Organics analysis in marine sediment and biota Zhang Yong East China Sea Environmental Monitoring Center, S.O.A, Shanghai, China, 200137 October 2007

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

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-)

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

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

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

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

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

Conditions of the Instrument The temperature program : 80℃(1min ) 20 ℃/min 200 ℃( 5min) 200 ℃ 10℃/min 300℃( 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.

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

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.

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.

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

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

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)

Conditions The temperature program : 80℃(1min ) 20 ℃/min 120 ℃ The injection port was 250 ℃,the detector was 300 ℃ Carrier gas : Nitrogen (99.999 %) The results were calculated by the external standards method.

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

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.

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.

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

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

Standard deviation /ng·g-1 Table 4 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

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

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

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

Standard deviation /ng·g-1 Table 8 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

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

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

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

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.

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%

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.

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