Document 2JenVrKbog3VYyzvMk5VbmdZ6
Copyr'i *. 1973
I
C E l 'i " r ; / r V Vol. 13 . No. 3 . December 1973
A M ibsidin ry of
New England Nacdear
A t'iu ilir U ci'io n n l h u h ortilory. !\tilinnal lir s r a r r li C .ininril o f Canntla. H a lifa x , A o rn S cu lia AM)
I{ulgcr8u'crkcy Cuttrop-Hunxel, Germany
Jn recent years there has been increasing concern about the possible harmful effects of organic compounds in the environment. An important class of pollutants are the polycyclic aromatic hydrocarbons (PAH) which have been shown to occur in air, water and food (see Table 1) via automobile and engine exhausts, the burning of fossil fuels, oil spills, food processing, tobacco smoking, and from natural sources. Moreover several PAH have been shown to possess carcinogenic (1-4) and mutagenic (5, 6 ) properties. This review is designed as an introduction to the general literature on PAI1 with particular emphasis on environmental analysis of these compounds.
. \ l `\ l i : v I.AJ 1 !
Although several systems of nomenclature for polycyclic aromatic hydrocarbons have coexisted in the past (7, 8) the 1UPAC system (9) is becoming generally accepted now.
Common names for the basic ring systems are retained (see Fig. 1 on page 2). For the construction of more highly condensed aromatic hydrocarbons the basic system is lettered (a, b, c, etc., (see Fig. 2 on page 3) and the "added" rings numbered in the fashion shown in Pig. 2.
IN THIS ISSUE
Article, Polycyclic Aromatic
Hydrocarbons .......................... 1-11
Polynuclear Hydrocarbon
Standards .................................. 12-13
Article, The Solubilities of
Twenty-one Chlorobiphcnyls
in Water ............
14-10
Article, Progress Reports on
PCB Isomers ............. 10-19
PCH Isomers, 99% P u re ............. 20
Polyurcthnn Foam Plug*
PCI! and Pesticide Extraction
21
IVrclilorlnatlon Kits for Analysis of
Polvchlnrinnted Aromatics ...... 21
Polychlorinated Diphenyl Mixtures,
Dilrenzo-P-Dioxins and
DiDenzoFurans ................. .... 22
Pesticide Standards
23-30
Precoated TLC Plates
.. 30
Pesticide Solvents .............
31
Pollution Standards, Catalog
32
JJ-:\t IONS A M ) R E A C T IV IT Y
The standard reference books on the chemistry of polycyclic hydrocarbons are Clar's two volumes ( 10) and chemicoltcelmicnl aspects of diphenyl and the terphcnyls arc discussed in an encyclopedia article (11). The analysis of FAll Iras been reviewed ( 12).
Most polycyclic hydrocarbons undergo the typical substitution reactions which nro known from the parent compound, benzene.
In addition, many of the polycyclic hydro carbons show a tendency for addition re actions (cf. Fig. 3 on page 3) ("fixed double bonds").
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"J1it* reactivity oJ jrolycyclie hydrocarbons towards addition reactions can be (wplaiiicd and predicted qualitatively by O a r's * -sc.vtett theory (13. M ). A rjuantmn mechanical explanation of O ar's theory lias l>ccn given (15. 16).
The stability oi polycyclic aromatic hydrocarbons depends on the structure as well as on the numlrcr of rings. 1lesalrcn/.woronenc (Fig. 4) for example is an extremely
2 NEV 0 3 6 8 4 4
i
J
i
Bcnzo [a] pyrene in city air (meg/ 1000 m ')
Los Angeles .....................................................................................
5
London ........................................................................................................... 63
Bonn .............................................................................................................. 133
Benzo (a] pyrene in food (m eg/kg) Vegetables .......................................................................................... Smoked foods .......................................................................................
10 1-10
Carcinogenic Polycyclic Hydrocarbons In waiter (m eg/m 3) G roundw ater................................................................................... Waste water ..................................................................................
1*10 100,000
Benzo [a] pyrene In cigarette smoke 1 meg in the smoke of 40 cigarettes
Adapted from M. Zander, "Analysis of Polycyclic Aromatics" presented at the "Third Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants," Athens, Ga., May 1973.
nophtho [ 2,1-a ] onthracsn* Fig. 2. Nomenclature for more highly condensed ring systems.
Fig. 3. Examples for addition reactions occurring with PAH.
Fig. 5. Heptacene ring system.
F ig . 4 . Hexabenzcoronene ring system.
stable hydrocarbon; even at 700CC neither decomposition nor melting takes place.
Heptacene (Fig. 5) on the other hand, is extremely unstable with a reactivity that
surpasses many free radiculs.
The photochemical stability of a number of PAH has been investigated (17); the
literature on the photodecomposition of the carcinogen benzo [a] pyrene is discussed
in reference (18).
3
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I'All occur n.iliir.ilK' in petroleum and arc also m uIL, i/ cu !\ living organisms
stuli as highci )'>l.u11s. algae and niicmorgancn.s \ i I. IS. I!);.
r Ml in' toimcd as p\ml\s)<. products at high Oinpciatmes {20-2?) and can. there
fore. I< loiiiul in coal t.n. automobile exhaust. in emission hum hiill um: fossil furls
I haeeo smoke.
\ pai' l. studs ng p,nlisnla'v p . s c \cIK lit.mi m .it'ii 'i'ONJ concluded r-t enth
!' nation-wide cinimssiiin o* l>rn /t< |a | p\s 11 * in tin l S . i,owi.t I i. -is
f !..: and |v,-\< i *rn< lalinn. (>''* 1rs fimii i'.*fM"* I'timat" n- n ns ii. - m l,-
. i: i 1 ' liii' I*' ini :iin*i v ' 11**% i .? Ai
i. ; ;li * l `.\ll *s aim * i.r\
.
.
; . * ... ** J l J' i:i *p.*i l :;*.I\
a. . ' )i< I. in-.i. n:i,r ir i iiliK. hi. 'Vi, o a: !;i eo.l ,i a:.!
a;:- I**? and dtsiilhcd Hi rcfei'UiM IG<* >2 .
In cans ul tin- direct iulaki in lainian mill 11 i . m uch v. .at. has bee., c a m e l .mi
In dc\c lop analyliral methods and d rlrn n in r levels >1 )*lyc\clic aromatic hydrocailioiis
in ikxIs (23, 33-I3). le vels arc highest in smoked Inods (occasionally values > Jl) ppm
total polycyclic hydrocarbon arc observed), whereas levels in unsmoked loud pioduels
are generally lower than 1 ppm.
A large number of polycyclic aromatic (including Irenzo fa | pyrene) and licleroaro-
m.itic hydrocarbons as well as related compounds have been identified in tobacco
smoke (41-16).
Polycyclic hydrocarlrons are also released into the environment from general oil
pollution and the ever-increasing oil spills (47, 48). Analytical methods for the
identification of hydrocarbon pollutants on seas and beaches are reviewed in reference
(49). The uptake and cfled ol oil (including the polycyclic aromatic hydrocarbons)
on marine life is of increasing concern (50-52).
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The extraction, separation (clean up) and analysis of I'A11 have been extensively
investigated (53-56) and a review article on chromatographic procedures gives a
useful comparison of the various methods (57).
As is general for the analysis of any trace component, the need is felt (97) for nn
extended collection of reference standards of polynuclear hydrocarbons and their alkyl
and hydro derivatives. The later type of derivatives is of great importance since it
is not ordinarily discovered by the conventional UV or fluorescence methods and is
best identified and measured by MS. The alkyl derivatives arc in many instances
more carcinogenic than the parent compound.
The carcinogenic PAH benzo [a] pyrene has understandably been studied in some
detail and a thorough comparison of the analytical methods used in the determination
of this compound from air particulates lias been reported by Sawicki (58). Analysis
of benzo [a] pyrene in cigarette smoke (59), air (60), bitumen and plants (61)
mid water and other commodities (62) has recently been described.
Thin layer and paper chromatography --TLC and paper chromatography lias been
used successfully for the separation of polycyclic hvdrocarlxins (57, 63). Cellulose,
.act viated cellulose and aluminum oxide (64) and silica arc the preferred layers. A
mciliiiiidl-cthcr-wutcr (4:4:1) mixture (65) has been recommended for acetylatcd
lelbilosc layers. A typical chromatogram employing this system is shown in Fig. 6. (66)
1apn i Iihiiii.ttngr.iphy on acdvlatcd paper lias Ihtii used for the chromatography of
l.Ml with solvents similar to the ILC separation >n acctslatcd cellulose powder (67).
l.leetimi acceptor reagents can lx- used to visualize l'AJl on paper and thin layer
i liioniatogiains. I be Ilydroenlimns can be reinsert'd urn banged from the characteristi
cally coloml clinigc transfer complexes (see section on mass spectrometry). The
native fluoiesccnee or phosphorescence of PAM. however, oilers a much more sensitise
method of detection (see section on luminescence spectroscopy).
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Two dimensional thin layer chromatogram. Layer: acetylated cellulose -- aluminum oxide, 1:2. Solvents: System I, n-hcxane, n-pentane, toluene (90:5:5). System II, methanol, ether, water 4:4:1: Compounds 1, dibenzo [a, e) pyrene; 2, dibenz [a, h] anthracene; 3, dibenz [a, c] anthracene; 4, perylene; 7, benzo [e] pyrene; 8, pyrene; 9, anthracene.
