Geoderma 130 (2006) 35 – 46

www.elsevier.com/locate/geoderma

Black carbon contribution to soil organic matter composition in

tropical sloping land under slash and burn agriculture
C. Rumpela,T, M. Alexisa, A. Chabbia, V. Chaplotb, D.P. Rassea,
C. Valentinb, A. Mariottia
a
UMR CNRS-INRA-Université Paris VI, Laboratoire de Biogéochimie des Milieux Continentaux, Centre INRA Versailles-Grignon,
Bâtiment EGER, F-78850 Thiverval-Grignon, France
b
IRD, UR049, Erosion et Changement d’Usages des terres BP 06, Vientiane, Laos
Received 2 April 2004; received in revised form 16 November 2004; accepted 12 January 2005
Available online 22 February 2005

Abstract

Tropical soils are generally depleted in organic carbon (OC) due to environmental conditions favouring decomposition and
mineralisation of soil organic matter (SOM). In Northern Laos, sloping soils are subjected to slash and burn agriculture, which
leads to production of black carbon (BC), a stable SOM fraction. BC may directly influence the quantity and quality of SOM
sequestered in tropical soils. The aim of this study was to quantify BC content and evaluate its impact on the chemical and
stable isotope composition of SOM along a catena composed of Dystrochrepts at the bottom of the slope, Alfisols (midslope)
and Inceptisols at the top of the slope for different burning frequencies. Six soil profiles, situated on a slope ranging from a river
bank to the summit of a hill, were sampled. The stable isotope compositions (13C and 15N) of samples from both organo-mineral
A and mineral B and C horizons were determined. The chemical composition of SOM analysed by 13C CPMAS NMR
spectroscopy and the contribution of BC determined by dichromate oxidation were compared to OC and iron oxide content as
well as land management including the burning cycle.
The highest C contents were recorded at midslope positions. At any position on the slope, y13C and y15N ratios showed an
enrichment in 13C and 15N with increasing soil depth. The OC content of soil horizons was related to their aryl C content, which
is the component most likely driven by BC inputs. The BC contributions analysed by dichromate oxidation ranged from 3% to
7% of total OC. A positive correlation was obtained between aryl C and the BC content of SOM. Comparison of BC content
and stable isotope composition of SOM showed that BC influenced the y13C and the y15N stable isotope ratios of these soils.
BC was not associated with the mineral phase. The highest BC contents were measured under intensive slash and burn practice
in the vicinity of the boundary of Alfisols at the top of the slope, where erosion was severe. Therefore, BC, a SOM component
strongly influencing OC sequestration of these soils, is susceptible to translocation down the slope.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Tropical soil; Organic matter composition; Black carbon

T Corresponding author. Tel.: +33 1 30 81 54 79; fax: +33 1 30 81 53 97.

E-mail address: cornelia.rumpel@grignon.inra.fr (C. Rumpel).

