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Abstract
Anaerobic digestion of organic matter, which is generally used for wastewater
treatment, it occurs the generation of biogas, mainly composed of methane
(CH4) and carbonic gas (CO2), besides occasionally producing sulfidric gas
(H2S), nitrogen (N2) and hydrogen (H2), depending on the composition of the
organic matter present in the wastewater and on the physical-chemical
conditions of the process. Moreover, methane and hydrogen may be used as
alternative sources of renewable energy. So, it is very important to monitor the
biogas (composition and quantification), which is made by gas chromatography.
The validation of the method by gas chromatography with thermal conductivity
detection (GC/TCD) described here was assessed by the following parameters:
linearity (between 0.9948 and 0.9986), precision of the method by the
coefficient of variation (CV %)of the chromatographic areas (from 0.29% to
12.57% related to the chromatographic area) and instrumental precision (from
5.92% to 8.0%) and limits of detection (from 0.06 to 0.20 moles) and
quantification (from 0.19 to 0.60 moles). The results attested that it is suitable
for determination of N2, CH4, CO2 and H2S in the biogas generated by anaerobic
processes treatment of wastewater.
Keywords: anaerobic processes, gas chromatography, composition of biogas.
Introduction
The determination of the composition of the biogas formed in the anaerobic
degradation of organic matter by microorganisms is important because in these
processes are formed mainly carbon dioxide and methane (a renewable energy
source) and, occasionally, H2S, H2, NH3, among others. They can be released to
atmosphere, causing environmental impact and unpleasant smell (3). Anaerobic
digestion is an efficient technology for waste treatment, including municipal,
agricultural and industrial organic wastes. Some advantages of this process are
the low energy consumption and the probability of energy recovery. The
accumulation of organic acids produced in anaerobic digestion, as well as the
decrease of production rate of methane is usually an indicator of the inhibition of
this process (2). The composition of biogas depends on the organic matter
considered, on the pH, alkalinity, temperature and other substances which may
be present in the organic matter to be degraded (5).
Also, the biochemical methane potential test is a parameter used to determine the
methane yield of an organic matter substrate subjected to a specific anaerobic
process and it requires the quantification of the methane in the assay to measure
the digestibility of a particular substrate (4).
In this work we developed a rapid method by GC/TCD (Gas Chromatography
with Thermal Conductivity Detector) for the determination of nitrogen, methane,
carbon dioxide and hydrogen sulfide (N2, CH4, CO2, and H2S respectively) with
manual injection in samples from anaerobic reactors treating wastewater. The
validation parameters were evaluated (linearity, limits of detection and
quantification LOD and LOQ and precision) according to Ribani et al. (2004).
Methods
Two cylinders, one with a standard mixture of N2, CH4 and CO2 and another of
pure H2S were used for the construction of the calibration curves after the
injection of different volumes (from 10 to 1000 L) of the standard gases at
ambient pressure and temperature. The H2S was bubbled into a solution of 6N
NaOH and the injection of all standards was made manually by a plastic syringe
connected to a push-botton valve in which the needle and the syringe are
easily replaceable (Figure 1), through a silicone tube. The injected volumes were
transformed into number of micromoles through Equation 1 and then it was
plotted the number of micromoles against the chromatographic areas. Each
volume of gas was injected by three different persons, in triplicate (9 replicates
at all).
PV = nRT
(Equation 1)
Equation (2)
LOQ = 10 * s/S
Equation (3)
Where s is the standard deviation of the linear coefficient and S is the average of
the angular coefficient of the equations of the regression lines.
The precision of the method was calculated based on the coefficient of variation
(CV %) of the chromatographic areas (Equation 4) and the instrumental
precision was determined after 10 injections of the same volume of the gases.
CV % = w/ * 100
Equation (4)
LOQ
(moles)
(moles)
4555.82
0.20
0.60
0.9985
7134.77
0.06
0.19
y = 19252.23x + 2724.84
0.9986
7884.40
0.09
0.27
y = 27150.47x 5074.59
0.9936
1087.36
0.11
0.33
Gas
Equations
Ftest
N2
y = 18143.03x + 3075.73
0.9976
CH4
y = 14408.18x + 1847.35
CO2
H 2S
Standard
deviation
Average
Standard
deviation
CV %
N2
23426.12
1385.82
5.92
1.942
0.002
0.11
CH4
18131.67
1253.68
6.91
2.141
0.002
0.08
CO2
24582.36
1678.46
6.83
2.741
0.002
0.07
H 2S
95245.96
7617.33
8.00
4.223
0.005
0.11
Conclusion
The validation parameters evaluated attested good linearity, precision and low
limits of detection and quantification to this method, which is suited to
determine N2, CH4, CO2 and H2S in biogas generated in anaerobic processes by
manual injection. Since there are different types of reactors (batch or continuous,
for example) this method allows manual injection with a low cost without the
need for online analysis with special devices for injection.
Acknowledgments
The authors acknowledge financial support from Finaciadora de Estudos e
Projetos (FINEP), Conselho Nacional de Desenvolvimento Cientfico e
Tecnolgico (CNPq) and Fundao de Amparo Pesquisa (FAPESP).
References
1. Bratinova, S., Raffael, B. and Simoneau, C. 2009 Guidelines for
performance criteria and validation procedures of analytical methods used
in controls of food contact materials. JRC Scientific and Technical Reports,
EUR 24105 EN 1st. edition, Publications Office of the European Union,
Italy.
2. Chen, Ye, Cheng, J. J. and Creamer, K. S. 2008 Inhibition of anaerobic
digestion process: A review. Bioresource Technology, 99, 40444064.