Liquid chromatography - The behavior of 18 polycyclic hydrocarbons on two column materials (Durnpak OPN and 40% cellulose acetate) were investigated using an ultraviolet detector (68). Although neither system could resolve all components of the mixture, the method was shown to be of potential utility. A number of polynuclear nza-heterocyclic hydrocarbons were separated by high pressure liquid chromatography using Zipax packing impregnated with silver ions (69) and a chemically bonded phase (70). Polycyclic aromatic hydrocarbons were also separated by liquid chromato graphy using Corasil 1 impregnated with the complexing reagent 2, 4, 7-trinitrofluorenone (7 1 ). A number of column packings have been compared in the separation of polynuclear hydrocarbons in engine oils (72).
Gas chromatography -- Ultraviolet absorption and luminescence analysis have dom inated the analysis of polycyclic hydrocarbons for some time, more recently gas chromatography has played an important role in the separation, detection and identifi cation of these compounds (57, 73-77).
The use of capillary gas chromatography with its great resolution potential has markedly increased the analytical potential of this technique. Application of capillary G. C. have been reported in the analysis of polycyclic aromatic hydrocarbons and related compounds in anthracene oil (78), cigarette smoke (45, 79), air and car exhaust (80, 81), soot samples (75) as well as for quantitative determinations (82). Gouw et al. (83) have shown that PAH can be separated effectively on short capillary columns (10 m ). A typical capillary column chromatogram is shown in Fig. 7 (see Tuble 2).
Ultraviolet spectroscopy - U.V. spectra of PAH show in the spectral range accessible by commercial instruments three electronic transitions which are differentiated by oscillator-strength polarisation and temperature dependency. The most intense bands in the U. V.-spectra of PAH nre the so-called p --or 'Bb-bands which show a molar extinction coefficient of ca. (10r ). The extinction coefficient for the para --or 'La-bands and the y --or `Lb*bnnds are ca. 104- 10r' and (10*- JO*) respectively. For analytical purposes, the para-bands are the most suitable.
U. V. spectra are usually recorded in liquid solution at room temperature. It is some times advantageous, to measure the U. V. spectra in a solid matrix at low temperatures, frequently the bands are more intense and very narrow (84).
5
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3li.i JJihenz | a. c] anthracene 30b Dilrcnz [a, li] anthracene 37 Heuzoletra phene 38a Henzo (g ,h , I) pcrylenc 3bb Pivenc 39 A nlhantlircne JO D ib cn zo [a, e] p y ren e 41 Curoncnc 42 Dibcnzo [a, o] pyrene 43 Dibcnzo | a, i] pyrene 44 Dibenzo [n, h] pyrene
(^uaiitilativc analysis of PAH by U. V. spectroscopy is possible after separation (r. g, bv TLC). Tor llu*. analysis in mixtures the qualitative composition most be known and a large number of key bands be measured. Mathematical treatment of data is usually done by computer (85). A collection of U. V. spectra including a large number of polycyclic compounds is available (80).
Fig. 7.
Clnonm Ingram nf a standard mixture of hydrocarbons. Glass capillary colum n co aled will) S lv o 2 . Linen) p ro g ram m e d te m p e ra tu re J 00-301 . ra te 1 .8 /in m . N um bers correspond to com pounds in T able 2.
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Fig. 8. Electronic spectra of phenanthrene. A. absorption (UV) spec*
tram (cyclohexane); F, fluorescence spectrum (benzene); P, phosphore scence spectrum (ethanol, isopentane, ether, 2;5:5; 77K).
!00 300 00 40) too
Luminescence spectroscopy --The fluorescence qunntum yield for most PAH is relatively high to make fluorimetry a very sensitive and therefore widely used analytical method for these compounds. (For spectra of polycyclic hydrocarbons see (87). Fluorescence of individual members of a mixture can be observed when their absorption spectrn differ and selective excitation wavelengths ore used (88).
Fluorescence spectra are usually recorded in solution at room temperature. Spectra obtained at low temperature in a suitable mnitrix ( n -alkanes, n -pentane to n -decane; cyclohexane)' frequently give very characteristic spectra showing many bands (ShpoVskiispeetra).
An interesting new technique is the so-called "quenchofluorimetry" (89) of multicomponent mixtures. This method is based on the fact that the fluorescence of some compounds Is quenched more than of others if a "quencher" is added to the mixture. PAH with the fluoranthene ring system (89; quencher: nitromethane) and perylene (90; quencher; methyl iodide) for instance can be determined in complex PAH mixtures by this method.
Phosphorescence spectra which are measured in solid solution at low temperatures usually show a higher selectivity than fluorescence spectra. Fig. 8 shows the U.V.-- fluorescence and phosphorescence speotrum of phenanlhrene. A comparison of U. V.-- fluorescence and phosphoresence spectroscopy is given in Table 3. For the analysis of PAH in the environment separation prior to analysis by U, V. or luminescence spectroscopy is necessary. The most commonly used combination is TLC fluorescence. Samples for quantitative analysis can either be eluted from the TLC plates or more elegantly determined by in sifw measurements (91).
Mass spectrometry--Mass spectrometric analysis plays an important role in the Identification of polycyclic aromatic hydrocarbons (92-98) and this technique is particularly useful in combination with gns chromatography. The combined CC-MS
TABLE 3
C o m p a ris o n ^ oX L:.V . flu o re s c e n c e a n d p h o s p h o re s c e n c e
sp ectro sco p y
Method
Selectivity
Sensitivity
Reproducibility
.V. Fluorescence Phosphorescence
+ ++ +++
+ + 4-+ 444-
+ H --b excellent
4-4-j- average
++ ++ ++
'Adapted from M. Zander, "Analysis of Polycyclic Aromatics" presented at the "third Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants,"
Athens, Co., May 1973
NEV 036849
: 69
*
n
4* "*T3T
Fig. 9. 70 eV mass spectmm of benzo [a] pyrene 9*cyanoinethylene-2, 4, 7-trinitroHuorene complex eluted from TLC at different sample tem peratures (as indicated); (a), benzo [a] pyrene (b).CNTNF.
technique (97) has been used in studies in which the identity of the observed gas chromatographic peaks has been confirmed by the characteristic mass spectra of the components.
PAH may be located on TLC plaites by the characteristic color they form with electron acceptor reagents. The complexes may be transferred directly to a mass spectrometer sample tube and individual spectra of the compounds be obtained by thermal dissociation and fractional sublimation in the ion source of a mass spectrometer (98). Mass spectra of benzo [a] pyrene and the complexing agent 9-dicyanomethylene2, 4. 7-trinitrofluorene obtained at different sample temperatures from the complex are shown In Fig. 9.
The mass spectra of most polycyclic aromatic hydrocarbons exhibit several common fragmentation pathways; i.e.i
1) The molecular ion Is usually the most abundant ionic species and this greatly facilitates the determination of the molecular formula of the hydrocarbon.
2) In addition* the M +-1. M t *2 and M t -8 species are also relatively intense, 3) Methyl substituted aromatic hydrocarbons exhibit M f -15 ions, 4) Doubly-charged ions are observed for most of the aforementioned ionic species. These characteristics indicate that mass spectrometry does not readily distinguish between isomeric polycycolic aromatic hydrocarbons since very few fragment Ions are produced and the molecular ion tends to dominate the spectra. This characteristic can, however, be an advantage with the GC-MS technique since the separation of many isomeric hydrocarbons can readily be effected by gas chromatography and the resulting mass spectra gives confirmation of the GG assignments. Infrared spectra --IR spectra ore useful for identifying alkyl derivatives of naphtha lene. IR spectra, do not, however, have any advantages over U.V. spectra in the identification of unsubstituted FAH, but are very useful in the structure determination
of new compounds (12).
Surftur
.v..:.!.';.. .>t-.
Proton magnetic resonance spectroscopy can be used for the identification of PAH
and their alkyl derivatives (12, 14). Experimental difficulties exist with the highly
condensed systems because of their low solubility.
220 MHz Proton magnetic resonance spectrum of benzo [a] pyrene has recently
been published (99) and C-13 NMR spectra of several simple condensed systems have
been recorded (100).
1'!! V, *
.
It is now generally accepted (101) that to be carcinogenic, polycyclic aromatic hydrocarbons undergo metabolic activation. Epoxides (102, 103) may be involved and reaction with nucleic acid components (99, 103, 104) have been suggested. The
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t. i.-.rii-. J!. \\ .. 1n 'if .'i- jj ,,it:! I'.i' '(`lifiii'sl; ' j | Annuali.- IJydmeal lions." KK-'iu. A.ii-'eliliiii). lilt*').
i. IVliluih. J... \V. I'laumi -.lini II. 1,, Falk, ''Chemical M utagens/' Academic I'leys, .Now York. 11)7b, jx 275.
(>. Miller, lx (.*, anil J. A. Miller, in "Chemical Mutagens" (A. 1lulhiendcr, Editor) N*il. 1. Plenum Press, New Yurk. JU7J, p. JU5.
