Supelco Dioxin Prep System - Florisil
Transcription
Supelco Dioxin Prep System - Florisil
THE SUPELCO “DIOXIN PREP SYSTEM - FLORISIL VERSION” : A MULTI-LAYER SILICA GEL COLUMN CONNECTED IN SERIES TO AN ACTIVATED FLORISIL MICRO-COLUMN FOR RAPID DETERMINATIONS OF PCDD/Fs AND PCBs IN ENVIRONMENTAL SAMPLES Eric Aries1, David R. Anderson1, Nicholas Ordsmith2, Lisa Fitzpatrick3 and Fiona Barclay3 1CORUS R, D and T, Swinden Technology Centre, Rotherham, UK S60 3AR 2HALL ANALYTICAL LABORATORIES, Manchester, UK M23 9YJ 3SIGMA ALDRICH COMPANY Ltd., Poole, Dorset, UK BH12 4QH 1 POPs Workshop_30March2006 Overview • Brief review on standard analytical procedures for PCDD/Fs and PCB analyses • Collaboration between Corus / Hall Analytical / Supelco on the Dioxin Prep Systems • Supelco Dioxin Prep Systems Dual Carbon Column Version Florisil Version Validation data Sample throughput • Acknowledgements 2 Standard analytical procedures for PCB and PCDD/F analyses Ñ Ñ Ñ Ñ Method US EPA 1613 B : PCDD/Fs in solids, waste waters and sediments Method US EPA 23 : PCDD/Fs in stack emissions Method EN1948 : European method for PCDD/Fs and PCBs in stack emissions Method 1668A : PCBs in water, soil sediment and tissue ISOTOPE DILUTION : 13C12 PCDD/F and PCB internal standards High Resolution Gas Chromatography / High Resolution Mass Spectrometry HRGC / HRMS SEVERAL DAYS OF SAMPLE PREPARATION ¾ Extraction (Soxhlet, Dionex ASE) ¾ Solvent concentration ¾ Successive clean-up steps (Silica, Florisil, Alumina, Activated Carbon) ¾ Data processing 3 Supelco Dioxin Prep System Collaboration Corus / Hall Analytical / Supelco 2002 : Development and validation of the Dioxin Prep System – Dual Carbon Column Version in Japan for fast determinations of PCDD/Fs. (Japan Quality Assurance Organisation and Kawajyu Techno Service) 2003 : Evaluation of the Dioxin Prep System – Dual Carbon Column Version by Corus and Hall Analytical prior to its UK commercial launch. 2004 : A collaboration agreement is signed by Corus, Hall and Supelco to develop and validate an enhanced version of the Dioxin Prep System. 2005 : Development and validation of the Supelco Dioxin Prep System - Florisil Version by Corus and Hall Analytical Laboratories. 4 Testing Laboratories Trace Organic Analysis Laboratory (Corus R, D and T) Hall Analytical Laboratories Hall Analytical Laboratories Manchester, UK Contract laboratory UKAS (ISO 17025) accreditation for PCDD/F and PCB analyses 2 HRGC – HRMS instruments Corus R, D & T Swinden Technology Centre, Rotherham, UK Researches into the emissions and the formation of PCDD/Fs and PCBs from UK steel plants (iron ore sintering, EAF steel-making) UKAS (ISO 17025) accreditation for PCDD/F and PCB analyses Micromass Autospec Ultima HRGC - HRMS 5 Corus and Hall Analytical standard procedures for determination of PCDD/Fs and PCBs in environmental samples Addition of 13C12 PCBs & 2,3,7,8-PCDD/Fs EMISSION OR DUST SAMPLES EXTRACTION (ASE 200) MULTI-LAYERED SILICA CHROMATOGRAPHY PCBs FLORISIL CHROMATOGRAPHY Saturated hydrocarbons BASIC ALUMINA CHROMATOGRAPHY PCBs Saturated hydrocarbons PCDD/Fs HRGC / HRMS US EPA 23 or 1613B EN-1948 HRGC / HRMS Method 6 US EPA 1668 A Sample throughput at Trace Organic Analysis Laboratory (Corus) using standard analytical methods 1 fully trained technician / 8 samples Extraction and concentration (ASE 200) = 1 to 2 days Multi-layer silica clean-up = 1 day Florisil step = 1 