Graphitized Carbon Black: A Unique Adsorbent for Gas
Chromatography and Related Techniques
F. Bruner* / G. Crescentini / F. Mangani
Istituto di Scienze Chimiche, Universit~t di Urbino, Piazza Rinascimento 6, 1-61029 Urbino,
Key Words
Gas-chromatography
Graphitized carbon black
Sample trapping and concentration
Summary
The p r o p e r t i e s of graphitized carbon blacks which
have been exploited in gas chromatography and re-
lated techniques, are reviewed together with some of
the many applications accomplished in the last twenty
years. G r a p h i t i z e d carbon blacks are non-specific,
non-porous adsorbents, characterized by a high sur-
face homogeneity. These adsorbents can therefore be
used in gas-solid chromatography even for the elution
of polar compounds, though gas-liquid-solid chroma-
tography is the main field of application. In fact, by
changing the type and a m o u n t of liquid modifier,
highly selective and efficient (packed or capillary)
columns, tailored for the separation of very complex
mixtures, can be prepared. Graphitized carbon blacks
also possess hydrophobic properties so that they can
be efficiently used for the trapping and the precon-
centration of organic compounds contained in air and
water samples.
Graphitized carbon blacks (GCBs), a rather large fa-
mily of adsorbents obtained when some carbon blacks
are h e a t e d at high t e m p e r a t u r e in an oxygen-free
atmosphere, were extensively studied on account of
their special properties, by chemical physicists in the
fifties and sixties [1, 2].
Carbon blacks undergo graphitization to a higher or
lower extent according to the starting material, usually
petroleum or natural gas, and the operating condi-
tions. T h e r e f o r e these materials may differ essentially
in their surface area and extent of graphitization, the
larger the graphitization, the smaller the surface area,
which ranges between 100 and 6 m 2 g-1. In the latter
case, GCB approaches the properties of pure graphite
and in general it can be said that the most pure and
h o m o g e n e o u s adsorbent is the one with the lowest
surface area [3].
Chromatographia Vol. 30, No. 9/10, November 1990
0009-5893/90/11 0565-08 $ 03.00/0 9 1990 Fricdr. Viewcg & Sohn Verlagsgcsellschaft mbH
Italy
Graphitized carbon blacks as adsorbent for gas chro-
matography were studied in the sixties by Kiselev and
his coworkers [4], who carried out pioneering work in
this field, as well as Horvath [5] and Guiochon and
corworkers [6].
Some unusual properties make graphitized carbon
blacks markedly different from other adsorbents and
affect their chromatographic behaviour.
Such properties can be summarized as follows:
1. The surface is homogeneous and without micro-
pores;
2. as a consequence of the physical homogeneity of
the surface the distribution of the energy of ad-
sorption can be considered for the "Gaussian" type;
3. GCBs are non-specific adsorbents, which means
that L o n d o n dispersion forces are the driving
forces in the adsorption process.
A straight consequence of these properties is that very
polar and small molecules such as water, are not
strongly adsorbed in practice from the gas phase, and
show very low heats of adsorption. The behaviour of
water on graphitized carbon black in comparison with
that of the non-graphitized material is well shown in
Figures 1 and 2, taken by the original work of Millard
et al. [7]. Obviously the graphitization process, ex-
pecially if followed by hydrogen treatment at high
temperature, eliminates the specific adsorption sites
and hinders the formation of hydrogen bonds. Thus
the water molecules "slide off" the adsorbent, which is
then unaffected by the action of this ubiquitous
compound. Thus burns out to be a very i m p o r t a n t
property when GCB is used as a stationary phase in
gas chromatography and related techniques (such as
solid-phase extraction and air sampling).
The further treatment of GCB with hydrogen at about
1200 ~ eliminates the few remaining specific adsorp-
tion sites to such an extent that linear adsorption iso-
therms are obtained for polar compounds such as
methanol, even at very low coverage. Linear gas-solid
chromatography is obtained for alcohols at the nano-
gram level, while one order of magnitude higher is still
necessary for linear elution of free fatty acids and
amines [8]. Even with these limitations, the possibility
of eluting small amounts of polar compounds in a gas-
solid chromatographic column [9] accounts for the
Reviews 565
 I c~
~, ~ 0 ~ 1..~0U
5 3-5
E 80

70
u3"0 ',
"~ GO
43
2.5 "--,

40 2.0
o
E 30
<

20
;~ 1.5I
3,5 2.700 ~
i10
~ 2'000~

0.1 0.2 0.2 0.4 05 06 0.7 0 B 0 9 3"0

P IPo 15
Figure 1 d~z.5
Adsorption isotherms for water at 30 ~ o on ungraphitized
carbon black (Spheron 6); 9 on same carbon black graphitized
(Graphon), hydrogen treated. (From Millard et al. [7]; courtesy
American Chemical Society).
AICt
0 I 2 0 I 2 3
VIVa,
Figure 3
13 Calorimetrically measured heats of adsorption of argon on
0 Spheron carbon blacks at - 195 ~ against surface coverage, for
blacks graphitized at progressive higher temperatures. Broken line
represents untreated black. (From Becbc and Young [10]; courtesy
American Chemical Society).