T. Stel/m-r. B. ami Kuh, Lil. lleg. Org. Chem. 3, 21 (J9 2 J). N J`attri stili, A. M., J. Ainer. Cileni. So;*. -17, 543 (J925). 9. U PA C-. Hides JU57. Di. d a r, I-;., "Polycyclic llvdrucarbons/' \ 'ol, 1 and 2, Academic Press, London
(PJO-J).
11. J'olleiilirigi-r. .\. mid II. L. Hubbard, `'Diphenyl and Tcrphenyls" in Encyclopedia ul Chemical Technology'' Yol. 7, p. 191.
1-. Zander, M. "tsolirrung und hlenlifiziertmg von nroinalisehen KolilcnwasstTstofTcn." in. "Mellnleu dcr orgai lische Chcmie/' Thienie, Stuttgart, in press,
l x Zander. M,, Augew. Chem. 72, 5J3 (I9 6 0 ). 14. C.'lar. K,, "'Jlie Arumatie Scxtcll/' J. Wiley,' London, J972.
15. Polamky, O. E. and G. Derllinifer, ln(. ]. Quantum Chem. J, 379 (J9G7). Hi. Zander, M., Ann. Chem. 723, 27 (1909).
L . Kiuatsnne. M., and T. Hirohnla, in "Analysis of Carcinogenic Air Pollutants/' (E. SawJcki, Editor), National Cancer Institute Monograph No. 9, Washington, 1962, p. 117.
IS. Amlclniun,' J. It. and M. J. Suess, "The Photodeeomposilion of 3, 4-Benzpyrcnc
suiIh'iI on Calcium Carbonate" in, "Organic compounds In Atjualic Environments" (S. D. Faust and J. V. Hunter, Editors), Marcel Dckker, New York, JU71, p. 439. 19. Slcnbiiig, L., Angew, Hot. 45, I (J9 7 J). 2(1. Badger, G. M.. U,oc. boy. S'oe. 87 (J956). 21. Badger, C. M.. Symposium on the Analysis of Carcinogenic Air Pollutants, Ciueiuiiali. Ohio, August, 1961. 22- Ling. K, ]*.. It. lbilllrb ami M. Zander, Krdoel Kolile 16, 944 (1963),
23. Anna., Chem, Foe. News Sept. IS. 11)72. p. 17. 2l. Heltelie. II. () ..'hehriMenr. tier Laiidrs.mstuU fur Immissitms -
zuiigssehul/ ties Landes Nordihcin-WeMlalrn 12, 92 (1968). 5- SiMieki. K., Ai eh. la .ben. llrah b . 1J, 46 (1967). * Alum.. Cileni. Kmr. News Sept. IS, J972. p. 17.
und Bodcmmt-
J. Air W .il. J'otl. 9. 515 ( 1965) .GImIuI, :.. M. C.islegn.uu/J. Buche ami H. Ftmtunges. Clirom:ilngraphta, 3, 5U7 (JU70).
9 NEV 0 3 6 8 5 1
Cl
2S. Romei). Jj. Cu.* - miti Wasscrfach. ] OS, Ji72 (1907).
30. Il- ( 'n;i1 Tur JIi'vi.imIi Assnriuliun, `T h e Ct;d Tnr Data Hook." 1033. 31. Ki libri. J).. A. larjlhr! and S. G igulrii. FnSol, Laide. S, 637 { 1035).
JJ. 1 mg. K . ). tini 1. Migri t. l 'n il* c l:i. C lim i. Marvch. S, 9 J (UC>7 ; . 33. Criminer. e:.. Mrtul Kalile IO. 57S ili'OO). -i l. tan n ilir. I'. \. .uni I . Iliv/elli. Iti .hit- Iv.v. 0. 00 (1065).
3 r>. Ih m ani. J. W.. It. I !t ,;giie Jr.. 11. M. W],:u aliti li. li. Firy. Jr., J. Assoe. Oli.
(.Iteli;. -IO. "05 t l'ifiii ,
;!*. 1!... ..Ml. j. W.. 1:. 11. Wj,iU |>. K. J;n \ (.. .nul J-', W. TiinYr!!:I, (, Avmx\ 1. ( .linn. !a. M i i 1'!(.*() i.
3, 15-- 1 : !.. i : *:. A-.*. Hyp. JO-.-* ` !Vi. !*" . - .
. i
C . . i . J. 1
I y A i ' t i .i, ; ! ; i :,
V. V.-
I i.l
' ! '.. \ . I , i - *U:.\: r... : 11 . F ; r \
: * . . ! li
- r.i/it*. |. A ;i. 1`a:;.: (
17, 5-7 1 *
11. ! *1 D. 1- . II. 1>au:i. loiihie Ke\. 27, `9 (1909).
u. (
A. Ililtiiiji.niil!. |. A.vstx\ Oil. Anal. Chem. 53, 631 (J972).
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54. Sawicki, 15., CUC CriUcal Rev. Anal, Cliein. 275 (1970).
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50. Dubois, L., Corkery, A. and Monkman, J. 1*, Ini. J. Air Poll. 2, 236 (1960).
57. Schaad, R. E., Chroma tog. Rev. 13, 61 (1970).
58. Sawicki, E., T, \Y. SUmley, W. C. Elbert, j. Meeker and S. McPherson, Atmosph. Environ. 1. 131 (1967). -
59. Davis, H. J., Anal. Chem. 40, 1583 (1968). 60. Strombcrg, L. E. nml G. Widmurk, J. Chromalog, 49, 340, (1970).
01. Scliamp, N. and F. van Wassenhove, J. Chromalog. 69, 421 (1972). 02. Sfddlql, 1, nml K. 11. Wagner, Chemospbere, 83, (1972). 03. Sawicki, C, R. and E. Sawicki, "Thin Layer Chromatography in Air Pollution
Research" in Progcss in Thin Layer Chromatography and Related Methods, A. Xicdcrwiescr and G. Pataki (Editors) Vol. Ill, Ann Arbor Science Publishers, Ann Arbor, J972, p. 233. 04. Sawicki, E., T. W . Stanley, W. C. Elbert, awl J. D. Pfaff, Anal. Cliem. 30, 497
(1904). 05. W ielam l. T li., C . L u b en , ami II. D o ten n u n n , E x ponent in 18. 432 (1 9 6 2 ). 00. Kolder. M., C.uldcr. 11. and ScInVsser. R., Z Anal. Cliem. 206, 430 (1964). 07. Wielaml. 'J'Ji., and W. Krucht, Angew. Chem. 69, 172 (1957). OS. J\e*. N. F. ami J.. Cmflnda, J. Ass. Olfic. Anal. Cliem. 55, 757 (1972). 09. Yivilecchiu, Jt., M. Tliiebaml ami H. W. Frci.J. Chrunmtog. Sei.TO. 411 (1972). 7(1. Ray, S. and R. W. Frei, J, Chromalog. 7J. 451 (1972). 7J. Larger, IJ. 1.., M. Marlin, j. Lohcuc and J. Gunchon, Anal. Chem. 45, 490 (1973).
10
NEV 036652
\ . t . :. < ' I. U. and K , I .p i. Environ. S ii. T u Inni'. 1. >2::
r.
New ^ml., i liJii')1.
s s - S.n-.iVki. I*... T. U, llauw r, u. T. \V. Stanley. l.itrr. J, Air Pollution 2. 253 (I960). s.iwii-U. K., T. W. Manley, u. \V. C. Elbert, Tahu ita J j. J-13*3 (1964).
9U. "/jit. Ut , M., / . tuul. Chon. 203, 19 {1973). i)l. S.iuicki. anti J. 1). IMafl, Anal, Chini. Acta 32, 52J (1965). 9~ M.ijc-r, J. H.. lVrry. . ami cadi*. M. J., J. Chrom., 48,326 (1U70). bJ- lam. 1!. ('.. Thomas. H. S,, Montanan, J. 1. and Puttie, . Symposium un the
Jilnililiaation and Measurement of' Environmental Pollutants, .National Hesearch ( `t'limil. Ottawa, Canada, 144 (197J). *Jl. lVu\. It.. Symposium on the Identification and Measurement of Environmental Pullula)?, National Research Couneil, Ottawa, Canada, J30 (1971), Ua. |,,m. ];. c., Thomas, H.S. and Montanan, J. L., Intern. J. Environ. Anal. Chum., J, 1ST 0 9 7 2 ). !,i> Sale, S.. and O. 11utzingcr, "Mass Spectrometry of Pesticides and Pollutants" CJU.' press, Cleveland, in press,
w*. *';t0*K* C., Thomas, H. S., Oja, H. and Duhois, L., Anal. Cliem. 45, 908 (1973), llutzinger, O., and S. Safe, unpublished data.
W. Cavalieri, E. ami M. Calvin, Prue. Nat. Acad. Sci. USA, 08,1251 (1971). Hl. Sluthers, J. Ih, "Carhon-13 NMR Spectroscopy," Academic Press, New York,
!b"2, p. 90.
}J* N5illt>r- J- A., Cancer lies. 30, 559 (1970). -- Selkirk, J. K., E. Huberman and C. Hicdclbcrger, Diochem. Biophys. Res, Commun. 43, 1010 (1971).
inj G.t0VVr*P- L ' rtnd p *Sims*Bioclicm, J. 129, 4 IP, (1972).
in* ^*1,Va^*erh lb and M, Calvin, Photoeliem. Phot ninni. 14, 641 (1971).
