Methods of Soil Analysis 3-961

Published 1996
Chapter 34
Total Carbon, Organic Carbon,
and Organic Matter
D. W. NELSON, University of Nebraska, Lincoln, Nebraska
L. E. SOMMERS, Colorado State University, Fort Collins, Colorado
GENERAL INFORMATION
This chapter is an updated, revised version of the material contained in Chapter
29, in Volume 2, of Methods of Soil Analysis, 2nd edition (Nelson & Sommers,
1982). Much of the material presented in the original chapter has been modified
or replaced by more modem procedures and recent literature pertaining to the
methods has been included. In addition, the total C section has been modified to
include the latest information on automated instruments for analysis of C.
Total C in soils is the sum of both organic and inorganic C. Organic C is
present in the soil organic matter fraction, whereas inorganic C is largely found
in carbonate minerals. Not all soils contain inorganic C because of dissolution
during soil formation of carbonate minerals originally present in parent material.
However, organic C is present in all agricultural soils. In soils formed from calcareous parent material under arid conditions, it is not unusual for the inorganic
C concentration to exceed the amount of organic C present.
Organic C is contained in the soil organic fraction, which consists of the
cells of microorganisms, plant and animal residues at various stages of decomposition, stable "humus" synthesized from residues, and highly carbonized compounds such as charcoal, graphite and coal (elemental forms of C). Organic C in
soil may be estimated as the difference between total C and inorganic C. Organic C can be determined directly by total C procedures after removal of inorganic
C or by rapid dichromate, oxidation-titration techniques. In the absence of inorganic C, a total C analysis can be used to determine organic C and recover all
forms of organic C in soils. However, organic C methods based on dichromate
oxidation recover variable proportions of elemental C (e.g., charcoal) and, in
some procedures, variable amounts of organic C contained in "humus."
Copyright 1996 Soil Science Society of America and American Society of Agronomy, 677 S.
Segoe Rd., Madison, WI 53711, USA. Methods of Soil Analysis. Part 3. Chemical Methods-SSSA
Book Series no. 5.
961
962
NELSON & SOMMERS
Calcite and dolomite are the principal carbonate minerals present in soil,
and most inorganic C is associated with these compounds. However, in some
alkali soils, significant amounts of inorganic C may be present in soluble carbonate and bicarbonate salts. The amounts of soluble carbonates present in soil
may be determined by procedures outlined in Chapter 15 (Loeppert & Suarez,
1996), and a variety of methods for the estimation of total inorganic C in soils are
presented in Chapter 15 (Loeppert & Suarez, 1996).
Total C analysis of soil involves conversion of all forms of C in soils to carbon dioxide (C02) by wet or dry combustion and subsequent quantitation of
evolved CO2 by gravimetric, titrimetric, volumetric, spectrophotometric, or gas
chromatographic techniques. Dry combustion is conducted by heating (-I000C)
a soil-catalyst mixture in a resistance furnace or induction furnace in a stream of
O2 or COrfree air, followed by quantitation of evolved CO2. Wet combustion is
normally carried out by boiling a soil sample with a mixture of potassium dichromate (K2Cr207)' sulfuric acid (H2S04), and phosphoric acid (H3P04) in a closed
system flushed with a stream of COrfree air and absorbing evolved CO2 in a
tared weighting bulb filled with Ascarite (Arthur H. Thomas Co., Philadelphia,
PA) (Allison, 1960). Alternatively, wet combustion may be carried out in a Van
Slyke-Neil apparatus and evolved CO2 estimated by manometric procedures
(Bremner, 1949). 1\vo dry combustion and one wet combustion procedures for
total C analysis are described in this chapter.
Soil organic matter has been defmed as the organic fraction of soil, including plant, animal, and microbial residues, fresh and at all stages of decomposition, and the relatively resistant soil humus (SSSA, 1979). Soil organic matter is
normally restricted to only those organic materials that accompany soil particles
through a 2-mm sieve. It is difficult to quantitatively estimate the amount of
organic matter present in a soil. Procedures used in the past involve determination of the change in weight of a soil sample resulting from destruction of organic compounds by H20 2 treatment or by ignition at high temperature. Both techniques are subject to error. The H20 2 method does not quantitatively remove
organic matter and the ignition method gives an overestimate because both inorganic and organic constituents in soils during ignition can be minimized by
removing aluminosilicates with hydrofluoric acid (HF)/hydrochloric acid (HCI)
prior to heating or ignition at temperatures that decompose organic matter without appreciable dehydroxylation of inorganic materials. Alternatively, the organic matter content of a soil may be estimated by multiplying the organic C concentration by a constant factor based on the percentage of C in organic matter.
Published organic C-organic matter conversion factors for surface soils have varied from 1.724 to 2.0. The appropriate factor must be determined experimentally
for each soil by independent analysis of organic matter and organic C. Although
neither the direct determination of organic matter nor the calculation of organic
matter content is completely accurate, the most useful procedures currently available are described in this chapter. Because of the problem associated with determining the organic matter content of a soil, it is strongly suggested that investi-
CARBON AND ORGANIC MATIER
963
gators determine and report the organic C content as an index of the organic matter in a soil.
TOTAL CARBON
Introduction
Analytical procedures used for determining total C in soils must quantify
both inorganic and organic forms. In humid regions where extensive leaching of
the soil profile has occurred, organic C will be the predominant form present. In
arid or semiarid regions, carbonate minerals (e.g., calcite, dolomite) along with
soluble carbonate salts may constitute a significant percentage of the total C.
Dry combustion and wet combustion are the two basic approaches used to
quantify total C in soils. In both instances, the CO2 liberated from organic and
inorganic C is determined through spectrophotometric, volumetric, titrimetric,
gravimetric, or conductimetric techniques. An apparatus for performing total C
analysis by dry combustion can be fabricated from conventional laboratory
glassware and a medium-temperature (-1000C) resistance furnace. Dry combustion procedures using either high-temperature (> 1500C) or induction furnaces are found in commercially available, automated total C analyzers. The
major~ty of dry combustion methods employ gravimetric determination .of CO2
although titrimetric techniques also are described. Wet combustion methods for
total C employ a strong oxidant, such as K2Cr207, in an acid digestion mixture
for quantitative oxidation of organic C and dissolution of carbonate minerals. A
comparison of principles, advantages, and disadvantages of commonly used
methods for total C determination is given in Table 34-1.
The developments in instrumental methods in recent years should be
assessed before choosing a procedure for determining total C in soils. The majority of instruments are automated versions of primarily dry combustion procedures. The relative advantages and disadvantages of manual and instrumental
methods should be considered before initiating total C analysis. From a cost
standpoint, manual procedures can be set up, in many cases, with apparatus
already present in most laboratories; however, they are time-consuming and
tedious and require use of careful analytical technique. In contrast, instruments
are costly, typically greater than $20 000, but they are capable of analyzing a
large number of samples with minimal variability due to operator error. Nearly
all commercial units are available with autosamplers and computer interfaces to
aid in data acquisition and handling. In addition, several commercial units enable
the simultaneous determination of elements (C, H, N, or S).
The methods presented for total C are essentially identical to those proposed by Allison et ai. (1965) in the first edition of Methods of Soil Analysis
(Black et aI., 1965) and subsequently updated in the second edition (Nelson &
Sommers, 1982). Much of the text presented is used with only minor alterations
to update the equipment available and the literature cited. A brief description has
Wet combustion
(combustion
train)
Dry combustion
(automated
methods)
Sample is mixed with CuO and heated

Gravimetric,
to -lOOOC in a stream of O2 to
titrimetric
convert all C in sample to CO2
Gravimetric,
Sample is mixed with Fe or accelerators and rapidly heated to > 1650C
titrimetric
in stream of O2 to convert all C in
to CO 2
Sample is mixed with catalysts or acThermal conductivity,
celerators and heated with resistance
conductimetric, inor induction furnace in a stream of
frared detector,
O2 to convert all C in sample to CO2
gravimetric
Sample is heated with K2Cr207-H2S04- Titrimetric, graviH3P04 mixture in a COrfree air
metric
stream to convert all C in sample
to CO2
Dry combustion
(resistance
furnace)
Dry combustion
(induction
furnace)
CO 2 determination
Principle
Method
Table 34-1. Comparison of methodologies used for determination of total C in soils.
Expensive equipment, slow release of

CO 2 from alkaline earth carbonates
with resistance furnace
Time-consuming, gravimetric determination of CO2 requires careful
analytical techniques, titrimetric
determination of CO 2 less precise.
Equipment readily available, good accuracy, easily adapted to analysis of

solutions, titrimetric analysis of CO2
less subject to operator error
Time-consuming, leakfree, O 2 sweep

train is required, slow release of
CO 2 from alkaline earth carbonates.
Leakfree O 2 sweep train is required,
induction furnace is expensive.
Disadvantages
Rapid and simple, good accuracy and

precision
Reference method widely used in other

disciplines, variable sampling sizes,
variable sample size
Rapid combustion, high temperature
ensures conversion of all C to CO 2
Advantages
C"I.l
~
Z
CARBON AND ORGANIC MATTER
965
Fig. 34-1. Block diagram of dry combustion trains. Option A is based on Allison (1965). Option B is
adapted from Rabenhorst (1988).
to update the equipment available and the literature cited. A brief description has
been added on the principles employed in selected commercially available total
C analyzers.
Total Carbon by Dry Combustion

Introduction
The dry combustion method is based on oxidation of organic C and thermal decomposition of carbonate minerals in a medium-temperature resistance
furnace. The CO 2 liberated is commonly trapped in a suitable reagent and determined titrimetrically or gravimetrically. Spectrophotometric, volumetric or conductimetric procedures are used to determine CO 2 in some commercial instruments. Alternatively, the CO 2 released can be reduced to CH 4 and quantitated
with a gas chromatograph fitted with a flame ionization detector (Geiger &
Hardy, 1971). The following description of a medium-temperature dry combustion is that presented by Allison et al. (1965).
Principles
In the dry combustion procedures described here, the sample is burned in
a stream of purified O2 and CO2 in the effluent gas stream is absorbed by
Ascarite or some other suitable absorbent and weighed. Other absorbable gases
formed during combustion are removed from the O2 stream before they reach the
CO2 absorption bulb. A typical combustion train is comprised of 10 basic elements as diagrammed in Fig. 34-1. The make-up of the individual elements are
modifications (AOAC, 1975, p. 924-926; Chemists U.S. Steel Corp., 1938, p.
40-54; Salter, 1916; Winters & Smith, 1929) of those recommended by Fleming
(1914) for the rapid determination of C in Fe and steel.
NELSON & SOMMERS
The O2 supply (commercial compressed O2) is first scrubbed by passage

through a train consisting of concentrated H2S04 to remove ammonia (NH3) and
hydrocarbons, an absorbent such as soda lime to remove CO2, and anhydrous
magnesium perchlorate Mg(CI04)z to remove water vapor. The rate of O2 flow
is controlled by a needle valve and is measured by a flow meter.
A furnace provides the heat necessary for combustion of the organic C to
CO2 and for decomposition of carbonates. In a resistance furnace, the sample is
heated by radiation, conduction, and convection in a tube surrounded by heating
elements made of high-resistance materials such as Nichrome (in medium-temperature models) or silicon carbide (in high-temperature models). In an induction
furnace, the source of energy is high-frequency electromagnetic radiation. Ferrous metals and certain other materials can be heated to high temperatures by
electromagnetic induction if enough energy is present. Materials such as soil that
do not heat by induction can be heated indirectly by radiation, conduction, and
convection from susceptors (materials that do heat) in the induction field. The
susceptor may take the form of iron or tin chips that are mixed with the sample
to be burned, or a radiator [e.g., the Pt cage (Simons et aI., 1955), quartzenclosed carbon crucible (Allison et aI., 1965)] that will surround a crucible containing the sample to be burned.
The type of furnace determines the packing of the combustion tube. With
medium-temperature furnaces, cupric oxide (CuO) or another accelerator is
mixed with the soil to aid in combustion of the organic matter and elemental C.
With high-temperature furnaces, the organic and elemental C is generally oxidized to CO2 by gaseous O2 without special assistance. When medium-temperature furnaces are used, catalysts must be included in the combustion tube at the
rear of the heated zone to ensure essentially complete oxidation of carbon
monoxide (CO) or other volatile C compounds. Platinized asbestos or CuO wire
may be used as a catalyst. However, with any type of furnace, some CO may pass
through. A low-temperature (-250C) catalyst furnace, with catalyst supplied by
the manufacturer, may follow the main combustion tube to convert any CO to
CO2
Medium-temperature combustion is not entirely satisfactory for soils containing alkaline-earth carbonates because these minerals release CO2 slowly at
950C (C02 may not be released completely in 30 min). High-temperature combustion, on the other hand, causes rapid and quantitative release of CO2 from
both Na2C03 and alkaline-earth carbonates.
The gas stream leaving the furnace is freed of particulate matter by a dust
trap in the exit end of the combustion tube. The removal of nitrogen oxides, sulfur oxides, and halogen gases can be effected in several ways. Activated Mn02
appears satisfactory as a dry absorber for the oxides of Nand S and the halogens
(Robertson et aI., 1958). To protect the catalysts in the catalyst furnace from
being poisoned by these substances, a trap of activated Mn02 must be inserted at
the combustion tube outlet. Liquid absorbers for these interfering gases include
solutions of H2S04-Cr03, Ag2S04, and KI but they are not recommended for
insertion ahead of the catalyst furnace. Most of the water vapor formed during
combustion is removed by a concentrated H2S04 tower immediately following
the catalyst furnace. The little water vapor passing through is trapped by a tower
967
of anhydrous Mg(CI04h next in line. The CO 2 is finally absorbed in a suitable

bulb containing Ascarite or other absorbent backed by anhydrous Mg(CI04h to
ensure that water vapor pressure is the same in exit gas as in entering gas.
Rabenhorst (1988) evaluated many of the parameters involved in determining organic and inorganic C in soils by dry combustion using gravimetric
determination of C collected in an absorption bulb. He concluded that sequential
combustion of the same sample at 575C for 15 min followed by combustion at
1000C for 10 min would quantitatively recover organic and inorganic C, respectively, from soils. He also described a simplified analytical apparatus that consisted of the following components: (i) compressed O2; (ii) concentrated H 2S04;
(iii) Ascarite; (iv) Mg(CI04h; (v) quartz or ceramic combustion tube to hold the
sample boat and containing CuO wire and glass wool at distal end; (vi) Drierite;
(vii) Mg(CI04)2 and; (viii) Nesbitt bulb containing layers of glass wool, ascarite
and Mg(CI04)2. This simplified gas handling train is listed as Alternative C (see
"Alternative Arrangements" below; Fig. 34-1) in the following. method and
should be considered if dry combustion will be used for total C analysis.
Medium-Temperature Resistance Furnace Method
Special Apparatusl
1. Oxygen cylinder and pressure regulator (A).
2. Oxygen purifying train consisting of concentrated H 2S04 for removal
of NH3 and hydrocarbons, Ascarite for removal of CO2 and acid gases,
and anhydrous Mg(CI0 4)2 for removal of water vapor (B).
3. Flow indicator and needle valve for O2 control (C).
4. Furnace unit (D): (a) Resistance furnace equipped with temperature
controller and indicator (Lindberg multiple-unit combustion-tube furnace or equivalent) for operation at 900 to 1000C; (b) Sample inserter (LEC0 2 no. 501-062, Alpha3 AR-061 or equivalent); (c) Combustion tube, 2.5-cm diam. by 75 cm (zircon ceramic or equivalent).
5. Dust trap (LECO no. 501-010 or equivalent) inserted in the exit end of
the combustion tube (E).
6. Sulfur trap filled with activated Mn02 (LECO no. 503-033 or equivalent) (F).
7. Catalyst furnace and tube (LECO no. 507-010 or equivalent) (G).
8. Gas scrubber (H): (a) Sulfuric acid tower to absorb most of the water
vapor and to prolong the life of the anhydrous Mg(CI04h trap that follows (especially desirable when combusting organic soils and other
organic materials; (b) Water vapor trap filled with anhydrous
Mg(CI0 4h (LECO no. 598-157 or equivalent).
9. Carbon dioxide absorption tube, a Nesbitt, Fleming, or Turner bulb
packed with an indicating CO2 absorbent and anhydrous Mg(CI0 4)(I).
The bulb contains from bottom to top: (i) glass wool, (ii) 3-cm layer
Capital letters in parentheses refer to units in Fig. 34-1.

