Determining soil organic carbon for agricultural soils: a comparison between the Walkley & Black and the dry combustion methods (north Belgium)

Mapping soil organic carbon (SOC) and establishing any change over time are important because of CO₂ fluxes between soil and atmosphere and cropland decreases in SOC. The latter is one of the main causes of soil fertility decline and increased erodibility. As most analytical methods underestimate total SOC content, correction factors are needed to avoid methodological bias when comparing SOC data from sampling campaigns using different analytical procedures. The traditional method for SOC analysis used to be, and in most cases still is wet oxidation in potassium dichromate, better known as the Walkley & Black method. In this study, we aim to estimate correction factors for the classic and modified version of the Walkley & Black method for different land use and soil type combinations for agricultural soils in north Belgium. General correction factors of 1.47 for the classic Walkley & Black method and 1.20 for the modified Walkley & Black method are proposed. The results show that sandy grassland soils are characterised by lower recoveries than silt loam grassland soils. Furthermore, the correction factor appears to increase with soil wetness.     

Recovery rate of organic c in organic matter fractions of Grantsburg soils

Abstract

Walkley‐Black method is a simple and rapid method for organic carbon analysis. Because of incomplete oxidation of organic carbon (C), the recovery of organic C is low with this method. Assuming the 77% recovery of organic C with Walkley‐Black method, the results are corrected with a correction factor of 1.30. The objective of this study is to determine the soil organic C recovery rate and appropriate correction factor for Walkley‐Black (wet combustion) method for tilled soils in southern Illinois. Soil samples were collected in 1995 and 1996 from a trial established in southern Illinois on a moderately well drained, Grantsburg (fine‐silty, mixed, mesic Oxyaquic Fragiudalf) soil. Organic C contents with the Leco analyzer (dry combustion) were significantly higher as compared to the Walkley‐Black method in different tillage systems (no‐till, chisel plow and moldboard plow), soil organic matter fractions (whole soil and mineral fraction) and soil depths (0–5 and 5–15 cm). The recovery percentage of organic C was lower than the assumed percentage with the Walkley‐Black method. No significant differences in organic C recovery percentage were found due to differences in tillage systems and depths, whereas the recovery percentage was lower in mineral fraction as compared to the whole soil. The lower organic C recovery percentage was due to the more stable organic C compounds in the mineral fraction. On the basis of these findings, correction factors of 1.35 and 1.41 are proposed for whole soil and mineral organic C analysis with Walkley‐Black method, respectively for tilled Grantsburg and other similar soils in southern Illinois.     

Automated instrumental analysis of carbon and nitrogen in plant and soil samples

Abstract

An automated CHN Analyzer was compared with the Walkley‐Black and Kjeldahl methods for organic carbon (C) and nitrogen (N). Four organic compounds, twenty nine plant materials and five soils were tested. The CHN Analyzer gave C and N values that were not significantly different (P<0.05) to the theoretical weight percents of the organic compounds. The Walkley Black method gave soil C values significantly lower (P<0.05) than those obtained with the CHN Analyzer. The Kjeldahl method gave soil N values significantly lower (P<0.05) than the CHN Analyzer on three of five soils tested. The discrepancies observed between methods appear to be due to different oxidation efficiencies. CHN Analyzer and Kjeldahl N analyses were not significantly different (P<0.05) for the plant materials except where samples contained greater than 0.7% NO3‐N. Potassium nitrate was also added as a spike to a tall fescue sample. Based on recovery of the spiked NO3‐N, the Kjeldahl method was a poor measure of total N for plant materials containing greater than 0.7% NO₃‐N. The findings suggest the CHN Analyzer can be used for the rapid, accurate and simultaneous determination of C and N in plant and soil samples.     