11
I0 I I I , I I I,. I
~--2~-I-
0.2 0-~ 0.~ 0-6
P/Po
Figure 2
Isosteric heats of adsorption of water against coverage (1) on un-
graphitized carbon black (Spheron 6); (2) on same carbon black,
graphitized (Graphon), hydrogen treated. (From Millard et al. [7];
courtesy American Chemical Society).
unique p r o p e r t i e s of G C B with respect to other ad-
sorbents such as silica gel and alumina.
A n o t h e r i m p o r t a n t feature of GCB, due to the high
uniformity of the energy of adsorption, is that when a
molecule is adsorbed from the gas phase, the adsorp-
tion energy is affected by the presence of molecules of
the same substance previously adsorbed. The modifi-
cations induced are due to lateral interactions with the
m o l e c u l e u n d e r g o i n g the a d s o r p t i o n process. This
effect causes an increase in the heat of adsorption with
surface coverage, as shown in Figure 3, w h e r e the
change in heat of adsorption with coverage is reported
for a carbon black at different degrees of graphiti-
zation. This fine work by Beebe and Young [10] shows
several i m p o r t a n t effects that occur when a homo-
geneous a d s o r b e n t is modified by different a m o u n t s
adsorbed on its surface.
Initially, the first molecules adsorbed "cover" the most
active sites as shown by the sharp decrease in the heat
of adsorption at low coverages for the lower tempera-
ture G C B (less graphitized). A t higher coverages,
lateral interactions take place and a substantial in-
crease of the heat of adsorption, followed by a maxi-
m u m and a sharp decrease is observed. The latter is
interpreted as the effect of m o n o m o l e c u l a r layer for-
mation, which hinders new molecules f r o m the gas
p h a s e fully interacting with the adsorbent. In many
cases a second m a x i m u m is observed that takes into
account a second monolayer formation. It is generally
agreed that m o n o l a y e r f o r m a t i o n coincides with the
inflection po!nt in the heat of adsorption curve.
W h e n the gas c h r o m a t o g r a p h i c (GC) method became
available, Kiselev et al. confirmed with this technique
what had b e e n found calorimetrically with very good
agreement between the two kinds of m e a s u r e m e n t [11].
M e a s u r e m e n t s carried out using n-hexane as adsorbate
a g r e e d within 10 %. It is i m p o r t a n t to note that,
qualitatively, the curves obtained by Beebe and Young
are identical to those of Kiselev and Yashin.
In the early seventies our group became interested in
g r a p h i t i z e d c a r b o n b l a c k s m o d i f i e d with small
amounts of liquid phase, as stationary phases for GC.
Very good separations were obtained for deuterated
and tritiated isotopic hydrocarbons [12, 13] by coating
G r a p h o n and Sterling FT with very small amounts of a
non-polar liquid phase such as squalane.

566 Chromatographia Vol. 30, No. 9/10, November 1990 Reviews

In the same years, outstanding separations were ob-
tained for either basic [14] or acidic [15] compounds

/t
=,,.~ I l r u n e r f:l: h i .
using polar modifiers. Subsequently, the term Gas-
Liquid-Solid C h r o m a t o g r a p h y (GLSC), first intro-
duced by Purnell [16], was used to indicate the tech- t~H
KI n e l r ~ v c n l o r l meLt-It
Ih c,,ll.,,olel
nique of coating an adsorbent with small amounts of
appropriate substances to obtain particular GC sta-
tionary phases.
'[ I;
~)~_/ b"'~176176 " .

