1. Organics analysis in marine sediment and biota
Zhang Yong East China Sea Environmental Monitoring Center, S.O.A, Shanghai, China,
October 2007

2. Content Introduction Materials and Method Results
Quality control and the problems in the Analysis

3. Table 1 Variables for Organics Inter-calibration Excersise
Introduction
Table 1 Variables for Organics Inter-calibration Excersise
Priority PAHs
OCPs
PCBs
Naphthalene
Aldrin
CB 52
Acenaphthylene
Chlordane
CB 101
Acenaphthene
pp’ DDE
CB 105
Fluorene
pp’ DDD
CB 110
Phenanthrene
pp’ DDT
CB 118
Anthracene
op DDE
CB 128
Pyrene
op DDD
CB 138
Benzo[a]anthracene
op DDT
CB 153
Chrysene
Dieldrin
CB 180
Benzo[b]fluoranthene
Endrin
CB 189
Benzo[k]fluoranthene
Heptachlor
Benzo[a]pyrene
Heptachlor epoxide
Indeno[1,2,3-cd]anthracene
HCB
Benzo[ghi]perylene
HCH isomers (a-, b-, g-)

4. Table 2 Variables analyzed
Introduction
Table 2 Variables analyzed
Priority PAHs
OCPs
PCBs
Naphthalene
Heptachlor epoxide
CB52
Acenaphthylene
HCB
CB 105
Acenaphthene
pp’ DDE
CB 110
Fluorene
pp’ DDD
CB 128
Phenanthrene
pp’ DDT
CB 138
Anthracene
Dieldrin
CB 153
Pyrene
aHCH
CB 180
Benzo[a]anthracene
bHCH
CB 189
Chrysene
gHCH
Benzo[a]pyrene
Benzo[ghi]perylene

5. Materials and method The analysis of PAHs in biota and sediment
The analysis of OCPs and PCBs in biota and sediment

6. Chemicals
The Instruments and conditions of Instrument
The procedures of the sample pretreatment

7. Chemicals
Standard PAHs (16 components) were purchased from the company of SUPELCO .
Solvent
hexane and dichloromethane were HPLC grade

8. Instruments GC-MS Thermo electron PolrisQ ASE
DB5-MS(30 m ×0.25 mm ×0.25μm )
ASE
Dionex ASE300
Concentration workstation (Turbo Vap Ⅱ)
加点东西

9. Conditions of the Instrument
The temperature program :
80℃(1min ) ℃/min ℃( 5min)
200 ℃ ℃/min ℃( 8 min)
Temperature :
The injection port was 250 ℃,the MS temperature was 250 ℃
transfer line temperature was 280℃,
Carrier gas : helium(99.999%) ,
EI（70ev）, The monitoring mode was SIM,
The results were calculated by the external standard method.

10. The procedures of the sample pretreatment
Extraction procedures
Clean-up procedures

11. Extraction procedures
The samples were weighed 5.0 grams, put into a 34 mL extraction cell, and mixed into 0.5 g copper powder to eliminate the interference of sulfide. The extraction temperature was set 100 degrees centigrade and the extraction cell was preheated 5 min before the extract dichloromethane-hexane（1:1）was added into the cell, then the sample was static extracted for 10min and was eluted quickly with solvent for several times , the elution volume was 60% of the cell volume. The eluent was concentrated by Concentration workstation and hexane was added to make a 1ml solution.

12. Clean-up procedures
To remove the interference before GC-MS analysis, the extract was purified by using silica gel column consisting of 5 grams anhydrous sodium sulphate, 20 g silica gel (deactivated with distilled water) and glass wool. The extract was concentrated by Concentration workstation and hexane was added to the extract to make a 2ml solution, the solution was then injected into the column and eluted with 1:1 hexane-dichloromethane up to 50ml. The eluent was concentrated again and hexane was added to form a 0.5ml solution. At last this concentrated solution was analyzed by GC-MS.

13. The analysis of OCPs and PCBs
Chemicals
The Instruments and condition of instrument
The Procedures of the Sample Pretreatment

14. Chemicals
The standard PCBs (15 components) solutions were purchased from the company of Dr. Ehrenstorfer. The standard OCPs solutions were purchased from the company of SUPELCO .
Solvent
Hexane and Acetone were HPLC grade

15. Instrument GC ASE Concentration workstation (Turbo Vap Ⅱ)
Agilent 7890A
HP5 (30 m ×0.32 mm ×0.25μm )
DB-1701P (30 m ×0.25 mm ×0.25μm )
ASE
Dionex ASE300
Concentration workstation (Turbo Vap Ⅱ)

16. Conditions The temperature program : 80℃(1min ) 20 ℃/min 120 ℃
The injection port was 250 ℃,the detector was 300 ℃
Carrier gas : Nitrogen ( %)
The results were calculated by the external standards method.

17. The procedures of the sample pretreatment
Extraction procedures
Clean-up procedures

18. Extraction procedures
The samples were weighed 5.0 g, put into a 34 mL extraction cell, and mixed into 0.5 g copper powder to eliminate the interference of sulfide. In the process of extraction, acetone-hexane（1:1）was adopted as an extract, the extraction cell temperature was set 100℃ and preheated 5 min, sample was static extracted for 10min and was eluted quickly for several times with solvent, the elution volume was 60% of the cell volume.