A comparison of some methods for soil organic carbon determination

Abstract

This study compared three dichromate‐oxidation methods adapted for use with 100‐mL digestion tubes and 40‐tube block digester (for controlled heating), the Walkley‐Black method, a loss‐on‐ignition procedure and an automated dry combustion method for the determination of organic carbon in soils of the northwestern Canadian prairie. The Walkley‐Black method required a correction factor of 1.40. The modified Tinsley method and the Mebius procedure, adapted for use with 100‐mL digestion tubes, recovered 95% and 98%, respectively, of soil carbon against the dry combustion procedure. The presence of elemental carbon in some soils probably caused, at least partially, the slightly incomplete recovery; thermal decomposition of dichromate may not have been accurately corrected for. A dichromate‐oxidation procedure with controlled digestion at 135°C gave 100% recovery, but somewhat more variable results. The loss‐on‐ignition procedure, even when allowance was made for clay content of the soils, was the least satisfactory of the methods tested. All procedures produced correlation coefficients of 0.980 or better against the dry combustion method.     

Comparison of Analytical Methods for Organic Matter in Composts and Organic Mulches

Abstract

The conventional dichromate (Walkley and Black), carbon analyzer, and weight loss‐on‐ignition (WLOI) methods are compared for determination of organic matter contents in composts and organic mulches. The objective of this study was to evaluate these three methods for their reliability in determining the organic matter contents of composts and organic mulches that also contain inorganic carbon. The carbon analyzer method overestimated organic matter contents for samples containing inorganic carbon (C) as carbonate or charcoal C. The removal of inorganic C improved the correlation coefficients (r) of results obtained by the carbon analyzer method and the Walkley and Black method (0.95 vs. 0.89). The WLOI method produced results more similar to those obtained with the Walkley and Black method than with a carbon analyzer. Oven drying samples for 16–24 h at 105°C as a basal temperature for WLOI improved results compared with a basal temperature at 70°C, which is commonly used. A heating temperature of 500°C for 12 h resulted in organic matter determinations by the WLOI method in the closest agreement with those obtained by the Walkley and Black method.     

Does the walkley‐black method determine soil charcoal?

Abstract

The Walkley‐Black Method is shown to recover charcoal carbon (C) from both charcoal samples made in the laboratory from a range of plant materials as well as from soils containing various amounts of relic charcoal. The rate of recovery of charcoal C depends on the nature of the material from which it is derived and its particle size but not on its surface area. From the data presented, it is clear that the Walkley‐Black Method recovers charcoal C with a high enough efficiency so that, at the concentrations of charcoal found in soil, given its fine particle size and the potentially diverse nature of its origin, it is not possible to differentiate between charcoal C and other organic forms found in soil by this method.     

A comparison between the walkley‐black and a dry combustion method for determining organic carbon in a humic brown soil,Papua New Guinea

Abstract

Regression equations for the relationship between Walkley‐Black carbon and carbon by dry combustion in a tropical humic brown clay soil were variable in four different vegetation regimes. In one case, statistically different correlation coefficients were obtained for grassland surface and the corresponding subsurface soils.

Calibration of the Walkley‐Black method against dry combustion carbon is recommended for each treatment in soil fertility studies as soil organic matter might have a different composition and hence carbon recovery value because of treatment.     

Direct Determination of Organic Carbon by Dry Combustion in Soils with Carbonates

Abstract

In acid soils, where organic carbon (C) corresponds to total C, direct determination of organic C by dry combustion is possible, whereas in soils with carbonates also a separate measurement of inorganic C is required. In this case, direct quantification of organic C can be accomplished by the Walkley‐Black method, which is time‐consuming and involves greatly polluting by‐products. Hence, a method able to determine directly organic C by dry combustion is strongly needed for soils with carbonates. This study proposes such a method, after it was found to be highly reliable in calcareous soils of a Mediterranean island. The correction factor to use in the Walkley‐Black method to account for nonrecoverable C was calculated. It does not show any overall relationship with the contents of either organic C or inorganic C, and for all land uses examined in the island, it is not significantly different from the commonly suggested value 1.30.     

Recovery of organic carbon by the walkley and black procedure in highly weathered soils

Abstract

The effect of soil series, cultivation, soil depth, and parent material on the correction factor which should be applied to organic carbon values determined by the method of Walkley and Black, has been examined using 450 low‐activity‐clay soil samples from high rainfall tropical Queensland. There were minimal effects due to soil depth, and differences between virgin and cultivated soils were greatest in soils formed on beach sands. However, soils formed on granitic or metamorphic rocks require a factor of 1.24, whereas the originally recommended factor of 1.32 (Walkley and Black) has been confirmed for soils formed on basalt, alluvium, and beach sands.     