LECO Corporation, 3000 Lakeview Ave., SI. Joseph, MI 49085-2396.
3 Alpha Resources, Inc., 3090 Johnson Rd., Stevensville, MI 49127-0199.
1
NELSON & SOMMERS
968
of 8- to 14-mesh (1.4-2.36 mm) absorbent (e.g., Ascarite), (iii) 2-em

layer of 14- to 20-mesh (0.85-1.4 mm) absorbent, (iv) l-cm layer of
anhydrous Mg(CI04)z, and (v) glass wool (also described in "Special
Apparatus" under "Wet Combustion Method").
10. Bubbler trap to seal the train from the atmosphere and indicate flow of
exit gas (J).
11. Alternative arrangements; (i) The O2 purifying train (B) and the flow
indicator (C) are available as a combined unit (LECO no. 516-000); (b)
The scrubber-absorption train described in "Special Apparatus" under
"Wet Combustion Method" (Units F-K) can substitute for units H, I,
and J (Items 8-10); (c) Items 4-8 can be replaced as follows. Item 4,
pack combustion with 7 to 10 cm of cupric oxide wire followed by
plug of glass wool; Items 5 to 7 are deleted; Item 8, replace with by
trap of Drierite followed by trap of anhydrous Mg(CI04)z.
12. Accessory items: (i) Combustion boats, ceramic (Alundum, zircon,
etc.), (LECO no. 528-053 or equivalent); (b) Boat puller with eye
shield (LECO no. 501-062 or equivalent); (c) Combustion tube cleaning brush (LECO no. 501-082 or equivalent); (d) Plastic tubing (Tygon
or equivalent) for connecting components. (Rubber is permeable to
CO2.) Any deposits due to malfunctions can readily be observed in
transparent tubing); (e) Analytical balance (Mettler H31AR, Mettler
Instrument, Hightstown, NJ; or equivalent) on grounded metal plate.
Reagents
1. Oxygen gas.
2. Sulfuric acid, concentrated.
3. Manganese dioxide (Mn02), activated (LECO no. 501-060 or equivalent).
4. Platinized asbestos, 5% Pt (J. T. Baker Chemical Co.; no. 0922,
Philipsburg, NJ; or equivalent); or CuO, wire or granular, low in C for
combustion tube catalyst.
5. Cupric oxide powder, low in C, to serve as an accelerator when mixed
with soil in the boat.
6. Alundum or Sinderite or equivalent, refractory grade, 60- or 90-mesh
(165-250 ~m) size, C free.
7. Anhydrous magnesium perchlorate (Anhydrone, Dehydrite, etc.).
8. Carbon dioxide absorbent, indicating, 14- to 20-mesh (0.85-1.4 mm)
size [Ascarite, Caroxide (Fisher Scientific, Pittsburgh, PA), Indicarb
(Fisher Scientific, Pittsburgh, PA), or Mikhobite (G. Frederick Smith
Chemical Co., Columbus, OH).
9. Standard C source [dextrose (CJI1206) or benzoic acid (C2H60 2) of
reagent-grade or primary-standard quality].
Procedure
Loosely pack the combustion tube with a 7.5-em core of platinized asbestos
so that it will come within the exit end of the heated zone of the furnace. Alter-
969
natively, use coarsely granular CuO, held in position by two plugs of asbestos
fiber packed no more tightly than is necessary to hold the CuO in place.
Bring the furnace to 950C to lO00C. Connect the train, and sweep the
apparatus with O2 at the rate of 100 mL/min for 10 min. Remove and weigh the
CO 2 absorption bulb. Repeat this step until the CO2 absorption bulb has attained
a weight constant to 0.2 mg. Replace the CO2 absorption bulb in the train, and
introduce well within the heated zone of the combustion tube a ceramic boat containing 1.0 g of finely divided CuO. Admit O2 and continue the flow at 100
mL/min for 10 min. Close the stopcocks on the CO2 absorption bulb, disconnect
the bulb, and weigh it. The increase in weight of the bulb represents the blank.
Remove the boat from the combustion tube. Repeat the determination until a
reproducible blank is obtained. With a properly prepared train and high-quality
reagents, the blank should be negligible, i.e., within limits of weighing error.
Grind soil to be analyzed for C to pass through a 100- or 140-mesh sieve
(0.149- or 0.105-mm openings). Mix 1.000 g of mineral soil of known water content with 1.0 g of finely divided CuO in a combustion boat, cover the mixture
lightly (-2 mm) with Alumdum or Sinderite, and follow the procedure used for
the blanks. For soils high in organic matter, use a 0.500-g sample. The increase
in weight, corrected for blank, should represent the CO 2 from the sample. The
calculation is as follows
Total C, % =
[g CO2, sample] - [g CO2, blank]

g water-free soil
x 0.2727 x 100
[1 ]
Comments
Cleanliness is proverbial in the C laboratory, especially when one is dealing with low C samples or doing work of the highest order of accuracy. In such
instances, freedom from dust, dirt, or fumes is essential. It is advisable habitually to ignite all boats at -900C before use and to store boats out of contact with
the atmosphere. Handling boats and covers only with tongs is considered good
practice.
Some experience is usually necessary before reproducible weights of CO2
absorption bulbs can be obtained. Thermal equilibrium with the atmosphere is
important. The surface must be kept clean and free of static charge. The following points may be helpful:
1. Before each weighing, the absorption bulb should be wiped slowly
with a lint-free paper tissue, such as Kimwipes or napkin stock. Paper
is superior to cloth. Rapid wiping builds up the static charge .Handling
the absorption bulb with clean cotton gloves may be helpful.
2. After the CO 2 absorption bulb has been wiped, it should be touched to
a grounded plate to remove the static charge before weighing. If the
bulb is in temperature equilibrium with the atmosphere, repeated
weighing should agree within 0.2 mg. The position of the absorption
bulb on the balance pan may be critical. With some balances, accuracy is dependent on careful centering of the objects to be weighed.
970
NELSON & SOMMERS
3. The CO2 absorption bulb is brought to constant weight by inserting it

in the combustion train and operating the train as a blank. Cold bulbs
characteristically gain several milligrams on blank runs before attaining a weight constant to 0.2 mg. If a steady gain in weight is obtained
in repeated trials with the bulb properly handled and placed on the balance pan, one or more of the absorbers in the train may not be functioning properly.
Fine grinding 150 !lm or <100 mesh) of soil samples is especially important in obtaining reproducible results in determinations of C. Only from finely
ground, homogeneous samples, can uniform small subsamples be drawn. Poor
replication often can be traced to poor sampling. Fine grinding is a task at best.
Where many samples are to be processed, a mechanical mortar and pestle unit, a
high-speed impact shaker, or a ball mill will save much time and labor.
When C in soil extracts or other liquids is determined, the sample may be
evaporated and dried, preferably under vacuum at 60C in porcelain or nickel
boats of 5- or 10-mL capacity. Liquids will slowly seep through the usual grade
of ceramic boats. Porcelain boats are short lived, even at 950C. Unglazed boats
may be rendered leakproof by treating with a glazing mixture and firing in a laboratory furnace (Lindbeck & Young, 1964). An alternative method for analyzing
soil extracts involves filling ceramic combustion boats with siliceous earth, i.e.,
Kieselgur (Tiessen et aI., 1981). Since Kieselguhr will absorb about four times its
weight in liquid, multiple 3-mL samples of a soil extract can be added to the boat
if water is evaporated on a hot plate for 10 min at 80C between additions.
Combustion tubes eventually develop fine cracks in the hottest region and
need to be replaced. Erratic results are one indication of a cracked combustion
tube. After every 50 or 100 analyses, the tube should be tested for leaks under
operating pressure by stoppering the exit and observing if O2 passes the H2S04
tower in the purifying train. Combustion tube life is prolonged if, during contemplated daily use, the furnace is kept on continuously.
A standard C source, such as analytical reagent or primary standard-quality glucose or benzoic acid, should be run from time to time to check the apparatus. The organic standard should be diluted and covered with Alundum or Sinderite to prevent explosion.
Explosive combustion will blow stoppers, and even the boat, from the combustion tube. After an explosion, it is essential to bum off the C deposits from the
cooler areas inside the tube before additional analyses are made.
A two-tube furnace is advantageous even though only one tube is used routinely. The second tube serves as a reserve in the event the other cracks during a
series of analyses or when C deposits resulting from an explosion must be burned
out.
The insert dust trap should be cleaned and refilled with glass wool after 40
or 50 determinations or more frequently if deposits appear in the exit tubing.
The Mn02 used to remove S02 from the combustion products before they
enter the catalyst furnace should be changed after about 50 determinations or
before all the granules appear gray or agglomerated. Peterson (1962) pointed out
that the accumulation of combustion reaction products on the Mn02 changes its
CO2 absorption-desorption pattern so that longer flushing times must be used, as
CARBON AND ORGANIC MAITER
971
in the gasometric determination of C. Peterson recommended a specially prepared Pb02 as a substitute for Mn02 to increase the efficiency of S02 removal
but no evidence was presented concerning its capacity to absorb nitrogen oxides
or the halogens.
Air-dry samples are preferred to oven-dry samples, because oven drying
may result in lower values for total C in some soil samples.
A slight pressure in the combustion tube will be noticed when the stopper
is removed after a determination. If this pressure becomes pronounced, it indicates increased resistance to gas flow in the S trap or in the water vapor trap.
These traps should be examined and repacked or replaced as necessary.
Temperature> 1OOOC must be avoided. Heating elements will be subject to
burnout, and fusion of CuO is likely to occur and cause slagging and tube rupture
on cooling. Attention to this is especially important if a temperature controller is
not used.
A supply of boats can be rendered C free by preliminary ignition in a muffle furnace at 850 to 900C. These ignited boats should be kept in dust-free storage until used.
High-Temperature Induction Furnace Method
Special ApparatusS
1.
2.
3.
4.
S.
6.
7.
8.
9.
10.
11.
Oxygen cylinder and regulator (A).

Oxygen purifying train (B).
Flow meter and needle valve (C).
Furnace unit: (i) Induction (high-frequency) furnace (Alpha no. AR521 or equivalent) for operation at 1400 to 1600C; (b) Combustion
tube (LECO no. 550-122 or equivalent); and (c) Crucible (LECO no.
528-018) with cover.
Dust trap for induction furnace, external (LECO no. 501-0lD or equivalent).
Sulfur trap filled with activated Mn02 (LECO no. 503-033 or equivalent).
Catalyst furnace and tube (G).
Gas scrubber (H).
Carbon dioxide absorption tube (I).
Bubble trap (1).
Alternative arrangements: (a) The O 2 purifying train (B) and the flow
indicator (C) are available as a combined unit (LECO no. 516-000); (b)
The induction furnace actually is a complex unit that combines the furnace (D), dust trap (E), Strap (F), and catalyst furnace (G) (Items 4-5
above), in a single unit; and (c) Various combinations of the 10 basic
elements that comprise the train (Fig. 34-1) are available under various trade names such as Leco. The output of the furnaces (resistance
or induction) can be put through a water vapor trap (H, a single V-tube
filled with anhydrone) into a CO 2 absorption tube (I). No exact com-
Capital letters in parentheses refer to units in Fig. 34-1.
NELSON & SOMMERS
972
bination of units is prescribed here since many suitable combinations

are possible.
12. Analytical balance (Mettler H31AR or equivalent).
Reagents
1. Reagents 1, 2, 3, 7, 8, and 9 described in "Reagents" under "MediumTemperature Resistance Furnace Method."
2. Tin metal accelerator (LECO no. 501-076 or equivalent).
3. Iron chip accelerator, C free (LECO no. 501-077 or equivalent).
4. Tin-coated copper accelerator (LECO no. 501-263 or equivalent).
5. Scoop for adding 1 g of accelerators (LECO no. 503-032 or equivalent).
Procedure Using Iron, Tin, and Tin-coated Copper Accelerators