Our group also carried out a detailed study to estab-

lish the working mechanism of GLSC [17]. Increasing
amounts of two liquid phases with very different
polarities, squalane and glycerol, were coated re-
spectively on Graphon. It should be pointed out that
Graphon was obtained by graphitization of Spheron 6,
which is the same carbon black used by Beebe and
Young for the determination of differential heats of
adsorption of argon. The isosteric heats of adsorption,
obtained from retention volumes at different tempera- . . . . , . . . . , . . . . ,,
0 c15 10 1.5 2.0 ~ ~.5
tures, have been measured for n-hexane, for different
' ; ' ' ' ' ' '"- ' .2t2
squalane coverage of the Graphon surface. The curve, 0 02 U,,| (t.G (tl] .L) I
- '~'o ~el"'~lnwe'
heat of adsorption vs coverage, is compared with those
Figure 4
obtained chromatographically and calorimetrically by
lsostcric heat of adsorption for n - h c x a n c on graphitizcd carbon
Kiselev [11] in Figure 4. From this comparison and
black at various coverages calculated by GLSC and other methods.
remembering the curves of Figure 3, it can be easily (Bruner et al. [17]; ccmrtcsy American Chemical Society).
seen that, by covering the adsorbent with increasing
amounts of the adsorbate or a liquid phase, with a
chemical structure similar to that of the adsorbate,
similar heats of adsorption curves are obtained. Other
type of GCBs of lower specific surface, such as
A v ~, o=o
Sterling FT, P-33 and Sterling MT yielded the same
results [18, 19]. The working mechanism has been
explained with the simple model reported in Figure 5
[20,21] which describes the different situations en-
B <p 9 cp ~
countered by a molecule adsorbed from the gas phase
as the surface coverage changes. This takes into ac-
count the deactivating effect of the modifier at very c o 9 o-.-o 9 o
low coverages (B), when the relatively few active sites
are preferentially covered so that the isosteric heat of
adsorption decreases. In situation (C) the effect of
lateral interactions is shown and the adsorbed mole-
cule is u n d e r the influence of both the adsorbent
D OOOvO--O/OXg--QOO o=l.o

surface and modifier. Situations (D) and (E) are of

obvious interpretation.
Situation (C) is perhaps the most interesting for
analytical purposes. It] fact, by appropriately changing
the liquid modifiers, one is able to change the polarity
and introduce specific interactions which allows se-
lective separations. By using squalane at 0.4 % (w/w),
a coverage of the Graphon surface of about 3 % was
obtained, and this enhanced the anomalous isotope
effect [22]. In fact, when lateral interactions are
stronger, not only the absolute heat of adsorption
reaches a maximum, but also the differences between
isotopic molecules are maximized [21]. With such a
column, the separation of CH3D from natural C H 4 w a s
achieved by means of a recycling technique [12]
according to the chromatogram shown in Figure 6. By
using a p p r o p r i a t e modifiers and exploiting the
counteracting effects of a polar modifier such as
Carbowax [19] or picric acid [23], and of the graphitic
surface, outstanding separations have been obtained
with packed columns.
E~ 0 = 1 . 5
Fig.re 5
Model explaining behaviour of isostcric heat of adsorption with
surface coverage, o Molcculcs of modifier, 9 molecule of com-
pound clutcd.
The most interesting example: separation of all C1-C5
aliphatic alcohols is reported in Figure 7. H e r e the
effect on the separating power of the column in terms
of the separation factor is shown. By changing the
liquid phase from 0.15 % to 0.19 % a significant shift
of the peaks takes place. In Figure 8 the separation of
the C4 hydrocarbons on GCB modified by picric acid
is also shown.
Linear and fast elution of small amounts of sulphur
compounds was obtained by modifying the carbon

Chromatographia Vol. 30, No. 9/10, November 1990 Reviews 567

 Cyct~11I
t~ "7
cyete I Cyc/~ II [I
L~

2,: C),clP II e

~,.
.. t~
z
z
Figure 6
Successive enrichments of CH3D starting from natural methane.

A l
Hatched areas, trapped; white areas, ventcd. (Courtesy McMillan
Journal Ltd.).

| ! [ I
0 8 12 t i m e (rain/ 76

4 13
12 ~
Figure 8
C hydrocarbons at 50 ~ on 2.2 m x 2 mm I.D. column containing
Carbopack C (100-120 mcsh) + 0.19 % picric acid; pressure drop:
14 15 16 4.8 Kg/cm2; linear carrier gas velocity: 10.9 cm/s 1. (Courtesy
American Chemical Society).

I I I I I [ ....

.0 I 2 3 4 5

-!

1/
13
b
16
~2,~, .'I U ppb

111-

!
0

Figure 7
2
I I
3
,, I

Separation of C~-Cs alcohols on 80 100 mesh Carbopack F coated

4
rain
I
5

~ I ~ I L I
1-1 20 p p b

I
0 1 P.
with 0.19 % (a) and 0.15 % (b) Carbowax 1500. time [ m l n l
Column: glass, 2 m x 2 mm I.D. Temperature: 128 ~ Flame ioni-
zation detection. Peaks: 1 = methanol; 2 = ethanol; 3 : 2-propanol; 4 Figure 9
= 1-propanol; 5 = 2-methyl-2-propanol; 6 = 2-butanol; 7 = 2-methyl- Chromatogram of artificial mixture of sulfur compounds in air.
1-propanol; 8 = J.-butanol; 9 = 2-methyl-2-butanol; 10 = 2,2-di- Column: 80 c m x 0.4 cm I.D., Graphon 40-60 mesh + 0.7 %
methyl-l-propanol; 11 = 3-methyl-2-butanol; 12 = 3-pentanol; 13 = 2- phosphoric acid + 0.7 % XE60. Room temperature, carrier gas:
pentanol; 14 = 2-methyl-l-butanol; 15 = 3-methyl-l-butanol;16 = 1- nitrogen; Flow rate: 100 ml min :; inlet pressure: 0.6 Kg cm 2.
pcntanol. (Courtesy Elsevier Scientific Publishing). (Courtesy American Chemical Society).

