Document V32jDMkq5eGVO0wMYxBoadpwq
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Elcclnm*Cin>iuring Compounds and Selected Elements in Paper
>y
J. W, Si.iium', S. C. Tonc\ L. K. St. John Jn.s, C. A. DACHr,*,
11, H. Mr.nTr.NS-' nrnl 1). J. I.,isk:
' 'Deportment of Chemistry, `I'extieide Ketirlue I.nhorntoTy,
'Deportment rtf Jnhnnt Seienee, Cnritell IhtieenitY. Ithneo.
A'ck1 York l lll'iO, 'He.wnreh unit /i.-i t (oprnrnt [.nliornlorir.x, Coniin# (Ibmj IF'or/u, Comiuir, ISetv VmJi It'tli) .
Many novel aolutlono to the nationwide problem of solid waotc dfspor.nl have born proponed. A recent one which has been studied is the feed hip, of paper products to farm animals such ns dairy cattle ns a source of cellulose (WHITENS et al. 1971a). Cattle will consume rations containing, up to 20 weight 7. paper and asgiraiiate up to 907. of the dry matter of certain of them such ns brown card board (linvir.HK et al. 197 1b). Office paper has also been advanta geously i nmrnnfii (p.d in sheep rations (NIK1IIMUTA et al. 1969).
It Is known that comnounds such as the polychlorinated bi phony 1H (TCP's) ore used as dye carriers tn specialt'y print lng inks. Hip.lt concentrations of TCP's have, been reported as present In carbon loss copying paper (MASUDA ct al. 1972). It Is possible that these compounds may survive when specialty paper products nrc regenerated for use in other paper products such ns cardboard. Vaperbonrd hns been reported to contain PCU-typc compounds (ANONY MOUS 1972). These compounds could he transferred to covo' inilk or moot no residues. Contamination of food by conLnct is possible if the paper material becomes part, of n food container. Electron cnpturinp, penks In extracts of cereal p.ralns have been traced to the presence of corresponding compounds in cloth bags (EEV1 and NOWICUI 1972). Certain metals may also be present In paper a9 constituents of the Ink or as a re.sult of the printing process. Furthermore deep rooted trees may absorb unusual elements from lower sol) horizons (ROBINSON el al. 19.10) which may then be present In paper. in the work reported a survey uf abo_.L 100 papers and paper products has been made for the presence of chlorinated organic compounds using gas chromatography with electron niilnity and elec trolytic. conductivity detectors and the combination gas chromato graphy-mass spectrometry. Metals and other elements in paper were also determined by spark source mass spectrometry.
F.xpcr Jmenta 1
Paper namplcs were obtained and millc' to a fine powder and mixed. The newspapers analyzed issued between December, 1970 and April, 1971. In sampling newspapers and magazines prior to grinding, only the center portions of pages were taken to minimize contamination from human handling near page edp.es. Twenty five grams of the powdered paper was blended with 200 ml of hexane In an Ice bath and Lhc solution was decanted and filtered. The paper was blended twice more with 50 ml portions of hexane and the solutions were filtered, combined, concentrated by rotary evapora tion to about 10 ml and made, to a final volume of 25 ml. The
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Electron capturing compounds In various papers
Paper Newspapers (lilnck and white)
No. of penks
Afro-American (ISaltimnrc, Mil.)
Tlic At lama Journal 6 Constitution
The. Al Inula Journal A Constitution - Magazine
'Hie Haiti more Sun
Jloslon Globe - Magazine
buffalo Evening News
Chicago Tribune
Chicago Tribune - Magazine
Christian Science Monitor
The Clarion-hedger (Jac.kson, Miss.)
Commercial Appeal (Memphis, Tcnn.)
Courier Jumnal (I.'ville, Ky.)
Courier Journal A Tines - Magazine (h'ville, Ky.)
The Dallas Morning News
Delia Democrat-Times (Greenville, Miss.)
Hie Denver Dost
The Denver Post - Sunday Empire
Hie Detroit: News
Tin: Detroi t Hc.wo - Magazine
Discover - Sunday bulletin (Tillladolphfa, Pa.)
