ANALYTICA

CHIMICA
ACTA
ELSEVTER Analytica Chimica Acta 311 (1995) 85-91

Determination of trace elements in heavy oil samples by graphite

furnace and cold vapour atomic absorption spectrometry after
acid digestion
Minna Turunen a,*, Sirpa PerZniemi a, Markku Ahlgren a, Henrik Westerholm ’
a Unilwsity of Joensuu, Department of Chemistry, P.O. Box I I I, FIN-80101 Joensuu, Finland
b Neste Oy, P.O. Box 310, FIN-06101 Por~~oo.Fmland

Received 3 January 1995; revised 13 March 1995; accepted 15 March 1995

Abstract

A procedure was developed to determine the concentrations of trace elements (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb and
V) in heavy oil samples. The wet digestion (HNO,-H,SO,) method developed for the sample preparation was both
repeatable and quantitative and allowed element determinations by graphite furnace atomic absorption spectrometry
(GFAAS) or cold vapour atomic absorption spectrometry (CVAAS) from the same sample solution. The detection limits
were low, and low concentrations of analyte could be determined accurately. V and Ni were determined also by inductively
coupled plasma atomic emission spectrometry (ICP-AES), in samples merely diluted with xylene (1 :lO), the ICP-AES
results were in good agreement with the GFAAS results.

Keywords: Atomic absorption spectrometry; Inductively coupled plasma spectrometry; Atomic emission spectrometry: Metals. trace
elements; Heavy oil samples

1. Introduction to be accurately determined because of the risk they

Trace elements in crude oil and petroleum prod-
ucts have received considerable attention in recent
years because of the value of trace element data in
understanding petroleum geochemistry and origin
[1,2]. Information on trace elements (such as As, Cu,
Fe, Hg, Ni, Pb, S and V) is also important in
petroleum cracking and refining, because these ele-
ments may cause corrosion or poisoning of the pro-
cess catalyst [3-61. In addition, trace elements need
* Corresponding author.
pose to health and the environment. It is well-known
that the trace elements in petrochemical products are
released during combustion, some of them (e.g., As,
Cd, Hg, Se, Pb) with harmful effects on human
health and environment [6-91.
If a trace element is present in an oil sample in a
sufficiently high concentration, it can easily be mea-
sured directly by neutron activation analysis (NAA)
[l,lO-121 or X-ray fluorescence spectrometry (xRF)
[9-111 with no need for sample preparation. Both
methods are rapid and nondestructive and allow mul-
tielement analysis. Element concentrations in oil
samples can also be measured by inductively cou-