s u r f a c e w i t h p r o p e r a m o u n t s of two m o d i f i e r s , a n i q u e , a n d m u c h use of p a c k e d c o l u m n s is m a d e by
cyanosilicone GEXE60 a n d o r t h o p h o s p h o r i c acid c h r o m a t o g r a p h e r s , especially for e n v i r o n m e n t a l anal-
[24], as s h o w n in F i g u r e 9. ysis, since the p r o d u c t b e c a m e c o m m e r c i a l l y a v a i l a b l e
T h e e x a m p l e s given, t o g e t h e r with the c h r o m a t o g r a m [27].
in F i g u r e 10, w h e r e the s e p a r a t i o n of the m o s t widely More recently o u r g r o u p s u c c e e d e d in m a k i n g fused
u s e d c h l o r o f l u o r o c a r b o n s is r e p o r t e d [25, 26], are silica capillary c o l u m n s with the i n n e r surface coated
t h o s e t h a t show b e s t the selectivity o b t a i n e d in G C with m o d i f i e d G C B [28, 29]. O n e i n t e r e s t i n g f e a t u r e o f
with g r a p h i t i z e d c a r b o n blacks. M a n y m o r e s e p a r a - these c o l u m n s is that the C t e r m of the V a n D e e m t e r
t i o n s of p r a c t i c a l i n t e r e s t are possible with this tech- e q u a t i o n is a n o r d e r of m a g n i t u d e lower with respect