Weigh the CO2 absorption bulb on the analytical balance, insert the bulb in
the train, and open the stopcocks. Set the O2 flow at the rate of 1.5 Umin. Place
an empty crucible in the induction furnace. Fire the furnace, following the manufacturer's instructions, for 5 min. At the end of the combustion period, remove
the crucible, tum off the O2 flow, and then close off and remove the CO2 absorption bulb. Weigh the CO2 absorption bulb (see "Comments" under "MediumTemperature resistance Furnace Method"). Repeat this process until a blank
reproducible 0.2 mg is obtained. Alternatively, ignite two or more blanks (crucible containing 1 scoop each of iron chip, tin and tin-coated copper accelerators)
until a blank reproducible to 0.2 mg is obtained.
Transfer a 0.5000-g sample of soil that passes through a 100- or 140-mesh
(106-150 /-lm) sieve to a crucible. Add one scoop of tin metal accelerator, one
scoop of iron chip accelerator, and one scoop of tin--coated copper accelerator,
and cover the crucible. Insert the covered crucible in the induction furnace. Set
the O2 flow at a rate of 1.5 Umin. Fire the furnace according to a manufacturer's
instructions. At the end of the combustion period, remove the crucible, tum off
the flow of O2, and close off, remove and weight the CO2 absorption bulb (see
"Comments" under "Medium-Temperature Resistance Furnace Method"). The
increase in weight of the CO 2 absorption bulb, after correction for the blank,
should be due to CO 2 released from the soil sample. Flush the train (without the
CO2 absorption bulb) with O2 for about 1 min between successive runs. Determine the blank for the crucible and accelerators using the same procedure.
Total C,
nt
70
[g COz, sample] - [g COz, blank]

g water-free soil
x 0.2727 x 100
[2]
Comments
Comments in "Comments" under "Medium-Temperature Resistance Furnace Method" on weighing of absorption bulbs and on sample grinding are fully
applicable to this procedure. Other comments in "Comments" under "MediumTemperature Resistance Furnace Method" also are applicable.
Under optimum conditions, the two procedures yield comparable results.
Adequately high temperature (> 1650C) can be developed with the proper addi-
CARBON AND ORGANIC MAITER
973
tions of Sn and Fe, but the temperature maximum is held only briefly. The temperature rises steadily until the susceptors melt and fuse with the sample, and
thereafter, it falls rapidly. Occasionally this temperature rise and fall occurs
before thermal decomposition of C is complete, perhaps because of inadequate
contact between the sample and the susceptor material. For most soils, this does
not appear to be a major problem since Fe, Sn, and tin-coated copper accelerators
(-1 g of each/sample) have been found to yield accurate total C values in a range
of calcareous and noncalcareous soils and standard carbonate minerals (Tabatabai
& Bremner, 1970).
If the organic matter content of the soil is high, the sample weight should
be reduced appropriately. Organic materials can be analyzed by this technique,
but sample weights must be reduced to 20 or 30 mg if explosions are to be avoided. Alternatively the organic material in amounts up to 60 mg can be mixed and
covered with Alundum or Sinderite as described in "Procedure" under "MediumTemperature Resistance Furnace Method."
The gravimetric determination of CO 2 following combustion with the Leco
induction furnace was found by Carr (1973) to yield total C levels comparable
with manual wet and dry combustion methods. In addition to gravimetry, an automated CO2 analyzer based on thermal conductivity measurements of the effluent
gases was applicable to soil analysis (Tabatabai & Bremner, 1970).
Alternatively, a titrimetric method was developed to allow estimation of
both total C and 14C in soil samples amended with 14C compounds (Cheng & Farrow, 1976). A bypass valve and a 12S-mL gas washing bottle (e.g., Corning
31760) are used in place of the CO 2 absorption bulb of Fig. 34-1. All CO2
released by combustion is trapped in SO mL ofO.S M NaOH followed by removal
of one aliquot for liquid scintillation counting to quantify 14C2 and a second
aliquot for titration with standard HCI to determine total C. The total C data
obtained were comparable to those obtained by a wet combustion procedure.
Recent data also indicates that titrimetric and thermal condl'ctivity methods are
comparable for the determination of CO2 (Winter et aI., 1990).
Instrumental Methods
The following section describes representative commercial instruments for
determining total C in soils. They were chosen to illustrate the principles
involved in instrumenting total C analysis. The inclusion of the following three
instruments does not imply that they are superior or inferior to others currently
being marketed. As with all instruments, various evaluation procedures should be
used to determine and to confirm the validity of data obtained in comparison to
accepted, standard methods. Tabatabai and Bremner (1991) described automated
instruments available for determining total C in soils as well as which instruments
are capable of simultaneous determination of N or S.
Carbo-Erba NA 1500. Carlo-Erba Instruments (Milan, Italy) developed an

automated instrument capable of simultaneous determination of C, H, and N in
geologic materials, soils, and other environmental samples. The principles
involved, development of the instrument and a description of modes of operation
are presented by Pella (1990a,b). A sample is placed in a tin sample cup, crimped
NELSON & SOMMERS
974
Helium (continuous flow)

Sample in Sn
container
Thermal
Conductivity
Sample Detector
Reference
Cu
NiO
Chro atographic
colum
Co,Oj Ag
Fig. 34--2. Schematic diagram for Carlo-Erba Model NA 1500 analyzer.
to confine it, and introduced into a quartz reactor. For mineral soils, a typical sample size is 5- to 10 mg, necessitating the use of samples finely ground in a ball
mill or similar apparatus. The quartz reactor is maintained at 1050C with a constant flow of He. Flash combustion will occur if a pulse of O2 is injected into the
quartz reactor shortly after introduction of the sample. Under these temperature
and O2 conditions, the tin is oxidized to SnOz resulting in the temperature
increasing to 1700 to 1800C and the complete combustion of soil organic matter. The combustion products (C02, N oxides, and HzO) are swept by the helium
carrier gas through chromium dioxide (Cr02) to catalyze oxidation of organic
fragments and C030 4 coated with Ag to remove halogens and sulfur oxides. The
gases then flow through a heated Cu (650C) column to remove excess oxygen,
Mg(CI04)z to remove H20 and into a chromatographic column for separation of
N2 and COz. The different gases are detected with a thermal conductivity detector. A generalized flow diagram for this instrument is shown in Fig. 34-2.
Schepers et al. (1989) evaluated the NA 1500 coupled with a mass spectrometer for simultaneous determination of C, N, and 15N in soil and plant materials. The NA 1500 yielded Nand 15N data comparable to that obtained with conventional manual methods (Kjeldahl digestion followed by mass spectroscopy
analysis). A detailed comparison of C data was not conducted although realistic
values for total C in soils and plant materials were obtained. An evaluation of
sample preparation methods (soil grindinglWiley mill vs. ball milling) indicated
that homogeneous soil and plant samples were essential to reduce analytical variability, especially in view of the typical sample size of 10 mg. Verardo et al.
(1990) have described procedures for using the NA 1500 to determine C and N
in marine sediments. Due to the analysis of 5 to 10 mg, careful sample preparation and grinding are needed on insure that a representative sample is analyzed.
A" with any analytical method, the inclusion of appropriate standards and blanks
is essential tinsure valid total C data. The capability of coupling this instrument
with a mass spectrometer is a potential benefit as well.
CARBON AND ORGANIC MATfER
975
Leco Instruments. The LECO Corporation (St. Joseph, MI) has marketed
instruments for automated analysis of total C in soils and other solid materials for
the past several decades.
A description of Leco instruments is presented by Tabatabai and Bremner
(1991). Earlier results with the Leco automatic 70-s C analyzer (Tabatabai &
Bremner, 1970; Carr, 1973) indicate that reliable soil total C data are obtained
using Fe, Sn, and tin-coated copper accelerators in an induction furnace followed
by thermal conductivity to quantitate CO2, The newer LECO IR-12 instrument
involves combustion of a soil sample in an induction furnace using an O 2 atmosphere followed by passing the gas mixture over a catalyst to convert CO to CO2
and CO 2 quantitation with an infrared detector. A related instrument, model
DC-12 Duo-Carb, involves combustion of samples mixed with V205 (vanadium
pentoxide) in an induction furnace heated to 1000C under an O2 atmosphere.
The COz produced is measured with a thermal conductivity detector.
In 1993, LECO marketed two instruments for determining total C in soils.
Both instruments utilize resistance furnaces to combust samples at >950C. In the
Model CR-412, a sample contained in a ceramic boat is placed in a specially
designed horizontal resistance furnace maintained at a constant temperature in the
range of 950 to 1400C under Oz flow. After a delay, Oz is directed onto the sample and carries the COz released through dust and water vapor traps and into an
infrared detection system. Merry and Spouncer (1988) evaluated the earlier
model CR-12 and found that it gave reasonable soil organic C values when operated at 1200C. In an evaluation of combustion temperature on C recovery from
noncalcareous and calcareous soils, it was found that both inorganic and organic
C were recovered between 600C and 1000C. Total C determined by the CR-12
and the Allison method (Allison, 1960; see "Wet Combustion Method") were in
close agreement for 20 Iowa soils (Yeomans & Bremner, 1991).
Chichester and Chaison (1992) evaluated the CR-12 for determining organic C and inorganic C by combusting samples at 575C and 1000C, respectively.
They recommended combustion at 575C for 250 to 360 s to determine organic
C followed by combustion at 1000C for 250 s to determine inorganic C. In addition, the time required for analysis of inorganic C could be reduced from 250 to
60 s by increasing the combustion temperature from 1000C to 1371C. In summary, total C could be determined by a single combustion at 1371 C as found by
other investigators.
A second LECO instrument is the model CHN 600 which is capable of
simultaneous analysis of C, H, and N. A flow diagram for the CHN 600 is shown
in Fig. 34-3. The successor to the CHN 600 is the model CHN 1000. A soil sample 200 mg) is placed in a tin capsule and combusted in a resistance furnace at
950C using Oz as a carrier gas. The gases formed are scrubbed to remove S gases
and equilibrated in a ballast chamber. Mter equilibration, the gas mixture flows
through two infrared detectors set to detect COz and HzO. An aliquot of the gas
mixture is analyzed for N z by thermal conductivity after reduction of N oxides
and removal of COz and HzO.
The CHN 600 has been used in several soils studies. Total C results from
20 Iowa soils were essentially the same using the CHN 600 and a standard wetcombustion method (Yeomans & Bremner, 1991). A comparison of data obtained
NELSON & SOMMERS
976
950C
Dual Heat Zone

Furnace
Exhaust
Fig. 34-3. Schematic diagram for LECO Model CHN 600 analyzer.
by the CHN 600 with a LECO induction furnace instrument and a wet-oxidation
method indicated that the CHN 600 was the most precise total C technique
(0.014>.12% C) and enabled a technician to perform 90 to 100 analyses in an 8h d (Sheldrick, 1986). The CHN 600 has been shown to recover 100% of the C
in a range of pure organic C compounds [acetanilide (N-acetylaniline), sucrose
(C 12H 22 0 1), sulfanilic acid (C6H7N03S), and EDTA (ClOH16N20S)] and, as expected, to yield soil organic C values 16 to 59% greater than those obtained by
the Walkley-Black method (McGeehan & Naylor, 1988). In general, the CHN
600 has shown to be a reliable and accurate instrument for the determination of
total C in soils.
Perkin-Elmer CHN2400. The Perkin-Elmer (Perkin-Elmer Corp., Instrument Division, Norwalk, CT) simultaneously measures C, H, and N using the
principles employed in the traditional Pregl and Dumas procedures. A sample
contained in a platinum boat is oxidized with O2 at -lOOOC for 2 min in a combustion tube in the absence of carrier gas (He) flow. Mter combustion, He flow
is initiated and the CO 2, H 20, and N2 bases produced by combustion are passed
over CuO to convert CO to CO2 and silver mesh (silver vanadate on silver wool)
to remove S and halogen gases. The gases then flow into a tube maintained at
650C and packed with copper granules between end plugs of silver wool, where
quantitative reduction of N oxides to N2 occurs. The gases are brought to constant
pressure and volume in a gas mixing chamber and then allowed to expand into
the analyzer portion of the instrument. The analyzer consists of three thermal conductivity (TC) detectors connected in series and separated by two traps. The
sequence of TC detectors and traps enabling quantification of H, C, and N is as
follows:
1. TC detector 1 (output equals total gas composition).
2. Magnesium perchlorate trap to remove H 20.
3. TC detector 2 (decrease in output from detector 1 is proportional to H
content).
4. Soda asbestos plus Mg(Cl04)2 trap to remove CO 2.
977
5. TC detector 3 (decrease in output from Detector 2 is proportional to C

content).
6. The remaining gases in the sample are N2
All operations within the instrument are automatic. Additional work is needed to
evaluate this instrument for soil analysis.
The above discussion is an overview of instrumental methods for total C
analysis of soils. At present, the LECO instruments have been the most widely
used for soil analysis. Several research laboratories have begun using Carlo-Erba
instruments for total C analysis of soils. Due to rapid changes in technology and
instrumentation, it is essential that manufacturers be contacted for currently available models followed by an evaluation of the instrument.
Total Carbon by Wet Combustion

Introduction
The wet combustion analysis of soils by chromic acid digestion has long
been a standard method for determining total C, giving results in good agreement
with dry combustion. The main advantages for wet combustion are that the cost
of apparatus is but a small fraction of the cost for dry combustion equipment and
that the parts needed to assemble the apparatus are standard equipment in most
laboratories. The chief disadvantage of the earlier wet combustion procedures
(e.g., Heck, 1929) is that they use macro equipment, which is tedious to assemble and disassemble, and which occupies considerable bench space more or less
permanently. Wet combustion also is used when the special manometric Van
Slyke-Neil apparatus (Van Slyke & Folch, 1940; Bremner, 1949) is employed to
estimate total C in soils.
The wet combustion method of Allison (1960), described here, embodies
important refinements from published procedures, such as simple and effective
digestion acid mixture (Clark & Ogg, 1942), a simple purification and absorption
train assembled on a small panel (McCready & Hassid, 1942), and a more rapid
procedure than formerly used (Heck, 1929; Jackson, 1958, p. 211). The significant features of this apparatus (Fig. 34--4) are as follows: (i) it can be assembled
from simple parts and requires no ground-glass connections, (ii) the small internal volume precludes the necessity for preaeration under most laboratory conditions, (iii) it requires only a short period of aeration following digestion, and (iv)
the entire assembly (F-K) occupies only a small area. This method is satisfactory for salt-affected soils high in Cl- and also for the dry residues of soil extracts
rich in organic matter. A rapid treatment to remove carbonates described in "Pretreatment Prior to Wet Combustion" permits determination of organic C on the
residue of a pretreated calcareous soil. The following description of wet combustion methodology was presented by Allison et al. (1965).
Principles
The soil sample is digested in a 60:40 mixture of H2S04 and H3P04 containing K2Cr207' The boiling temperature of this mixture, 210C, is high enough
to ensure complete oxidation of carbonaceous matter, yet low enough to prevent
NELSON & SOMMERS
978
To Trap
I or"
Trop I
~
Ga,-
MglCIO ) JFiber Qloss

.2
Ascarite-
Fibtr Qloss
2t
T'OP
~I
Go.-
.
"
mon
Mods
NoOH
K
Nesbitt
bulb
250 ml Side. arm

