Automation of Sample Preparation in Ion Chromatography

Transcription

1 Automation of Sample Preparation in Ion Chromatography Praha, nd October 04 Ing. Roman Repáš ACO Sales Manager (IC and SP) Agenda Thermo Scientific Dionex Sample Preparation Products Automation of Sample Preparation in Ion Chromatography ph and Conductivity Measurement Inline Filtration Inline Sample Preparation Matrix Elimination using Dionex InGuard Chemistries Matrix Elimination with Selective Analyte Trapping

2 Thermo Scientific Dionex Sample Prep Product ine Thermo Scientific TM Dionex TM ASE TM 0 and 30 Accelerated Solvent Extractor Thermo Scientific Dionex AutoTrace TM 80 Solid-Phase Extraction (SPE) Instrument Thermo Scientific Dionex SolEx TM SPE Cartridges Genevac Rocket TM Evaporator Novel & Innovative Solutions How Does Accelerated Solvent Extraction Work? Cell loading Fill, heat, (min) equilibrate to 9 dynamic extraction Solvent Solvent Solvent Pump Mixing Valve Static extraction 0 to 99 cycle static extraction Relief Valve Rinse with 0. fresh solvent dynamic extraction Oven Extraction Cell Purge with nitrogen Static Valve Extract Total (min) ready 0 Collection Bottle

3 AutoTrace 80 : Automated SPE Extraction of large volume of liquid samples Automated SPE instrument for large volume aqueous samples (0 m to 4 ) Extracts 6 samples with unattended operation All SPE parameters automatically controlled EPA approved for drinking water extraction Dionex SolEx Solid-Phase Extraction Cartridges Cartridges designed for fast, and easy preconcentration of contaminants prior to analysis Offered in a variety of chemistries and sizes to fit your sample extraction needs Silica-Based SPE Cartridges SolEx C8 SolEx C8 SolEx C8-Clean (Phthalate-Free) SolEx C8-Clean (Phthalate-Free) SolEx C8- SolEx Unbonded Silica Carbon Based SPE Cartridges SolEx Activated Carbon SolEx Graphitized Carbon Polymeric New SolEx Phases SolEx HRPHS SolEx SAX SolEx SCX SolEx WAX SolEx WCX 3

4 Rocket Evaporator Rocket Evaporator ASE Pucks Flip Flop Vials Fully Automated Workflow: Fills gap not addressed by ASE or AutoTrace Reduces aboratory Error: Pucks allow direct sample transfer from the ASE Expedites Sample Processing: Flip Flops evaporator directly into autosampler vials Total Workflow Solution: Our Key Advantage Key Applications: Fracking: ASE and C/MS Cr(VI) in soil: ASE and IC Pesticides in beverages: AutoTrace and GC/MS Key Regulations: China GB and GB : SVOC in drinking water and wastewater EPA Method 34A: POPs in solid matrices EU Water Framework Directives Productivity: Thermo Scientific as the single sources of complete analytical workflow Reduced solvent use by as much as 90% Reduced extraction time to min/sample ASE 0 and ASE 30 AutoTrace 80 GC and GC/MS C/MS Rocket Evaporator IC 4

5 Automation of Sample Preparation in Ion Chromatography ph-conductivity Accessory A small unit mounts inside an AS-AP autosampler Conductivity detector and ph flow cells in series Measurements done prior (!) to injection Conditionals in CM USB connection for power and control/communication Fluidics connections Conductivity mode only- (no ph) just leave plug in place Outlet Port USB Connector ph Cell Port ph Cable Connector Inlet line

6 ph-conductivity Accessory Easy to install USB Connection for Power and Control eave plug for conductivity only Install ph electrode, if ph measurement is desired Conductivity based Method Selection 4 : Eluent Source: Eluent: Temp.: Thermo Scientific Dionex IonPac CSA, 3 0 mm EGC-MSA 0 mm MSA Ambient Inj. Volume: A:. µ 3 6 Flow Rate: B: µ 0. m/min Detection: Suppressed conductivity 0 B A 0 Minutes 0 Sample: 6 cation standard in 00 mm HCl. ithium 0. mg/m. Sodium 3. Ammonium. 4. Potassium. Magnesium. 6. Calcium 6

7 Inline Filtration with Thermo Scientific Dionex AS-DV Thermo Scientific Dionex AS-DV positive displacement autosampler Each sample uses a separate filter, NO carryover Filter caps (0 µm pore size) Very low dead volume Particulates tend to settle to the bottom, filter moves from top down oop and concentrator loading No sample waste ow cost autosampler No sample pump needed Dionex AS-DV: How Sample Injection Works To Injection Valve Filter (0 µm) 4 7

8 Inline Filtration with Cartridges and Valves High pressure In-ine filters Multiple configurations available Filter in sample line before injection valve Inline on high pressure side Dual filters and 0-port valve with backflush pump High capacity, high volume filter stack of 3 µm, 7 µm and 0.4 µm filters ow capacity, low volume filter frit, 0. µm Advantages Entire sample is filtered- no sample loss Small sample volume loaded onto filter maximizes capacity Filter backflush minimizes carryover and extends filter lifetime Inline Filtration: Easy to implement! Detector Suppressor Analytical Guard Auto- Sampler W S P C Inline Filter Waste Pump System Backpressure Indicates When to Exchange Filter 8

