Polychlorinated Biphenyls PCBs by Gas Chromatography:

Capillary Column Technique

(EPA Method !"# $!%
Description
Method 8082 is used to determine PCBs as Aroclors in extracts from a variety of
matrices. !ee !"P #$0%0& $020 for preparatory information' (he sample extract is
introduced into the )C *y direct in+ection post solvent extraction or dilution. (he )C is
temperature pro,rammed to allo- capillary column to separate the compounds& -hich are
measured& via an .lectron Capture Detector .CD'. !ystem method sensitivity varies *y
matrix. (he estimated /uantitation limits on avera,e are %.0m,01, -et -ei,ht' for soils
and oils& and %.0,02 for -aters. A measured volume or -ei,ht one 2iter for li/uids& 23
40,rams for solids' is extracted usin, the appropriate extraction techni/ue.
!ample Preservation and Preparation5
!amples to *e analy6ed must *e collected in a ,lass container -ith a (eflon3lined lid.
!amples must *e transported and retained under refri,eration at 78C until extraction.
!amples may *e held for 9 days prior to extraction and 70 days prior to analysis under
refri,eration.
:nterferences
!ample analysis *y )C re/uires attention to preparatory detail to prevent analytical
interference. :nterference can exist as a result of the sample matrix itself or
contaminated rea,ents and instrumentation cleanliness. .levated sulfur or parafin
re/uires additional cleanup via copper -ash& silica ,el& or ;lorisil. All ,lass-are
associated -ith the extraction and concentration processes must *e thorou,hly cleaned&
solvent rinsed and oven *a<ed prior to use. :t is found that soaps have *een the source of
contamination as -ell as acetone& -hich may *e used durin, cleanup. A ri,orous
preventative maintenance routine is mandatory to maintain instrument performance.
Apparatus and Materials
3Column5 DB3=& 0.=4mm:D and 0.84m film thic<ness
DB3%90%& 0.=4mm:D and 0.84m film thic<ness
DB3$08& 0.=4mm :D x 40M len,th
3)as Chromato,raph5 >P =8?0 !eries ::& Dual Detector !ystem
>P =8?0A
3Data !ystem5 >P Chemstation %90%B
Procedure $9%0
@evised 04009
%
@ea,ents and !tandards
3!tandards are purchased as certified solutions
3"r,anic ;ree rea,ent -ater
3All solvent lots used are pesticide /uality or e/uivalent and should *e phthalate
free.
3!urro,ate !tandards3 Decachloro*iphenyl and (etrachloro3m3xylene mix is used
as surro,ate and is added to each sample prior to extraction
3Cali*ration !tandards for Aroclors5 A multi3point initial cali*ration employin, a
mixture of Aroclor %0%$ and %2$0 in e/ual ratio at five concentrations& is
used to demonstrate the linearity of the detector response. "ther Aroclors
need to *e run at -or<in, ran,e of the detector to calculate @; and for
sample identification. !ee (a*le :: for standard preparation.
.
3Matrix !pi<e !tandard5 Aroclor %0%$0%2$0 mixture is used for matrix spi<e in
most of the samples *ut -hen a particular Aroclor is expected in samples
the specific Aroclor should *e used for spi<in,.
32a*oratory Control !ample 2C!'. Aroclor %0%$0%2$0 mixture is used for 2C!
Aote5 All standards are stored at B%08C to B208C in am*er *ottles -ith (eflon3
lined scre- caps. All stoc< standards are sta*le for one year.
Procedure
1.0 Initial Calibration
%.% Perform re/uired preventative maintenance includin, evaluatin, the auto36ero
num*er for saturation of the .CD detector& -hich should *e less than %= and
should not vary more than %.0 from the previous days run.
%.2 An initial five3point cali*ration is performed usin, mixture of Aroclors
%0%$0%2$0. (he concentration should correspond to the expected ran,e of
concentrations found in real samples and should *rac<et the linear ran,e of the
detector. !ee (a*le :: for concentration of analytes at cali*ration level.
%.4 !tandards of the other five Aroclors are run for pattern reco,nition and also to
determine sin,le point cali*ration for each Aroclor.
Procedure $9%0
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2
%.7 )C operatin, conditions are esta*lished for proper resolution and sensitivity.
!ee (a*le : for )C conditions. (he same operatin, conditions are to *e used
for *oth cali*rations and sample analysis.
%.= 22 of in+ection enters the ,uard column. (he splitter then simultaneously
in+ects on *oth column and detector systems. ;or a sin,le channel detector&%ul
is in+ected onto the column.
%.$ A minimum of five pea<s are chosen for identification purposes. "ne of the
chosen pea<s must *e that uni/ue to the Aroclor. Also at least five pea<s for
the Aroclor %0%$0%020 mixture& none of -hich should *e found in *oth of
these Aroclors.
%.9 !ee (a*le ::: for dia,nostic pea<s in each Aroclor alon, -ith their retention
times @('.