Inn* \ ll*p ' A .,/. Naturici.st-li. 27b, 731 and 650 (1972).
In- ^'^Itlnu-istcr, A., D. Tsai and X. D. Weiner, J. Pharm. Pharmacol. 01, 1065 (1972).
< Johnson, M .|). am! Calvi. M.. Nature, 2 4 , 271 ( 1973).
Wilhums, It. T., *'J)elmicatiiin Mediunisms" Chapman is Hall, Lnudon, ( 1959).
,l l! * D .lU
\\f
l v V i . ..
. . . . . . . . . . . ,*
.
, i n n 1 - l i v n v
(1972).
JM J ,,IIS* P*. RiiH'hem. J. 130, 27 (1972). S',,,s* P*. Biocliem. J. 131, 405 (1973).
11
036853 NV
h\i!' ,: Ji\ ; i***c 1\ , \ ' g
/'l.ii/l.Ci
\i t naphtlivnv uiulii.i*
I.i : . .. * 1
J ' . : ! : Sl/IKlIJI/JII
: . i-V Hi*
*-** i . i in . !*>!/ Ci] . ''In.r.ii-:. -7. j.'-
J o 1J'*is
i>,.
jV
. S', i ;! i
i, J-J'.' II.'I'lNU.iti. Ill
1.2- Hi
1;}ll lit -
*.. `h fp!;-tvm'
.Mi-Uvnz.u lb J carlinzn)f' Sn- 2. 3-Jlvil/tH`ill'll.lZ.l'lv
HXIHUO HXlUHft 11X11031 HXJ1032 -- -- KX11033 -- 11X11000
11X11010 HCSOOl iix ijo n J`Ml 1012 HN1I013 UX11010
n x iio ir
HXHOlS
__ -- -- --
11X11019
11X11020
r*c:sofi7 HCS070 11X1102J K \ 1101.1 11MI015
11X11022 --
J>iii70 Inj Dimr.iJitlmu* IW-iizo ig. li, ij lliitu'.iiiOii'm1. 2-Heii/tiIlimri,m*
.j-llrii/.iiiliuifi iii' Hen/ p.h.i, ( pi), pvrylvm.* 1, 12-lieiizupvr> Ivne !J, JO Hi-jizoitlii-M.Mtllircm* Jlriizn Ini pyrene 3, -Mlcn/ipyrene ij, O.Hi'nz.oijiJimtlim.'
Jii jizu Hi ijuinulfm* 1, l-liinuphthyl Jiiplieny] Carla)zoic Chrysene Cmunono
1, 2,3,4Dil>eii2anlhraccne 1,2,5,0bibcnzanthraccnc 1,2 7,8Dibriiznnthruccnc Dibenz In, t*l anthracene Dilwinz lu, h] anthracene Dihenz (n, j] anthracene
1, iS-Denzopcrylenc See llviizn lg, li,iJ I'erylenc Si r Triphciiylcnc 3 ,4-llvnziipyrcnc Sit. Denz.n La] pyrene Uvnzn Ifj quinoline ut ( i -Xnphlhoqmnolitic Set*5, (i-UvnzoqiunoHiiv
Dinrnz. (a, cJ Anthracene 1>ibenz la, h] Anthracene
Dihvuz la, jl anthracene See 1, Q, 3, 4-Ditwnxanllirnccnc Svv 1, 2 ,5 ,6-Dibcnzantliraccne See 1,2,7, 8-lXbenxnnthracene
2.3,5,6Ililieti/.fluunuitlienc
3, 4, 5, 61)ilu'iiziii-.irl>4i/.(>]e. 1)ilicirz.n.ji-cli(i\in
I>i}rt-iiznliiraii
1. 2. -I. 5-1iiWir/.ipyrene
I)i[ilirn> Ivllt'MllIilli*
1.2,6, 0IIjtiiii/peiitiKTiie !). lO-Diliyiliiiatilltiiiifin'
| b, 15-1)ihyilni~M1-1Jiinilrno Sit TrnNVlu* il.2 a -r,2 V J Vliitin'itr
12
Mill.
Purity
oo;;.
!W*; pi
1`iivc
7.n0/100mg 14.00/IUOihr 45.00/JOiiig 7.00/1 Mon* 10.00.H'me T.tHMOrai* ).;n:i >i : ;
il.SC 7.00/JUOnn;
!J.V,r 14.00/Wing 'M'fo 12.00/1(Klmg
13.00/1 (Wing ny/<- J7.00/J00mg yy% IO.OO/lOmg wr/o 10.(K)/10nifi m r/o lO.OO/lOing
u s e 17.00/10(lni8
ou%> 10.00/lQQing
5% 10.00/100(118 W95t 7,(10/500mg m% 7.00/100n>g 09% 14.00/100mg use 18.00/lOmg
lO.OO/lOmg
99% 7,00/lOmg
955b 12.00/Wing
" 98% 14.00/Wmg
05% 8.00/lGiug
0!)% 15.00/50WK 0% 7.00/5lH)mg o se 17.00/1001118 (10% 7.00/1(K)iii8 00% 14.00/Wmg
00% 17.(m/100mg
NEV 036854
J 'o ly m u lra r
TT\I> o i-ar!jci"
Si .'tjK lan
ti I'ttnluct
Aiin. P u rity Trice
hMlHM Djiinh'im 11,2,3-cd-l', 2', IVriilanlhene J'-JwJ J'erylenu
<j H% y.oo/ioorog
I,M1024 3. (i*J)imrlhylpIicmti>lbrem!
II.MIU25 0, Ifi-Oililn iiylunlJiiatme
-- 1liplicivli-ncMillide
See Diiien/.tilliioplK'iu*
09% 7.09/10ing 90% 7.00/UHJmj;
liMtl* fi 1i.:;!tt.il.>(!i'itrfplu,n>lene MUM 1'll . av
I, 2. -1. 5.Telriiinetli>]lit>nzene
90% 7.00/lOiyniji o.n% 7.00/1 IHhm*
`-Il0.il I
lie
00% 7.00/IOOiiiR
. !:i.i;cik*
XJK'jff lit xani-. t)^JU*n/vnt* Iiidi'tin J, 2,3-edJ pyrene
See ii-1'In m lempyrriie
99%..,, 14.00/1 WhtiR 00% 7.00/lOthtig
JAI
KNJIlUJ HMI0J2 1IM1013 HM1014 HX11045 KX11040
9(3072
HX11U47 UM1048
9X11040 HX1I050 HXU051 HXH052 HXH0S3 HNH054 HXJI0S5 NH056 KXU057 KXH058 HX'HOSQ BCS030 HCSOoo HCSOOl ftXHoeo HXHOOl
2-Milli>I:mtlirneene
.* yy% 8.00/1Wing
*!NKlhylaiilhracvne "
99.99% 14.00/100mg
.(-Mvlhjl Biphenyl * ' ,r*' .J-ThfHiUuhu'm' . I,S-MeUiylenephcnimOircne
V% 99%
lO.OO/lUOiiig 19.00/HMmg
2- MelhylIhujre J-Mvthylplicnnntliremj
05% 7.00/1 OOnrg m% 7.00/100mg
2*Methyl plifiianllm-ne
99% 7.00/lU0mg
3-Methyl phenanlhrem! Xaphlluiccnu
See Tetraccne
95%. 7.00/I00m g
Naphthalene fi -Xaphtluxiuinolma
See 5, &-Ik-it<etK|iiim>line
99% ">
7.00/500m g
(Miideeahydroehrysene
. 95%, 14.00/I00nig
I'cntaccfu! iViiilitnUtcne
) 98% See Diindeno U, 2, 3-cd-l', 2', 3'-
18.00/lQtng
inu perylenc
iVrylwMJ
99%, 14.00/100nig
J'Jicnanlhrenc
` 99%, 7.00/100mg
riivnuuthruncqulnene
\ ,` *
95% 14.00/lW m g
9*Theny)anlliracene a-l'livn)lenepyrene'
Iiidcnu 11,2,3-cdJ pyrene
; 93% 99%
14.00/1 oOmg. 7.00/10m g
2-rhcnylnuphtltaIene M'hunyltoluene .
-J ' ' 4-Melhyl biphenyl
99% 19.00/lOOnig 99%,
l'ittne
12.00/lOOing
Tyrone
99% 7.00/100mg
p-Quaterphenyl
-.v
! 98% 14.00/lOmg
in*Quini|ucphenyl , o-Tcrplicnyl iii-Terpcnyl
p-Tcrphcnyl
*t*\** :
:.V *
-
95% '99% 99% :99%
32.Q0/10mg 7.00/100m g 7,00/100m g 7.00/100m g
'lVlrncene
Xaphtacene
99% 14.00/lOmg
Tclradecabydrophenanittrone
:%
:05% 18.00/100rog
1.2.3.41 elrahydrofluoranthcno
f^ .
