IAEA/AL/180 WORLD-WIDE AND REGIONAL · 2011. 2. 24. · WORLD-WIDE AND REGIONAL INTERCOMPARISON FOR THE DETERMINATION OF ORGANOCHLORINE COMPOUNDS, PETROLEUM HYDROCARBONS AND STEROLS

IAEA/AL/180 IAEA/MEL/80

WORLD-WIDE AND REGIONAL INTERCOMPARISON FOR THE

DETERMINATION OF ORGANOCHLORINE COMPOUNDS,

PETROLEUM HYDROCARBONS AND STEROLS IN SEDIMENT SAMPLE

IAEA-159

INTERNATIONAL ATOMIC

ENERGY AGENCY MARINE ENVIRONMENT

LABORATORIES

Report No. 80

WORLD-WIDE AND REGIONAL INTERCOMPARISON FOR THE DETERMINATION OF

ORGANOCHLORINE COMPOUNDS, PETROLEUM HYDROCARBONS AND STEROLS IN THE SEDIMENT SAMPLE IAEA-159

J.-P. Villeneuve, J. R. Oh and C. Cattini

June 2007

International Atomic Energy Agency Marine Environment Laboratories

4 Quai Antoine 1er MC-98000 MONACO

Prepared in Collaboration with :

CONTENTS Page 1. Introduction 1 2. Scope of the intercomparison 2 3. Description of the material 3 4. Homogeneity Test 3 5. Moisture Content 3 6. Sample dispatch and data return 4 7. Evaluation of the results 5 7.1. Data Tables 5 7.2. Analytical methods 5 7.3. Statistical evaluation 5 7.4. Z-scores 6 7.5. Assignement of “Reference Values” for the data 7 8. Discussion 16 8.1. Organochlorine compounds 16 8.2. Petroleum hydrocarbons 18 8.3. Z-scores 19 9. Recommendations 19 Annex I: Data report - IAEA-159 23 Annex II: Data evaluation - graphs 91 Annex III: Z-scores for chlorinated pesticides, PCBs and Petroleum 103 hydrocarbons - IAEA-159 Annex IV: List of participants 151

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IAEA INTERCOMPARISON RUN 159. THE DETERMINATION OF ORGANOCHLORINE COMPOUNDS, PETROLEUM

HYDROCARBONS AND STEROLS IN SEDIMENT SAMPLE. 1. INTRODUCTION The Marine Environmental Studies Laboratory (MESL) of IAEA-MEL has conducted intercomparison exercises on trace organic compounds for over thirty years as part of its contribution to IAEA’s Analytical Quality Control Service, UNEP’s Regional Seas Programme, and occasionally, in association with the Intergovernmental Oceanographic Commission of UNESCO,Global Investigation of the Pollution in the Marine Environment (GIPME) programme. These exercises are organized on a continuous basis, once per year. The accurate and precise determination of organochlorine compounds and petroleum hydrocarbons in marine samples is fundamental to pollution assessment in coastal and ocean environments. Intercomparison exercises represent an essential element of method testing and allow analysts to check the accuracy of their results. Furthermore, intercomparison exercises are used as a basic tool for evaluating data quality on global and regional levels. Results of previous intercomparison exercises have revealed serious difficulties for many regional laboratories to obtain comparable data. To help improve the quality of analytical data, MESL intensified the quality assurance programme. This includes more training of analysts in modern measurement techniques, production and supply of appropriate and reliable reference methods and materials and, whenever possible, improving analytical instruments in IAEA Member State laboratories. Moreover, it includes an enhanced programme of intercomparison exercises using suitable marine samples. This report describes and evaluates results of the IAEA/UNEP Intercomparison study for the chemical analysis of organochlorine compounds, petroleum hydrocarbons and sterols in a sediment sample (IAEA-159) prepared and distributed to world-wide laboratories in July 2006.

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A total of 85 laboratories from 47 countries reported results. They included 64 laboratories participating in UNEP’s Regional Seas Programme and distributed as follows: Number of Laboratories Number of Countries Mediterranean Action Plan 31 13 Caribbean Action Plan 9 8 East Asian Seas 1 1 South-West Atlantic Action Plan 6 2 Black Sea Environmental Programme 6 4 South East Pacific 1 1 Kuwait Action Plan 6 3 West and Central African Action Plan 1 1 East Africa 1 1 South Asian Seas 1 1 North West Pacific 1 1 The data sets reported by laboratories and the statistical evaluation of results for each determinand are given in this report. The final results for this intercomparison exercise will enable individual participants to assess their performances and where necessary, to introduce appropriate modifications in their analytical procedures. Each laboratory performance (in terms of accuracy) has been evaluated by “Z-scores”. As the series of statistical criteria for a number of compounds were fulfilled, the sample can now be used as a Reference Material for quality control of data in the determination of chlorinated compounds and petroleum hydrocarbons in environmental samples. Participants who require further information or who have questions concerning this report are encouraged to write to:

IAEA-MEL, MESL, 4 Quai Antoine 1er, MC-98000 MONACO . mailto: [email protected]

2. SCOPE OF THE INTERCOMPARISON For the organochlorine part of this exercise the participants were requested to determine as many compounds as possible including: HCB, lindane, pp’ DDE, pp’ DDD,

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pp’ DDT, Aroclor 1254, and Aroclor 1260. The participants were also requested to report the PCBs as individual congeners whenever possible. For the petroleum hydrocarbon part of this exercise, the participants were requested to report individual aliphatics, such as n-C17, n-C18, pristane, phytane, total resolved and unresolved aliphatics, and all individual aromatic compounds that could be identified. IAEA-MEL/MESL, however, was also interested in receiving results for additional compounds, such as sterols. 3. DESCRIPTION OF THE MATERIAL 100 kg of sediment, provided by the Quasimeme Project, was collected in Kilbrannan Sound, in the river Clyde’s estuary, Scotland. This sediment sample was dried, ground and sieved. This powder, about 26 kg, was homogenized by mixing in a stainless steel rotating drum for three weeks. Then, aliquots of about 45 grams were packaged into glass bottles with aluminium screw caps, labeled IAEA-159 and sealed with Teflon tape. 4. HOMOGENEITY TEST The homogeneity of the material for organochlorine compounds and petroleum hydrocarbons was assessed by determining the concentration of these compounds in 10 sample aliquots taken randomly from the bulk dry powder. A one way variance analysis of the results indicated that the material could be considered as homogeneous. 5. MOISTURE CONTENT The water content of the lyophilized material, as determined by drying an aliquot to a constant weight at 105 °C, was found to be 1.2 ± 0.11 % at the time of preparation of this sample. Since, however, the moisture content may change with the ambient humidity and temperature, it was recommended that the water content of this material be determined again by the analyst laboratories in a separate sub-sample (not that taken for analysis of contaminants) by drying for 48 hrs at 105 °C at the time of analysis in the laboratory.

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6. SAMPLE DISPATCH AND DATA RETURN In July 2006, 136 bottles of sediment sample labeled IAEA-159 were distributed to laboratories world-wide along with a sample description and general instructions to analysts.

Participants were requested to analyze chlorinated compounds and petroleum hydrocarbons by their usual technique. They were also requested to make at least one, but preferably three separate determinations for each compound, and to report the results together with a short description of the method used (extraction, clean-up, gas chromatographic conditions). A suitable form was attached to the information sheet for this purpose. It was stated that concentrations were to be reported as net values (i.e. after correcting for blank, moisture content, etc.), leaving as many significant figures as justified by the precision of the method used. For each group of compounds the participants were requested to report: 1. The average weight of the sample taken for analyses 2. Hexane Extractable Organic Matter (H.E.O.M.) and moisture content 3. Methods used to confirm identity of the compounds 4. Calculation of the results 5. Summary of the quality control procedures routinely employed within the laboratory 6. The arithmetic mean value and the relative standard deviations (in %) of determinations Results of analyses were reported by 85 laboratories of which, 36 provided data for both chlorinated and petroleum hydrocarbons, 29 provided results for organochlorine compounds only and 20 laboratories provided data only for petroleum hydrocarbons. Sterols were reported only by 2 participants.

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7. EVALUATION OF THE RESULTS 7.1. Data Tables Results are presented in Annex I (Tables 1-3). For the purpose of this report, each laboratory is represented by a code number which remains unchanged throughout the data tables. The numbers do not correspond to the sequence of laboratories in the list of participants given at the end of the report, so that the anonymity of each laboratory is preserved.

Laboratory means, when reported, are presented as reported, regardless of significant figures justified by the precision of the method used. When a laboratory reported replicate determinations of a given compound, the laboratory value shown in the Tables is the computed arithmetic mean. In these Tables, laboratories using QA/QC are indicated by an asterix close to their code numbers. 7.2. Analytical methods Information on the pretreatment of samples for the determination of chlorinated compounds and PCBs is given in Table 7 of Annex I and the gas chromatographic conditions are reported in Table 8. Pretreatment of samples for petroleum hydrocarbons is described for each laboratory in Table 9 of Annex I and gas chromatographic conditions are reported in Table 10. 7.3. Statistical evaluation For each of the data sets in Tables 1-3 of Annex I, the range of determinations, arithmetic mean, and standard deviation for each analyte is based on the laboratory means. Outliers were then removed using the Box-and-Whisker plot of Statgraphics Plus for Windows 4.0, and the range, mean and standard deviation were recalculated.

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A summary of the results is presented in Tables 4-6 of Annex I. These tables provide information of two types: a) information on the reported results (analyte units, number of laboratories, and the range of laboratory means) and b) accepted results (% outliers, number of accepted laboratory means and range of the means, overall arithmetic mean and standard deviation). In addition to the above tables, the distribution of laboratory means for selected parameters is illustrated graphically in Figures 1-18 of Annex II. The data sets are: HCB, lindane, pp’ DDE, pp’ DDD, pp’ DDT, Aroclor 1254, PCBs 52, 101, 118, 138, 153, 180, phenanthrene, chrysene, pyrene, benz[a]anthracene, benzo[a]pyrene and benzo[g,h,i]perylene. In these examples, the average and the average ± 1 standard deviation are reported. Outliers have been removed from these graphs. These figures also identify monitoring laboratories with UNEP’s Regional Seas Programme (○: MEDPOL, �: CEPPOL, �: South West Atlantic, �: Black Sea Environmental Program, : ROPME and �: World Wide) 7.4. Z-scores For the assessment of laboratory performance, a Z-score is calculated according to the formula:

Z=(xi-xa)/sb where xi is the robust mean of the reported values of the analyte concentration in the sample; xa is the assigned value (a mean value of the acceptable results in the world-wide intercomparison run); and sb is the target standard deviation. This score effectively expresses the difference between the robust mean of the laboratory and the assigned value in units sb. Performance is considered acceptable if |Z| ≤ 2. The measurement is regarded as out of control when |Z| > 3. This score represents a simple method of giving each participant a normalized performance score for bias. The procedure has been accepted as a standard by ISO/IUPAC 1. 1 Thompson and R. Wood (1993). The international harmonized protocol for the proficiency testing of (chemical) analytical laboratories. IUPAC/ISO/AOAC. J. Pure. Appl. Chem. 65(9), 2123-2144.

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The selection of the right target value, sb, depends on the monitoring objectives. The criteria for PCB congeners is usually set so that laboratories should have at least a relative bias equal or better than 25 % (2sb, sb = 12.5 %). For chlorinated pesticides, PCBs and petroleum hydrocarbons, the uncertainty of assigned values is substantial and it has to be taken into account. This should therefore be included in the target value for bias according to the formula:

Z=(xi-xa)/(sb2 + stu2)0.5 where sb is the target standard deviation and stu is the uncertainty of the assigned value. Z-scores for participating laboratories are presented graphically in Annex III (outliers are excluded). 7.5. Assignement of “reference values” for the data The data for many of the determinands are sufficiently well grouped to permit characterization of the sediment sample as a reference material. Criteria used in the certification are as indicated below:

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1. For a given concentration range the relative uncertainty of the overall median does not exceed the following limits: Chlorinated pesticides and PCBs: > 10 ng/g 30 % 1 - 10 ng/g 50 % 0.1 - 1 ng/g 60 % 0.01 - 0.1 ng/g 80 % < 0.01 ng/g 100 % Petroleum hydrocarbons: > 10,000 ng/g 30 % 1,000 - 10,000 ng/g 50 % 100 - 1,000 ng/g 60 % 10 - 100 ng/g 80 % < 10 ng/g 100 % 2. The overall mean is based on data obtained by at least two different methods. 3. The relative number of laboratory means rejected as outliers does not exceed a) 20 %, b) 50 %. 4. The overall mean is calculated on the basis of at least the following number of laboratory means a) 10, b) 5 On the basis of these criteria the following classes of reference values can be defined. Class A: when all criteria are met. Class B: when criteria 1,2,3(b),4(a) or 1,2,3(a),4(b) are met. Class C: (information values) when at least three laboratories give reasonable agreement. On the basis of these criteria the following certification classification is given.

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1. Chlorinated compounds ( ng/g dry weight ) Analyte Concentration * Standard N*** Class Deviation** HEOM (mg/g) 0.53 0.29 8 C HCB 0.17 0.15 20 C α-HCH 0.10 0.06 9 C β-HCH 0.24 0.17 5 C Lindane 0.21 0.18 24 C δ-HCH 0.57 0.60 4 C

pp’ DDE 0.89 0.50 36 B pp’ DDD 0.82 0.58 30 B pp’ DDT 0.71 0.69 30 C op DDE 0.19 0.09 4 C op DDD 0.39 0.22 5 B op DDT 2.32 4.33 4 C Heptachlor 0.31 0.21 11 B Heptachlor Epoxide 2.84 3.31 5 C Aldrin 0.17 0.15 11 C Dieldrin 0.48 0.37 18 B Endrin 0.77 0.81 10 C α-Endosulfan 1.11 1.02 7 C β-Endosulfan 1.49 1.93 7 C Endosulfan sulfate 3.46 3.69 6 C α-Chlordane 0.17 0.12 6 C γ-Chlordane 0.67 0.80 6 C Aroclor 1254 14.3 8.38 12 C Aroclor 1260 5.54 3.31 10 A * Average value expressed on a dry weight basis ** Standard Deviation *** Number of accepted laboratory means which were used for calculation of the recommended information values and standard deviation

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2. PCBs ( ng/g dry weight ) Analyte Concentration * Standard N*** Class (IUPAC Deviation** congener number) 8 0.37 0.21 3 C

18 0.74 0.53 10 A 28 0.57 0.28 22 A 31 0.28 0.05 7 C 44 0.35 0.14 8 B 49 0.32 0.09 4 C 52 0.67 0.25 25 B 66 0.41 0.07 5 B 70 0.62 0.30 3 C 74 0.20 0.03 3 C 87 0.44 0.25 4 C 95 1.26 1.17 3 C 99 0.40 0.20 4 C 101 0.52 0.16 25 B 105 0.41 0.31 12 C 110 0.54 0.16 7 C 118 0.52 0.21 27 A 128 0.27 0.27 7 C 138 0.60 0.31 30 B 149 0.52 0.14 9 B 153 0.56 0.09 21 B 156 0.32 0.43 8 C 170 0.15 0.04 11 B 177 0.20 0.10 4 C 180 0.26 0.10 25 B 183 0.27 0.32 4 C 187 0.39 0.05 3 C 194 0.09 0.04 8 B

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195 0.08 0.03 3 C 201 0.15 0.12 3 C 206 0.34 0.47 3 C 209 0.14 0.21 4 C

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Systematic numbering of PCB congeners. IUPAC No IUPAC No

Trichlorobiphenyl Heptachlorobiphenyl

18 2,2’,5 170 2,2’,3,3’,4,4’,5 28 2,4,4’ 174 2,2’,3,3’,4,5,6 31 2,4’,5 177 2,2’,3,3’,4’,5,6

180 2,2’,3,4,4’,5,5’ Tetrachlorobiphenyl 183 2,2’,3,4,4’,5’,6

187 2,2’,3,4’,5,5’,6 44 2,2’,3,5’ 49 2,2’,4,5’ Octachlorobiphenyl 52 2,2’,5,5’ 66 2,3’,4,4’ 194 2,2’,3,3’,4,4’,5,5’ 70 2,3’,4’,5 195 2,2’,3,3’,4,4’,5,6

201 2,2’,3,3’,4,5’,6,6 Pentachlorobiphenyl

Nonachlorobiphenyl 87 2,2’,3,4,5’ 95 2,2’,3,5’,6 206 2,2’,3,3’,4,4’,5,5’,6 99 2,2’,4,4’,5 10 2,2’,4,5,5’ Decachlorobiphenyl 105 2,3,3’,4,4’ 110 2,3,3’,4’,6 209 2,2’,3,3’,4,4’,5,5’,6,6’ 118 2,3’,4,4’,5

Hexachlorobiphenyl

128 2,2’,3,3’,4,4’ 138 2,2’,3,4,4’,5 149 2,2’,3,4’,5’,6 151 2,2’,3,5,5’,6 153 2,2’,4,4’,5,5’ 156 2,3,3’,4,4’,5

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2 3

4

5 6

2’ 3’

4’

5’ 6’

I I’

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3. Petroleum hydrocarbons ( dry weight basis ) Analyte Concentration * Standard Units N*** Class Deviation** EOM 0.65 0.37 mg/g 7 C UVF Chrysene 14 9.5 µg/g 5 C UVF ROPME Oil 180 65 µg/g 4 C Total aliphatics 55 54 µg/g 12 C Resolved aliphatics 6.9 4.8 µg/g 10 C Unresolved aliphatics 62 48 µg/g 8 C n-C17 105 56 ng/g 16 A Pristane 120 53 µg/g 13 A n-C18 92 40 ng/g 15 C Phytane 81 53 ng/g 16 A Σ n-alkanes (C14-C34) 3.9 2.4 µg/g 16 C Total aromatics 1.4 0.65 µg/g 7 C Resolved aromatics 0.90 0.29 µg/g 7 C Unresolved aromatics 8.4 9.8 µg/g 5 C Biphenyl 11 3.6 ng/g 4 C Naphthalene 23 13 ng/g 32 A 1-methyl naphthalene 20 10 ng/g 8 B 2-methyl naphthalene 30 19 ng/g 7 B 2,6-dimethyl naphthalene 21 4.2 ng/g 4 C Phenanthrene 59 29 ng/g 45 A 2-methyl phenanthrene 26 6.5 ng/g 9 C 1-methyl phenanthrene 20 9.6 ng/g 10 A Anthracene 11 5.1 ng/g 22 A Chrysene 58 26 ng/g 44 A Triphenylene 110 84 ng/g 3 C Fluorene 13 7.7 ng/g 17 A Fluoranthene 110 32 ng/g 41 A Pyrene 100 38 ng/g 50 A 1-methyl pyrene 17 4.8 ng/g 3 C

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Benzo[b]fluoranthene 100 42 ng/g 23 A Benzo[k]fluoranthene 49 14 ng/g 18 B Benzo[a]fluoranthene 15 7.1 ng/g 3 C Benz[a]anthracene 54 20 ng/g 45 A Perylene 27 11 ng/g 9 B Benzo[e]pyrene 82 8.2 ng/g 11 B Benzo[a]pyrene 58 26 ng/g 44 A Benzo[g,h,i]perylene 95 45 ng/g 42 A Indeno[1,2,3,cd]pyrene 120 34 ng/g 25 A Dibenz[a,h]anthracene 25 14 ng/g 17 A Acenaphthylene 6.4 5.4 ng/g 11 B Acenaphthene 6.0 4.0 ng/g 16 A Dibenzothiophene 6.5 2.8 ng/g 5 B * Average value expressed on a dry weight basis ** Standard Deviation *** Number of accepted laboratory means which were used for calculation of the recommended information values and standard deviation

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8. DISCUSSION 8.1. Organochlorine compounds In total, 65 laboratories reported data for organochlorine compounds, of which 44 also reported data for PCBs. A summary of the data is included in Tables 4 and 5 of Annex I. The number of laboratories with more than 50 % outliers for organochlorine pesticides and PCBs and the coefficients of variation compared to previous exercises on intercalibration samples, such as IAEA-142, -140, -383, -408, -406, –417, -432, and -435 are reported below in the table. IAEA -142 -140 -383 -408 -406 -417 -432 -435 Year 1996 1997 1998 1999 2000 2002 2003 2005 Sample Mussel Fucus Sediment Sediment Fish Sediment Mussel Tuna Participants 84 68 48 43 55 78 71 73 % labs with > 50 % outliers

20 % 25 % 13 % 17 % 2 % 6 % 21 % 11 %

CV range OC

49 – 160

12 - 130 47 - 150 41 - 120 3 - 115 45 - 140 42 - 170 18 – 190

CV range PCBs

37 – 91 5 – 160 19 - 180 13 - 150 7 - 160 1 - 160 10 - 110 23 - 110

With 29 % of laboratories reporting more than 50 % outliers for chlorinated pesticides and 23 % of laboratories reporting more than 50 % outliers for PCBs it is obvious that there has not been any improvement relative to the samples analysed years ago. Errors are associated with the analytical procedures and can have various causes. The description of the methods used by laboratories that produced more than 50 % “outlier” data for chlorinated pesticides are compiled in Table A1.

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Table A1: Analytical procedures used by the laboratories with more than 50 % outlier

data for chlorinated pesticides.

Lab Code

Number

Corrected for

moisture

Extraction Solvent used for extraction

Internal Standard

Clean-up procedure

Fractionation

4 Yes Shaker Hex./Acet. None Florisil No 9 Yes Ultrasonic Hex./Acet.

/Tol. CBs Copper No

19 Yes Soxhlet MeCl2. / Acet.

None Copper Florisil

21 Yes Soxhlet Hex./Acet. None EPA Florisil 22 Yes Soxhlet Hexane None Florisil Not indic. 24 No Soxhlet Hexane None None Florisil 28 No Ultrasonic MeCl2 Acenapht. C18 SPE No 38 Yes Distillation Hexane None Sulf. Acid No 39 Yes PSE Hex./Acet. CBs Copper Alumina 40 Yes Soxhlet Hexane CB 29 Copper Florisil 50 No Soxhlet Hexane CB 29 Mercury Florisil 56 No Soxhlet Hex./Acet. None Gel perm. Gel perm. 60 No Ultrasonic Hex./Acet. None Florisil No 65 Yes Soxhlet Hexane CB 29 Copper Florisil 74 No Soxhlet Hexane None Florisil Florisil 75 Not indic. Mixer MeCl2 /

Acet. Not indic. Filter No

78 Yes Soxhlet Toluene CB 209 Alumina Not indic. 79 Yes Soxhlet Hex. /

MeCl2 CB 209 Copper Silica gel

82 No Shaker MeCl2 None Mercury No 83 Yes Soxhlet MeCl2 CB 112 Gel perm. No 86 Yes Ultrasonic Hex. /

MeCl2 None Mercury Florisil

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From this Table, many reasons can be seen for obtaining poor quality data: Laboratories Nos 24, 28, 50, 56, 60, 74 and 82 did not take into consideration the residual moisture content of the sample and did not correct the results. Even worse, some laboratories (4, 19, 21, 22, 24, 38, 56, 60, 74, 82 and 86) did not use any internal standard in order to trace the recovery of the procedure. Laboratories Nos 28, 40, 50, 65, 78, 79 and 83 used only internal standards for the first fraction of the Florisil separation. Laboratories Nos 4, 9, 28, 38, 60, 75, 82 and 83 did not used any separation technique. For the first time, in this exercise, all participants used capillary columns. 8.2. Petroleum hydrocarbons In total, 56 laboratories provided data for petroleum hydrocarbons. A summary of the results is given in Table 6 of Annex I. The percentage of laboratories with more than 50 % outlier data and the coefficients of variation for some recent intercalibration samples are reported below.