568 Chromatographia Wol. 30, No. 9/10, November 1990 Reviews

 -T'I'O'C'-5"C~jb--HOLD----5"@mn 11 la ]O'~,c, . .-HOLD.--
I/1~ Ii1G II
6 ib 20 z'o 4o (mini
Figure 10
Separation of C1-C2 halearbons. Column: 3 m x 2 mm I.D.,
Carbopack B + 0.5 % SP1000. FID' AP = 4 Kg/cm initial flow rate:
40 ml rain I (nitrogen). Peaks: 1 = 'Ctl3CI; 2 = CFC22; 3 -- CH3Br;
4 = CFC12; 5 = C2H5CI; 6 = CFC21; 7 = CH3I; 8 = CH2CIx,
9 = CFCll4; 10 = CFCll; 11 = 1,1-dichloroethane; 12 = CHCI;
13 = CFCll3; 14 = 1,2-dichloroethane; 15 - CCI3CH3; 16 = CCI4;
17 = 1,1,2-trichlorocthylene; 18 = 1,1,2-trichloroethane; 19 = C2C14.
(Courtesy Elsevier Scientific Publishing).
5
I
12
t ! * with C a r b o p a c k B m o d i f i e d with 1 % w/w of SP1000.
a s iiiin
Figure 11
Separation of selected halocarbons on fused silica capillary
column (32 m x 0.53 mm I.D.) coated with Carbopack B + 1%
SP1000. Carrier gas: hydrogen, u = 30 cm/sec. Temperature pro-
gram: 30 ~ (2'), then 20 ~ mm -t up to 180~ Peaks: 1 = CFC12; 2 =
CFCII4; 3 = CFCll; 4 = C2H2C12; 5 = CFCl13; 6 = CCH3CI3; 7 =
CC14; 8 = C2C1r
to c o n v e n t i o n a l G L C c o l u m n s , as t h e o r e t i c a l l y f o r e -
cast b y G i d d i n g s f o r v e r y h o m o g e n e o u s a d s o r b e n t s
[30], s o t h a t f a s t e r a n d m o r e effective s e p a r a t i o n s can
be o b t a i n e d .
F u r t h e r , t h e s e c o l u m n s s h o w t h e s a m e e f f i c i e n c y as
c o n v e n t i o n a l W C O T c o l u m n s . T h u s , t h e high selec-
tivity t y p i c a l of G L S C c o u p l e d to the high efficiency of
c a p i l l a r y G C m a k e t h e s e c o l u m n s a p o w e r f u l tool for
the s e p a r a t i o n of v e r y c o m p l e x m i x t u r e s . If c o l u m n s
c o u l d b e p r e p a r e d c o a t e d with G C B s m o d i f i e d with
Chromatographia Vol. 30, No. 9/10, November 1990
I~
go
.i, ' ~ ' 4. . . . 6 h ' Inhl ,
Figure 12
Separation of C3-C5 hydrocarbons mixture on same column as
Figure 11. Column tcmpcrature: 30 ~ u = 27 cm scc-1, carrier gas:
hydrogen. Peaks: 1 -- propane; 2 = propylenc; 3 -- isobutane, n-
butane, isobutylcnc, 1-butcne, trans-2-butenc, 1,3-butadiene, cis-2-
butene, 4 = isopcntane; 5 = pcntane.
p r o p e r a m o u n t s of d i f f e r e n t l i q u i d p h a s e s , t a i l o r e d
c o l u m n s of u n a c h i e v e d r e s o l u t i o n p o w e r w o u l d b e
a v a i l a b l e . T w o r e c e n t results o b t a i n e d with this t y p e of
c o l u m n s a r e s h o w n in F i g u r e 11 and 12.
F i g u r e 11 s h o w s t h e s e p a r a t i o n of s o m e h a l o c a r b o n s
c a r r i e d o u t in less t h a n 5 m i n u t e s on a c o l u m n c o a t e d
In F i g u r e 12 t h e s e p a r a t i o n of a C3-C5 m i x t u r e u n d e r
i s o t h e r m a l c o n d i t i o n s is r e p o r t e d . N o t e w o r t h y is t h e
s e p a r a t i o n of t h e C4 h y d r o c a r b o n s . T h e s a m e p r o -
p e r t i e s t h a t m a k e G C B s w i d e l y used G C s t a t i o n a r y
p h a s e s , m a k e t h e m v e r y g o o d m a t e r i a l s for t r a p p i n g
a n d e n r i c h m e n t of o r g a n i c p o l l u t a n t s f r o m air a n d
water samples.
T h e a d s o r b e n t s u s e d for the e v a l u a t i o n of o r g a n i c
c o m p o u n d s in o p e n a i r o r in t h e a t m o s p h e r e o f
w o r k i n g sites can b e g e n e r a l l y p u t in two c a t e g o r i e s :
" s t r o n g a d s o r b e n t s " such as a c t i v e c h a r c o a l , w h i c h
r e q u i r e s o l v e n t e x t r a c t i o n , a n d "light a d s o r b e n t s " such
as G C B s , T e n a x a n d o t h e r s which r e q u i r e t h e r m a l
d e s o r p t i o n . T h e m a i n d i s a d v a n t a g e s in t h e use o f
" s t r o n g a d s o r b e n t s " a r e t h e n e e d to s a m p l e l a r g e
v o l u m e s of air a n d m o r e c o m p l e x m a n i p u l a t i o n of t h e
s a m p l e [26]. O n t h e o t h e r h a n d " l i g h t a d s o r b e n t s "
s h o u l d p o s s e s s c e r t a i n p r o p e r t i e s to a v o i d i r r e p r o -
ducible results and contamination ("ghost com-
p o u n d s " ) . F i r s t t h e y s h o u l d b e a b l e to t r a p t h e l a r g e s t
Reviews 569
n u m b e r o f c o m p o u n d s even w h e n large v o l u m e s o f air v o l u m e ) , so t h a t l a r g e v o l u m e s of air n e e d to be
n e e d to b e s a m p l e d . S e c o n d l y , t h e y s h o u l d n o t p o s s e s s a m p l e d . This p r o b l e m has b e e n s o l v e d by using cold
sites a c t i v e t o w a r d s t h e c o m p o u n d s of i n t e r e s t a n d t r a p p i n g on G C B s [25, 32]. T a b l e II shows t h e B T V of
s h o u l d r e l e a s e h i g h e r b o i l i n g c o m p o u n d s by h e a t i n g at t h e s e c o m p o u n d s o n C a r b o p a c k B a n d C a r b o p a c k C.
low t e m p e r a t u r e . In this way, p o s s i b l e d e c o m p o s i t i o n M o s t o f t h e h a l o c a r b o n s a r e lost at r o o m t e m p e r a t u r e
or o t h e r u n d e s i r e d r e a c t i o n s a r e a v o i d e d . T h i r d l y , t h e y on C a r b o p a c k B while this d o e s n o t o c c u r at - 93 ~
should not retain significantly ubiquitous compounds,
in p a r t i c u l a r w a t e r , which m a y s t r o n g l y affect b o t h the
t r a p p i n g efficiency of the a d s o r b e n t a n d the successive
d e t e r m i n a t i o n by G C . A l l t h e s e r e q u i r e m e n t s a r e m e t
by G C B s t h a t , as p r e v i o u s l y d i s c u s s e d , a r e n o n - p o l a r ,
Table II Break-through volumes (ml) of Halocarbons on Carbo-
i n e r t a d s o r b e n t s with h y d r o p h o b i c p r o p e r t i e s . pack B and C. (Courtesy Elsevier Scientific Publishing)
T a b l e I [30, 31] s h o w s t h e r e c o v e r i e s o b t a i n e d with
C a r b o p a c k C a n d C a r b o p a c k B, two k i n d s of G C B s Carbopack B Carbopack C
(specific surface: 12 m e g q a n d 90 m 2 g-a r e s p e c t i v e l y ) , Compound
20~ _ 93~ -93 ~
for s e v e r a l classes of c o m p o u n d s w h i c h m a y be of
i n t e r e s t in t h e m o n i t o r i n g of the i n d o o r air of w o r k i n g CH3CI 6.1 8.000 -
sites. It can b e c l e a r l y s e e n t h a t t h e G C B with t h e CFC22 6.5 10.000 30
s m a l l e r s u r f a c e r e q u i r e s t h e s a m p l i n g of v e r y s m a l l CFC12 32 65.000 300
CFC21 71 100.000 4.000
v o l u m e s o f air, since t h e c o m p o u n d s show a v e r y small
CH2C12 200 > 4(X).000
b r e a k - t h r o u g h v o l u m e ( B T V ) on C a r b o p a c k C. T h i s CFC114 250 > 400.(X)0 -
i n c o n v e n i e n c e is o v e r c o m e by u s i n g C a r b o p a c k B CFC11 400 > 400.(XX) > 10.000
w h i c h a l l o w s a full r e c o v e r y of t h e c o m p o u n d s of CHCI2CH3 450 > 400.(X)0 > 10.(X)0
m a j o r i n t e r e s t , with air s a m p l e s up to 0.5 L. CHCI3 500 > 400.0(0) > 10.000
CFCll3 600 > 400.0(X) > 10.000
Another interesting application concerns the deter- CH2CICH2C1 700 > 400.000 > 10.000
m i n a t i o n of h a l o c a r b o n s in o u t d o o r air s a m p l e s in t h e CCH3CI3 2.000 > 400.000 > 10.000
context of the chlorofluorocarbons (CFC's)-ozone CC14 2.000 > 400.000 > 10.000
p r o b l e m [31]. T h e v o l a t i l i t y of C F C ' s d i f f e r q u i t e CCI2CHCI > 10.000 > 400.000 > i0.000
strongly and their average background concentration CHCI2CH2CI > 10.000 > 4(X).000 > 10.000
r a n g e s b e t w e e n 0 . 5 p p b a n d a few p p t (10 -12 by C2C14 > 10.000 > 400.000 > 10.13130

