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Elemental analysis of Kuwaiti petroleum and combustion products

Article in Nuclear Geophysics · March 1993

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Nuc/. Geophys. Vol. 7. No. I. pp. 81-86,1993 0886-0130/93 $6.('l+0.00
Printed in Great Britain. All rights reserved Copyright to 1993 Pergamon Press Ltd

Elemental Analysis of Kuwaiti Petroleum and

Combustion Products

J. S. REID.' T. A. CAHILL,' E. A. GEARHART,' R. G. FLOCCHINI,'

J. S. SCHWEITZER2 and C. A. PETERSON2
I Air QualityGroup, Crocker Nuclear Laboratory, University of California, Davis, CA 95616-8569, U.S.A.
lSchlumberger.Doll Research, Ridgefield, cr 06877-4108, U.S.A.

(Received 2 January /993)

A"tract-Crude oil from eight Kuwaiti fields and aerosols generated by their combustion in the laboratory
have been ana.lyzed by composition and particulate size. Liquid petroleum and petroleum combustion
products were subjected to elemental analysis by proton induced x·ray techniques and by x-ray florescence
techniques. The mean sulfur content of the burning wells was weighted by their production rates to obtain
the mean sulfur content of the burning oil, 2.66%. The liquid samples were also analyzed by neutron
activation analyses. Results show that Kuwaiti oil and smoke aerosols from laboratory combustion
generally contain very low amounts of chlorine, contrary to what is found in airborne samples above
Kuwait. Trace element signatures were developed to aid in tracing smoke from the oil fires.

INTRODUCTION

The uncontrolled combustion of approx. 5 million barrels of oil per day (WMO, 1991) into a
limited geographical area resulted in an unprecedented density of smoke and combustion products
in and around Kuwait. This study was designed to aid in the interpretation of aerosol samples we
took downwind of Kuwait in May and June 1991, with the National Center of Atmospheric
Research (NCAR) and by the University of Washington flights (Hobbs and Radke, 1992). Our
data from these flights showed large amounts of Na and Cl, consistent with NaC!, in the smoke,
and we wished to ascertain the source of this material (Cahill et ai., 1991). This study also provides
trace element signatures necessary to evaluate whether Kuwaiti smoke was observed at distant sites.
The experiment was performed in two distinct steps. First, analyses of the oils were performed,
and compared to previous data available on Kuwaiti oils. Second, the oil was combusted in a
manner designed to mimic to some degree the oil fires, in an open flaring bum, and with heavy,
black smoke. The resulting aerosols were analyzed, as well as the residue of combustion. Finally,
these data are compared with data from aerosols collected over Kuwait (Cahill el a/., 1992).

ANALYSES OF KUWAITI OILS

In 1977, eight samples of Kuwaiti oils were obtained by Schlumberger-Doll Research as part of
an effort to develop a library of reasonably diverse, globally representative crude oil samples. Six
of the samples were from wells operated by the Kuwait Oil Company, and the other two were
from wells operated by the Joint Operating Committee. The data provided with the samples included
information on oil density and sulfur concentration (Table I). Samples of these oils were used in
a number of research studies, during which additional data were obtained on at least some of these
oils, including the carbon, hydrogen, nitrogen, sulfur and oxygen concentrations for three of them
(Waldo el ai., 1992). In 1991, approx. 6Ocm3 of each of the eight oils was designated for combustion
and analysis at the University of California, Davis.

81
82 J. S. REID et al.

Table 1. Characteristics of Kuwaiti crude oil samples

Specific Sulfur Asphaltene content/API

Sample gravity (%) gravity/water content

I 0.8575 2.23 4.5%/28.8% .0%

2 0.8510 2.12 2.3%/31.6<>;0.0%
3 0.8640 2.33 3.4%/30.6°/0.2%
4 0.8645 2.58 3.6%/25.9% .0%
5 0.8710 2.73 3.1%/28.2% .0%
6 0.8975 3.75 10.8%/23.6% .0%
7 NA 3.5* 7.1%23.4% .3%
8 NA NA 4.5%(22.8°/9.7%

• This value was measured in the current study.