IAEA -142 -140 -383 -408 -406 -417 -432 -435 Year 1996 1997 1998 1999 2000 2002 2003 2005 Sample Mussel Fucus Sedimen

t Sediment Fish Sediment Mussel Tuna

Participants 40 38 22 24 22 55 45 31 % labs with > 50 % outliers

10 % 8 % 4 % 9 % 9 % 4 % 14 % 10 %

CV range 19 - 88 11 - 160 20 - 100 10 - 140 9 - 130 6 - 140 19 - 140 6 - 160 With only 1 laboratory (2 %) with more than 50 % outliers, there is a great improvement since the last mussel sample in 1996. The description of the method used by the laboratory that produced more than 50 % “outlier” data for petroleum hydrocarbons is compiled in Table A2 below.

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Table A2: Analytical procedures used by the laboratory with more than 50 % outlier data

for petroleum hydrocarbons. Lab Code

Corrected for moisture

Internal standard Clean-up Fractionation

33 No None Alumina Silica gel This laboratory did not apply the correction for the moisture content, did not use any internal standards for the recovery, did not use a clean-up procedure for the sample, except alumina chromatography. This laboratory also used HPLC for the quantification. 8.3. Z-scores Performance of the laboratories in terms of accuracy was assessed by Z-scores, which have been calculated for each individual compound. Z-scores are presented in Annex III of this report. The performance is considered satisfactory if Z-scores are equal to or less than 2. Z-scores from 2 to 3 indicate that the results are of questionable quality. Z-scores equal to or higher than 3 indicate that the measurements are out of control. Outliers are excluded in the graphical presentations. The general impression is that a large number of the laboratories have achieved satisfactory performance. However, it should be emphasized that this is basically due to the substantial uncertainty which resulted in broad confidential intervals. Each laboratory should therefore examine their own performance, taking into account the monitoring objectives. 9. RECOMMENDATIONS Participants are recommended to review their data and “score” them by evaluating whether the mean value obtained for each compound has |Z| value lower than or equal to

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2. This range is, of course, arbitrary and is only presented as a simple guideline for the user. The precision required for data depends upon its final application - e.g. long term trend data must be more precise than that used for “hot spot” pollution monitoring. Nevertheless, the use of this guideline will help to detect and correct systematic errors in accuracy (e.g., from calibration error, contamination, erroneous use of separation protocols) and will help to optimize data quality. Some laboratories have still to improve their quality assurance/quality control procedures. Participants in the intercomparison should retain their IAEA-159 samples as a Reference Material. The sample is suitable to check the accuracy of analytical measurements when sediment samples from polluted and unpolluted coastal areas are to be analyzed for petroleum hydrocarbons and chlorinated compounds. Participation is encouraged in the next round of intercomparison in which a biota sample from a medium polluted area will be examined. This material will extend the range of concentrations and matrices available for quality control purposes. Intercomparison exercises represent only one aspect of data quality assurance and can only provide occasional indicators of data quality. The most valuable approach to quality assurance is through the regular analysis of certified reference materials and by plotting the resulting data on quality control charts. This provides a continuous feed-back to the analyst and is an essential tool for monitoring the quality of data and assuring accurate and comparable results in future exercises. Additional information on these procedures and on the IAEA/UNEP/IOC Reference Methods can be obtained from the following reference:

UNEP/IAEA/IOC: Guidelines for the use of Reference Methods in Marine Pollution Studies, UNEP, Nairobi, 1990.

In addition, the participants are advised to consult the following Reference Methods:

RM No. 20: UNEP/IAEA/IOC Determination of petroleum hydrocarbons in marine sediments, UNEP, Nairobi, 1992 RM No. 71: UNEP/IOC/IAEA/FAO Sample work-up for the analysis of chlorinated hydrocarbons in the marine environment, UNEP Nairobi, 1996 (Draft)

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RM No. 72: UNEP/IAEA/IOC/FAO Determination of petroleum hydrocarbons in selected marine organisms, UNEP, Nairobi, 1996 (Draft)

IOC/NOAA/IAEA/UNEP: Standards and Reference Materials for Marine Science. Revised edition. IOC Manuals and Guides 25, UNESCO, Paris, 1993

These methods are available free of charge from IAEA-MEL in Monaco.

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Annex I

Data Report IAEA - 159

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Table 1: Results of chlorinated pesticides in sediment sample IAEA-159.

Laboratory HEOM HCB alpha beta Lindane delta pp' DDE pp' DDD pp' DDT op DDE op DDD op DDT Heptachlor Code HCH HCH HCH

Number ( mg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) 1* - - 0.13 0.38 0.24 0.56 0.74 1.01 0.74 - - - 0.05 3 - - 0.06 - 0.12 - 0.32 0.25 0.21 - - - - 4 - - - - 1065 - < 0.5 9.55 5.71 - - 8.81 < 1.25 5* 0.35 0.083 0.035 0.068 0.10 - 0.77 1.1 0.28 0.12 0.64 0.07 n.d. 6 - - - - - - 1.27 0.63 0.65 - - - - 7 - 0.17 0.29 - 0.53 - 1.59 0.29 3.1 - - - 0.58 8* 0.744 0.37 - - 0.104 - 0.917 0.884 0.65 - - - - 9* < 0.01 n.d. - - n.d. - 1.6 2.1 2.1 - - - n.d. 10* 0.0796 0.25 - - 0.38 - 1.03 0.14 0.27 0.21 0.37 0.36 0.38 14 - < 0.5 - - < 0.5 - 0.7 0.8 0.5 - - - < 0.5 15 - < 10 - - - - < 10 < 10 < 10 - - - < 10 16 0.73 0.06 - - 0.11 - 6.11 2.03 1.83 - - - - 17* 0.38 < 1.0 - - < 1.0 - < 1.0 < 1.0 < 1.0 - - - < 1.0 19 - - 22.2 15.6 13.1 40.6 0.5 74.1 4.3 - 328.3 - - 20 - - 0.21 0.42 < 0.1 1.43 < 0.1 < 0.1 1.88 - - - - 21 - - 12.36 - 2.13 - < 3.0 < 3.0 < 3.0 - - - < 3.0 22 - 1.17 - - 11.69 - - - - - - - - 24 - - - - - - - - 3.91 - - - - 25 - - - - 0.011 - 0.41 0.6 < 0.1 - - - < 0.1 26 - - - - - - 0.47 0.73 0.57 - - - - 29* - 0.24 0.13 < 0.13 0.66 0.17 0.43 0.68 <0.26 0.3 0.16 < 0.27 0.41 31 0.404 - - - - - 0.94 - 1.9 - - - - 32 - < 0.2 - - - - - - - - - - - 35* 0.57 0.06 - - 0.11 - 0.82 1.16 0.21 - - - 0.17 38 - < 0.3 < 0.3 < 0.3 < 0.3 - 9.3 8.3 51.7 - - - < 0.3

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Table 1: continued

Laboratory HEOM HCB alpha beta Lindane delta pp' DDE pp' DDD pp' DDT op DDE op DDD op DDT Heptachlor Code HCH HCH HCH

Number ( mg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) 39 - 0.47 - - 1.2 - 1.97 4.86 1.96 - - - n.d. 40* - 0.9345 - - < 3.91 - 16.4054 - - - - - - 41 - 0.19 - - 0.114 - 0.65 3.061 0.349 - - - < 0.05 42 9.74 - 0.09 - 0.36 0.13 0.19 0.11 - - - - 0.67 44* - 0.043 - - 0.265 - 1.0 0.725 0.22 - - - < 0.2 46* - 0.1 - - 0.2 - 0.7 0.9 0.1 - 0.2 - - 48* - 0.49 0.15 0.24 0.38 - 2.88 3.29 2.98 - - - 0.21 50 - - - - 3.275 - 2.028 - - - - - 2.086 51 - 0.17 - 1.34 0.05 - 2.0 1.33 0.21 - - - 0.09 52 - 0.05 - - 1.0 - 0.5 0.05 < 0.05 - - - 0.33 53 - 0.13 - - n.d. - 1.16 n.d. n.d. - - - - 54* - - - - 0.019 - 0.006 0.01 0.054 - - - - 55 1.0 - - - - - 1.0 3.0 1.0 - - - < 1.0 56 1.66 - - - 5.95 - 26.77 116.13 25.55 - - - - 57 - 0.98 - - 0.37 - 0.37 0.23 0.2 - - - - 59 - 0.3287 - - 0.4826 - 2.29028 4.789 1.80877 - - - - 60 - < 5.0 - - < 5.0 - < 5.0 < 5.0 < 5.0 - - - - 61 - 0.035 - - 0.038 - 0.652 0.854 0.16 - - - - 64 - - - - 111.65 - - 1.55 - - - - - 65* 44.8 8.19 - - 18.97 - 11.7 38.76 58.44 - - - 30.36 67 - - - - 0.032 - 0.472 1.313 0.326 - - - 0.043 68 - 0.06 - - < 0.05 - 1.42 0.45 0.08 - - - n.d. 70 - - 0.04 0.07 0.15 - 0.86 1.14 0.23 0.12 0.6 0.05 - 71 - 0.036 0.0865 - 0.025 - 0.543 0.156 0.1677 - - - -

- 26 -

Table 1: continued

Laboratory HEOM HCB alpha beta Lindane delta pp' DDE pp' DDD pp' DDT op DDE op DDD op DDT Heptachlor

Code HCH HCH HCH Number ( mg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g )

74 - 3.14 - - 6.04 - 1.35 < 0.5 - - - - - 77* - 0.03 - - 0.12 - 0.8 0.76 0.25 - - - 0.47 79 - - - - n.d. - 4.0 4.02 39.1 - - - 1.93 82 - - - - - - - - - - - - - 83* - 1.0 - - 2.1 - 1.2 0.7 1.6 - - - < 0.6 85 1.6 < 0.5 - - - - 0.82 1.99 0.74 - - - - 86 - 71 - - 28 - < 30 < 15 < 700 - - - < 1

Number of Results 12 27 12 7 37 5 44 41 39 4 6 4 14

Min. Value 0.0796 0.03 0.035 0.068 0.011 0.17 0.006 0.01 0.054 0.12 0.16 0.05 0.043 Max. Value 44.8 71 22.2 15.6 1065 40.6 26.77 116.13 58.44 0.3 328.3 8.81 30.36

Mean 5.2 3.33 2.98 2.59 34 8.6 2.54 7.18 5.54 0.19 55 2.32 2.7 St.Dev. 13 14 7.0 5.75 175 18 4.9 22 14 0.09 130 4.33 7.99 ( % ) 250 420 240 220 520 210 190 310 250 47 240 190 300

- 27 -

Table 1: continued

Laboratory Heptachlor Aldrin Dieldrin Endrin alpha beta Endosulf. alpha gamma Cis Aroclor Aroclor

Code Epoxide Endosulf. Endosulf. Sulfate Chlordane Chlordane Nonachlor 1254 1260 Number ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g ) ( ng/g )

1* - 0.05 13.33 1.53 - - - - - - - - 4 < 0.4 < 0.25 < 0.6 13.21 - - - - - - - - 5* - 0.01 0.34 n.d. n.d. n.d. n.d. 0.021 0.063 0.029 7.6 2.9 6 - - - - - - - - - - - - 7 - - - - 2.06 0.71 - - - - - - 8* - - 0.4 0.107 - - - - - - 11.71 12.33 9* n.d. 1.9 n.d. 5.1 n.d. n.d. 6.8 - - - - - 10* 0.15 < 0.09 0.4 0.74 < 0.09 < 0.08 - 0.12 0.25 < 0.08 - - 14 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 - - < 15 15 < 10 < 10 < 10 < 10 < 10 < 10 - - - - < 100 < 100 16 0.4 0.06 0.25 - 2.89 0.5 0.3 0.11 0.21 - 20.32 7.16 17* < 1.0 < 1.0 < 1.0 < 1.0 - - - - - - < 1.0 < 1.0 19 - 0.3 7.7 0.2 - 28.7 265.1 - - - - - 20 7.92 3.41 - - < 0.1 < 0.1 < 0.1 - - - - - 21 < 3.0 < 2.0 < 3.0 < 2.0 < 2.0 < 2.0 < 3.0 < 3.0 < 2.0 - < 10 < 10 22 - - - - 0.88 - - 1.75 1.8 - 27.7 - 24 - 2.46 - - - - 33.35 - - - - - 25 - < 0.1 0.12 < 0.1 < 1.0 < 1.0 - - - - - - 26 - 0.09 0.24 - - - - - - - 15.77 2.76 28 - - - - - - - - - - 22 16.5 29* - < 0.17 0.17 < 0.14 - - - 0.14 < 0.11 - - - 31 - - - 8.22 - - - - - - - -

- 28 -

Table 1: continued

Laboratory Heptachlor Aldrin Dieldrin Endrin alpha beta Endosulf. alpha gamma Cis Aroclor Aroclor Code Epoxide Endosulf. Endosulf. Sulfate Chlordane Chlordane Nonachlor 1254 1260

Number ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g ) ( ng/g ) 35* - 0.24 0.21 < 0.07 - - - - - - 8.02 5.51 38 - < 0.3 2.5 - - - - - - - - - 39 - 0.64 n.d. n.d. n.d. 3.42 - - - - - - 41 < 0.05 < 1.0 < 10 < 10 < 0.1 < 0.1 < 0.1 < 0.05 < 0.05 - 6.802 3.014 42 - - - 1.35 0.53 - 0.12 0.29 0.11 0.24 - - 48* - 0.2 0.7 0.11 - - - - - - 28.9 7.97 50 - 15.535 3.124 - - - - - - - - - 51 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 - - - - - - 52 < 0.05 < 0.05 1.0 0.12 0.4 0.12 2.4 0.35 < 0.05 - - - 53 - - - - - - - n.d. n.d. - - - 54* - 0.009 - - 0.009 0.011 - - - - - - 55 < 1.0 < 1.0 < 1.0 < 1.0 1.0 5.0 2.0 - - - - - 56 4.44 71.73 - - - - - - - - - - 57 - 0.5 0.15 - - - - - - - - - 59 - 0.18011 0.89548 2.51688 - - - - - - - - 60 - < 5.0 - - - - - - < 5.0 - - - 61 - - 0.14 - - - - - - - - - 64 - - 0.98 - - - - - - - - - 65* - 48.87 n.d. 23.16 - - - - - - - - 68 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 8.34 4.0 74 - - 0.32 - - - - - - - - - 75 - 33 - - - - - - - - - -

- 29 -

Table 1: continued

Laboratory Heptachlor Aldrin Dieldrin Endrin alpha beta Endosulf. alpha gamma Cis Aroclor Aroclor Code Epoxide Endosulf. Endosulf. Sulfate Chlordane Chlordane Nonachlor 1254 1260

Number ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g ) ( ng/g ) 77* - 0.27 0.24 0.2 - - - - - - 9.0 8.0 79 n.d. 5.55 12.6 4.79 14 22.7 9.15 n.d. - - - - 82 - - - - 15.7 - - - - - - - 83* 1.3 - 1.4 0.8 < 0.5 0.7 < 0.4 < 0.6 1.6 - - - 85 - < 0.5 0.6 < 0.5 - - - - - - 5.83 1.76 86 < 1.0 < 5.0 < 8.0 < 12 < 1.0 < 2.0 - - - - - -

Number of Results 5 20 23 15 9 9 8 7 6 2 12 11

Min. Value 0.15 0.009 0.12 0.107 0.009 0.011 0.12 0.021 0.063 0.029 5.83 1.76 Max. Value 7.92 71.73 13.33 23.16 15.7 28.7 265.1 1.75 1.8 0.24 28.9 16.5

Mean 2.84 9.25 2.08 4.14 4.16 6.87 40 0.40 0.67 0.13 14 6.54 St.Dev. 3.31 19 3.81 6.45 6.14 11 92 0.61 0.80 0.15 8.38 4.56 ( % ) 120 210 180 160 150 160 230 150 120 120 60 70

- 30 -

Table 2: Results of PCBs in sediment sample IAEA-159.

Laboratory PCB 8 PCB 18 PCB 20 PCB 26 PCB 28 PCB 31 PCB 44 PCB 49 PCB 52 PCB 60 PCB 66 PCB 70 PCB 74 Code Number ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g )

1* - 0.86 0.49 - 0.77 0.51 < 0.01 - 0.89 0.45 - - - 3 - - - - 0.42 - - - 0.82 - - - - 5* 0.18 0.29 - - 0.44 0.33 0.31 0.3 0.56 - 0.42 - - 7 - 0.71 - - - - 0.43 - - - - - - 9* - - - - 3.0 - - - 2.3 - - - - 10* 0.33 1.61 - - 0.88 0.23 0.25 0.24 0.71 0.12 0.38 0.42 0.17 14 - - - - < 0.5 < 0.5 - - < 0.5 - - - - 15 - - - - < 10 - - - < 10 - - - - 20 - - - - 6.34 - - - 1.79 - - - - 24 - - - - 8.27 - - - 0.54 - - - - 25 - - - - 0.86 - - - 0.43 - - - - 26 - - - - 0.81 - - - 0.91 - - - - 29* 0.59 0.38 - 0.16 0.59 - 0.48 0.45 0.74 - 0.47 - - 30 - - - - - - 0.85 - 0.92 - - - - 32 - - - - 0.48 - - - 0.44 - - - - 35* - - - - 0.40 - - - 0.48 - - - - 36 - - - - < 5.0 - - - < 5.0 - - - - 39 - 1.22 - - 0.72 1.69 2.43 - 1.08 - - - - 41 - - - - 0.563 - - - 1.012 - - - - 42 - - - - - - - - - - - 0.97 - 44* - - - - - - - - 0.73 - - - - 46* - - - - 0.3 - - - 0.6 - - - - 48* - 0.37 - - 1.38 1.4 0.39 2.28 - - 0.49 - -

- 31 -

Table 2: continued


50 - - - - 25.888 - - - 25.902 - - - - 51 - - - - 0.4 - - - 4.46 < 0.05 - - 0.21 52 - - - - 0.87 - - - 0.57 - - - - 53 - - - - - - 0.3 - 0.45 - 0.31 0.47 0.23 58* - - - - < 1.0 - - - < 1.0 - - - - 60 - - - - < 5.0 - - - < 5.0 - - - - 61 - - - - 0.249 0.28 - - 0.343 - - - - 62* - - - - 0.29 - - - 0.36 - - - - 67 - 1.461 - - 0.351 0.32 0.546 - 1.09 - - - - 68 - - - - - - - - 0.27 - - - - 70 - - - - 0.49 0.34 - 0.3 0.6 - - - - 71 - - - - 0.259 0.239 - - 0.639 - - - - 73* - 0.22 n.d. - - - n.d. - 1.57 - - - - 77* - 0.24 - - 0.28 0.25 0.09 - 0.48 - - - - 78 - - - - - - - - 2.83 - - - - 79 - - - - 0.67 - - - 3.73 - - - - 83* - - - - 1.6 - - - 1.1 - - - -


Min. Value 0.18 0.22 0.49 0.16 0.249 0.23 0.09 0.24 0.27 0.12 0.31 0.42 0.17 Max. Value 0.59 1.61 25.888 1.69 2.43 2.28 25.902 0.45 0.49 0.97 0.21

Mean 0.37 0.74 2.13 0.56 0.61 0.71 1.85 0.29 0.41 0.62 0.20 St.Dev. 0.21 0.53 5.1 0.53 0.67 0.88 4.5 0.23 0.07 0.3 0.03 ( % ) 57 72 240 95 110 120 240 79 17 48 15

- 32 -

Table 2: continued


1* - 0.64 0.81 0.77 - 0.69 1.14 0.59 1.42 0.79 - 0.43 0.7 3 - - - - - - 0.61 - - 0.37 - 0.03 - 5* - - 0.26 0.42 0.19 - 0.58 0.2 0.45 0.5 - 0.11 - 6 - - - - - - 0.54 - - - - - - 7 8.03 - - - - - 1.49 - - - - - - 9* - - - - - - 2.5 - - 2.0 - - - 10* - - 0.34 - < 0.05 0.3 0.69 0.49 0.6 0.65 - 0.81 - 14 - - - - - - < 0.5 < 0.5 - < 0.5 - - - 15 - - - - - - < 10 - - < 10 - - - 19 - - - - - - 13.6 - - - - - - 20 - - - - - - 0.38 - - 0.27 - - - 24 - - - - - - 0.53 - - 0.10 - - - 25 - - - - - - 0.48 - - 0.15 - - - 26 - - - - - - 0.86 0.99 - 1.5 - - - 29* - - 0.36 - - - 0.63 0.73 0.26 0.53 - 0.16 - 30 - - - - - - 0.75 - - 0.57 - - - 32 - - - - - - 0.41 - - - - - - 35* - - - - - - 0.46 - - 0.65 - - - 36 - - - - - - < 5.0 - - < 5.0 - - - 39 - - - - - - 1.15 - - 3.23 - - - 41 - - - - - 0.308 0.693 0.307 0.579 0.814 - - - 42 - - - - - - 1.6 0.84 - 0.71 - 0.27 - 44* - - - - - - 0.72 - - 0.58 - - - 46* < 0.1 - - - - - 0.6 0.3 - 0.5 - 0.1 - 48* - - - - - - 0.99 - 0.68 0.74 - - -

- 33 -

Table 2: continued


51 < 0.05 - - - - - < 0.05 < 0.05 - < 0.05 1.41 - - 52 - - - - - - 0.53 - - 0.73 - - - 53 - - - - - 0.29 0.49 - 0.45 0.41 - - - 58* - - - - - - 0.2 - - 0.245 - - - 60 - - - - - - < 5.0 - - < 5.0 - - - 61 - - - - - - 0.33 0.055 - 0.313 - - - 62* - - - - - - 0.35 0.13 - 0.38 - < 0.1 - 67 - - - - - - 0.27 - - 0.762 - - - 68 - - - - - - 0.47 - 0.74 0.44 - - - 70 - - - - - - 0.56 0.19 - 0.52 - - - 71 - - - - - - 0.406 0.152 - 0.394 - - - 73* - - - - - - 1.58 n.d. - 0.55 - - - 77* - - - - - - 0.51 - - 0.52 - - - 78 - - - - - - 1.88 - - - - - - 79 - - - - - - 1.1 - - 0.94 - - - 83* - - - 2.6 - - < 1.0 < 1.0 1.6 < 1.0 - - -


Min. Value 8.03 0.64 0.26 0.42 0.19 0.29 0.2 0.055 0.26 0.10 1.41 0.03 0.7 Max. Value 0.81 2.6 0.69 13.6 0.99 1.6 3.2 0.81

Mean 0.44 1.26 0.40 1.15 0.41 0.75 0.70 0.27 St.Dev. 0.25 1.17 0.20 2.23 0.31 0.45 0.61 0.27 ( % ) 57 93 50 190 76 60 87 100

- 34 -

Table 2: continued


1* 1.87 0.27 0.64 < 0.01 1.58 1.02 - - - - 0.15 - < 0.01 3 0.61 - - - 0.62 - - - - - 0.17 - - 5* 0.73 - 0.47 - 0.63 0.052 - - - - 0.16 - 0.15 6 1.04 - - 0.28 0.37 - - - - - - - - 7 0.33 - - - 0.2 - - - - 0.48 - - - 9* 2.1 - - - 1.8 - - - - - - - - 10* 1.02 - - - 0.86 < 0.06 < 0.06 < 0.04 < 0.05 - 1.09 - - 14 < 0.5 - - - < 0.5 < 0.5 - - - - - - - 15 < 10 - - - < 10 - - - - - - - - 19 4.4 - - - 1.9 - - - - - - - - 20 0.04 - - - 0.19 - - - - - - - - 24 0.01 - - - 0.08 - - - - - - - - 25 1.27 - - - 0.59 - - - - - - - - 26 1.14 - - - 0.54 0.12 - - - - - - - 29* 0.36 - 0.49 0.22 < 0.21 - < 0.09 - - < 0.17 0.22 - - 30 0.31 - 0.46 - 0.41 - - - - - - - - 32 0.52 - - - 0.51 - - - - - - - - 35* 0.63 - - - 0.52 - - - - - - - - 36 < 5.0 - - - < 5.0 - - - - - - - - 39 9.6 - 3.18 - 1.15 - - - - - 0.58 - - 41 0.473 - - - 0.653 0.095 - - - - 0.12 - - 42 0.93 - - - 0.49 0.1 - - - - 0.17 0.13 - 44* 0.835 - - - 1.25 - - - - - 0.21 - - 46* 0.6 - - - 0.5 < 0.1 - - - < 0.1 < 0.1 - - 48* 0.98 - 0.77 - 0.61 - - - - - 0.11 - 0.07

