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939-Article Text-1496-1-10-20160817
939-Article Text-1496-1-10-20160817
1
Jurusan Kimia, FMIPA UNHAS ISSN 1441-2132
ABSTRACT
Comparison of MEA, DEA and TEA as CO2 absorbent to measure carbon-14 activity of coral
sample has been performed. This research aimed to Determine the age of coral reef sample of
Spermonde Islands by measuring the activity of carbon-14 using the method Liquid
Scintillation Counting (LSC). The sample of coral reef were collected in Langkai Island. The
research were conducted by following steps of sample preparation, the CO2 absorption using
the solutions of MEA, DEA and TEA. The measurement of the carbon-14 activities was
performed using the Liquid Scintillation Counter (LSC) Hidex 300 SL. The research results
indicated that the absorption capacities of MEA, DEA and TEA were 0.5180, 0.5903 and
0.2608 mol CO2/mol amine respectively. The specific activity of the coral reef sample using
the absorbents of MEA, DEA and TEA were 14.44, 14.59, and 14.42 DPM/g C respectively.
The age of the coral reef sample, which was calculated based on the specific activity values
using the absorbents of MEA, DEA and TEA were 480.15 ± 37; 390.11 ± 60 and 488.22 ±
87 years respectively.
Keywords : LSC (Liquid Scintilation Counter), Carbon-14, CO2 Absorption,
Alkanolamine, Langkai Island
INTRODUCTION
Spermonde Islands is one area of method based on the calculation of the 14C
coral reefs spread evenly wide. Recently, activity was contained in a sample. This
the study of the genesis and historiography value is then converted into age after the
of Spermonde islands as coral-based activity compared to modern reference
exposure remains a mystery, especially in standard (Satrio and Abidin, 2007; Satrio
the initial information reveals the and Sidauruk, 2010).
formation of the reef . Carbon-14 measurements by liquid
Determination of the age of the coral scintillation counting method is based on
reefs in the waters has a huge benefit in two methods of pretreatment, the method
studying the geography of marine origin of synthesis of benzene and CO2
such coral samples to trace and study the absorption method (Satrio and Abidin,
formation sector in coastal rock 2007). CO2 absorption method is an
formations, especially if an area is an area alternative pretreatment method in the last
of islands with very high coral reef two decades. It was developed for
biodiversity levels (Yuliati and Akhadi, measuring the Carbon-14 in various
2005). environmental samples such as soil, river
Radiosiotop 14C is a radioactive water, sediment and coral reefs (Varlam et
isotope that is most commonly used for al., 2007; Mazeika et al., 2009; Varlam, et
dating hydrology, geology and archeology al., 2010; Faurescu et al., 2010; Satrio and
samples. Age determination using 14C Sidauruk, 2010; Maming, et al., 2014).
often referred to as radiocarbon dating, a
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Comparison of MEA, DEA And TEA … Vol. 16 No.1
CO2 absorption approach is based on column, glass cup, mortar, oven, hammer
the same basic principle as the benzene- and tools glasses commonly used in
LSC method. The main difference is the laboratories as well as β radiation count
CO2 produced from the sample is absorbed
tool of carbon-14 sample is LSC Hidex
directly into the appropriate cocktail with
high CO2 affinity and directly counted by 300 SL.
LSC without further changes. The method
is simple, safe, and significantly reducing Sampling
time analysis and cost compared to Coral sample taken at seawater near
conventional methods. one of the islands in the Spermonde
Alkanolamine compounds such as Archipelago, which is in Langkai Island at
monoethanolamine (MEA), a depth about 4-5 m. Langkai Island
diethanolamine (DEA) and located on coordinate S: 05o 01’ 47,055” E:
triethanolamine (TEA) is a reactive CO2 119o 05’ 50,272”.