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86 M. Turunen et al. /Analytica
pled plasma atomic emission spectrometry (ICP-
AES) [13] if the samples are diluted with an appro-
priate solvent (e.g., xylene). None of these methods,
however, is sensitive enough for direct trace element
determination, and a preconcentration step is re-
quired, e.g., dry or wet ashing for decomposition of
organic material in order to obtain aqueous solutions
[6,7,12,14]. The dry ashing method has the advan-
tage that inorganic standards can be used for the
calibration, but usually the accuracy suffers due to
losses of highly volatile elements [2,15]. Trace ele-
ment losses may also occur through absorption on
the walls of the ashing flask and/or by retention in
the acid-insoluble fraction of the ash [16]. Wet diges-
tion, with various acids, has been widely and suc-
cessfully applied for the determination of a variety of
elements [4,15-171. Wet digestion is fast and, owing
to the lower temperature, does not cause the
volatilization losses associated with dry ashing
[14,16].
NAA and ICP-AES techniques have been used
[l&19] for the determination of trace element con-
centrations in digested oil samples, but both are
highly expensive [12,19]. One disadvantage of the
ICP-AES technique is spectral interferences, which
make accurate trace element determinations in com-
plex matrices difficult. In addition, the detection
limits are not as good as those obtained by graphite
furnace atomic absorption spectrometry (GFAAS)
[12,19], which also has been successfully employed
for the determination of trace elements in oil samples
[8,12,15]. Among the advantages of GFAAS are
rapidity, simplicity, sensitivity, and good precision
[6,10]. For trace mercury determinations in digested
oil samples, cold vapour atomic absorption spec-
trometry (CVAAS) is the most sensitive AAS tech-
nique [lo]. The high sensitivity of these AAS meth-
ods means that extreme care is required to avoid
contamination [ 121.
In this work we developed and tested a wet
digestion method for heavy oil samples involving
decomposition in a HNO,-H,SO, medium. The
concentrations of the analytes in the resulting acidic
sample solution were measured by CFAAS or
CVAAS. The optimal analytical conditions and de-
tection limits for the AAS determination were inves-
tigated separately for each analyte. Vanadium and
nickel concentrations were also determined by the
Chimica Acta 31 I 11995) 85-91
ICP-AES method. The new digestion method was
used for the digestion of three different heavy oil
samples.
2. Experimental
2.1. Standard solutions, reagents and materials
Titrisol standards (Merck) for As, Cd, Co, Cr, Cu,
Hg, Mn, Ni, Pb, and V were used for the calibration
of the AAS. Standard stock solutions (1000 mg
metal/l) were stored in polyethylene bottles.
Organometallic reference standards were used for the
investigation of the digestion procedure. All stan-
dards were Conostan sulfonate metallo-organic stan-
dards (As and Hg 100 mg kg-‘, Cd and Cu 5000 mg
kg-‘, Co, Cr, Mn, Ni, and V 900 mg kg-‘), except
for Pb, which was Petrostandard lead naphthenate
(433.8 f 4 mg kg- ’ 1. The samples used for testing
the digestion procedure were prepared by diluting
metallo-organic standards with an appropriate
amount of Conostan Base Oil. In the GFAAS deter-
minations NiC12 (Merck, Titrisol, 1000 mg Ni/l) or
2% (NH,),HPO, (Merck, p.a.) was used as matrix
modifier, if necessary. Acids and all other reagents
were analytical reagent grade. Ultrapure water
(Mini-Q Plus) was used throughout the procedure.
The glassware was acid-washed (5% HCl and 10%
HNO,) overnight. The heavy oil samples was from
the North Sea area.
2.2. Apparatus
The digestion apparatus consisted of, a three-
necked round-bottomed flask, a regular addition fun-
nel, an addition funnel with by-pass tube, and a
Friedrichs condenser (Fig. 1). The flask was heated
by a heating mantle. If necessary, the thermoelement
can also be used for temperature monitoring. Trace
element concentrations were measured with a Varian
SpectrAA- atomic absorption spectrometer,
equipped with a GTA-96 graphite tube atomizer or
VGA-76 vapour generation accessory. Metal hollow
cathode lamps and a D,-background correction lamp
were used with the MS devices. V and Ni were also
measured with an Applied Research Laboratory ICP
3520 sequential atomic emission spectrometer.
 M. Turunen et al. /Analytica Chimica Acta 311 (1995) 85-91 87

Except for Pb and Cd, pyrolytic coated partition

Fig. 1. Wet digestion apparatus.
tubes (Varian, part No. 63-100012-00) were used in
all determinations. With the use of pyrolytic coated
tubes with platform instead of partition tubes for Pb
and Cd, the sensitivity of the Pb and Cd determina-
tions was doubled. In the case of the platform tubes,
samples had to be injected at a slower rate because
otherwise the platform, which was situated freely in
tube without any support, could be stirred and sam-
ple fell into the wall of the tube; at the same time the
formation of the sample drop was improved. Opti-
mum pyrolysis and atomization temperatures were
determined separately for each element and these are
shown in Table 1 together with the other instrumen-
tal parameters for the GFAAS determinations. Vana-
dium should be determined first, with a new tube,
because with a used tube the sensitivity is decreased
significantly. Because the signal shape was good and
the background low, a matrix modifier was not
needed in the determinations of Co, Cr, Mn, Ni, and
V. A matrix modifier was, however, required for As
(4 ~1 1000 mg 1-l Ni), Cd, Cu. and Pb (1 ~1 2%
(NH,),HPO,).

2.3. Measurement procedures
GFAAS
As, Pb, Cu, Cd, Co, Cr, Mn, Ni, and V were
determined with the atomic absorption spectrometer
equipped with the graphite tube atomizer (GTA-96).
The standards used for the calibration of the instru-
ment were prepared from Titrisol standard solutions
by diluting in such a way that they contained 25%
H,SO, in the blank and each standard solution.
CVAAS
Mercury was determined by cold vapour method
with the atomic absorption spectrometer equipped
with the vapour generation accessory (VGA-76). This
employs continuous flow technique. The calibration
standards were prepared as for the GFAAS determi-
nations, from Titrisol standard so that they contained
25% H,SO, in the blank and each standard solution.
25% w/v SnCl, in 20% v/v HCl was added as a
reducing agent. Determinations were performed us-
ing wavelength 253.7 nm and slit width of 0.5 nm.