The sulfur content of the Kuwaiti crude was also measured by PIXE for four
other samples giving results +0.4% (±O.2%) higher than the prior values. this
dife
f rence w

EXPERIMENTAL TECHNIQUES

X-ray analysis
The liquid petroleum samples were placed on pre-weighed teflon filters. After spending 18 h
under high vacuum to allow volatiles to outgas, they were gravimetrically analyzed. In addition,
2 mL of liquid oil from each well field was encased in modified petri dishes with mylar windows
for analysis as liquid oil. Both types of samples were analyzed by proton induced x-ray emission
(PIX E) techniques at Crocker Nuclear Laboratory (Cahill, 1991; Cahill et al., 1987; Cahill, 1990).
This method provides an x-ray spectrum analysis of elements from sodium through uranium. The
filters were subjected to a 4.5 MeV proton beam in high vacuum for up to 600s each (Eldred et al.,
1984). Each sample was run at least three times. The encased liquid petroleum samples were placed
in an open air external beam for 600s each (Eldred et al., 1983). A selected number of these samples
were then subjected to further analysis by x-ray fluorescence techniques (XRF) in the Stanford
Synchrotron Radiation Laboratory (SSRL) at the Stanford Linear Accelerator Center (SLAC) for
increased sensitivity to x-rays from vanadium through bromine. Polarized x-rays with an energy
of 15 keV were used to excite the samples for a duration of 600s each. A helium filled low Z plastic
vessel was constructed to enclose the filter target and detector to reduoc background. In addition,
all materials used inside the vessel were constructed from acrylic to minimize x-ray scattering and
background noise. All x-ray spectra were evaluated with programs developed at U.C. Davis
(Harrison and Eldred, 1974).

Activation analysis
Neutron activation analyses were performed on the eight samples of oil. Each was held in
polycarbonate containers (of approx. 250cm' of oil) and irradiated for 7.5 h. The delayed activity
was monitored for 15 h. The samples were irradiated in a water tank with a souroc of 14 MeV
neutrons at an output in excess of 108 n/s. The samples were monitored in a lead cave with a 96%
efficient Ge detector. Most of the delayed activity was due to thermal neutron capture in sodium,
chlorine and vanadium. The spectra were analyzed to obtain the relative mass concentrations of
detected elements to that of vanadium. The vanadium concentrations determined by the PIXE and
XRF analysis were then used to convert the mass ratio into weight concentrations.

Results of the oil analyses

Table 2 presents the results of these analyses for the most significant elements detected. The data
in each column are identified by the analytical technique used to determine the conocntration.
Measurements of the sulfur conocntration were in good agreement with the values shown in Table
1, to 0.4%, suggesting minimal alteration of the samples sinoc they were acquired. Thus, we can
 Analysis of Kuwaiti oil combustion products 83

Table 2. Composition of Kuwaiti oil (relative to sulfur)

Sample V/Ni,
Sulfur· Nickel· Sodiumt '
No. Vanadium· ratio· Chlorine

1 - 1000 0.50±0.08 0.094 5.3 0.26±0.04 0.29±0.1I

2 -1000 1.50 <0.06 NO 0.47±0.04 NO
3 -1000 0.83 0.25 3.3 0.21±O.OI NO
4 -1000 0.77 0.09 8.2 O.l 3±O.OI 0.51±0.20
5 -1000 0.65±0.26 0.19 3.4 0.25±0.1O 0.47±0.32
6 -1000 0.50±0.06 O.l 9±0.05 2.6 0.21±0.03 0.31 ±0.09
7 -1000 0.34±0.06 0.1O±0.03 3.4 5.33±0.97 1O.70±2.00
8 -1000 <0.10 0.12 NO 0.59±0.03 1.06 ± 0.09

•Proton induced x-ray emission. (Values with uncertainties represent repeated measurements using dife
f rent
tNeutron activation analysis. The Na and CI values of Sample No. 8 assume V =0.10.
Results are generally consistent with Na and CI present as NaCI to within ±20%. but other sources of Na and/or CI
tannot be excluded.

accept our measurement of the sulfur content of oil in Sample 7, 3.5%. It is interesting to note
that CIIS ratios were between 3 x 10-4 and 10-2 for the six samples where chlorine could be
measured and below detectable limits for the other two samples.
The absolute concentration of sulfur in number 8 was not measured directly, but estimated at
3.5% for the ratios since the values shown in Table 2 are relative to sulfur.
The values of Tables 1 and 2 can be used to establish the mean sulfur content of burning oil, if
one knows how much oil is combusted. Estimates have been prepared of the number of burning
wells and the approximate mean field oil production rate of the wells (Robinson, 1992). With these
assumptions, we can estimate a mean sulfur content of 2.2% for the fields north of Kuwait City,
2.7% for fields south of Kuwait City, and 2.66% for the weighed average of all Kuwait prior to
control of the fires. This may be compared to the values of 3.3% for the southern fields, an assumed
1.5% for the northern field, for a mean sulfur content of 3.0% used by Johnson et al. (1991).