Relationship between total organic carbon and oxidizable carbon in calcareous soils

Abstract

The oxidable carbon content of 46 calcareous soils from the South‐East of Spain was determined by the Walkley and Black method and compared with the total organic carbon (C) content obtained by an automatic microanalysis method. The results were fitted to linear, curvilinear, and exponential equations which permit the conversion of the oxidable C values into those of total organic C when no direct means of analysis of the latter is available. A conversion factor of 1.26 is recommended.     

Walkley–Black analysis of forest soil organic carbon: recovery, limitations and uncertainty

Organic carbon levels of 542 soil samples from temperate lowland forest were determined by the original and modified Walkley–Black (WB) dichromate methods and total organic carbon (TOC) analysis. The performance and the lower and upper quantification limits of the WB method were assessed. Variable recovery rates were related to laboratory and field conditions and to the sample composition. The percentage carbon recovered by the original WB method was found to be systematically lower than commonly accepted, and the correction factor was estimated at 1.58 instead of 1.30–1.35. However, a good linear relationship with TOC enabled acceptable prediction of soil organic carbon which was most precise when using the original WB method. Texture class and pedogenetic horizon showed significant differences in recovery. Depending on the modifications of the WB method, recoveries varied significantly between laboratories, explaining up to 29% of the total variation of the topsoil carbon assessment of a site. Low recovery from samples was partly attributed to charcoal and resistant elementary carbon particles. No interference was found to be caused by iron or manganese compounds. In order to use WB carbon data of forest soils, laboratory‐ and method‐specific determination of the recovery rate using a total analyser is strongly recommended. The original WB method was unable to predict reliably forest soil carbon contents higher than 8% TOC.     

Variable carbon recovery of Walkley-Black analysis and implications for national soil organic carbon accounting

There is considerable interest in the computation of national and regional soil carbon stocks, largely as the result of the provisions of the Kyoto Protocol. Such stocks are often calculated and compared without proper reference to the uncertainties induced by different analytical methodologies. We illustrate the nature and magnitude of these uncertainties with the present soil organic carbon (SOC) study in Belgium. The SOC recovery of the Walkley‐Black method was investigated based on a database of 475 samples of silt loam and sandy soils, which cover different soil depths and vegetation types in northern Belgium. The organic carbon content of the soil samples was measured by the original Walkley‐Black method and by a total organic carbon analyser. The recovery was computed as the ratio of these two results per soil sample. Land use, texture and soil sampling depth had a significant influence on the recovery as well as their three‐way interaction term (land use × texture × sampling depth). The impact of a land use, texture and sampling depth dependent Walkley‐Black correction on the year 2000 SOC inventory of Belgium was determined by regression analysis. Based on new correction factors, the national SOC stocks increased by 22% for the whole country, ranging from 18% for cropland to 31% for mixed forest relative to the standard corrected SOC inventory. The new recovery values influenced therefore not only C stocks in the year 2000, but also the expected SOC change following land use change. Adequate correction of Walkley‐Black measurements is therefore crucial for the absolute and comparative SOC assessments that are required for Kyoto reporting and must be computed to take into account the regional status of soil and land use. ‘Universal’ corrections are probably an unrealistic expectation.     

Relationships between four methods of organic carbon determination in leaves of nitrogen‐fixing trees and lignite‐based organic fertilizers