Table I
Operating parameters for the GFAAS determinations
Parameter AS Cd co Cr cu Mn Ni Pb L

Wavelength (nm) 193.7 228.8 240.7 357.9 324.8 279.5 232.0 283.3 318.5
Slit width (nm) 1.0 0.5 0.2 0.2 0.5 0.2 0.2 0.5 0.2
Measurement time (s) 1.7 2.9 2.1 2.2 2.6 2.1 1.7 2.5 2.1
Sample volume (~1) 3 x 20 2 x 20 20 20 2 x 20 20 20 20 20
Pyrolysis temp. (” C) 1200 800 1200 600 1000 600 1000 1000 IO00
Pyrolysis time (s) 17.0 40.0 20.0 5.0 17.0 5.0 17.0 ‘5.0 S.(l
Atomizing temp. (” C) 2400 1800 2200 2100 2000 1800 2400 1’150 2600

Measurement mode: peak area.

88 M. Turunen et al. /Analytica Chimica Acta 311 (1995) 85-91

Table 2 published procedure [lo]. The oil sample (about 5 g)

Operating parameters for the ICP-AES determinations
was weighed directly into a 500-ml round-bottomed
Parameter Value flask. The digestion apparatus was constructed and
Torch Minitorch 2.5 ml cont. sulfuric acid and 2.5 ml cont. nitric acid
Effect (W) 700 were added through the regular addition funnel. The
Ar gas flows (I/min)
stopcock of the addition funnel with by-pass tube
carrier 0.7
plasma 0.8
was kept closed during the entire digestion proce-
coolant 11 dure. The temperature of the reaction mixture was
Pump speed (ml/min) 1.7 slowly increased by means of the heating mantle
Wavelengths (nm) until fumes of nitrogen dioxide appeared. Gentle
Ni 231.604
heating was continued until mustard yellow turbulent
V 311.070
fumes were observed (at about 80” C) and during this
vigorous reaction slow addition of cont. nitric acid
(total amount 50 ml) was carefully begun. If the
With a delay time of 70 s and measuring time 10.0 s, cont. nitric acid was added too fast, the destruction
three replicate measurements were made. of the sample was interrupted and at a later stage of
the digestion procedure, when the heating was in-
ICP-AES creased, a violent and harmful reaction was induced
Ni and V were also determined by ICP-AES in which the sample foamed into the addition fun-
technique, in heavy oil samples diluted with xylene nels. Likewise, if the heating was too strong, a
1:lO. The calibration standards were prepared from violent reaction occurred, causing the pressure in the
Conostan S-21 organometallic standard by diluting flask to increase too fast and the sample to ignite.
with the appropriate amount of Base Oil to ensure Previous hazards can be avoided by monitoring the
the right viscosity. After this the mixtures were temperature of the reaction mixture (80-85” C) by
diluted with xylene l:lO, in the same way as the thermoelement.
samples. The ICP-AES parameters are shown in After the vigorous reaction was over the heating
Table 2. was increased and more cont. nitric acid was added,
at a sufficient rate to produce nitrogen dioxide fumes
2.4. Sample preparation at a steady rate. The green distillate began to con-
dense into the addition funnel with by-pass tube. The
The digestion of samples for AAS was performed temperature was then kept at 180-200” C until the
in HNO,-H,SO, medium with a modification of a solution was less viscous and dark brown. After that

Table 3
Recovery, R.S.D., and DL for synthetic oil samples (V= 20 ~1, n = 5)
Element Concentration Recovery R.S.D. DL
(mg kg- ’ sample) (%I (%I (mg kg- ’ sample)
As 20.00 96 f 9 3.6 0.046 a
Cd 0.052 95 f 13 7.8 0.003 a
co 1.00 95 f 6 2.4 0.010
Cr 1.00 99 f 8 3.2 0.004
CU 1.02 110 f 14 8.4 0.005 a
Hg b 0.45 71 f8 4.4 0.004
Mn 1.00 94 f 7 2.7 0.006
Ni 0.98 lOOk 2.4 0.009
Pb 1.12 95 f 8 3.0 0.016
V 0.98 98 f 4 1.7 0.021

