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