8 2.14 0.327 3.12 SRM 1974b Obs Conc 2.5 0.4 2.4 0.7 14.8 20.6 4.2 10.4 6.9 2.1 1.6 1.8 0.7 2.4 % Difference -2.3 27.5 8.9 -25.4 13.7 -14.4 10.4 1.8 -7.0 34.0 44.4 15.7 -107.0 22.1 % Recovery 102 72 91 125 86 114 90 98 107 66 56 84 207 78

QuEChERS with Dispersive Solid Phase Extraction (dSPE) Calibration standards for this method is based upon a 10 g seafood sample; the procedure is described in Figure 2. The standards were prepared in acetonitrile, with the intent to directly inject the final extracts into the GC/MS/ MS without performing additional solvent exchange steps. PTV injection is ideal because most of the acetonitrile can be evaporated at an inlet temperature below the boiling point of the solvent prior to splitless transfer into the analytical column. This helps avoid peak splitting or tailing of early eluting PAHs, such as naphthalene. In addition, PTV injection allows more sample loading in the inlet, thus improving method sensitivity. In order to investigate potential contamination and/or recovery loses during the dSPE clean- up step, two sets of calibration standards were
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prepared in acetonitrile. One set was directly injected into the GC/MS/MS. The other set was first treated with Restek Q-sep Q251, 150 mg MgSO4/50mg PSA /50 mg C18, packaged in 2 mL centrifuge tubes. 1 mL of the each standard was added to the 2mL tube, vortexed, and centrifuged, which is the same procedure that a sample extract would follow. Calibration curves (Figure 10) and results are listed in Tables 6 through 9. Variable results with high RSDs for the PAHs highlighted in Table 7 were observed with the Q-Sep treated standards. Major variation in analyte responses were observed at levels less than 10 ng/g. The contamination was traced to the 2 mL polypropylene centrifuge tube containing the dSPE reagent. Tests performed at Restek Corporation showed that the contamination could be eliminated or greatly reduced if the reagent is removed from the tube and washed with organic solvents. Shrimp and oyster seafood spikes, along with the ASTM 1974b SRM material, were analyzed to evaluate method performance. As expected, high biased results were observed due to contamination of the dSPE reagent. Results were better against the dSPE treated calibration standards, however it is not recommended since reagent contamination cannot be reasonably controlled.

Figure 10: Calibration curves for phenanthrene. Left: Calibration in pure acetonitrile. Right: Calibration with acetonitrile standards treated with Q-Sep Q-251.

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Table 6: Calibration statistics using QuEChERs-dSPE method. The table represents standards prepared in pure acetonitrile and injected into the Bruker 300 -MS. The standards were not treated with Q-Sep Q251. PT V injection, 6 L.
RRF Compound Name Naphthalene Acenaphthylene Acenapthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene Corr. 0.99901 0.99883 0.99882 0.99834 0.99995 0.99879 0.99899 0.99920 0.99734 0.99947 0.99910 0.99966 0.99952 0.99999 0.99922 0.99989 Avg. RRF 0.9784 2.6312 1.3941 0.7356 1.5797 1.2566 1.5925 1.6502 1.4605 1.7802 2.2638 2.2978 1.2479 1.3090 1.0844 1.2724 % RSD 29.1 4.8 12.3 22.5 12.6 8.6 18.4 16.2 21.2 11.4 11.5 9.9 14.7 14.7 17.1 5.4 0.5 ng/g 1.3935 2.5003 1.6388 0.9767 1.8488 1.3092 2.0278 2.0491 1.9019 2.0608 2.6458 2.6280 1.5131 1.5821 1.3602 1.3164 RRF 2 ng/g 0.9345 2.7593 1.2591 0.7083 1.6093 1.3787 1.4831 1.5232 1.4369 1.7960 2.1775 2.2623 1.2180 1.3043 1.0220 1.3438 RRF 10 ng/g 0.7776 2.5491 1.2976 0.6090 1.4320 1.1401 1.3929 1.4796 1.1994 1.6041 2.0616 2.1195 1.1578 1.1827 0.9562 1.2255 RRF 20 ng/g 0.8080 2.7161 1.3808 0.6484 1.4286 1.1983 1.4660 1.5491 1.3038 1.6597 2.1705 2.1814 1.1028 1.1667 0.9990 1.2038