absorbent. Alkanolamine compound has
the advantage of absorbing CO2 due to Phisical and Chemical Cleaning
rapid absorption rate, low cost and high Cleaning methods are designed to
heat absorption (Vaidya and Mahajani, remove contaminating carbon sources that
2006; Kim, et al. 2013). accumulate both while the specimen is on
According to research conducted by the sea floor and while it is stored on land
Kim, et al (2013), CO2 absorption after collection. Water rinses and
capability of a solution of 30 % MEA, scrubbing with a brush remove sediment
30% DEA and 30 % TEA are 0.565; from inside the coral and between the
0.658 and 0.486 mol CO2 / mol amine septa. Samples are then immersed in a 1:1
respectively. CO2 absorption capability mixture of 30% H2O2 and 1N NaOH and
allows the use of relatively large ultrasonicated for 15 minutes. However,
alkanolamine compounds as alternative this process often leaves a
CO2 absorbent for Carbon-14 brownish/orange organic stain on the
measurements. CaCO3. Quick dips (30 seconds to 2
Carbon-14 analysis which is correct minutes) in a 1:1 mixture of 30% H2O2
and accountable is the most important and 1N HClO4 effectively remove this
factor in assessing the status of a coral stain. After the dilute perchloric step,
reef. Therefore, in this study will be samples are rinsed thoroughly with clean
conducted to determine the capacity of distilled water. For the second acid wash,
MEA, DEA and TEA as CO2 absorbent for pre-weighed samples are dipped into 6N
radiocarbon measurements in coral HCl for 15–60 seconds followed by rinses
sample. in two separate beakers of distilled H2O.
After drying for several minutes in a 60 °C
MATERIAL AND METHOD oven, the samples are cooled and
Materials reweighed to determine the percent of
The materials of this study was 30% sample removed. Samples are then crushed
in an agate mortar and pestle to facilitate
H2O2, HClO4 1 N, 1 N NaOH,
dissolution in the reaction flasks (Adkins,
ethanolamine, N2 gas HP (High Purity), et al., 2002)
10% HCl, AgNO3, silica gel, marble,
scintillator aqualight LLT, filter paper, Carbon Dioxide Absorption
distilled water and coral reefs . Dried coral were transferred to flask
Apparatus that connected to a separation funnel as
hydrochloric acid reservoir. Prior to
Preparation tool in the form of round-
carbon dioxide absorption, the nitrogen
bottom flask, impinger, funnel, absorption
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Comparison of MEA, DEA And TEA … Vol. 16 No.1
gas was streamed along the system. impurities and carbon source on the
Solution of 10 % HCl was added by drops surface up to 8,63 %. The result of these
to the sample until bubles formed experiments are not much different from
(Fig.1).Gas is channeled into an impinger the result of deep-sea coral sample cleanup
contains 40 mL of 30 % MEA, DEA or was done by Adkins et al. (2002) and
TEA as CO2 absorben after passed acid Maming et al. (2014). The missing part of
trap and water trap. The process was the sample is a natural contaminant that
stopped when the gas not formed by accumulates over the coral reef waters and
adding the hydrochloric acid. dissolved matrix surface.