day Basic Alumina step = 1 day PCBs Analysis overnight Data processing = 1 day PCDD/Fs Analysis overnight Data processing = 1 day PCDD/Fs : 4 to 5 working days PCBs : 5 to 6 working days Additional Tasks : Packing and activation of columns 7 SUPELCO “DIOXIN PREP SYSTEMS” The dual-carbon column version Description Analytical methods Validation data The Florisil version Description Analytical methods Validation data Sample throughput using Supelco Dioxin Prep system - Florisil Version 8 Supelco Dioxin Prep System - Dual Carbon Column Version Carboxen 1016 (75 m2 / g) Carboxen 1000 (1200 m2 / g) Multi-layer Silica gel column Dual carbon reversible tube Silica gel layer Silica gel layer Vacuum manifold 9 Analytical procedure Dioxin Prep System – Dual Carbon Column Version ENVIRONMENTAL SAMPLES Addition of 13C12 2,3,7,8-PCDD/Fs and WHO-12 PCBs EXTRACTION (ASE 200) Toluene 100 mL CLEAN - UP Dual - carbon column fitted to an empty silica column Back elution of dual-carbon column WASTE PCDD/F FRACTION 200 ml n-hexane 10 HRGC / HRMS Analysis of a waste sinter dust (QC material) for PCDD/Fs using the Dioxin Prep System- Dual Carbon Column Version 400 Corus data using standard US EPA 23 analytical method (N = 59) Corus data using Dioxin Prep system (N = 2) Hall Analytical data using Dioxin Prep system (N = 3) 300 ng / kg 200 100 2, 3, 1, 7,8 -T 2, 3, C D 7, F 8 2, -P 3, e 4, C D 7, 1, F 82, P 3, eC 4 D 1, ,7,8 F 2, H 3, xC 6, D 7, 2, F 83, H 4, x 6 C D 1, ,7,8 F 2, H 3, x 7, C 1, D 8, 2, F 9 3, H 4, x 6, 1, 7, CD 2, F 83, H 4, pC 7, D 8, F 9H pC D F O C To D F ta lI -T EQ (n g/ kg ) 2, 3, 1, 7,8 -T 2, C 3, D 7, 1, D 8 2, Pe 3, 4 C D 1, ,7,8 D 2, H 3, x 6, C D 7, 1, D 82, H 3, xC 7, 1, D 8, 2, D 93, H 4, xC 6, 7, D D 8H pC D D O C D D 0 11 Supelco Dioxin Prep System - Florisil Version Schematic 250 mL solvent reservoir (28449-U) 24/24mm PP Connector (21216-U) Multi-layered silica tube (28397-U) 6.35/10 mm Reducing union (28398-U) Florisil micro-column 6.35/10 mm Reducing union (28398-U) Vacuum Manifold (28403-U) 12 Supelco Dioxin Prep System - Florisil Version Multi-layer silica and activated Florisil Multi-layer Silica MULTI - LAYER SILICA Designed to meet requirements of Japanese Industrial Standard Methods K- 0311 / K - 0312 AgNO3(10%) 3g Silica gel 0.9 g H2SO4(22%) 6g H2SO4(44%) 4.5g Glass filter KOH(2%) 3g ACTIVATED FLORISIL Empty Florisil tubes and connectors. Flame sealed ampoules containing 1g activated Florisil (60/100 mesh) 13 Analytical procedure Dioxin Prep System - Florisil Version ENVIRONMENTAL SAMPLES Addition of 13C12 labelled internal standards PCDD/Fs ELUTION 50 mL DCM EXTRACTION CLEAN-UP Multi-layer silica Florisil micro-column WASTE + PCBs 175 ml n-hexane WASTE (Mainly saturated hydrocarbons) WASTE + PCBs 25 ml Hexane/DCM (98 / 2, v/v) ALUMINA CLEAN - UP PCBs PCDD/Fs HRGC / HRMS 14 2,3 1,2 Certified values (ng / kg) DX-3 Replicate 2 (ng / kg) DX-3 Replicate 4 (ng / kg) Te CD Ds Pe CD Ds Hx CD Ds Hp CD Ds Te CD Fs Pe CD Fs Hx CD Fs Hp CD Fs 5000 ,7, 8-T ,3, 7,8 CDF 2,3 -P e ,4, 7,8 CDF 1,2 -P ,3, eC 4, 7 DF 1,2 ,8Hx ,3, CD 6 F 2,3 ,7,8Hx ,4, CD 6 F 1,2 ,7,8Hx ,3, CD 7, 8 1,2 ,9F ,3, Hx 4, 6 C 1,2 ,7, 8-H DF ,3, 4, 7 pC ,8, 9-H DF pC DF OC DF 1,2 ,7, 8-T ,3, 7,8 CDD 1,2 -P ,3, eC 4, 7 DD 1,2 ,8H ,3, xC 6 DD 1,2 ,7,8H ,3 xC 1,2 ,7,8, 9-H DD ,3, 4, 6 xC ,7, 8-H DD pC DD OC DD 2,3 Determination of PCDD/Fs in DX-3 certified reference sediment using the Dioxin Prep