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Table 7: Calibration statistics using QuEChERs-dSPE method. The standards were treated with Q-Sep Q251. PT V injection, 6 L.
RRF Compound Name Corr. Avg. RRF % RSD 0.5 ng/g RRF 2 ng/g RRF 10 ng/g RRF 20 ng/g

Naphthalene Acenaphthylene Acenapthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene

0.82370 0.99960 0.97610 0.99573 0.97074 0.99988 0.99896 0.99941 0.99992 0.99968 0.99932 0.99979 0.99978 0.99935 0.99913 0.99830

20.3712 2.6823 5.3532 1.8312 6.2973 1.5404 1.9754 1.7742 1.2782 1.7564 2.1337 2.1812 1.1713 1.1087 1.0048 1.2105

139.8 8.6 116.3 106.2 129.6 34.7 48.5 22.6 4.1 10.6 11.4 6.5 12.1 7.0 11.2 16.3

62.3529 2.9251 14.5400 4.7250 18.4875 2.3260 3.4078 2.3363 1.3254 2.0319 2.4771 2.3250 1.3799 1.2151 1.1461 1.4888

13.8277 2.8296 3.8871 1.2155 3.3188 1.4267 1.5962 1.7788 1.3193 1.6885 2.1255 2.2807 1.1349 1.1108 1.0414 1.2057

3.1513 2.4574 1.4863 0.7250 1.7827 1.2069 1.4336 1.5351 1.2452 1.6831 1.9256 2.0426 1.0737 1.0317 0.8961 1.0381

2.1529 2.5169 1.4992 0.6593 1.6001 1.2021 1.4641 1.4465 1.2228 1.6220 2.0068 2.0764 1.0969 1.0774 0.9357 1.1093

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Table 8: Matrix spikes at 5 ng/g for oyster and shrimp. These values were calculated against untreated acetonitrile calibration standards.
Compound Naphthalene Acenaphthylene Acenapthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene Spike Level (ng/g) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Shrimp Obs Conc 30.4 4.9 7.7 7.3 8.4 5.6 5.9 5.7 5.3 5.3 5.0 4.9 5.9 4.4 5.2 3.9 Oyster Obs Conc 14.3 5.8 7.6 7.1 7.6 5.3 6.1 5.6 5.4 6.0 5.0 5.3 5.1 4.4 5.4 4.6 Ave % Recovery 447.4 107.8 153.2 144.0 160.9 109.6 119.5 113.5 106.4 112.5 100.1 102.4 109.3 87.6 105.6 84.6

Table 9: SRM 1974b results against untreated acetonitrile calibration standards.

Compound Naphthalene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene/ Trphenylene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(123-cd)pyrene Dibenz(ah)anthracene Benzo(ghi)perylene Certified Value (ng/g) 2.43 0.494 2.58 0.527 17.1 18.04 4.74 10.63 6.46 3.16 2.8 2.14 0.327 3.12 SRM 1974b Obs Conc 34.1 2.0 5.3 1.8 17.7 18.1 4.3 9.1 6.4 2.2 2.0 1.3 0.4 2.5 % Difference -1302.5 -311.9 -106.4 -246.7 -3.3 - 0.5 10.3 14.7 1.2 31.4 28.6 38.0 -18.3 20.7 % Recovery 1402 412 206 347 103 100 90 85 99 69 71 62 118 79

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Results Summary The QuEChERS-dSPE method with PTV injection is much quicker and easier than solvent exchanges / traditional silica-gel type clean-ups Convenient packaging of dSPE materials in 2mL centrifuge tubes bodes well for high production labs Good recovery of all PAHs was obtained using the technique The main problem was contamination seen at low ng/g levels- It originated from dSPE reagent packaging. For low-level work, it is recommended to remove the reagents from the packaging and clean with organic solvents. QuEChERS Express Extraction and Screening with the Chromatoprobe inlet A semi-quantitative screening method with Chromatoprobe provided reliable data for levels above 20 ng/g. Seafood samples were rapidly extracted with ethyl acetate, followed by centrifugation. The crude extract was placed into the Chromatoprobe device for rapid analysis. Figure 11 shows a 100 ng/g standard run in under 6 minutes, with relatively good separation and response. The ASTM SRM 1974b was analyzed, and response was detected for fluoranthene and pyrene, which are near the certified value of 20 ng/g. Because crude extracts are injected, it may be necessary to analyze a solvent blank to clean the system out after a highly contaminated sample. Carryover was minimized by ramping the PTV to a high temperature with high split flow rate.