ANALYSIS OF COMBUSTION PRODUCTS FROM KUWAITI OILS

Eight petroleum samples were combusted at Davis. An attempt was made to mimic the open
flame combustion of the Kuwaiti well fires by preheating and arranging for an oxygen deficient,
smoke rich fire. Though we clearly cannot reproduce the exact physical characteristics of a burning
well, the experiment combustion apparatus did create a smoke which was physically similar to
that produced in Kuwait. Oil was pooled in a high walled crucible and heated to boiling temperatures,
causing large droplets to be ejected from the surface of the oil. The surface of the oil was then
ignited. Because of the high walls of the crucible, the amount of available oxygen for combustion
was low. Electron micrographs of the smoke particles showed that their structure was similar in
size and morphology to those found in airborne samples taken over Kuwait, though without the
well-formed spherical agglomerates (Cahill et aI., 1992). The smoke was then cooled to quasi
ambient temperature and relative humidity in a 0.5 m' chamber before release to the atmosphere
where it was sampled by a stacked filter unit (SFU) (Cahill et al., 1977, 1990). The SFU system
consists of two stages; the first stage containing a 47 mm dia Nuclepore filter for collecting all
aerosols with diameters > 2.5 I'm and the second containing a 25 mm dia teflon filter to collect the
finer aerosols below 2.5 I'm dia. This system was identical to that used in the flights above Kuwait.
After the petroleum had been completely combusted, the ash residue was collected and placed
on mylar. After spending 18 h in vacuum (10-4 torr) to allow for the removal of volatiles, both the
aerosol and the ash samples were analyzed gravimetrically and by PIXE.
Tables 3, 4, and 5 give the elemental concentrations from PIXE analyses of the ash residue,
coarse particles and fine particles from the combustion of Kuwaiti oil samples. These results are
presented relative to the sulfur content of the analyzed material to allow comparison with data
from aerosols obtained above Kuwait.
84 J. S. REID er ai.

Table 3. Major elemental composition of Kuwaiti crude oil ash (relative to sulfur)

Sample No. S CI V Ni VfNi

I "" 1000· <10 9.1 2.7 3.0

2 =1000 <10 9.0 4.0 2.3
3 =1000 <10 7.6 3.3 2.3
4 =1000 <10 6.2 2.7 2.3
5 =1000 <10 8.7 3.9 2.2
6 =1000 <10 4.8 3.5 1.4
7 =1000 300 4.2 2.5 1.7
8 =1000 <10 4.3 3.2 I .l

'" By definition.

Table 4. Major elemental composition of coarse particles, D,>2.5pm, from combusted

Kuwaiti crude oil. relative to sulfur

Sample No. S CI V Ni VfNi

I = 1000· <23 7.9 <2.6 >3.0

2 -1000 125 11.6 <4.2 >2.7
3 =1000 <43 17.0 17.0 1.0
4 = 1000 69.1 13.4 <3 >4.5
5 =1000 <19.9 22.9 <2.4 >9.5
6 =1000 15.6 2.8 <1.3 >2.1
7 =1000 <II 5.4 <1.4 >3.8
8 =1000 68.2 <5.6 <2.3 >2.4

'" By definition.

