Document ba9ZmOz50zOXjQy8ywEg5nar0
H 1*. Wheeler
Determination of Polychlorinated Biphenyl (PCB's) Residues in Grades of Pulp, Paper and Paperboard
by S. L Shahied, Richahd P. Stanovick, David E. MclNTURFF,*nd Emil Missachi
Biochemistry Department DazeIton Laboratories, Inc.
yienna, Lirginia 221 HO
Polychlorinated biphenyls (PCB's, ArocloP^ 1242 and 125b)
are of widespread use in the manufacturing of electrical insu lators, varnishes, paints, lubricants and heat transfer fluids. They are also used as plasticizers. JENSEN, et al, (1,2) and WIDMARK (3) identified a group of PCB's in the Swedish environ ment through the use of g^s chromatography and mass spectroscopy. This was the first time that PCB's were recognized as environ mental pollutants.
The purpose of this study was to determine residues of PCB's in different grades of pulp, paper and paperboard samples. These grades included both food packaging and non-food packaging grades. The samples were procurred from members of The American Paper Institute frqm various geographic locations throughout the country during the months of November and December of 1971.
Materials and Methods
Ten grams of sample were weighed, shredded into small pieces, and transferred to a 500-ml round bottomed flask. One-hundred milliliters of 2% methanolic potassium hydroxide were added to the sample and refluxed for 30 minutes. The bydrollzed sample was filtered and bo ml were taken for extraction with petroleum ether.
The bO-ml aliquot (b.O gm sample) from the extract was
transferred to a 250-ml. separatory funnel. The aliquot was shaken
vigorously with 20 ml of petroleum ether and bO ml of distilled
water. The aqueous layer was drained into a second separatory
funnel containing bo ml of petroleum ether, the separatory funnel
was shaken vigorously, and the aqueous layer discarded. The
petroleum ether extracts were combined and washed with three 20-ml
portions of distilled water. The petroleum ether extract was
taken through a column of anhydrous sodium sulfate into a 100-ml
volumetric flask. The volume was adjusted to the mark with petro
leum ether.
A 10-ml aliquot (O.b gm sanple) was taken fhom the above-
mentioned 100-ml sample, and concentrated to a known volume. A 1- to 5-pl sample was Injected into a gas chranatocraph equipped with an Nl63 electron capture detector system. A standard curve was plotted each day for Aroclors 12b2 and 125b.
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. Oas chrcnatographlc column, 6' x 1/4" O.D. glass, packed with 3% OV-17 on 100/200 mesh Gas-chran Q
Oolumn Temperature:
200 C
Detector Temperature: 245 C
Inlet Temperature:
275 C
Carrier Gas (Nitrogen): 86 ral/Mn flow
TABLE 1
Sumary of Aroclor 1242 and 1254 residues detected in pulp, paper and paperboard.
Sample Identification
Aroclor 1242 Found
ppm
Aroclor 1254 Fcund
ppm
Total* Aroclor
Found ppm
Unbleached Kraft Pulp
81
<0.50
<0.50
<0.50
3
<0.50
<0.50
<0.50
39
<0.50
<0.50
<0.50
Bleached Kraft Pulp
44
<0.50
<0.50
<0.50
11
1.33
<0.50
1.33
82
<0.50
<0.50
<0.50
55
<0.50
<0.50
<0.50
Virgin Newsprint
47
<0.50
<0.50
<0.50
15
0.58
0.42
1.00
48
<0.50
-<0.50
<0.50
Recycled Newsprint
45
<0.50
<0.50
<0.50
86
<0.50 .
<0.50
<0.50
36
1:38
<0.50 .
1.38
* Recycled Bond Paper
35** 35** 17
91-00 -
265.00
-
22.50 25.00
113.50 290.00
Bleached Kraft Llnerboard
54
<0.50
<0-50
<0.50
* 1242 and 1254
* Aroclor 1242 was assayed from a 50-rnl final volume.
Aroclor 1254 was assayed from a 4-ml final volume. The
total of 1242 and 1254 is indicated in column labeled
Total ppm.
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Sample Identification
Aroclar 1242 Found ppm
Aroclar 1254 Found
ppm
Unbleached Kraft Linerboard
33
<0.50
<0.50
23
<0.50
<0.50
41
<0.50
<0.50
72
<0.50
<0.50
51
<0.50
<0.50
61
<0.50
<0.50
40
<0.50
<0.50
Total* Aroclar
Found ppm
<D.50 <0.50 <0.50 <0.50 <0.50 <0.50 <D-50
Solid Bleached Sulfate Board Nonclay Coated
25
<0.50
<0.50
<0.50
75
<0.50
<0.50
<0.50
83
<0.50
<0.50
<0.50
32
<0.50
<0.50
<0.50
30
1.92
<0.50
1.92
50
<D.50
<0.50
<0.50
Solid Bleached Sulfate Board Clay Coated
84
<0.50
<0.50
80
<0.50
<0.50
38
<0.50
<0.50
49
<0.50
<0.50
71
<0.50
<0.50
31
<0.50
<0.50
74
<0.50
<0.50
Solid Unbleached Sulfate Board Clay Coated
<0.50 <33.50
<0.50 <0.50 <0.50
<0.50 <0.50
73
<0.50
<0.50
<0.50
Patent White Newsback Paperboard (also known as White Lined, White Lined News, and White Lined Manila Back)
87
10.70
<0.50
10.70
69
3.21
1.29
4.50
66
2.42
1.67
4.09
64
18.80
4.17
23.00
28
<0.50
10,35
10.35
13
35.00
7.50
42.50
26
1-55
0.22
1.77
52
<0.50
<0.50
<0.50
9
1.50
1.00
2.50
Patent White Newsback Clay Coated Paperboard (Also Known as Clay Coated News and Clay Coated White Back)
88 , 68
65 1242 and 1254
2.75 2.92
2.83
82
<0.50 0.92 1.50
2.75 3.84 4.33
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TABLE 1 (contin.)