Erlenmeyer
c
Fig. 34-4. Diagram of apparatus used to determine C by the wet combustion method. Trap I or II is
used for determination of CO2 evolved by gravimetric or titrimetric techniques, respectively (diagram is not drawn to scale).
excessive fuming in the condenser. The CO 2 evolved is absorbed by a suitable

absorbent and weighed, although it may be absorbed in a standard base and titrated.
A combination of fuming H2S04 , phosphoric acid (H3P04), iodic acid
(HI03) [added to potassium iodate (KI03)], and cr03 has been used for determining C in organic compounds (Van Slyke & Folch, 1940) and in soil (McCready & Hassid, 1942). The reported advantages of this oxidation mixture are
that it vigorously attacks and dehydrates resistant forms of C, thereby reducing
boiling time for complete oxidation, and that it facilitates conversion of CO to
CO2, Carbon monoxide is often produced when readily oxidizable carbohydrates
are present in the sample. Extensive comparisons of the Van Slyke-Folch and the
60:40 H2S04-H 2P04 oxidizing mixtures on many soils indicate that the two mixtures are equally effective in converting total soil C to CO2, The more rapid digestion with the Van Slyke-Folch mixture, resulting in a saving of 3 or 4 min per
determination, is not sufficient advantage to offset the difficulties of preparing
and maintaining a digestion acid that contains fuming H2S04, Moreover it was
found that the need for HI0 3 in the digestion mixture does not exist, which indicates that soil organic matter contains little or no active carbohydrate capable of
producing CO during digestion (Allison, 1960).
Salt-affected soils frequently contain sufficient Cl- to give errors by wet
combustion analysis whether the CO 2 is determined titrimetrically (Clark & Ogg,
1942) or gravimetrically (Allison, 1960). When soil high in Cl- is heated in a
digestion mixture containing Cr20-r-, chromyl chloride (CrOzCI2) is formed by
the following reaction before boiling begins
979
The reddish Cr02Cl2 decomposes at about 190C, releasing free C12, with
a color change to pale green. Any Cl2 and traces of undecomposed Cr02CI2 that
pass the purification train are retained in the CO2 absorption bulb to give a positive error.
In the methods described, Cl2 interference is prevented by including two
traps in the purifying train, one containing KI and one containing silver sulfate
(Ag2S04) (Traps F and G in Fig. 34-2). The use of Ag2S04 alone gives protection up to about 0.2% Cl- (Allison, 1960), but its protective value becomes questionable at higher Cl- concentrations, Since KI has a very high capacity to absorb
free Cl 2 by the reaction
2KI + Cl 2 =2KCl + 21 2,
[4]
the use of a KI trap is recommended for soils high in Cl-. With both traps in the
system, Cl- up to 5% of the sample weight does not interfere, provided proper
precautions are observed during the early stages of sample digestion. Use of the
Ag2S04 trap in conjunction with the KI trap serves to indicate when the latter is
exhausted. For soils containing trace or low amounts of Cl-, the carrier stream
may flow directly into the Ag2S04 trap.
Wet Combustion Method
The wet combustion method was described by Allison (1960).
Special Apparatus
The apparatus is shown in Fig. 34-4. Assemble the apparatus from the following parts: (A) Hoke needle valve: (B) 25-cm high soda-lime tower; (C) 100mL Kjeldahl flasks to fit a no. 2 stopper; (D) Allihn four-bulb condenser, fitted
with a no. 2 stopper at the delivery end; (E) 60-mL open-top separator funnel;
(F-H) 25- by 90-mm shell vials with no. 4 stoppers; (I and 1) I5-cm long CaCl2
U-tube; and (K) Nesbitt absorption bulb. Use neoprene stoppers and gum rubber
tubing for all connections. Coat all rubber tube connections lightly with silicone
lubricant.
Items C through E can be ground-glass joint glassware if desired (Fig.
34-4). All joints are standard-taper 24/40. The following parts are needed: (C)
100-mL round-bottom flask (Coming 4320); (C-I) distilling adapter tube (Coming 9421), which contains inlet tube for bubbling C0z-free air into digestion acid
mixture; (D) Allihn condenser, -300-mm jacket length (Coming 2480); (E-1) distilling tube with suction side arm (Coming 9420) (side arm is connected to purifying traps); (E) graduated separator funnel (Coming 6382A). A heating mantle
and rheostat are used to heat the 100-mL digestion flask.
Provide a C0z-free carrier stream by releasing air from an air pressure line
through Valve A and passing it through soda-lime Tower B. Connect B in a glass
tube 4-mm o.d. that extends downward through Condenser D and dips about 1 cm
below the surface of the oxidizing acid in Digestion Flask C. Shorten the stem of
Funnel E to a length of about 9 em, and reduce the tip opening of the stem to a
diameter of about 2 mm. Adjust the position of the Funnel E to extend into D at
NELSON & SOMMERS
980
least 5 cm below the stopper to avoid contact between oxidizing acid and stopper. Lubricate Stopcock E with the digestion acid mixture or with syrupy H3P04
Regular stopcock lubricant should not be used on stopcocks.
Assemble the purifying traps, F to J, on a panel to provide stability. Fit the
vials of traps F, G, and H with no. 4 stoppers they have approximately 6 cm of
the bottom cut off to provide a tight seal with the vials. Reduce the tip openings
of the inflow tubes in F and G, but do not make them smaller than 1 mm in diameter, or sealing may occur. Fill traps F and G approximately two-thirds full with
50% KI solution and saturated Ag2S04, respectively. Adjust the inflow tubes so
that they extend into the solutions not more than 3.8 cm for Trap F and 1.3 cm
for Trap G; otherwise back pressure may develop and cause leaks in the system.
Fill Trap H not more than one-third full with concentrated H2S04, Prepare
the inflow tube for H from the barrel of a 5-mL pipette with the tip extending not
more than 1.3 cm into the acid (note that Trap H connects directly to Trap I).
Place a fiberglass disc in the bottom of the V-tube; and fill the right side, Trap [,
with 30-mesh (600 !lm) granular Zn for absorbing any acid fumes that escape
past H. Fill the left trap, Trap J, with anhydrous Mg(CI04)2, which absorbs water
from the carrier stream containing evolved CO2 before it enters K.
Fill the Nesbitt absorption bulb K with any good, self-indicating absorbent
having a high capacity for absorbing CO2, Indicarb and Mikhobite are excellent
for this purpose. When filled as shown in Fig. 34--4, the bulb contains successively a 3-cm layer of 8- to 14-mesh (1.4-2.36 mm) absorbent, a 2-cm layer of
14- to 20-mesh (0.85-1.4 mm) absorbent, and a l-cm overlayer of anhydrous
Mg(CI04)2, with a wad of glass wool above and below the column.
Reagents
1. Digestion acid mixture: Pour 600 mL of concentrated H2S04 into 400
mL of 85% H3P04 , cool the mixture, and store it in a glass-stoppered
bottle. Keep the bottle well stoppered to prevent absorption of water
vapor.
2. Potassium dichromate, reagent grade.
3. Potassium iodide solution, 50%: Dissolve 100 g of KI in 100 mL of
water.
4. Silver sulfate solution, saturated.
5. Carbon dioxide absorbent, self-indicating, 7- to 14- (1.4-2.8 mm) and
14- to 20-mesh (0.85-1.4 mm) size; Suitable materials are Mikhobite
(G. Frederick Smith Chemical Co., Columbus, OH), Caroxite or Indiearb (Fisher Scientific, Pittsburgh, PA), or Ascarite (Arthur H. Thomas
Co., Philadelphia).
6. Soda lime, 8- to 14-mesh size (0.85-1.4 mm).
7. Granular Zn, <30-mesh 600 !lm)size.
8. Anhydrous magnesium perchlorate (Anhydrone, Dehydrite, or equivalent).
Procedure
Place a finely ground soil sample containing 20 to 40 mg of C (usually
0.5-3 g of oven-dry soil) into digestion flask C, and add about 1 g of K2Cr207'
981
Wash down the neck of the flask with 3 mL of distilled water, and connect the
flask to Condenser D. Weigh the Nesbitt bulb ("Comments" under "MediumTemperature Resistance Furnace Methods" and the following "Comments" section), attach it to the system, and immediately open the valve at the top of the
bulb. Pour 25 mL of the digestion acid mixture into Funnel E above the condenser, and cover the funnel with a small beaker. Open StopcockE, allow the acid
to flow through D into Flask C, and close the stopcock immediately to prevent
loss of CO2, Adjust the air delivery tube that passes through D into C so that its
tip extends not more than 1 cm into the acid during digestion.
At this point, tum on the cooling water. Adjust the carrier stream to a flow
rate of about 2 bubbles/s, and maintain this rate during digestion. Place the heating mantle around the flask or apply a flame 5 to 6 cm high, and bring the sample to boiling in 3 or 4 min. If Cl- is high, heat the mixture slowly at first, and
bring it to boiling in about 5 min. Continue gentle boiling, avoiding excessive
frothing, for a total heating period of 10 min. Reduce the rate of healing if visible white fumes of S03 occur above the second bulb of D during digestion.
Remove the heating mantle or flame at the end of the digestion period, and
aerate the system for 10 min at the rate of 6 to 8 bubbles/so When aeration is complete, shut off the air stream, and disconnect the digestion flask from the condenser. Close the stopcock on the Nesbitt bulb, and disconnect it from the system.
Brush the bulb with camel's hair to remove any lint and dust, and weight it immediately. Make a blank determination, using the identical procedure, but without
sample. Add four to five glass beads to the blank to prevent bumping. The calculation is as follows
Total C, % =
[g CO2, sample] - [g CO2, blank]

x 0.2727 x 100
g water-free soil
[5]
Comments
Soil samples should be ground to pass through a sieve with openings 0.5
mm or smaller in diameter. This is necessary to reduce errors due to the presence
of occasional fragments of carbonate minerals in a predominantly noncalcareous
matrix.
A single analysis, involving all operations from weighing the sample to calculation of results, requires 25 min. By using two sets of apparatus, one may analyze two samples concurrently, thereby reducing the overall time required to 15
min per determination, provided the digestion phase of one sample coincides with
the aeration phase of the other.
Because CO2 absorption bulbs change weight on standing overnight or for
longer periods, it is necessary to bring the bulb to constant weight by the following procedure before beginning C or blank determinations. Without being
weighed, the bulb should be connected to the system, all reagents (but no soil)
should be added to the digestion flask, and the apparatus should be operated as
directed for sample determinations. After aeration, the bulb should be detached
and weighed, and this weight should be used as the initial (constant) weight of the
bulb. See "Comments" under "Medium-Temperature Resistance Furnace Methods" for additional comments on care and use of CO2 absorption bulbs.
NELSON & SOMMERS
982
Blank determinations have ranged from 0.8 to 1.2 mg of CO2, for which an
average value of 1.0 mg has been used. If blanks are found to be high, preaeration may be necessary. The system may be preaerated by placing the digestion
flask (containing all materials except the digestion acid) in position for digestion, disconnecting the rubber tube between D and F, opening Valve A, and
directing a stream of C0z-free air (about 10 bubbles/s) into C and through D for
2 min (spattering of the contents in C must be avoided). The air flow is then readjusted to about 2 bubbles/s, D is connected to F, and the analysis is performed as
directed.
The H2S04 in the Trap H should be renewed at the beginning of each day's
operation or more often if frothing occurs. The KI solution in Trap F has a high
capacity for absorbing Cl-, and the need for its renewal is indicated by the first
trace of an AgCI precipitate in Trap G.
The Nesbitt absorption bulb, when filled as described, weighs about 125 g
and will absorb about 10 g of CO2, equivalent to about 100 determinations averaging 100 mg of CO 2 each.
When the apparatus is idle overnight or for longer periods and the Nesbitt
bulb is detached, the tube connecting J and K should be clamped off to prevent
entrance of water vapor into the desiccant in Trap J.
A titrimetric procedure for CO 2 determination is readily adaptable to the
above procedure (Fig. 34-4). Replace the Nesbitt bulb with a 250-mL sidearm
Erlenmeyer (filtering flask) fitted with a no. 61/2 stopper containing a 22-cm by
14-mm diam. glass tube. This bubble tower should extend to within 0.5 cm of the
flask bottom and should be filled with glass beads. Through the glass tube, 25 mL
of 1 M KOH should be added, and the soil sample should be oxidized as described previously. The acid-base indicator Tropaeolin 0 (e.g., Sigma Chemical
Co., St. Louis, MO; Aldrich Chemical Co., Milwaukee, WI; Fisher Scientific,
Pittsburgh, PA) can be added to the KOH to ensure that sufficient alkalinity
remains after trapping the CO2 evolved. After oxidation, the KOH is washed
from the bubble tower with distilled water, treated with 5 mL of saturated BaCl2
and several drops of phenolphthalein, and titrated with standard HC!. The data are
calculated from
'"
tIC ,70
Of
.0 a
m4,lank - mi-sample
.
g soIl
NHCl
06
[6]
The basic principle of the above wet-combustion procedure has been used in
developing tubelflask digestion methods for total C analysis. In essence, these
methods involve mixing a soil sample, solid K2Cr07, and 3:2 concentrated
H2S04 :concentrated 85% H3P04 in a sealed vessel containing NaOH to trap CO2
evolved from oxidized organic C and solubilized carbonates. Snyder and Trofymow (1984) and Coughtrey et a!. (1986) describe methods using modified culture
tubes and Erlenmeyer flasks, respectively. The sample containers are heated in a
digestion block or on a hot plate at about 120C for 2 h followed by diffusion of
CO 2 into an alkali trap for 12 h. The amount of OH- remaining is determined by
titration. These methods also have the advantage of being readily adapted to
determination of both 12C and 14C in the same sample. In addition, they are rapid,
983
provide comparable data to established methods and use relatively inexpensive

equipment.
ORGANIC CARBON
Introduction
Carbon is the chief element present in soil organic matter, comprising from
48 to 58% of the total weight. Therefore, organic C determinations are often used
as the basis for organic matter estimates through multiplying the organic C value
by a factor. For many years the Van Bemmelen factor of 1.724 was used based on
the assumption that organic matter contains 58% organic C. However, a number
of studies have shown that the proportion of C in soil organic matter is highly
variable for a range of soils and there is no factor appropriate for all soils. If a factor must be selected for converting organic C concentrations of organic matter
contents, values of 1.9 and 2.5 for surface and subsoils, respectively, are most
appropriate (Broadbent, 1953). The factor varies not only from soil to soil but
also between horizons in the same soil. This finding suggests that it is most
appropriate to determine and report the organic C in a soil rather than convert the
analytically determined organic C value to organic matter content through use of
an approximate correction factor.
o.rganic C may be determined by: (i) analysis of a soil for total C and inorganic C and subtraction of the inorganic C concentration for the total C content,
(ii) a total C determination on the sample after destruction of inorganic C, and
(iii) oxidation of organic C compounds by Cr20r- and subsequent determination
of unreduced Cr2o.1- by oxidation-reduction titration with Fe2+ or by colorimetric methods. Table 34--2 summarizes the principles, advantages, and disadvantages of several methods for determination of organic C in soils. All current methods have inherent problems associated with them, and the investigator should use
the method most applicable for the soils to be analyzed and the required accuracy of the results.
In this section, procedures are described for the determination of organic C
in both calcareous and noncalcareous soils based on the difference between total
C and inorganic C concentrations. Two methods also are given for organic C estimations based on destruction of inorganic C compounds prior to total C determinations. In addition, two rapid dichromate oxidation procedures are described.
The Walkley and Black (1934) method that oxidizes organic C through heat-ofdilution of H2SO.4 is given because it is simple, rapid, widely used, and requires
minimal equipment even though the results obtained cannot be considered quantitative. Many soil testing and soil survey personnel have need for a method that
gives an approximate organic C concentration. A tube digestion techniques (Nelson & Sommers, 1975) that involves extensive heating of the chromic acid-soil
mixture is given because it is quantitative, rapid, and represents the best combination of digestion reagents, heating procedure, and titration reagents of the modem dichromate methods. Dichromate procedures are widely used in soil investigations because of their simplicity and rapidity compared with wet or dry com-
Dichromate oxidation
with external heat
Total C and inorganic C are determined on separate

samples: organic C =total C - inorganic C
Difference between
total C and inorganic C
Determined as total C
after removal of
inorganic C
Dichromate oxidation
without external heat
Useful if total C and
inorganic C are routinely determined
Accurate if dolomite
is absent from soil
Advantages
Total C is determined in soil sample after removal

of inorganic C with an acid pretreatment:
organic C = total C
Dichromate oxidizes organic C to CO2 in acid
Very rapid and simple,
medium; amounts of Cr20:r- reduced is quantino special equiptatively related to organic C present; not all
ment needed
organic C in samples is oxidized when external
heat is omitted, and a correction factor is required
This is the same as the dichromate method above
Rapid and simple, comexcept that all organic C in the sample is oxidized,
plete oxidation of orand no correction factor is required
ganic C occurs
Principle
Method
Table 34-2. Comparison of methodologies used for determination of organic C in soils.
Incomplete oxidation of organic C necessitates use of a

correction factors, which often results in erroneous
values; chloride, Fe 2+, and Mn02 interfere with method; it assumes soil organic C has an average valence
of 0; variable recovery of C from carbonized materials
Chloride, Fe 2+, and Mn02 interfere with method; some
specialized equipment is needed; it assumes soil organic C has an average valence of 0; variable recovery of
C in carbonized materials
Two separate analyses are required, total C determination

requires special equipment, organic C calculated by
difference has some inherent error
Not all dolomite in soil may be removed by acid treatment, specialized equipment needed.
Disadvantages
Roo
oz
985
bustion. However, the rapid K2Cr207 methods are subject to interference by oxidizable or reducible soil constituents such as Cl-, Fe2+, and Mn02'
Organic Carbon as Calculated from Total Carbon Determinations

