Reference method for PCDDs and PCDFs in pulp and paper mill effluents: figures

List of Figures

• Figure 1: Alumina Conditioning Column
• Figure 2: Extraction Schematic for Pulp and Paper Mill Effluents
• Figure 3: Cleanup and Analysis Schematic for PCDDs/PCDFs in Pulp and Paper Mill Effluents
• Figure 4: Cleanup Columns
• Figure 5: Acceptable Chromatographic Separation for 2,3,7,8-TCDD and 2,3,7,8-TCDF
• Figure 6: Peak Display for PFK m/z 304.9824 at 10 000 Resolution
• Figure 7: Noise Determination
• Figure 8.1: Effluent Sample Data Sheet - Part I
• Figure 8.2: Effluent Sample Data Sheet - Part II
• Figure 9: Sample Submission/Custody Sheet
• Figure 10: Method Performance Test Data Sheet
• Figure 11: Multi-point Calibration Data Sheet
• Figure 12: Calibration Verification Data Sheet
• Figure 13: GC/MS Detection Limits Verification Data Sheet

Figure 2

The picture shows the schematic for the extraction with the following steps/components:

1. Effluent
2. Surrogates SPIKE
3. Suction Filtration
4. Solids
   1. Air Dry
   2. Soxhlet Extraction; 20 hours with Toluene
5. Liquids
   1. Liquid/Liquid Extraction with Dichloromethane
   2. Dry over Na₂SO₄
   3. Rotary Evaporation to 3 to 5 mL
6. Rotary Evaporation to 1 to 2 mL
7. Exchange to Hexane
8. Dry Over Na₂SO₄
9. Rotary Evaporation to 3 to 5 mL
10. Ready for Cleanup

Figure 3

The picture shows the schematic for the cleanup and analysis with the following steps/components:

1. Concentrated extract
2. Acid/Base/Silver Nitrate/Silica Column
3. Rotary Evaporation
4. Basic Alumina Column
   1. Hexane Elution (Archive)
   2. 1.5 % CH₂cl₂ in Hexane Elution (Archive)
   3. 50 % CH₂cl₂ in Hexane Elution (PCDD/PCDF)
5. Rotary Evaporation
6. Exchange to Hexane
7. Rotary Evaporation
8. (Supplementary Cleanup such as:
   • Repeat Alumina Column
   • Carbon/Silica Column)
9. Concentrate to Dryness under N₂
10. Prepare to Final Volume with Recovery Standard Solution
11. GC/MS Analysis

Figure 4

The picture shows two columns: first column (on left side)

Figure 5

The figure shows two chromatograms: First chromatogram is acquired on a DB-5 column and it displays four peaks in elution order corresponding to following isomers: 1,2,3,4-TCDD at 28:11 min, 1,2,3,7-/1,2,3,8-TCDD at 28:17 min, 2,3,7,8-TCDD at 28:25 min and 1,2,3,9-TCDD at 28:37 min. None of the peaks are baseline resolved: The valley between first two peaks is ~ 65%, between second and third peak ~25% and between third and fourth peak ~20%. The ratio between second valley X and the third peak height Y is less than 0.25.Second chromatogram is acquired on a DB-225 column and displays three peak in elution order corresponding to following isomers: 2,3,4,7-TCDF at 19:59 min, 2,3,7,8-TCDF at 20:15 min and 1,2,3,9-TCDF at 20:34 min. These peaks are not baseline resolved. The valley between first and second peak is ~ 15% and between second and third peak ~ 10%. The ratio between first valley X and second peak height Y is less than 0.3.

Figure 6

The picture shows mass distribution for PFK m/z 304.9824 in the grid of 10, 25, 50 and 75% intensity in vertical direction and 200 ppm span in horizontal direction. The peak is centered at the m/z 304.98245.

Figure 7

The picture shows a sequence of the chromatogram and the way how the signal S to noise N for the peak is calculated. S is the peak height and N is estimated by zooming the baseline close to the peak (e.g. 10 times). Ratio S/N must be higher than 3.

Equation 1

Left side of the equation: RRFn (is equal to), Right side of the equation: Numerator: Ac multiplied by Csc, Denominator: Asc multiplied by Cc. All terms are explained in the text.

Equation 2

Left side of the equation: RRFs (is equal to), Right side of the equation: Numerator: Asc multiplied by Crc, Denominator: Arc multiplied by Csc. All terms are explained in the text.

Equation 3

Left side of the equation: C(X) (is equal to), Right side of the equation: Numerator: bracket opened, sum of Ak for k equal 1 to n, bracket closed, multiplied by Qss, Denominator: Ass multiplied by RRFn multiplied by V. All terms are explained in the text.

Equation 4

Left side of the equation: %R(X) (is equal to), Right side of the equation: Numerator: Ass multiplied by Qrs multiplied by 100, Denominator: Ars multiplied by Qss multiplied by RRFs. All terms are explained in the text.

Equation 5

Left side of the equation: MDL (is equal to), Right side of the equation: Numerator: 3 multiplied by N multiplied by A/H multiplied by Qss, Denominator: Ass multiplied by RRFn multiplied by V. All terms are explained in the text.