palmork_wilhelmsen-1987.pdf (2.342Mb)

ORGANOCHLORINES IN BCR REFERENCE CANDIDATE FISH

OILS

A Report to

The Vrije Universiteit» lnstituut voor Milieuvraagstukken» Amsterdam

by

K. H. PALMORK AND S. WILHELMSEN

INSTITUTE OF MARINE RESEARCH N -5024 BERGEN - NORDNES

NORW AV.

MARCH» 1987

has requested the Institute of Marine Research to take part in an extended collaborative exercise, also including organochlorine other than PCB's. The background for this is as follows:

At a BCR meeting in Bruxelles July 2. 1986, Dr. B. Griepink considered it useful if other determinants than PCB's could be included and the results be "appended to the certification report as indicative values". Dr. D. E. Wells, of the Freshwater Fisheries Laboratory, Pitlochry, Scotland, sent a letter to all members of the PCB Group dated July 23.

1986 (APPENDIX I), where he requested us, especially those of us with a special interest in fish oils, to extend our analyses to include our usual organochlorines range for 2/3 of the replicates, if not all five. Several laboratories agreed to do this and standards covering these extra determinants, organochlorines and PCB compounds, were sent out to the different laboratories in October 1986. A follow-up letter of December 9., 1986, with a standard result form for organochlorines and PCB compounds with extra space allocated for further determinants (APPENDIX 11) were sent out.

Check out of the standards received from Dr. We11s.

The 6 ampoules received October 28., 1986 were labeled as follows:

A: is a mixture of D2-D 18 (dichlorobenzylether) DCBE at 0.5 µg/ml iso-octane.

B: is a solution of D6 at 10µg/m1 iso-octane.

C: is a solution of D 12 at 10µg/m1 iso-octane.

D: is a solution of D 16 at 10µg/m1 iso-octane.

E: is a mixture used for (GC)2 calibration.

F: is a mixture used for (GC)2 calibration.

( GC)2 =gas chromatography -glass capillary

Sample E and F were checked towards two standard solutions used da1 ly 1n our laboratory. The Standard-SR was obtained from BCR and the Standard-A from Lars Reutergardh, Naturvardsverket, Special Analytiska Laboratorium, Stockholm , Sweden.

The following compounds were added to standard-A:

gamma-HCH aldrin

dieldrin 4,4-DDE 4,4-DDD 4,4-DDT

DCBE-14, supplied from BCR in an earlier Ring Test, was used as an internal standard.

All the standard solutions were diluted with iso-octane to give approximately the same concentrations (approx. 20 ng/mD. The

concentr~t.ion of DCBE-14 was 455 ng/ml.

The samples were injected on-column because of severe adsorption in the inlet system when inject1ng spl1tless, especially of DDT.

MATER I AL AND METHODS

Table I. Chemicals used during the analyses of the fish oils.

Chemicals

Pentane Sulphuric acid Silica

I so-octane Dich loromethane Nitrogen

Grade of purification

Merck, Art. 7179, Uvasol Merck, Art. 731 , pro analysis

Merck, Art. 7734, 63-200 um Merck, Art. 4 718, Uvaso 1 Distilled technical grade 99. 99% purity

Tab1e II. lnstrumenta1 cond1tions.

Gas chromatograph : HP-5880A EC-detector : Ni-63 Column

Carrier gas Oven temp. prog.

Injection

Ana1ytica1 procedure

: Fused silica, SE-54, CB, 50 x 0.32 mm, 0.17µm.

Hydrogen, 20 cm/sec.

1 min. 90 °C-3 °C/min.-260 °C On-column, 3µ1.

The samples - 0.2 g fish oil - were treated with concentrated sulphuric acid and the PCB's and DDT's were separated on a silica column as described in: Determination of PCB-Congeners in Candidate Reference Material (Fish Oils), by S. Wilhelmsen and K. H. Palmork, January 1987.

The PCB's were eluted with 1

o

o

pentane: dichloromethane ( 1: 1 ). DCBE-14 was used as an internal standard.

Results and comments.

The concentrations of the standards supplied by Wells were given in µg/kg. Since we always use µg/1 when dealing with liquids, the concentrations were transformed to these units. ( 1 1 iso-octane = 0.692 kg).

Tab Jes IV and V shows our results compared to the given concentrations both in µg/l and µg/kg. As can be seen from the tables, our results in µg/l are in agreement with the given results in µg/kg.

