.-

CA% -CHROoMtzTOG~APHIC ID&WICATION OF SOME ORGANOCIILORINE &&KIDtiS AND TREIR .PtiOTOALTERATIONPRODUCTS BY ME&%. OF -KOV_4T%’ RETENTION INDICES iF.I. ONUSG

and M. E; CCh3A

(7anadaCwurefor hdard W&v-s, Analysfcai Metho& Research Section, P.0. Box 5050, 867 Lake~sliore I&MC!, Burfington, Ontrvio .&7R 4A6 (Cmuzacin) ~eCei&d

August 22nd, 1975)

SUMMARY Kovats’ retention indices and temperature caegcients for some chlorinated methanonaphthalene and methanoindene pesticides and their photoproducts were determined on an OV-17 silicone liquid phase at three diiferent temperatures. A de: tailed p&edurc for the o&line calculation of the retention indices, aZ/aT and Z values are described. The program, written in BASIC, calculates the indices at three different temperatures and provides a cotiputer-written report.

-INTRODUCI-ION

Occurrence of photoaltered species of bridged polycyclic chlorinated hydrocarbons in the environment is of considerable importance and often goes undetected due to a lack of structural information. Several methods are available for their determination but these are either time-consuming, or highly specialized, and not normally performed in routine monitoring laboratories. In view of this, we focused our atten-tion on the dete&ation of Kovats’ retention indices of some previously identified metabolites and organochlorine pesticides’“. Standarc&ation of retention data in the form of a retention index system was proposed by Kovats* and EttrG. The retention index (Z) of the substance eluted from a column relates its retention time to the retention timesof a series of n-alkanes on the same stationary phase and thus becomes independent of other experimental parameters. Furthermore, it has been shown that identical structurai_difGerences between pairs of compounds lead to practically ide$ical retention index difFerenti 6. Takacs and coworkers7-*o have shown that KOv#s’ retention indices may be predicted and are directly .proportional to the freeenerm of solution of a compound in a stationary phase, which, in tti, can be related to the -functional &roups constituting the molecule. -Thus,-retentionindices ark not only useful as compound-specific data, but may &oi;ide structural information also.

:33fi

.:

.. :

F. Ii +USKA, :. -- :’

Mk&Otii

.wERimm&

Apparatzti. The work was performed using a Perkin-Elmer Model 990 gas c@romatograph -with a flame @iz&ion detector. As the temperature scale on this instrument .could not be read to better than + OS”, this teinperatu~ error _-v+&taken into account. A 2()-m@ waiting period for column equilibration was considered to be suflicitit for accurate retention tim& within the error limit. A &ass colti (184 cm x 2.1 mm I.D.) packed with-3 oA OV-17 silicone oil on Chromosorb .W-HP was used. The carrier 9s was helium at a Bow-rate of about 3oml/miu. Determkation of retention. in+es Retention indices were calcu&d using a Varian 62OL-SS K!O MS computer or Wang 6UOcakulator. Retention times were measured by means of a stopwatch. A program was written in BASK and is detailed in Appendix I. The particular phctoaltered product was mixed with an appropriate number of n-aikties, or when overlapping prevented this method,. the sample Bad @.xtire of n-alkanes were ruu alteruately. The gas hold-up time was evaluated by injecting methane. The difference between the value thus obtained and. t&e true .gg hold-up time was insignificant in the present instance as the lowest retention indices determined .were as high as 2008. The three standard temperatures used for measurement of retention indices were 190,200, and 210”. In addition, the retention indices of the photoendrins were measured at 210, 220 and 230” and retention indices were obtained at lower temperatures by extrapolation. RESULTS AND

