You are on page 1of 4

CHINESE JOURNAL OF ANALYTICAL CHEMISTRY

Volume 35, Issue 10, October 2007


Online English edition of the Chinese language journal

Cite this article as: Chin J Anal Chem, 2007, 35(10), 14551458.

RESEARCH PAPER

Determination of Isotope Composition of Dissolved


Inorganic Carbon by Gas Chromatography-Conventional
Isotope-ratio Mass Spectrometry
Li Zhong-Ping1, Tao Ming-Xin2,*, Li Li-Wu1, Wang Zuo-Dong1, Du Li1, Zhang Ming-Feng1
1

Key Laboratory of Gas Geochemistry, Chinese Academy of Sciences, Lanzhou 730000, China
State Key Laboratory of Earth Surface Processes and Resource EcologyCollege of Resource Science and Technology, Beijing Normal
University, Beijing 100875, China

Abstract: The studies of dissolved inorganic carbon (DIC) have important scientific significance and wide applications. In this study,
a series of DIC samples with different concentrations were prepared by using NaHCO3. In this experiment, a novel method was
established to analyze DIC carbon isotope compositions. The results achieved by the method were stable and reliable, and the different
concentration samples showed only 0.20.5 of deviation between the DIC sample and the NaHCO3. By referring to the results of
the control group, this method proved to be effective to prevent the interference from atmospheric CO2 and other organic materials,
which ensured the accuracy of the test results. Besides these, the method has the advantage to meet the requirements of DIC research in
the absence of specialized equipments, and it can be done under the conventional conditions in the lab. The method also does not
require the pretreatment equipments and can be easily done offline. Therefore, the operation is simple, fast, and low cost, and it is
applicable to the various DIC samples in nature, particularly for a lot of DIC samples.
Key Words: Dissolved inorganic carbon (DIC); Carbon isotope composition; Gas chromatography/conventional isotope-ratio mass
spectrometry

Introduction

Coal-seam water or oil-field water generally contains


dissolved inorganic carbon (DIC). The forms of DIC are
HCO3, CO32, H2CO3, CO2, and so on, wherein most of them
are derived from organic evolution or dissolved carbonate
minerals, for example, CaCO3 + CO2 + H2O Ca2+ +
2HCO3. Because carbon isotope can act as geochemical
tracer, the DIC carbon isotope has been widely employed in
the field of environmental studies[13]. In addition, it can also
be employed in the oil and gas research. So DIC carbon
isotopic composition has lot of scientific significance in oil
and gas research. For example, based on DIC carbon isotopic
composition, some valuable scientific geochemical
information about oil and gas migration, reservoir condition,

and its formation mechanism can be achieved. As a novel


method, the DIC carbon isotope research has received
increased attention, and it has also been given immense
importance in the studies related to secondary biogenic
methane[4,5].
The precipitation method was commonly used to analyze
carbon isotope of DIC[6], yet the process was complicated and
time-consuming. The errors emerge frequently in the
precipitation process and it was not easy to grasp. On the
basis of previous studies, Bishop[7] proposed a method of
standard precipitation, which was proved efficient in
achieving accurate carbon isotope values, but this method did
not apply to high-concentration sulfate samples, which could
lead to incomplete DIC precipitation and be prone of being
subjected to isotope fractionation.

Received 14 December 2006; accepted 11 June 2007


* Corresponding author. Email: mxtao@ires.cn; Tel: +86 10-58802253; Fax: +86 10-58802253
This work was supported by the National Basic Research Program of China (No. 2002CB211701) and the Major Projects of the Chinese Ministry of Education
(No.307007).
Copyright 2007, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.

LI Zhong-Ping et al. / Chinese Journal of Analytical Chemistry, 2007, 35(10): 14551458

With the development of DIC research, particularly in


environmental research, a great number of samples need to be
analyzed. However, the precipitation method has its own
deficiency, and the research had been constrained. Therefore,
some new methods, such as vacuum-online-degassing method
and helium-flushing method, had been developed[811].
Although the acquired result was accurate (13C 0.15),
the process was more complicated.
With the development of DIC isotope research,
Thermo-Finnigan have developed a new device (Gasbench) to
the carbon isotope analysis. It proved to be highly accurate
and could be analyzed fast, but only a few laboratories were
equipped with this device because of the higher price. In this
study, the DIC testing-method was developed. The novel
method was of high precision, low cost, and fast to analyze. It
is easy to master and it has been proved to have good
analytical results.