9 Inline Filtration: ow Pressure or High Pressure Detector Auto- Sampler Auto- Sampler Detector W S C Suppressor 0 Suppressor Waste P Pump Analytical Guard 3 4 Waste AXP W S C Analytical Guard AXP Waste Waste P Pump Filter on the high pressure side Filter on the low pressure side Auxiliary Valves, ICS-000 and ICS-00 Auxiliary Valves Enable Many Sample Prep Solutions 9

10 Thermo Scientific Dionex InGuard Cartridges Cartridges are high capacity Cartridge Type Ag H Na HRP Na/HRP Cartridge Capacity to. meq to. meq to. meq g resin 0% Na / 0% HRP Inline approach- sample volume per cycle equals injection volume Small amount loaded onto cartridge increases effective capacity to many samples per cartridge Reduced sample processing time, labor and cost High Capacity and Small Sample Volume: Many Samples / Cartridge Description of Matrix-Elimination using Thermo Scientific Dionex InGuard Products An autosampler or pump is used to pass the sample through the cartridge to remove matrix components. The cartridges have very low backpressure but the chemistries usually function optimally at flow rates between 0. and m/min. This Sample Preparation is suitable for both standard bore and microbore IC systems The number of samples that can be treated with an Dionex InGuardproduct depends on the matrix composition, concentration of compounds to be removed and the sample injection volume. 0

11 What is the General Setup? Pump Waste W Dionex InGuard Cartridge C P W S S Auto- Sampler P Pump C Concentrator or arge Transfer oop Guard Analytical Suppressor Detector Autosampler: Thermo Scientific Dionex AS-DV, AS-AP Thermo Scientific Dionex InGuard Cartridges Application example: Anion analysis in.6% NaCl, treat with Dionex InGuard Ag followed by Dionex InGuard Na 7.6% NaCl w/o InGuard : Thermo Scientific Dionex IonPac AG and AS, 4 mm Eluent: 3 mm KOH, EGC Flow rate: m/min Sample Prep: Dionex InGuard Ag and Na cartridges Injection vol: 00 µ Detection: Suppressed conductivity, Thermo Scientific Dionex ASRS Minutes 40.6% NaCl blank without InGuard.6% NaCl with DionexInGuardAgand Na Water blank with DionexInGuard Std of ppm nitrite, sulfate, nitrate in.6% NaCl using Dionex InGuard Peaks: mg/ (in standard) Chloride Nitrite 3 Carbonate 4 Nitrate Sulfate Dionex InGuardeasily removes interfering chloride, automatically

12 Anions in 0% NaOH Chloride Chlorate Sulphate min : Thermo Scientific Dionex IonPac AS9 w/ guard Eluent: mmol/ KOH Transfer Eluent: Water Flow: 0. m/min Transfer Flow: 0. m/min Sample Pretreatment: InGuard-H Detection: Suppressed conductivity Background Signal: <. /cm Suppressor: Thermo Scientific Dionex Anion ASRS 300, recycle mode Suppressor Current: 0 ma Temperature: 30 C Injection Volume: 0 µ Sample Transfer m oop: Sample Preparation: The samples 0% NaOH were diluted ad 0 with ultrapure water and immediately analysed Matrix-Elimination Using Analyte Trapping Eluent Pump Conc. Col. Guard Waste H O Transfer Pump ASRS AS Detector

13 Determination of Anions in -Propanol : Thermo Scientific Dionex IonPac AS8, x 0 mm Eluent: 8 to 48 mm KOH (EG) in 0 min Flow Rate: 0. m/min Inj. Volume: m concentrated on UTAC-UP Detection: Suppressed conductivity Temperature: 30 C Suppressor: Thermo Scientific Dionex ASRS, recycle mode with CRD Minutes Sample : Sample : Peaks: SEMI-grade IPA 4 µg/ spiked SEMI-grade IPA. Fluoride. Chloride 3. Sulfate 4. Nitrate. Phosphate 3488 Trace Anion Analysis of Electronic Grade Acetone Minutes 3 s: Thermo Scientific Dionex IonPac AG9-HC, AS9-HC, mm Concentrator : Dionex IonPac AG9-HC, 4 mm Eluent: 8.0 mm Sodium carbonate. mm Sodium hydroxide Eluent Flow Rate: 0. m/min Rinsing Flow Rate:.0 m/min Sample Volume:.0 m Detection: Suppressed conductivity, Thermo Scientific Dionex ASRS II, AutoSuppression external water mode Peaks:. Chloride 0.00 µg/ (ppb). Nitrate Sulfate