- 35 -

Table 2: continued


50 9.963 - - - - - - - - - - - - 51 0.2 - - - 0.24 < 0.05 < 0.05 - < 0.05 < 0.05 < 0.05 - - 52 0.83 - - - 0.6 - - - - - - - - 53 - - 0.38 - - - - - - - - - - 58* 0.348 - - - 0.213 - - - - - - - - 60 14 - - - < 5.0 - - - - - - - - 61 0.487 - 0.336 - 0.687 - - - - - - - - 62* 0.5 - - - 0.46 < 0.1 - - - - 0.10 - - 67 0.449 - - - 0.693 - - - - - - - - 68 0.63 - - - 0.59 - - - - - - - - 70 0.53 - 0.46 - 0.64 0.08 - - - - 0.14 - - 71 0.292 - - - 0.47 0.0697 - - - - - - - 73* 0.88 - n.d. - 1.68 - - - - - n.d. - - 77* 0.56 - 0.64 - 0.54 - - - - - 0.08 - - 78 2.78 - - - 2.14 - - - - - - - - 79 0.45 - - - 0.7 - - - - - - - - 83* 2.2 - 1.4 - 1.4 1.0 - - - - < 1.0 - - 86 - - - - - - - - - - 2.0 - -


Min. Value 0.01 0.27 0.336 0.22 0.08 0.052 - - - 0.48 0.08 0.13 0.07 Max. Value 14 3.18 0.28 2.14 1.02 2.0 0.15

Mean 1.71 0.84 0.25 0.76 0.32 0.38 0.11 St.Dev. 2.99 0.83 0.04 0.52 0.43 0.54 0.06 ( % ) 180 99 16 68 130 140 55

- 36 -

Table 2: continued


1* 0.24 0.38 < 0.01 - 0.39 - 0.07 0.11 - - 0.14 - - 3 - 0.28 - - - - - - - - - - - 5* 0.12 0.27 0.094 - 0.34 0.052 0.051 - - - 0.033 0.054 0.025 6 - 0.33 - 0.15 - - - - - - - - - 7 - 1.29 - - - 0.33 - - - - - - - 9* - n.d. - - - n.d. - - - - - - - 10* - 1.31 0.12 - 0.43 0.15 0.11 < 0.04 - 0.29 - 0.88 0.46 14 - < 0.5 - - - - - - - - - - - 15 - < 10 - - - - - - - - - - - 20 - 0.28 - - - - - - - - - - - 24 - 0.08 - - - - - - - - - - - 25 - 0.39 - - - - - - - - - - - 26 - 0.28 - - - - - - - - - - - 29* - 0.2 < 0.17 - 0.18 < 0.28 < 0.17 - - - - < 0.28 < 0.28 30 - 0.14 - - - 0.09 - - - - - - - 32 - < 0.2 - - - - - - - - - - - 36 - < 5.0 - - - - - - - - - - - 39 - 2.55 - - - - - - - - - - - 41 - 0.215 - - - - - - - - - - - 42 0.31 0.43 0.75 - 0.65 0.11 - - - - 0.28 0.09 0.05 44* - 0.355 - - - - - - - - - - - 46* - 0.3 - - - - - - - - - - < 0.1 48* 0.11 0.17 0.11 - - 0.07 - - 0.06 - - - -

- 37 -

Table 2: continued


50 - 7.016 - - - - - - - - - - - 51 - < 0.05 - - - - - - - - - - - 52 - 0.5 - - - - - - - - - - - 58* - 0.129 - - - - - - - - - - - 60 - 11 - - - - - - - - - - - 61 - 0.187 - - - - - - - - - - - 62* - 0.22 - - - - - - - - - - - 67 - 0.227 - - - 0.154 - - - - - - - 68 - 0.32 - - - - - - - - - - - 70 - 0.26 - - - 0.07 - - - - - - 0.03 71 - 0.118 - - - - - - - - - - - 73* - 0.16 - - - n.d. - - - - - - - 77* - 0.27 - - - 0.03 - - - - - - - 78 - 1.16 - - - - - - - - - - - 79 - 0.66 - - - - - - - - - - - 83* - < 1.0 - - < 0.1 - - - - - - - - 86 - 3.0 - - - - - - - - - - -


Min. Value 0.11 0.08 0.094 0.15 0.18 0.03 0.051 0.11 0.06 0.29 0.033 0.054 0.025 Max. Value 0.31 11 0.75 0.65 0.33 0.11 0.28 0.88 0.46

Mean 0.20 1.04 0.27 0.40 0.12 0.08 0.15 0.34 0.14 St.Dev. 0.10 2.21 0.32 0.17 0.09 0.03 0.12 0.47 0.21 ( % ) 50 210 120 43 75 38 80 140 150

- 38 -

Table 3: Results of petroleum hydrocarbons in sediment sample IAEA-159. Laboratory EOM PH equiv. PH equiv. Total Resolved Unresolved n-C17 Pristane n-C18 Phytane Σ Alk. Total Resolved

Code Chrysene ROPME Aliphatics Aliphatics Aliphatics C14-C34 Aromatics Aromatics Number ( mg/g ) (µg/g ) (µg/g ) (µg/g ) (µg/g ) (µg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (µg/g ) (µg/g ) (µg/g )

2* - - - - - - - - - - - - - 5* 0.31 25 202 92 10 82 138 136 114 61 5.0 23 3.9 9* < 0.01 - - - - - 27.6 14.1 17 16 - - 0.7204 11* 2.91 7.18 - 180.93 33.33 147.6 143.43 85.13 168.27 104.87 14.46 - - 12 1.0 - - - - - - - - - - - - 16 1.13 - - 7.17 - - 160 190 1770 170 6.73 0.34 - 17* 0.38 1410 830 19.6 4.3 15.3 82 173 91 57 - 2.14 0.55 18* 0.448 - 111.437 - - - 576.036 - 396.144 - - - - 19 - - - 33.19 3.13 - 31 37 57 42 1.466 - 0.8295 20 - - - 1.45 1.45 - - - 150 - 1.45 1.34 - 23 - - - - - - - - - - - - - 24 - - - - 1.94 - 100 80 110 120 1.94 - 2.32 27* - 52.07 260.09 - - - 103.87 123.5 49.13 23.07 1.07538 - - 29* - - - 7.06 7.06 - 140 140 90 90 4.03 1.3056 1.3056 34 - 7.5 - - - - 497 - 506 - - - - 36 - - - - - - - - - - 273 - - 37 - - - - - - - - - - - 0.865 -

- 39 -

Table 3: continued Laboratory EOM PH equiv. PH equiv. Total Resolved Unresolved n-C17 Pristane n-C18 Phytane Σ Alk. Total Resolved

Code Chrysene ROPME Aliphatics Aliphatics Aliphatics C14-C34 Aromatics Aromatics Number ( mg/g ) (µg/g ) (µg/g ) (µg/g ) (µg/g ) (µg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (µg/g ) (µg/g ) (µg/g )

38 - - - - - - - - - - - - - 39 - - - - - - 5.2 n.d. - 2.6 0.074 - 1.2837 41 - - - 36.04 24.801 11.239 372 292 366 186 8.587 1.737 0.736 42 9.74 - - - - - - - - - - - - 45 - 7.6 - 23.18 7.28 15.4 280 860 100 140 3.06 - - 55 1.0 - - - - - - - - - - - - 63* - - - 93.92 17.22 76.7 143 158 84 60 5.91 - - 65* 44.8 - - - - - - - - - - - - 68 - - - - - - 53 611 55 347 1.777 - - 72 - - - 112 10.9 99 211 156 398 84 6.7 - - 77* - - - - - - 120 94 110 59 4.374 2.043 - 79 - - - - - - 76.58 - 61.66 - 4.68853 - - 80 0.3 24.7 149.8 54.51 5.48 49.03 137.5 159.5 124.3 79 4.979 20.22 0.905


Min. Value 0.3 7.18 111.437 1.45 1.45 11.234 5.2 14.1 17 2.6 0.074 0.34 0.55 Max. Value 44.8 1410 830 180.93 33.33 147.6 576.036 860 1770 347 273 23 3.9

Mean 6.2 220 310 55 11 62 170 210 240 97 19 5.9 1.4 St.Dev. 14 530 300 54 9.8 48 150 220 390 82 63 9.0 1.1 ( % ) 230 240 97 98 89 77 88 105 160 85 330 150 79

- 40 -

Table 3: continued Laboratory Unresolved Biphenyl Naphthalene 1 methyl 2 methyl 2,6 dimethyl Phenanthrene 2 methyl 1 methyl Anthracene Chrysene

Code Aromatics Naphthalene Naphthalene Naphthalene Phenanthrene Phenanthrene Number (µg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g ) ( ng/g )

2* - - 16.65 - - - 63.1 - - 15.85 44.55 5* 19 13 31 20 33 20 90 33 25 17 71 7 - - 49.82 - - - 50.9 - - - - 9* - - 21.4 - - - 72.7 32.7 5.7 - 65.1 12 - - - - - - 25.8 - - 2.7 59.2 14 - - 30 - - - 50 - - - 30 15 - - < 50 - - - < 50 - - - 50 16 - - 20 - - - - 170 - - - 17* 1.59 - - - - - 200 - - - - 18* - - 8.435 3.506 6.427 - 13.561 - - 2.578 9.809 19 - - 0.3 - - - 44.2 - - 2.4 72.9 20 - - 10 - - - 110 - - 230 280 23 - - 177.9 - - - 36.3 - - 8.8 36.7 24 - - 20 - - - 10 - - - - 25 - - - - - - 45 - - 11 73 26 - - - - - - - - - - 12.06 27* - - 9.05 - - - 58.51 16.1 11.16 - 76.42 28* - - - - - - 93.3 - < 1.0 - 61.2 29* - 5.74 20.05 16.37 23.41 14.86 74.98 22.11 21.99 9.38 38.11 30 - - - - - - 74 19 17 33 70 33 - - - - - - 1998.78 - - - - 34 - - - - - - - - - - 87.4

- 41 -


Code Aromatics Naphthalene Naphthalene Naphthalene Phenanthrene Phenanthrene Number (µg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) (ng/g) ( ng/g )

36 - - 61.3 - - - 36 - - - < 30 37 - - 29 - - - 21 - - 10 133 38 - - < 10 - - - 17.3 - - 3.6 34.5 39 - - 22.8 - - - 135.1 - - - 215.7 41 1.002 - 19 - - - 68 27 24 - 90 42 - - - - - - 104.6 - - 17.3 98.5 43 - - 16 - - - 66 - - - 75 46* - - 19 - - - 62.6 - - 7.4 78.6 47 - - < 30 - - - 34 - - - 42 49* - - 43.2 - - - 70.5 - - 12.8 73.2 52 - - 35 - - - 146.7 - - - 60 53 - 13.69 35.41 26.01 38.71 24.55 81.38 - 19.87 15.58 67.95 54* - - 9.0 - - - 76 - - - - 55 - - 26 - - - 35 - - - 49 62* - - 26.2 - - 65.2 - - 13.1 75 63* - - 36 - - - 77 - - 11.2 66 65* - - 91.51 - - - 0.84 - - - 21.3 66 - - 44.3 - - - 83.1 - - - 49.1 68 - - < 0.1 - - - 21.3 - - - 39 69* - 11.6 36.9 35.4 61.8 22.7 72.7 - 21.5 13.2 75.6 70 - - 30 30 40 - 80 30 40 20 80 72 - - 32.6 - - - 59.5 21.1 - 8.3 47 73* 0.97122 - 162.34 - - - 164 - - 41.41 16.64

- 42 -


Code Aromatics Naphthalene Naphthalene Naphthalene Phenanthrene Phenanthrene Number (µg/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) (ng/g) ( ng/g )

76* - - - - - - 55.71 - - - 58.19 77* - - 86 - - - 155 63 61 32 124 78 - - 9.09 - - - 32 - - - 36.4 79 - - n.d. - - - 30.97 - - n.d. 13.27 80 19.32 - 16.7 14 - - 85.7 32 10.7 15.7 117.7 81 - - 3.509 - - - 45.75 - - 9.926 72.969 83* - - - - - - 67.3 - - - 47.4 84 - - 6.5 11.72 8.45 - 35.96 - - - 41.21 86 - - 296.4 - - - 109.8 - - 15.1 39.8

Number of Results 5 4 38 8 7 4 50 11 11 26 47

Min.Value 0.97122 5.74 0.3 3.506 6.427 14.86 0.84 16.1 5.7 2.4 9.809 Max.Value 19.32 13.69 296.4 35.4 61.8 24.55 1998.78 170 61 230 280

Mean 8.4 11 42 20 30 21 110 42 23 22 68 St.Dev. 9.9 3.6 57 10 19 4.2 280 44 15 43 48 ( % ) 120 33 140 50 63 20 255 105 65 200 71

- 43 -

Table 3: continued Laboratory Triphenylene Fluorene Fluoranthene Pyrene 1 Methyl Benz[b] Benzo[k] Benzo[a] Benz[a] Perylene Benzo[e]

Code Pyrene Fluoranthene Fluoranthene Fluoranthene Anthracene Pyrene Number (ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g ) ( ng/g )

2* - 20.25 108.65 116.7 - 128.75 56.9 - 50.7 - - 5* 33 10 161 127 20 120 68 18 92 36 148 7 - - 18.98 48.08 - - - - 29.47 - 3.42 9* - - 129.9 102.6 - - - - 71.3 - 72 12 - - 117 73.3 - 19.3 - - 28.1 - - 14 - - 90 70 - - - - 40 - - 15 - - 90 90 - - - - 60 - - 16 - - 90 90 - - - - - - - 17* 200 - 160 160 - 210 40 - - - - 18* - 1.744 19.164 19.127 - 15.574 5.518 - 8.12 - - 19 - - 146.8 97.8 - 83.4 39.4 - 45.7 - - 20 - 50 240 170 - 160 320 - 70 - - 23 - 7.7 59.1 57.2 - 49.8 7.6 - 30.9 - - 24 - - 230 170 - - - - - - - 25 - - 112 97 - 154 112 - 56 - - 26 - - - 66.97 - - - - 24.63 - - 27* - 53.17 440.43 91.81 - 76.38 86.83 - 80.73 - 83.28 28* - - 123 102 - - - - 56.9 15.1 36.9 29* n.d. 9.61 137.62 123.95 - 78.96 22.18 - 65.96 - 85.09 30 - < 23 99 92 - 95 47 - 59 33 74 33 - 273.37 - 342.47 - 1367.55 141.21 - 123.41 - - 34 - - 18.7 179 - - - - - - - 36 - - < 30 79.7 - - - - 83 - -

- 44 -

Table 3: continued Laboratory Triphenylene Fluorene Fluoranthene Pyrene 1 Methyl Benzo[b] Benzo[k] Benzo[a] Benz[a] Perylene Benzo[e]

Code Pyrene Fluoranthene Fluoranthene Fluoranthene Anthracene Pyrene Number (ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) (ng/g) ( ng/g )

37 - 52 151 246 - - - - 82 - - 38 - - 63.6 64.6 - - - - 44.2 - - 39 - - 212.2 183.8 - - - - 180.7 - - 41 - - 145 129 - - - - 80 - 70 42 - 25.6 144.1 130.6 - 89.6 56 - 70.6 - - 43 - - 121 97 - 116 141 - 67 - - 46* - 4.9 102 120.2 - 111.7 46.7 - 59.3 - - 47 - - 96 105 - - - - 30 - - 49* - 10.9 123 112 - - 26.1 6.86 64.4 6.99 36.9 52 - - 136.7 148.3 - 108.3 55 - 56.7 - - 53 - 11.5 121.21 108.57 - 165.57 41.58 - 62.95 28.68 89.52 54* - - 122 170 - - - - 41 - - 55 - - 36 41 - - - - 30 - - 62* - - 107 96.5 - - - - 63.5 - - 63* - - 127.3 96.7 - - - - 54.6 29.9 83.3 65* - - 44 46.94 - - - - 15.41 - - 66 - - 134.3 139.6 - - - - 75.3 - - 68 - - 55.8 67.5 - 60.5 64.4 - 34.8 - - 69* - 11.2 122.3 107.6 - 176.9 50.4 - 70.1 34.2 91.3 70 - 20 130 130 20 - - 20 80 40 80 72 - 7.0 94.3 84.2 - 132.4 40.9 - 41.3 22.3 77.7 73* - n.d. n.d. 150.7 - 97.76 38.64 - 32.78 - - 76* - - 104.5 96.72 - - - - 53.73 - 95.41

- 45 -

Table 3: continued Laboratory Triphenylene Fluorene Fluoranthene Pyrene 1 Methyl Benzo[b] Benzo[k] Benzo[a] Benz[a] Perylene Benzo[e]

Code Pyrene Fluoranthene Fluoranthene Fluoranthene Anthracene Pyrene Number ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) (ng/g) ( ng/g )

77* - 19.7 222 214 - 241 77 - 142 - - 78 - - 91 80.3 - - - - 47.9 - - 79 - n.d. 44.8 n.d. - - - - 33.43 - - 80 - 7.7 126.7 139 11.7 - - - 66 257.3 128.7 81 95.148 8.521 132.968 121.379 - 119.075 - - - - - 83* - - 113.7 99.3 - 92.2 47.9 - 59.5 - - 84 - 12.4 70.94 66.73 - - - - 51.36 - - 86 - 30.6 - 44.7 - 86.8 55.3 - - - -

Number of Results 3 21 49 53 3 26 25 3 48 10 16

Min.Value 33 1.744 18.7 19.127 11.7 15.574 5.518 6.86 8.12 6.99 3.42 Max.Value 200 273.37 440.43 342.47 20 1367.55 320 20 180.7 257.3 148

Mean 110 31 120 110 17 160 68 15 58 50 79 St.Dev. 84 58 68 55 4.8 250 63 7.1 31 73 34 ( % ) 76 190 57 50 28 160 93 47 53 150 43

- 46 -

Table 3: continued Laboratory Benzo[a] Benzo[ghi] Indeno[123-cd] Dibenz[a,h] Acenaphthylene Acenaphthene Dibenzothiophene 1 Methyl 4 Methyl

Code Pyrene Perylene Pyrene Anthracene Dibenzothiophene Dibenzothiophene Number (ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g )

2* 66.6 195.4 260.3 36.5 16.9 15.1 - - - 5* 116 147 151 26 3.1 4.0 5.1 2.0 10 7 7.51 12.8 - - - - - - - 9* 65.3 81.7 - - - - - - - 12 22.1 - - - - - - - - 14 100 120 - - - - - - - 15 50 70 - - - - - - - 17* 500 170 - - - - - - - 18* 9.729 12.861 13.72 1.937 0.351 0.838 - - - 19 47.8 151.5 70.8 25.3 - - - - - 20 230 230 170 650 30 30 - - - 23 32.7 12.7 82.2 7.1 4.2 4.2 - - - 24 230 270 - - - - - - - 25 149 51 - - - - - - - 26 26.46 - - - - - - - - 27* 75.35 13.18 - - - - - - - 28* 40.5 79.7 - - - - - - - 29* n.d. 89.25 104.56 n.d. n.d. 4.67 2.8 - - 30 75 83 92 35 < 56 < 34 - - - 33 254.22 208.16 - 115.49 - - - - - 34 132 - - - - - - - - 36 < 30 < 30 46.3 77.7 - 105 - - -

- 47 -


Code Pyrene Perylene Pyrene Anthracene Dibenzothiophene Dibenzothiophene Number (ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g )

37 64 136 166 - - 456 - - - 38 29.1 48.8 - - - - - - - 39 68.2 265 - - - - - - - 41 84 - - - - - - - - 42 90.5 146.5 161.8 26.7 8.25 12.7 - - - 43 78 108 132 38 - - - - - 46* 70.5 83 94.1 96.3 - < 0.5 - - - 47 50 62 - - - - - - - 49* 31.2 104 109 - - - - - - 52 68.3 98.3 110 - - - - - - 53 62.61 98.07 118.11 18.22 6.0 5.83 8.48 - - 54* 26 65 - - - - - - - 55 32 122 - - - - - - - 62* 63.2 111.4 111.6 - - - - - - 63* 73.8 104.3 115.8 - - - - - - 66 74.4 140.4 - - - - - - - 68 30.4 90.2 - 7.0 - - - - - 69* 45.6 140.7 193.5 38.3 3.2 3.2 - - - 70 100 110 120 - n.d. 10 10 - - 72 56.3 119.2 112.6 21.6 2.3 3.5 6.0 - - 73* 53.39 103.13 114.74 n.d. 34.66 2.44 - - - 76* 60.41 100.5 - - - - - - -

- 48 -


Code Pyrene Perylene Pyrene Anthracene Dibenzothiophene Dibenzothiophene Number ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) ( ng/g ) (ng/g) ( ng/g )

77* 114 286 157 28 12.7 7.4 - - - 78 48.8 8.36 - - - - - - - 79 58 108.38 137.04 16.41 n.d. 4.66 - - - 80 87.7 95 141.7 58 - 5.7 - - - 81 76.605 155.469 147.619 23.813 1.19 1.873 - - - 83* 62.1 109 105.5 12.2 - - - - - 84 45.24 67.88 - - 12.07 10.02 - - - 86 15.9 45.5 38.6 - 211.4 - - - -

Number of Results 50 47 28 21 14 19 5 1 1

Min.Value 7.51 8.36 13.72 1.937 0.351 0.838 2.8 2.0 10 Max.Value 500 286 260 650 211.4 456 10 - -

Mean 81 110 120 65 25 36 6.5 St.Dev. 80 65 49 140 55 100 2.8 ( % ) 99 59 41 220 220 280 43

- 49 -

- 50 -

Table 4: Summary of the results of the inter-laboratory comparison exercise IAEA-159 for chlorinated pesticides.

Reported results Accepted results

Analyte Units No of Lab. Means

Mean Range of Lab. Means

Outliers ( % )

No of Lab. Means

Range of Lab. Means

Mean Mean’s Standard Deviation

HEOM mg/g 12 5.2 0.08 - 44.8 33 8 0.08 - 1.0 0.53 0.29 HCB ng/g 27 3.33 0.03 - 71 26 20 0.03 - 0.49 0.17 0.15 α HCH ng/g 12 2.98 0.04 - 22 25 9 0.04 - 0.21 0.10 0.06 β HCH ng/g 7 2.59 0.07 - 16 29 5 0.07 - 0.42 0.24 0.17 Lindane ng/g 37 34 0.01 - 1065 35 24 0.01 - 0.66 0.21 0.18 δ HCH ng/g 5 8.6 0.17 - 41 20 4 0.17 - 1.43 0.57 0.60 pp’ DDE ng/g 44 2.54 0.01 - 27 18 36 0.01 - 2.0 0.89 0.50 pp’ DDD ng/g 41 7.18 0.01 - 116 27 30 0.01 - 2.1 0.82 0.58 pp’ DDT ng/g 39 5.54 0.054 - 58 23 30 0.054 - 2.1 0.71 0.69 op DDE ng/g 4 0.19 0.12 - 0.3 0 4 0.12 - 0.3 0.19 0.09 op DDD ng/g 6 55 0.16 - 328 17 5 0.16 - 0.64 0.39 0.22 op DDT ng/g 4 2.32 0.05 - 8.8 0 4 0.05 - 8.8 2.32 4.33 Heptachlor ng/g 14 2.7 0.04 - 30 21 11 0.04 - 0.67 0.31 0.21 Heptachlor Epoxide

ng/g 5 2.84 0.15 - 7.9 0 5 0.15 - 7.9 2.84 3.31

Aldrin ng/g 20 9.25 0.009 - 72 45 11 0.009 - 0.5 0.17 0.15 Diedrin ng/g 23 2.08 0.12 - 13 22 18 0.12 - 1.4 0.48 0.37 Endrin ng/g 15 4.14 0.107 - 23 33 10 0.107 - 2.5 0.77 0.81

- 51 -

Table 4: continued




Outliers ( % )

No of Lab. Means

Range of Lab. Means


α Endosulfan ng/g 9 4.16 0.01 - 16 22 7 0.01 - 2.89 1.11 1.02 β Endosulfan ng/g 9 6.87 0.01 - 29 22 7 0.01 - 5.0 1.49 1.93 Endosulfan Sulphate

ng/g 8 40 0.12 - 265 25 6 0.12 - 9.2 3.46 3.69

α Chlordane ng/g 7 0.40 0.02 - 1.75 14 6 0.02 - 0.35 0.17 0.12 γ Chlordane ng/g 6 0.67 0.06 - 1.8 0 6 0.06 - 1.8 0.67 0.80 Aroclor 1254 ng/g 12 14 5.8 - 29 0 12 5.8 - 29 14.3 8.38 Aroclor 1260 ng/g 11 6.54 1.76 - 17 9 10 1.76 - 12 5.54 3.31

- 52 -

Table 5: Summary of the results of the inter-laboratory comparison exercise IAEA-159 for PCB congeners. Reported results Accepted results



Outliers ( % )

No of Lab.