Figure 11: 100 ng/g standard with Chromatoprobe, TIC MRM chromatogram.

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Figure 12: ASTM SRM 1974b with Chromatoprobe Results Summary Method is rapid, and ideal for screening only Carryover is reduced by heating injector to 350C at the end the GC cycle and limiting amount of extract to 1-2 L added to micro-vial Ideal for screening seafood above 20 ng/g Limited to manual injections only

Conclusion High-throughput QuEChERS methodology was successfully applied to the analysis of seafood samples. The use of the Bruker 300 -MS triple quadrupole mass spectrometer effectively removed matrix interference and provided sub- ng/g detection limits with good precision and accuracy. The QuEChERS-SBSE-BE method demonstrated the advantages of cleaner extracts and analyte enrichment via back extraction with a small volume of GC-suitable solvent (hexane). More investigation into the extraction conditions is needed to improve recovery observed for late-eluting PAHs. The QuEChERS-dSPE cleanup method using commercially prepared dSPE reagents provided excellent recovery for all PAHs studied. Contamination was observed in calibration standards processed with the reagents, and was traced to the packaging. Cleaning the reagents with organic solvents or storing them in PAH-free containers will allow for lower limits of detection (less than 10 ng/g). Both of the techniques were evaluated with PTV injection, which improved precision and accuracy. PTV is particularly important for extracts prepared in acetonitrile due to potential peak splitting for early eluting PAHs. The Chromatoprobe device provided a good screening tool for PAHs in seafood. Levels greater than or equal to 20 ng/g in seafood were easily detected. Careful attention to potential carryover from highly contaminated samples is required.

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Shrimp and oyster seafood spikes, along with the ASTM 1974b SRM material, were analyzed to evaluate method performance. As expected, high biased results were observed due to contamination of the dSPE reagent. Results were better against the dSPE treated calibration standards, however it is not recommended since reagent contamination cannot be reasonably controlled.

Figure 13: Blank run (green) run after 100 ng/g matrix spike (red) in shrimp References [1] NOA A Technical Memorandum NMFS-NWFSC-59, Extraction, Cleanup, and Gas Chromatography/Mass Spectrometry Analysis of Sediments and Tissues for Organic Contaminants, Catherine A. Sloan, Donald W. Brown, Ronald W. Pearce, Richard H. Boyer, Jennie L. Bolton, Douglas G. Burrows, David P. Herman, and Margaret M. Krahn, Northwest Fisheries Science Center, Environmental Conservation Division, 2725 Montlake Blvd East, Seattle, Washington 98112, March 2004 [2] M. Anastassiades, S.J. Lehotay, D. Stajnbaher and F.J. Schenck, J AOAC Int 86 (2003) 412. [3] Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Seafood using Gas Chromatography-Mass Spectrometry: A Collaborative Study Katerina Mastovski et.al., Covance Laboratories Inc., 671 S. Meridian Road, Greenfield, IN 46140 [4] The QuEChERs Approach with GC-TOFMS and GCxGC-TOFMS for PAHs in Oil Contaminated Seafood; Jack Cochran, Restek Corporation, 110 Benner Circle, Bellefonte, PA 16823, Florida Pesticide Residue Workshop, 2010. [5] High Throughput Method for the Determination of PAHs in Seafood by QuEChERS-SBSE-GC-MSE; Edward A. Pfannkoch, John R. Stuff, Jeffrey H. Moran and Jacqueline A. Whitecavage GERSTEL Inc., 701 Digital Drive Suite J, Linthicum MD 21090, Public Health Laboratory, Arkansas Department of Health, 201 South Monroe Street, Little Rock Arkansas 72205. [6] Semi-Automated Stir Bar Sorptive Extraction (SBSE) in Combination with HPLC - Fluorescence Detection for the Determination of Polycyclic Aromatic Hydrocarbons in Water; Barbara Hauser, Peter Popp, Coretta Bauer, UZE-Centre
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for Environmental Research, Leipzig-Halle, Department of Analytical Chemistry, Permoserstr. 15, D- 04318, Leipzig, Germany. Keywords Tandem mass spectrometry, seafood, food safety, polycyclic aromatic hydrocarbons (PAH), Gulf oil spill Instrumentation and Software Bruker 300 -MS Bruker 450 -GC Combi-PAL Autosampler Chromatoprobe MSWS 7.0 Restek column Rtx-5 Sil-MS Restek dSPE Q-Sep

Author: Ed George

For research use only. Not for use in diagnostic procedures.

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