Table I Recovery (%) of organic compounds from air samples using Carbopack B and C traps. (Courtesy F.
Vieweg & Sohn/Pergamon Press)

Carbopack C

Sampling volumc (nil) 10 50 100 200 300 400 500

Methanol 11.0 1.6 1.2 0 0 0 0
Ethanol 60.2 2.1 1.8 0 0 0 0
Acetone 100 4.5 4.0 0 0 0 0
Methylethylketone 100 100 100 3.7 2.9 0.7 0.1
Ethyl acetate 100 100 100 100 18.8 15.7 3.5
Cyclohexane 100 100 100 6.2 2.8 2.2 1.5
Methylcyclopentane 100 100 100 100 100 6.6 1.6
Dichloropropane 100 100 100 100 8.6 5.1 3.4

Carbopack B

Sampling volume (ml) 10 50 100 200 300 400 500

Methanol 90.4 14.l 12.6 2.2 2.2 2.2 2.2
Ethanol 100 100 100 100 80 75.3 32.4
Acetone 100 100 100 100 100 I(X) 100
Methylethylketone 100 100 100 100 100 100 100
Ethyl acetate 100 100 100 100 100 100 100
Cyclohexane 100 100 100 100 100 i00 100
Methylcyclopentane 100 100 100 100 100 100 100
Dichloropropane 100 100 100 100 100 100 100

* Hexane isomers, Cyclohexanone, Benzene, Toluene 100 % recovery in each case.