DISCUSSION

The photoisomerization of heptachlor, chlordene and I-hydroxychlordene corresponded to the photo-conversion of enrio-dicyclopentadiene derivatives to pentacycIodecanes and resultant caged structures.The chromatograms of irradiated hepta&or and chlordene (Figs. i and 2) showed both completely converted to their respective full-caged isomers. I-Hydroxychlordene formed two photoproducts, which are weli separated by gas chromatography (Fig. 3). Peak 1 represented a. dehydrochtorinated product of 1-hydroxychlordene with subsequent formation to a halfcaged ketone structure. The lwaer value obtained for its retention index can be attributed to the presenti of +e carbony functional group and dehydrochlorination as compared to the caged photoisomer (peak 2), where the hydroxyl group tias retained and the-index much higher. These vahies are srrmmarizedin Table I, with the --. retention data obtined for heptachlor and -chlordene. Die&in formed one photoisomer, as demonstrated in Fig. 4 and &&bit&d a large d1 in komparison to the ‘other photoproducts observed.. This may be attributed to &e formation of the caged structure with retention of the epoxide fu@onai group: In &&r&t, six photoproducts were obser&dn the chr&uatogr&u of @adiated .aldrin (Fig. 5).-T% isomer of aldr& fo,midi- represetifed by p@k 5, occurred ti. a very IOw yield and d&prayed .a _di.fferenceof dP* = -15 iCKovats’ retention index compared to a &nda%d. of photoaId&:- The major pro&& ol&tied was a. hydios

23GG

_oy

o-------o-

22aa I.4

21ac

s/eM /t----Y zoo

2Gfx

190

Zhiordene

Hepkxhlcr

0 L

TIME

(min)

*

2Q66 Go6 Fig 1. Gas chromatogram of irradiatedheptachlor. Fig 2. Gas chromatogram cf irradiatedchlordene.

2300 _.2200 F

--o---7---o-

.---

10

OC

I

270

HeptachIor

ci

OH

\

Photoheptachfor

2308.6

1717

1828

94.3

2

H Cl H

Y .,I

:

Chlordene

2067.8

29.9

0.0

31.9

~/K-/X-X.

cJ_+p_o_+p_n

.

2305.8

Photochiordene

-\ 1-Hydroxychlordene

Photo-i-hydroxychlordene

l-Hydr&c&lordex@

phatoprcduct

: .:

2283.2

15.2

238.0

93.4

0.0

96.5

H

H

2938

2ei6 I"0 Fig.

40

TME (min)

0

4. Gas chromatogram 2800 t

of irradiated dieIdria

Die&In

2466.2

16.0

PhotodieIdrin

2908.0

9.5

441.8

2206.2

5.6

0.0

2129.3. 2367.9 2463.9 2589.7 2636.9

44.5 47.4 23.9 46.2 52.4-

AIdrin AIdrin Mdrin Aldrin Aldrin

photoproduct ~hoto&duct photoproduct photoproduct phqtoproduct

AI&in photo@roduct

1

2 3 4 5

6

27328

63.4

-76.9

161.7 259.7 3835 430.7

526.6

47.3 120.9 176.4 281.0 335.4

unidentitied unider&ied _mident&d midentifiexj GosaCf=ge4 :

TIME

0

iminl

2408

20 t 2601

IM

:;Fig.

8:

G& chromatosarxi of irrizdiatedmn..mo~or.

cis-chlordane

Photo-cis-chlordane

trcns-Chlordene

Photo-~ranrcblordane

2

.2600.9

14.1

2380.Q

24.9

2247.2

38.5

2731.5

18.5

0.0

--i38.8

135.2

a3.1

H-

2159.5

24.2

-238.6

imns-Nonachlor ph$opmduct

1

tram-Nonachlor photoproduct.

2

2285.2

18-O

-111.9

tmzs-Nonachlor photoproduct

3

2309.0

17.7

-

trcm-Nonachloi phcitoproduct

4

2329.0

21.0

70.0

cg5

C’2

-/ /

98.3

88.1

110.0

68.f

115.8

photoheptachlor

Cl

:mzs-Nonachlor photoproduct ~.

5

2459.1

16.0

62.0

179.0

&

H

Cl

C’5

H Cl

H

2576.6

21.5

:

179.5

Cl

I_:_’

.

