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Evaluation of organic carbon oxidation efficiencies of a modified wet

combustion and Walkley-black procedures in Nigerian soils
A. Olayinka a; A. Adebayo a;A. Amusan a
a
Soil Science Department, Obafemi Awolowo University, Ile-Ife, Nigeria

To cite this Article Olayinka, A. , Adebayo, A. andAmusan, A.(1998) 'Evaluation of organic carbon oxidation efficiencies
of a modified wet combustion and Walkley-black procedures in Nigerian soils', Communications in Soil Science and
Plant Analysis, 29: 17, 2749 — 2756
To link to this Article: DOI: 10.1080/00103629809370149
URL: http://dx.doi.org/10.1080/00103629809370149

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 COMMUN. SOIL SCI. PLANT ANAL., 29(17&18), 2749-2756 (1998)

Evaluation of Organic Carbon Oxidation

Efficiencies of a Modified Wet Combustion
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and Walkley-Black Procedures in Nigerian

Soils

A. Olayinka, A. Adebayo, and A. Amusan

Soil Science Department, Obafemi Awolowo University, Ile-Ife, Nigeria

ABSTRACT

The organic carbon (C) oxidation efficiencies of the Walkley-Black and

modified wet combustion procedures were evaluated in soil samples taken
from different ecological zones and diverse parent materials in Nigeria. Dry
combustion using a C analyzer was the standard to evaluate the efficiency of
the modified wet combustion method. The efficiency of the Walkley-Black
method was later compared to that of the modified wet combustion procedure.
The results indicated that the modified wet combustion and the dry combustion
procedures were highly correlated (r=0.99**)- Significant correlation (r=0.96**)
was also found between the Walkley-Black and the modified wet combustion
procedures. There was no correlation between the C data obtained using the
modified wet digestion method and the % DCB-Fe2O3. These results suggest
the absence of strong organo-mineral complexes in these soils. Organic C
recoveries by the Walkley-black method were not affected by fine-grinding
(<0.5 mm) of the soil samples. It is suggested that both the modified wet
combustion and the Walkley-Black methods may be used without a correction
factor in Nigerian soils. The modified wet combustion procedure was also
found to be an adequate substitute for the dry combustion procedure.

2749

Copyright © 1998 by Marcel Dekker, Inc. www.dekker.com

 2750 OLAYINKA, ADEBAYO, AND AMUSAN

INTRODUCTION

The Walkley-Black (1934) method assumes a 77% recovery of organic C—

average for 20 British and foreign soils with individual recoveries ranging from
60 to 86%—in the soil. Hence, the use of a correction factor of 1.30 for converting
organic C oxidized to total C. Percent recoveries have been found to vary between
soils and within profiles. Bornemisza et al. (1979) and Zunino et al. (1982)
attributed the differences to the clay and allophane contents of the soils.
Bornemisza et al. (1979) determined C recoveries in representative Costa Rican
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surface and subsoils. Based on 75.5% oxidation, they suggested a factor of 1.32
for the surface soils. The high C recoveries in the subsoils averaging 82.7-95.3%
were attributed to the lower organic matter contents and relative accumulation of
the low molecular weight fulvic acids.
Total C determination is often required in the study of soil organic matter. The
dry and wet combustion procedures recover organic C quantitatively. However,
fine-grinding is recommended in order to ensure the recovery of total C (Allison,
1960; Metson et al., 1979; Bremner and Yeomans, 1988). The finding by Lekwa
and Whiteside (1986) that the accumulations of dithionite-extractable Fe and Al
(Fe2O3-d and Al2O,-d) and NH4-oxalate Fe and Al (Fe2O3-O and A12O3-O) in
Coastal Plain soils of southwestern Nigeria were accompanied by high organic
matter contents suggests the presence of organo-mineral complexes in these soils.
If strong enough, adsorption of organic matter by soil mineral matter would reduce
the digestion efficiency of the Walkley-Black method in Nigerian soils. Differences
in the magnitudes of the stable soil organic C pools could lead to differences in C
recoveries. Hsieh (1996) found that the stable soil organic C pools in two tropical
soils of Belize, Central America, have significantly shorter mean residence times
than those of temperate soils. Dry combustion equipment is expensive and
therefore scarce in Nigeria. The wet combustion procedure is, however, adaptable
to resources available in most laboratories. This study was therefore designed to
assess the applicability of the Walkley-Black conversion factor and the efficiency
of a modified wet combustion procedure for determining total C in Nigerian soils.