0016-7061/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.geoderma.2005.01.007
36 C. Rumpel et al. / Geoderma 130 (2006) 35–46
1. Introduction
Population pressure on agricultural land leads to
the exploitation of mountainous areas in many tropical
countries. This is particularly true in Laos, where
population growth (2.4–2.8% per year) and opening
of the country to the common Asian market favoured
cultivation of marginal land (Roder et al., 1997). The
main agricultural practice in the country is slash and
burn agriculture, which covers one third of the arable
land (Fujisaka, 1991; Dufumier and Weigel, 1996).
Slash and burn practices, which rely on fallows lasting
20 years or longer, are gradually replaced by very
short fallow periods lasting between 1 and 2 years.
This practice has numerous drawbacks, such as a
decrease in soil fertility, increase of soil erosion and
invasion by weed species.
Organic matter is an important long-term nutrient
source as well as a soil structuring agent. Moreover,
soil organic matter (SOM) may be a sink for
atmospheric CO2, thereby counteracting the global
warming process. Organic matter derived from plant
material is usually rapidly mineralised under tropical
climate conditions, where interaction with minerals
plays an important role in SOM stabilisation (Feller
and Beare, 1997). Land use, e.g. farming practices,
may be detrimental to carbon sequestration in the
tropics. For instance, SOM contents were found to
decrease by 60% after 3–5 years of continuous
cultivation of sandy tropical soils, and after 5–10
years for soils with a loamy texture (Feller and Beare,
1997). However, an assessment of the impact of
agricultural practices on SOM pools including types
and chemical composition has yet to be undertaken
for tropical areas (Flint and Richards, 1991; Walker,
1994; Zech et al., 1997).
In regions where slash and burn is practiced, a part
of SOM may consist of black carbon (BC), a
carbonaceous material produced by fire (Skjemstad
et al., 1996; Schmidt and Noak, 2000; Glaser et al.,
2001). Two forms of BC are commonly differentiated:
(a) charcoal, which is composed of incomplete
biomass combustion products that represents the main
portion of BC on a mass basis; and (b) condensation
products of hot combustion (soot) (Gelinas et al.,
2001). It is generally accepted that BC materials do
not support microbial activity and thus represent a
long-term carbon sink in soil (Kuhlbusch, 1998). The
contribution of BC, which is a fraction with high
aromaticity, may change the chemical composition of
SOM as has been shown for temperate areas
(Skjemstad et al., 1996; Schmidt et al., 1999).
The objective of this study was to quantify the BC
content and evaluate its impact on the chemical and
stable isotope composition of SOM along a tropical
soil catena in northern Laos, for different burning
frequencies. The chemical composition of SOM was
determined by 13C cross polarization magic angle
spinning-nuclear magnetic resonance (13C-CPMAS-
NMR)-spectroscopy. Interaction with the mineral
phase was studied by evaluating organic carbon
(OC) loss after treatment with hydrofluouric acid
and quantification of iron oxides (Eusterhues et al.,
2003). The BC contribution to SOM was studied after
chemical oxidation of labile OC compounds. This
method allows the isolation of an operationally
defined part of the BC continuum which represents
the oxidation resistant elemental carbon (OREC, Bird
and Gröcke, 1997).
2. Material and methods
2.1. Study site
The study site is located in the Luang Prabang
province 10-km South of Luang Prabang city. It is a
catchment of about 62 ha. Its exact location was
determined by a GPS system. Its Universal Transverse
Mercator 1983 coordinates (zone 48) were between
203245.14 to 204679.65 and 2197318.4 to
2198825.04. This catchment is representative of no-
input slash and burn systems and has been subjected
to a reduction of the fallow period from 5 to 2 years.
At Luang Prabang, average annual rainfall over the
last 30 years was 1403 mm. Mean annual temperature
was 25 8C. Two distinct seasons characterise the study
site: a wet season from April to October and a dry
season from November to March.
Field observations performed over the catchment
indicated that the geological substrate is formed
mainly of argilites, siltstones and fine grained sand-
stone of Permian to Upper Carboniferous age.
Altitudes estimated from a 10-m Digital Elevation
Model generated from theodolithe data points ranged
from 405-m at the catchment outlet to 718 m. It is a
 C. Rumpel et al. / Geoderma 130 (2006) 35–46 37

typical catchment of sloping land area with mean
slope of 56%.
Eighty percent of the catchment land is under crop
and short fallow rotations, whereas less than 15% is
under forest. Upland rice and Job’s tears (Coix
lacryma–jobi L.) are the most common crops. Slash
and burn practices have long been used in the region,
but since 1975 a shortening of the fallow period was
introduced. Hillslopes are mostly devoted to crops,
the bottomlands are under tree plantations, and the
summits remain under forest.
2.2. Soil distribution along the catena situated along
the catchment slope
Soil distribution along the catena was surveyed
using soil profiles and additional auger-probe sam-
plings to precisely establish the boundaries of soil
type distributions. A total of 6 soil profiles and 35
auger-probe samplings were conducted. At each
location, morphological, physical and chemical char-
acteristics either observed in-situ or measured in the
laboratory allowed identification of the soil types.
From the bottom to the top of the slope, soils varied
from Dystrochrepts at the bottom of the slope,
Alfisols (midslope) and Inceptisols at the top of the
slope. Dystrochrepts (Soil Survey Staff, 1999) were
located from the stream bank to the upper limit of the
bottomland area, and were marked by fluvic proper-
ties and redoximorphic features. Sedimentation pro-
cesses by the stream may control the relative
extension of Dystrochrepts. Alfisols were deep (from
2.5 to 4.5 m, Fig. 1), and exhibited high clay contents
(55% on average). They showed a typical argillic B
sub-surface horizon. This horizon is frequently
exposed following surface erosion. With increasing
erosion rate, especially in the upslope direction, the
argillic horizon disappeared and Inceptisol formation

C
Profile 6

Profile 5

Profile 4 0 ppm
A

Profile 3 A
Profile 2 300 200 100 0 ppm
300 200 100 0 ppm
A A
B1
Profile 1
300 200 100 0 ppm
B2