Range of Lab. Means


PCB 8 ng/g 3 0.37 0.18 - 0.59 0 3 0.18 -0.59 0.37 0.21 PCB 18 ng/g 10 0.74 0.22 - 1.61 0 10 0.22 - 1.6 0.74 0.53 PCB 28 ng/g 27 2.13 0.25 – 26 19 22 0.25 - 1.4 0.57 0.28 PCB 31 ng/g 10 0.56 0.23 - 1.69 30 7 0.23 - 0.34 0.28 0.05 PCB 44 ng/g 10 0.61 0.09 - 2.43 20 8 0.09 - 0.55 0.35 0.14 PCB 49 ng/g 5 0.71 0.24 - 2.28 20 4 0.24 - 0.45 0.32 0.09 PCB 52 ng/g 32 1.85 0.27 - 26 22 25 0.27 - 1.1 0.67 0.25 PCB 66 ng/g 5 0.41 0.31 - 0.49 0 5 0.31 - 0.49 0.41 0.07 PCB 70 ng/g 3 0.62 0.42 - 0.97 0 3 0.42 - 0.97 0.62 0.30 PCB 74 ng/g 3 0.20 0.17 - 0.21 0 3 0.17 - 0.21 0.20 0.03 PCB 87 ng/g 4 0.44 0.26 - 0.81 0 4 0.26 - 0.81 0.44 0.25 PCB 95 ng/g 3 1.26 0.42 - 2.6 0 3 0.42 - 2.6 1.26 1.17 PCB 99 ng/g 4 0.40 0.29 - 0.69 0 4 0.29 - 0.69 0.40 0.20 PCB 101 ng/g 35 1.15 0.2 - 14 29 25 0.2 - 0.86 0.52 0.16 PCB 105 ng/g 12 0.41 0.06 - 0.99 0 12 0.06 - 0.99 0.41 0.31 PCB 110 ng/g 9 0.75 0.26 - 1.6 22 7 0.26 - 0.74 0.54 0.16 PCB 118 ng/g 30 0.70 0.1 - 3.2 10 27 0.1 - 0.94 0.52 0.21

- 53 -

Table 5: continued




Outliers ( % )

No of Lab.

Range of Lab. Means Mean

Mean’s Standard Deviation

PCB 128 ng/g 7 0.27 0.03 - 0.81 0 7 0.03 - 0.81 0.27 0.27 PCB 138 ng/g 38 1.71 0.01 - 14 21 30 0.01 - 1.27 0.60 0.31 PCB 149 ng/g 11 0.84 0.34 - 3.18 18 9 0.47 - 0.77 0.52 0.14 PCB 153 ng/g 35 0.76 0.08 - 2.14 40 21 0.37 - 0.7 0.56 0.09 PCB 156 ng/g 8 0.32 0.052 - 1.02 0 8 0.052 - 1.02 0.32 0.43 PCB 170 ng/g 14 0.38 0.08 - 2.0 21 11 0.08 - 0.22 0.15 0.04 PCB 177 ng/g 4 0.20 0.11 - 0.31 0 4 0.11 - 0.31 0.20 0.10 PCB 180 ng/g 33 1.04 0.08 - 11 24 25 0.08 - 0.5 0.26 0.10 PCB 183 ng/g 4 0.27 0.094 - 0.75 0 4 0.094 - 0.75 0.27 0.32 PCB 187 ng/g 5 0.40 0.18 - 0.65 40 3 0.34 - 0.43 0.39 0.05 PCB 194 ng/g 9 0.12 0.03 - 0.33 11 8 0.03 - 0.154 0.09 0.04 PCB 195 ng/g 3 0.08 0.05 - 0.11 0 3 0.05 - 0.11 0.08 0.03 PCB 201 ng/g 3 0.15 0.03 - 0.28 0 3 0.03 - 0.28 0.15 0.12 PCB 206 ng/g 3 0.34 0.05 - 0.88 0 3 0.05 - 0.88 0.34 0.47 PCB 209 ng/g 4 0.14 0.025 - 0.46 0 4 0.025 - 0.46 0.14 0.21

- 54 -

Table 6: Summary of the results of the inter-laboratory comparison exercise IAEA-159 for petroleum hydrocarbons.


Analyte Units No of Lab. Mean

Range of Lab. Means

Outliers ( % )

No of Lab.

Range of Lab. Means


E.O.M. mg/g 10 6.2 0.3 - 45 30 7 0.3 - 1.13 0.65 0.37 PH equiv. Chrysene

µg/g 7 220 7.2 - 1410 29 5 7.2 - 25 14 9.5

PH equiv. ROPME

µg/g 5 310 111 - 830 20 4 111 - 260 180 65

Total aliphatics

µg/g 12 55 1.45 - 181 0 12 1.45 - 181 55 54

Resolved aliphatics

µg/g 12 11 1.45 - 33 17 10 1.45 - 17 6.9 4.8

Unresolved aliphatics

µg/g 8 62 11 - 148 0 8 11 - 148 62 48

n-C17 ng/g 20 170 5.2 - 576 20 16 5.2 - 211 105 56 Pristane ng/g 16 210 14 - 860 19 13 14 - 190 120 53 n-C18 ng/g 20 240 17 - 1770 25 15 17 - 168 92 40 Phytane ng/g 17 97 2.6 - 347 6 16 2.6 - 186 81 53 Σ Alkanes: n-C14-n-C34

µg/g 18 19 0.07 - 273 11 16 0.07 - 8.6 3.9 2.4

Total aromatics

µg/g 9 5.9 0.34 - 23 22 7 0.34 - 2.1 1.4 0.65

Resolved aromatics

µg/g 9 1.4 0.55 - 3.9 22 7 0.55 - 1.3 0.90 0.29

Unresolved aromatics

µg/g 5 8.4 0.97 - 19 0 5 0.97 - 19 8.4 9.8

- 55 -

Table 6: continued




Outliers ( % )

No of Lab.

Range of Lab. Means


Biphenyl ng/g 4 11 5.7 - 14 0 4 5.7 - 14 11 3.6 Naphthalene ng/g 38 42 0.3 - 296 19 32 0.3 - 50 23 13 1-Methyl Naphthalene ng/g 8 20 3.5 - 35 0 8 3.5 - 35 20 10

2-Methyl Naphthalene ng/g 7 30 6.4 - 62 0 7 6.4 - 62 30 19

2,6-Dimethyl Naphthalene ng/g 4 21 15 - 25 0 4 15 - 25 21 4.2

Phenanthrene ng/g 50 110 0.84 - 2000 10 45 0.84 - 135 59 29 2-Methyl Phenanthrene ng/g 11 42 16 - 170 22 9 16 - 33 26 6.5

1-Methyl Phenanthrene ng/g 11 23 5.7 - 61 9 10 5.7 - 40 20 9.6

Anthracene ng/g 26 22 2.4 - 230 18 22 2.4 - 20 11 5.1 Chrysene ng/g 47 68 9.8 - 280 7 44 9.8 - 124 58 26 Triphenylene ng/g 3 110 33 - 200 0 3 33 - 200 110 84 Fluorene ng/g 21 31 1.7 - 273 19 17 1.7 - 31 13 7.7 Fluoranthene ng/g 49 120 18.7 - 440 16 41 36 - 161 110 32 Pyrene ng/g 53 110 19 - 343 6 50 19 - 184 100 38 1-Methyl Pyrene ng/g 3 17 11.7 - 20 0 3 11.7 - 20 17 4.8

Benzo[b] Fluoranthene ng/g 26 160 15.6 - 1368 12 23 15.6 - 177 100 42

- 56 -

Table 6: continued




Outliers ( % )

No of Lab.

Range of Lab. Means


Benzo[k] Fluoranthene ng/g 25 68 5.52 - 320 28 18 22 - 77 49 14

Benzo[a] Fluoranthene ng/g 3 15 6.86 - 20 0 3 6.86 - 20 15 7.1

Benz[a] Anthracene ng/g 48 58 8.12 - 181 6 45 8.12 - 92 54 20

Perylene ng/g 10 50 6.99 - 257 10 9 6.99 - 40 27 11 Benzo[e] Pyrene ng/g 16 79 3.42 - 148 31 11 70 - 95 82 8.2 Benzo[a] Pyrene ng/g 50 81 7.51 - 500 12 44 7.51 - 116 58 26 Benzo[g,h,i] Perylene ng/g 47 110 8.36 - 286 11 42 8.36 - 195 95 45

Indeno[1,2,3-cd] Pyrene ng/g 28 120 14 - 260 11 25 46 - 194 120 34

Dibenz[a,h] Anthracene ng/g 21 65 1.94 - 650 19 17 1.94 - 58 25 14

Acenaphthylene ng/g 14 25 0.35 - 211 21 11 0.35 - 17 6.4 5.4 Acenaphthene ng/g 19 36 0.84 - 456 16 16 0.84 - 15 6.0 4.0 Dibenzo- Thiophene ng/g 5 6.5 2.8 - 10 0 5 2.8 - 10 6.5 2.8

Table 7: Chlorinated compounds and PCBs - treatment of samples.

Lab. Moisture Extraction procedure used Internal Clean-up Fractionation Method for Code No Correction Instrument Solvent Time standard Procedure Procedure Confirmation

1 No Soxhlet Hexane 16 hrs Mirex and Octachloronaphthal.

Sulf. Acid Silica and Alumina

Standard Retention Times

4 Yes Shaker Hex. / Acetone ( 1:1 )

12 hrs None Florisil None Use of 2 columns

5 Yes Microwave Hex. / MeCl2 ( 1:1 )

30 min. CBs 29, 198, ε-HCH, Endos. I d4

Copper Florisil (3 fractions)

Use of 2 columns

6 Yes Soxhlet Hex. / Acetone ( 3:1 )

8 hrs None Sulf. Acid None Standard Retention Times

8 Yes Soxhlet Hex. / MeCl2 (1:1 )

8 hrs CBs 29, 198, ε-HCH, Endos. I d4

Hg Florisil (3 fractions)


9 Yes Sonication Hex. / Acet. / Tol. ( 2:1:1 )

Not indic.

CBs 30 and 185, op DDT d8

Florisil None GC - MS, SIM

10 Yes Soxhlet Hex. / MeCl2 (1:1 )

17 hrs CBs 103 and 198, DBOFB, TCMX

Silica / Alumina

None Use of 2 columns

14 No Soxhlet Hex. / MeCl2 Not indic.

CB 198 and o-Dichlorobenzene

Sulf. Acid. Silica gel

None Standard Retention Times

15 Yes Sonication and Shaker

Hex. / Acetone ( 1:1 )

Not indic.

None Sulf. Acid, Copper


16 No Soxhlet Hex. / MeCl2 ( 1:1 )

8 hrs CBs 29, 198, ε-HCH, Endos. I d4

Not indicated

Florisil (3 fractions)


- 57 -

Table 7: continued

Lab. Moisture Extraction Procedure Used Internal Clean-up Fractionation Method for Code No Correction Instrument Solvent Time standard Procedure Procedure Confirmation

17 Yes Not indicated


3 times CB 29 Copper 2 fractions Standard Retention Times

19 Yes Soxhlet MeCl2 / Acetone ( 1:1 )

20 hrs None Copper Florisil (3 fractions)


20 Yes Soxhlet Hexane 8 hrs None Not indicated




Not indic.

None EPA method

Florisil Standard Retention Times

22 Yes Soxhlet Hexane Not indic.

None SPE Florisil column

Not indicated Standard Retention Times

24 No Soxhlet Hexane 8 hrs None None Florisil (2 fractions)


25 No Sonication MeCl2 Not indic.

2 deuterated PAHs SPE Not indicated Standard Retention Times

26 Yes Soxhlet Cyclohexane 8 hrs ε-HCH and CB 198 Mercury Florisil (3 fractions)


28 No Sonication MeCl2 3x10 min.

Acenaphthene d10 C18 SPE column

None GC - MS, SIM


8 hrs CB 103 and DBOFB

Alumina None GC - MS, SIM

- 58 -

Table 7: continued

Lab. Moisture Extraction procedure Used Internal Clean-up Fractionation Method for Code No Correction Instrument Solvent Time Standard Procedure Procedure Confirmation

30 Yes Sonication Acetonitrile 5x15 min.

None SPE, Copper


32 Yes ASE Hexane Not indic.

13C labelled CBs: 28, 52, 101, 138,

153, 180

Alumina None GC - MS, SIM

35 Yes Soxhlet Hex. / MeCl2 ( 1:1 )

8 hrs CBs 29, ε-HCH, Endosulfan I d4



36 No Soxhlet Hex. / Acetone ( 1:1 )

5 hrs CB 40 Florisil column

None GC - MS, SIM

38 Yes Distillation Hexane Not indic.

None Sulfuric acid


39 Yes PSE (110 °C) Hex. / Acetone

( 1:1 ) 3x15 min.

Bromophosmethyl, CB 65 and 166

Copper Alumina (2 fractions)

GC - MS, SIM

40 Yes Soxhlet Hexane 8 hrs CB 29 Copper Florisil (2 fractions)


41 No Sonication Acetone/Tol. ( 1:3 )

Not indic.

13C pesticides and 13C PCBs

Copper Silica and Florisil



8 hrs Mirex Florisil column


GC - MS, SIM

- 59 -

Table 7: continued


44 Yes Soxhlet Toluene 24 hrs 13C lindane, pp’DDE and PCB

Sulfuric acid, Silica

None GC - MS, SIM

46 No ASE (Dionex)

Petr. Ether / MeCl2 (60:40)

3 cycles at 1500 psi

CBs 206, 207 and 208

Copper None Standard Retention Times

48 Yes Soxhlet Hexane 8 hrs CB 29 Florisil Florisil (3 fractions)


50 No Soxhlet Hexane 8 hrs CB 29 Mercury Florisil (3 fractions)


51 Yes Microwave Hex. / Acetone ( 1:1 )

10 min. None Copper, Mercury


52 Yes Cold extraction


Not indic.

CBs 103 and 187 C18, Florisil


53 No Soxhlet MeCl2 8 hrs CBs 103, 198 and TCMX

Alumina / Silica, Copper

None GC - MS, SIM

54 No Soxhlet MeCl2 Not indic.

None Alumina, Florisil

None GC - MS, SIM

55 Yes Soxhlet Hexane 6 hrs CBs 30 and 204 SPE Liquid / liquid partition


- 60 -

Table 7: continued



Not indic.

None GPC GPC (2 fractions)


57 Yes Shaker Acetone and Petr. ether

20 min. 15 min.

None Alumina and TBA

Silica gel (2 fractions)



Pentane and Hexane

Not indic.

Mirex and Perchloro

pentacyclodecane

Florisil clean-up


59 No Soxhlet Hexane Not indic.

CBs 29, ε-HCH, Endosulfan I d4

Florisil Florisil (3 fractions)


60 No Sonication Hex. / Acetone ( 1:1 )

Not indic.

None Florisil None Standard Retention Times


8 hrs CB 108 Copper, Alumina

Silica gel Standard Retention Times


Not indic.

CB 209 Alumina Silica gel Use of 2 columns

64 No Soxhlet MeCl2 24 hrs None Florisil Florisil (3 fractions)


65 Yes Soxhlet Hexane 8 hrs CB 29 Copper Florisil (3 fractions)

GC - MS, SIM

- 61 -

Table 7: continued


67 Yes In a flask in a water bath


2 hrs None Sulfuric acid, Copper



12 hrs CB 29 Copper Alumina / Silica

(2 fractions)


71 Not indicated

Soxhlet Hex. / Acetone ( 1:1 )

Not indic.

TCN Alumina Silica Standard Retention Times


Not indic.

None Sulfuric acid, Pot. Permang.

EPA 3630C Method

GC - MS, SIM

74 No Soxhlet Hexane 8 hrs None Florisil Florisil (3 fractions)


75 Not indicated

Mixer (2 minutes)

Acetone / MeCl2 ( 1:1 )

Stand 24 hrs

Not indicated Filter None Standard Retention Times


16 hrs CBs 29, ε-HCH, Endosulfan I d4



78 Yes Soxhlet Toluene Not indic.

CB 209 Alumina Not indicated Standard Retention Times

- 62 -

Table 7: continued



18 hrs CB 209 Copper Silica gel GC - MS, SIM

82 No Shaker MeCl2 4 times None Mercury, Alumina / Silica


83 Yes Soxhlet MeCl2 8 hrs CB 112 GPC Bio-Beads


85 Yes Soxhlet Hexane, then MeCl2

8 hrs each

Trifluralin Mercury Florisil (3 fractions)


86 Yes Sonication Hex. / MeCl2 (4:1 )

1 hr None Mercury Florisil and Silica gel


- 63 -

64

Table 8: GC conditions - chlorinated pesticides and PCBs.

Lab. Code No

Instrument type

Detector type

Injection technique

Injector temp. (oC)

Injection volume

Splitter time

1 Agilent 6890 ECD-63Ni On-column 250 1 µl - 4 Agilent 6890 ECD-63Ni Splitless 250 1 µl Not indic. 5 Agilent 6890 ECD-63Ni Splitless 250 1 µl 0.8 min. 6 Varian 3800 ECD-63Ni Splitless 280 1 µl 0.7 min. 8 Chrompack ECD-63Ni Splitless 280 1 µl Not indic. 9 Agilent 6890 MSD Splitless 250 5 µl 1.5 min. 10 HP 5890 ECD-63Ni Splitless 290 1 µl 0.89 min. 14 Agilent 6890 ECD-63Ni Splitless 300 1 µl Not indic. 15 Varian 3800 ECD-63Ni Splitless 250 1 µl 0.01 min. 16 Agilent 6890 ECD-63Ni Splitless 280 1 µl Not indic. 17 Shimadzu ECD-63Ni On-column 280 1 µl - 19 Varian 3800 ECD-63Ni Splitless 300 1 µl Not indic. 20 Agilent 6890 ECD-63Ni Splitless 320 1 µl 0.75 min. 21 HP 5890 ECD-63Ni Splitless 250 1.8 µl Not indic. 22 Agilent 6890 ECD-63Ni Splitless 250 1 µl 2 min. 24 HP 5890 ECD-63Ni Splitless 260 1 µl 0.75 min. 25 HP 5890 MSD Splitless 300 2 µl 1 min. 26 Agilent 6890 ECD-63Ni Splitless 250 2 µl Not indic. 28 Varian 3600 MS / MS Splitless 150-300 2 µl 0.5 min. 29 Agilent 6890 ECD-63Ni Splitless 300 1 µl 1.25 min. 30 6000 Vega ECD-63Ni Splitless 280 1 µl 2 min. 32 Agilent 6890 MSD Splitless 250 1 µl Not indic. 35 Agilent 6890 ECD-63Ni Splitless 250 1.5 µl 0.8 min. 36 Agilent 6890 MSD Splitless 230 1 µl 2 min. 38 Kristall 2000 ECD-63Ni Splitless 250 1 µl 20 min. 39 HP 5890 ECD-63Ni Splitless 250 2 µl 0.5 min.

65

Table 8: continued

Lab. Code No

Instrument type

Detector type

Injection technique

Injector temp. (oC)

Injection volume

Splitter time

40 Varian 3380 ECD-63Ni Splitless 250 2 µl 0.75 min. 42 Agilent 6890 MSD Splitless 265 1 µl Not indic. 44 Thermo trace MSD Splitless 240 1 µl 1 min. 46 Agilent 6890 ECD-63Ni Splitless 225 1 µl Not indic. 48 Fisons Mega ECD-63Ni Splitless 190 2 µl Not indic. 50 HP 6890 ECD-63Ni Splitless 250 1 µl 0.8 min. 51 Varian 3380 ECD-63Ni Splitless 270 2 µl 0.75 min. 52 HP ECD-63Ni On-column 300 2 µl - 53 Agilent 6890 MSD Splitless Not indic. 2 µl 1 min. 54 HP 5890 MSD Splitless 250 1.9 µl Not indic. 55 Agilent 6890 ECD-63Ni Splitless 240 1 µl 1 min. 56 Agilent 6890 ECD-63Ni On-column 150 1 µl - 57 Agilent 6890 ECD-63Ni Splitless 250 1 µl Not indic. 58 Shimadzu ECD-63Ni Splitless 200 1 µl 1 min. 59 Varian 3380 ECD-63Ni Splitless 260 1 µl Not indic. 60 Varian 3000 ECD-63Ni Splitless 150 1 µl Not indic. 61 Fisons 8000 ECD-63Ni On-column 40 1 µl - 62 Agilent 6890 ECD-63Ni Splitless 220 1 µl 1 min. 64 Varian 3300 ECD-63Ni Splitless 220 2 µl Not indic. 65 P.-E. Clarus ECD-63Ni Splitless 260 1 µl 1 min. 67 Agilent 6890 ECD-63Ni Splitless 250 1 µl Not indic. 68 Carlo Erba ECD-63Ni Splitless 280 2 µl 0.5 min. 71 Not indicated ECD-63Ni Splitless Not indic. Not indic. Not indic. 73 Agilent 6890 MSD Splitless 250 Not indic. Not indic. 74 Agilent 6890 ECD-63Ni Splitless 250 1 µl Not indic. 75 Shimadzu ECD-63Ni Splitless 250 1 µl Not indic.

66

Table 8: continued

Lab. Code No

Instrument type

Detector type

Injection technique

Injector temp. (oC)

Injection volume

Splitter closing time

77 Agilent 6890 ECD-63Ni On-column 250 1 µl - 78 Not indicated MSD Splitless 280 1 µl Not indic. 79 Agilent 6890 MSD Splitless 250 1 µl 1 min. 82 Agilent 6890 ECD-63Ni Splitless 275 1 µl 0.75 min. 83 HP 5890 ECD-63Ni Splitless 280 1 µl 2 min. 85 Varian 3300 ECD-63Ni Splitless 275 5 µl Not indic. 86 Varian 3400 ECD-63Ni Splitless 240 2 µl 1 min.