MATERIALS AND METHODS

Soil Samples
Top soil (0-15 cm) samples were obtained from 30 sites in Nigeria spread over
different ecological zones stretching from the Rain Forest in the south to the Sudan
Savannah in the north. Within each geographical region, sampling was done in
soils formed over the basement complex (igneous and metamorphic rock) and
sedimentary material (Table 1). The samples were air dried and passed through 2
mm sieve. Ten samples, representative of the different vegetational zones and
parent materials, were subsampled and ground to pass through 0.5 mm sieve.
 EVALUATION OF ORGANIC CARBON OXIDATION EFFICIENCIES 2751

TABLE 1. Location, classification, and selected properties of the soil samples.

II Location/ SoU PH Texture % DCB-

H ecological zone taxonomy water FeA
Basement Complex:
Rain Forest
1 Ile-Ife Oxic Paleustalf 6.4 SL1 2.31
2 Itagunmodi Oxic Paleustalf 6.4 SCL 5.07
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3 Gambari Plinthic Haplustlf 6.9 SCL 2.33

4 Ikom Oxic Paleustalf 6.2 C 3.35
3 Itawure Haplustalf 6.0 SL 2.04
6 Ado-Ekiti Oxic Paleustalf 6.2 C 3.35
7 Ikare Oxic Paleustalf 6.0 SL 2.04
Savanna
8 Okene Oxic Paleustalf 6.3 SCL 2.06
9 Offa Oxic Haplustalf 6.2 SL 0.87
10 Awe Oxic Paleustalf 6.5 LS 0.81
11 Igbeti Typic 6.8 SCL 1.97
Dystropepts
12 Minna Oxic Haplustalf 6.4 SL 2.43
13 Suleija Typic 6.6 LS 0.52
Dystropepts
14 Awi Oxic Paleustalf 5.6 SL 0.56
15 Kaduna Oxic Haplustalf 6.3 SL 0.46
16 Samara Oxic Haplustalf 6.7 SCL 0.51
17 Kano Typic 6.7 SL 1.74 •
Dystropepts
18 Numan Typic Pelleusterts 6.9 SC 0.17
19 Kaduna Typic Dystroppts 6.3 LS 0.33
Sedimentary Rain Forest
20 Ijebu Ode Oxic Paleustalf 6.5 LS 2.32
21 Owode Oxic Haplustalf 6.4 SCL 3.62
22 Okitipupa Tropofluerent 6.8 LS 0.35
23 Shaeamu Oxic Paleustalf 6.1 LS 2.40
24 Ilaro Oxic Haplustalf 6.3 C 5.22
25 Ore Oxic Paleustalf 5.9 SCL 1.89
26 Sapoba Oxic Paleustalf 5.7 SCL 2.47
Savanna
27 Lokoja Oxic Haplustalf 6.8 SL 0.31
28 Badeggi Oxic Paleustalf 6.7 SL 0.33
29 Jebba Tropofluent 6.5 SL 0.17
30 Mokwa Oxic Paleustalf 6.7 SL 0.36

'C=clay, LS=loamy sand, SC=sandy clay, SCL=sandy clay loam, SL=sandy

loam.
 2752 OLAYINKA, ADEBAYO, AND AMUSAN

TABLE 2. Soil organic carbon contents by the Walkley-Black (1934), modified wet
combustion and dry combustion procedures, and the modified wet combustion oxidation
efficiency.