570 Chromatographia Vol. 30, No. 9/10, November 1990 Reviews

A v o l u m e of 7 L is sufficient for the simultaneous Table ill Recoveries of some chlorinated pesticides from
d e t e r m i n a t i o n of all the c o m p o u n d s listed, while different adsorbents.
(Courtesy Elsevier Scientific Publishing)
volumes as small as 50 ml may be used [33] if only the
most important compounds [34] are measured. In this
respect, C a r b o p a c k C may also be used if the m o r e Recovery (%)
Pesticide
volatile compounds(i.e. CFC 22) are excluded. Carbopack B Tenax Porapak P C18
Graphitized carbon black cartridges have also b e e n
cz-BHC 93 8i 55 95
used with success for solid phase extraction (SPE) of
~-BHC l(/0 81 61) 93
organic pollutants such as polynuclear a r o m a t i c hy- ~/-B HC 100 77 51 93
drocarbons (PAHs), chlorinated pesticides, phthalates Heptachlor 97 94 70 96
and herbicides from water. The compounds of interest 6-B HC 97 94 50 96
are then eluted from the cartridge by using the right Aldrin 96 88 71 88
amount of a suitable solvent (or solvent mixture). In Hcptachlor epoxide 95 100 63 99
this field SPE is the emerging technique because of the 4,4'-DDE 100 87 77 93
Dieldrin 100 95 8(1 95
well-known advantages offered over liquid-liquid ex- Endrin 99 89 75 94
traction and because cartridges packed with a variety 4,4'- D D D 100 83 63 92
of a d s o r b e n t s are now commercially available. The 4,4'-DDT 100 86 55 95
experimental parameters, type and a m o u n t of extrac-
tion solvent, are obtained from elution and recovery
curves, such as those shown in Figure 13, which are
also helpful in understanding the working mechanism spiking the a d s o r b e n t (at n a n o g r a m level) and the
of the various solvents [36]. These curves show that by water (at ppt level) with the compounds of interest. In
using a mixture of two solvents (toluene-light petro- general, recovery data are very good with the excep-
leum) a similar and very good recovery can be ob- tion of the heavier P A H s . This problem may be solved
tained for the three c o m p o u n d s though different be- by using hot extraction or GCBs of lower surface area.
haviouris observed when the single solvents are used. T h e small differences between the data of columns A
It seems that the role of light p e t r o l e u m consists in and B are probably caused by adsorption on the glass
removing the compounds (see heptachlor curves) from wall of the reservoir while the large differences ( P A H s
the few sites for which toluene is active. This tech- and di-n-octyl phthalate) can be explained by the poor
nique was further d e v e l o p e d and extended to other solubility of these c o m p o u n d s in water. It should be
compounds [37]. Table Ill shows the comparison with pointed out that these results have been obtained using
other adosrbents in the recovery of chlorinated pesti- 50 mg of adsorbent and 1 ml of the extraction mixture.
cides: P o r a p a c k P gives very low recoveries while High preconcentration ratios can be reached (1 : 2000)
T e n a x T A shows a better performance although some taking also into account that light p e t r o l e u m can be
problems exist with the elution of BHCs. rapidly eliminated by nitrogen flushing.
C a r b o p a c k B gives the best overall recoveries with in conclusion cartridges containing G C B s can be effi-
values near 100 % in most cases and lower, but stitl ciently used in e n v i r o n m e n t a l analysis for sampling
good recoveries, are o b t a i n e d with C18. H o w e v e r organic pollutants from air and water. An important
twice the usual a m o u n t of adsorbent was used for the feature is that these cartridges can be easily cleaned
latter case. Table III shows the recoveries obtained by and reused without any limitation.

10( . . . . 100

~0

60 6O

/.ll

/(/
40 40

2C 11/ 20

~ ' a g - ~ 4 6 8 Vim II
2
. . . . . ~ , ~ , i i t

1 2 1 2

Figure 13
Elution and recovery curves for some pesticides with different solvents on Carbopack B traps: 9 light petroleum-toluene (2 : l); ~ toluene;
o light petroleum (Courtesy American Chemical Society).