Sample Identification
62 27 12
6 53
7
Aroclar 1242 Pound ppn
5.42
1.55 28.40 7.50 <0.50
1.71
Aroclor 1254 Found ppm
1.46 0.30 2.20 1.10 <0.50 0.67
Total* Aroclar
Found ppm
6.88 1.85 30.60 8.60 <0.50 2.38
Shell Stock (Any Dry Pood Packaging Grade Which Will Be Overwrapped with a Printed Wrapper, May be a lined Sheet such as Manila lined News)
89
23.12
<0.50
70
2.46
1.09
67
2.29
1.25
63
1.63
0.08
29
8.4o
2.40
14
41.00
8.00
58
3-25 '
<0.50
8
3-10
3.84
Unbleached Kraft Bag or Wrapper Stock
23.12
3-55 3.54
1.71 10.80 49.00
3.25 6.94
59
<0.50
<0.50
<0.50
2
<0.50
<0.50
<0.50
Bleached Kraft Bag, Wrapper or Tag Stock
57
<0.50
<0.50
78
<0.50
<0.50
77
<0.50
<0.50
19
1.00
<0.50
<0.50 <0.50 <0.50
1.00
-Glassine
20
1.10
0.25
1.35
60
<0.50
<0.50
0.50
5
<0.50
<0.50
<0.50
Greaseproof
10
<0.50
<0.50
<0.50
37
<0.50
<0.50
<0.50
76
<0.50
<0.50
<0.50
42
43 22 1242 and 1254
Publication Paper
<0.50 ' <0.50 <0.50
.
<0.50 <0.50 <0.50
<0.50 <0.50 <0.50
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Sample Identification
79 21
4 1 16 85 34
TABLE 1 (contin.)
Aroclor 1242 Aroclor 125*)
Found ppm
Pound ppm
Virgin Bond Paper
<0.50 8.50
<0.50 <0.50
2.10 <0.50
1.60
<0.50 <0.50 <0.50 <0.50
<0.50 <0.50
<0.50
Total# Aroclor
Found PFm
<0.50 8.50
<0.50 <0.50
2.10 <0.50
1.60
1242 and 1254
TABLE 2
Recovery of Aroclor 1242 and Aroclor 1254 from pulp, paper and paperboard sanples.
Sample Identiflcation
50
45 52
5 1
10 3
63 52
63 10
1
Paperboard Grade
Solid Bleached Sulfate Board Nonclay Coated
Recycled News print
Clay Coated Unbleached Patent White Newsback
Glasslne
Virgin Bond Paper
Greaseproof
Unbleached Kraft
Pulp
Shell Stock
Patent White Newsback
Shell Stock
Greaseproof
Virgin Bond Paper
Spike Level 1242 1254
ppm ppm 0.61
1.21
2.42
4.85 9-70
14.54 29.10
121.10
2.065
103.250 14.450 10.330
84
Recovery 1242 1254 ~r ...i 92.2
93.0
88.0
75.0 88.0
80.5 86.0
82.0
99-0
97.0 82.5 108.5
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Results and Discussion
The results obtained for the surveyjihe summarized in Table 1. The sensitivity of the method for PCTfe? ls_0.50 ppm. Recovery data to validate the method are presented-irr Table 2. The average recovery for Aroclor 12^12 is 8&L and-that for Aroclor 125*4 is 98?.
Typical chromatograms for'ar'StandarcL (Aroclor 12*42) and
fortified samples are presented in Figure 17 irraddition, typical
chromatograms for a standard (Aroclor-125^)"and fortified paper
board samples are shown in Figure 2.
. __
We found that 11? of the different grades of pulp'Tpaper, and paperboard samples contained PCB residues higher than 1CLQ ppm, 4? of the samples contained PCB residues of 6.0 to lO.O-pprrand 25? of the-samples contained PCB residues `.IrTthe range of 1.0 to 5-0 ppm. However, PCB residues were found to be less than 0.50 ppm in 58? of all samples analyzed. It should be'noted, however, that this sur vey was conducted during the November-December 1971 period, and if a new survey is made, levels"'of PCB residues in samples would most likely-be "lower-due to'the effort put forth by the paper Industry.
As shown in Table 1, PCB residues .were..also found in virgin newsprint and virgin bond paper. . However-, -it is suspected that the .manufacturing processes may be-the cause of the residues.
Acknowledgments
-_The research was supported-by The-American Paper Institute (API) . We thank all members for`their support and-cooperation. Special thanks go to Dr. Paul Trout who is with-Container Corpo ration of America and Mr. Einar T. Wulfsberg, .Consultant to API.
-------- References
1. JENSEN, S., A New Chemical HazardNew-Sei-^-32, 612 (1966).
2. JENSEN, S., et al., DDT and PCB in Marine' Animals from Swedish
Viaters, Nature, 22^ 2fl7-250 (1969)- --,,_____
3. WUMARK, G., Possible Interference -by Xhdorinatecr Biphenyls,
J.A.O.A.C. , 50, 1069 (1967).
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