300 200 100 0 ppm

300 200 100 0 ppm

13
Fig. 1. Chemical structure of organic matter in the soil horizons along the toposequence as revealed by solid-state C NMR spectroscopy.
38 C. Rumpel et al. / Geoderma 130 (2006) 35–46
within saprolite horizons occurred (Profile 6, Fig. 1).
Inceptisols were shallow (0.5 to 1 m) and showed a
high stone content, but still with a clayey texture (35%
clay on average). The mineral horizons exhibited an
increase in the proportion of stones with depth.
2.3. Soil toposequence, sampling, and sample
pre-treatment
Within this catchment, soil sampling was per-
formed along a soil catena showing a typical
succession from the bottom to the top of the slope
between Dystrochrepts, Alfisols and Inceptisols. Six
soil profiles were considered along the catena and
across land use types. Profile 1 was located at the
stream bank and profiles 2 and 3 in the downslope
area under banana plantation. Profiles 4 and 5 were
located at midslope and upslope position under Job’s
tears and finally, profile 6, at the summit, was under
forest.
The hillslope where the soil profiles are situated is
170 m long. Altitudes range from 505 m in the
stream bed to 584 m at the summit and the mean
slope gradient is 46%. At the downslope position, the
average slope gradient is 30% with values ranging
from 5% to 33%. Slopes first increase in the upslope
direction to reach a mean of 54% at midslope
position and afterwards decrease to 25% at the hill
summit.
At the time of sampling, at the end of the dry
season (March 2003), Job’s tears were the common
crop. The fields were subject to rice cultivation during
the rainy season. All profiles were characterised by
the absence of dead organic material or humus layer
on top of the mineral soil. A and B and C horizons of
the soil profiles were sampled before burning of the
sites. Additionally, charcoal was sampled right after
burning. For determination of OC pools in the
laboratory, 0.5 kg samples of each soil horizon were
air-dried and subsequently sieved to pass a 2-mm
sieve.
2.4. pH, OC and N content, stable OC and N isotopes
The pH was measured in a 1:2.5 (mass/vol) soil
solution. Soil pH ranged between 5 and 6, which
precludes the presence of mineral carbonates and
implies that total C content equals OC content.
OC and N contents were determined by the dry
combustion method using a CHN auto-analyser (CHN
NA 1500, Carlo Erba) coupled to an isotopic ratio
mass spectrometer (VG Sira 10) yielding the ratio of
stable OC isotopes (y13C). Stable N isotope ratios
(y15N) were determined with a CHN analyser coupled
with an Isochrom III Isotopic mass spectrometer
(Micromass-GVI Optima). Results for isotope abun-
dance were reported in per mil (x) relative to the Pee
Dee Belemnite standard (PDB) and relative to air N2
for y13C and y15N, respectively. Analytical precision
was F0.1 mg g 1 for OC and F0.05 mg g 1 for N
content. Analytical precision for isotope measure-
ments was F0.3x.
2.5. Treatment with hydrofluouric acid and analysis of
iron oxides
Removal of soil minerals was carried out by
shaking 5 g soil for 12 h with 50 mL of 10%
hydrofluouric acid (HF, Goncalves et al., 2003).
After centrifugation at 3000 RPM, HF was renewed,
and the soil suspension shaken again. This proce-
dure was repeated five times. Thereafter, samples
were washed five times with distilled water, and
freeze dried before being subjected to OC and N
measurements.
Total content of iron oxides was measured as Fed
on sodium dithionite extracts of soil samples (Mehra
and Jackson, 1960) by inductively coupled plasma
optical emission spectroscopy. Oxalate extracted
samples provided Fe bound to poorly crystalline
oxides such as ferrihydrate (Feo). The ratio of Fed/
Feo can be used as an indicator for soil development
because with ongoing pedogenesis amorphous iron
develops into more crystalline forms.
2.6. Black carbon
The BC contribution to total OC content was
estimated as the oxidation resistant elemental carbon
(OREC, Bird and Gröcke, 1997), and analysed on
HF treated, mineral-free samples. Briefly, 150 mg of
a HF treated sample was mixed with a potassium
dichromate solution (0.1 M K2Cr2O7 in 1 L 2M
H2SO4), and oxidised at 60 8C in an ultrasonic bath.
The solution was changed several times during the
treatment. Thereafter the samples were washed four
 C. Rumpel et al. / Geoderma 130 (2006) 35–46 39