14 Anions from Water Insoluble Drug 4.0 Drug Formulation Methanol Blank Instrument: Thermo Scientific Dionex ICS-3000 and AS Concentrator: UTAC-UP ( x 3 mm) : Thermo Scientific Dionex IonPac AG ( mm)/ AS ( mm) RFIC-EG: KOH Gradient Temperature: 30 C Flow Rate: 0.4 m/min Inj. Vol.: 00 µ Detection: Suppressed conductivity Sample: Procedure: Drug formulation in Methanol. Sample passed through UTAC. Anions collected; drug passed to waste 3. UTAC flushed with water from AS to remove MeOH 4. Anions injected onto column Fluoride Sulfate Phosphate Pump Guard Chloride Nitrate Concentrator Waste Suppressor Minutes 30 Anions Trapped and Drug Substance Removed Autosampler Detector Determination of Trace Anions in Organic Solvent 4

15 Determination of Trace Anions in Organic Solvent.0 ÌS F Cl NO NO3.00 Concentration:.00 mm min SO Collector: IonSwift MAC-00 ( mm) : IonPac AG8-Fast capillary Guard(0.4 3mm) +IonPac AG8-Fast capillary(0.4 0mm) Switching-time: 0- min Eluent (KOH): 0-6min mm; 6-min -mm; -30min -4mM; 30-40min 4mM Flow-rate:0µ/min Sample volume: 0 μ Methanol Acetonitrile Isopropanol Acetone F Cl NO NO SO PO4 N.D. N.D N.D. Anions in Hydrogen Peroxide 8 Concentrator : TAC-P Trap : ATC- : Thermo Scientific Dionex IonPac AG, AS Eluent: KOH (EG40) Temperature: 3 C Flow Rate: m/min Injection Volume: 400 µ Detection: Suppressed conductivity Minutes Peaks:. Fluoride 9.8 µ (ppb). Acetate 3. Formate 4. Chloride Carbonate 6. Sulfate Oxalate 8. Nitrate Phosphate 3.64

16 Cations in Electronic Grade Hydrogen Peroxide 0,40 0,30 NH + 4 Na + (3,70 µg/) (3,77 µg/). 0,0 0, Minutes? K + (0,67 µg/) : Thermo Scientific Dionex IonPac CS0 with Guard (4mm) Concentrator: Thermo Scientific Dionex IonPac CGA (4mm) Eluent: 40 mmol/ MSA Flow Rate: m/min Injection volume: 000 µ Detection: Suppressed conductivity Suppressor: Thermo Scientific Dionex CSRS-Ultra, ext. Water Trace Anions in High Purity 4.% HF Pretreatment : Thermo Scientific Dionex IonPac ICE-AS6 ICE Eluent: Deionized water ICE Flow Rate: 0. m/min Sample Volume: 70 µ Minutes : Thermo Scientific Dionex IonPac AG9-HC, AS9-HC, mm Concentrator: Dionex IonPac AG9-HC, 4 mm IC Eluent: 8.0 mm Sodium carbonate. mm Sodium hydroxide IC Flow Rate: 0. m/min Detection: Suppressed conductivity, Thermo Scientific Dionex ASRS UTRA, AutoSuppression, external water mode Peaks:. Fluoride µg/ (ppb). Chloride Carbonate 4. Nitrate Unidentified 6. Sulfate Phosphate

17 Trace Anions in High Purity 8% Phosphoric Acid Ion Exclusion (ICE) Pretreatment : Thermo Scientific Dionex IonPac ICE-AS6 ICE Eluent: Deionized water ICE Flow Rate: 0.0 m/min Sample Volume: 00 µ mm Sodium Hydroxide Clean Up : Concentrator: IC Eluent: IC Flow Rate: Detection: Thermo Scientific Dionex IonPac AG-HC, AS-HC, mm Dionex IonPac AG-HC, 4 mm 0 mm Sodium hydroxide 0.38 m/min Suppressed conductivity, Thermo Scientific Dionex ASRS, AutoSuppression, external water mode Peaks:. Chloride 36 µg/ (ppb). Unidentified 3. Sulfate Nitrate. Phosphate Minutes Determination of Trace Anions in Weak Acids 7

18 Cl - NO 3 - Trace Anions in Formic acid Capillary IC st Dimension : Sample volume: 0 µ Thermo Scientific Dionex IonPac ICE-AS(0 9 mm) ion-exclusion column SO 4 - PO 4 3- nd Dimension Concentr. Col.: Thermo Scientific Dionex IonSwift MAC-00 ( mm) : Thermo Scientific Dionex IonPac AG8-Fast w/ guard (0.4 0mm) Eluent: KOH-Gradient (RFIC) Flow rate: 0 µ/min Detection: Suppressed Conductivity Suppressor: Thermo Scientific Dionex ACES (Recycle Mode) 0.0 Concentration:.00 mm min Trace Anions in Acetic Acid Capillary IC st Dimension : Sample volume: 0 µ Thermo Scientific Dionex IonPac ICE-AS(0 9 mm) ionexclusion column Cl - SO 4 - PO 4 3- nd Dimension Concentr. Col.: Thermo Scientific Dionex IonSwift MAC-00 ( mm) : Thermo Scientific Dionex IonPac AG8-Fast w/ guard (0.4 0mm) Eluent: KOH-Gradient (RFIC) Flow rate: 0 µ/min Detection: Suppressed Conductivity Suppressor: Thermo Scientific Dionex ACES (Recycle Mode) Concentration:.00 mm min 8

19 Thank you! 9