Concentration of CO2 absorbed was
quantified from the difference of weight Carbon Dioxide Absorption
before and after absorption process The main component coral as
carbonate that have been grinded are
separated by reaction with hydrochloric
acid, based on the reaction:
CaCO3 (s) + HCl (aq) CaCl2 (aq) + CO2 (g) + H2O (aq)
Carbonate in this reaction is released
as CO2 gas when the sample react with
acid. Carbon dioxide is absorbed by MEA
through chemical reaction as carbamate,
based on the reaction (Kim et al, 2013;
Figure 1. Design of absorption system of Singh, 2011) :
carbon dioxide from coral CO2 (g) + 2 RNH2 (aq) RNHCOO−(aq) + RNH3+ (aq)
sample (R = -CH2-CH2-OH)
Carbon dioxide is absorbed by DEA
The same method is used to absorb CO2 through chemical reaction as carbamate,
from Marble for use in the measurement of based on the reaction (Kim et al, 2013;
the Background Singh, 2011):
CO2 (g) + 2 R2NH (aq) R2NCOO−(aq) + R2NH2+ (aq)
(R = -CH2-CH2-OH)
Carbon-14 Counting
TEA, a tertiary amine, cannot directly
Approximately 8 mL of sample or
react with CO2. TEA acts as a base catalyst
background mixture with 12 mL
to form bicarbonate ions, based on the
scintillator in 20 mL vial. The mixture was
reaction (Kim et al, 2013; Singh, 2011):
homogenated by shaking and saved from CO2 (g) + R3N (aq) + H2O (l) R3NH+(aq) + HCO3−(aq)
light exposure, and then lied on 20 mL vial (R = -CH2-CH2-OH)
plate tray. Counting the sample as protocol The existence of carbamate or
LSC Hidex 300 SL and it was counted at bicarbonate ions as reaction products is
5-240 minutes in range. identified by the difference of solution
weight before and after absorption. The
correlation between weight of CO2
RESULT AND DISCUSSION absorbed using MEA, DEA and TEA to
Phisical and Chemical Cleaning the weight of sample is showing on the
Coral sampel that have been physically figure 2.
and chemically cleaned looked clean and
white. The chemical cleaning removed
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Comparison of MEA, DEA And TEA … Vol. 16 No.1
5,000
3,000
MEA
2,000
DEA
1,000 TEA
0,000
0,000 50,000 100,000
weight of sample(g)
Figure 2. Correlation between weight of sample with amount of CO2 absorbed using MEA,
DEA and TEA
Table 1. The optimum amount of CO2 absorbed by MEA, DEA and TEA
Amount of CO2
Absorbent mol CO2/mol
Weight of CO2 (g)
alkanolamine
MEA 30 % 4,572 0,5180
DEA 30 % 3,236 0,5903
TEA 30 % 1,033 0,2608
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Comparison of MEA, DEA And TEA … Vol. 16 No.1
6000
5000
MEA + CO2 sample
4000 MEA
DPM
3000 MEA + CO2 marble
2000
1000
0
0 50 100 150 200 250 300
Counting Time(minute)
140
120
100
DEA + CO2 sample
DPM
80
60
DEA
40
20 DEA + CO2 marble
0
0 50 100 150 200
Counting Time(minute)
120
100
80
TEA + CO2 Samplel
DPM
60
TEA
40
0
0 20 40 60 80 100 120 140 160
Counting time (minute)
In figure 3,4 and 5 shows that the activity of marble background is used to
measurement of Carbon-14 marble as correct activity of Carbon-14 from
background showed lower activity than samples.
the sample. Therefore, the Carbon-14
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Comparison of MEA, DEA And TEA … Vol. 16 No.1
0,700
0,600
0,500
0,400
TDCR
MEA
0,300
DEA
0,200
TEA
0,100
0,000
0 30 60 90 120 150 180
Counting Time(minute)
From Table 2 shows that the TDCR for MEA absorbent less stable in
efficiency of the order of enumeration the early minutes when compared to the
(TDCR) using absorbent MEA, DEA and DEA and TEA TDCR absorbent.
TEA are TEA> DEA> MEA. The order of
enumeration efficiency is influenced by Specific Activity and Coral Age
the type of ions generated in the process of Estimation
CO2 absorption. DEA and MEA absorp Determination of specific activities
CO2 as carbamate ions while the TEA are needed in order to determining the age
produces bicarbonate ions. The order of of the sample. The specific activity is the
stability of the species which resulted from basis for calculating the age of the coral
CO2 absorption is MEA-carbamate ion> sample obtained from the activity value of
DEA-carbamate ion> bicarbonate ion DPM divided by the total carbon weight of
(Singh, 2011). Differences in the type and sample mixed with scintillator. The value
stability of the species causes the of specific activity expressed in units of
difference of interaction with the solvent DPM per unit mass. Specific activity data
in the scintillator and give an effect on the of coral sample is shown in Table 3. The
count rate. Figure 6 shows a comparison specific activity value (As) shows the
of the efficiency of enumeration (TDCR) actual number of 14C atoms which
absorbent MEA, DEA and TEA to time. disintegration per minute (dpm) in each
From the graph shows that the value gram of the element carbon.