The Evening bulletin
"
Family Weekly - Magazine
Greenfield Recorder (Maso.)
Hc.rnItl-Aincrlean - Empire (Syracuse, N.Y.)
Il.iincn Journal
.
Journal A Guide (Norfolk, Virginia)
Los Angeles Sentinel
1os Anceles Times
J,o3 Angeleo Times - Magazine
.
Manceste.r Guardian (England)
The Miami Hews
Mid-South - Magazine (Memphis, Tcnn.)
Hie Minneapolis Tribune
Tbo Minneapolis Tribune. - Magazine
The Montreal Star - WeekendMagazine
New llnmswick Daily (N.J.)
New York Post
New York Times
New York Times - Magazine
Tlic Oregonian (Portland, Oregon)
Parade - Magazine (Albany, N.Y.)
'lhe Plain Dealer (Cleveland, Oblo)
The Plain Dealer - Magazine
Hie Post Standard (Syracuse, N.Y.)
Rochester Democrat A Chronicle - Upstate Magaz.lnc
San Francisco Examiner - Magazine
4 12 14 13
V 10
9 10 12 12 19 14 17 'P'25
9
5 .5
18 21 17 T23 33 15 17 15 ' 13 13 12 10 >23 22 23
8 10 >25 21
7 9 7 20 10 17 16 30 21 6
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SC.. I/Oula Pont Dispatch St. l,ouln Poi:t. Dispatch - Magazine Seattle l'oiiL-lute 1H gnice The Sun - Magazine (Washington) Sunday News (Now York, N.Y.) Sunday Telegram (lilmirn, M.Y.) Hie Times Picayune (New Orleans) The. Times Picayune - Magazine (New Orleans) Tlio Times Union (Albany, N.Y.) The Washington Pvoning Star The Washinglon livening Star - Magazine The Washington Pont The Washington Post - Magazine The Washington Pont - Potomac Magazine
Newspapers (colored)
The Atlanta Journal U Conatltution host on Sunday Cliche lint falo livening Nt-wg Chicago Tribune The Courier Journal & Times (h'ville, Ky.) The. Delta Democrat Times (Greenville, Miss.) The Denver' Post The Detroit Sunday News Herald American (Syracuse, N.Y.) The Minneapolis Tribune The Plain Denier (Cleveland, Ohio) Rochester Democrat & Chronicle St, I,ou1g Post Dispatch San Francisco examiner & Chronicle The Sun (Baltimore, Md.) The Sunday Bulletlne (rhlladelphia, Pa.) Sunday Telegram (Clmirn, N.Y.) The Times Picayune (New Orleans) Thu Times Union (Albany. N.Y.) Washington Pout
MagazI ncs
American Home FeeuhLuiC Hoard's Dairyman Mfo Newsweek Playlioy Saturday Review Science ' Successful Panning Sunset U.S. News t. Wurld Report
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7 9 34 10 25 >29 10 10 11 20 7 9 11 15
21 10 29 30 20 23 >-11 18 16 14 10 19 26 14 20 21 20
8 25 12
28 >20
23 20 23 25 23 18 17 25 17
90
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Ml nco 11 iinroun product
Brown cardboard Hvown paper towels Brown paper bop,n (mloccIlnncous sourceo) - 7 Columbln-Minnonrlan, Newsprint
block Ink without Ink colored Ink Computer Taper Gray cardboard Sollwi floe (purified woodcellulose) W.-ndi. Stale Univ. Ililltoplcs
26 15 >6 -^20
25 >20
18 >22 19
23 >21
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resulting solution was analyzed by gas chromatography lining nn
electron affinity and an electrolytic conductivity detector in
the chlorine mode. The column was 6 feet long, pocked with 107, PC-700 on Ga3-Chroiu Q and operated at 200C. Selected paperii were also Bpecitlcally analyzed for the presence of polychlori nated Mphenyl compounds (nee Flg.ure 1) using adaptations oi the puh 11 idled procedurcn (CHANT et al. 1971; SNYP!:i! ami HP. INERT 1971) involving sulfuric acid partitioning and column chromatography on oil lea pet followed by electron affinity gas chromatography, A Pcrkln-K liner Model 270 and a Flnnignn Model 1013 ipiadrnpole pas chromatograph-mass spectromctor were also used in analysis for these compoundn. Following dry ashing oi the paper at 900C certain of the papers were also analyzed for metal content by spark source, mass spectrometry using a Model M.9-7 (Associated Electrical Industries) Instrument with silver as an internal
standard.