Methods previously described for total C are basic for many of the procedures used to determine organic C in soils. However, soils may contain both
organic and inorganic C and, thus, total C analysis procedures recover both forms
of C. In noncalcareous soils and soils not recently limed, the total C can be considered to be organic C. With calcareous or recently limed soils, organic C may
be estimated as the difference between total C and inorganic C concentrations.
Organic Carbon in Noncalcareous Soils

Prepare soil samples, and conduct a total C determination by dry or wet
combustion using titrimetric, gravimetric, volumetric, infrared, or thermal conductivity techniques to quantitate evolved CO2 as described in "Total Carbon."
Report the total C determined as percentage organic C in the sample (i.e., total C
=organic C).
Organic Carbon in Calcareous Soils

Prepare soil samples, and conduct a total C determination on the sample by
dry or wet combustion techniques as described in "Total Carbon." Determine
inorganic C on a separate sample by one of the quantitative methods described in
Chapter 15 (Loeppert & Suarez, 1996). Calculate the percentage organic C in the
sample from the relationship
organic C, %
=% total C -
% inorganic C
[7]
Wet and Dry Combustion Techniques for Direct Measurement

of Organic Carbon in Calcareous Soils
In contrast to noncalcareous soils, inorganic C must be removed from calcareous or recently limed soils before the analysis if wet or dry combustion techniques are used to directly measure the organic C present.
Inorganic C is conveniently removed before wet combustion by pretreating
the sample contained in a digestion flask with a mixture of dilute H2S04 and ferrous sulfate (FeS04)' The FeS04 is added to the mixture to minimize oxidation
and decarboxylation of organic matter by added H2S04 or by Mn02 present in
soil (Allison, 1960). After pretreatment, the digestion flask containing soil is
transferred to the combustion train, and a total C determination is carried out as
described in "Total Carbon by Wet Combustion."
Inorganic C removal is generally more difficult before determination of
organic C by dry combustion techniques. Treatment of soil at room temperature
with sulfurous acid (H 2S03) followed by heating to remove excess H 2S03 is normally used to decompose inorganic C compounds (Piper, 1942, p. 221-222;
Bremner, 1949); however, several difficulties are apparent with the procedure.
NELSON & SOMMERS
986
Little destruction of organic matter occurs during room temperature treatment of

samples with HZS03, but some decarboxylation is possible as the sample is heated (Bremner, 1949). It is difficult to decide when all inorganic C has been
removed and when H ZS03 treatment should be discontinued. It is doubtful that
dolomite is completely decomposed by the relatively mild HzS03 treatment
employed (Allison, 1965). Nommik (1971) suggested that inorganic C may be
effectively removed from soil samples by treatment with a metaphosphoric acid
solution for 30 min at room temperature and 30 min at 130C. However, Nommik's procedure has not been evaluated with a variety of soils.
Test for Presence of Inorganic Carbon

Place finely ground soil on a spot plate, and moisten with a few drops of
water. Add 4 M HCI dropwise to the wetted sample, and observe any effervescence. Allow sufficient time for dolomite to react (-5 min). If inorganic C is
absent from the soil, proceed with organic C (total C) analysis as per the section
on "Total Carbon." If inorganic C is present or the test is not definitive, proceed
as described below.
Pretreatment Prior to Wet Combustion
Special Apparatus6
Reagents
1. Digestion reagent for carbonates (HzS04-FeS04): Dissolve 57 mL of
concentrated HzS04 and 92 g of ferrous sulfate heptahydrate (FeS04
7HzO) in 600 mL of deionized water, cool, and dilute to 1 L.
2. Potassium dichromate, reagent grade, pulverized.
3. Other reagents as described in "Reagents" under "Wet Combustion
Method."
Procedure
Prepare soil samples as described in "Procedures" under "Wet Combustion
Method." Transfer a sample of known water content and containing 20 to 40 mg
of C (but not more than 2 g of soil) to the flask used for the wet combustion apparatus (e.g., a 100-mL Kjeldahl digestion flask or standard taper round bottom).
Using 3 mL of the HZS04-FeS04 digestion acid, wash down any soil that adheres
to the neck of the flask. Place the flask in a rack or beaker, and allow the sample
to digest at room temperature with occasional turning of the flask for at least 20
min or until effervescence appears to cease. Then hold the flask upright over a
flame 2 cm high, and boil the contents slowly for 1.5 min to destroy any remaining carbonate. Rotate the flask continuously during boiling to avoid excessive
frothing. Allow the sample to cool.
Insert a long-stemmed funnel into the flask, and add 2 g of pulverized
KZCrZ07. Immediately connect the flask to the reflux condenser (Fig. 34-4), and
See the special apparatus listed in "Special Apparatus" under "Wet Combustion Methods."
987
proceed with the determination of organic C as directed in "Procedure" under

"Wet Combustion Method" beginning with the third sentence.
Report the C present in the pretreated sample as percentage organic C.
Comments
The 3 mL of 1 M (2N) HZS04-5% FeS04 used in this procedure replaces
the 3 mL of distilled water used in the total C procedure described in "Procedure"
under "Wet Combustion Method." Three mL of this reagent adds 3 millimoles (6
meq) W, which will neutralize 0.3 g of CaC03 (Le., 15% CaC03 in a 2-g soil
sample). An appreciable excess of acidity must be present to ensure complete
decomposition of carbonates. Rather than using >3 mL of the 1 M reagent for
soils containing more than -10% CaC03 equivalent, it is preferable to use 3 mL
of a 1.5 M or even a 2 M HZS04-5% FeS04 reagent.
Pretreatment Prior to Dry Combustion
Special Apparatus'
Reagents
1. Sulfurous acid, approximately 5%: Bubble SOz through distilled water
until a saturated solution is obtained. Keep the bottle well stoppered to
prevent rapid loss of SOz.
2. Sodium hydroxide (NaOH), pellets.
Procedure
Transfer a soil sample that passes through a 100- or 140-mesh (106-150
/lm) sieve (see "Comments" under "Medium-Temperature Resistance Furnace
Method") and of known water content to a nonporous combustion boat that has
been previously ignited and cooled. Based on an estimate of inorganic C present,
treat the sample with an excess of a 5% HZS03 solution. After several hours,
remove the water and excess HZS03 by leaving the boat overnight in an evacuated desiccator containing NaOH pellets. Repeat the treatment until evolution ceases on addition of HZS03
Proceed with the determination of organic C by one of the dry combustion
methods (see "Medium-Temperature Resistance Furnace Method" or "HighTemperature Induction Furnace Method"). Report the C present in the pretreated
samples as percentage organic C.
Organic Carbon in Soil Extracts

Special Apparatus
See the special apparatus listed in "Special Apparatus" under "Wet Combustion Method."
7 See the special apparatus listed in "Special Apparatus" under "Medium-Temperature Resistance
Furnace Method" and "Special Apparatus" under "High-Temperature Induction Furnace Method."
NELSON & SOMMERS
988
Reagents
See the reagents listed in "Reagents" under "Wet Combustion Method."

Procedure
Place an aliquot of the extract (10 to 50 mL, depending on the organic C

content) in a l00-mL Klejdahl digestion flask, and add 1 mL of the H2S04-FeS04
reagent. Immerse the bulb of the flask in boiling water, and direct a stream of dry,
dust-free air onto the surface of the liquid in the flask. Reduce the volume of solution in the flask to 3 mL or less. Add five or six glass beads and 1 g of K2Cr207
to the flask, and proceed with the determination of organic C as directed in "Procedure" under "Wet Combustion Method."
Comments
Drying of extracts is best accomplished in l00-mL flasks of the Kjeldahl

type. A 2-L beaker conveniently holds four flasks.
Rapid Dichromate Oxidation Techniques
Introduction and Principles
Schollenberger (1927) first proposed that the organic matter in soil may be
oxidized by treatment with a hot mixture of K2Cr207 and H2S04 according to Eq.
[8].
2 Cr20~- + 3 CO + 16 H+ =4 cr3+ + 3 CO2 + 8 H20
[8]
After the reaction, the excess Cr20~- is titrated with Fe(~h(S04)2 6H20, and
the Cr201- reduced during the reaction with soil is assumed to be equivalent to
the organic C present in the sample. It must be emphasized that all methods based
on determination of Cr201- remaining or cr3+ formed assume that C in soil
organic matter has an average valence of zero. Although most dichromate oxidation procedures described since the original Schollenberger method have
involved chromic acid solutions or mixtures of concentrated H2S04 and aqueous
K2Cr207 solutions (Table 34-3), the use of other oxidants has been proposed.
Degtjareff (1930) suggested that a mixture of H20 2 and chromic acid be used to
oxidize organic matter. However, Walkley and Black (1934) conclusively established that the addition of H20 2 to chromic acid procedures gave fictitiously high
values for organic C because H20 2 reduced Cr201- in acid solution. Edson and
Mills (1955) suggested that organic C be oxidized by Cl2 (1 % solution) and residual Cl2 determined colorimetrically by reaction with o-tolidine (C14Hl~2)' The
intensity of yellow color was proportional to organic C oxidized. Others have
suggested that organic C in aqueous extracts of soil can be determined by oxidation with a Mn(III)-pyrophosphate complex (Bartlett & Ross, 1988). The loss of
color from Mn(III) is proporti~nal to the amount of organic C oxidized. Tmsley
(1950) and Kalembasa and Jenkinson (1973) proposed that the chromic acid mixture used to oxidize organic C compounds be 3 and 1.5 M (9 and 4.5 N), respec-
0.058
0.066
0.055
0.027
0.027
0.045
0.033
0.066
0.033
0.055
0.066
0.145
0.066
K2Cr20 7
18
9
12
11
7.2
10
9
10.8
10.8
12
10.8
10.2
10.8
H2SO 4
t Reagents used by Bremner and Jenkinson (1960a).

:j: As described by Nelson and Sommers (1982).
Schollenberger (1927)
Tyurin (1931)
Walkley-Black (1934)
Anne (1945)
Tinsley (1950)t
Mebius (1960)
Kalembasa & Jenkinson (1973)
Nelson & Sommers (1975)
Modified Mebius:j:
Heanes (1984)
Yeomans & Bremner (1988)
Ciavatta et al. (19898)
Soon & Abboud (1991)
Method
1.67
H3P04
Digestion reagent concentrations
1.00
0.50
0.46
0.67
0.42
0.067
0.67
0.67
0.50
0.67
0.77
0.67
v:v
Ratio of H2O/acid
Table 34-3. Characteristics of dichromate methods for determining organic C in soils.
Tube heated by flame at 175C for 90 s