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Comparison of MEA, DEA And TEA … Vol. 16 No.1
C-total
Absobent DPM As (DPM/gC) As C-14 life* 5
(g)
MEA 30 % 3,576 0,2477 14,44 ± 1,12 15,30 ± 0,1
DEA 30 % 2,576 0,1765 14,59 ± 2,23 15,30 ± 0,1
TEA 30 % 0,812 0,0563 14,42 ± 2,58 15,30 ± 0,1
Based on the following equation can be E.A., Edwards, R.L., Shen, C.C.
obtained The Age estimation of coral (2002) Radiocarbon Dating of Deep-
sample is obtained based on the specific Sea Corals. Radiocarbon. 44 (2) : 567-
activities that have been obtained 580.
previously. Canducci, C., Bartolomei, P., Magnani, G.,
Rizzo, A. (2013) Upgrade Of The CO2
t1/2 Ao Direct Absorption Method For Low
t= 𝑙𝑛 Level 14C Liquid Scintillation
ln 2 𝐴𝑡 Counting. Radiocarbon. 55 (2-3): 260-
267.
Where: Faurescu, I., Varlam, C., Stefanescu, I.,
Cuna, S., Vagner, I., Faurescu, D.,
A = Radioactive 14C in the sample
Bogdan, D. (2010) Direct Absorption
Ao = Radioactivity of 14C isotopes in
Method And Liquid Scintillation
living organisms 15.3 DPM / gC 5
Counting For Radiocarbon
t1/2 = half-life = 5730 years
Measurements In Organic Carbon
ln2 = 0.693
From Sediments. Radiocarbon. 52 (2-
3): 794–799.
The age of coral sample calculated from Kim, E.Y., Lim,J.A., Jeong, S.K., Yoon,
the specific activity using absorbent MEA, Y. I., Bae, S.T., and Nam, S.C. (2013)
DEA and TEA was 480.15 ± 37; 390.11 ± Comparison of Carbon Dioxide
60 and 488.22 ± 87 years respectively. Absorption in Aqueous MEA, DEA,
TEA, and AMP Solutions. Bull.
CONCLUSION Korean Chem. Soc. 34 (3): 783-787
In this study concluded that the Libby, W.F.(1960) Radiocarbon Dating.
Absorption capacity of MEA, DEA and Nobel Lecture. Elsevier Publishing
TEA was 0.5180; 0.5903 and 0.2608 mol Company: Amsterdam.
CO2/mol amine, respectively. The specific Maming, Noor, A., Zakir, M., Raya, I.,
activity of coral sample using absorbent Jauhari, Kartika, S.A. (2014)
MEA, DEA and TEA was 14.44; 14.59; Aplication in Liquid Scintillation
and 14.42 DPM/g C, respectively. The age Method om Carbon Dating in
of coral sample calculated from the Determination of Coral Ages from
specific activity using absorbent MEA, Spermonde Archipelagos. Marine
DEA and TEA was 480.15 ± 37; 390.11 Chimica Acta. 15 (1): 31-35.
± 60 and 488.22 ± 87 years, respectively. Mažeika, J. , Guobytė, R., Kibirkštis, R.,
Petrošius, R., Skuratovič, Z.,
Taminskas, J. (2009) The Use Of
REFERENCES Carbon-14 And Tritium For Peat And
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Cheng, H., Druffel, E.R.M., Boyle, Case Of Čepkeliai Peatland,
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Comparison of MEA, DEA And TEA … Vol. 16 No.1