Abstract

Organic carbon (OC) in leaves of seven nitrogen (N₂)‐fixing trees and fifteen lignite‐based fertilizers was measured by loss‐on‐ignition (LOI at 500°C), wet oxidation by the Walkley‐Black method (CWB), Tinsley Dichromate Method (CTS), and dry combustion method using a LECO SC444 Carbon/ Sulphur Resistance Furnace Analyzer (CTO). There were significant differences in the capabilities of the methods in measuring OC from the organic materials with the quantity measured in the following order: LOI > CTO > CTS > CWB. A highly significant difference between LOI and CTO values suggested that components other than organic carbon (C) were removed by LOI since CTO gives total C value. The result also showed that N content in the organic materials was highly correlated with OC measured by individual methods. The LOI, CWB, and CTS were significantly correlated with CTO. The regression equations which were specific for either plant leaves or lignite‐based fertilizers indicated that any of the methods could be used to predict total C in the organic materials with a high degree of precision. In addition to the regression approach, an estimated correction factor of 1.4550 would be more appropriate to predict CTO from CWB for plant leaves than the 1.30 factor usually used for estimating oxidizable C in soils when CWB method is used. Also, a factor of 0.36180 could be used to estimate total C from LOI method for lignite fertilizers instead of merely regarding the difference in weight loss as the total organic matter.     

Automated elemental analysis: A rapid and reliable but expensive measurement of total carbon and nitrogen in plant and soil samples

Abstract

The performance of a commercial automated CHN elemental analyzer was evaluated by comparison with classical wet methods and with another commercial analyzer. With proper standardization, calibration, and sample preparation, the Perkin‐Elmer 2400 CHN elemental analyzer was shown to give reliable carbon (C) and nitrogen (N) analyses of plant and soil materials. Precision was demonstrated by the consistent reference rice straw C and N results obtained (1.6 to 2.8% CV for N, and 0.3 to 0.7% CV for C) when 11 samples were analyzed consecutively within a day or on other days. A simple linear regression analysis showed generally higher plant N values measured by the CHN analyzer than the Kjeldahl method. Predicted analyzer plant N values were only slightly lower than Kjeldahl N, with plant materials containing less than 1% N. Recovery of different amounts of nitrate‐N (NO₃‐N) added to rice straw samples was better with the CHN analyzer than with both the common and the salicylic acid‐modified Kjeldahl method. A very good 1:1 relationship between analyzer soil N values and the permanganate‐reduced iron modified Kjeldahl N values was also shown at the range measured (0.005–0.200% N). However, the soil C values determined by the analyzer were generally lower than the Walkley‐Black C values. Based on precision, analyzer soil C results with 0.4 to 5% CV appear to be more reliable than the Walkley‐Black C results with 0.3 to 18% CV. In spite of its reliability, speed of analysis, and low manpower requirement, studies showed the high cost of analyzing samples (minimum of US$2.38 per plant and US$3.83 per soil sample) with the CHN analyzer and of maintaining such a sensitive equipment.     

Loss‐on‐ignition as an estimator of soil organic carbon in a‐horizon forestry soils

Abstract

The determination of soil organic matter by wet digestion techniques is a slow and laborious analysis. Loss‐on‐ignition (LOI) provides a simple alternative technique for the estimation of soil organic carbon in non‐calcareous A horizon soils of the Natal midlands and Zululand forestry regions. Using multiple regressional techniques, the relationships between loss‐on‐ignition, Walkley organic carbon and soil texture for 55 soils were determined over a range of ignition temperatures. The relationships hold best for soil samples with relatively low organic carbon contents (< 5%). The optimum temperature for ignition was found to occur at 450°C and resulted in the relationship: Soil organic carbon = 0.284*LOI percent. No advantage is gained through ignition at higher temperatures due to the loss of clay mineral structural water, even if the soil texture is accurately known.     

Is the Walkley–Black Method Suitable for Organic Carbon Determination in Chilean Volcanic Soils?

Although dry combustion (DC) carbon dioxide (CO₂) is an accurate method to measure total soil carbon (C), it is a rather expensive one. Therefore, wet oxidation by the Walkley–Black (WB) method is widely used in acidic Chilean volcanic soils, although there are no studies comparing both WB and DC. The aim of this article was to compare DC and WB in a range of volcanic soils containing between 2% and 9% of soil C on a regional scale. Results indicated that the recovery (R) of soil C by WB with respect to DC varied between 70% and 82%. Consequently, the correction factor (100 / R) ranged between 1.26 and 1.47. The standardized major axis regression analysis indicated that the slope and the intercept of the fitted line on volcanic soils were similar to 1:1 line. In conclusion, WB was an economically suitable method to determine the soil C content of Chilean volcanic soils.     