Flask with funnel boiled at 140C for 5 min
Flask with no external heat, max. temp is 120C
Flask with condensor refluxed at 178C for 5 min
Flask with condenser refluxed for 2 h at 150C
Flask with condensor refluxed for 30 min at 159C
Flask with condenser refluxed for 20 min at 165C
Tube heated in block at 150C for 30 min
Flask with condenser refluxed at 150C for 30 min
Special flask heated over flame at 1160C for 10 min
Digestion conditions
1.4-1.9
8.5
1.6-4.2
1.3
0.8-3.1
1.2-1.8
0.8
3.5
1.0-3.6
4.1
1.0-4.4
5.4
2.7
CV,%
Reported precision
tol
::c
(=)
I::'
z
~
990
NELSON & SOMMERS
tively, with respect to H3P04 (Table 34-3). There is no evidence, however, to suggest that oxidation mixtures containing H3P04 are more efficient in oxidizing
organic matter than K2Cr20TH2S04 mixtures. The oxidizing mixtures used in
most published methods are between 0.0267 and 0.0583 M (0.16 and 0.35 N) in
K2Cr207 and 7.5 and 12.5 M (15 and 25 N) in H2S04 (Table 34-3). However,
Tyurin (1931) Tinsley (1950), Nelson and Sommers (1975) and Yeomans and
Bremner (1988) used an aqueous H2S04-water mixture that was 0.145 M (0.87
N) in K2Cr207. Schollenberger (1927) used concentrated H2S04 (-18 M or -36
N) as the solvent for K2Cr207.
Rapid dichromate oxidation techniques have employed heating times and
temperatures that vary from no external heat to extensive boiling of chromic acid
mixtures. Schollenberger (1927) suggested that the soil-H2S04-K2Cr207 mixture
be heated in a Pyrex test tube over a flame until the solution temperature reached
175C at which time heating was discontinued. Later investigators realized that
the time and temperature of heating were critical and must be standardized to
insure that a constant proportion of soil organic matter was oxidized and that a
consistent amount of dichromate was thermally decomposed during the digestion.
Degtjareff (1930), Tyurin (1931), Schollenberger (1945) and Jackson (1958) suggested that the soil-chromic acid mixtures be heated for defined periods (5-10
min) in test tubes submerged in H2S04 or oil baths maintained at prescribed temperatures (140-170C).
Walkley and Black (1934), however, proposed that the heat of dilution of
H2S04 (120C) was satisfactory for oxidizing 75% of the organic C in soils and
that a correction factor could be used to account for incomplete digestion. Several investigators have found that an extended period of heating is required to
obtain quantitative oxidation of soil organic C by chromic acid (Anne, 1945;
Tinsley, 1950; Mebius, 1960; Kalembasa & Jenkinson, 1973; Heanes, 1984).
High digestion temperatures (>145C) lead to thermal decomposition of dichromate and resultant high blank values (Tinsley, 1950; Metson et aI., 1979; Heanes,
1984). Clay minerals have been reported to catalyze the thermal decomposition
of Cr20,y- (Walkley, 1947) but a recent study has shown little thermal decomposition when high clay soils free of organic matter were heated with K2Cr20T
H2S04 for 60 min at 125 or 145C (Heanes, 1984). Digestion temperature is normally regulated by the ratio of water/H2S04 in the mixture (Table 34-3) and the
temperature rises as water vapor is lost during heating. Tinsley proposed that cold
finger condensers fitted on Erlenmeyer flasks be used to prevent loss of water
during digestion, whereas other investigators have used Erlenmeyer flasks fitted
with Liebig condensers. Heating times employed in reflux methods have varied
from 20 min to 2 h. Ciavatta et ai. (1989) have recently proposed that a chromic
acid mixture successfully oxidizes soil organic C when samples are heated in a
200 mL narrow-necked digestion flask by direct flame at 160C for 10 min. The
neck of the flask serves to reflux the digestion reagents.
Nelson and Sommers (1975) proposed that organic C could be determined
by heating soil-chromic acid mixtures under reflux in 50 mL Folin-Wu nonprotein nitrogen tubes placed in an aluminum block on a hot plate. Heating time and
digestion temperature recommended were 30 min and 150C, respectively. Subsequently, a number of other similar tube digestion methods have been proposed
991
for estimation of organic C all employing 100-mL tubes. Heanes (1984), Yeomans and Bremner (1988), and Soon and Abboud (1991) recommended heating
for 30 min at 135C, 170C, and 155C, respectively. Yeomans and Bremner
(1988) and Soon and Abboud (1991) specify the same digestion reagents as Nelson and Sommers (1975), i.e., 5 mL of 0.167 M K2Cr207 and 7.5 mL of concentrated H2S04, whereas Heanes (1984) recommends 10 mL of 0.167 M K2Cr207
and 20 mL of H2S04, Tube digestion procedures have been reported to yield
organic C values that approximate those from dry and wet combustion techniques.
Diphenylamine was the first oxidation-reduction indicator used for the
titration of excess Cr20j- with Fe2+ (Schollenberger, 1927, 1931, 1945; Allison,
1935). Later studies suggested that the diphenylamine end point could be
improved by addition of H3P0 4, NaF, or HF before titration (Schollenberger,
1931, 1945; Walkley & Black, 1934), and these substances were widely used in
dichromate titrations. Peech et al. (1947) established that barium diphenylamine
sulfonate (diphenyl-4-sulfonic acid) in combination with H3P04 was as effective
and more stable compared with diphenylamine (C 12H ll N) and has been used as
an indicator in other procedures (Tinsley, 1950). Jackson (1958) recommended
that o-phenanthroline (C 12HgN2) be used as an indicator in Cr20j- titrations
because the color change (formation of the complex with Fe2+) occurs at higher
oxidation-reduction potential compared with diphenylamine. A mixture of 0phenanthroline and H3P04 is normally used to give a good end point; however,
the indicator has been successfully used without H3P0 4 addition. A problem with
o-phenanthroline is that the indicator tends to be absorbed by some suspended
soil materials, thereby obscuring the color change at the end point. therefore, the
diluted chromic acid-soil mixture is often passed through an acid fast filter paper
on Buchner funnel before titration. Simakov (1957) proposed that N-phenylanthranilic acid (C13HnHO) be used as an indicator in Cr20j- titrations with Fe2+.
Mebius (1960) confirmed that N-phenylanthranilic acid gives a very sharp and
clean end point and this compound is currently the indicator of choice for Cr20jtitrations.
Other methods of titration not involving oxidation-reduction indicators
have been used to estimate reacted Cr20j-. One approach is to add a slight excess
of Fe 2+ to the Cr20j--H2S04-Soil mixture and then back-titrate the Fe2+ with
KMn04 (Smith & Weldon, 1941). In this titration procedure, the only reagent that
requires standardization is KMn04 if the same amounts of Fe2+ and Cr20j- are
added to both samples and blanks. The end point in the titration of Cr20j- with
Fe2+ also may be estimated very accurately by monitoring the oxidation-reduction potential with platinum and calomel electrodes attached to a potentiometer
(Raveh & Avnimelech, 1973). The end point of the titration involves a potential
change of -400 mV with 0.02 mL of titrant.
The amount of Cr20j- remaining after reaction with soil organic matter
also may be estimated by colorimetry after removal of soil by filtration or centrifugation (Carolan, 1948). Perrier and Kellogg (1960) proposed that any possible interference of cr3+ in Cr20j- determination be eliminated by dilution and
subsequent reaction of excess dichromate with s-diphenylcarbazide (C13H14N40)
to yield a violet colored complex with an absorption maxima at 540 nm. Con-
NELSON & SOMMERS
versely, colorimetry has been widely used to determine the amounts of cr3+
formed from the reaction of Cr20.y- with soil (Wilde, 1942; Graham, 1948; Carolan, 1948; Datta et aI., 19862; Sinha & Prasad, 1970; Sims & Haby, 1971;
DeBolt, 1974; Gupta et aI., 1975; Baker, 1976; Heanes, 1984). The green color
due to cr3+ is normally quantitated at wavelengths of 590 to 625 nm and the
absorbance is usually related to organic matter concentrations in soil by a standard curve prepared from sucrose (Graham, 1948; Sims & Haby, 1971; DeBolt,
1974; Heanes, 1984). Baker (1976) used a probe colorimeter to measure cr3+
absorbance directly in the reaction vessel after centrifugation, thereby avoiding a
transfer into a spectrophotometer cuvette. From a comparison of the methods that
quantitate Cr20.y- and those that determine cr3+, Metson (1965) concluded that
measurement of cr3+ is the preferred procedure.
Dichromate methods that use heat of dilution or minimal heating do not
give complete oxidation of organic compounds in soil although the most active
forms of organic C are converted to CO2, Walkley and Black (1934) found that
on the average about 76% of the organic C in 20 soils was recovered by the heat
of dilution procedure, and they proposed that a correction factor of 1.32 be used
to account for unrecovered organic C. However, the actual recoveries of organic
C from the soils tested varied from 60 to 86%. Schollenberger (1945) reported
that the Walkley and Black procedure oxidized an average of 79% (range
70-86%) of organic C in soils he studied. Allison (1960) reviewed available
information on the recovery of organic C in a wide variety of soils by the Walkley and Black procedure and showed that the average recovery with different
groups of soils varied from 63 to 86% and that the correction factor varied from
1.16 to 1.59. Table 34-4 gives data on the correction factor found to be required
for the Walkley and Black procedure in investigations carried out during the past
30 yr. Recoveries of organic C by the Walkley and Black technique were highly
variable, and the correction factor appropriate for individual soils varied from 1.0
to 2.86. The average correction factor appropriate for a group of soils varied from
1.03 to 1.41. This data clearly show that Cr20~--H2S04 methods that involve
minimal heating give variable recovery of organic C from soils. An average correction factor found for a group of soils may be applicable to the "average" soil
in the group but will give erroneous values for many soils in the group. Therefore, procedures such as the Walkley and Black should be considered to give
approximate or semi-quantitative estimates of organic C in soil because of the
lack of an appropriate correction factor for each soil analyzed. If an experimentally determined correction factor is not available for a particular groups of soils,
the use of 1.3 as the factor appears most reasonable over a range of soils. Methods that involve extensive heating, such as those of Tinsley (1950), Mebius
(1960), Nelson and Sommers (1975), Heanes (1964) or Yeomans and Bremner
(1988) do not require a correction factor because all of the organic C in the soil
is oxidized to CO2. However, methods that involve minimal heating (e.g., Schollenberger, 1927; Tyurin, 1931) require a small correction factor (e.g., 1.15) to
account for unoxidized organic C.
The rapid dichromate methods are subject to interferences by certain soil
constituents that lead to spurious results with some soils (Walkley, 1947). Chloride, ferrous iron and higher oxides of Mn have been shown to undergo oxida-
CARBON AND ORGANIC MAllER
993
Table 34-4. Correction factors for organic C in surface soils not recovered by the Walkley-Black
method.
Reference
Origin
of samples
Tinsley (1950)
Bremner & Jenkinson (1960a)
Kalembesa & Kenkinson (1973)
Orphanos (1973)
Richter et at. (1973)
Bornemisza et at. (1979)
Rhodes et at. (1981)
Richardson & Bigler (1982)
England
England
England & Wales
Cyprus
Argentina
Indiana
Costa Rica
Sierra Leone
North Dakota
Heanes (1984)
Amacher et at. (1986)
Gillman et at. (1986)
Australia
Louisiana
Queensland
Willet & Beech (1987)

Lowther et at. (1990)
Australia
Australia
Alberta
t
*
'II
Number
of soils
studies
Organic C recovery, %
Range
Average
10
15
22
12
12
10
50
10
21
77-92
27-92
46--80
69-79
79-87
44-88
69-81
93-100
35-91
83.6
84
12
179
450
85-98
46--87
65-95
30
38
39
60-144
74-102
62-87
77
75'
83
79
75
97
88
92
71
76
8111
85
88
71.4
Average
correction
factor
1.20
1.19
1.30
1.30
1.20
1.27
1.33
1.03
1.33t
1.13*
1.09
1.41
1.32
1.24
1.18
1.14
1.40
Low C samples.
Other samples.
Soils derived from basalt, alluvium, or beach sand.
Soils derived from granite or metamorphic rocks.
tion-reduction reactions in chromic acid mixtures leading to incorrect values for

organic C. The presence of significant amounts of Fe2+ or Cl- in soil will lead to
a positive error, whereas reactive Mn02 in soil samples will result in a negative
error and low values for organic C.
Chloride interferes with dichromate methods through the formation of
chromyl chloride, as indicated in Eq. [3], which results in consumption of
Cr20?-. Chloride interference may be eliminated by washing the soil free of Clbefore analysis or by precipitating the Cl- as AgCl by addition of Ag2S04 to the
digestion acid (Walkley, 1947; Quinn & Salomon, 1964; Gupta et aI., 1975).
Alternatively, Walkley (1947) found that Eq. [9] may be used to correct organic
C values for soils having CUC ratio of ~5.1
organic C in soil (%) = (apparent % C in soil) - (% CU12)
[9]
It has recently been reported that Ag2S04 addition did not eliminate Clinterference in a low temperature tube digestion method and that an assay for Clcoupled with stoichiometric correction for chromyl chloride loss is necessary for
accurate estimates of organic C (Heanes, 1984).
When present in soil, Fe2+ will be oxidized to Fe3+ by Cr20?-, as indicated
in Eq. [10], resulting in a positive error in the analysis, i.e., giving high values for
organic C content
[10]
994
NELSON & SOMMERS
Appreciable Fe2+ may be present in highly reduced soils, and errors may
result when dichromate methods are applied to undried samples of anaerobic soils
before drying (Lee, 1939). However, Walkley (1947) found that thorough air-drying of reduced soils before analysis resulted in oxidation of Fe2+ to Fe3+ and accurate determination of the organic C present. The amounts of Fe2+ present in wellaerated soils are so small relative to the amounts of organic C present that no
detectable interference is likely. Pyrite also is oxidized during treatment of soils
with dichromate and samples containing pyrite sulfur concentrations >0.29%
result in significant over estimation of organic C by the Walkley and Black
method (Willett & Beech, 1987). Metallic iron (FeO) present in soil samples also
may lead to positive interferences in dichromate methods, (Allison, 1935;
Heanes, 1984). Therefore, care should be taken to ensure that soils are not ground
with iron or steel equipment before analysis. The higher oxides of Mn (largely
Mn02) compete with Cr20j- for oxidizable substances when heated in an acid
medium according to Eq. [11].
[11]
Therefore, any reactive Mn02 present will give a negative error when soils are
analyzed by dichromate techniques. Although soils contain substantial amounts
of Mn02 and other higher oxides of Mn, Walkley (1947) and Heanes (1984) concluded that in most soils the quantity of reactive (reducible) oxides ofMn is small
because only the freshly precipitated Mn02 will take part in redox reactions.
Even in highly manganiferous soils, only a small fraction of the Mn02 present is
able to compete with Cr20j- for oxidation of organic C compounds. Therefore,
interference from Mn02 is not thought to be a serious error in the vast majority
of soils. In soils with large amounts of reactive Mn02' Walkley (1947) suggested
pretreatment of samples with the exact amount of FeS04 necessary to reduce the
amount of reactive Mn2 present prior to treatment with K2Cr207 and H2S04,
Other problems associated with dichromate methods involve assumptions
about the average oxidation state of organic C in soils (i.e., equivalent weight of
C) and recovery of highly reduced forms of organic C from soils. All dichromate
methods assume that the organic C in soil has an average oxidation state of zero
and an equivalent weight of 3 g per equivalent when reacted with dichromate
according to Eq. [8] even though no studies have been conducted to evaluate this
assumption. However, the fact that dichromate methods using extensive heating
give organic C values similar to those obtained with wet or dry combustion where
CO2 is determined directly suggests that this assumption is reasonably correct.
Dichromate methods that involve little or no external heating give very
poor recovery of organic C present in carbonized materials (e.g., charcoal,
graphite, coal, coke, and soot). For example, Walkley (1947) found that the Walkley and Black method recovered only 2 to 11 % of the organic C present in such
materials. In a detailed study, Bremner and Jenkinson (1960b) found that the
Walkley and Black method gave low recovery (0-57%) of organic C from carbonized materials, whereas methods involving external heat such as those of
Tinsley gave substantial (64-104%) and variable recovery or organic C from such
materials. Conversely, Heanes (1984) found that very little organic C in charcoal
995
or coke was oxidized by a tube digestion procedure at 135C. Other investigators