Table 5. Major elements in the fine aerosol particle, D,<2.SJUn. from combusted Kuwaiti
crude oil. relative to sulfur

Oil
(sample No.) S a V Ni VfNi

I "'" I (X))'" <1.4 2.8 <0.2 >14

2 -1000 <1.4 \.6 <0.5 >3.2
3 -1000 <0.9 0.62 0.2 3.1
4 -1000 < \,7 2.9 \,7 \.7
5 -1000 <2.1 3.2 7.4 0.43
6 -1000 < \.9 5.0 4.9 \.0
7 -1000 <2.0 4.4 3.8 \.I
8 -1000 <2.0 3.76 4.1 0.9

t
Aerosol

5/21 -1000 1818 <4.2 <2.1 ND

5/26 -1000 1756 4.6 2.5 0.9
5/ 30 -1000 2340 7.0 6.3 \.I
6/1 =1000 2317 15.9 7.6 2.1

'" By definition.
'
Cahill er .1. (1992).
Also included are fine aerosol data from four flights over Kuwait that included the most
sensitive trace element analyses.
NO -nol determined.
The uncertainties in the V and Ni data over Kuwait ranged (rom 20-60%.

COMPARISON OF LABORATORY AEROSOLS WITH AIRBORNE MONITORING

Electron micrographs of coarse (>2.Sl'm) aerosols from the laboratory combustion of sample
No.5 had some similarities with coarse aerosols coUected over Kuwait (Cahi11 el al., 1992). Both
had linked ftuffy chains of particles associated with smoke. However, the roughly spherical - 20 I'ffi
agglomerates seen in the samples taken over Kuwait were not found in the laboratory aerosols
although some smaUer agglomerations were present. We attribute this difference to the shorter
 Analysis of Kuwaiti oil combustion products 8S

time between combustion and collection in the laboratory ( 2 min) and the hours that elapsed
-

between combustion and collection of the samples on flights over Kuwait. Another difference is
that the non-soot, or crystalline particles, commonly seen in the airborne samples were largely
absent in the laboratory samples.
Some of the ratios of elemental concentrations obtained from the laboratory data can be compared
with the corresponding results from the analyses of the samples obtained by airborne monitoring
over Kuwait. A number of interesting points can be noted. The airborne Cl/S ratio from the coarse
filter was 3.3±2.6, and from the fine filters are 2.2±0.6. It should be noted that the largest value
in laboratory data is 0.3, with the next highest value substantially lower. Thus, clearly, the very
high levels of chlorine seen over Kuwait are not from the oil, but most likely from the co-ejection
of oil field brines into the combustion plumes. This is also a plausible explanation for the white
and grayish plumes seen over some well sites in Kuwait.
The V(Ni ratios ranging from 0.4 to 3.1 (and above) in the fine particle laboratory samples are
similar to the ratios seen in the airborne samples which ranged from 0.9 to 1.2 (in the fine fraction).
Note that this is also in good agreement with the other laboratory samples. This indicates that
our laboratory combustion may be, in some way, an adequate simulation of Kuwaiti well fire
combustion.
Probably more surprising is the relatively good agreement between the V/S ratio from fine
particles in airborne samples and those produced in fine particles from the laboratory combustion.
Much of the sulfur is evolved as S02 (Hobbs and Radke, 1992). Yet, despite the large differences
in combustion processes, the different time delays between combustion and sampling, and the
presence of fine soil particles and salt above Kuwait (Cahill et al., 1991), there appears to be
agreement within about a factor of 3 in this ratio.

CONCLUSION

Elemental analyses have been performed on eight samples of oil from Kuwaiti oil fields. Portions
of each of these eight samples were burned in the laboratory. The smoke particles were separated
into coarse (> 2.5 I'm) and fine « 2.5 I'm) fractions, and residual ash samples were also obtained.
Elemental analyses were performed on these samples. Fractionation was observed in the combustion
products. Sulfur-to-metals ratios tended to be higher in the fine-particle fraction. The laboratory
results were compared with similar analyses of airborne samples taken over or downwind from
Kuwait. Good agreement was found between vanadium, sulfur and nickel mass concentrations in
the fine fractions obtained in the laboratory with those obtained from airborne sampling. This
allows us to conclude that the high chlorine-to-sulphur ratios seen in airborne sampling are not
due to the combustion itself, but due to an additional source of chlorine, such as from oil field brines.
The uncontrolled burning of the Kuwaiti wells could result in an increased pressure differential
between the borehole and the formations, which could result in the production of connate, injected
or coning water. Such a scenario, it should be noted, may also result in a variation of the types
of oil and gas entering the borehole, as compared with what would be produced under controlled
conditions (such as those under which the samples analyzed here were obtained). Thus the type
of oil and gas burned may have been changed during the course of a well's burning, and our results
may better reflect the oil and gas burning soon after ignition rather than that burned at a later time.

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