Predicting Total Organic Carbon Content of Soils from Walkley and Black Analysis

Globally, there is problem of computing soil carbon stock because the Walkley–Black method gives only an approximation of soil organic carbon content. Until now, no universal relationship between Walkley–Black carbon (WBC) and total soil organic carbon (TOC) has been developed that could be applicable in all kinds of soil. In the present study, relationships between WBC and TOC were established from samples collected from central and northern India. TOC was measured by dry combustion technique and WBC was determined by wet digestion methods. A relationship between WBC and TOC was developed by taking into account silt + clay content (SICL) of soil and mean annual rainfall (MAR) of the region (adj. R² = 0.99, n = 100). The present study gives an easy approach to measure TOC by easily available data sets (WBC, SICL, and MAR). Using this relationship, computation of soil carbon stock that was done earlier with WBC values could be revisited and improved.     

Determination of total organic‐C in soils by an improved chromic acid digestion and spectrophotometric procedure

Abstract

An improvement to the Walkley‐Black wet digestion method for the rapid determination of organic carbon over the range 0.2–5.5% in air‐dry soil is described. It permits total recovery of the organic‐C in finely ground soil samples digested with the heat of dilution from mixing N K₂ Cr₂ O₇ with concentrated H₂SO₄. in test tubes followed by external heating from a hot‐plate digestor. The organic‐C concentrations are determined directly, as the Cr product in diluted soil digests, by absorptiometry at 600 nm with calibration against similarly treated sucrose standards in solution. For the soils tested, there were negligible interferences from carbonates, wood charcoal, coke, Fe⁺² and readily reducible Mn; Cl does not interfere with the organic‐C assay in non‐saline soils but for saline soils a correction based on 1/12 Cl^‐ assay of the soil is necessary. The present method is compared with Tabatabai and Bremner's dry combustion procedure and Allison's manometric adaptation for calcareous soils. The procedure described here does not require carbonate to be determined and is therefore simpler. In addition it is cheaper, faster and more effective in controlling interferences than dry combustion procedures.     

Quantification of Organic Matter in Agricultural Soils from the Central Region of Paraná State,Brazil

The organic matter (OM) quantity in soils is of fundamental importance for agriculture. The indirect determination of the OM through the Total Organic Carbon (TOC) quantity is performed by most soil laboratories in Brazil using the Walkley–Black (WB) method. This procedure involves oxidation with potassium dichromate which is a cancerous reagent. The objective of this study is to optimize the parameters for OM determination by the gravimetric method and to estimate the van Bemmelen factor for the studied soil. The studied region is the second and third plateau of Parana State, Brazil, from which 50 agricultural soil samples were analyzed. The temperature and exposition time in muffle were determined after a thermal analysis. The optimized parameters for the gravimetric method were 3 h at 420°C in the muffle furnace. The results for WB and gravimetric methods presented a good correlation and the van Bemmelen factor for the studied soil was 4.37.     

Quantification of Organic Carbon in Soils: A Comparison of Methodologies and Assessment of the Carbon Content of Organic Matter

Abstract

Renewed interest in temporal soil organic carbon (SOC) stock changes has stressed the importance of reliable methods for quantitative assessment of organic compound (OC) content. Particularly with the establishment of modern dry‐combustion analyzers, which are replacing the traditional wet‐oxidation methods, the need for correct relationships between both is of crucial importance for comparison of past and current SOC data in long‐term SOC stock change studies. Dry combustion with a Variomax CNS‐analyzer was the standard to evaluate three other methods for Belgian agricultural soils. Excellent linear relationships were found with the Walkey and Black method and the Springer and Klee method, whereas a Shimadzu TOC‐analyzer slightly underestimated the OC content. Precision of the investigated methods was comparable and tended to be dependent on the sample size used for measurement. The OC oxidation efficiency of the most widely applied method of Walkey and Black for the soils in this study was very close to the generally accepted 75%. Mass loss on ignition at 800°C could be very well related to the soil OC content and the clay content. The traditional factor of 1.724 used to convert OC measurements to organic matter percentages is not valid for the investigated soils, which demonstrates that rather regional‐specific factors (in this study 1.911) should be determined and adopted.