67

Table 8: continued

Lab. Carrier Gas Column Code No Type Flow rate Length I. Diameter Phase Thickness

1 Helium 1.5 ml/min. 60 m 0.32 mm DB - 5 0.25 µm 4 Nitrogen 2.7 ml/min. 30 m 0.25 mm HP - 35 0.25 µm 5 Helium 1.2 ml/min. 30 m 0.25 mm HP - 5 0.25 µm 6 Nitrogen 1 ml/min. 25 m 0.25 mm CP Sil - 8 CB 0.45 µm 8 Nitrogen 5 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 9 Helium 1 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 10 Helium 1.2 ml/min. 30 m 0.25 mm DB - 5 0.25 µm 14 Helium 35 ml/min. 60 m 0.25 mm HP - 5 1 µm 15 Nitrogen 0.8 ml/min. 30 m 0.25 mm RTK - CL 0.25 µm 16 Nitrogen 1 ml/min. 30 m 0.32 mm HP - 5 0.25 µm 17 Nitrogen 2 ml/min. 25 m 0.32 mm NB - 1701 0.25 µm 19 Nitrogen 3 ml/min. 50 m 0.32 mm CP Sil - 8 CB 1.2 µm 20 Helium 6 ml/min. 30 m 0.25 mm HP - 5 0.25 µm 21 Nitrogen Not indic. 30 m 0.25 mm DB - 1701 0.25 µm 22 Nitrogen 2 ml/min. 25 m 0.32 mm HP - 1 0.52 µm 24 Helium 1 ml/min. 30 m 0.25 mm HP - 5 0.25 µm 25 Helium 10 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 26 Helium 1.1 ml/min. 30 m 0.25 mm HP - 1 MS 0.25 µm 28 Helium 2 ml/min. 30 m 0.25 mm VB - 5 0.25 µm 29 Hydrogen 2 ml/min. 30 m 0.25 mm HP - 5 MS 0.5 µm 30 Helium 160 kPa 60 m 0.25 mm CP Sil - 8 CB 0.25 µm 32 Helium 1.3 ml/min. 30 m 0.25 mm ZB - 50 0.25 µm 35 Nitrogen 1 ml/min. 30 m 0.32 mm HP - 5 0.25 µm 36 Helium 2 ml/min. 60 m 0.25 mm HP - 1 MS 0.25 µm 38 Nitrogen 42 ml/min. 30 m 0.25 mm ZB - 5 0.25 µm 39 Helium 2 ml/min. 50 m 0.25 mm CP Sil - 8 CB 0.25 µm

68

Table 8: continued

Lab. Carrier Gas Column Code No Type Flow rate Length I. Diameter Phase Thickness

40 Nitrogen 2 ml/min. 30 m 0.25 mm DB - 17 0.25 µm 42 Helium 1.2 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 44 Helium 1 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 46 Helium 2.6 ml/min. 30 m 0.32 mm DB - 35 MS 0.25 µm 48 Nitrogen 1.5 ml/min. 25 m 0.32 mm DB - 5 1 µm 50 Helium 1 ml/min. 25 m 0.20 mm HP - 5 0.33 µm 51 Helium 0.6 ml/min. 60 m 0.25 mm Rtx - 5 MS 0.25 µm 52 Ar./Methane 2.4 ml/min. 60 m 0.25 mm CP Sil - 8 CB 0.25 µm 53 Helium 0.4 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 54 Helium 1.5 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 55 Nitrogen 1.5 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 56 Nitrogen Not indic. 30 m 0.53 mm DB - 608 0.83 µm 57 Nitrogen 0.9 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 58 Nitrogen 7.2 ml/min. 30 m 0.25 mm ZB - 5 0.25 µm 59 Nitrogen Not indic. 30 m 0.25 mm CP Sil - 8 CB 0.25 µm 60 Helium 1.9 ml/min. 30 m 0.25 mm Rtx - 5 MS 0.25 µm 61 Hydrogen 2 ml/min. 30 m 0.32 mm DB - 5 0.25 µm 62 Helium 1 ml/min. 60 m 0.25 mm Rtx - 5 0.25 µm 64 Nitrogen 1.7 ml/min. 30 m 0.25 mm HP - 5 0.25 µm 65 Helium 1 ml/min. 30 m 0.32 mm Elite 5 MS 0.25 µm 67 Helium 2.5 ml/min. 25 m 0.2 mm HP - 1 0.33 µm 68 Hydrogen Not indic. 30 m 0.32 mm SE - 54 0.3 µm 71 Hydrogen Not indic. 30 m 0.25 mm HT - 8 Not indic. 73 Helium 1.5 ml/min. 30 m 0.32 mm HP - 5 MS 1 µm 74 Nitrogen 69 ml/min. 30 m 0.32 mm HP - 5 0.25 µm 75 Nitrogen 3 ml/min. 30 m 0.25 mm CP Sil - 24 CB 0.25 µm

69

Table 8: continued

Lab. Carrier Gas Column Code No Type Flow rate Length I.Diameter Phase Thickness

77 Helium 1 ml/min. 30 m 0.25 mm DB XLB 0.25 µm 78 Helium 1 ml/min. 30 m 0.25 mm DB - 5 0.25 µm 79 Helium 1 ml/min. 30 m 0.25 mm TRB - 5 MS 0.25 µm 82 Nitrogen 1.1 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 83 Helium 1.7 ml/min. 60 m 0.25 mm DB-5 / DB-17 0.25 µm 85 Nitrogen 2 ml/min. 30 m 0.53 mm ZB - 1701 1 µm 86 Helium 30 m/s 30 m 0.25 mm Rtx - 5 0.25 µm

70

Table 8: continued Lab. Temperature programme (oC) No Init.

Temp. Isoth. (min.)

1st rate To: Isoth.

(min.) 2nd rate To: Isoth.

(min.) 3rd rate To: Isoth.

(min.) 1 60 1 10 160 - 2 280 10 - - - 4 180 1 5 220 16 - - - - - - 5 70 2 3 260 25 - - - - - - 6 90 1 25 120 - 4 290 54 - - - 8 70 2 3 300 15 - - - - - - 9 80 2 25 130 - 3 235 - 25 300 15 10 100 - 1.5 245 1 10 300 3 - - - 14 70 1 30 180 15 5 215 30 2 290 25 15 60 1 30 170 2 2.5 207 - 13 310 6 16 70 3 3 240 - 5 260 - - - - 17 100 2 20 150 - 6 280 25 - - - 19 150 5 5 300 5 - - - - - - 20 90 2 30 180 - 1 200 - 10 300 6 21 150 1 6 270 10 - - - - - - 22 175 2 10 275 - - - - - - - 24 90 2 30 180 - 1 200 - 10 300 6 25 70 1 20 140 - 6 250 2 20 300 3 26 70 2 3 260 25 - - - - - - 28 40 - 15 140 - 8 300 3.5 - - - 29 100 1 5 140 1 1.5 250 1 10 300 5 30 90 1 40 210 0.5 5.6 230 10 5.6 275 20 32 45 0.5 18 175 - 10 275 15 - - - 35 70 2 3 260 25 - - - - - - 36 70 2 15 210 1 6 250 1 15 280 23 38 210 Isoth. - - - - - - - - - 39 70 1 15 150 15 3 300 8 - - -

71


Temp. Isoth. (min.)

1st rate To: Isoth.



(min.) 40 70 2 3 260 15 - - - - - - 42 90 1 15 160 2 20 270 - - - - 44 75 1 20 180 1 2.5 240 10 - - - 46 110 1 15 260 10 15 320 10 - - - 48 70 1 4 260 10 - - - - - - 50 50 2 20 210 - 10 285 2 - - - 51 90 1 30 180 1 2 240 20 5 260 11 52 60 0.5 30 190 20 20 215 25 7 310 25 53 100 - 10 200 - 5 260 1 - - - 54 85 1.5 30 190 - 3.6 240 2 - - - 55 80 1.5 20 160 - 5 250 - 10 300 5 56 140 2 10 240 5 5 265 15 - - - 57 150 5 10 280 2 - - - - - - 58 120 1 10 300 10 - - - - - - 59 55 1 10 160 - 3 260 10 - - - 60 150 5 4 210 - 2 275 - - - - 61 40 1 40 160 10 4 290 10 - - - 62 50 1 30 165 - 1.5 210 25 2 270 - 64 160 2 2 190 2 1 209 2 17 250 - 65 100 - 20 220 14 5 260 2 - - - 67 80 - 30 180 4 2.5 220 - 10 260 3 68 80 2 4 280 10 - - - - - - 73 100 2 15 160 - 5 270 10 - - - 74 70 5 30 280 7 - - - - - - 75 150 3 5 250 10 10 290 20 - - -

72


Temp. Isoth. (min.)

1st rate To: Isoth.



(min.) 77 100 1 10 300 7 - - - - - - 78 120 1 30 180 - 2 220 - 25 300 5 79 40 5 12 290 6 20 320 10 - - - 82 70 - 5 140 - 1.5 250 - 10 300 5 83 60 2 30 220 - 0.5 240 - 2.5 280 10 85 150 2 2 250 25 - - - - - - 86 60 1 20 150 - 6 250 8 - - -

73

Table 8: continued Lab. Code

No Detector temp. (oC) Make-up gas Make-up flow Recorder / Integrator

1 300 Nitrogen 60 ml/min. Agilent chemstation 4 250 Not indicated Not indicated Agilent chemstation 5 300 Nitrogen 59 ml/min. Agilent chemstation 6 300 Nitrogen 29 ml/min. Galaxie Workstation 8 300 Nitrogen 25 ml/min. Integrator Chrompack 9 Source: 230 N.A. N.A. Agilent chemstation 10 Not indicated Nitrogen 28 ml/min. Not indicated 14 Not indicated Ar. / Methane Not indicated Agilent chemstation 15 300 Helium 30 ml/min. Star Workstation 16 300 Helium 50 ml/min. Agilent chemstation 17 280 Nitrogen 25 ml/min. Chromatopack C-R3A 19 320 Nitrogen 25 ml/min. Star Workstation 20 320 Nitrogen 60 ml/min. Agilent chemstation 21 350 Nitrogen 30 ml/min. Agilent chemstation 22 300 Nitrogen 60 ml/min. Software 24 320 Nitrogen 40 ml/min. HP 3396 series II 25 Not indicated N.A. N.A. Agilent chemstation 26 300 Nitrogen 59 ml/min. Agilent chemstation 28 200 N.A. N.A. Saturn Workstation 29 320 Nitrogen 30 ml/min. Agilent chemstation 30 320 Nitrogen Pres.: 160 kPa Computer software 32 Source: 230 N.A. N.A. RTE integrator 35 300 Nitrogen 60 ml/min. Agilent chemstation 36 Not indicated N.A. N.A. Agilent chemstation 38 300 Nitrogen Not indicated Not indicated 39 310 Nitrogen 5 ml/min. Not indicated

74


No Detector temp. (oC) Make-up gas Make-up flow Recorder / Integrator

40 300 Nitrogen 28 ml/min. Not indicated 42 Quad.: 105 N.A. N.A. Agilent chemstation 44 Not indicated N.A. N.A. Xcalibur software 46 325 Nitrogen 20 ml/min. Agilent chemstation 48 300 Nitrogen 60 ml/min. Chromcard Windows 50 Not indicated Nitrogen 60 ml/min. HP laserjet 51 350 Nitrogen 29 ml/min. Star Workstation 52 300 Not indicated 7.6 ml/min. Agilent chemstation 53 Not indicated N.A. N.A. Agilent chemstation 54 280 N.A. N.A. Agilent chemstation 55 300 Nitrogen 60 ml/min. Agilent chemstation 56 325 Nitrogen 30 ml/min. Agilent chemstation 57 300 Nitrogen 46 ml/min. Agilent chemstation 58 Not indicated Nitrogen 30 ml/min. Integration software 59 Not indicated Nitrogen Not indicated Not indicated 60 Not indicated Nitrogen 30 ml/min. Computer software 61 320 Nitrogen 30 ml/min. Chromcard software 62 Not indicated Nitrogen Not indicated Agilent chemstation 64 320 Nitrogen 1.9 ml/min. Varian 4290 65 300 Nitrogen Not indicated Computer software 67 Not indicated Nitrogen 30 ml/min. Agilent chemstation 68 330 Nitrogen 30 ml/min. Chromcard software 71 Not indicated Ar. / Methane Not indicated Not indicated 73 300 N.A. N.A. Agilent chemstation 74 320 Nitrogen 60 ml/min. Agilent chemstation 75 300 Nitrogen 30 ml/min. GC solution software

75


No Detector temp. (oC) Make-up gas Make-up

flow Recorder / Integrator 77 320 Nitrogen 60 ml/min. Agilent chemstation 78 Not indicated N.A. N.A. RT INT 79 Not indicated N.A. N.A. Agilent chemstation 82 275 Nitrogen 40 ml/min. Agilent chemstation 83 300 Nitrogen 60 ml/min. Agilent chemstation 85 325 Nitrogen 80 ml/min. EZ chromatography 86 320 Nitrogen 30 ml/min. Star Workstation

Table 9: Petroleum hydrocarbons - treatment of samples.

Extraction Procedure Used Lab. Code

Moisture Correct. Instrument Solvent Time

Internal Standard

Clean-up Procedure

Fractionation Procedure

Method for Confirmation

2 No Soxhlet Hex. / Acetone 6 hrs p-Teraphynl. Alumina (10 %)

None HPLC, Fluorescence

5 Yes Microwave Hex. / MeCl2 ( 1:1 )

30 min. 4 deuterated compounds

Copper Silica / Alumina (2 fractions)

GC-MS, SIM

9 Yes Sonication Hex./Acet./ Tol. ( 2:1:1 )

Not indic.

Not indic. Florisil Not indic. GC-MS, SIM

11 Yes Sonication Hex. / MeCl2 ( 1:1 )

30 min. C16, C22, C28 Mercury Silica / Alumina (1 fraction)


12 Yes Sonication Cyclohexane 1 hr None Silica gel None Standard Retention Times

14 No Sonication MeCl2 Not indic.

None Silica / Alumina


15 Yes Shaker Hex. / Acetone ( 1:2 )

Not indic.

C10, C40 Florisil None Standard Retention Times


8 hrs C18.1, C32, 9,10 Dihydroanthr.

Not indic. Silica / Alumina (3 fractions)


17 Not indic.

Shaker Hexane 3 times n-C18, n-C23 Not indic. Not indic. Standard Retention Times


8 hrs o-terphenyl Not indic. Silica / Alumina (3 fractions)

GC-MS, SIM

- 76 -

Table 9: continued


Moisture Correct. Instrument Solvent Time

Internal Standard

Clean-up Procedure



19 Yes Soxhlet MeCl2 20 hrs None Silica gel Silica gel (2 fractions)



8 hrs None Not indic. Silica / Alumina (2 fractions)


23 Yes Liquid / liquid

MeOH, KOH Hexane

1.5 hrs 3 deuterated PAHs Silica column

Silica gel (2 fractions)

GC-MS, SIM

24 No Soxhlet Hex. / MeCl2 8 hrs None None Silica / Alumina (2 fractions)


25 No Sonication MeCl2, Hex., Acetone

Not indic.

Squalene and 2 deuterated PAHs

SPE Not indicated Standard Retention Times

26 Yes Soxhlet Cyclohexane 8 hrs 9,10 Dihydroanthr. Copper Silica / Alumina (2 fractions)



8 hrs C18.1, C32, 9,10 Dihydroanthr.



28 No Sonication MeCl2 3x10 min.

Acenaphth. d10, Fluorene d10

None Silica / Alumina (2 fractions)

GC-MS, SIM


8 hrs 5 deuterated PAHs, Hexadecene,Eicosene

Silica / Alumina

Silica / Alumina (2 fractions)

GC-MS, SIM

- 77 -

Table 9: continued


Moisture Correction Instrument Solvent Time

Internal Standard

Clean-up Procedure



30 Yes Sonication Acetonitrile 5x15 min.

None TLC. Copper None Standard Retention Times

33 No Sonication Hex. / Acetone (1:4, 1:1, 4:1)

3 times

None Alumina (11 % water)

Silica gel Standard Retention Times


8 hrs 4 deuterated PAHs, Hexamethylbenz.,

Cadalene




5 hrs 3 deuterated PAHs Florisil None GC-MS, SIM

37 Yes Soxhlet MeCl2 Not indic.

2-Fluorobiphenyl Silica None Standard Retention Times

38 Yes Sonication Acetone Not indic.

None Alumina (ISO 13877)


39 Yes PSE 110 °C Hex. / Acetone

( 1:1 ) 3x15 min.

Triphenylamine, 3 deuterated PAHs

Copper Alumina (3 fractions)

GC-MS, SIM

41 No Sonication Hex. / Acetone ( 3:1 )

Not indic.

5 deuterated PAHs Copper Not indicated GC-MS, SIM

- 78 -

Table 9: continued



Internal Standard

Clean-up Procedure




8 hrs 4 deuterated PAHs Silica Silica (2 fractions)

GC-MS, SIM

43 No EPA 3550 Method

MeCl2 Not indic.

Not indicated Not indicated

Not indicated GC-MS, SIM

45 No Soxhlet Hex. / MeCl2 8 hrs 9,10 Dihydroanthracene

None SW-846 Method 3611B


46 No Sonication MeOH / Acetone (3:2)

Not indic.

None Centrifug., filtration


47 No Sonication MeOH/MeCl2 ( 9:1 )

2x15 min.

None None None Standard Retention Times

49 Yes Pressurised Fluid

Extraction

MeCl2 200 psi

3 cycles 5 min.

Deuterated PAHs None None GC-MS, SIM

52 Yes Extractor Buchi

Hex. / MeCl2 ( 1:1 )

Not indic.

CBs 103 and 187 Florisil None Standard Retention Times

53 No Soxhlet MeCl2 8 hrs 7 deuterated PAHs (5 surrog.+ 2 I.S.)

Alumina / Silica, Copper

None GC-MS, SIM

54 No Soxhlet MeCl2 Not indic.

None Alumina, Florisil

None GC-MS, SIM

- 79 -

Table 9: continued



Internal Standard

Clean-up Procedure



55 Yes Soxhlet MeCl2/ MeOH ( 1:1 )

6 hrs 3,6 Dime phenanthr. 22’ biphenyl

SPE Liquid / liquid partition



Not indic.

6 deuterated PAHs CB 155

Alumina None GC-MS, SIM

63 No Soxhlet MeCl2 8 hrs 5 deuterated PAHs, n-C24 d50

Not indicated

Silica / Alumina (2 fractions)

GC-MS, SIM

65 Yes Soxhlet Hexane 8 hrs Not indicated Copper Silica / Alumina GC-MS, SIM 66 Yes ASE Hex. / Acetone

( 1:1 ) Not

indic. None Alumina

cartridge None Standard

Retention Times 68 No Soxhlet Hex. / MeCl2

( 1:1 ) 12 hrs None Copper Silica / Alumina

(2 fractions) Standard

Retention Times 69 No Soxhlet Hex. / MeCl2 16 hrs 6 deuterated PAHs Silica /

Alimina Size exclusion

HPLC GC-MS, SIM

72 No Soxhlet MeOH/MeCl2 (2:1 )

Not indic.

7 deuterated PAHs, n-C24 d50

Saponification

Silica column (2 fractions)

GC-MS, SIM

73 Yes EPA Acetone/MeCl2 (1:1 )

Not indic.

None EPA Method

Not indicated Standard Retention Times

- 80 -

Table 9: continued



Internal Standard

Clean-up Procedure




Not indic.

2 Me Chrysene Copper Alumina Standard Retention Times

77 Yes ASE SFE

MeCl2 CO2

Not indic.

4 deuterated PAHs, Tetracosane d58

Copper Not indicated GC-MS, SIM


Hexane 2 times 4 deuterated PAHs Not indicated Not indicated Standard Retention Times


18 hrs Deuterated PAH Copper Silica gel GC-MS, SIM


8 hrs C18.1, C32, 9,10 Dihydroanthracene




14 hrs CB 29 Silica gel (EPA 36230C)

Silica gel (EPA 3630C)

GC-MS, SIM

83 Yes Soxhlet MeCl2 8 hrs None Gel permeat. Bio-Beads


84 Yes Sonication MeCl2/MeOH (5:1 )

2x10 min.

None Copper, Silica gel

None GC-MS, SIM

86 Yes Sonication Hex. / MeCl2 ( 4:1 )

1.5 hr None Mercury Florisil Standard Retention Times

- 81 -

- 82 -

Table 10: GC conditions - petroleum hydrocarbons Lab.

Code No Instrument type Detector

type Injection technique

Injector temp. (oC)

Injection volume

Splitter time

2 HPLC - - - - - 5 Aliph.: Fisons

Arom: Agilent FID MSD

On-column Splitless

30 270

1 µl 1 µl

N.A. 1 min.

9 Agilent 6890 MSD Splitless 250 5 µl 1.5 min. 11 Varian 3800 FID Splitless 250 1 µl 0.7 min. 12 HPLC - - - - - 14 HPLC - - - - - 15 Aliph.: Varian

Arom.: HPLC FID -

On-column -

350 -

5 µl -

0.01 min. -

16 Agilent 6890 FID Splitless 275 1 µl Not indic. 17 Kristall 2000 PID Splitless 240 1 µl 1 min. 18 Agilent 6890 MSD Splitless 275 1 µl Not indic. 19 Varian 3800 FID Splitless 300 1 µl Not indic. 20 HP 5890 II FID Splitless 300 1 µl 0.75 min. 23 Not indicated MSD Splitless 300 1 µl Not indic. 24 HP 5890 II FID Splitless 320 2 µl 0.75 min. 25 HP 5890 II Alk.: FID

PAH: MSD Splitless Splitless

300 300

2 µl 2 µl

1 min. 1 min.

26 HPLC - - - - - 27 HP 5890 II FID Splitless 250 1 µl 1 min. 28 Varian 3600 MS/MS Splitless 150-300 2 µl 0.5 min. 29 Agilent 6890 MSD Splitless 280 2 µl 1.25 min. 30 Saturn 2100 MSD Splitless 310 1 µl 2 min. 33 HPLC - - - - - 34 Varian 3800 FID Splitless 275 5 µl Not indic. 36 Agilent 6890 MSD Splitless 230 1 µl 2 min. 38 HPLC - - - - - 39 Thermofinnigan MSD Splitless 250 1 µl 0.8 min.

- 83 -

Table 10: continued Lab.

Code No Instrument type Detector

type Injection technique

Injector temp. (oC)

Injection volume

Splitter time

41 Shimadzu QP MSD Splitless 240 2 µl 0.1 min. 42 HP 5890 II MSD Splitless 290 2 µl 1 min. 43 Agilent 6890 MSD Splitless 250 1 µl Not indic. 45 Shimadzu 17A FID Splitless 300 1 µl 0.8 min. 46 HPLC - - - - - 47 HPLC - - - - - 49 GC/MS MSD Splitless 250 1 µl 1 min. 52 Agilent 6890 FID On-column 40 1 µl N.A. 53 Agilent 6890 MSD Splitless Not indic. 2 µl 1 min. 54 HP5890 II MSD Splitless 300 1.9 µl Not indic. 55 Agilent 6890 FID Splitless 280 2 µl 1 min. 62 Agilent 6890 MSD Splitless 270 1 µl 0.5 min. 63 Aliph.: Focus

Arom.: Finnigan FID MSD

Splitless Splitless

250 250

2 µl 1.5 µl

Not indic. Not indic.

65 Perkin-Elmer MSD Splitless 300 1 µl Not indic. 66 HPLC - - - - - 68 Fisons 8000 FID Splitless 280 2 µl 0.5 min. 69 Agilent 6890 MSD Splitless 300 2 µl 1 min. 72 Not indicated MSD Splitless 280 1 µl 1.5 min. 73 HPLC - - - - - 77 Agilent 6890 FID Splitless 250 1 µl Not indic. 78 Not indicated MSD Splitless 300 1 µl Not indic. 79 Agilent 6890 MSD Splitless 250 1 µl 1 min. 81 Agilent 6890 MSD Splitless 300 2 µl 1 min. 83 HPLC - - - - - 84 Agilent 6890 MSD Splitless 290 1 µl 5 min. 86 HPLC - - - - -

- 84 -

Table 10: continued

Carrier Gas Column Lab. Code No Type Flow rate Length I.Diameter Phase Thickness

5 Helium Helium

1.9 ml/min. 1.6 ml.min.

30 m 30 m

0.32 mm 0.25 mm

HP - 5 MS DB-XLB MS

0.25 µm 0.25 µm

9 Helium 1 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 11 Helium 1.5 ml/min. 30 m 0.25 mm CP Sil - 8 CB 0.25 µm 15 Hydrogen 1.6 ml/min. 15 m 0.32 mm Mineral oil 0.1 µm 16 Nitrogen 1 ml/min. 30 m 0.32 mm HP - 5 0.25 µm 17 Nitrogen 2 ml/min. 50 m 0.32 mm DB - 1701 0.5 µm 18 Helium 1 ml/min. 30 m 0.25 mm VF - 5 MS 0.25 µm 19 Nitrogen 3 ml/min. 15 m 0. 25 mm CP Sil - 5 CB 0.25 µm 20 Helium 1 ml/min. 30 m 0.25 mm HP - 5 0.25 µm 23 Helium 2 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 24 Helium 1 ml/min. 30 m 0.25 mm HP - 5 0.25 µm 25 Hydrogen

Helium 2 ml/min. 2 ml/min.