(Is there a possibility of a misprint so that the given concentrations should be in µg/1 ?).

Tables VI and VI I shows the results of our analyses of the extra organochlorine components in Cod liver oil and Mackerel oil respect 1ve ly.

Table 111. Concentrations of the chlorinated compounds appearing in our standards Ci,tg/ml).

Compound Standard-SR Standard-A

PCB-28 0.50

PCB-52 0.50 1.18

PCB-44 1.00

PCB-95 0.82

PCB-101 0.50 1.00

PCB-110 1.00

PCB-118 0.50 1.00

PCB-153 0.50 1.00

PCB-138 0.50 1.00

PCB-128 1.00

PCB-180 0.50 1.00

PCB-170 1.00

PCB-194 1.00

gamma HCH 1.05

Aldrin 0.98

Dieldrin 1.00

4.4-DDE 1.05

4.4-DDD 1.00

4.4-DDT 1.00

Table IV. Results from the analys1s of Standard-E in the order of elut1on from column CP SU 5 CB and SE-54.

Given Found ( n=3)

Compound ug/l ug/kg ug/1 RSD

HCB 66.9 97

D6 345.0 500

PCB 28 67.6 98 101.1 3.7

Heptachlor 66.9 97

PCB 52 67.6 98 92.4 0.1

Aldrin 67.6 98 86.3 2.1

PCB 44 66.9 97 89.2 0.7

2.4-DDE 67.6 98

PCB 101 67.6 98 92.4 1.4

4.4-DDE 67.6 98 89.4 2.3

PCB 118 67.6 98 92.4 2.4

PCB 153 67.6 98 87.1 2.4

PCB 137 67.6 98

PCB 138 67.6 98 92.3 2.1

PCB 128 67.6 98

D12 345.0 500

PCB 180 67.6 98 97.3 2.5

Mirex 68.3 99

PCB 195 67.6 98

PCB 194 67.6 98 87.3 1.4

D16 345.0 500

Table V. Result from the analysis of Standard-F in the order of elut1on from column CP 511 5 CB.

Given Found (n=3)

Compound µg/l µg/kg µg/l RSD

alpha HCH 67.6 98

beta HCH 142.1 206

gamma HCH 67.6 98 96.9 3.5

D6 345.0 500

Heptachlor 67.6 98

alpha chlordene 68.3 99

gamma chlordene 66.2 96

Heptachlor epoxide 66.9 97

Oxych lordane 66.2 96

gamma chlordane 66.9 97

Endosulfan I 66.9 97

2.4-DDE 67.6 98

alpha chlordane 67.6 98

trans nonach lor 67.6 98

Dieldrin 67.6 98 97.1 2.2

2.4-DDD 66.9 97

Endrin 67.6 98

4.4-DDD 66.9 97 99.7 3.8

2.4-DDT 66.7 98

4.4-DDT 66.7 98 100.1 3.2

D12 345.0 500

PADS 174.0 252

t.:is permethrin 704.0 1021 trans permethrin 711.0 1031

D16 345.0 500

Table VI. Sample: Cod liver oil, individual results expressed on fat basis Cng/g).

Compound 2 3 x RSD

alpha HCH 32 37 39 36 9.7

gamma HCH 78 88 88 85 7.3

4.4-DDE 285 272 327 295 9.7

4.4-DDD 161 180 182 174 6.6

4.4-DDT 63 70 68 67 5.8

PCB-44 94 85 85 88 5.6

PCB-95 207 204 205 205 0.7

PCB-110 226 222 219 222 1.6

PCB-128 241 237 240 239 0.9

PCB-170 84 77 91 84 8.3

Table VI I. Sample: Mackerel oil, individual results expressed on fat basis Cng/g).

Compound 2 3 x RSD

alpha HCH 23 26 22 24 7.5

gamma HCH 51 56 49 52 6.5

4.4-DDE 97 100 92 96 4.2

4.4-DDD 78 85 81 81 4.7

4.4-DDT 105 91 109 102 9.1

PCB-44 39 40 43 41 5.1

PCB-95 106 101 115 107 6.6

PCB-110 114 107 121 114 6.1

PCB-128 82 72 88 81 10.0

PCB-170 17 16 18 17 5.9

APPENDIX I

CHROMATOGRAMS

1. ST AND ARDS E (TABLE IV)

2. ST AND ARDS F (TABLE V)

3. BCR COD LIVER OIL

4. BCR MACKEREL OIL

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