Results and Discussion
Table 1 Hats ihe number of peaks observed in tlie various p.iper samples by electron affinity gas cluomaLo,graphic analysis. ''Greater than" a ccrlain number of peaks are indicated when a cluster oi them could not be separated. Response by electrolytic conductivity detection indicated Lhe presence of chlorine-containing compounds in these came paper samples. Since these compounds were, extracted with hexane, It would Indicate that they are fat soluble and therefore would be of concern if they entered onlmaL or human foods. The peaks eluted Had retention times up to about 25 minutes. The specific retention times of many of the peaks were Identical from one paper sample to another and elso identical with various of the isomers found in the polychlorinated bi phenyls (1292, 1298, 1239 and 1260) which were concurrently chromatographed. Rased on the comparative detector responses of the compounds in the papers surveyed to those of known quantities of I'CR standards the papers contained from about 2 to 90 ppm (as equivalent PCIf's) of these con t ami nan t s.
Table 2 lists analysis of several papers for various elements. The precision of the method Is about -307.. The samples of Ithaca Journal and buffalo Evening News were black and white while Parade magazine was both black and white and colored. 'Hie high levels of certain elements such as antimony, lead and barium In the Parade Magazine paper is noteworthy from a toxicologic standpoint. The presence of lead in the cardboards in substantial concentrations would indicate that it survives the process of regeneration of paper into cardboard. The concentrations of boron and gallium shown may be low owing to possible vaporization losses during, sample ashing. Although not listed in Table 2, silicon and oodluin were, also found as major elements in the papers.
Figure 1 chows chromatograms of computer paper (the injected volume of extract represented 7.8 milligrams of paper) and 3 nano gram;) of the I'CR, Aroclor 1260, The paper sample, was analyzed by cleft run affinity pan chromatography following preliminary separa tion procedures (GRANT et nl. 1971; SNYDER and REINERT 1971)
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TABLli 2
Sc lectcd elements In varlouo papers
l (ppm by weight)
( Buf fn lo
11 linen Evening Pa riuto
Cray
Broun
Cninpii i 0 r
]
JoninaI flews
Mafia 7.1 nn Cardboard Cardboard J'OIH'V
1B
260
3.6
31
550
900
25
i >'r, 960
1 A1 (1.3,000
1K
26
600 500 760
920 530 1800
4800 27,000
330
940 2000
40
400 75,0C0
1)00
Ca 6600
1000
3900
4300
1900
890
' TI 1000
36
250 620 300
3700
v
3.7
0.58
2.7
5.2
0. 15
29
Cr 19
6.0
25
60
3.2
50
Hn no
190
220
98 120
8.3
Fc 250
200
100 45
70
1100
Co 0.7 0. 16
0.52
1.2
3.2
2.5
Nl
3.3
1.7
0.45
4.5
130
14
Cu 15
8.6
9.0 25
5.2
2. 1
Zn no
150
86 690
8.0
9.5
Ca
3. 1
0.3
1.0 3.2
1.5
31
Co
0. 10
0.02
0.27
0. 12
0. 11
0.05
A9
0.10
0.02
0.11
0.22
0.04
0. 1
Kb
0.61
2.4
1.5
0.30
0.64
3.3
Sr 1.4 0.78
4.3
19
9.6 11
Zr
0.56
0.05
0.60
0.57
0.92
13
Y
0.11
0.01
0.12
0.06
0.006
0.089
Sb
0.1
0.29
6.5
0.01
0.24
0.2
Da 15
4.6
2.3
0.18
6.6
1.5
Cc
0.21
0.03
0.45
15
0.01
0.21
I-a
0.26
0.04
0.23
0.01
0.01
0.12
I'b 10
5.0 ieo
8.3
3.3
0.02
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mentioned earlier specifically de a ignod to isolate PCR'c. It io
obvlnun that several ot the peaks in the sample of computer paper
are (similar in retention time to those of Aroclor 1260, Other
earlier eluting peaks In the computer paper sample correspond in
retention time to those in ga n eh roma t oprams to f Aroclor 1266.