20 m 30 m

0.25 mm 0.25 mm

DB - 5 MS DB - 5 MS

0.25 µm 0.25 µm

27 Nitrogen 1 ml/min. 25 m 0.32 mm HP Ultra 2 0.17 µm 28 Helium 2 ml/min. 30 m 0.25 mm VB - 5 0.25 µm 29 Helium 2 ml/min. 30 m 0.32 mm HP - 5 MS 0.17 µm 30 Helium 2.2 ml/min. 60 m 0.25 mm VF - 5 MS 0.25 µm 34 Nitrogen Pres.: 8 psi 25 m 0.32 mm CP Sil - 8 CB 0.12 µm 36 Helium 2 ml/min. 60 m 0.25 mm HP - 1 MS 0.25 µm 39 Helium 1.2 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 41 Helium 1.4 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 42 Helium 1.2 ml/min. 30 m 0.25 mm DB - 5 0.25 µm 43 Helium 11 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm 45 Helium 2.4 ml/min. 30 m 0.25 mm DB - 1 0.25 µm 49 Helium 1.2 ml/min. 30 m 0.25 mm HP - 5 0.25 µm 52 Nitrogen 1.2 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm

- 85 -

Table 10: continued

Carrier Gas Column Lab. Code No Type Flow rate Length I.Diameter Phase Thickness 53 Helium 0.4 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 54 Helium 1 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 55 Nitrogen 1.5 ml/min. 60 m 0.25 mm HP - 5 MS 0.25 µm 62 Helium 1 ml/min. 20 m 0.18 mm ZB - 5 MS 0.18 µm 63 Helium

Helium 2 ml/min. 1.2 ml/min.

30 m 30 m

0.32 mm 0.25 mm

HP - 5 DB - 5 MS

0.25 µm 0.25 µm

65 Helium 1 ml/min. 30 m 0.25 mm Elite 5 MS 0.5 µm 68 Hydrogen 2 ml/min. 25 m 0.34 mm SE - 54 0.2 µm 69 Helium 1 ml/min. 30 m 0.25 mm DB - 5 MS 0.25 µm 72 Helium 1.2 ml/min. 30 m 0.25 mm DB - 5 0.25 µm 77 Not indic. Not indic. 30 m 0.25 mm HP - 5 MS 0.25 µm 78 Helium 1 ml/min. 30 m 0.25 mm DB - 5 0.25 µm 79 Helium 1 ml/min. 30 m 0.25 mm TRB - 5 MS 0.25 µm 81 Helium 1.5 ml/min. 25 m 0.25 mm HP - 5 MS 0.25 µm 84 Helium 0.6 ml/min. 30 m 0.25 mm HP - 5 MS 0.25 µm

- 86 -


Temp. Isoth. (min.)

1st rate

To: Isoth. (min.)

2nd rate

To: Isoth. (min.)

3rd rate

To: Isoth. (min.)

5 60 60

- 1

3.5 10

300 100

22 -

- 3.5

- 290

- 20

- -

- -

- -

9 80 2 25 130 - 3 235 - 25 300 15 11 65 1 3 100 - 5 280 1.3 - - - 15 60 3 35 340 6 - - - - - - 16 70 2 2.5 290 15 - - - - - - 17 120 2 6 260 35 - - - - - - 18 40 2 15 145 - 5 250 - 3 300 3 19 60 2 10 300 - - - - - - - 20 Alk.: 70

PAH:90 3 0.5

20 18

180 212

1 3

15 12

260 270

- 7

5 1.5

300 300

18 12

23 40 1 25 140 - 10 290 2 - - - 24 90 0.5 18 212 3 12 270 7 1.5 300 8 25 60

80 2 1

10 10

310 160

5 -

- 6

- 300

- 8

- -

- -

- -

27 60 - 1 65 1 3 200 - 7 300 30 28 40 - 8 320 5 - - - - - - 29 40 - 20 60 - 5 290 5 10 300 10 30 120 2 30 240 4 25 275 19 5 280 15 34 90 2 3 285 3 - - - - - - 36 70 2 15 210 1 6 250 1 15 280 23 39 70 1 15 150 - 6 320 10 - - - 41 50 2 6 180 - 8 280 6 - - - 42 45 1 10 295 15 - - - - - - 43 45 3 6 120 - 10 280 - - - - 45 60 - 11 130 - 5.5 180 - 11 300 15 49 60 1 40 120 15 4 270 30 - - -

- 87 -


Temp. Isoth. (min.)

1st rate

To: Isoth. (min.)

2nd rate

To: Isoth. (min.)

3rd rate

To: Isoth. (min.)

52 40 5 10 315 20 - - - - - - 53 60 - 15 150 - 5 220 - 10 300 - 54 40 1 25 140 - 10 320 2 - - - 55 60 2 12 250 - 3 310 10 - - - 62 50 2 10 300 10 - - - - - - 63 50

50 0.75 5

20 50

80 80

- -

6 6

310 280

20 17

- -

- -

- -

65 90 - 10 260 10 - - - - - - 68 80 2 4 280 10 - - - - - - 69 60 2 6 300 13 - - - - - - 72 60 2 25 80 - 5 300 10 - - - 77 40 1 30 170 - 4 240 - 12 300 10 78 80 2 5 300 12 - - - - - - 79 40 5 12 290 6 20 320 10 - - - 81 80 1 20 200 2 10 280 10 - - - 84 80 1 15 220 1 5 290 15 - - -

- 88 -

Table 10: continued Lab. Code No

Detector temp. (oC)

Make-up gas

Make-up flow

(ml/min.)

Air flow (ml/min.)

Hydrogen flow

(ml/min.)

Recorder / Integrator

5 310 Source: 230

N.A. N.A.

N.A. N.A.

320 N.A.

27 N.A.

Agilent Chemstation Agilent Chemstation

9 Source: 230 N.A. N.A. N.A. N.A. Agilent Chemstation 11 300 Nitrogen 25 300 30 Star Workstation 15 350 Nitrogen 30 300 30 Star Workstation 16 300 Nitrogen 45 450 40 Agilent Chemstation 17 245 Nitrogen 20 200 20 Computer 18 250 N.A. N.A. N.A. N.A. Masslynx Data Sys. 19 340 Nitrogen 27 300 30 Star Workstation 20 Alk.: 300

PAH:320 Nitrogen 10 300 30 HP 3396 Series II

23 Not indic. N.A. N.A. N.A. N.A. Not indicated 24 320 Nitrogen 40 450 40 HP 3396 Series II 25 310

Not indic. Not ind. N.A.

Not ind. N.A.

Not ind. N.A.

Not ind. N.A.

Agilent Chemstation Agilent Chemstation

27 300 Nitrogen Not ind. 418 58 Not indicated 28 200 N.A. N.A. N.A. N.A. Saturn Workstation 29 325 Nitrogen 30 350 30 Agilent Chemstation 30 210 He 2.2 N.A. N.A. Saturn Workstation 34 325 Nitrogen 25 300 30 Not indicated 36 Not indic. N.A. N.A. N.A. N.A. Agilent Chemstation 39 310 He 1.2 N.A. N.A. Not indicated 41 240 N.A. N.A. N.A. N.A. Not indicated 42 Not indic. N.A. N.A. N.A. N.A. Agilent Chemstation 43 Not indic. N.A. N.A. N.A. N.A. Agilent Chemstation 45 320 He 74 500 50 Electronic Digital 49 Transf: 280 N.A. N.A. N.A. N.A. Agilent Chemstation

- 89 -

Table 10: continued Lab. Code No

Detector temp. (oC)

Make-up gas

Make-up flow

(ml/min.)

Air flow (ml/min.)

Hydrogen flow

(ml/min.)

Recorder / Integrator

52 330 Nitrogen 1.2 350 30 Agilent Chemstation 53 Not indic. N.A. N.A. N.A. N.A. Agilent Chemstation 54 320 N.A. N.A. N.A. N.A. Agilent Chemstation 55 350 Nitrogen 45 300 40 Agilent Chemstation 62 Not indic. N.A. N.A. N.A. N.A. Agilent Chemstation 63 290

Source:200 Nitrogen N.A.

Not ind. N.A.

Not ind. N.A.

Not ind. N.A.

ChromQuest 4.1 Xcalibur

65 280 N.A. N.A. N.A. N.A. PC - soft 68 280 Not ind. Not ind. Not ind. Not ind. Chromcard 69 280 N.A. N.A. N.A. N.A. Agilent Chemstation 72 Not indic. N.A. N.A. N.A. N.A. Not indicated 77 Not indic. Not ind. Not ind. Not ind. Not ind. Agilent Chemstation 78 Not indic. N.A. N.A. N.A. N.A. RT INT 79 Not indic. N.A. N.A. N.A. N.A. Agilent Chemstation 81 Source:230 N.A. N.A. N.A. N.A. Agilent Chemstation 84 Not indic. N.A. N.A. N.A. N.A. Agilent Chemstation

- 90 -

- 91 -

Annex II

Data Evaluation Graphs

- 92 -

Fig. 1: Data Evaluation - HCB - IAEA-159

Laboratory code numbers77 61 71 44 52 16 35 68 5 46 53 7 51 41 29 10 59 8 39 48

Conc

entra

tions

(ng/g

)

-0.4-0.20.00.20.40.60.81.0

Fig. 2: Data Evaluation - Lindane - IAEA-159

Laboratory code numbers25 54 71 67 61 51 5 8 16 35 41 3 77 70 46 1 44 42 57 10 48 59 7 29

Conc

entra

tions

(ng/g

)

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

- 93 -

Fig. 3: Data Evaluation - pp' DDE - IAEA-159

Laboratory code numbers54 42 3 57 25 29 26 67 19 52 71 41 61 14 46 1 5 77 35 85 70 8 31 44 55 10 53 83 6 74 68 7 9 39 51

Conc

entra

tions

(ng/g

)

0.0

0.5

1.0

1.5

2.0

2.5

Fig. 4: Data Evaluation - pp' DDD - IAEA-159

Laboratory code numbers54 52 42 10 71 57 3 7 68 25 6 29 83 44 26 77 14 61 8 46 1 5 70 35 67 51 64 85 16 9

Conc

entra

tions

(ng/g

)

0.0

0.5

1.0

1.5

2.0

2.5

- 94 -

Fig. 5: Data Evaluation - pp' DDT - IAEA-159


Conc

entra

tions

(ng/g

)

0.0

0.5

1.0

1.5

2.0

2.5

Fig. 6: Data Evaluation - Aroclor 1254 - IAEA-159

Laboratory code numbers85 41 5 35 68 77 8 26 16 28 22 48

Conc

entra

tions

(ng/g

)

0

5

10

15

20

25

30

35

- 95 -

Fig. 7: Data Evaluation - PCB 52 - IAEA-159

Laboratory code numbers68 61 62 25 32 53 35 77 24 5 52 46 70 71 10 44 29 3 1 26 30 41 39 67 83

Conc

entra

tions

(ng/g

)

0.2

0.4

0.6

0.8

1.0

1.2



Conc

entra

tions

(ng/g

)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

- 96 -


Laboratory code numbers24 25 58 20 61 3 62 71 53 68 5 46 70 77 29 73 30 44 10 35 42 52 48 67 1 41 79

Conc

entra

tions

(ng/g

)

0.0

0.2

0.4

0.6

0.8

1.0

1.2



Conc

entra

tions

(ng/g

)

0.00.20.40.60.81.01.21.4

- 97 -


Laboratory code numbers6 30 62 71 42 46 32 35 26 77 25 68 52 48 3 5 70 41 61 67 79

Conc

entra

tions

(ng/g

)

0.3

0.4

0.5

0.6

0.7

0.8



Conc

entra

tions

(ng/g

)

-0.2

0.0

0.2

0.4

0.6

0.8

- 98 -

Fig. 13: Data Evaluation - Phenanthrene - IAEA-159

Laboratory code numbers65 24 18 38 37 68 12 79 78 47 55 84 36 23 19 25 81 14 7 76 27 72 46 2 62 43 83 41 49 9 69 30 29 54 63 70 53 66 80 5 28 42 86 20 39

Conc

entra

tions

(ng/g

)

0

20

40

60

80

100

120

140

Fig. 14: Data Evaluation - Chrysene - IAEA-159

Laboratory code numbers18 26 79 73 65 14 38 78 23 29 68 86 84 47 2 72 83 55 66 15 76 12 52 28 9 63 53 30 5 19 81 25 49 43 62 69 27 46 70 34 41 42 80 77

Conc

entra

tions

(ng/g

)

0

20

40

60

80

100

120

140

- 99 -

Fig. 15: Data Evaluation - Pyrene - IAEA-159

Laboratory code numbers18 55 86 65 7 23 38 84 26 68 14 12 36 78 72 15 16 27 30 62 63 76 25 43 19 83 28 9 47 69 53 49 2 46 81 29 5 41 70 42 80 66 52 73 17 20 24 54 34 39

Conc

entra

tions

(ng/g

)

50

100

150

200

Fig. 16: Data Evaluation - Benz[a]anthracene - IAEA-159

Laboratory code numbers18 65 26 12 7 47 55 23 73 79 68 14 54 72 38 19 78 2 84 76 63 25 52 28 30 46 83 15 53 62 49 29 80 43 20 69 42 9 66 41 70 27 37 36 5

Conc

entra

tions

(ng/g

)

0

20

40

60

80

100

- 100 -

Fig. 17: Data Evaluation - Benzo[a]pyrene - IAEA-159

Laboratory code numbers7 18 86 12 54 26 38 68 49 55 23 28 84 69 19 78 15 47 73 72 79 76 83 53 62 37 9 2 39 52 46 63 66 30 27 81 43 41 80 42 14 70 77 5

Conc

entra

tions

(ng/g

)

0

20

40

60

80

100

120

140

Fig. 18: Data Evaluation - Benzo[g,h,i]perylene - IAEA-159

Laboratory code numbers78 23 7 18 27 86 38 25 47 54 84 15 28 9 30 46 29 68 80 53 52 76 73 49 63 43 79 83 70 62 72 14 55 37 66 69 42 5 19 81 17 2

Conc

entra

tions

(ng/g

)

0

50

100

150

200

250

- 101 -

- 102 -

- 103 -

Annex III

Z-scores for chlorinated pesticides, PCBs and petroleum hydrocarbons

IAEA - 159

- 104 -

Table A3: Z-scores: Assessment of laboratory performance for the determination of organochlorine pesticides.

Lab Code No

1 3 4 5 6 7 8 9 10 14 15 16 17 19 20

HEOM - - - -0.61 - - 0.72 - -1.51 - - 0.67 -0.50 - - HCB - - - -0.57 - 0.00 1.32 - 0.53 - - -0.73 - - - α HCH 0.49 -0.65 - -1.06 - 3.10 - - - - - - - 361 1.79 β HCH 0.81 - - -1.00 - - - - - - - - - 89 1.04 Lindane 0.16 -0.49 5850 -0.60 - 1.76 -0.58 - 0.93 - - -0.55 - 71 - δ HCH -0.02 - - - - - - - - - - - - 66 1.42 pp’ DDE -0.29 -1.11 - -0.23 0.74 1.37 0.05 1.39 0.27 -0.37 - 10 - -0.76 - pp’ DDD 0.32 -0.97 15 0.48 -0.32 -0.90 0.11 2.17 -1.15 -0.03 - 2.05 - 124 - pp’ DDT 0.04 -0.72 7.19 -0.62 -0.09 3.44 -0.09 2.00 -0.63 -0.30 - 1.61 - 5.16 1.68 op DDE - - - -0.75 - - - - 0.21 - - - - - - op DDD - - - 1.11 - - - - -0.09 - - - - 1460 - op DDT - - 1.50 -0.52 - - - - -0.45 - - - - - - Heptachlor -1.22 - - - - 1.26 - - 0.33 - - - - - -

| Z | < 2: performance is acceptable 2 < | Z | < 3: measurements are questionable | Z | > 3: measurements are inacceptable Shaded areas represent unacceptable results. “-“ : no results

- 105 -

Table A3: Z-scores: continued

Lab Code No

1 3 4 5 6 7 8 9 10 14 15 16 17 19 20

Heptachlor Epoxide

- - - - - - - - -0.81 - - -0.73 - - 1.53

Aldrin -0.79 - - -1.06 - - - 11 - - - -0.73 - 0.86 21 Dieldrin 34 - - -0.37 - - -0.21 - -0.21 - - -0.61 - 19 - Endrin 0.93 - 15 - - - -0.81 5.31 -0.04 - - - - -0.70 - α Endosulfan - - - - - 0.92 - - - - - 1.73 - - - β Endosulfan - - - - - -0.40 - - - - - -0.51 - 14 - Endosulfan Sulfate

- - - - - - - 0.90 - - - -0.85 - 70 -

α Chlordane - - - -1.22 - - - - -0.41 - - -0.49 - - - γ Chlordane - - - -0.75 - - - - -0.52 - - -0.57 - - - Aroclor 54 - - - -0.78 - - -0.30 - - - - 0.70 - - - Aroclor 60 - - - -0.78 - - 2.01 - - - - 0.48 - - - | Z | < 2: performance is acceptable 2 < | Z | < 3: measurements are questionable | Z | > 3: measurements are inacceptable Shaded areas represent unacceptable results. “-“ : no results

- 104 - - 105 - - 106 - - 107 - - 108 - - 109 - - 110 -

- 111 - - 112 - - 113 - - 114 - - 106 - - 106 -


Lab Code No

21 22 24 25 26 28 29 31 32 35 38 39 40 41 42

HEOM - - - - - - - -0.42 - 0.13 - - - - 31 HCB - 6.60 - - - - 0.46 - - -0.73 - 1.98 5.05 0.13 - α HCH 200 - - - - - 0.49 - - - - - - - -0.16 β HCH - - - - - - - - - - - - - - - Lindane 11 63 - -1.09 - - 2.47 - - -0.55 - 5.44 - -0.53 -0.82 δ HCH - - - - - - -0.66 - - - - - - - -0.73 pp’ DDE - - - -0.94 -0.82 - -0.90 0.10 - -0.14 16 2.11 30 -0.47 -1.37 pp’ DDD - - - -0.37 -0.15 - -0.24 - - 0.58 13 6.86 - 3.8 -1.21 pp’ DDT - - 4.60 - -0.20 - - 1.71 - -0.72 73 1.80 - -0.52 - op DDE - - - - - - 1.18 - - - - - - - - op DDD - - - - - - -1.02 - - - - - - - - op DDT - - - - - - - - - - - - - - - Heptachlor - - - - - - 0.47 - - -0.66 - - - - 1.69


- 107 -


Lab Code No

21 22 24 25 26 28 29 31 32 35 38 39 40 41 42

Heptachlor Epoxide

- - - - - - - - - - - - - - -

Aldrin - - 15 - -0.53 - - - - 0.46 - 3.10 - - - Dieldrin - - - -0.96 -0.64 - -0.83 - - -0.72 5.39 - - - - Endrin - - - - - - - 9.13 - - - - - - 0.71 α Endosulfan - -0.22 - - - - - - - - - - - - -0.56 β Endosulfan - - - - - - - - - - - 1.0 - - - Endosulfan Sulfate

- - 8.05 - - - - - - - - - - - -0.90

α Chlordane - 13 - - - - -0.25 - - - - - - - 0.98 γ Chlordane - 1.40 - - - - - - - - - - - - -0.70 Aroclor 54 - 1.56 - - 0.17 0.90 - - - -0.73 - - - -0.88 - Aroclor 60 - - - - -0.82 3.24 - - - -0.01 - - - -0.75 -


- 108 - - 108 -


Lab Code No

44 46 48 50 51 52 53 54 55 56 57 59 60 61 64

HEOM - - - - - - - - 1.58 3.80 - - - - - HCB -0.84 -0.46 2.11 - 0.00 -0.79 -0.26 - - - 5.35 1.05 - -0.89 - α HCH - - 0.82 - - - - - - - - - - - - β HCH - - 0.00 - 6.37 - - - - - - - - - - Lindane 0.30 -0.05 0.93 17 -0.88 4.34 - -1.05 - 32 0.88 1.50 - -0.95 610 δ HCH - - - - - - - - - - - - - - - pp’ DDE 0.21 -0.37 3.88 2.22 2.17 -0.76 0.53 -1.73 0.21 51 -1.02 2.73 - -0.46 - pp’ DDD -0.16 0.14 4.19 - 0.87 -1.31 - -1.38 3.70 196 -1.0 6.74 - 0.06 1.24 pp’ DDT -0.70 -0.88 3.26 - -0.72 - - -0.94 0.42 36 -0.73 1.58 - -0.79 - op DDE - - - - - - - - - - - - - - - op DDD - -0.84 - - - - - - - - - - - - - op DDT - - - - - - - - - - - - - - - Heptachlor - - -0.47 8.32 -1.03 0.09 - - - - - - - - -


- 109 -


Lab Code No

44 46 48 50 51 52 53 54 55 56 57 59 60 61 64

Heptachlor Epoxide

- - - - - - - - - 0.48 - - - - -

Aldrin - - 0.20 101 - - - -1.06 - 472 2.18 0.07 - - - Dieldrin - - 0.59 7.05 - 1.39 - - - - -0.88 1.11 - -0.91 1.22 Endrin - - -0.81 - - -0.80 - - - - - 2.14 - - - α Endosulfan - - - - - -0.69 - -1.07 -0.11 - - - - - - β Endosulfan - - - - - -0.71 - -0.76 1.81 - - - - - - Endosulfan Sulfate

- - - - - -0.29 - - -0.39 - - - - - -

α Chlordane - - - - - 1.48 - - - - - - - - - γ Chlordane - - - - - - - - - - - - - - - Aroclor 54 - - 1.70 - - - - - - - - - - - - Aroclor 60 - - 0.72 - - - - - - - - - - - -


- 110 -


Lab Code No

65 67 68 70 71 74 75 77 79 82 83 85 86

HEOM 149 - - - - - - - - - - 3.60 - HCB 53 - -0.73 - -0.88 20 - -0.92 - - 5.48 - 468 α HCH - - - -0.98 -0.22 - - - - - - - - β HCH - - - -0.98 - - - - - - - - - Lindane 103 -0.98 - -0.33 -1.02 33 - -0.49 - - 10 - 153 δ HCH - - - - - - - - - - - - - pp’ DDE 21 -0.82 1.03 -0.06 -0.68 0.90 - -0.18 6.07 - 0.61 -0.14 - pp’ DDD 64 0.84 -0.63 0.54 -1.13 - - -0.10 5.43 - -0.20 1.99 - pp’ DDT 83 -0.55 -0.91 -0.69 -0.78 - - -0.66 55 - 1.28 0.04 - op DDE - - - -0.75 - - - - - - - - - op DDD - - - 0.93 - - - - - - - - - op DDT - - - -0.52 - - - - - - - - - Heptachlor 141 -1.25 - - - - - 0.75 7.59 - - - - | Z | < 2: performance is acceptable 2 < | Z | < 3: measurements are questionable | Z | > 3: measurements are inacceptable Shaded areas represent unacceptable results. “-“ : no results

- 111 -


Lab Code No

65 67 68 70 71 74 75 77 79 82 83 85 86

Heptachlor Epoxide

- - - - - - - - - - -0.46 - -

Aldrin 321 - - - - - 217 0.66 36 - - - - Dieldrin - - - - - -0.43 - -0.64 32 - 2.45 0.32 - Endrin 28 - - - - - - -0.70 4.93 - 0.04 - - α Endosulfan - - - - - - - - 13 14 - - - β Endosulfan - - - - - - - - 11 - -0.41 - - Endosulfan Sulfate

- - - - - - - - 1.53 - - - -

α Chlordane - - - - - - - - - - - - - γ Chlordane - - - - - - - - - - 1.16 - - Aroclor 54 - - -0.70 - - - - -0.62 - - - -0.99 - Aroclor 60 - - -0.46 - - - - 0.73 - - - -1.12 - | Z | < 2: performance is acceptable 2 < | Z | < 3: measurements are questionable | Z | > 3: measurements are inacceptable Shaded areas represent unacceptable results. “-“ : no results

- 112 -

Table A4: Z-scores: Assessment of laboratory performance for the determination of PCB congeners.