Table 1 (Wilson, 1987). Tentative assignments of chemical

Tentative assignments of chemical structures to chemical shift structures to the chemical shift regions are presented
regions of the 13C CPMAS NMR spectra (after Knicker and
Lüdemann, 1995)
in Table 1. The variation in integration due to the
treatment of a well resolved FID (Fourier trans-
Chemical Tentative assignment
shift (ppm) formation, phasing and baseline correction) is less
than 5% (Knicker, 1993).
Alkyl C 0–45 lipids, waxes, cutin,
suberin and other
aliphatic 2.8. Statistical analysis
biomacromolecules
O-alkyl C 45–110 polysaccharides, Regression analysis and Student’s t-test for sig-
methoxyl groups in
nificance among data sets were performed using the
lignin, N-alkyl C derived
from proteins computer software SIGMA PLOT 8.0.
Aryl C C substituted 110–140 aromatic C–C and C–H
of lignin, BC and other
aromatic compounds 3. Results and discussion
O substituted 140–160 aromatic C–O and C–N
of lignin, BC and other
aromatic compounds 3.1. Chemical parameters
Carboxyl C 160–220 carboxyl, carbonyl,
amide The OC content of soil horizons ranged from 12.1
to 26.5 mg g 1 in the A horizons and from 4.4 to
15.9 mg g 1 in the B and C horizons (Table 2). The
times with distilled H2O before being freeze dried, highest OC contents were recorded in A and B
weighed and analysed for elemental and isotope
composition. The oxidation time needed to isolate
Table 2
OREC, i.e., the fraction considered as BC, was
Chemical parameters and isotopic signature of vegetation, charcoal
evaluated in a preliminary study. To assess the and the organic matter in the soil profiles along the toposequence
stability of SOM, plant tissue, BC and mineral soil Horizon Depth, OC, N, C/N y13C, y15N,
(0–5 and 5–10 cm) sampled in vicinity of profile 5 cm g kg 1
g kg 1
ratio x x
were HF treated and oxidised over 1, 5, 24, 48 and BC (Charcoal) 417 8.1 52 29.2 3.0
100 h. Profile 1
A 0–40 12.1 1.2 10 23.2 7.1
13 Profile 2
2.7. C CPMAS NMR spectroscopy
A 0–20 17.1 1.5 11 24.8 6.2
13 B1 20–35 8.1 0.9 9 22.4 7.2
Solid-state C NMR spectra of HF treated, B2 35–60 5.0 0.6 8 22.3 7.8
mineral-free soil samples were obtained on a Bruker Profile 3
DSX-200 NMR spectrometer. Cross polarization A 0–30 17.9 1.6 11 25.2 9.1
with magic angle spinning (CPMAS) (Schaefer and B1 30–60 9.9 1.1 9 22.2 9.3
Stejskal, 1976) was applied at 6.8 kHz. The 13C B2 60–80 7.5 0.8 9 21.3 9.1
Profile 4
chemical shifts were referenced to tetramethylsilane. A 0–25 20.4 1.7 12 25.3 7.0
A contact time of 1 ms was used and pulse delay B1 25–55 11.8 1.2 10 22.7 8.7
was 400 ms. Solid-state 13C NMR signal was B2 55–75 7.6 0.8 8 21.3 9.2
recorded as free induction decay (FID) and Fourier Profile 5
transformed to yield a NMR spectrum. The spectra A 0–5 26.5 1.6 14 26.4 6.0
B1 5–15 15.9 1.4 11 24.3 8.3
were integrated using the integration routine of the B2 15–40 11.6 1.0 12 22.4
spectrometer. The chemical shift regions 0–45, 45– Profile 6
110, 110–140, 140–160 and 160–220 ppm were A 0–10 14.9 1.2 12 26.2
referred to alkyl C, O-alkyl C, C substituted aryl C, C1 10–25 7.5 0.8 9 24.2 7.6
O substituted aryl C and carboxylic C, respectively C2 25–50 4.4 0.5 9 23.0 8.5
40 C. Rumpel et al. / Geoderma 130 (2006) 35–46