Extracts of grey cardboard were subjected -to thin layer cliromdtop.raphy on alumina and eluted with heptane. The itf value of the
spot: developed with silver nitrate also corresponded to Aroclor 12 Vs.
Cray cardl-oard is n composite. o regenerated papers from many
sources. 1-oglcally, then, ft In more apt to contain I'Cll's and
>
/ other foreign coinpouiids. Jt was decided to use pan chromntop.rnphy
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m\d mass spec t rome ( ry for verification of the presence of VCR' n in (;ray cardboard and computer paper. Roth a Terkin Elmer Model
( 2/0 and a Finnignn Model 101,'i ipiadrapolo p.as ehroMnlop.rnph-mans
1 spectrometer and computer system were employed. Samples were I extracted and possible VCR's were isolated by adaptations of
I published procedures (PESTICIDE ANALYTICAL MAMMAL 1971). Complete
inasa spectra were obtained at approximately 3 second intervals oh (.as t h romi t opraph i e effluents. evidence for the presence of VCR's
was indicated by the appearance ot isotopic chlorine clusters ot
I the appropriate, manses lor l'CR-typo compounds. To further enhance sensitivity selective monitor lop, of the specific VCR chlorine mans
clusters wan performed and the presence of VCR's was again indicated.
The existence of other chlorinated components was evidenced by tbe
appearance of chlorine clusters at masses not corresponding to
VCR's. It io possible that other chlorinated aromntic compounds
uucli n the chlorinated naphthalenes (ARMOUR and BURKE 1971) would
nloo he isolated by the procedure (PESTICIDE ANALYTICAL MANUAL 1971),
From the preliminary analysis of paper presented here it is obviouo
that there is a need for caution and further investigation when
I paper is regenerated for use in food containers or os proposed for I line no a cellulose suhatltute in animal feedo.
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I Acknowledgements
The. nuthoro thank Corning Glass Works for allowing use of their spark source maos apeclrometer. The gas chromatographic maos cipcctroaictrlc analysis was in part facilitated by the National Institutes oi Health sponsored Cornell high resolution mass opccLrometry fnrlHty UK-00355.
References
ANONYMOUS: "Polychlorinated Riphcnylo, Application Uighlightn" 7.A,
1 (1972) Waters Associates Inc., Fountain St., Framingham, Maas.
ARMOUR, J, A. and J, A. BURKE: J.A.O.A.C. 56, 175 (1971).
GRANT, 1), L. , PHILLIPS, W, F-. J. and D. C. V1LLENEUVE: Bull. Environ.
Contain. Toxicol. G, 102 (19/1).
LEVI, 1. ami T. W. NOW1CKI: Bull. Environ, Contain. Toxicol. 2* 133
(1972).
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MAWPA, V., KM'AWA, R. mid H. KURATSUNK: Nature 37, '1 (1972).
MEIU'EHS, !). R., CAM'liF.l.L, J.. It., MART?,, F. a. mid E. S. llll.DKR-
RRANP: J, Dairy Set. 56, 667 (1971).
,
HKRTENS, I). R., MAJRTZ, F. A. nml J. R. CAMPDELl.i J. Dairy Scl. Vi, 93) 0971).
Ill Sill MUTA, .1. F. , SHERROD, L, I). , FURR, R. D. nml K. R. HANSEN:
J. An. 6c1. 20, 662 (1969).
PESTICIDE ANALYTICAL MANUAI,: Vc>l. 1, Si-clloim 211. 16n, 211.161)
mid 211.16(1. l/,S, Dept. Ilcnltli, Education 6 Welfare, rood nml
Pnif; Admlnlnlration, Washington, D, C. revised 1971.,
ROD 1.NS0M, W, 0, , MASIRON, II. and K. J. MIJRATA: Gcochlm. Conmochlm,
Acta J6, 65 (1950).
SNYDER, D, nml R, REINERT: Hull. Environ. Com. am. Toxicol. 6,
305 (1971).
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