Organic Carbon Oxidation Conversion

efficiency2 factor
1
Location WB MWC LKJ %
2 mm 0.5mm 0.5mm 0.5mm

Basement ComDlex
Ile-ffe 0.90 1.04 0.71 0.68 104 0.96
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Ikom 2.21 2.18 1.82 1.74 105 0.95

Ikare 0.44 0.45 0.36 0.39 92 1.09
Igbeti 2.67 2.67 2.12 2.12 100 1.00
Minna 0.62 0.66 0.50 0.52 96 1.04
Kano 0.37 0.34 0.30 0.31 97 1.03
Sedimentarv
liebu Ode 1.20 1.20 0.93 0.92 101 0.99
Haro 1.00 1.00 0.74 0.72 103 0.97
Ore 1.62 1.72 1.23 1.18 104 0.96
Sapoba 1.15 1.16 0.89 0.87 102 0.98
Range 92-105 0.96-1.09
Mean 100.4 1.00
Standard deviation 4.23 0.04

'WB=Walkley-Black, MWC=modified wet combustion, DC=dry combustion.

2
MWC oxidation efficiency based on DC data as standard.

Analytical Procedure
Particle size analysis was done by the hydrometer method (Bouyoucos, 1962)
and pH was measured potentiometrically in a soil suspension using a soihwater
ratio of 1:2.5. Organic C was determined in triplicates according to Walkley-
Black (1934) method. Total C was determined by dry combustion (Leco CNS
1000 Analyzer, Leco Corp, St. Joseph, MI) in ten representative samples. The
digestion efficiency of a modified wet combustion method was compared to that
of dry combustion as standard in these ten samples. The modified wet combustion
procedure was also used to determine total C in all samples. Allison's (1960)
method was modified by dispensing with the purification and absorption trains,
while digestion was carried out under reflux. One gram air-dry soil sample was
digested for 15 minutes with continuous aeration in 20 mL of IN K2Cr207 solution,
25 mL 60:40 mixture of cone. H2SO4 and 85% H3PO4. The condenser was washed
down with 5 mL of distilled water. On cooling the organic C content was
determined as in the Walkley-Black (1934) procedure, but without the use of a
correction factor. The Walkley-Black C data were later compared to those of the
modified wet combustion as standard. Total free ion oxides were extracted by the
dithionite-citrate-bicarbonate (DCB-Fe2O3) method (Mehra and Jackson, 1960)
and the Fe content determined using atomic absorption spectrophotometer.
 EVALUATION OF ORGANIC CARBON OXIDATION EFFICIENCIES 2753

RESULTS AND DISCUSSION

Selected Properties of the Soil Samples
Table 1 shows the locations, classifications and ecological zones from where
the soil samples were taken, as well as some selected physical and chemical
properties. Most of the soils were slightly acidic to neutral in reaction. The soil
textures were dominated by sand with the textural classes ranging from loamy
sand to sandy clay loam. The percent DCB-Fe2O3 were generally higher in the
soils under rain forest than in the savanna.
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Effect of Particle Size on Walkley-BIack Carbon

Organic C data obtained using the Walkley-BIack modified wet combustion
and dry combustion procedures are presented in Table 2. Grinding samples to a
smaller size (<0.5 mm) did not significantly (P=0.05) increase C recoveries over
those of unground (<2 mm) samples using the Walkley Black method (Table 2)
Hence, a low degree of complexation of organic matter by soil mineral matter is
indicated. Strong adsorption of organic matter by reactive silicate clays such as
montmorillonite and vermiculite have been found to reduce C recoveries in soils
(Smith et al., 1951; Bornemisza et al., 1979). The predominance of Kaolinite in
Nigerian soils (Nye, 1955; Jungerius and Levelt, 1964; Gallez et al., 1975),
therefore, would be responsible for the ineffectiveness of grinding in increasing
C recovery by the Walkley-BIack method.

Efficiency of the Modified Wet Combustion Procedure

The soil total C contents determined by dry combustion and the modified wet
combustion procedures were compared in 10 finely-ground (<0.5 mm) subsamples
(Table 2). With dry combustion as standard, C recoveries obtained with the
modified wet combustion method ranged between 92 and 105% (mean= 100.4%)
with a conversion factor of 1.00. The C data obtained with the two procedures
were highly correlated (r=0.99"). There was no correlation between the modified
wet combustion data and % DCB-Fe2Or These results suggest the absence of
strong organo-mineral complexes that could reduce the efficiency of C recovery.
Therefore, in the absence of dry combustion equipment, the modified wet
combustion procedure would be adequate for total C determination in these soils.