Lab Code No

1 3 5 6 7 9 10 14 15 19 20

CB 8 - - -0.88 - - - -0.19 - - - - CB 18 0.22 - -0.84 - -0.06 - 1.69 - - - - CB 28 0.69 -0.52 -0.45 - - 8.41 1.07 - - - 20 CB 31 3.77 - 0.82 - - `- -0.82 - - - - CB 44 - - -0.27 - 0.55 - -0.68 - - - - CB 49 - - -0.20 - - - -0.81 - - - - CB 52 0.83 0.57 -0.42 - - 6.18 0.15 - - - 4.25 CB 66 - - 0.12 - - - -0.35 - - - - CB 70 - - - - - - -0.65 - - - - CB 74 - - - - - - -0.77 - - - - CB 87 1.45 - -0.70 - - - -0.39 - - - -


- 113 -

Table A4: continued

Lab Code No

24 25 26 29 30 32 35 36 37 39 41

CB 8 - - - 1.02 - - - - - - - CB 18 - - - -0.67 - - - - - 0.89 - CB 28 27 1.0 0.83 0.07 - -0.31 -0.59 - - 0.52 -0.02 CB 31 - - - - - - - - - 23 - CB 44 - - - 0.89 3.41 - - - - 14 - CB 49 - - - 1.32 - - - - - - - CB 52 -0.49 -0.91 -0.91 0.27 0.95 -0.87 -0.72 - - 1.56 1.30 CB 66 - - - 0.69 - - - - - - - CB 70 - - - - - - - - - - - CB 74 - - - - - - - - - - - CB 87 - - - -0.31 - - - - - - -


- 114 -

Table A4: continued

Lab Code No

42 44 46 48 50 51 52 53 58 60 61

CB 8 - - - - - - - - - - - CB 18 - - - -0.69 - - - - - - - CB 28 - - -0.93 2.80 88 -0.59 1.04 - - - -1.11 CB 31 - - - 18 - - - - - - 0.00 CB 44 - - - 0.27 - - - -0.34 - - - CB 49 - - - 20 - - - - - - - CB 52 - 0.23 -0.27 - 96 14 -0.38 -0.83 - - -1.24 CB 66 - - - 0.92 - - - -1.15 - - - CB 70 1.13 - - - - - - -0.48 - - - CB 74 - - - - - 0.26 - 0.77 - - - CB 87 - - - - - - - - - - -


- 115 -

Table A4: continued

Lab Code No

62 67 68 70 71 73 77 78 79 83 86

CB 8 - - - - - - - - - - - CB 18 - 1.34 - - - -0.97 -0.93 - - - - CB 28 -0.97 -0.76 - -0.28 -1.08 - -1.00 - 0.35 3.56 - CB 31 - 0.66 - 0.98 -0.67 - -0.49 - - - - CB 44 - 1.34 - - - - -1.77 - - - - CB 49 - - - -0.20 - - - - - - - CB 52 -1.18 1.59 -1.52 -0.27 -0.12 3.41 -0.72 8.19 12 1.63 - CB 66 - - - - - - - - - - - CB 70 - - - - - - - - - - - CB 74 - - - - - - - - - - - CB 87 - - - - - - - - - - -


- 116 -

Table A4: continued

Lab Code No

1 3 5 6 7 9 10 14 15 19 20

CB 95 -0.42 - -0.71 - - - - - - - - CB 99 1.41 - - - - - -0.49 - - - - CB 101 3.59 0.52 0.35 0.12 5.62 12 0.98 - - 76 -0.81 CB 105 0.57 - -0.67 - - - 0.25 - - - - CB 110 5.07 - -0.52 - - - 0.35 - - - - CB 118 1.23 -0.68 -0.09 - - 6.73 0.59 - - - -1.14 CB 128 0.59 -0.88 -0.59 - - - 1.98 - - - - CB 138 3.98 0.03 0.41 1.38 -0.85 4.70 1.32 - - 12 -1.76 CB 149 0.78 - -0.32 - - - - - - - - CB 153 8.95 0.53 0.61 -1.67 -3.16 11 2.63 - - 12 -3.25 CB 156 1.62 - -0.62 - - - - - - - -


- 117 - - 117 -

Table A4: continued

Lab Code No

24 25 26 29 30 32 35 36 37 39 41

CB 95 - - - - - - - - - - - CB 99 - - - - - - - - - - -0.45 CB 101 0.06 -0.23 1.97 0.64 1.33 -0.64 -0.35 - - 3.65 1.00 CB 105 - - 1.85 1.02 - - - - - - -0.33 CB 110 - - - -1.61 - - - - - - 0.22 CB 118 -1.91 -1.68 4.46 0.05 0.23 - 0.59 - - 12 1.34 CB 128 - - - -0.40 - - - - - - - CB 138 -1.85 2.10 1.69 -0.75 -0.91 -0.25 0.09 - - 28 -0.40 CB 149 - - - -0.19 -0.39 - - - - 17 - CB 153 -4.21 0.26 -0.18 - -1.32 -0.44 -0.35 - - 5.17 0.82 CB 156 - - - - - - - - - - -0.52


- 118 -

Table A4: continued

Lab Code No

42 44 46 48 50 51 52 53 58 60 61

CB 95 - - - - - - - - - - - CB 99 - - - - - - - -0.53 - - - CB 101 6.25 1.16 0.46 2.72 - - 0.06 -0.17 -1.85 - -1.10 CB 105 1.37 - -0.35 - - - - - - - -1.13 CB 110 - - - 0.81 - - - -0.52 - - - CB 118 0.86 0.27 -0.09 1.00 - - 0.96 -0.50 -1.25 - -0.94 CB 128 0.00 - -0.62 - - - - - - - - CB 138 1.03 0.74 0.00 1.19 29 -1.25 0.72 - -0.79 42 -0.35 CB 149 - - - 1.62 - - - -0.91 - - -1.19 CB 153 -0.61 6.05 -0.53 0.44 - -2.81 0.35 - -3.04 - 1.11 CB 156 -0.51 - - - - - - - - - -


- 119 -

Table A4: continued

Lab Code No

62 67 68 70 71 73 77 78 79 83 86

CB 95 - - - - - - - - - 1.14 - CB 99 - - - - - - - - - - - CB 101 -0.98 -1.45 -0.29 0.23 -0.66 6.14 -0.06 7.87 3.36 - - CB 105 -0.89 - - -0.70 -0.82 - - - - - - CB 110 - - 1.15 - - - - - - 6.10 - CB 118 -0.64 1.10 -0.36 0.00 -0.57 0.14 0.00 - 1.91 - - CB 128 - - - - - - - - - - - CB 138 -0.31 -0.47 0.09 -0.22 -0.97 0.88 -0.13 6.84 -0.47 5.02 - CB 149 - - - -0.39 - - 0.78 - - 5.70 - CB 153 -0.88 1.17 0.26 0.70 -0.79 9.82 -0.18 14 1.23 7.37 - CB 156 - - - -0.56 -0.58 - - - - 1.57 -


- 120 -

Table A4: continued

Lab Code No

1 3 5 6 7 9 10 14 15 19 20

CB 170 0.00 0.45 0.23 - - - 21 - - - - CB 177 0.39 - -0.78 - - - - - - - - CB 180 1.14 0.19 0.10 0.67 9.80 - 9.99 - - - 0.19 CB 183 - - -0.55 - - - -0.47 - - - - CB 187 0.00 - -0.72 - - - 0.57 - - - - CB 194 - - -0.91 - 5.78 - 1.44 - - - - CB 195 -0.32 - -0.92 - - - 0.95 - - - - CB 201 -0.08 - -0.96 - - - - - - - - CB 206 - - -0.61 - - - 1.14 - - - - CB 209 - - -0.55 - - - 1.52 - - - -


- 121 -

Table A4: continued

Lab Code No

24 25 26 29 30 32 35 36 37 39 41

CB 170 - - - 1.58 - - - - - 9.73 -0.68 CB 177 - - - - - - - - - - - CB 180 -1.71 1.24 0.19 -0.57 -1.14 - - - - 22 -0.43 CB 183 - - - - - - - - - - - CB 187 - - - -3.01 - - - - - - - CB 194 - - - - 0.00 - - - - - - CB 195 - - - - - - - - - - - CB 201 - - - - - - - - - - - CB 206 - - - - - - - - - - - CB 209 - - - - - - - - - - -


- 122 -

Table A4: continued

Lab Code No

42 44 46 48 50 51 52 53 58 60 61

CB 170 0.45 1.36 - -0.91 - - - - - - - CB 177 1.07 - - -0.87 - - - - - - - CB 180 1.62 0.90 0.38 -0.86 64 - 2.28 - -1.25 102 -0.69 CB 183 1.49 - - -0.50 - - - - - - - CB 187 3.72 - - - - - - - - - - CB 194 0.48 - - -0.48 - - - - - - - CB 195 - - - - - - - - - - CB 201 1.07 - - - - - - - - - CB 206 -0.53 - - - - - - - - - CB 209 -0.43 - - - - - - - - -


- 123 -

Table A4: continued

Lab Code No

62 67 68 70 71 73 77 78 79 83 86

CB 170 -1.13 - - -0.23 - - -1.58 - - - 42 CB 177 - - - - - - - - - - - CB 180 -0.38 -0.31 0.57 0.00 -1.35 -0.95 0.10 8.56 3.80 - 26 CB 183 - - - - - - - - - - - CB 187 - - - - - - - - - - - CB 194 - 1.54 - -0.48 - - -1.44 - - - - CB 195 - - - - - - - - - - - CB 201 - - - - - - - - - - - CB 206 - - - - - - - - - - - CB 209 - - - -0.52 - - - - - - -


- 124 -

Table A5: Z-scores: Assessment of laboratory performance for the determination of petroleum hydrocarbons.

Lab Code No

2 5 7 9 11 12 14 15 16 17 18 19 20 23

EOM - -0.90 - - 5.87 0.92 - - 1.27 -0.71 -0.53 - - - PH Chrysene - 1.14 - - -0.71 - - - - 145 - - - - PH ROPME - 0.32 - - - - - - - 9.45 -1.00 - - - Total aliphatics

- 0.68 - - 2.31 - - - -0.88 -0.65 - -0.40 -0.98 -

Resolved aliphatics

- 0.64 - - 5.42 - - - - -0.53 - -0.77 -1.12 -


- 0.41 - - 1.76 - - - - -0.96 - - - -

n-C17 - 0.57 - -1.35 0.67 - - - 0.96 -0.40 8.19 -1.29 - - Pristane - 0.29 - -1.92 -0.63 - - - 1.27 0.96 - -1.51 - - n-C18 - 0.53 - -1.80 1.83 - - - 40 -0.02 7.31 -0.84 1.39 - Phytane - -0.37 - -1.20 0.44 - - - 1.65 -0.44 - -0.72 - -


- 125 - - 125 -

Table A5: continued

Lab Code No

24 25 26 27 28 29 30 33 34 36 37 38 39 41

EOM - - - - - - - - - - - - - - PH Chrysene - - - 3.94 - - - - -0.67 - - - - - PH ROPME - - - 1.16 - - - - - - - - - - Total aliphatics

- - - - - -0.88 - - - - - - - -0.35

Resolved aliphatics

-1.02 - - - - 0.03 - - - - - - - 3.67


- - - - - - - - - - - - - -1.04

n-C17 -0.09 - - -0.02 - 0.61 - - 6.82 - - - -1.74 4.64 Pristane -0.73 - - 0.06 - 0.36 - - - - - - - 3.12 n-C18 0.43 - - -1.03 - -0.05 - - 9.95 - - - - 6.58 Phytane 0.72 - - -1.07 - 0.17 - - - - - - -1.45 1.95


- 126 -

Table A5: continued

Lab Code No

42 43 45 46 47 49 52 53 54 55 62 63 65 66

EOM 24 - - - - - - - - 0.92 - - 117 - PH Chrysene - - -0.66 - - - - - - - - - - - PH ROPME - - - - - - - - - - - - - - Total aliphatics

- - -0.58 - - - - - - - - 0.71 - -

Resolved aliphatics

- - 0.08 - - - - - - - - 2.12 - -


- - -0.96 - - - - - - - - 0.30 - -

n-C17 - - 3.04 - - - - - - - - 0.66 - - Pristane - - 13 - - - - - - - - 0.69 - - n-C18 - - 0.19 - - - - - - - - -0.19 - - Phytane - - 1.09 - - - - - - - - -0.39 - -


- 127 -

Table A5: continued

Lab Code No

68 69 70 72 73 76 77 78 79 80 81 83 84 86

EOM - - - - - - - - - -0.92 - - - - PH Chrysene - - - - - - - - - 1.11 - - - - PH ROPME - - - - - - - - - -0.44 - - - - Total aliphatics

- - - 1.05 - - - - - -0.01 - - - -

Resolved aliphatics

- - - 0.82 - - - - - -0.29 - - - -


- - - 0.76 - - - - - -0.27 - - - -

n-C17 -0.90 - - 1.84 - - 0.26 - -0.49 0.57 - - - - Pristane 8.91 - - 0.65 - - -0.47 - - 0.72 - - - - n-C18 -0.89 - - 7.35 - - 0.43 - -0.73 0.78 - - - - Phytane 4.93 - - 0.06 - - -0.41 - - -0.04 - - - -


- 128 -

Table A5: continued

Lab Code No

2 5 7 9 11 12 14 15 16 17 18 19 20 23

Σ Alkanes - 0.45 - - 4.31 - - - 1.16 - - -0.99 -1.00 - Total aromatics

- 32 - - - - - - -1.57 1.10 - - -0.09 -

Resolved aromatics

- 9.64 - -0.58 - - - - - -1.13 - -0.23 - -


- 1.08 - - - - - - - -0.69 - - - -

Biphenyl - 0.52 - - - - - - - - - - - - Naphthalene -0.48 0.60 2.01 -0.12 - - 0.53 - -0.23 - -1.09 -1.70 -0.98 12 1-Methyl naphthalene

- 0.00 - - - - - - - - -1.60 - - -

2-Methyl naphthalene

- 0.15 - - - - - - - - -1.22 - - -


- 129 - - 129 -

Table A5: continued

Lab Code No

24 25 26 27 28 29 30 33 34 36 37 38 39 41

Σ Alkanes -0.80 - - -1.15 - 0.05 - - - 110 - - -1.56 1.91 Total aromatics

- - - - - -0.14 - - - - -0.79 - - 0.50

Resolved aromatics

4.57 - - - - 1.30 - - - - - - 1.23 -0.53


- - - - - - - - - - - - - -0.75

Biphenyl - - - - - -1.36 - - - - - - - - Naphthalene -0.23 - - -1.05 - -0.22 - - - 2.88 0.45 - -0.02 -0.30 1-Methyl naphthalene

- - - - - -0.35 - - - - - - - -


- - - - - -0.34 - - - - - - - -


- 130 -

Table A5: continued

Lab Code No

42 43 45 46 47 49 52 53 54 55 62 63 65 66

Σ Alkanes - - -0.34 - - - - - - - - 0.82 - - Total aromatics

- - - - - - - - - - - - - -

Resolved aromatics

- - - - - - - - - - - - - -


- - - - - - - - - - - - - -

Biphenyl - - - - - - - 0.70 - - - - - - Naphthalene - -0.53 - -0.30 - 1.52 0.90 0.93 -1.05 0.23 0.24 0.98 5.15 1.60 1-Methyl naphthalene

- - - - - - - 0.58 - - - - - -


- - - - - - - 0.45 - - - - - -


- 131 -

Table A5: continued

Lab Code No

68 69 70 72 73 76 77 78 79 80 81 83 84 86

Σ Alkanes -0.87 - - 1.14 - - 0.19 - 0.32 0.44 - - - - Total aromatics

- - - - - - 0.96 - - 28 - - - -

Resolved aromatics

- - - - - - - - - 0.02 - - - -


- - - - -0.75 - - - - 1.11 - - - -

Biphenyl - 0.16 - - - - - - - - - - - - Naphthalene - 1.04 0.53 0.72 10 - 4.73 -1.04 - -0.47 -1.46 - -1.24 21 1-Methyl naphthalene

- 1.49 0.97 - - - - - - -0.58 - - -0.80 -


- 1.64 0.52 - - - - - - - - - -1.11 -


- 132 -

Table A5: continued

Lab Code No

2 5 7 9 11 12 14 15 16 17 18 19 20 23

2,6 Dimethyl naphthalene - -0.20 - - - - - - - - - - - - Phenanthrene 0.14 1.04 -0.27 0.46 - -1.11 -0.30 - - 4.71 -1.52 -0.49 1.70 -0.76 2-Methyl phenanthrene - 0.96 - 0.92 - - - - 20 - - - - - 1-Methyl phenanthrene - 0.50 - -1.44 - - - - - - - - - - Anthracene 0.92 1.14 - - - -1.57 - - - - -1.59 -1.63 41 -0.42 Chrysene -0.50 0.48 - 0.26 - 0.04 -1.04 -0.30 - - -1.79 0.55 8.22 -0.79 Triphenylene - -0.90 - - - - - - - 1.06 - - - - Fluorene 0.92 -0.38 - - - - - - - - -1.43 - 4.70 -0.67 Fluoranthene -0.04 1.46 -2.61 0.57 - 0.20 -0.57 -0.57 -0.57 1.44 -2.61 1.06 3.73 -1.46 Pyrene 0.42 0.67 -1.30 0.06 - -0.67 -0.75 -0.25 -0.25 1.50 -2.02 -0.05 1.75 -1.07 1-Methyl pyrene - 0.57 - - - - - - - - - - - - Benzo[b]fluoranthene 0.66 0.46 - - - -1.84 - - - 2.51 -1.93 -0.38 1.37 -1.15 Benzo[k]fluoranthene 0.52 1.24 - - - - - - - -0.59 -2.85 -0.63 18 -2.71


- 133 -

Table A5: continued

Lab Code No

24 25 26 27 28 29 30 33 34 36 37 38 39 41

2,6 Dimethyl naphthalene - - - - - -1.24 - - - - - - - - Phenanthrene -1.64 -0.47 - -0.02 1.15 0.53 0.50 65 - -0.77 -1.27 -1.39 2.54 0.30 2-Methyl phenanthrene - - - -1.36 - -0.54 -0.96 - - - - - - 0.14 1-Methyl phenanthrene - - - -0.89 - 0.20 -0.30 - - - - - - 0.40 Anthracene - 0.00 - - - -0.31 4.17 - - - -0.19 -1.40 - - Chrysene - 0.56 -1.70 0.68 0.12 -0.74 0.44 - 1.09 - 2.78 -0.87 5.84 1.19 Triphenylene - - - - - - - - - - - - - - Fluorene - - - 5.10 - -0.43 - 33 - - 4.96 - - - Fluoranthene 3.45 0.06 - 9.49 0.37 0.79 -0.32 - -2.62 - 1.18 -1.33 2.93 1.00 Pyrene 1.75 -0.07 -0.83 -0.20 0.05 0.60 -0.20 6.06 1.97 -0.51 3.65 -0.88 2.09 0.72 1-Methyl pyrene - - - - - - - - - - - - - - Benzo[b]fluoranthene - 1.23 - -0.54 - -0.48 -0.11 29 - - - - - - Benzo[k]fluoranthene - 4.12 - 2.48 - -1.76 -0.13 6.03 - - - - - -


- 134 -

Table A5: continued

Lab Code No

42 43 45 46 47 49 52 53 54 55 62 63 65 66

2,6 Dimethyl naphthalene - - - - - - - 0.72 - - - - - - Phenanthrene 1.52 0.23 - 0.12 -0.84 0.38 2.93 0.75 0.57 -0.80 0.21 0.60 -1.94 0.81 2-Methyl phenanthrene - - - - - - - - - - - - - - 1-Methyl phenanthrene - - - - - - - -0.01 - - - - - - Anthracene 1.19 - - -0.68 - 0.34 - 0.87 - - 0.40 0.04 - - Chrysene 1.50 0.63 - 0.76 -0.59 0.56 0.07 0.37 - -0.33 0.63 0.30 -1.36 -0.33 Triphenylene - - - - - - - - - - - - - - Fluorene 1.60 - - -1.03 - -0.27 - -0.19 - - - - - - Fluoranthene 0.98 0.32 - -0.23 -0.40 0.37 0.77 0.32 0.34 -2.12 -0.09 0.50 -1.89 0.70 Pyrene 0.76 -0.07 - 0.50 0.12 0.30 1.21 0.21 1.75 -1.47 -0.09 -0.08 -1.33 0.99 1-Methyl pyrene - - - - - - - - - - - - - - Benzo[b]fluoranthene -0.24 0.37 - 0.27 - - 0.19 1.50 - - - - - - Benzo[k]fluoranthene 0.46 6.02 - -0.15 - -1.50 0.39 -0.49 - - - - - -


- 135 -

Table A5: continued

Lab Code No

68 69 70 72 73 76 77 78 79 80 81 83 84 86

2,6 Dimethyl naphthalene - 0.34 - - - - - - - - - - - - Phenanthrene -1.26 0.46 0.70 0.02 3.51 -0.11 3.21 -0.90 -0.94 0.89 -0.44 0.28 -0.77 1.70 2-Methyl phenanthrene - - 0.55 -0.67 - - 5.09 - - 0.83 - - - - 1-Methyl phenanthrene - 0.15 2.02 - - - 4.13 - - -0.94 - - - - Anthracene - 0.42 1.70 -0.51 5.76 - 3.98 - - 0.89 -0.20 - - 0.78 Chrysene -0.70 0.65 0.82 -0.41 -1.53 0.01 2.45 -0.80 -1.66 2.21 0.55 -0.39 -0.62 -0.67 Triphenylene - - - - - - - - - - -0.17 - - - Fluorene - -0.23 0.89 -0.76 - - 0.85 - - -0.67 -0.57 - -0.08 2.24 Fluoranthene -1.56 0.35 0.57 -0.45 - -0.16 3.22 -0.55 -1.87 0.48 0.66 0.11 -1.12 - Pyrene -0.81 0.19 0.75 -0.39 1.27 -0.08 2.85 -0.49 - 0.97 0.53 -0.02 -0.83 -1.38 1-Methyl pyrene - - 0.57 - - - - - - -1.01 - - - - Benzo[b]fluoranthene -0.90 1.75 - 0.74 -0.05 - 3.22 - - - 0.44 -0.18 - -0.30 Benzo[k]fluoranthene 1.01 0.09 - -0.53 -0.68 - 1.83 - - - - -0.07 - 0.41


- 136 - - 136 -

Table A5: continued

Lab Code No

2 5 7 9 11 12 14 15 16 17 18 19 20 23

Benzo[a]fluoranthene - 0.41 - - - - - - - - - - - - Benz[a]anthracene -0.16 1.80 -1.16 0.82 - -1.23 -0.66 0.28 - - -2.17 -0.39 0.76 -1.09 Perylene - 0.78 - - - - - - - - - - - - Benzo[e]pyrene - 5.03 -5.99 -0.76 - - - - - - - - - - Benzo[a]pyrene 0.32 2.15 -1.87 0.27 - -1.33 1.56 -0.30 - 16 -1.79 -0.38 6.37 -0.94 Benzo[g,h,i]perylene 2.16 1.12 -1.77 -0.29 - - 0.54 -0.54 - 1.61 -1.76 1.21 2.90 -1.77 Indeno[1,2,3-cd]pyrene 3.78 0.83 - - - - - - - - -2.86 -1.32 1.35 -1.02 Dibenz[a,h]anthracene 0.80 0.07 - - - - - - - - -1.61 0.02 44 -1.25 Acenaphthylene 1.92 -0.60 - - - - - - - - -1.11 - 4.32 -0.40 Acenaphthene 2.24 -0.49 - - - - - - - - -1.27 - 5.90 -0.44 Dibenzothiophene - -0.48 - - - - - - - - - - - -