System – Florisil Version ng / kg 6000 DX-3 Replicate 1 (ng / kg) DX-3 Replicate 3 (ng / kg) 4000 3000 2000 1000 0 15 Determination of WHO-12 PCBs in DX-3 certified reference sediment using the Dioxin Prep System – Florisil Version ng / g 25.00 20.00 Certified values (ng / g) DX-3 Replicate 1 (ng / g) DX-3 Replicate 2 (ng / g) DX-3 Replicate 3 (ng / g) DX-3 Replicate 4 (ng / g) 15.00 10.00 5.00 Hx CB 169 1 Te CB 8 Pe CB 126 7 Te CB 7 Hp CB 18 9 Hx CB 167 Hx CB 157 Hx CB 156 Pe CB 123 Pe CB 118 Pe CB 114 Pe CB 105 0.00 16 Determination of ‘non dioxin-like’ PCBs in DX-3 certified reference sediment using the Dioxin Prep System - Florisil Version 20 Information values (ng/g) DX-3 concentrations (ng/g) [Replicate 1] DX-3 concentrations (ng/g) [Replicate 2] DX-3 concentrations (ng/g) [Replicate 3] DX-3 concentrations (ng/g) [Replicate 4] 18 16 14 12 10 8 6 4 2 09 DeC B2 B2 08 NoC B2 06 NoC 205 OcC B 202 OcC B 194 OcC B 49 HxC B1 B1 80 HpC 38 HxC B1 53 HxC B1 PeC B1 01 B5 2 TeP C 28 0 TrC B ng / g 17 13 C2,3 13 ,7, C8-T 1,2 13 CD , 3 ,7, CD 8-P 1,2 13 ,3, eC C6,7 DD 1,2 ,8,3, H xC 4,6 DD ,7, 8-H pC DD 13 COC DD 13 C2,3 13 ,7, C8-T 1,2 13 CD , 3 ,7, CF 8-P 1,2 13 , e 3,6 CD C,7, 1,2 F 8-H ,3, xC 4,6 DF ,7, 8-H pC DF 13 CPe CB 13 10 C5 Pe C B 13 11 C4 Pe C B 13 11 C8 Pe CB 13 12 C3 Pe C B 13 15 C6 Pe C B 13 15 C7 Pe CB 13 16 C7 Pe CB 13 18 C9 Pe C B 13 77 CPe CB 13 C81 Pe C B 13 12 C6 Pe CB 16 9 Typical recoveries of 13C12 labelled PCDD/Fs and PCBs using the Dioxin Prep System - Florisil Version % 120.0 DX-3 Replicate 1 (%) DX-3 Replicate 3 (%) DX-3 Replicate 2 (%) DX-3 Replicate 4 (%) 100.0 80.0 60.0 40.0 20.0 0.0 18 Fish tissue (WMF-01, Wellington Laboratories) and sandy soil (CRM 529, Supelco) – Validation data using the Dioxin Prep System - Florisil Version WMF-01 Fish Tissue - PCDD/F data ng / kg Certified values (ng / kg) WMF-01 Replicate 1 (ng / kg) WMF-01 Replicate 2 (ng / kg) WMF-01 Replicate 3 (ng / kg) WMF-01 Replicate 4 (ng / kg) 160000 18 16 140000 14 120000 12 100000 10 80000 8 HxCB 169 PeCB 126 TeCB 81 TeCB 77 HpCB 189 HxCB 167 HxCB 157 HxCB 156 2,3,4,7,8PeCDF 1,2,3,7,8PeCDD 7000 PeCB 123 0 PeCB 118 20000 0 PeCB 114 2 1,2,3,6,7,8HxCDD 40000 Soil CRM 529 - PCDD/F data Certified values (ng / kg) CRM529 Replicate 1 (ng / kg) CRM529 Replicate 2 (ng / kg) CRM529 Replicate 3 (ng / kg) CRM529 Replicate 4 (ng / kg) ng / kg 6000 5000 4000 3000 2000 1000 F F ,6,7,8 -HxC D ,7,8,9 -HxC D 1,2,3 F ,6,7,8 -HxC D 2,3,4 F 1,2,3 ,4,7,8 -HxC D CDF 2,3,4 ,7,8-P e CDF 1,2,3 ,7,8-P e 2,3,7 ,8-TC DF ,8,9-H xCDD 1,2,3 ,7 ,7,8-H xCDD 1,2,3 ,6 ,7,8-H xCDD 1,2,3 ,4 1,2,3 ,7,8-P eCDD ,8-TC DD 0 2,3,7 2,3,7,8-TCDD 4 PeCB 105 60000 6 1,2,3 20 WMF-01 Fish Tissue - PCB data ng / kg 180000 19 Sample throughput at Trace Organic Analysis Laboratory (Corus) using the Supelco Dioxin Prep System – Florisil Version 1 fully trained technician / 9 samples Extraction and concentration (ASE 200) = 1 to 2 days Multi-layer silica clean-up + Florisil = 1 day Basic Alumina step = 1 day PCBs Analysis overnight Data processing = 1 day PCDD/Fs Analysis overnight Data processing = 1 day PCDD/Fs : 3 to 4 working days PCBs : 4 to 5 working days No additional tasks (column packing and activation) 20 Acknowledgements • Shelley Richardson Corus R, D & T • Laurent Ragava, Florian Mure University of Aix-Marseille III, France • Rasika Fernando University of Sheffield • Sue and Katie Hall Analytical Laboratories 21