’ Multiple injection used (2 X 20 ~11.

b Hg measured by CVAAS, others by GFAAS.
 M. Turunen et al. /Analytica Chimica Acta 311 (1995) 85-91
the temperature was increased until fumes of sulfuric
acid appeared (> 230” C) and the heating was con-
tinued until the solution was a pale straw color or
almost colorless (45-60 min). At this stage the
addition rate of cont. nitric acid (additional 30 ml)
must be slow enough to avoid temperature decrease.
The digestion of samples took about 2-3 h.
The solution was allowed to cool down and the
addition funnels and the condenser were removed.
The distillate (about 100 ml) collected into the addi-
tion funnel with by-pass tube was discharged and the
sample (20-25 ml) was quantitatively transferred
from the flask to a lOO-ml volumetric flask. The
digestion apparatus was rinsed with water (75 ml)
and poured into the volumetric flask which was
filled to the mark with cont. sulfuric acid.
3. Results and discussion
3.1, Digestion procedure
The digestion procedure was tested on synthetic
oil samples, which were prepared by diluting
CONOSTAN metallo-organic standards with Base
Oil. The samples (about 5 g) were decomposed as
described above and the metal contents were deter-
mined in acidic sample solution by GFAAS, except
Hg which was determined by CVAAS. The recovery
with confidence limits (calculated at 95 probability
level) and the R.S.D. values of the analytes are
shown in Table 3. Recoveries were good for all
analytes except Hg. For Hg the recovery was only
about 70%, probably because Hg was partly
volatilized during the digestion procedure. The re-
covery was found to be independent of the concen-
tration, however, and so could be taken into account
in calculating the Hg results; or the calibration stan-
dards could be treated in the same way as the
samples. The recovery of Cu slightly exceeded 100%
probably due to contamination: large amounts of Cu
were observed particularly in the new flasks, and
although the flasks were carefully acid washed, con-
tamination was not completely avoided. The contam-
ination was eliminated by cleaning the flasks with
cont. HNO, and cont. H,SO, according to the
digestion procedure.
Besides the digested oil samples, also the analyte
x9
contents of distillates formed during the digestion
procedure were investigated. The distillates did not
contain detectable amounts of Co or Mn and only
traces of As, Cr, Cu, Ni, and V. Considerable vapor-
ization losses of these elements are not expected to
occur during the digestion. The distillates did not
contain detectable amounts of mercury either, al-
though recovery tests showed that part of it was lost
during the digestion procedure. Apparently mercury
was released with the fumes formed during digestion
and escaped out of the top of the digestion apparatus.
A few problems occurred with the GFAAS determi-
nations of distillates. In the case of Cd and Pb the
background signal was strong and caused overcorrec-
tion problems so that these elements could not be
measured. Distillates also quite rapidly consumed the
graphite tubes and platforms and caused decrease in
the sensitivity. Furthermore, the volume of distillates
varied a little so the results were not completely
accurate.
The analytes should be determined as soon as
possible to avoid contamination problems and loss of
the analytes. The Hg concentration was observed to
increase and Pb concentration to decrease during
storage, so these elements should be determined first.
As to the other analytes, the storage time had no
effect on the concentrations in digested sample solu-
tion.
3.2. AAS determinations
The detection limits CDL) of GFAAS and CVAAS
determinations were determined separately for each
analyte with low concentration standards (made from
Titrisol standard by dilution), which gave a signal of
about 0.020 A. Blank and standard solutions were
prepared in 25% H,SO,. Ten replicate measure-
ments, alternating between the blank and the stan-
dard, were made. The detection limits were then
calculated from the mean absorbance of the blank
corrected standard and the standard deviation of the
blank signal [20]. The results of the DL determina-
tions are shown in Table 3 (the lower recovery was
taken into account in calculating the DL of mercury).
The detection limits are low and low concentrations
of the analytes in heavy oil samples can be deter-
mined accurately. Since oil samples usually contain
very low amounts of As, Cd, Cu, and Pb, the feasi-
90 M. Turunen et al. /Analytica Chimica Acta 311 (1995) 85-91