horizons of profiles situated in midslope positions 70% of the OC present (Table 3). Total iron oxide
(profiles 4 and 5). Profile 6, situated on the hill content (Fed) varied between 38 and 73 mg g 1
summit, showed the lowest OC content in all three (Table 3). The content of amorphous iron (Feo)
horizons. The OC content generally decreased down ranged from 1 to 6 mg g 1, indicating that the major
the soil profile. The C/N ratios ranged between 8 and portion of iron oxides occurred as iron oxides of
14. The horizons of profile 5 showed the highest C/ high chrystallinity. The Feo/Fed ratio increased
N ratios. Lower C/N ratios were recorded in profiles somewhat downslope, showing a higher degree of
1, 2 and 3, which were located at the bottom of the weathering and more reactive iron oxides at the
slope under a banana plantation and generally not bottom of the toposequence.
subject to burning. OC loss after HF treatment of the tropical soils
The OC contents recorded in the soil profiles under slash and burn agriculture was higher than that
were slightly lower than OC contents recorded in recorded for A and B horizons of temperate soils
other tropical soils in Northern Laos (Roder et al., (Eusterhues et al., 2003) and in the range of values
1997). The OC content of the A horizons was lower recorded for Ferralsols under subtropical climate
than the OC content of humid tropical ecosystems (Goncalves et al., 2003). This illustrates that in
under forest (Solomon et al., 2002; Veldkamp, 1994). tropical soils, OC is most likely to be stabilised by
Lower OC content in soils under slash and burn interaction with the mineral phase (Feller and Beare,
agriculture compared to forest soils has been found 1997). SOM stabilisation is generally related to
by many authors (for example, Feller and Beare, surface area (Torn et al., 1997), which is mainly
1997). Fynn et al. (2003) showed that repeated attributed to iron oxides (Kaiser and Guggenberger,
burning combined with short fallow periods reduced 2000). To test whether the OC content in tropical
the SOM content and increased slightly correspond- soils under slash and burn agriculture is related to
ing C/N ratios. On the steep slopes of this watershed,
water erosion most likely redistributes considerable
Table 3
amounts of soil. In slash and burn systems situated
pH, Total iron oxide concentration (Fed) and content of amorphous
on steep slopes, considerable soil mass is exported iron oxides (Feo) and C loss after HF treatment
every year by splash and tillage erosion and trans- Horizon pH, Fed, FeO, FeO/Fed, OC loss after
ported downslope (Pimentel and Kounang, 1998). H2 O mg g 1
mg g 1
100 HF treatment,
Soil loss and SOM loss are closely related processes % of initial C
(Ritchie and McCarty, 2003). Therefore, variations of Profile 1
OC content along the slope may partly be explained A 5.7 38.6 6.4 17 32
by soil erosion processes, leading to depletion of OC Profile 2
on top of the hill and accumulation of SOM rich A 5.2 45.7 5.8 13 30
B1 5.0 36.1 4.7 13 n.d.
material along the slope. Few studies have been B2 5.5 46.7 3.0 7 53
carried out on the type of SOM subject to erosion Profile 3
(Lal, 2003) or on the factors governing carbon A 5.4 52.4 3.4 7 25
sequestration in soils situated on steep slopes. In B1 4.7 57.1 3.1 6 47
the following sections, the possibility of OC seques- B2 4.8 64.3 3.0 5 56
Profile 4
tration due to interaction with soil minerals or due to A 5.4 53.9 2.9 6 28
the presence of stable chemical structures will be B1 5.2 73.2 2.8 4 44
assessed. B2 5.1 63.4 2.5 4 70
Profile 5
3.2. Mineral-bound organic matter A 5.8 51.0 2.5 5 28
B1 5.4 60.3 2.9 5 33
B2 5.1 59.1 2.7 5 44
The proportion of mineral-bound OC given as Profile 6
OC loss upon HF treatment was about 30% in the A A 5.3 28.4 1.4 5 24
horizons and generally increased down the soil C1 5.1 33.7 1.0 3 40
profile, where it usually accounted for 50% to C2 5.3 35.6 0.9 3 57
 C. Rumpel et al. / Geoderma 130 (2006) 35–46 41