99% lS.OO/lOOing
1.2.4. BluUnmelhylbcnzeno
See Durcne
[,-\'U0G3
Tvtnipheno 1. 2. 3. 4-
Tetruphenylnuphtbnlenu
See 1,2-Jlenzanlhrnccnc
07% 7.00/lOOmg
tX'IKiOS ^MlOOO
Triphenylene 'Irtplycenc
'l'i nsenu
9, 10-Bt`n?.p]nun111relie
JJ, lO-o-Henzeno-9,lO-diliydroulithraerno JO, lS-Pilnilrn-SH-diindeno 11,2-n 1*. 2',-cl flutirene
ut>% 05%
10.00/1 Oh.k 18.00/lQmg
14.00/100mg
13 NEV 036855
v i r . NvN i w w . n ie s o r r . ; v : v o \ i a w in y n a w
1*. K . W allno fcr, M . Koniger
J)ayi')iM`lic Lundcsanslnh Ini' D o d cn k u ltu r and l 'fltin/,i'nb;Mi, Munchi'i), G n i u a n v
iiml O. Hill/in per
AllmLk- lit-yinii.il I ,.ilii ntitnry, National R c m \ ! u ,! i C'<>uiicil of ('mao.-.. Halifax, Nova Scotia, Cau-id.i
l'Cli preparations consist oi complicated mixtures ol chlnn .biphenyls with dillerent chloiinc content anti their isomers. The comjwstlmn uf thesi" technical products lias only recently been established
A knowledge of the solubilities of PCB components is necessary for experiments involving individual isomers and may also he useful for the evaluation of PCB distribution in natural waters. . Considerable .differences in the solubilities of chlorobuphenyls with different numbers of chlorination ns welt as positional isomers were indicated by change in the GC peak pattern of Aroelor 1254 re-extracted from aqueous solutions with hexane1 Solubilities of five mono-nnd dichlorobiphenyls also vary widely".
We wish to present the results of our study on the solubilities of twenty-ono chloiobiphenyls in water. Most of the compounds investigated are majur components of commercial PCB preparations. Since water soluble humic substances were recently reported to act as carriers for lipopbylic compounds including pollutants0*10 the solubility of 4, 4'-dfchlurobipheuyl in aqueous extracts of humic acid was also measured. The solubility of this compound was also determined in the presence of different con centrations of Tween 80. Aroelor preparations have an Increased solubility in water in the presence of solubilizers11 and the presence of the biologically relatively inert Tween 80 (e.g. 2% Tween 80 in nutrient solution showed no measurable growth inhibition in n number of microorganisms ,a) may allow the use of higher concentrations of . chlorobiphenyl in many experiments. *
EXPERIMENTAL
Imtntmentatlon. Gas chromatography (GC) was carried out on a Varian 1800 instrument using' a ' glass column (5 ft. x 2 mm i.d.) packed .with 1.5% XE-60 on Anakrom Q operated at temperatures of 160-190C depending on the compound. Carrier gas was nitrogen at a flow rate of 30 ml/min. Injector and electron capture detector were kept at 220C.
Chemicals. Chloroblphenyls (99% pure) were either Syntherized or obtained from Analaks Inc. (North Haven, Conn., U.S.A.). Humic acid was purchased from Aldrich Chcm. Co. (Milwaukee, Wise., U.S.A.).
Methods. An example for the determination of the solubility of one' chlmobiphcnyl in water is given below.
A hexane solution of the chlorobiphenyl (1 mg) was pipetted into a 300 ml Erlenmeyer flask and the" solvent evaporated to give a thin film of the compound. Water (100 ml) was added, the flask sealed with purnfilm and the mixture shaken at 30C for 10 days. After this time the aqueous suspension was allowed to equilibrate at 22-246C for 3 hr. Contact oi aqueous chlorobiphenyl solution with glass was kept to a minimum after this step because of the known adsorption effects'3. An aliquot (10 nil) was drawn using a syringe carrying a small filter compartment and Immediately
14 NEW 0 3 6 8 5 6
i titIt 'iN-A.inr (2 a 10 m l/. Thi! bcvanc extract w.n .w . :.;i..icrl lo 10 ml mul
i.tt u ric iii)Vili`tl intn tlu* gas iluumutiigiapli,
evaluation was
In measuring llie peak height using calibration cmvc 1* kumvn unitamts of
>!.*;>! slandanl in hexane. Sampling ami analyses wm - e.mieu mil in (luplcate.
iv l tin* prillilciiis w ith adsorption anil lmv snhiluk:*. 1:n experim ents w ere
..... ;.i i:l\ r solubility ilata as absolute pliysfr.il e-r.
bill were i1ended
: - ..i!. *>>i- i
.ivjwable a rte a e * ft:
nneitts.
. . 'i" e`i!: -bip'it ;.y>' in wulvi an
: ,iMo 1.
'MUM. I
Solubility of chlorobiphcnyls iu water
Compound
Solubility (mg)
Monochlorobiphcnyls
2 -....................................... 6.0
3 -....................................... 3.35
4 -................................ :..... 1.20
Dichlorobiphcnyls
,
2, 4. ................................. 1.40
2, 2 '-................................. 1.56
2, 4`- .................................. 1.90
4, 4 - ................................. o;o8
Trichlorobiphenyls
2, 4, 4'- ............... ;........... 0.085
3, 4, 2*- ............................ 0.075
Tetrnchlorobiphonyls
2, 2\ 5. 5*- ...................... 0.046
2, 3, 2\ 3'- ............... 0.037
2, 3, 2', 5'- ...................... 0.170
2, 4, 2 \ 4- ............. ;....... . 0.070
2, 4, 3', 4'- ...................... 0.055
2, 5, 3 \ 4*- .......;............ 0.041
3, 4 /3 ', 4'- ...................... 0.175
Pentachlorobiphenyls
2, 3, 4, 2\ 5'- ................ 0.021
2, 4, 5, 2*. 5 '- ................... 0.035
Hexiichlornhiphenyl
2, 2', 4, 4', 5, 5'- ............ 0.0088
Octachlorobipbenyl
2, 3, 4, 5, 2', 3', 4 \ 5'- .. 0,0068
IX'tfleliloi obiphcnyl
0.015
4, T-Dichlorobiphenvl .......
+ Tween 10 0.17 ........... 6.2 + Tween 80 1% ............ 10.0 + Humic acid extract ..... 0.075
(ppm)
. 5.8 3.6 1.17
1.40 .1.44 1.85 0.07
0.085 0.080
0.046 0.030 0,170 0.065 0.080 0.041 0.175
0.023 0.028
0.0088
0.0072 0.015
5.5 10.0 0.06
15
Q 36fl5^
We thank l)r. K in d for supplying data prior III publication. P.HAV. expresses his gratitude tu tin* "Deutsche Kurscliuiigsgeuiinschair' for linnncial support, Purl nl Ibis work as ca ril'd mit h ilf O. H. was on leave at the IIuM-risehe I.aiidesau'-lali. This author would like to thank the "Deutsche Akademisch)- AusUiuxchdicuts" lur die :n\iht<i).n to miany and linnncial aid.
J. i *. S '.- a ::.; i i. W V hi |. (.d ittiin n lii'-'r. (id. J 7 i i 'jVI .
: \\.
A t \ McCall. J. Ass. Oflir. Anal t hem. .*i\ T-p: . 1'fTi!.
... .'hi. V Tmhso-.- K. Ogmi, M. A11iniur:i an t M. I[.iiii.u,.i. I nkimLa /.tssld (2, 'I i, lii'f l - : Client. Ahslr. 7-1. II(i2!M t I I .
n
I. A. C. Tas and H. 11. deVos. Environ. Sei. Tcclniol. 5, 1210 11971).
5. A. C. 'las* and H. J. C, Kleinpool. Hull, Environ. Contain. Toxicol. H, 32 (1972).
0. D. K. Willis and It. !'. Addison, J. Kish. lies. lid. Canada 29, 592 (1972).
7. V. 11. Freed, personal cmnimm cation (Some physical chemical properties of the polychlorinated biphenyls-Arocloi J25-1; manuscript).
8. it. C. Webb, PCI! Newsletter (1970).
9. G. Ogner and M. Selmit/er, Science 170, 317 (1970).
10. K. M alsuda and M. Schnitzer, Hull. E nviron. Camtarn. Toxicol. 0, 200 (1 9 7 1 ).
J ). V. Zitko, Fish. lies. lid. Canada, Manuscript Report Series No. 1083 (1970).
12. II, J. Rellin. S. Lauror-Ucydcnrcfch and 1'. Wallnofer. Z. Lcbcusm. 'Unters. Forchung J35, 117 (1960).
13. M. L. Hatlnla, Dansk. Tidskr. Farm. 45, 259 (1971).
V U O G U E SS H K rO U T S ON 1T.I5 ISO M EK S
By: Michael Holgar
Given the toxicity and persistence oi the widely dispersed polychlorinated biphenyls (PCH's) it seems logical that the U.S. Interdepartmental Taskforce on PCB's in their 181-page May 1972 Report (Cmn-7a*l0419) would include as part of llieir recommenda tion (page 18) the following additional studies, (italics arc ours):
1. Toxicologicnl c.txilnalinn of a select ilumber nf representative, purified PC if Isomers as well as purified trace contaminants such as the chlorinated dihenzofurans.
2. Definitive mammalian elaboration of the kinetics, absorption, distribution, meta bolism, and excretion of the technical PCBs ns well as a number of kcij isomers and the chlorinated dihenzofurans.
3. Elaboration of the sillreelhilar and intracellular actions of the technical PCHs as well as ti number of representative isomers and chlorinated dihenzofurans.