have found that the Walkley and Black procedure completely recovers C in
weathered coal seams, i.e., coal "blooms" (Kalisz & Sainju, 1991). These conflicting results suggest that recovery of organic C from carbonized materials is
highly dependent upon the characteristics of the materials and digestion conditions (i.e., temperature, reagent concentrations). It is appropriate to conclude that
dichromate methods cannot be used to quantitatively recover carbonized materials from soils or to discriminate between C in carbonized materials and C in soil
organic matter because organic C recovery varies with type of carbonized material and time and temperature of heating of the chromic acid mixture. Therefore,
unreliable results for organic C will be obtained if dichromate methods are
applied to soils containing significant amounts of carbonized materials. Dry combustion methods are most appropriate for soils containing large amounts of elemental C.
Walkley-Black Method
The Walkley-Black Method was described by Walkley (1946), Peech et al.
(1947) and Greweling and Peech (1960).
Reagents
1. Potassium dichromate, 0.167 M (1 N): Dissolve 49.04 g of reagentgrade K2Cr207 (dried at 105C) in water, and dilute the resclution to a
volume of 1000 mL.
2. Sulfuric acid, concentrated (not less than 96%): If Cl- is present in soil,
add AgzS04 to the acid at the rate of 15 g per liter.
3. Phosphoric acid, concentrated.
4. o-Phenanthroline-ferrous complex, 0.025 M: Dissolve 14.85 g of 0phenanthroline monohydrate and 6.95 g of ferrous sulfate heptahydrate
(FeS04 7H20) in water. Dilute the solution to a volume of 1000 mL.
The o-phenanthroline-ferrous complex is available under the name of
Ferroin from the G. Frederick Smith Chemical Co. (Columbus, OH).
5. Barium diphenylamine sulfonate: Prepare a 0.16% aqueous solution.
This reagent is an optional substitute for no. 4.
6. Ferrous sulfate heptahydrate (FeS04 7HzO) solution, 0.5 M (0.5 N):
Dissolve 140 g of reagent-grade FeS04 7H zO in water, add 15 mL of
concentrated sulfuric acid, cool the solution, and dilute it to a volume
of 1000 mL> Standardize this reagent daily by titrating it against 10
mL of 0.167 M (1 N) potassium dichromate, as described below.
Procedure
Grind the soil to pass through a 0.5-mm sieve, avoiding iron or steel mortars. Transfer a weighed sample, containing 10 to 25 mg of organic C, but not in
excess of 10 g of soil, into a 500-mL wide-mouth Erlenmeyer flask. Add 10 mL
of 0.167 M (1 N) KZCrZ07, and swirl the flask gently to disperse the soil in the
solution. Then rapidly add 20 mL to concentrated HZS04, directing the stream
into the suspension. Immediately swirl the flask gently until soil and reagents are
mixed, then more vigorously for a total of 1 min. Allow the flask to stand on an
NELSON & SOMMERS
insulated sheet for about 30 min. Then add 200 mL of water to the flask, and fIlter the suspension using an acid resistant fIlter paper (e.g., Whatman 540), if
experience shows that the end point of the titration cannot otherwise be clearly
discerned. Add three to four drops of o-phenanthroline indicator and titrate the
solution with 0.5 M (0.5 N) FeS04. As the end point is approached, the solution
takes on a greenish cast and then changes to a dark green. At this point, add the
ferrous sulfate heptahydrate drop by drop until the color changes sharply from
blue to red (maroon color in reflected light against a white background). Make a
blank determination in the same manner, but without soil, to standardize the
K2Cr207. Repeat the determination with less soil if >75% of the dichromate is
reduced.
Calculate the results according to the following formula, using a correction
factor ''/' =1.30 or a more suitable value found experimentally
2
Organic C, % = -. .:. (m_4.. . ; .; : 18=nk,--_m_Ls.. ; ; 8=m=ple: .:. .). .;.(M.. . . ; . ;Fe_+.:. . )..:....(0_.0_0-'3)'-('-lO_0....:.,.) x f
wt. water-free soil, g
[12]
Comments
The coefficient of variation for the Walkley-Black procedure has been
reported to vary between 1.6 and 4.2% (Table 34-3). Ferrous ammonium sulfate
also is a suitable titrant for excess Cr20?- in conjunction with the Walkley-Black
method. The Smith and Weldon (1941) modification involving complete reduction of Cr20:r- with Fe2+, and subsequent back-titration of excess Fe2+ with
Mn04" solution also may be used to estimate unreacted Cr20:r-. Other oxidationreduction indicators that have provided satisfactory results include barium
diphenylamine sulfonate and N-phenylanthranilic acid. The amounts of Cr20?reduced to Cr3+ by reaction with soil organic matter also may be estimated colorimetrically or by potentiometric titration with a ferrous ammonium sulfate solution. Grinding samples to <0.2 mm has been shown to reduce sampling errors and
the coefficient of variation even when relatively large sample sizes (1 g) are used
(Metson et aI., 1979). Heanes (1984) reported that reduction in particle size from
0.5 to 0.15 mm significantly increased recovery of organic C in 12 soils.
Thbe Digestion Method
Special Apparatus
1. Pyrex digestion tubes (lOO mL) sized for block digestor.

2. Block digestor: 40-tube Kjeldahl block digestor supplied by Technicon
Instruments Corp., Tarrytown, NY, or Tecator Inc., Herndon, VA, or
equivalent.
Reagents
1. Potassium dichromate solution, 0.167 M (1.0 N)-dissolve 49.025 of
K2Cr207 (dried at 140C) iIi 800 mL of distilled water and dilute the
solution with water to a volume of lOoo mL in a volumetric flask. This
is the primary standard for the procedure.
997
2. Concentrated sulfuric acid-specific gravity 1.84.

3. Ferrous ammonium sulfate solution 0.2 M (0.2 N)-Dissolve 156.8 g
of ferrous ammonium sulfate [Fe(NH4)z(S04)2 6H20] in 100 mL of
concentrated sulfuric acid and dilute the solution with water to a volume of 2 L in a volumetric flask. This solution must be standardized
daily because it undergoes slow oxidation.
4. Indicator solution-Dissolve 0.1 g of N-phenylanthranilic acid and 0.1
g of Na2C03 in 100 mL of distilled water.
Procedure
Weigh an amount of soil air dried and ground to <0.15 mm containing not
greater than 8 mg of organic C (usually 100--500 mg) into a clean, dry digestion
tube and add 5 mL of 0.167 M (1.0 N) K2Cr207 solution and 7.5 mL of concentrated H2S04. Place the tube in the digestion block preheated to 150C for exactly 30 min. Remove the digestion tube from the block and allow the samples to
cool for 30 min at room temperature. Quantitatively transfer the contents of the
tube to a 125-mL Erlenmeyer flask and titrate the sample with 0.2 M (0.2 N) ferrous ammonium sulfate solution using 0.2 mL of the N-phenylanthranillic acid
solution as the indicator. The color change at the end point is from violet to bright
green and is very rapid. An illuminated background is recommended for ease in
observing the end point and the titration should be performed using a 25-mL
burette calibrated at O.l-mL intervals and a variable speed magnetic stirrer and
teflon coated stiffing bar.
Each set of soil samples should be analyzed with two unheated reagent
blanks and two reagent blanks that are heated at the same time as the samples.
The unheated blanks are used to standardize the ferrous ammonium sulfate solution. The difference in titration values between heated and unheated blanks is
used to correct all sample titration values for the amount of dichromate consumed
by thermal decomposition during the heating process.
Computation of the organic C content of soil is performed as follows: (i)
subtract sample titration values (mLsoi/) from the average titration value of the
heated (boiled) blank (mL bb ), (ii) correct the resulting [mLbb - mL,.oil] value for
thermal decomposition of dichromate by dividing the difference in average titration value for unheated and heated blanks by the average titration value for the
unheated blank, multiplying the correction factor (normally 0.04-0.08) by the
[mLt,b - mL,.oil] value, and adding the product to the [mLt,b - mLsoi1 ] value (Eq.
[13]). The resulting value, labeled "A" is proportional to the amount of organic C
present in the soil, (iii) complete the calculation of organic C content using Eq.
[14]
where ub is unboiled blank and bb is boiled blank.

(,A....:.-)-,-(M---,F=e2~+)-'..(0_.0_O--,3)-O.(1_0---"-.0)
Organic C, % = -
wt. water-free soil, g
[14]
998
NELSON & SOMMERS
Comments
The coefficient of variation for the method has been reported as 3.5% (Nelson & Sommers, 1975). Coefficients of variation reported for other tube digestion
methods have ranged from 1.1 to 4.4% (Heanes, 1984; Yeomans & Bremner,
1988; Soon & Abboud, 1991). The precision of the method can be improved by
using a computer-aided automatic titration system (Yeomans & Bremner, 1988).
Colorimetric analysis of cr3+ also can be used to estimate the amount of dichromate that has reacted with organic C during tube digestion (Heanes, 1984; Soon
& Abboud, 1991). The potassium dichromate solution is the primary standard for
the method and care should be taken in its preparation. This solution is quite stable and may be stored at room temperature indefinitely. The ferrous ammonium
sulfate solution oxidizes slowly and thus must be standardized each time it is
used. Small particle size reduces the sampling error and increases recovery of
organic C. Heanes (1984) found that organic C values increased by about 2% as
particle size was reduced from 0.5 to 0.15 mm.
Thermal decomposition of dichromate occurs at temperatures exceeding
136C (Heanes, 1984) and the degree of decomposition is quite dependent upon
the heating conditions. Therefore, it is recommended that the digestion tubes by
dry before use to eliminate differences in acid/water ratio and that the heating
temperature and time be accurately controlled. A variety of temperatures varying
from 135 to 170C have been recommended for tube digestion methods (Table
34-3). When thermal decomposition of dichromate is accurately taken into
account with a heated blank, the four tube digestion methods have quantitatively
determined organic C in a variety of soils.
Interferences present in the Walkley-Black procedure also are a problem
with tube digestion methods. As a result of extensive heating, the tube digestion
methods give complete recovery of organic C from soils and, thus, do not require
a factor to account for incomplete oxidation of organic matter. Heanes (1984)
reported that little organic C in charcoal and coke was recovered by the tube
digestion procedure that he described.
The tube digestion technique can be used to estimate organic C in soil
extracts by carrying out the digestion with 1 or 2 mL of extract and 4 or 3 mL of
dichromate solution, respectively. It is essential that the acid/water ratio be maintained at 1.5 in the digest so the volume of dichromate solution must be reduced
as the volume of extract is increased. Both heated and unheated blanks should be
prepared using the same volume of blank extracting solution and the dichromate
solution as that employed for the extracts.
The modified Mebius method described by Nelson and Sommers (1982) is
recommended as an accurate and precise dichromate oxidation procedure for
those investigators not having access to a block digestor. The major advantage of
the tube digestion procedure is the decreased analysis time per sample because of
the relatively large number of samples (40) that can be heated at one time.
Comparison of Methods for Determining Organic Carbon
Most studies have shown that very good agreement is obtained when wet
combustion, dry combustion, and Van Slyke-Folch (1940) methods are used to
999
determine organic C in soils (Bremner & Jenkinson, 1960a; Kalembasa & Jenkinson, 1973; Nelson & Sommers, 1975). For this reason, wet and dry combustion
methods are normally considered to yield absolute values for organic C in soils
and other methods are calibrated against the combustion procedures.
A number of studies have been conducted to compare rapid dichromate oxidation methods with dry or wet combustion methods (Table 34-5). Many studies
have shown that the Walkley-Black method yields variable recovery of organic C
from soil, i.e., in some soils >95% of organic C may be oxidized but in other soils
<60% of the organic C is converted to CO 2 For example, Bremner and Jenkinson (1960a) showed that for 15 soils the recovery of organic C by the WalkleyBlack method (using a correction factor of 1.3) varied from 73 to 119% of wet
combustion values. Kalembasa and Jenkinson (1973) observed that with 22 soils
the recovery of organic C by the Walkley-Black procedures with correction varied from 60 to 122% of wet combustion values although the average recovery by
the Walkley-Black method was 102%. Nelson and Sommers (1975) found that
the Walkley-Black method with correction gave organic C values for 10 soils that
varied from 57 to 114% (average of 102%) of those obtained with wet combustion. More recent studies have found that organic C in soils from Sierra Leone
and Australia is much more susceptible to oxidation by dichromate in the Walkley-Black procedure than was expected, e.g., average uncorrected recoveries of
organic C varied from 88 to 97% of wet or dry combustion (Rhodes et ai., 1981;
Heanes, 1984; Lowther et ai., 1990). The Walkley-Black method employing a
correction factor for unoxidized organic C is not highly accurate for an individual soil, but for a group of soils the average recovery is good when compared with
organic C values determined by dry or wet combustion. This is particularly true
when the appropriate correction factor has been determined for the group of soils
under study. Furthermore, the simplicity and rapidity of the Walkley-Black method, in part, compensate for the lack of accuracy inherent in the procedure.
Dichromate methods that involve limited periods of heating (Schollenberger, 1927; Tyurin, 1931) have been shown to yield good recoveries of organic C if
appropriate correction factors are applied (Allison, 1935; Crowther, 1935; Smith
& Weldon, 1941; Kalembasa & Jenkinson, 1973). The usual correction factors
are 1.15 and 1.08 for the Schollenberger and Tyurin methods, respectively. Ciavatta et al. (1989) found that no correction factor was needed when a modified
Schollenberger procedure was used with heating at 160C for 10 min.
Modem dichromate oxidation methods that involve an extended period of
heating, often under reflux, (e.g., Anne, 1945; Tinsley, 1950; Mebius, 1960; Nelson & Sommers, 1975; Heanes, 1984; Yeomans & Bremner, 1988) give organic
C values equivalent to those obtained by dry or wet combustion (Table 34-5).
Bremner and Jenkinson (1960a) found that the Tinsley method gave organic C
values of 15 soils that varied from 88 to 106% (avg. 101%) of wet combustion
values. Kalembasa and Jenkinson (1973) showed that the Tinsley and Mebius
methods yielded organic C recoveries from 22 soils that averaged 95 and 94%,
respectively, of wet and dry combustion values. Nelson and Sommers (1975)
reported that the Mebius procedure recovered from 92 to 110% (avg. 103%) of
the organic C found in 10 soils by the wet combustion method. Tube digestion
methods have given excellent average recoveries of organic C in soils [Nelson &
71
8
69
15
10
22
7
10
12
15
2
38
12
No. of
samples
Wet
combustion
21.8
12.4
21.1
19.6
25.6
238.7
12.5
37.6
40.4
16.5
114.9
35.0
25.6
235.9
26.0
Avg. mg C/kg soil -
Dry
combustion
99#
109
100
100
96
Schollenbergert
Tinsley II
Modified
Mebius
92
115
95tt
125
120
100
101
109
102
104
96:j::j:
95
94
98
84
103
94
Avg. % of wet or dry combustion
Walkley &
Black:j:
t Values corrected for incomplete oxidation of organic C using a factor of 1.15.