:

I

.f

-_

:

:_-

-_:,_

(- I. ;~:-F* g+&.g~;.

g_ &,&

f&-caged product of trrms-chiorddrie, having 8 __@&culai ~cokpbsitititi OE C&I&. Peaks i and 2 ib the gas’ chrti~q~Nogram of itidi~te&zvs-no&&&

IF~D(I,~J)>=(C(Kt-l.J+ 1)) &EEmmj10

340

IWTT 62,

2..30253

.: :

_-‘_

:

LIST B&6GiC(K+-

350

LET I(I- 1,~)s IOO*((B~-B~)/(B~-B~))*

--I, Jt

NEXT I-

37o

ZXT

386

FOR I= 1 TO N2

+O

-- ’

-.~.53=LOC_iC(~,J+.-9))*Bl~

34.6 -_360

.-

:

y,

342. LET. l32=LCG(Di%,&j'B1 : 344

397

.:.

335.

q/

:

-. :

j. . .. . _I> ~T~~~'~35

:--~oo_:.~:.~~_-acI;aj,cia,Ji

1: 316 gi?ziyc~i+ -~33*, (.&o,joo~.

.~

x-K+

11) *Bl

loOCC(K. 1)

.

J. .

~FOR -JJ=1 TO T- 1

-.

400 -LET I(I,JtT)=I(I,Jc I)-1(1,3) .410

Nixm J

.42ONExTI KOVATS' _IGTZSTfOP~INDICES'~ _--------------------------tt _______-_---________-------

430

PRINT -I1

440

PRINT I'

450

PRIXT

480

PRINT "COLUMN USED :”

470

PRIti "SAMPLE ANALYZED :”

480. PRINT 490

PRIG

500

PRINT It

510

PRINT 1,

520

PRINT

RSTEZTION INDICES" *tCL*t*t*+Cf*t**tt***

530. PRINT TAB( 14) ;:~I~~*;TAB( 27);~~12~*;~A~(40);"13" -540 .PRINT ~~~~~&~ND~~;TAB( ++);~~*;TAB( 27);w9;T~B( 550

4o);Yy

PRIKT 'iXB( 12);D( 1, l);TAB( 25);D( 1, 2>;TA3( 38);D( I, 3)

600. --PR.INT 610 :FOR I= l-TO N2 640~ PRINT TAi( 13);1(1, -l);TAB( 26);1(1, 2);TAB( 39);I(I, 3);TAB( 52); 641

PRINT I(I, 4);TAB( 63i);I(I, 5)

660 ~IIExT.I 670 -_rnxT.L 68O.G. &_ 10. -&SIC pk c&&t& Kd&t$ retentionindices. Fok variable, s the list OIIP. 398. $5a&l J are index counters for ffie variablesY and T for valuc~ of (1 to Yl) znd (1 to Ttl). Bl = CotivezSiotifactor to titural l&arithpS; Et = fX; B3 = L; !H = L+z-

GC OF PESk%CIDES ‘&ND -Fm

-1 ~~.-O&&~d

PHOT0PR~DUCl-S

399

M. E. &&tJ,-&:@j%_ A~kChein., 58 (1975) 4: h&M. E. .0k&ai -Ehec%-M’E Speckxn., ‘2 (1975) X69. :3 F. &- Or&& &d-M. E. -Coti% Biomeuf.&hiss Specztmti.,2 (1975) :I76 --&‘E. Kovats, Heiv. Chh. &?a, 41 (l%i) 19fk 5 L. S..Et& hzut. Chem.,~36(196?) 31A. 6-~D.cSissans._~d_D.-Welt&I. Chromaiogr., 60 (1971) is.. .. 7.J. T&$c%C. S&a and G. rarj&,rs. Chwn~togr., 56 (1971) 1. 8 J..-Ta+s,Zs_ T&s,% Ber@th, Gy. Cz&& and A. Fischer, I. Chrontatogr_, 67 (1972) 203. ~9 Z,-Szentkmay, G. T&j&n and J. Talc&, J. Cfuomarogr., 73 (1972) 11. i0 J. M. TaMcs, E. Kac~i,~E. Garamv~&yi, ,E. Eckhart, T. Lombosi, St Nyiredy, Jr., I. Borbt?ly and:Gy. Krasznzi, i. chrainarog., 81 (1973) 1. ..-11.R.~B. Hzrrisckf, D. C. HoImes, J. Robum and. J. O’G. Tattoh, J. Sci. Food Agri, 18 (l&7) IO. 12-R. G. Nash and M. L. Beall; Jr_, J. Ass. Ofic. Anal: %henr., 54 (1971) 959.

2 -F. .I; th&&