stabilisation by the mineral phase, it was compared 3.4. Chemical composition of the soil organic matter
to the OC loss after HF treatment and the iron oxide as revealed by 13C CPMAS NMR spectroscopy
content (Tables 1 and 2). No significant positive
correlations between these parameters were obtained, Solid-state NMR spectra of mineral soil along the
showing that the OC content of the soils is slope are shown in Fig. 1. The chemical composition
dominated by SOM other than that bound to iron of SOM in profile 6 under forest was characterised by
oxides. It is generally believed that mineral inter- a high contribution of O-alkyl C (N40%, Table 4). The
action is important for the stabilisation of soil OC, dominant peak in this region at 72 ppm together with
but in this case we find that a large part of the soil the peak at 105 ppm is generally assigned to
OC in tropical soils managed by slash and burn polysaccharides (Kögel-Knabner, 1997). The contri-
agriculture is not in close association with minerals. bution of methoxyl C derived from lignins and a-C of
proteins gives rise to the signal at 53 ppm (Skjemstad
3.3. Stable isotope composition of soil organic matter et al., 1983). In profile 6, O-alkyl C increased with
increasing depth, while alkyl C and aryl C decreased.
The stable N isotope ratio (y15N) ranged from Alkyl C may be assigned to lipids, waxes and other
6.2x to 9.3x and showed the highest enrichment in plant or microbial derived aliphatic biomolecules
the soil horizons of profile 4 (Table 2). The stable OC (Golchin et al., 1997). In the aryl C region of the
isotope ratio (y13C) of SOM in the A horizons of soils spectra, the peaks at 140 to 160 ppm are assigned to
situated along the slope ranged between 24.8x and O-substituted aromatic C. Signals from unsubstituted
26.4x and increased with depth in the B horizons, and for substituted aromatic C are found between 110
reaching up to 21.3x in the B2 horizon of profiles 2 and 140 ppm. Lignin C contributes to both types of
to 5. The A horizon of profile 1 situated at the aryl C (Knicker and Lüdemann, 1995). Additionally,
riverbank showed a stable OC isotope ratio of signals derived from tannins can be found in the aryl
23.4x. The stable OC and N isotope ratios of C region (Lorenz et al., 2000). The chemical
charcoal were similar to those of C3 type vegetation, composition of SOM in this profile was characteristic
indicating that fire in most cases does not change the of soils rich in clay content (Wattel-Koekkoek et al.,
isotopic composition of the organic matter (Czimczik
et al., 2002).
Table 4
The stable N isotope ratio (y15N) of the bulk soil Quantitative contribution of C species (% of total C) in the soil
was in the range of values recorded by Krull and profiles along the toposequence
Skjemstad (2003) for a similar soil type. Average y15N Horizon Depth, cm Alkyl C O-alkyl C Aryl C Carbonyl C
values of 9.1x were reported by Martinelli et al. % of total C
(1999) for soils from tropical regions, whereas
Profile 1
temperate soils show lower values. A strong prefer- A 0–40 18 34 29 19
ential 15N accumulation is usually thought to be the Profile 2
result of microbial processing of organic matter (Silfer A 0–20 16 34 32 17
et al., 1992). B1 20–35
Increases of y13C ratio with depth have been B2 35–60 18 42 25 15
Profile 3
observed by many authors (e.g. Balesdent et al., A 0–30 20 36 29 15
1993; Krull et al., 2002). The reasons for this increase Profile 4
are not yet completely clear (Ehleringer et al., 2000), A 0–25 18 35 30 17
although enrichment of microbial material (Hobbie et Profile 5
al., 1999) and/or physicochemical protection of A 0–5 18 31 35 15
B1 5–15 16 38 29 17
polysaccharide material (Krull and Skjemstad, 2003) B2 15–40 18 44 24 14
seem to be most likely. It is possible that 13C Profile 6
enrichment in the soils of this watershed may be A 0–10 26 44 19 11
due to contribution of resilient SOM derived from a C1 10–25 24 47 17 12