%.8 Cali*ration factor C;' is calculated as ,iven *elo- on the five3point
cali*ration !(D as ,iven in %.2.
C; C Pea< area in the !(D'0(otal mass of !(D in+ected n,'
;ive sets of C; -ill *e ,enerated for the Aroclor %0%$0%2$0 mixture& each set
consistin, of the C; for each of the five pea<s chosen for the mixture. (his
data is used to determine mean C;& standard deviation !D' and relative
standard deviation @!D'. Percent @!D should *e less than 20D for linear
response.
%.? @etention time -indo-s5 :n+ect mixture of %0%$0%2$0 three times over a
period of 92 hours calculate mean and !(D deviation of at least five chosen
pea<s. (he -idth of the retention time -indo- for each analyte& surro,ate
and ma+or constituent in multi3component analytes is defined as E03 4 times
the !D of the mean a*solute retention esta*lished durin, the 923hour period.
(a*le :F lists a summary of retention times of Aroclors.
%.%0 @etention times of the surro,ate should *e monitored more closely.
Ghenever the o*served retention time of the surro,ate is outside of the
esta*lished retention time -indo-& the cause of the pro*lem *e determined
and corrective action ta<en *efore continuin, analyses.
2.0 GC Analysis of sample extract
2.% Mix of %0%$0%2$0 is used as cali*ration chec< !(D. (he C; for each analyte
calculated from the cali*ration verification standard C;
v
' must not exceed a
difference of more than E03 %=D -hen compared to the mean C; from the
initial cali*ration curve.
Procedure $9%0
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4
D Difference C HC;3C;v'0C;I J %00
D Difference should *e K %=D
2.2 Ferify cali*ration each %23hour shift. A cali*ration !(D must also *e in+ected
at intervals of not less than once every 20 samples and at the end of the
analysis se/uence.
2.4 :f the D difference exceeds %=D& inspect the ,as chromato,raphy system to
determine the cause and perform -hatever maintenance is necessary. :f
reanalysis of cali*ration verification !(D fails& a ne- initial cali*ration must
*e performed.
2.7 :f the pea< response is less than 2.= times the *aseline noise level the validity
of the /uantitative results may *e /uestiona*le. Cali*ration !(D should also
*e used to evaluate retention time sta*ility.
3.0 Qualitative Analysis
4.% (he identification of PCBs is *ased on retention time match and also *ased
on a clearly identifia*le Aroclor pattern. Positive PCB must *e verified *y a
second column confirmation. Ghen samples are analy6ed from a source
<no-n to contain specific Aroclors& the results from a sin,le3column analysis
may *e confirmed on the *asis of a clearly reco,ni6a*le Aroclor pattern.
4.0 Quantitation of PC!s as Aroclor
7.% (he Luantitation of PCB residues as Aroclors is accomplished *y comparison
of the sample chromato,ram to that of the most similar Aroclor standard.
Compare the response of at least five ma+or pea<s in the sin,le point
cali*ration standard for that Aroclor -ith the pea<s o*served in the sample
extract. (he amount of Aroclor is calculated usin, the individual cali*ration
factor for each pea< selected. (he concentration is determined *y avera,in,
the concentration of all selected pea<s.
7.%.% Geatherin, of PCBs in the environment and chan,es
resultin, from -aste treatment processes may alter the
PCBs to the point that the pattern of a specific Aroclor is no
lon,er reco,ni6a*le. !amples also containin, more than one
Aroclor present similar pro*lems. Ghen /uantitation and
identification is done in these types of situation& the pro*lem
is documented and descri*ed to the data user.
Procedure $9%0
@evised 04009
7
Luality Control
:nitial demonstration of proficiency is demonstrated *y ,eneratin, data of
accepta*le accuracy and precision for tar,et analytes in a clean matrix.
LC reference sampleM %0m,02 mixture of %0%$0%2$0 is used as LC reference
sample. %m2 of this standard is spi<ed into %2 of or,anic free rea,ent -ater.
>o-ever& -hen specific Aroclors are <no-n to *e present of expected in
samples& the specific Aroclors are used for the LC reference sample. LC
reference sample is analy6ed % per 20 samples or % per *atch if less than 20
samples. Accepta*le recovery limit is 803%20D.
Cali*ration !(D should *e run every 20 samples. (he cali*ration factors for
the cali*ration should *e -ithin %=D of the initial cali*ration chec<.
Matrix spi<e& matrix spi<e duplicateM %0m,02 mixture is used for matrix spi<e
and spi<e duplicate. >o-ever& -hen specific Aroclors are <no-n to *e
present or expected in samples& the specific Aroclors should *e used for
spi<in,.
A la*oratory control sample 2C!'. 2C! is spi<ed -ith matrix spi<e standard
%0%$0%2$0 in clean matrix.
!urro,ate recoveriesM !urro,ate recovery data from individual samples is
compared -ith the surro,ate control limits developed *y the la*oratories.