- 137 -

Table A5: continued

Lab Code No

24 25 26 27 28 29 30 33 34 36 37 38 39 41

Benzo[a]fluoranthene - - - - - - - - - - - - - - Benz[a]anthracene - 0.09 -1.39 1.27 0.14 0.57 0.24 3.29 - 1.37 1.33 -0.46 6.00 1.23 Perylene - - - - -1.03 - 0.52 - - - - - - - Benzo[e]pyrene - - - 0.10 -3.44 0.24 -0.61 - - - - - - -0.91 Benzo[a]pyrene 6.37 3.37 -1.17 0.64 -0.65 - 0.63 7.27 2.74 - 0.22 -1.07 0.38 0.96 Benzo[g,h,i]perylene 3.76 -0.95 - -1.76 -0.33 -0.12 -0.26 2.43 - - 0.88 -0.99 3.65 - Indeno[1,2,3-cd]pyrene - - - - - -0.42 -0.75 - - -1.98 1.24 - - - Dibenz(a,h)anthracene - - - - - - 0.70 6.31 - 3.67 - - - - Acenaphthylene - - - - - - - - - - - - - - Acenaphthene - - - - - -0.33 - - - 24 110 - - - Dibenzothiophene - - - - - -1.27 - - - - - - - -


- 138 -

Table A5: continued

Lab Code No

42 43 45 46 47 49 52 53 54 55 62 63 65 66

Benzo[a]fluoranthene - - - - - -1.11 - - - - - - - - Benz[a]anthracene 0.79 0.62 - 0.25 -1.14 0.49 0.13 0.42 -0.62 -1.14 0.45 0.03 -1.83 1.01 Perylene - - - - - -1.74 - 0.15 - - - 0.25 - - Benzo[e]pyrene - - - - - -3.44 - 0.57 - - - 0.10 - - Benzo[a]pyrene 1.20 0.74 - 0.46 -0.30 -0.99 0.38 0.17 -1.19 -0.96 0.19 0.59 - 0.61 Benzo[g,h,i]perylene 1.11 0.28 - -0.26 -0.71 0.19 0.07 0.07 -0.64 0.58 0.35 0.20 - 0.98 Indeno[1,2,3-cd]pyrene 1.12 0.32 - -0.70 - -0.30 -0.27 -0.05 - - -0.23 -0.11 - - Dibenz[a,h]anthracene 0.12 0.91 - 4.97 - - - -0.47 - - - - - - Acenaphthylene 0.34 - - - - - - -0.07 - - - - - - Acenaphthene 1.65 - - - - - - -0.04 - - - - - - Dibenzothiophene - - - - - - - 0.68 - - - - - -


- 139 -

Table A5: continued

Lab Code No

68 69 70 72 73 76 77 78 79 80 81 83 84 86

Benzo[a]fluoranthene - - 0.68 - - - - - - - - - - - Benz[a]anthracene -0.91 0.76 1.23 -0.60 -1.01 -0.01 4.17 -0.29 -0.97 0.57 - 0.26 -0.13 - Perylene - 0.63 1.13 -0.41 - - - - - 20 - - - - Benzo[e]pyrene - 0.71 -0.15 -0.33 - 1.02 - - - 3.56 - - - - Benzo[a]pyrene -1.02 -0.46 1.56 -0.06 -0.17 0.09 2.07 -0.34 0.00 1.10 0.69 0.15 -0.47 -1.56 Benzo[g,h,i]perylene -0.10 0.98 0.32 0.52 0.17 0.12 4.10 -1.86 0.29 0.00 1.30 0.30 -0.58 -1.06 Indeno[1,2,3-cd]pyrene - 1.98 0.00 -0.20 -0.14 - 1.00 - 0.46 0.58 0.74 -0.39 - -2.19 Dibenz[a,h]anthracene -1.25 0.93 - -0.24 - - 0.21 - -0.60 2.30 -0.08 -0.89 - - Acenaphthylene - -0.59 - -0.75 5.18 - 1.15 - - - -0.95 - 1.04 38 Acenaphthene - -0.69 0.98 -0.61 -0.87 - 0.34 - -0.33 -0.07 -1.01 - 0.99 - Dibenzothiophene - - 1.20 -0.17 - - - - - - - - - -


- 140 -

Z-scores for HCB

Laboratory Code Numbers77 61 71 44 52 16 35 68 5 46 53 7 51 41 29 10 59 8 39 48

Z-sc

ores

-1.5

-1.0-0.5

0.0

0.51.0

1.5

2.02.5

Z-scores for Lindane

Laboratory Code Numbers25 54 71 67 61 51 5 8 16 35 41 3 77 70 46 1 44 42 57 10 48 59 7 29

Z-sc

ores

-2

-1

0

1

2

3

- 141 -

Z-scores for pp' DDE

Laboratory Code Numbers54 42 3 57 25 29 26 67 19 52 71 41 61 14 46 1 5 77 35 85 70 8 31 44 55 10 53 83 6 74 68 7 9 39 51 50 59

Z-sc

ores

-2

-1

0

1

2

3

Z-scores for pp' DDD

Laboratory Code Numbers54 52 42 10 71 57 3 7 68 25 6 29 83 44 26 77 14 61 8 46 1 5 70 35 67 51 64 85 16 9

Z-sc

ores

-2

-1

0

1

2

3

- 142 -

Z-scores for pp' DDT


Z-sc

ores

-2

-1

0

1

2

Z-scores for Aroclor 1254

Laboratory Code Numbers85 41 5 35 68 77 8 26 16 28 22 48

Z-sc

ores

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

- 143 -

Z-scores for PCB 52

Laboratory Code Numbers68 61 62 25 32 53 35 77 24 5 52 46 70 71 10 44 29 3 1 26 30 41 39 67 83

Z-sc

ores

-2

-1

0

1

2

Z-scores for PCB 101

Laboratory Code Numbers58 67 61 62 20 71 32 35 68 25 53 77 24 52 6 70 5 46 3 29 10 41 44 30 26 48

Z-sc

ores

-2

-1

0

1

2

3

- 144 -


Laboratory Code Numbers24 25 58 20 61 3 62 71 53 68 5 46 70 77 29 73 30 44 10 35 42 52 48 67 1 41 79

Z-sc

ores

-3

-2

-1

0

1

2

3



Z-sc

ores

-2

-1

0

1

2

- 145 -


Laboratory Code Numbers24 71 58 30 73 48 61 29 41 62 67 70 5 77 3 20 26 46 68 6 44 1 25 42 52

Z-sc

ores

-2

-1

0

1

2

3


Laboratory Code Numbers51 6 30 62 71 42 46 32 35 26 77 25 68 52 48 3 5 70 41 61 67 79 10

Z-sc

ores

-3

-2

-1

0

1

2

3

- 146 -

Z-scores for Phenanthrene

Laboratory Code Numbers65 24 18 38 37 68 12 79 78 47 55 36 84 23 19 25 81 14 7 76 27 72 46 2 62 43 83 41 49 9 69 30 29 54 63 70 53 66 80 5 28 42 20 86 39 52

Z-sc

ores

-2

-1

0

1

2

3

Z-scores for Chrysene

Laboratory Code Numbers18 26 79 73 65 14 38 78 23 29 68 86 84 47 2 72 83 55 66 15 76 12 52 28 9 63 53 30 5 19 81 25 49 43 62 69 27 46 70 34 41 42 80 77 37

Z-sc

ores

-2

-1

0

1

2

3

- 147 -

Z-scores for Pyrene

Laboratory Code Numbers18 55 86 65 7 23 38 26 84 68 14 12 36 78 72 15 16 27 30 62 63 76 25 43 19 83 28 9 47 69 53 49 2 46 81 29 5 41 70 42 80 66 52 73 17 20 24 54 34 39 77

Z-sc

ores

-2

-1

0

1

2

3

Z-scores for Benz[a]anthracene


Z-sc

ores

-2

-1

0

1

2

- 148 -

Z-scores for Benzo[a]pyrene


Z-sc

ores

-2

-1

0

1

2

3

Z-scores for Benzo[g,h,i]perylene

Laboratory Code Numbers78 7 23 18 27 86 38 25 47 54 84 15 28 9 30 46 29 68 80 52 53 76 73 49 63 43 79 83 70 62 72 14 55 37 66 69 42 5 19 81 17 2 33 20

Z-sc

ores

-2

-1

0

1

2

3

- 149 -

- 150 -

- 151 -

Annex IV

List of participants IAEA - 159

- 152 -

- 153 -

Laboratory Investigator Results: Addresses: Names: Received: ALBANIA Institute of Public Health Ms. L. TAFAJ / Mrs. S. BINO OC, PCB, PH Rr. Alexander Moisiu No 80 TIRANA ARGENTINA Department of Oceanography Mr. L. J. JANIOT OC, PCB Servicio de Hydrografia Naval Avda Montes de Oca 2124 1271 BUENOS AIRES AZERBAIJAN AZECOLAB Dr. B. SULEYMANOV OC, PCB, PH Av. H. Javid 31 a BAKU BELGIUM CLO - GENT Dr. K. PARMENTIER OC, PCB Sea Fisheries Department Ankerstraat 1 8400 OOSTENDE BRAZIL Universidade de Sao Paulo, Instituto de Oceanografico

Dr. R. R. WEBER OC, PCB, PH, Sterols

Praca do Oceanografico 191 Cidade Universitaria- Butanta 05508-900 SAO PAULO

- 154 -

Instituto de Quimica UFBa Dr. T. TAVARES OC, PH Departamento de Quimica Analitica Campus Universitario da Federacao 40-210 340 SALVADOR , BAHIA Laboratorio de Radioisotopos E. Penna Franca

Dr. J. P. MACHADO TORRES PH

Instituto de Biofisica Carlos. Chagas Filho/UFRJ Bloco G/CCS, Ilha do Fundao RIO DE JANEIRO, RJ Instituto de Estudos do Mar Almirante Paulo Moreira -IEAPM

Dr. P. P. de OLIVEIRA PINHEIRO

PH

Departamento de Oceanografia Rua Kioto no 253 - Praia dos Anjos Arraial do Cabo, RJ CEP: 28930-000 RIO DE JANEIRO Laboratorio de Estudos Marinhos e Ambientais (LABMAM)

Prof. A. WAGENER PH

Departamento de Quimica, PUC - Rio Rua Marques de Sao Vicente, 225. Gavea, RJ 22453-900 RIO DE JANEIRO BULGARIA Executive Agency for the Environment MOEW

Mr. D. NIKOLOV PCB, PH

Regional Laboratory - Burgas k-s Lazur, 67 Perushtica str., P.O. Box 675 8001 BURGAS

- 155 -

COLOMBIA Centro Control de Contaminacion del Pacifico

Mr. R. CASANOVA ROSERO PH

Narino, Apdo postal 187 TUMACO COSTA RICA Centro Investigacione en Contaminacion

Dr. E. CARAZO A. ROSELLO CALDERON

OC

Ambiental (CICA) University of Costa Rica SAN JOSE CROATIA Zavod Za Javno Zdavstvo Mr. A. ZIVKOVIC PH Primorsko-Goranske Zupanije Kresimirova 52A 51000 RIJEKA Rudjer Boskovic Institute Dr. M. PICER OC, PCB Center for Marine Research 10000 ZAGREB Institute of Oceanography and Fisheries Mr. Sc. V. MILUN OC, PCB Setaliste Ivana Mestroviaea, 63 P.O. Box 500 21001 SPLIT Institute for Medical Research and Dr. V. DREVENKAR OC, PCB Occupational Health Ksaverska Cesta 2, POB 291 HR-10001 ZAGREB

- 156 -

Institute of Public Health Zadar Mr. J. SANGULIN PCB Kolovare 2 23000 ZADAR CUBA Plant Protection Research Institute Mr. G. F. DIERKSMEIER OC Calle 110 No 514 esq 5 ta B Municipio Playa CIUDAD DE LA HABANA CZECH REPUBLIC Water Laboratories Department Ms. E. ZEJDOVA OC, PCB, PH Povodi Moravy M. PRISTAKOVA Drevarska 11 CZ-601 75 BRNO Institute of Public Health Ostrava Dr. T. TOMSEJ OC, PCB Partyzanske namesti 7 702 00 OSTRAVA Institute of Chemical Technology Mr. J. HASLOVA OC, PCB, PH Department of Food Chemistry Technicka 3 CZ-166 28 PRAGUE 6 ECUADOR Comision Ecuatoriana de Energia Atomica

Dr. R. CASTRO OC, PCB, PH

Juan Lanea 534 y Riofrio P.O. Box 17 01 25 17 QUITO

- 157 -

FRANCE Faculte de Pharmacie Dr. E. WAFO OC, PCB Laboratoire d'Hydrologie 27 Blvd Jean Moulin 13005 MARSEILLE Eurofins Environnement Mme K. LOUVET OC, PCB, PH 20 rue du Kochersberg 67700 SAVERNE Laboratoire Departemental de la Sarthe Mr. J. M. BERTHION PCB, PH 128 rue de Beauge 72018 LE MANS Cedex Laboratoire de Developpement et d'Analyses

Mr. E. MARENGUE OC, PCB, PH

des Cotes d'Armor 7 rue du Sabot, BP 54 Zoopole 22440 PLOUFRAGRAN BGRM - Service Metrologie, Monitoring, Analyse

Mme LEDUC PH

B. P. 36009 3 Ave Cl. Guillemin 45060 ORLEANS Cedex 2 GERMANY Bayerisches Landesamt fur Umwelt Dr. M. SENGL OC, PCB Kaulbachstrasse 37 D-80539 MUNCHEN German Federal Institute of Hydrology Dr. D. LOFFLER OC, PCB, PH Am Mainzer Tor 1 56068 KOBLENZ

- 158 -

Institut fur Ostseeforschung Warnemunde

Dr. R. SCHNEIDER OC, PCB

an der Universitat Rostock Seestrase 15 D-18 119 ROSTOCK GHANA Water Research Institute Ms. G. A. DARTEY OC, PH (CSIR) P.O. Box AH 38 ACHIMOTA GREECE Hellenic Centre for Marine Research Mr. I. HATZIANESTIS PH P.O. Box 712 ANAVISSOS 10 013 Department of Marine Sciences Dr. M. KOSTOPOULOU PH University of the Agean KARADANELLI University Hill 811 00 MYTILINI, LESVOS HONDURAS Centro de Estudios y Control de Contaminantes

Mrs. D.SABILLON / I.K.SERRA

OC

Barrio Morazan G. PADILLA / A.CASTILLO Frente Central de Bomberos TEGUCIGALPA

- 159 -

HUNGARY Water Ressources Research Center Dr. F. LASZLO / M. BIHARI OC, PCB, PH VITUKI Rt Kvassay J. ut 1 H-1095 BUDAPEST INDIA Environment Assessment Division Dr. G.G. PANDIT OC, PCB, PH Bhabha Atomic Research Center Trombay MUMBAI 400 085 IRAN Marine Environment Bureau Dr. S.M.B. NABAVI PH Department of the Environment Hemmat Highway P.O. Box 1463913111 TEHRAN Iranian Research Institute of Plant Protection

Dr. M. MOROWATI OC

Pesticides Residue Analysis Laboratory P.O. Box 1454 19395 TEHRAN Iranian National Center for Oceanography

Mrs. M. HASHTROUDI Mr. P. EGHTESADI-ARAGI

PCB, PH

Marine Living Science Department 9 Etemadzadeh Avenue Fatemi Street P.O. Box 14155-4781 TEHRAN, 1411813389

- 160 -

ISRAEL Israel Oceanographic and Limnological Research Company

Dr. D. WYNNE Dr. R. PARPAROVA

OC

The Ygal Allon Kinneret Limnological Laboratory P.O. Box 447 14950 MIGDAL Quality Assurance Dr. A. SKALSKI /L. CHARNES PH Bactochem Hacharassh str. 7 NES-ZIONA 74031 ITALY Central Institute for Marine Pollution - ICRAM

Dr. G. SESTA OC, PCB, PH

Via Casalotti 300 00166 ROMA ISMAR - CNR Castello 1364/A

Dr. G. CAMPESAN D. CASSIN

OC, PCB, PH

30122 VENEZIA KOREA Chemical Oceanography Division Dr. Sang Hee HONG PH KORDI 391, Jangmok-ri, Jangmok-myem Geoje 656-830, GYANGNAM KUWAIT Environmental Public Authority Mrs. F. M. MALALLAH PH P.O. Box 24395 Mr. A. ALNATOUR 13104 SAFAT

- 161 -

K.I.S.R. Dr. A. AL-OMAIR OC, PCB, PH Central Analytical Laboratory P.O. Box 24885 13109 SAFAT LITHUANIA Center for Marine Research Dr. G. GARNAGA OC Ecotoxicological Department Taikos pr. 26 91149 KLAIPEDA MEXICO Laboratorio de Analisis Instrumental - UAM-Xochimilco

Drs. G. DIAZ GONZALEZ R. GUTIERREZ

OC, PCB, PH, Sterols

Calzada del Hueso 1100 Colonia Villa Quietud 04960 MEXICO, D.F. Instituto de Ciencias del Mary Limnologia

Dr. A. VASQUEZ BOTELLO OC, PCB, PH

Universidad Nacional Autonoma de Mexico Apartado Postal 70305 04510 MEXICO, D.F. MOLDOVA Hydrometeorological Service Dr. A. CUMANOVA OC, PCB Environmental Center 193 Grenoble str. CHISHINEV 2043 Laboratory of Geochemistry "GEOLAB"

Dr. O. BOGDEVICH PH

Academy str. 3 CHISINAU, MD-2028

- 162 -

MONACO IAEA-MEL/MESL Ms. C. CATTINI OC, PCB, PH 4 Quai Antoine 1er MOROCCO Institut National d'Hygiene 27 Ave. Ibn. Batuta

Dr. EL ABIDI Mrs. N. BARAKATE

OC

B.P. 769 AGDAL RABAT SULTANATE OF OMAN Food and Environmental Monitoring Center

Mr. H. AL-AKHZAMI PH

(FEMC, located between Golden Tulip Hotel and Office of Oman Air at SEEB) P.O. Box 323 Postal Code No 113 MUSCAT REPUBLIC OF PANAMA Laboratorio de Analisis Industriales S.A. (LAISA)

Mr. V. DUKE Prof. I. CAMACHO

OC

Apartado 6-3491, El Dorado PANAMA PHILIPPINES National Crop Protection Center Dr. C. M. BAJET OC Univ. of the Philippines Los Banos COLLEGE , LAGUNA 4031

- 163 -

POLAND Marine Pollution Laboratory Assoc. Pr. G. KOWALEWSKA PCB, PH Institute of Oceanology, Polish Academy of Sciences ul. Powstancow Warszawy 55 81-712 SOPOT ROMANIA Research and Engineering Institute Dr. A. VARDUCA OC, PH For Environment Spl. Independentei No 294, sector 6 BUCHAREST 77748 National Institute for Marine Research and Development

Ms. V. COATU OC, PH

"Grigore Antipa" Blvd Mamaia 300 R-900581 CONSTANTA, CT-3 RUSSIAN FEDERATION Research Institute of the Azov Sea Dr. I. KORPAKOVA OC, PH Fisheries Program (AzNIIRKH) Beregovaya str. 21/2 344006 ROSTOV-ON-DON Special Laboratory of Monitoring for Krasnodar Krai Ms. V. YATSENKO OC, PH 2/1 Korolenko str. 350000 KRASNODAR Eco-Analytical Laboratory Dr. N. KLYUEV OC, PCB, PH A.N. Severtsov Inst. Ecological & Evolutionary Problem

Dr. A. SHELEPCHIKOV

Russian Academy of Sciences Leninsky Prospekt 33 117071 MOSCOW

- 164 -

SANTA LUCIA Caribbean Environmental Health Institute

Mrs. P. AQUING Mrs A. ENTWISTLE

OC

P.O. Box 1111 The Morne CASTRIES SEYCHELLES Seychelles Bureau of Standards Mr. V. RADEGONDE OC P.O. Box 953 VICTORIA MAHE SLOVAKIA Water Research Institute Dr. L. SUSTER PH L. Svobodu 5 81249 BRATISLAVA Ekologicke a Veterinarne Laboratoria, EL spol.sr.o.

Ing. E. BLAHUTOVA OC, PCB

Radlinskeho, 17A 052 01 SPISSKA NOVA VES SLOVENIA Dept. of Environmental Sciences Dr. E. HEATH OC, PCB, PH Josef Stefan Institute Jamova 39 1000 LJUBLJANA Marine Biological Station Mr. O. BAJT PH Fornace 41 6330 PIRAN

- 165 -

SPAIN Grupo INTERLAB Dr. P. AZPEITA / A. CASTRO OC, PCB, PH Maria Tubau, 4, 3a Planta 28050 MADRID IIQAB-CID-CSIC Dr. J. M. BAYONA OC, PCB, PH Jordi Girona 18 08034 BARCELONA Instituto Espanol de Oceanografia Dra. FRANCO and Dra VINAS PH P.O. Box 1552 36280 VIGO Servicios Tecnicos de Investigacion Drs. P. BLASCO /P. CANDELA OC, PCB, PH Facultad de Ciencias, University of Alicante Carretera San Vicente del Raspeig E-03000 ALICANTE SYRIA Atomic Energy Commission of Syria Dr. R. AL-MEREY OC Quality Assurance Office (AECS) P.O. Box 6091 DAMASCUS TRINIDAD AND TOBAGO Chemistry Mr. A. McCARTHY OC Food and Drug Division 115 Frederick Street PORT OF SPAIN

- 166 -

TUNISIA INSTM, Departement Pollution Dr. N. MZOUGHI PH Unite Organique Port de Peche 2060 LA GOULETTE Centre International des Technologies

Dr. B. HANCHI OC, PCB

de l'Environnement de Tunis Boulevard de l'Environnement 1080 TUNIS TURKEY Dokuz Eylul University Dr. F. KUCUKSEZGIN OC Isnt. of Marine Sciences & Technology Inciralti 35340 IZMIR Middle East Technical University Prof. S. TUGRUL / D. YILMAZ OC, PH Institute of Marine Sciences P.K. 28 33731 ERDEMLI MERSIN TUBITAK, MRC Dr. L. TOLUN PCB, PH Chemistry and Environment Institute P.O. Box 21 41470 GEBZE-KOACALI UKRAINE Institute of Biology of the South Seas Dr. L. MALAKHOVA OC, PCB Academy of Sciences of UKRAINE Nahimova Prospekt 2 SEBASTOPOL 99011

- 167 -

Ukrainian Scientific Center of the Ecology of the Black Sea

Mr. Y. M. DENGA OC, PCB

89 Frantsusky Boulevard ODESSA UNITED KINGDOM SEPA East Region Mr. W. BROWN PH Heriot Watt Research Park Avenue North, Riccarton EDINBURG EH14 4AP Agric. Food and Environmental Science

Dr. T. OLIVER PCB, PH

Department of Agriculture and Rural Development Northern Ireland Newforge Lane Malone Road BELFAST, BT9 PX U.S.A. NIST Dr. M.M. SCHANTZ PH 100 Bureau Drive, Stop 8392 8392 GAITHERSBURG , MD 20899 Geochemical and Environmental Research Group (GERG)

Dr. J. SERICANO OC, PCB, PH

Texas A. and M. University 833 Graham Road COLLEGE STATION, TX, 77845 OC: Organochlorine PCB: Polychlorinated biphenyls PH: Petroleum hydrocarbons

- 168 -

Documents

IAEA/AL/180 WORLD-WIDE AND REGIONAL · 2011. 2. 24. · WORLD-WIDE AND REGIONAL INTERCOMPARISON FOR THE DETERMINATION OF ORGANOCHLORINE COMPOUNDS, PETROLEUM HYDROCARBONS AND STEROLS