J. More definitive epidemiological studies of the PCHs with lmtli more representative population sampling and standardization on the basis of lipid content of the tissues.
In our list of biphenyls and 50 isomers of the 209 possible dilorobiphenyls we included a great number of the major components present in the commercial mixtures, l'or
1$ NEV 036858
instance, Willis and Addison1 report that the major components of Aroclor 1221 accounting for 92.3 weight per cent are biphenyl, 2-Cl, 4-C1, 2. 2'*C1X, 2, 4'-Cla (all available from Analabs stock). From Sissons and WeltiV list of the major com ponents of the more important Aroclor 1254 (we list more than half). Methods have been developed* to recover PCB's present in wtisie and river water and to increase detectability by perchlorinating the samples sensitizing them to electron-capture detection by gas chromatography4.
We have made the tools available (polyurethane foam plugs and perchlorfnation kits).
Assembled below is data of melting points taken of our pure isomers and taken from the literature. This list reveals interesting features of configuration/phystcal property corelation.
MELTING PO IN TS O F POLYCHLORINATED BIPHENYLS
Chlorine Position
Mono
2-C1 3-Cl 4-C1
Di
% 3-Cla 2, 4-Clj 2, 5-Cla 2, 6-Clj 3, 4-Cls 3, 5-Cl3 2, 2*-Cly 3, 3'-CIa 4, 4'-Cl2 2, 3'-Cl2 % 4'-Cl3 3, 4'-C)i
Tri 2, a, a , 2, 3, 3-Clg 2, 3, 6,-Clj 2, 4, 5-Cl, 2, 4, 0-CI, 2, 3, 2'-CI3 % 3, 4'-Cl3 2, 4, 4'-Cla 2, 5, 2'CIa 2, 5, 3'-Cla 2, 5, 4'-Cl1 3, 4, 2'-Clg * 3*.4, 4'-CI3 3, 5, 2'-Ci3 3, 5, 4'-Cla
Melting Points
32.0*32.5C oa 75.5*77.0C
Oil (Lit. 27.7-28.2C) Oil (Lit. 24-25C) Oil (Lit. 22-23C) 34-35C 47-48 C Oil (Lit. 31-32C) 60-61C 25-26C 148-149 C Lit. Oil 42.5-43.5C Lit. Oil
101-102 C Lit. 41C 5B-60C 76-78c'C 62.0-63.5C Lit, 28-29C Lit. 73C 57.0-57.5G 43-44C 40.0-40.5 C 03.5-64.5C 0O.O-6O.5C Lit. 87-88C Lit. 58C Lit. 88C
17 NEV 036359
i )
J
f;
\ ? mi 4; I7* P 0 11.V1 o r j ' C L Y a i L O U ^ A T E i ) B IP H E N Y L S
C ift'J'l.L,1 /'l.-M, fiJH
Trtro
2, 3, 4, S-C]4 2, 3, 5 0*C14 2, 3, 4, 4'*CI4 2, 4. 5, 4'-Cl4 2, 3, 2' 3'-Cl4 2, 3, 2' S'-C14 2, 4, 2r 4'-Cl 2, 4, 2' 5'-CI4 2, 4, 3' 4'-Cl4 2, 5, 2' 5*-CI4 2, 5, 3* 4*.C14 2, 0, 2'. 0'-Cl4 3, 4, 3', 4'-CI4 3, S, 3', S'-CI4
Penta
2, 3, 4, 5, 0.-C1, 2, 3, 4, 5, 4'-Cl5 2, 3, 4f 2', S'-Clj 2, 3, 4, 3* 4'-C11 2. 3, 0, 2' S'-CI, 2, 4, 5, 2' 3'-Cls 2, 4, 5, 2' 5*-Cl3 2, 4, 5, 3' 4'-Cl5
Hexa
2, 3, 4, 5, 8, 2'-Cl<j 2, 3, 4, 5. 0, 3'-Cl 2, 3, 4, 5. 0, 4'-Cl 2, 3, 4, 5, 2' 4'-Cl0 2, 3, 4, 5, 2' 5'*CI0 2, 3, 5, 6, 2* S'-Clt, 2, 3, 4, 2' 3' 4'-Cln 2, 3, 4, 2' 4' S'-Cl,, 2, 3, 5, 2' 3' 5'-Cl,t 2, 3, 6, 2' 3' 0'-CItl* 2, 3. 0, 2' 4' 5'*C),t 2, 4, 5, 2' 4' 5'-Cln 2. 4; 5, 2* 4' 0'-Cl,, 2, 4, 8, 2' 4' 8'-CIr 3, 4, 5, 3', 4* S'-Cla
./fi/in; / 'lin i.v
91.5-92.5C 77.0-77.5C Lit. 141-142C Ut. 125C 119.5-121.5C 40.5*47.0C 41-42C 04-60C 127-128C 88-87C 104-107C 190-200C (sublimes) 132-184C Lit. 104C
123-125C Ut. 98*99CC 1J1.5-H3.0C Lit. 101-105C 97-98 C 81-82C 70.5-77.5C Lit. 105-107C
Lit. 134-137C Lit. 97-100C Lit. 16O-105C Lit. 77-78C 89-91 G 100-101C 155-8C 78.5-80.0 C Lit. 128-129C U5-I17G Lit. Oil 102-104C Lit. Oil 113.5-114.5C Lit. 108
18
v
NEV 036860
$\
1
M E L 'IT '.' ; P l . V f U P PO .'.Vt
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Chlorine Position Hepta 2, 3, 4, 5, 6, 2' 5'-Cl7 2, 3, 4, 5, 6, 3', 4'-Cl, ` 2, 3, 4, 5. 2'. 3*. 4'-Clj 2, 3, 4, 5, 2' 3' 8'-ClT 2, 3, 4, 5, 2' 4' 5'*C1T 2, 3, 4, 5, 2' 4' 6'-C1t 2, 3, 4, 5, 3' 4' 5'-Cl,
Ocia 2, 3, 4, 5, 2' 3' 4' 5'-Cl8 2, 3, 4, 6, 2' 3' 4' 0'-Cl8 2, 3, 5, 0, 2' 3' 5' 0*-Cls
Nona 2, 3, 4, 5, 0, 2' 3' 4' 5'-Clu
Deea 2, 3, 4, 5, 0, 2' 3' 4' 5* '-CI
Melting Points
147-150C Lit. 110-118C Lit. 134.5-135.5WC Lit. 130.5-130.7C Lit. 109-110C Lit. 152-153C Lit. 162-163C
158*159C Lit. 132C 101-102C
204.5-206.5C
300-310C (sublimes)
All melting Points token on n Fischer-Johns melting point stage.
1. D, E. WilUs and R. F. Addison, J. Fish. Res. Board Canada, 29, No. 4, 592-595 (1972)
2. D. Sessons and D. Welti, J. Chromatography, 60, 15-32 (1971) 3. H. D. Gesser, A. Chow, F. C. Davis, j. F. Uthe and J. Reinke, Anal. Lett., 4,
883-6 (1971) 4. V. Zitko, O. Hutzinger and S. Safe, Bull. Environ. Contnm. Toxicol. 6, 160 (1971)
19 NEV 036861
1
99% Pure PCB Isom ers
For clarity we have kept the position numbering separate (or each ring. For Chemical Abstracts nomenclature transpose numbers listing lowest number first.