;ailure to meet /uality control accepta*le limits re/uires corrective action see
procedure 0%=0'. 2ocate and correct the source of the pro*lem and repeat the
test. ;ailure to meet /uality control accepta*le limits a,ain -ill re/uire ne-
cali*ration curve.
@eferences5
!G 87$ Method 8082 pp. 80823% to 808237%
@evision 0 Decem*er %??$
Procedure $9%0
@evised 04009
=
Procedure $9%0
@evised 04009
$
Gide *ore column
Column flo- =39 m20 minute
Carrier ,as0ma<e3up ,as A2 ??.?????D'
:n+ector (emperature 2=08C
Detector (emperature 4=08C
:nitial oven (emperature
(emperature rate 70 minutes
;inal (emperature
(otal Pro,ram (ime 7% minutes
(a*le :
GC "peratin# Con$itions for PC%s as Aroclors
40x0.=4mm:Dx0.84mm film DB%90%
40x0.=4mm:Dx0.84mm film DB=
%=08C hold for = minutes
29=8C hold for = minutes
!(D #% 2.= 20 =00 %
!(D #2 2.= =0 =00 2
!(D #4 2.= %00 =00 =
!(D #7 2.= %=0 =00 %0
!(D #= 2.= 200 =00 20
!(D
Conc.,0m2'
(a*le ::
Calibration &tan$ar$ Preparation
NN:ndividual cali*ration standards are re/uired for each Aroclor.NN.
%0%$0%2$0
Aroclors
!toc< Conc.
,0m2'
Folume !toc<
!olution ,0m2'
;inal Folume
,0m2'
Procedure $9%0
@evised 04009
9
Pea< Ao. @( on DB3$08 Aroclor
% 9.$8 %22%& %242
2 8.82 %22%& %242
4 %0.4= %22%& %242& %0%$
7 %0.?7 %22%& %242& %0%$
= %%.2 %0%$& %22%& %242& %272
$ %%.7$ %22%& %0%$& %242
9 %2.84 %0%$& %242& %272& %278
8 %7.22 %0%$& %242& %272& %278
? %7.89 %242& %0%$& %272& %278
%0 %=.4? %242& %0%$& %272
%% %=.79 %278& %2=7
%2 %$.$? %242& %0%$& %272
%4 %9.%$ %242& %0%$& %272& %278
%7 %9.$8 %2=7& %278& %272
%= %9.?% %0%$& %242& %272
%$ %9.?4 %278& %2=7& %272
%9 %8.24 %2=7& %2$0& %278
%8 %8.7= %2=7& %2$0& %278
%? %8.?8 %278& %272& %242& %2=7
20 20 %2=7& %2$0& %278& %272
2% 20.7% %2=7& %272& %278
22 20.84 %2=7& %278
24 2%.0= %2$0& %2=7
27 2%.47 %2=7& %2$0
2= 22.0? %2$0& %2=7
2$ 22.7% %272& %278& %2=7
29 22.$% %2$0& %2=7
28 22.?9 %2=7& %2$0
2? 27.$? %2$0
40 2=.47 %2$0& %2=7
4% 28.04 %2$0& %2=7
Pea<s are se/uentially num*ered in elution order
and are not isomer num*er
Onderline indicates lar,est pea< in the pattern for
that Aroclor
Pea's (ia#nostic of PC%s observe$ on 0.)3mm I(
Column $urin# sin#le column analysis
;or comparison use only
(a*le :::
Procedure $9%0
@evised 04009
8
Pea< Ao. %0%$ %22% %242 %272 %278 %2=7 %2$0
% 9.$8 9.$8
2 8.82 8.82
4 %0.4= %0.4= %0.4=
7 %0.?7 %0.?7 %0.?7
= %%.20 %%.20 %%.20 %%.20
$ %%.7$ %%.7$ %%.7$ %%.7$
9 %2.84 %2.84 %2.84 %2.84
8 %7.22 %7.22 %7.22 %7.22 %7.22
? %7.89 %7.89 %7.89 %7.89
%0 %=.4? %=.4? %=.4?
%2 %=.79 %=.79
%4 %$.$? %$.$? %$.$?
%7 %9.%$ %9.%$ %9.%$ %9.%$
%= %9.$8 %9.$8 %9.$8
%$ %9.%? %9.?% %9.?%
%9 %9.?4 %9.?4 %9.?4
%8 %8.24 %8.24 %8.24
%? %8.7= %8.7= %8.7=
20 %8.?8 %8.?8 %8.?8 %8.?8
2% 20.7% 20.7% 20.7%
22 20.84 20.84
24 2%.0= 2%.0=
27 2%.47 2%.47
2= 22.7% 22.7% 22.7%
2$ 22.$% 22.$%
29 22.?9 22.?9
28 27.$?
2? 2=.47 2=.47
40 28.04 28.04
(a*le :F
&ummary of *etention +imes of Aroclors or (,-0.
Procedure $9%0
@evised 04009
?