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Carbon isotopes in wood combustion/pyrolysis products: experimental and molecular simulation approaches

Helena Hercman
Helena Hercman
, 
Marek Szczerba
Marek Szczerba
, 
Paweł Zawidzki
Paweł Zawidzki
 and 
Agata Trojan
Agata Trojan
   | Jul 19, 2019
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Article Category: Regular Articles
Published Online: Jul 19, 2019
Page range: 111 - 124
Received: Dec 05, 2018
Accepted: Apr 02, 2019
DOI: https://doi.org/10.1515/geochr-2015-0110
Keywords
© 2018 H. Hercman. published by Sciendo
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Fig. 1

Estimation of the experiment’s temperature range (experiments with artificial air). CO2 emission (A) at the temperature increase (B) in pine wood experiment.
Estimation of the experiment’s temperature range (experiments with artificial air). CO2 emission (A) at the temperature increase (B) in pine wood experiment.

Fig. 2

Estimation of the experiment’s temperature range (experiments with artificial air). Mass loss in the furnace experiments with modern wood.
Estimation of the experiment’s temperature range (experiments with artificial air). Mass loss in the furnace experiments with modern wood.

Fig. 3

Carbon isotopic composition of combustion and low-temperature pyrolysis products from pine wood experiments.
Carbon isotopic composition of combustion and low-temperature pyrolysis products from pine wood experiments.

Fig. 4

Carbon stable isotope composition of combustion products from experiments in burning chamber. W– wood; S0 – soot with no pre-treatment; S1 – soot pretreated by HCl; S2 – soot pretreated by HCl and HF; C– “charcoal”; A – “Acid”; CO2 – carbon dioxide.
Carbon stable isotope composition of combustion products from experiments in burning chamber. W– wood; S0 – soot with no pre-treatment; S1 – soot pretreated by HCl; S2 – soot pretreated by HCl and HF; C– “charcoal”; A – “Acid”; CO2 – carbon dioxide.

Fig. 5

Carbon stable isotope composition of combustion products from furnace experiments. 1, 2 and 3 – general trends of isotopic composition changes for “charcoal”, “acids” and “bio-oil” fraction respectively.
Carbon stable isotope composition of combustion products from furnace experiments. 1, 2 and 3 – general trends of isotopic composition changes for “charcoal”, “acids” and “bio-oil” fraction respectively.

Fig. 6

Carbon stable isotope composition of combustion products from “time relationship“ experiments. General trends for: 1. “Acids”; 2. “Bio-oils”.
Carbon stable isotope composition of combustion products from “time relationship“ experiments. General trends for: 1. “Acids”; 2. “Bio-oils”.

Fig. 7

Comparison of cellulose and lignin decomposition and decomposition products evolution with temperature (1°C/ps) basing on molecular simulations.
Comparison of cellulose and lignin decomposition and decomposition products evolution with temperature (1°C/ps) basing on molecular simulations.

“Variation factor” of wood burning products from furnace experiments with estimated 95% confidence intervals*.

Variation factor ΔC (‰)
Temperature experiment
Beech: „Charcoal” Oil Acid
200°C 0.16 ± 0.26 0.97 ± 0.29
300°C 0.12 ± 0.25 0.77 ± 0.23 –2.38 ± 0.35
400°C –0.54 ± 0.26 1.13 ± 0.33 3.12 ± 0.54
500°C –0.58 ± 0.26 0.08 ± 0.28 –0.40 ± 0.27
600°C –0.91 ± 0.26 –1.30 ± 0.28
Pine:
200°C 0.21 ± 0.18
300°C –0.07 ± 0.24 2.44 ± 0.28
350°C 2.30 ± 0.22
400°C –0.76 ± 0.19 1.81 ± 0.26
500°C –0.92 ± 0.27 1.29 ± 0.27
600°C –0.86 ± 0.21 1.27 ± 0.20
Oak:
200°C 0.43 ± 0.36 –0.32 ± 0.39
300°C 0.61 ± 0.36 1.76 ± 0.37 –0.16 ± 0.42
400°C 0.19 ± 0.36 1.31 ± 0.31
500°C 0.01 ± 0.35 1.48 ± 0.32
600°C 0.06 ± 0.36 0.64 ± 0.37
Fossil oak:
200°C –0.16 ± 0.28 –2.48 ± 0.22 0.40 ± 0.28
300°C –0.43 ± 0.28 2.73 ± 0.29 –0.81 ± 1.73
400°C –0.93 ± 0.28 0.94 ± 0.56 –0.23 ± 0.28
500°C –2.64 ± 0.29 –2.21 ± 0.28
600°C –3.88 ± 0.29
–2.22 ± 0.28
(after 60 minutes marked as t’) –1.14 ± 0.28 (after 120 minutes marked as t’’)

Differences in energies and entropy of reactants and products for reactions 3.2–3.5 (in kJ/mol and J/mol·K, respectively) for temperatures of 27°C (300 K) and 427°C (700 K) recalculated for one carbon atom, along with equilibrium constants.

reaction temperature (°C) ΔEZPE* ΔEthermal** ΔGthermal*** ΔS**** K*****
27 0.02998 0.03427 0.06128 –0.08033 24.87
(3.2 – CO2) 427 0.02998 0.08385 0.07265 0.01423 12.56
27 –0.13872 –0.08699 –0.02306 –0.21004 –9.20
(3.3 – formaldehyde) 427 –0.13872 –0.00577 0.01466 –0.02761 2.52
27 –0.10346 –0.05799 –0.00923 –0.15648 –3.69
(3.4 – glycoaldehyde) 427 –0.10346 0.00692 0.02142 –0.01799 3.69
27 –0.08424 –0.06414 –0.03097 –0.39204 –12.34
(3.5 – acetone) 427 –0.08424 –0.02422 –0.00730 –0.52635 –1.25

Basic data of wood samples.

Wood Sample Locality Cut date Coordinates Growth (A.periodD.) a Nb Mean (‰VPDB) δ13C
Pine S2 Siedlce 2014, March 52°10′00″N 22°16′30″E 2013–2001 30 –26.5 ± 0.2
Oak D1 Ojców 2014, October 50°12′24″N 19°49′45″E 2009–2001 30 –27.4 ± 0.3
Beech B1 Błonie 2014, November 52°11′48″N 20°37′01″E 2009–2001 30 –24.7 ± 0.2
Fossil oak

“Variation factor” of wood burning products from combustion chamber experiments with estimated 95% confidence intervals*.

Variation factor ΔC (‰)
Beech Pinus Oak Fossil oak
S0 (no pretreatment) –0.50 ± 0.26 0.39 ± 0.28 0.80 ± 0.35 –0.49 ± 0.21
S1 (pretreated with HCl) –0.44 ± 0.22 0.22 ± 0.28 0.58 ± 0.35 –0.46 ± 0.21
S2 (pretreated with HCl and HF) –0.35 ± 0.25 0.45 ± 0.28 0.89 ± 0.36 –0.42 ± 0.21
Charcoal –0.79 ± 0.26 –1.54 ± 0.28 –0.13 ± 0.36
Ash –2.53 ± 0.25 –0.66 ± 0.28 0.14 ± 0.36 –0.69± 0.23
CO2 –0.21 ± 0.28 0.90 ± 0.38 1.05 ± 0.50 3.39 ± 0.21
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