C4 type vegetation enriched in 13C. C2 25–50 20 55 14 11
42 C. Rumpel et al. / Geoderma 130 (2006) 35–46
2001; Goncalves et al., 2003; Krull and Skjemstad,
2003).
A high contribution of aryl C (29–35% of total C,
Table 4) to the 13C CPMAS NMR spectra of the A
horizons was recorded for SOM of profiles 1 to 5. A
peak at 130 ppm was the dominant signal in this
region. Such a high aryl C contribution cannot be
accounted for by humification of SOM and is most
probably related to contribution of BC derived from
frequent burning of the plant biomass (Golchin et al.,
1997; Skjemstad et al., 1996; Schmidt et al., 1999).
The aryl C contribution decreased with soil depth.
Aryl C was present even in profiles 1, 2 and 3, which
were located under the banana plantation and not
burned regularly. Here, the contribution of aromatic C
may be explained by deposition of this carbon type
removed from soils on the top of the slope during the
erosion process. A significant correlation was
observed between the aryl C contribution to the
NMR spectra and the OC content of the soil
(r 2=0.77, Fig. 3). Therefore, aromatic C contribution
may be a determining factor for the OC content of
these soils. However, if the aryl signal was generated
by BC with a highly aromatic structure, the CPMAS
technique would be likely to severely underestimate
this contribution because carbon atoms not in close
proximity to protons are not recorded (Baldock and
Smernik, 2003). A single pulse experiment would
overcome these limitations. Due to long measuring
times, single pulse experiments cannot be carried out
in routine analyses. Therefore, the aromatic C con-
tributions recorded for soils rich in BC by 13C
CPMAS NMR spectroscopy are likely an under-
estimate of actual contents.
The contribution of carbonyl C (160–220 ppm)
increased in the A horizons downslope along the
toposequence (from profile 6 to profile 1, Fig. 1).
Together with a lower C/N ratio (see above), this
may indicate a higher degree of decomposition of
the organic matter situated at the bottom of the
slope.
Kramer et al. (2003) found a positive relationship
between the degree of decomposition of plant
material expressed as the alkyl/O-alkyl ratio and
the N stable isotope ratio (y15N). In this study, a
negative correlation between the two parameters
was found (r 2=0.68***, data from Tables 2 and 4),
which may indicate that it is the transformation of
plant biomass during fire events to govern SOM
composition.
3.5. Black carbon content
Black carbon is a broad continuum of carbon
types formed during fire which range from residues
derived from incomplete combustion of plant tissues
to inert graphitic carbon (Gelinas et al., 2001). Its
determination in soils relies on chemical and
thermal means, which determine an operationally
defined fraction of the BC continuum. In this study,
we determined the carbon fraction resistant to
chemical oxidation after demineralisation of the
samples by HF treatment (OREC, Bird and Gröcke,
1997). Optimum oxidation time for BC isolation
was determined in a preliminary study (Fig. 2). HF
treatment removed between 30% and 60% of OC
from Job’s tears (J.T.) and soils. BC sampled just
after the fire did not lose OC upon HF treatment.
Organic matter from J.T. was totally removed after
5-h oxidation. Oxidation between 5 and 24 h
resulted in a constant recovery of about 63% of
the initial BC. Thereafter, the remaining OC was
progressively oxidised. SOM from two depths of
120 0-5 cm
Carbon remaining after the treatment
5-10 cm
Job's tears
100
BC
80
(% of initial C)
60
40
20
0
initial
after demineralisation
1 5 24 48 100
Oxidation time (hours)
Fig. 2. Evolution of OC content in soil at two depths, in plant
material (Job’s tears) and in BC as the percentage of the initial OC
in the bulk soil taken in vicinity of profile 5 after different oxidation
times.
 C. Rumpel et al. / Geoderma 130 (2006) 35–46 43