:j: Values corrected for incomplete oxidation of organic C using a factor of 1.30.
Reagent concentrations as described by Bremner and Jenkinson (1960a).
'V Values corrected to incomplete oxidation of organic C with a factor of 1.08.
# Method was similar to Schollenberger except digestion reagent concentrations differed and samples were heated for 10 min.
tt Digestion carried out in 100 mL Pyrex tube.
:j::j: Digestion carried out in 100 mL Pyrex tubes in heating block.
Allison (1935)
Crowther (1935)
Smith & Weldon (1941)
Bremner & Jenkinson (1960a)
Kalembasa & Jenkinson (1973)
Metson et aJ. (1979)
Rhodes et aJ. (1981)
Heanes (1984)
Yeomans & Bremner (1988)
Ciavatta et aJ. (1989)
Lowther et aJ. (1990)
Reference
Table 34-5. Comparison of methods for determining organic C in soils.
99
97
100
99
99
100
Tube
digestion
105
Tyurin.
::
CIl
Ro
1001
Sommers (1975),99%; Heanes (1984),100%, Yeomans & Bremner (1988),99%;

Soon & Abboud (1991), 97%].
ORGANIC MATTER
Introduction
The organic matter content influences many soil properties, including (i)
the capacity of a soil to supply N, P, and S and trace metals to plans; (ii) infiltration and retention of water, (iii) degree of aggregation and overall structure that
affect air and water relationships; (iv) cation exchange capacity; (v) soil color,
which in turn affects temperature relationships; and (vi) adsorption or deactivation (or both) of agricultural chemicals. Determination of organic matter content
is a routine procedure carried out in soil analysis and testing laboratories throughout the world because of the importance of organic matter in supplying plant
available N and deactivating pesticides. However, no completely satisfactory
method exists for determination of the matter content of soils. The ignition
method described below is a modification of that presented by Ben-Dor and
Banin (1959). This method provides a reasonable estimate of organic matter concentrations in soils but cannot be considered quantitative.
Calculation of Organic Matter Content

The organic matter content of soil may be indirectly estimated through multiplication of the organic C concentration (as determined by procedures outlined
in "Organic Carbon") by the ratio of organic matter to organic C commonly found
in soils. The organic matter content is normally arrived at by multiplying the
organic C concentration by 1.724. However, a number of studies have suggested
that this factor is too low for many soils, and consequently the organic matter
content is underestimated. For example, Robinson et al. (1929) and Lunt (1931)
showed that the correct factor for peats is 1.86 to 1.89. In summarizing much of
the early work, Broadbent (1953) concluded that conversion factors of 1.9 and
2.5 would be appropriate for surface soils and subsoils, respectively. Other workers have found that factors of 1.9 to 2.0 were satisfactory for surface layers of
mineral soils (De Leenheer et aI., 1957; Howard, 1965; Ponomareva & Platnikova, 1967; Christensen & Malmros, 1982). Loftus (1966) reported that the appropriate factors for mineral and organic soils in Pennsylvania were 2.2 and 1.8,
respectively, whereas, Ranney (1969) found that the organic matter content of
Pennsylvania surface soils may be accurately estimated by the equation
organic matter, % = .35 + 1.80 x % organic C
[15]
It is evident that estimation of organic matter content from organic C concentrations is not highly accurate, because the organic C content of organic matter is variable from soil to soil and with depth in the profile. Accurate organic
matter content estimates require a knowledge of the factor for the particular soil
1002
NELSON & SOMMERS
studied. However, if an estimate of organic matter content of surface soils must

be based on organic C data and no information on the exact factor is available, a
factor of two appears to be more universally acceptable.
Direct Estimation of Organic Matter
Principles
To achieve a direct determination of soil organic matter, one must separate

it from the inorganic material, which in most soils makes up 90% or more of the
weight of the soil. Extraction procedures that bring part of the organic matter into
solution while leaving the inorganic material undissolved have only qualitative
value, sirice no solvent has been found that will dissolve all or even a major portion of the organic fraction. The alternative is to destroy the organic matter, after
which the loss in weight of the soil is taken as a measure of the organic content.
The requirements of a suitable method are that the treatment used to destroy the
organic matter should not destroy or alter the other soil constituents in such a way
that their weight is changed and that the organic matter should be quantitatively
removed.
The two most commonly used methods for achieving destruction of organic matter are: (i) oxidation of the organic matter with H20 2 and (ii) ignition of the
soil at high temperature. The H20 2 method (Robinson, 1927) has serious limitations in that the oxidation of organic matter by this reagent is incomplete, and the
extent of oxidation varies from one soil to another. This method is therefore
unsatisfactory as a means of determining total organic matter of soil, but it can be
useful as a means of comparing the readily oxidizable material in different soils.
The loss-on-ignition (LOI) method carried out at high temperature gives quantitative oxidation of organic matter, but inorganic constituents of the soil, chiefly
the hydrated aluminosilicates, lose structural water and carbonate minerals and
some hydrated salts are decomposed upon heating. Dehydroxylation and decomposition of inorganic constituents by heating results in weight losses considerably
in excess of the actual organic matter content. This problem is particularly pronounced with high clay soils containing low amounts of organic matter such as
subsoils (Christensen & Malmros, 1982; Howard & Howard, 1990).
Studies have shown, however, that temperatures exceeding 750C are needed to decompose carbonates and that little dehydroxylation of phyllosilicates
occurs at temperatures below 450C (Ball, 1964; Ben-Dor & Banin, 1989). Gibbsite is an exception because this clay mineral has been reported to lose structural
water when heated at 300 to 350C (Ranney, 1969; Gallardo et aI., 1987). Some
investigators have ignited soils and attempted to correct LOI values for dehydroxylation by multiplying a weight loss factor by the clay content of samples
(Howard, 1966; Ranney, 1969; Spain et al., 1982). Ranney (1969) also used a
low-temperature (100--200C) ashing procedure (organic matter was oxidized
under reduced pressure by activated O2 excited by a radio frequency electromagnetic field) for LOI estimation of organic matter content. He found that some
dehydroxylation (1.5% of soil weight) occurred when subsoils were subjected to
low-temperature ashing and that the procedure required 5 d for complete removal
of organic matter.
1003
The need in soil characterization and testing laboratories for a rapid and
semiquantitative technique for routine estimation of organic matter content has
resulted in development of a number of LOI method (Table 34-6). Environmental hazards associated with use and disposal of Cr has accelerated interest in alternatives to dichromate oxidation methods for estimation of organic matter
(Schulte et aI., 1991). Most investigators have attempted to obtain complete
removal of organic matter without dehydroxylating aluminosilicates or decomposing carbonates by heating samples at or below 450C for extended periods of
time. Excellent correlations have been obtained between LOI values and organic
matter content calculated from organic C data (Table 34-6). In Table 34-6, values of regression coefficient "b" below one suggest that some constituent other
than organic matter was lost during heating, whereas coefficients greater than one
indicate that incomplete removal of organic matter has occurred. In general, low
temperature (36(}-375C) procedures particularly those with short heating times
had coefficients greater than one whereas high temperature (>5OOC) procedures
much less than one. These findings suggest that ignition of soils at 400 to 450C
will remove all organic matter and cause minimal dehydroxylation of clay minerals. A heating time of 8 to 16 h at 400C results in near maximum weight loss
(Ben-Dor & Banin, 1989).
Reflectance and absorption spectroscopy also have been used to estimate
the organic matter content of soils. AI-Abbas et al. (1972) showed that relative
reflectance at 0.72 to O.80llm was related to the organic matter content of Indiana
soils. A curvilinear relationship was obtained between reflectance as measured by
Table
3~.
Relationship between soil organic matter content and weight loss-on-ignition (LOI).
Reference
Number
of soils
Ignition conditions
Temperature
Time
Regression coefficientst
b
,.z
0.916
0.94
-0.8
-0.96
0.99
1.11
0.983
0.985
+0.35
-0.64
-0.23
0.99
0.99
0.99
Ball (1964)
Howard (1965)
65
36
375
550
Ramney (1969)
Davies (1974)
Christensen &
Malmros (1982)
Spain et al. (1982)
Storer (1984)
Goldin (1987)
David (1988)
Ben-Dor &
Banin (1989)
Howard &
Howard (1990)
Lowther et al.
(1990)
Donkin (1991)
Schulte et al. (1991)
48
17
85
375
430
550
16
To constant
weight
28
24
4
766
215
60
174
91
950
500
600
450
400
0.5
4
6
12
8
0.796
0.937
0.810
1.04
0.972
-0.60
-1.70
-1.42
-0.03
-0.37
0.96
0.86
0.92
0.97
564
550
0.840
-1.68
0.98
38
450
16
0.914
45
316
450
360
6
2
0.568
1.126
0
0
-0.38
0.99
0.98
0.90
t Regression model used was: soil organic matter = (b LOI) + a, where units are g/100 of soil. Soil
organic matter content was estimated as two times organic C concentration. Organic C was determined by Walkley & Black, Tinsley, or dry combustion methods. calculations assume that organic
matter was 50% C.
NELSON & SOMMERS
1004
a color difference meter and organic matter content (Page, 1974). Krishnan et al.
(1980) found that the organic matter content of Illinois soils was highly correlated with reflectance at wavelengths of 0.624 and 0.564 um. Near infrared diffuse
reflectance at wavelengths of 1744,1870 and 2052 nm has been related to organic matter content of Australian soils (Dalal & Henry, 1986). Several investigators
have proposed that the organic matter content of soils be estimated by partial
extraction with alkaline reagents and determination of humic materials in the
extract by absorption spectrometry at 550 to 650 nm (Mehlich, 1984; Strek et aI.,
1990; Bowman et aI., 1991). Moore (1985) used absorbance at 330 nm to estimate dissolved organic matter in peat water samples. Although each of the techniques described above has promise as method for determining organic matter
content, none can be recommended at this time because of a lack of evaluation of
their usefulness and applicability to a wide range of soils.
Loss-On-Ignition Method
The Loss-On-Ignition Method is a modification of a method described by
Ben-Dor and Banin (1989).
Special Apparatus
1.
2.
3.
4.
Pyrex beakers or porcelain crucibles (20 mL).

Muffle furnace capable of :!:5C temperature control.
Drying oven (105C) with :!:5C temperature control.
Analytical balance capable of weighing :!:0.1 mg.
Procedure
Heat beakers or crucibles in muffle furnace at 400C for 2 h, cool, and
determine tare weight to 0.1 mg. Add 1 to 3 g of air-dried soil ground to <0.4 mrn
to a tared beaker and heat at 105C for 24 h. Cool the beaker in a dessicator over
CaCl2 and determine weight of beaker plus sample to 0.1 mg. Obtain weight of
oven-dried sample by subtraction. Ignite samples in a muffle furnace at 400C for
16 h. Cool beakers in a desiccator over CaCl2 and determine weight of beaker
plus ignited sample to 0.1 mg. Calculate weight of ignited sample by subtraction.
The LOI content of the sample is calculated as
LOI, % =
Weight105 - Weight400
Weight105
x 100
[16]
where "weight 105" is weight of soil sample after heating at 105C and "weight4oo"
is weight of soil sample after ignition at 400C. The organic matter content is
assumed to equal the LOI in most surface soils. The LOI can be corrected for
de hydroxylation of inorganic constituents through regression analysis. Determine
the LOI and the organic C content of representative samples having organic matter levels covering the range expected in soils under study. Regress organic matter content [organic C x 2 (or other suitable correction factor)] on LOI and use
the resulting relationship to convert LOI of test samples to organic matter. In
many cases the intercept of the regression line (LOI on Yaxis and organic matter
1005
onX axis) will be greater than zero indicating weight loss due to dehydroxylation
of clay minerals during heating.
Comments
Control of the heating of samples at 105C is as important as at 400C. The
use of an automatic balance connected to a laboratory computer as an automated
data acquisition system will greatly speed up analyses and tend to improve the
precision of the method (Storer, 1984). The coefficient of variation for LOI methods applied to soils containing> 1% organic matter has been estimated to be about
3.3% (Storer, 1984),5.0% (David, 1988),2.0% (Lowther et aI., 1990), and 3.5%
(Donkin, 1991). The coefficient of variation tends to decrease as the sample size
increases because relative weighing errors become less (Lowther et aI., 1990).
A more accurate estimation of organic matter content of soils may be
obtained by using the Rather (1917) method described by Nelson and Sommers
(1982). This method involves pretreating the sample with a mixture of HCI and
HF to remove hydrated mineral matter and carbonates prior to ignition. This pretreatment dissolves part of the organic matter so that a correction for the soluble
material is necessary. Both weight loss and CO 2 evolution are measured during
ignition so that the C content of organic matter can be calculated. The method has
a coefficient of variation of about 2%. The Rather method is undoubtedly the
most accurate available for determination of organic matter since it does not
involve the use of an arbitrary conversion factor. The tedious nature of the
method coupled with the requirement for pretreatment with HF limits its usefulness for routine organic matter determinations.
Expression of Soil Organic Matter Content

Due to the difficulty in directly estimating or calculating the amount of
organic matter present in soil, it appears that a more appropriate procedure would
be to determine and express the soil organic C content as a measure of organic
matter. Organic C concentrations in soil may be accurately and precisely measured by a variety of procedures, whereas organic matter content may be only
estimated. There would be little confusion in the amounts of organic matter. Furthermore, the analyst would be in a position to convert organic C data to organic
matter contents using the correction factor deemed most appropriate. On the other
hand, when organic matter concentrations are given, they are extremely difficult
to convert to organic C values unless the correction factor originally used also is
supplied. At the current point in the development of soil science, a uniform system for expression of the amounts of soil constituents is necessary. Therefore,
organic C concentration is preferable to the term soil organic matter content,
because the latter is not an appropriate or an accurately measurable entity.
ACKNOWLEDGMENTS
A joint contribution of the University of Nebraska Agricultural Research
Division, Journal Series no. 10742, Lincoln, NE 68583-0704; and The Colorado
NELSON & SOMMERS
1006
Agricultural Experiment Station, Colorado State University, Fort Collins, CO

80523. Mention of a trademark or product does not constitute a guarantee or warranty of the product by the University of Nebraska or Colorado State University,
nor does it imply its approval to the exclusion of other suitable products.
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CARBON AND ORGANIC MATIER

Sample is mixed with CuO and heated

Table 34-1. Comparison of methodologies used for determination of total C in soils.

Expensive equipment, slow release of

Equipment readily available, good accuracy, easily adapted to analysis of

Time-consuming, leakfree, O 2 sweep

Rapid and simple, good accuracy and

Reference method widely used in other

CARBON AND ORGANIC MATTER

Total Carbon by Dry Combustion

NELSON & SOMMERS

The O2 supply (commercial compressed O2) is first scrubbed by passage

CARBON AND ORGANIC MATIER

of anhydrous Mg(CI04h next in line. The CO 2 is finally absorbed in a suitable

Medium-Temperature Resistance Furnace Method

Capital letters in parentheses refer to units in Fig. 34-1.

NELSON & SOMMERS

of 8- to 14-mesh (1.4-2.36 mm) absorbent (e.g., Ascarite), (iii) 2-em

CARBON AND ORGANIC MATTER

[g CO2, sample] - [g CO2, blank]

NELSON & SOMMERS

3. The CO2 absorption bulb is brought to constant weight by inserting it

CARBON AND ORGANIC MAITER

High-Temperature Induction Furnace Method

Oxygen cylinder and regulator (A).

Capital letters in parentheses refer to units in Fig. 34-1.

NELSON & SOMMERS

bination of units is prescribed here since many suitable combinations

Procedure Using Iron, Tin, and Tin-coated Copper Accelerators

[g COz, sample] - [g COz, blank]

CARBON AND ORGANIC MAITER

Carbo-Erba NA 1500. Carlo-Erba Instruments (Milan, Italy) developed an

NELSON & SOMMERS

Helium (continuous flow)

Fig. 34--2. Schematic diagram for Carlo-Erba Model NA 1500 analyzer.

CARBON AND ORGANIC MATfER

NELSON & SOMMERS

Dual Heat Zone

CARBON AND ORGANIC MATTER

5. TC detector 3 (decrease in output from Detector 2 is proportional to C

Total Carbon by Wet Combustion

NELSON & SOMMERS

MglCIO ) JFiber Qloss

250 ml Side. arm

excessive fuming in the condenser. The CO 2 evolved is absorbed by a suitable

CARBON AND ORGANIC MATTER

NELSON & SOMMERS

CARBON AND ORGANIC MATTER

[g CO2, sample] - [g CO2, blank]

NELSON & SOMMERS

CARBON AND ORGANIC MATIER

provide comparable data to established methods and use relatively inexpensive

Total C and inorganic C are determined on separate

Total C is determined in soil sample after removal

Table 34-2. Comparison of methodologies used for determination of organic C in soils.

Incomplete oxidation of organic C necessitates use of a

Two separate analyses are required, total C determination

CARBON AND ORGANIC MATTER

Organic Carbon as Calculated from Total Carbon Determinations

Organic Carbon in Noncalcareous Soils

Organic Carbon in Calcareous Soils