Experimental

2.1

Principle

DIC exists mainly in the form of HCO3, CO32, H2CO3,


and CO2(soluble) in solution, which obeys the balance equation:
H2CO3
H+ + HCO3
2 H+ + CO32
CO2(gas) + H2O
The concentration of various constituents depends on the
pH values of the solution. With the decrease in pH value or
the increase in acidity, the DIC will be released from the
solution in the form of CO2. The released CO2 can be
separated from other impurities by chromatography and the
dehydration device can remove the water vapor in CO2, then
the dried CO2 is sent to mass spectrometer for analysis, and
the isotope values of DIC are available.
2.2

Instruments and their operating parameters

HP6890 gas chromatograph AgilientUSAwas used, the


column installed in GC was C-2000 type (30 m 0.53 mm
20 m), and the carrier gas was helium with a velocity of 15
ml min1, the inlet pressure was 10 MPa, and GC oven was set
at a constant temperature of 80 . DeltaPlus XP stable
isotope mass spectrometer (IRMS) was purchased from
Thermo Finnigan Corp., the ion source was electronic
bombardment type, and the electron energy was 70 eV.
The accuracy is better than 0.15 (PDB international
standard). The value of 13C was calculated according to the
following formula:
Rsam.  Rstd .
13 12
1000 (R = C/ C)
Rstd .

13C =
2.3

Reagents

CO2 was removed from distilled water. The purity of

NaHCO3 was greater than 99.9% (13CNaHCO3 = 8.2


0.02), and the concentration of phosphoric acid and helium
gas were greater than 98% and 99.999%, respectively. Some
syringes with a switch on the needle and borosilicate glass
bottles were used in the experiment.
2.4

Sample preparation

Sodium bicarbonate of 5, 25, 50 and 100 mg were dissolved


with distilled water in 250 ml. The four different
concentration samples (0.24, 1.19, 2.38 and 4.76 mM) were in
preparation marked with A, B, C and D, and then sealed for
use.
2.5

Experimental procedure

0.5 ml of phosphoric acid was transferred into 5 ml bottle at


25oC and then it was made air tight by using silica stopper.
Dual needles were inserted into the silica stopper and the
bottle was flushed with helium flows of 100 ml min1 for 5
min (as shown in Fig.1).

Fig.1 Flow chart of analysis process


1, drop phosphoric acid; 2, flush with helium; 3, add sample to the
vessel; 4, extract CO2 from the vessel; 5, GC separation; 6, automatic
dehydration; 7, mass spectrometer analysis

DIC sample of 0.252 ml was extracted, injected into the


bottle prepared as mentioned above, and shaken for about one
minute. The samples of 4 concentrations were prepared (4
parallel samples for every concentration, total of 16 bottles).
These samples were kept for 1, 4, 8 and 24 hours, respectively.
Thus, the CO2 generated in the bottles of A, B, C and D
samples was detected using GC-IRMS.
Most natural water contain trace organisms, which may
change DIC carbon isotope values. Therefore, a small drop of
HgCl2 should be added to the samples during the sampling
process. The operation environment should be protected with
helium to avoid air pollution, and the samples should be
collected through the enclosed syringe.

Results and discussion

3.1 Effect of the concentration and balance time


Sixteen samples of four series were analyzed. To decrease

LI Zhong-Ping et al. / Chinese Journal of Analytical Chemistry, 2007, 35(10): 14551458

accidental error from single testing, a five-parallel testing was


done for each sample and the average value was used. The
results are given in Table 1. The data above the line indicate the
range of the five-parallel testing values, and the data below the
line indicate the average of the five-parallel testing values.
After different balancing times (for 1, 4, 8 and 24 hours), the
average 13C values of series A were 7.4, 7.2, 7.9
and 8.0, respectively, and the range (interval between the
smallest and largest values in a frequency distribution) was
0.8. The average 13C values of series B were 7.5, 7.6,
7.4 and 7.9, respectively, and the range was 0.5. For
series C they were 7.7, 7.3, 7.6 and 7.7, and the

range was 0.4. For series D, they were 7.4, 7.5,


7.6 and 7.8, and the range were 0.4.
Among all the samples, the low concentration samples had
relatively larger range (0.8). However, among all the balance
time from 1 to 24 hours, the samples for 24 hours had the
smallest interval values with 13CNaHCO3 (8.2), and the
margin was 0.2 (as shown in Table 1).
The difference value of 13C was decreased with the increase
of the balance time, and the minimum values were obtained
after 24 hours of the balance time. Table 1 show that the
concentration has little influence on the results, and the
difference was in the range of 0.3 0.5.

Table 1 13C Values with different concentrations and different balance time (PDB)
Sample

1
7.3 ~ 7.6
7.4
7.3 ~ 7.6
7.5
7.4 ~ 7.8
7.7
7.2 ~ 7.5
7.4

A
B
C
D
E

Range

Difference value

Balance time / h
4
8
7.1 ~ 7.6
7.6 ~ 8.0
7.2
7.9
7.2 ~ 7.7
7.3 ~ 7.6
7.6
7.4
7.0 ~ 7.5
7.5 ~ 7.8
7.3
7.6
7.2 ~ 7.6
7.4 ~ 7.8
7.5
7.6

24
7.6 ~ 8.3
7.4
7.8 ~ 8.1
7.9
7.6 ~ 8.0
7.7
7.7 ~ 8.1
7.8

0.3

0.4

0.5

0.3

0.7

0.8

0.6

0.3

Range

Difference value

0.8

0.2

0.5

0.3

0.4

0.5

0.4

0.4

Range a are the values of samples with the same concentration and different balance time; range b are the values of samples with the same balance time and different
concentrations. Difference value a was the 24-hour sample value deviation from 13CNaHCO3, and the difference value b was the same balancing time sample deviation from
13CNaHCO3.