19. Clean-up procedures
To remove the interference before GC-ECD analysis, the extract was purified by using sulphuric acid. The extract was transferred into extraction funnel, then mixed into 50ml Na2SO4 solution. The mixture was shaken well and layered, the water phase was discarded, the organic phase was washed twice by water repeatedly. 20ml sulphuric acid was added into the organic phase in order to wash the hexane to colorless，then Na2SO4 solution was used to wash the remaining sulphuric acid，separated water phase，put the anhydrous sodium sulfate solid inside extraction funnel in order to absorb water in hexane . At last, the extract was concentrated to 0.5ml.

20. RESULTS PAHs OCPs PCBs MA-YSLME/ORG/1 Table 3 SD-YSLME/ORG/1 Table 4

21. Table 3 MA-YSLME/ORG/1
PAHs
Mean value
/ng·g-1 SD
RSD
(%)
Naphthalene
2.5
0.25
10.0
Phenanthrene 14
17.9
Fluoranthene
5.4
0.21
3.9
Pyrene
6.2
3.4
Benz(a)anthrancene
0.22
0.04
18.2
Chrysene
0.18
0.01
5.6
Benzo(a)pyrene
0.27
0.015
Benzo[g,h,i]perylene
0.15
0.036
24.0
Anthranene
9.6
0.26
2.7
Fluorene
1.3
0.31
23.8
Acenaphthylene 15
3.0
20.0

22. Standard deviation /ng·g-1
Table SD-YSLME/ORG/1
PAHs
mean value /ng·g-1
Standard deviation /ng·g-1
RSD
(%)
Naphthalene
95.4
27.4
28.7
Phenanthrene
631
189
30.0
Fluoranthene
1590
162
10.2
Pyrene
1662
256
15.4
Benz(a)anthrancene
815
175
21.5
Chrysene
1623
163
10.0
Benzo(a)pyrene
2713
360
13.3
Benzo[g,h,i]perylene
6460
361
5.6
Anthranene
711
23.1
3.2
Fluorene
105
3.79
3.6
Acenaphthylene
208
8.72
4.2

23. Standard deviation /ng·g-1
Table 5 MA-YSLME/ORG/1
OCPs
mean value /ng·g-1
Standard deviation /ng·g-1
RSD
(%)
HCB
2.2
0.31
14.1
γHCH
3.0
0.42
14.0
p,p＇DDE
0.21
0.015
7.1
p,p＇DDD
0.57
0.036
6.3
p,p＇DDT
1.3
0.15
11.5
Dieldrin
2.9
0.38
13.1
Heptachlor epoxide
1.8
11.7
αHCH
βHCH
0.2
11.1

24. Table 6 SD-YSLME/ORG/1 OCPs mean Value /ng·g-1 Standard
deviation /ng·g-1
RSD
(%)
HCB 16
2.5
15.6
γHCH
0.26
10.4
p,p＇DDE
3.3
0.2
6.1
p,p＇DDD
3.6
0.38
10.6
p,p＇DDT
0.44
0.036
8.2
Dieldrin
1.5
0.058
3.9
Heptachlor epoxide
0.85
0.035
4.1
αHCH
βHCH
0.025
2.9

25. Standard deviation /ng·g-1
Table 7 MA-YSLME/ORG/1
PCBs
mean value /ng·g-1
Standard deviation /ng·g-1
RSD
(%)
PCB52
5.1
0.44
8.6
PCB110
1.9
0.51
26.8
PCB105
4.7
0.47
10.0
PCB128
8.7
0.32
3.7
PCB138
0.43
0.021
4.9
PCB153
8.2
1.6
19.5
PCB180
0.39
0.035
9.0
PCB189
0.77
0.026
3.4

26. Standard deviation /ng·g-1
Table SD-YSLME/ORG/1
PCBs
mean value /ng·g-1
Standard deviation /ng·g-1
RSD
(%)
PCB52 80 5
6.3
PCB110
3.0
0.15
5.0
PCB105
0.77
0.068
8.8
PCB128
0.68
0.07
10.3
PCB138 73 11
15.1
PCB153 15
2.5
16.7
PCB180
4.6
0.31
6.7
PCB189
0.12
0.021
17.5

27. QC and the problems in the analysis
Solvent blank
Correction factor
Related standard deviation
the related coefficient of standard curve and recovery
Problems in the analysis

28. Correction factor( result of CRM / certified values)
Fig.1.
Fig.2.
Fig.3.

29. solvent blank Fig.5. the solvent blank of OCPs
Fig.4. the solvent blank of PAHs

30. RSD
The related standard deviations were 2.7%~30%.In analysis several kinds of material，the mean value RSD of PAHs were maximum, Biota was 2.7％～24％，sediment sample was 3.2％～30％. The RSD of OCPs in biota and sediment were 6.3％～14.1％ and 2.9％～15.6 ％ respectively. The RSD of PCBs in biota and sediment sample were between 3.4％～26.8％and 5％～17.5％ respectively.

31. Related Coefficients and Recovery
organics
Standard curve Related coefficients
Recovery
PAHs
0.988~0.999
66%~106%
OCPs
0.996~1.000
75%~140%
PCBs
0.998~1.000
76%~133%

32. Problem in the analysis
Complete baseline separation of all analysis objects was very difficult.
The large numbers of interferent in analysis actual sample were affected analysis dramatically.

33. THANK YOU!