RCS-001 Biphenyl.................................................................................. *7.00/500mg RCS-002 2-Chlorobiphenyl.................................................................... 7.00/100mg RCS-003 3-ChlorobiphenyI.................................................................... 7.00/100mg KCS-004 4-ChIorobiphenyl .................................................................... 7,00/100mg KCS-005 2 ,2'-Dichlorobiphenyl.......... .................................................. 18.00/100mg KCS-008 3 ,3'-Diohloroblphenyl............................................................. 18.00/100mg RCS-007 4 ,4'-Dich1oroblphenyl ............................................................ 18.00/100mg RCS-008 2, 4'-DichIorabiphenyl ............................................................ 32.00/50mg RCS-009 2 ,3*Dlchlorobiphenyl ............................................................ 14.00/100mg RCS-010 2 ,4-Diohlorobiphenyl ............................................................ 14.00/1OOmg RCS-01I 2 ,5-Dichlorobiphenyl ............................................................ 14.00/100mg RCS-012 2, 6-DiohlorobIphenyl ............................................................ 14.00/1OOmg RCS-013 3, 4-Dichlorobiphenyl ............................................................. 14.00/10Omg RCS-014 3 ,5-Dichlorobiphenyl ............................................................ 14.00/100mg RCS-015 2 ,4 ,4'-Trichlorobiphenyl ...................................................... 26,00/20mg RCS-052 2,4,3', 4'-Tetrachlorobiphenyl................................................ 32.00/20mg RCS-018 2 ,5 ,2'-Trichlorobiphenyl ....................................................... 28.00/50mg RCS-017 2,5,3'-Trichlorobiphenyl ........................................................ 28.00/50mg RCS-018 2, 5 ,4'-Trichlorobiphenyl ....................................................... 28.00/5Omg RCS-019 3, 4,2*-Trichlorobiphenyl ........................................................ 28.00/50mg RCS-020 2 ,3 ,4-Tricblorobiphenyl ....................................................... 26.00/50mg RCS-021 2 ,3 ,6-Trichlorobiphenyl........................................................ 36.00/50mg RCS-022 2,4, 5-Triohlorobiphenyl........................................................ 22.00/100mg RCS-023 2 ,4 ,0-Trichlorobiphenyl......................................................... 20.00/lOOmg RCS-024 2, 3 ,2 ', 3'-Tetrachlorobphenyl .................. ............................ 28,00/100mg RCS-025 2 ,4 ,2 ', 4'-Tetrachlorobiphenyl ............................................... 28.00/100mg RCS-028 2,5,2', 5'-Tetrachlorobiphenyl ............................................... 28.00/100mg RCS-027 2 ,6 ,2 ', 0'-Tetrnchlorobiphenyl ............................................... 28.00/100mg RCS-028 3,4,3', 4'-Tetrachlorobiphenyl ............................................... 28.00/100mg RCS-029 2 ,3,2', 5-TetrnchlorobiphenyI ............................................. 3S.0O/50mg RCS-030 2, 4,2', 5'*Tetrachlorobiphemyl............................................... 22.00/20mg RCS-031 2.5,3', 4*-Tetrachlorobiphenyl ............................................... 35.00/50mg RCS-032 2 ,3 ,4 ,5,-Tetrachlorobiphenyl ............................................... 20.00/50mg RCS-033 2 ,3 ,5 ,6-Tetrachlorobiphenyl ................................................. 20.00/50mg RCS-034 2 ,3 ,4 ,2\ 5'-Pentnchlorobiphenyl............................................. 25.00/20mg RCS-033 2 ,3 ,0 ,2 ', 5*-Pentachlorobiphenyl ........................................... 22.00/10mg RCS-030 2 ,4 ,5 ,2\`3'*Fentnchlorobiphenyl........................................... 22.00/10mg RCS-038* 2, 4 ,5 ,2 ', 5'-Pentachlorobiphenyl ........................................... 35,00/50tng RCS-039 2 ,3 .4 ,5 ,6-Pentachorobphenyl........................... ................. 28.00/lOOmg RCS-040 2 ,3 ,4 ,2 \ 3\ 4'-Hexach!orobiphenyl ..................... ................. 32.00/20mg RCS-041 2,3,4, 2', 4', 5'-Hexachlorobiphenyl ....................................... 28.00/lmg RCS-042 2 ,3 ,8 ,2\ 3', 0-Hexochlorobiphenyl ...................................... 36.00/20mg RCS-043 2 ,4 ,5 ,2\ 4*, S'-Hexnchlorobiphenyl ....................................... 36.00/lOOmg RCS-044 2,4 ,0 ,2 ', 4', 8'-Hexachlorobiphenyl ....................................... 32.00/50mg RCS-045 2 ,3 .4 ,5 . 2'. S'-Hcxnchlorobiphenyl ....................................... 28.00/10mg RCS-040 2, 3, 5, 6. 2', 5'*Hexachlorobiphenyl ....................................... 28.00/10mg RCS-047 2 ,3 .4 .5 , 0, 2', 5'-Heptachlorobiphenyl ................................ 30.00/lOmg RCS-048 2,3 ,4 ,5 , 2\ 3', 4', 5'*Octachlorobiphenyl ............................... 26.00/20mg RCS-049 2,3.5,0,1*, 3\ 5*. 0`-Octaohlirobipheityl ............................... 20.OO/2Omg RCS-050 2 ,3 ,4 ,5 ,0 , 2', 3', 4', 5'-Nonachlorobiphenyl ......................... 38.00/10mg RCS-051 2 ,3 ,4 ,5,0,2', 3\ 4', 5*, 6'-Decachlorobiphenyl ..................... 7.00/100mg
Diicount on tingle order of any 3 PCBV10% 10 PCB'f-13% BihltogropliT on PCD Literature nvnllnbk- on rcrjuctl.
20 NEV 036862
POLYURETHAINE-I'OAM PLUGS
For complete extraction of pesticides and PCB's from environmental water samples (for instance --river water). References:
1. The extraction and recovery of polychlorinated biphenyls (PCB) using porous polyurethane foam. H. D. Gesser, A. Chow, F. C. Davis, J. F. Uthe, and J. Reinke. Anal. Lett., 4, 883-6 (1971).
2. Extraction of organochlorine pesticides from water by porous polyurethane. J. F. Uthe, J. Reinke and H. Gesser, Environmental Letters, 3, 117-135 (1972).
Written procedure for extraction of pesticides and PCB's from water samples will be supplied with each order or on request.
Polyurethane-foam plugs (22mm x 38mm)
RCS-083 ..................... Untreated ........................................................ $10.00/50 RCS-084 ......................Washed ............................................................ 12.00/12 RCS-085 ......................Treated with 0.5% DC-200 ............................. 12.00/12
Chromatographic Tubes (20mm ID, 400mm long)
RCS-088 ......................Tube without fritted disc ............................... $13.00/2 tubes KCS-087 ......................Tube with fritted disc ................................... 11,00/eaeh
References:
Perchlorination Kits for Analysis of Polychlorinated Aromatics
1. Analysis of chlorinated aromatic hydrocarbons by exhaustive chlorination: Qualitative and structural aspects of the perchloto derivatives of biphenyl, naphthalene, terphenyl, dibenzofuran, dibenzodioxin and DDE. O. Hutzlngcr, S. Safe, and V. Zitko.
International Journal of Environmental Analytical Chemistiy, 2, 95 (1972).
2. Column chromatographic separation of polychlorinated biphenyls from chlori nated hydrocarbon pesticides, and subsequent gas chromatographic quanti tation in terms of derivatives. O. W, Berg, P. L. Diosady and G. A. V. Rees Bulletin of Environmental Contamination and Toxicology, 7, #6, 338*347, (1072).
3. Screening method for the detection of chlrwodibenzo-p*dioxins In the presence of chlorobiphenyls, chloronaphthalenes, and chlorodibenzofurans. D. T. Wil liams and B. J. Blanchfield, JAOAC. 55, 93-5 (1972),
RCS079...................... Perchlorination reagents Aj andA* ................................ $10.00 For PCB's, PCDD's, PCF's, and p,p'-DDE (in equal volumes).
RCS080...................... Perchlorination reagent B ................................................. 6.00 For PCB, PCT and p,p'-DDE
RCS081...................... Perchlorination reagent C .............................................. 6.00 For PCN'j
RCSQ82...................... Perchlorination kit (Alt A, B, C) ...................
16.00
Detailed perchlorination procedures will be supplied on request and with each order.
21 NEV 036863
K( *stn;(; .................... 'Ch-K h i f*'1each f i Arr.^-lo:-
Jir,
1-;S. 3.v;.
. . t.Otl/kil
.0 0 /
t .J
u t
Number oi Chi::: in**.*.............
---------- 1------ -1 " T--------] L j* 4 1
e --7
8
Tr of Chlorine ......................... 21.85 36.40 40.00 53.38 59.07 63.6 67.2 70.3
Referente: Behavior of ch)c>:inaled naphthalenes in analytical methods for orgnnochlorinalcd pesticides and pulvchlorinaled biphenyls. J. A. Annom and J. A. Burke, JAOAC, 54, 175-7 (1971).
KCS053-- l-Cldorodihcnzo-p-dioxin,..............................
20/50 mg
KCS054 ...2-Ch lorodiiu-uzo-p-dioxin........................................
20/50 mg
HCS067 . Diben/n-p-dioxi ......................................................................... $15.00/50 mg
HCS055 .-2, 3-Dichlorndihcii/o-p-dioxin...................................................................25/50 mg
KCS06S.. 2, V-Dichlorndibcnzo-p-dioxhi...................................................... 25.00/50 mg
1CSG69 ..1 ,2 ,3 , 4 ,6, 7, 8, 9-OeUuhlorodibenzo-p-dioxin.......................... 20.00/50 mg
HCS050 " ], 2, 4-TricliiormHbcnzo-p-dioxin......................
25/50 mg
HCS057---1, 2, 3, 4-Tctrndilormlibenzo-p-dioxin.................................................. 25/50 mg
References:
1. Tiin-laycr cliromatographic .separation of two ohlorodibenzo-p-dioxins from
somo polychlorinated biphenyls and organochlorme pesticides. D. T. Williams
and B. J. Blanchfield, JAOAC, 54, 1429-31 (1971).
2. Determination of polyohlorodibenzo-p-dioxms in chlorophenols and lipids. D. Firestone, Paper presented at the 162nd National ACS Meeting, Pesticide Div., Sept. 12*17,1971.
V'J'.< PCM,Y( '.I M.(J P JNATF.D ItfP.K N /O K U K A N S
RCS070 ..................Dibenzofuran....................................................... $ 7.00/500 mg KCS058................... 3, 6-Dichlorodibcnzoiuran.............................................30/20 mg RCS073 .................. 1,2,3,4,5,6,7,8-Octachlorodibenzofuran................ 15.00/50 mg
Reference: Identification and toxicological evaluation of chlorinated dilrenzxifuran and chlorinated naphthalene in two commercial polychlorfnntcd biphenyls. J. G, Vos, J. 11. Koeinan, II. L. van dcr Maas, M. C. Ten Nocvcr dc Brauw and 1\. 11. dc Vos, Food Cosmct. Toxicol., 8, 625-633 (1970).