bility of using multiple injection (2 X 20 ~1) was
tested. No problems arose in the case of As, Cd, and
Cu and the detection limits were improved. Multiple
injection could not be used for Pb, however, because
the background level increased due to increasing
acid concentration and disturbed the determination.
We expected the hydride technique to be more
sensitive (DL about 16 times lower) than GFAAS for
the As determinations. With digested oil samples,
however, KI, a reducing agent for modifying As(V)
to A.&II) in the hydride method, caused the forma-
tion of a dark lava-like deposit, which eventually
blocked the apparatus. Furthermore, the NaBH, used
for the hydride generation reacted vigorously with
the sample matrix, causing foaming in the gas-liquid
separator and inaccuracy in the results. For these
reasons, GFAAS was used instead for the arsenic
determinations.
3.3. Concentrations of analytes
Five replicates of each of the three heavy fuel oil
samples were decomposed with the developed diges-
tion procedure. The samples behaved in a different
way during the digestion procedure: two of them had
quite high viscosity and the digestion proceeded
normally, but the third was of lower viscosity and at
the beginning of the digestion there could occur a
violent reaction if temperature of the reaction mix-
ture was not controlled.
The trace element concentrations of the three
samples are shown in Table 4. All samples contained
relatively large amounts of Ni and V, compared to
other analytes, and moderate amounts of Co, Cu,
Mn, and Pb. The As, Cd, Cr, and Hg concentrations
were low, and for the As and Hg determinations the
R.S.D. values were high because the concentrations
in the samples were close to or below the detection
limit. The lower recovery of Hg was taken into
account in calculating the Hg concentration. To con-
firm the previous results, some spiked oil samples
(As, Cd, Cr and Hg) were prepared: a calculated
amount of synthetic standard was added to the heavy
fuel oil sample and the mixture was digested in the
regular way. After digestion the analyte concentra-
tions were determined by GFAAS or CVAAS and
the original analyte concentrations of the sample was
calculated by subtracting the added amount from the
measured amount. Results were repeatable and sup-
ported the results of unspiked oil samples.
The analyte contents of heavy oil samples were
also determined by ICP-AES, for which the un-
treated oil sample was diluted with xylene (1:lO)
before analysis. The sensitivity of the ICP-AES tech-
nique was sufficient only for the determination of Ni
and V. The ICP-AES results for Ni and V were in
good agreement with the GFAAS results: in samples
1, 2, and 3, Ni concentration were 11.2, 13.4, and
10.3 mg kg-’ sample and V concentration 25.4,
20.5, and 20.1 mg kg-’ sample, respectively.

Table 4
Concentration of elements in three fuel oils (V = 20 ~1, n = 5)
Element Sample 1 Sample 2 Sample 3
Content R.S.D. Content R.S.D. Content R.S.D.
(mg kg-‘) (%o) (mg kg-‘) (o/o) (mg kg-‘) (%I
AS <DL - 0.096 37 <DL -
Cd 0.031 3.2 0.013 4.3 0.025 3.4
co 0.289 2.2 0.182 3.1 0.185 7.2
Cr 0.058 4.1 0.035 10.6 0.062 6.7
CU 0.303 1.2 0.190 2.0 0.275 3.8
Hg a 0.008 37 0.007 34 < DL _
Mn 0.147 1.9 0.117 1.3 0.180 1.0
Pb 0.206 1.8 0.300 7.8 0.410 2.7
Ni 13.1 9.1 12.9 2.8 9.8 2.1
V 21.9 4.5 19.2 5.2 18.0 1.8

a Hg measured by CVAAS, others by GFAAS.

 M. Turunen et al. /Analytica
4. Conclusions
The wet digestion procedure (HNO,-H,SO,) ef-
fectively destroyed the organic matrix of the heavy
oil samples. The procedure was simple, repeatable
and relatively fast (2-3 h) and, except for mercury,
no significant losses of the analytes were observed
during the digestion. The recovery of mercury was
about 70%. However, the recovery was independent
of the mercury concentration and could be taken into
account in calculating the results. The digestion of
oil samples can be carried out with equipment avail-
able in most laboratories and all the analytes (As,
Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, and V) can
accurately be determined by GFAAS or CVAAS
from the same digested sample solution. The low
detection limits mean that even very low concentra-
tions of the analytes in heavy oil samples can be
determined.
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