Walkley-Black Oxidation Efficiency

Based on the assumption that the Walkley-Black method recovers 77% of total
C, organic C contents obtained for the thirty (30) samples (<2 mm) were
consistently higher than those of the modified wet combustion (Table 3).
Consequently, the correction factor of 1.30 over-estimates the organic C contents
of these soils. The C data obtained using both procedures were, however,
 2754 OLAYINKA, ADEBAYO, AND AMUSAN

TABLE 3. Organic carbon contents of soil samples over different parent materials
and ecological zones in Nigeria by the Walkley-Black (1934) and modified wet
combustion procedures.

Location/ Organic Carbon WB Conversion

Ecological % pxidation factor
Zone efficiency
WB1 MWC %
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2mm 2mm

Rain forest 0.9W0.69)1 0.74 94 1.06

1. Ile-Ife 2.20(1.69) 1.70 100 1.00
2. Itagunmodi 1.23(0.95) 0.96 99 1.01
3. Gambari 2.21(1.70) 1.81 94 1.06
4. Ikom 0.41(0.32) 0.32 99 1.01
5. Itawure 0.47(0.36) 0.39 93 1.08
6. Ado Ekiti 0.44(0.34) 0.34 100 1.00
7. Ikare
Savanna 0.66(0.51) 0.56 91 1.10
8. Okene 1.16(0.89) 0.96 93 1.08
9. Offa 0.77(0.59) 0.60 99 1.01
10. Awe 2.67(2.05) 2.17 95 1.05
11. Igbeti 0.62(0.48) 0.49 97 1.03
12. Minna 1.51(1.16) 1.17 99 1.01
13. Suleija 1.26(0.97) 0.99 98 1.02
14. Awi 1.21(0.93) 0.93 100 1.00
IS.Kaduna 0.40(0.31) 0.31 99 1.01
16. Saman 0.37(0.28) 0.29 98 1.02
17. Kano 1.06(0.82) 0.90 91 1.10
18. Numan 0.33(0.25) 0.26 98 1.02
19. Kadewa
Sedimentary
Rain forest 1.20(0.92) 0.93 99 1.01
20. Ijebu Ode 0.65(0.50) 0.53 94 1.06
21. Owode 1.95(1.50) 1.51 99 1.01
22. Okitipupa 0.84(0.65) 0.69 94 1.06
23. Shagamu 1.00(0.77) 0.78 99 1.01
24. Ilaro 1.62(1.25) 1.25 100 1.00
25. Ore 1.15(0.88) 0.89 99 1.01
26. Sapoba
Savanna 1.65(1.27) 1.28 99 1.01
27. Lokoja 1.14(0.88) 0.90 98 1.02
28. Badaggi 1.70(1.31) 1.32 99 1.01
29. Jebba 0.43(0.33) 0.36 92 1.09
30. Mokwa
Range 91-100 1.00-1.10
Mean 97.03 1.03
Standard 2.21 0.02
deviation

'WB=Walkley-Black, MWC=modified wet combustion.

2
Walkley-Black carbon data without correction factor.
 EVALUATION OF ORGANIC CARBON OXIDATION EFFICIENCIES 2755

significantly correlated (r=0.96"). It was found from this study that the Walkley-
Black (1934) procedure recovered between 91 and 100% of the total C with a
mean of 97% (Table 3). Hence, a more appropriate conversion factor for these
soils would be 1.03. These results are similar to those of Rhodes et al. ( 1981 ) who
worked with 10 top soil samples obtained from six physiographic positions in
Sierra-Leone. Hsieh (1996) also found that tropical soils contain significantly
younger stable organic C pools than in temperate soils. Hence such a high degree
of organic C recovery as found in this study, would be expected in these Nigerian
soils.
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CONCLUSIONS

The results indicate that the organic matter in these soils has probably not attained
as high a degree of humification as in temperate soils. Further, in the absence of
strong organo-mineral complexes, it is not surprising that the Walkley-Black (1934)
procedure oxidized virtually all the organic C in these soils. The Walkley-Black
method could therefore be used without a correction factor. Furthermore, the
modified wet combustion procedure could be used as an alternative to the dry
combustion procedure.

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