Chromatographia Vol. 30, No. 9/10, November 1990 Reviews 571

Table IV Recovering of pesticides, herbicides, phthalates and [7] B. Millard, E. G. Caswell, E. E Leger, D. R. Mills, J. Phys.
PAHs from Carbopack B obtained by spiking adsorbent (a) and Chem. 59, 976 (1955).
by spiking water (b). [8] A. Di Corcia, F. Brunet, Anal. Chem. 43, 1634 (1971).
(Courtesy Elsevier Scientific Publishing). [9] W. R. Betz, IV, R. Supina, J. Chromatogr. 471, 105 (1989).
[10] R. A. Beebe, D. M. Young, J. Phys.Chem. 58, 93 (1954).
[11] A. V. Kiselev, Y. L Yashin, "Gas Adsorption Chromatogra-
Compound Recovery (%) phy", Plenum Press, New York, 1969, p. 128.
type
Compound A B [12] F. Bruner, G. Canulli, A. Di Corcia, A. Liberti, Nature 231,
175(1971).
Pesticides ct-BHC 93 94 [13] F. Bruner, P. Ciccioli, A. Di Corcia, Anal. Chem. 44, 849
13-BHC 100 96 (1972).
~'-BHC 100 95 [14] A. Di Corcia, D. Fritz, F. Bruner, Anal. Chem. 42, 1500
Heptachlor 98 87 (1970).
6-BHC 98 94 [15] F. Bruner, A. Liberti, M. Possanzini, L Allegrini, Anal.
Aldrin 96 90 Chem. 44, 2070 (1972).
Heptachlor epoxide 95 97 [16] J. H. Purnell, "Gas Chromatography", Wiley, New York,
4,4'-DDE 100 92 1972, p. 376.
Dieldrin 100 97 [17] t;. Bruner, P. Ciccioli, (7i. Crescentini, M. T. Pistolesi, Anal.
Endrin 99 99 Chem. 45, 1851 (1973).
4,4'-DDD 100 94 [18] F. Bruner, G. BertonL P. Ciccioli, J. Chromatogr. 120, 307
4,4"-DDT I(X) 95 (1976).
[19] E Mangani, i7. Bruner, J. Chromatogr. 289, 85 (1984).
Herbicides 2,4-DME ~ 92
[20] G. Crescentini, Doctorate Thesis in Analytical Chemistry,
Trifluralin 98 92
Simazine 100 97 University of Rome, 1972.
[21] F. Bruner, G. Crescentini, F. Mangani, Pure & Appl. Chcm.
Atrazine 96 93
61, 1997 (1989).
Propazine 100 97
[22] A. Di Corcia, A. Liberti, Trans. Faraday Soc. 66, 967 (1970)
2,4,5-TME 96 92
and citation therein.
DCPA 99 98 [23] A. Di Corcia, R. Samperi, Anal. Chem. 47, 1853 (1975).
Phthalates Di-n-Butylphthalate 100 100 [24] F. Bruner, P. Ciccioli, F. Di Nardo, Anal. Chem. 47, 141
Butylbenzylphthalate 100 100 (1975).
Bis(2-Ethylhexyl)phthalate 100 100 [25] G. Crescentini, F. Brunet, Ann. Chim. 68, 343 (1978).
Di-n-octylphthalate I(X] 50 [26] /7. Bruner, G. Bertoni, G. Crescentini, J. Chromatogr. 167, 399
PAHs Acenaphthene 99 87 (1978).
Acenaphthylene 100 88 [27] Supelco Catalog no. 27, Bcllefonte, PA, USA, 1989.
Fluorene 89 89 [28] E 13tuner, G. Crescentini, 1~ Mangani, P. Palma, M. Xiang, J.
Phenanthrene 99 88 Chromatogr. 399, 87 (1987).
Anthracene 100 87 [29] F. t3runer, G. Crescentini, IZ Mangani, L. Lattanzi, J. Chro-
Fluoranthene 69 57 matogr. 473, 93 (1989).
Pyrene 65 48 [30] Z C. Giddings, Anal. Chem. 36, 1170 (1964).
[31] P. Ciccioli, G. Bertoni, E. Brancaleoni, R. Fratarcangeli, F.
Brunet, J. Chromatogr. 126,757 (1976).
[32] F. Mangani, A. R. Mastrogiacomo, O. Marras, Chroma-
tographia 15, 712 (1982).
[33] G. Crescentini, F. Mangani, A. R. Mastrogiacomo, A. Cap-
piello, F. Brunet, J. Chromatogr. 280, 146 (1983).
[34] M. Maione, G. Crescentini, I': Mangani, 1( /3runer, Paper
References presented at the "First Italian Meeting on the Antarctic
Project: Environmental Impact and Chemical Methodo-
[1] D. M. Young, A. D. Crowell, "Physical Adsorption of Gases", logies", Rome, June 8-9, 1990.
Butterworths, London, 1962, and references therein. [35] "Montreal Protocol on Substance that deplete the Ozone
[2] S. Ross, J. P. Oliver, "On Physical Adsorption", Intcrscience, Layer; Final Act". United Nations Environment Programme-
NewYork, 1964 and references therein. Montreal, Canada, Sept. 16, 1987.
[3] G. Crescentini, F. Mangani, A. R. Mastrogiacomo, P. Palma, [36] F. Mangani, G. Crescentini, F. Bruner, Anal. Chem. 53, 1672
J. Chromatogr. 392, 83 (1987). (1981).
[4] A. V. Kiselev, Y. L Yashin, "Gas Adsorption Chromatogra- [37] F. Mangani, G. Crescentini, P. Palma, 1,: Bruner, J. Chroma-
phy", Plenum Press, New York, 1969 and references therein. togr., 452, 527 (1988).
[5] L Halasz, G. Hovart, Anal. Chem. 34, 409 (1969).
[6] C. Vidal Madjar, G. Ganasia, G. Guiochon, "Gas Chroma- Received: June 21, 1990
tography 1970", R. Stock (Editor), Institute of Petroleum, Accepted: July 20, 1990
London, 1971, p.20. D

572 Chromatographia Vol. 30, No. 9/10, November 1990 Reviews