RCS077 .................. Hcxachluroplicne [212'-MclhylenebiS' (3,4,6-tiicIiloiophenoI)] ...................................... $ 5.00/1 mg
RCS078 ..................Perd donnalcd p.p-D D E...................................... 20.00/50 mg
22 NEV 036864
! 'i !,: l C i l i l . . - '
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23 NEV 036865
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Sre Tedimi Sm DDD-mli StrObplWD' Ser p. p'-DDU llnphn / Ttlredlfun TCD5
Str Trdioq Unni*
Endoratfan /
Mah*
/
Ser Zlnopbtt Sor Phalten Sw Parathion ITieaitdtlc llnmatoe Ttigon Cltlnruphol Diptera Dyta Nejuvwt IHptefet Qihtroplcdn
Aiiptlalte
Ptnvntoll
CarimplimnlttIna
Tnpm --------- Undcn - -- - . Vapor nsPIQl Vari
RM W Warforin
Str Trtchkirfon Sm Bypw Sre DMiImvm
Ctmmafcne
Adite anttkol
Orfaunrtli)ipprup(iiip]MtriunnIr
OllaaiethyfpymplmipUiMiidHe lA'aplithyl N-mrlhpl caHumalr l- ( l,l, ITHtIilunpiHMir ) pniphinc Add 2*(2,4, -VTridiloTVphentnr) piup* hatteAdd 3-dilnro~l,8-bii (elitifatino ) trUdne
Trliadtkn>-p4ietitu(|tUtianr Terpene jwlydilorinatei
I, S.Mr(lirWcdlitp.|-(2.((x-tyl nitdnyl) propri) fattene
* A .1. w .sn
W* w* WJ%
W J*
Tedi. M* Pilori W*
Film 11.00/1
H.OO/k ii.aviooma I0.0u/100n>t 6.10/U ll.KI/lWntf
6.00/ I6.0U/I
12,00/1
2,4,3-Tridikmjp|irin)'wrettc Acid 2.4, S.THeblurpphcnmt'acntfo Acid
UVA Trek
lA.OO/lUOms .ut/s
p-CMoropWn>l 2.4, Vliidilunn phceyl mlione
2,3,4.0 TetradtluTupItcmd
O.ODlrthjr13.( brillilo) mrtkrl pbosphorodllhloate 0 ,0 [Hrthyl S-{rthy1lliti>) iMthyl pSinphonidllNuutr 0,7, S,0,10, m-Hilavl>Viro.|, 3,3a, 0,0, Ondtrwlirdn^, U-mrltuitu 2,4,3faitodktiatlilrpin a^ixide
OH*
W*
Wt0 * 01* 06*
Pufjdilunitakd rompiarar
O, O Dmirtliyl {Mtrdttixyi, i, 2-ttW cblwortJtrD plwiphonatc
Tedi. OH*
lO.tD/j 12.00/lOOinf 10.0(1/1 eoo/n 23.im/l(XknB
17.00/b 12.00/g
TridilatanltTiNurtliane
3,4.3 TrRhlnrnpItetad 2,4,6 Trtchfaiptieiml S-[I p.CItltinriHimyl) thfcil mt-ikil) 0 ,0 dietliy) plwjplnim. Uttlihate
Methjrl bollilarvanole 3-1a '.4ti-limyHn*vW-llyilrmy
iwrauutn
OB* 12.00/m 00* 10.00/HKkn.9 0* in.no/mTiir 3* lo.on/a
211* Troll.
I2.1W/ tiino/iuuuie
NV 0 3 6 8 7 1
29
I'liSTUilUl-: STAiNDAJSDS
BSFIM BSP[09 asriw aspisT
Predict Zectna Zfctnn. tech. Zlmti Zinopho*
nsFiss RSF100
Zytnw Zytron. itch.
Spnonpa
DtthtM'tfoC Ftntatt Tlttanluln Cynrt Ncnuft m ir*
Active Ingredient
<-dimethyl amtruO, 3-iylyl-M.Mrlhyl cnilitmta 4-dinicthyl andno-3, .?-*>Jyl-N*MMhyl Indiamate Zinctthyknt UidltUtmftMBwl
O. O-Dtethyt-O-i-pyririnyl pho*pturfotMoat
Q*(1. t-DtchkmTphcnyl)-OmttUyl tor propyl pbmpbnnmldolhioala 0.(C. 4-Dtehlsnphenyl).0*(Mlh)il (mipnipyj plMvphawiaJiMjdtftla
%A.(.
W* T5
wr*> Tnb.
rte* 19.00/1 9.00/g 80.00/* lfl.UD/IWko*
li.OO/IOOni .TO/*
PRECOATED TLC PLATES
from ANALABS
Analabs TLC plates ore of precision quality. They are precoated using procedures developed by leading chromatographic Investigators.
The prescored 20 x 20 cm plate can be snapped in sections for two 10 x 20 cm,
or four 5 x 20 cm plates. Scoring on the uncoated side makes snapping the plates easy. A clear edge on the plate allows <the plate to be grasped without disturbing the coating. Separation information can be marked In this area.
ORDERING INFORMATION 20 x 20 cm PRECOATED PLATES 250/* thick. 25 PLATES/BOX
NUMBER CATALOG TLC PLATE TYPE
PRESCORED PRICE
UNSCORED PRICE
5 x 20 cm 10x20 cm 20 x 20 cm
TLP-001 TLP-002 TLP-003 TLP-004 TLP-005 TLP-008 TLP-007
TLP-008
Anasil G
Anasil GF (254) Anasil H Anasil HF (254) Silica Gel G Silica Gel GF (254)
Microcrystalline Cellulose (Avlcel)
Microcrystalline Cellulose, F (254)
(Avlcel)
$30 $30 $30 $30 $30 $30
$31
$31
$20 . $20 $28 $20 $20 $20
$27
$27
$22 $22 $22 $22 $22 $22
$23
$23
Analabs precoated plates are guaranteed to arrive at your laboratory in condition for immediate use. Any plates that arrive damaged will be replaced at no cost to you and no troublesome paperwork.
NEV 0 3 6 6 7 2
30
CEPP 147
I'ESTICIDECRADE SOLVENTS
-
Pesticidegrnde Solvents tire certified to contain no interfering substance greater than that equivalent to 10 parts per trillion of a chlorinated pesticide.
Catalog #
Solvent
SSP001 5SP002 SSPUU3 SSP004 'SSP005 SSF006 SSP007 SSPOOS SSP009 SSP010 SSP011 SSP012 SSP013 SSPOU SSP015
sspoie SSP017 SSP018 SSP010 SS
Acetone, Presticldgrade
Water ............................................. . 0.059 max.
Acetonitrile, Pesticldegrade
W ater............................................... . 0.05% max.
Benzene, Pesticldegrade
W ater..................................... ......... . 0.03% mux.
2-Butanone, Pesticldegrade
W ater........................ !..................... . 0.05% max.
Butyl Alcohol, Pesticldegrade
W ater............................................... . 0.05% max.
iso-Butyl Alcohol, Pesticldegrade
W ater............................................... . 0.05% max.
Cnrbon Tetrachloride, Pesticldegrade
W ater........................ ...................... . 0,02% max.
Chloroform, Pesticldegrade
W ater............................................... . 0.02% max.
Cyclohexane, Pesticidegrade
W ater............................................... . 0,02% max.
Dichloromethane, Pesticldegrade
W ater................................................0,02% max.
N, N-Dimethylformumide, Pesticldegrade
W ater............................................... . 0.05% max.
p-DIoxnne, Pesticldegrade
W ater............................................... . 0.05% max.
Ether, Pesticldegrade
W ater............................................... . 0.05% max.
Ethyl Acetate, Pesticldegrade
W ater............................................... . 0.05% max.
Ethyl Alcohol, Pesticldegrade
Completely Denatured
W ater........................... ................... . 0.05% max.
Heptane, Pesticldegrade
W ater............................................... . 0.03% max.
Hexane, Pesticldegrade
W ater............................................... . 0.02% max.
Methanol, Pesticldegrade
W ater............................................... . 0.05% max.
Methylsulfoxlde, Pesticidegrade
W aMi1
. 0.05% max.
SS
SS
Si
S:
Unit Price
1 Liter $14.00 1 Liter 15.00 1 Liter 12.00 1 Liter 13.00 1 Liter 12.00 1 Liter 15.00 1 Liter 16.00 1 Liter 17.00 1 Liter 16.00 1 Liter 16.00 1 Liter 19.00 1 Liter 17.00 1 Liter 12.00 1 Liter 13.00
1 Liter X Liter 1 Liter 1 Later 1 Liter
12.00 13.00 12.00
11.00
21.00
t
NEV 0 3 6 8 7 3
Aj'jMOUMCJS Jo/ ',9 7 A ?OUU7JON CH2AUCA1
J jt" \ J
.V / " \ j \
. T I jJ
J
^
Contains: PCT's PCB's PCN's Dioxins Pesticides Dibenzo Furans Polynuclear Hydrocarbons
Send In your name and address for a copy of our Pol lution Control Catalog. This catalog will only be sent on request. Available Febru-
80 Republic Drtv, North Haven. Connecticut 06473 Telephone: (303) 388-6463 Telex: 064516
i PAID
I North Haven, Conn I Permit No. 20
Nev 03687^