Aryl C vs C content
the mineral soil showed a rapid decrease during the (profiles 1-5)
first 5 h. OC loss from SOM was maximal after 24-
A r2= 0,77***
h oxidation. These results show that SOM has a
OREC pool which resists prolonged oxidation. In 40

Aryl C (% of total C)
the light of these results, 24-h oxidation treatments 30
were conducted to quantify OREC contents of
SOM. 20

The BC content, expressed as OREC of the soil 10

profiles ranged from 3% to 7% of the initial OC 0
content (Table 5). These values were higher than those 0 0,5 1 1,5 2 2,5 3
of Bird et al. (1999) recorded for a sandy savanna soil. Carbon content (%)
The BC contents in profiles 1 to 5 were related to the
aryl C content of the organic matter as recorded by Aryl C vs OREC
13 (profiles 1-5)
C CPMAS NMR spectroscopy (r 2=0.69***, Fig. 3). B r2= 0,69***
These data confirmed our hypothesis that BC may be
a major contributor to the aromatic C and therefore a Aryl C (% of total C) 40
determinant of the SOM content in these soils. 35
Negative relationships between BC content and stable 30
OC and N isotopic ratios of the bulk SOM (Fig. 4) 25
20
indicated that the BC contribution had an effect on the 15
stable isotope composition of SOM. The negative 10
correlation found between BC and OC lost after HF 5
treatment (r 2=0.82***, data in Tables 3 and 5) may 0
0 1 2 3 4 5 6 7 8
OREC (% of total C)
Table 5 Fig. 3. Relationship between the aryl C and the OC content (A) as
Content of OREC, y13C and C/N ratio of the material left after well as the oxidation resistant elemental carbon (OREC, B).
dichromate oxidation
Horizon OREC, y13C, x C/N ratio
% of initial C indicate that (1) BC is not bound to soil minerals and
Profile 1 (2) higher amounts of OC are present as BC in the
A 5.5 23.6 53 surface horizons, whereas increasing percentages of
Profile 2 OC are associated with the mineral phase with
A 5.5 25.6 29 increasing depth in soil profiles.
B1 3.7 22.8 17
B2 4.1 22.9
The OREC isolated from the A horizons was
Profile 3 characterised by C/N ratios ranging from 29 to 67 and
A 7.3 26.2 53 y13C ratios from 25.6x to 27x except for the A
B1 n.d. 22.7 horizon at profile 1 where a value of 23.6x was
B2 3.4 21.8 18 recorded (Table 5). The C/N ratios of the OREC were
Profile 4
A 5.9 26.2 53
narrower in the B horizons and the y13C ratios were
B1 3.5 23.2 28 more enriched in 13C. These results indicate that
B2 2.9 22.4 17 freshly produced BC, which has a C/N ratio of 53 and
Profile 5 a y13C of 29.2x (Table 2), contributed to SOM in the
A 6.8 26.8 67 surface horizons. The relatively 13C enriched OREC
B1 4.5 24.7 41
B2 4.6 22.8 33
having low C/N ratio in the B horizons may have been
Profile 6 subject to decomposition, leading to OC loss. N
A 6.8 27.0 37 immobilisation in BC may have occurred through the
C1 4.2 25.4 23 pyrogenic process, that can transform biomass N into
C2 4.0 24.5 16 heterocyclic N that is not available to micro-organ-
44 C. Rumpel et al. / Geoderma 130 (2006) 35–46

δ 15N vs OREC produces BC which was found to be a determinant of

A r2= 0,83***
the aryl C contribution to the organic matter of these
8 soils. The BC content was also found to influence the
P2A
OREC (% of total C)

7 stable isotope composition of SOM. A major part of

6
BC was not associated with the mineral phase and may
5
4
therefore be part of the light fraction. This organic
3 matter component is susceptible to erosion (Gregorich
2 et al., 1998) especially on steep slopes as are found in
1 the mountainous regions of northern Laos. More
0 studies are needed to analyse the potential of BC to
0 2 4 6 8 10 12
δ 15N (‰) be eroded preferentially in order to evaluate the
potential of these tropical soils to act a as source or
δ 13C vs OREC
r2= 0,77*** sink for the atmospheric greenhouse gas CO2.
B

8
7 Acknowledgements
OREC (% of total C)

6
5 The department dInstitut National des Science
4 d’UniversT of the dCentre National de Recherche
3 ScientifiqueT (France) is acknowledged for financial
2 support under the framework of the program
1 dDynamique et stabilisation des matières organiques
0 dans des sols tropicaux: influence des brûlis, de
-28 -26 -24 -22 -20 -18 -16 -14 -12
δ 13C (‰)
l’érosion et de la mise en cultureT. The authors wish to
thank the National Agricultural and Forestry Research
Fig. 4. Relationship between oxidation resistant elemental carbon Institute (Laos) for access to the site and collabo-
(OREC) and the stable isotope ratio of N (A) and OC (B).
ration. Without the help of Anneke de Rouw,
Bounsamai and the other colleagues of the Unité de
isms (Knicker et al., 1996). The BC characteristics Recherche dErosion et Changement UsageT of the
within the soil profiles were consistent with data dInstitut de Recherche pour le DeveloppementT and
presented by Bird et al. (1999) which showed that a International Water Management Institute based in
significant proportion of OREC in a savanna soil may Laos, this study would have not been possible. The
be degraded in decadal/centennial timescales (Bird et dLehrstuhl für BodenkundeT, dTechnische Universität
al., 1999). MünchenT (Germany) is acknowledged for providing
NMR facilities. The authors are indebted to Gerard
Bardoux, Cyril Girardin and Nicolas Pechot, who
4. Conclusion carried out the stable isotope measurements. We also
thank two anonymous reviewers and the editors for
The OC content, stable isotope and chemical useful comments on the manuscript. Naoise Nunan is
composition as well as the BC content of SOM in acknowledged for carefully reading and improving the
tropical soils on steep slopes subjected to slash and manuscript.
burn agriculture were analysed in order to elucidate the
factors governing SOM quantity and composition. The
OC content of the soils was not related to iron oxide
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