3.2 Stability test

3.3 Effect of atmospheric CO2

To test the stability of the samples and the results, a number


of separate parallel analyses were performed on the samples of
series A, B, and C after 3 days and 10 days. The averages were
7.8 and 7.9 for series A, 7.8 and 7.8 for series B,
and 7.8 and 7.7 for series C. These results were almost
identical with the above-mentioned 13C values of 24-hour
samples (Table 1). This result proves that the carbon isotope
composition of samples is stable, and the results are accurate.
Figure 2 indicates that the balance time has a certain
influence on the experimental results. However, after 24 hours,
the result should be satisfied with the experimental
requirements for different concentration samples.

The laboratory was located in Lanzhou, China. According


to the study, distribution of 13C value of atmospheric CO2 in
Lanzhou was in the range from 17.9 to 7.6, and the
average was 11.5 in a year[13].
The laboratory air was also collected and analyzed in
December 2005. The average 13CCO2 in the atmosphere was
15.6 (n = 5), which was smaller than the same month in
Lanzhou. The reasons may be as following: during the
analysis of carbon isotope, laboratory standard CO2 gas
(13CCO2 = 31.5) spills into the atmosphere and 13C values
of atmospheric CO2 may have inherent fluctuation.
To confirm the influence of the reliability environment on
the CO2 results of the atmospheric sample, the distilled water
was chosen without removing soluble CO2, then three DIC
samples were prepared as control group and numbered A-2,
B-2 and C-2.
During the operation, protective measures against the
atmospheric CO2 were not adopted (other conditions were
same with the former). Analysis was conducted for 24 hours;
the average 13C values of the three DIC samples were
10.2, 10.3 and 9.8, respectively (Table 2), and the
average of A-2, B-2 and C-2 were 10.2, 10.3 and
9.8, respectively. Compared with the A, B and C, the
negative difference value was 2.2, 2.4 and 2.1,

Fig.2 13C value distribution related with concentrations and time


The descriptions of the samples A, B, C, and D are in the text

LI Zhong-Ping et al. / Chinese Journal of Analytical Chemistry, 2007, 35(10): 14551458

respectively (as shown in Fig.3).


This result indicated that the samples of A-2, B-2 and C-2
were affected by atmospheric CO2, and their 13CDIC values
became lower. Also, this result indicated that this method was
available to determine the DIC carbon isotope in
environmental sample.
Table 2 13C values of DIC samples impacted by atmospheric CO2
( PDB; n = 5)
Sample

A-2
B-2
C-2

9.8
9.6
9.2

10.2
9.9
10.8

3
11.1
10.5
10.0

4
10.5
11.2
9.5

Average

9.6
10.2
9.7

10.2
10.3
9.8

acquired.

Acknowledgments
We thank two anonymous reviewers for their valuable
comments that improved an earlier version of the manuscript.
We also thank Dr. Taofik, who is from Nigeria, and Li Jing
from Beijing Normal University for their constructive
comments to improved the manuscript.

References
[1]

Anirban D, Krishnaswami S , Bhattacharya S K. Earth and


Planetary Science Letters, 2005, 236: 419429

[2]

Bauch

A,

Erlenkeuser

H,

Bauchc

D.

Marine

Micropaleontology, 2004, 51: 285300


[3]

Marfia A M, Krishnamurthy R V, Atekwana E A. Applied

[4]

Scott A R, Kaiser W R, Ayers W B. AAPG Bulletin, 1994, 78:

Geochemistry, 2004, 19: 937946


11861209
[5]
Fig.3 13C value comparisons between two group samples
The descriptions of the samples A, B, C, D, A-2, B-2 and C-2 are in
the text

[6]

Conclusions

A method of the DIC carbon isotope analysis has been


developed, which does not need to use pre-vacuum or cold-trap
enrichment devices, and the operation process is simple. Using
this method, DIC samples can avoid atmospheric pollution.
Compared with 13C value of NaHCO3, differently concentrated
samples show mere (0.20.5) deviation, which means that
the DIC samples are stable and DIC carbon isotopic values

Hassan A A. U.S. Geological Survey Water-Resources


Investigations Report, 1982, 6: 51

[7]

Aravena R, Harrison S M, Barker J F. Chemical Geology,


2003, 195: 219227

Bishop P K. Chemical Geology, 1990, 80: 251259

[8]

Graber E R, Aharon P. Chemical Geology, 1991,94: 137144

[9]

Kroopnick P. Deep-Sea Research, 1974, 21: 211227

[10]

Holt B D, Sturchio N C, Arehart G B. Chemical Geology,


1995, 122: 275284

[11]

Gregory G S, Lynn A R, Luis A C. Marine Chemistry, 2000,


69: 153161

[12]

Ortiz J D. Global Biogeochemical Cycles, 2000, 14: 917930

[13]

Zhang L M, Xu Y C. Chinese Science Bulletin, 1992, 37:


441444