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Review: Organic matter removal from soils using hydrogen peroxide, sodium
hypochlorite, and disodium peroxodisulfate

Article  in  Soil Science Society of America Journal · January 2005

DOI: 10.2136/sssaj2005.0120

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 Review: Organic Matter Removal from Soils using Hydrogen Peroxide,
Sodium Hypochlorite, and Disodium Peroxodisulfate
R. Mikutta,* M. Kleber, K. Kaiser, and R. Jahn
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
ABSTRACT
We compare the performance of three most accepted reagents for
organic matter removal: hydrogen peroxide (H2O2), sodium hypochlo-
rite (NaOCl) and disodium peroxodisulfate (Na2S2O8). Removal of
organic matter from soil is mostly incomplete with the efficiency of
removal depending on reaction conditions and sample properties.
Generally, NaOCl and Na2S2O8 are more effective in organic C re-
moval than H2O2. Alkaline conditions and additives favoring disper-
sion and/or desorption of organic matter, such as sodium pyrophos-
phate, seem to be crucial for C removal. Pyrophosphate and additives
for pH control (bicarbonate) may irreversibly adsorb to mineral sur-
faces. In soils with a large proportion of organic matter bound to the
mineral matrix, for example subsoils, or rich in clay-sized minerals
(Fe oxides, poorly crystalline Fe and Al phases, expandable phyllo-
silicates), C removal can be little irrespective of the reagents used.
Residual organic C seems to seems to represent largely refractory
organic matter, and comprises mainly pyrogenic materials and ali-
phatic compounds. If protected by close association with minerals,
other organic constituents such as low-molecular weight carboxylic
acids, lignin-derived and N-containing compounds may escape chemi-
cal destruction. For determination of mineral phase properties, treat-
ment with H2O2 should be avoided since it may promote organic-
assisted dissolution of poorly crystalline minerals at low pH, disinte-
gration of expandable clay minerals, and transformation of vermiculite
ⴙ
into mica-like products due to NH4 fixation. Sodium hypochlorite
and Na2S2O8 are less harmful for minerals than H2O2. While the NaOCl
procedure (pH 9.5) may dissolve Al hydroxides, alkaline conditions
favor the precipitation of metals released upon destruction of organic
matter. Prolonged heating to ⬎40ⴗC during any treatment may trans-
form poorly crystalline minerals into more crystalline ones. Sodium
hypochlorite can be used at 25ⴗC, thus preventing heat-induced min-
eral alteration.
R emoval of organic matter by chemical reagents is
a common pretreatment for analyses of the soil
mineral phase such as particle-size distribution (Gee
and Bauder, 1986), mineral composition (Tributh and
Lagaly, 1991), cation exchange capacity (CEC), and spe-
cific surface area (SSA; Kahle et al., 2003). Chemical
destruction of organic matter is also used to uncover
mineral surfaces for subsequent sorption experiments
(Jardine et al., 1989; Kaiser and Zech, 2000; Pagel-Wieder
et al., 2004) and to assess organically bound metals (e.g.,
Shuman, 1983). Other fields for the use of chemical degra-
dation of soil organic matter include the isolation of
refractory organic fractions (Balesdent, 1996; Righi et
al., 1995; Eusterhues et al., 2003) and the exploration
of organic matter properties (Cuypers et al., 2002). De-
Institut für Bodenkunde und Pflanzenernährung, Martin-Luther-Uni-
versität Halle-Wittenberg, Weidenplan 14, D-06108 Halle, Germany.
Received 18 May 2004. *Corresponding author (mikutta@landw.uni-
halle.de).
Published in Soil Sci. Soc. Am. J. 69:120–135 (2005).
© Soil Science Society of America
677 S. Segoe Rd., Madison, WI 53711 USA
120
termination of soil mineral properties requires complete
removal of organic matter without modification of the
mineral phase. An incomplete removal of organic mat-
ter hampers the evaluation of phyllosilicate clay miner-
alogy (Tributh and Lagaly, 1991), SSA determination
(de Jonge et al., 2000) and may also affect infrared (IR)
and differential thermal analysis (Mitchell and Farmer,
1962).
Hydrogen peroxide was introduced by Robinson
(1922) for soil texture analysis and became the most
widely used chemical reagent for organic matter de-
struction. Some alternative reactants have been pro-
posed to increase C removal efficiency and to reduce
possible effects of H2O2 on minerals. Sodium hypochlo-
rite (Anderson, 1963) and Na2S2O8 (Meier and Mene-
gatti, 1997) have emerged as reagents with the greatest
potential to replace H2O2. These reagents have been
recently applied to soils (Kaiser et al., 2002; Kiem and
Kögel-Knabner, 2002; Eusterhues et al., 2003) and sedi-
ments (Mayer, 1999).
To date, there is a vast number of oxidation protocols
and much uncertainty regarding the effects of oxidative
reagents on soil constituents. A thorough understanding
of treatments for soil organic matter removal with oxi-
dants is the key to a correct interpretation of experimen-
tal results. Thus, our objective is to review and compare
the suitability of H2O2, NaOCl, and Na2S2O8 for organic
matter removal from soils, sediments, and minerals.
Special emphasis was put on (i) the evaluation of indi-
vidual treatment procedures including reaction condi-
tions required, (ii) mechanisms of interaction between
the reagents and organic matter, (iii) the organic C re-
moval efficiency and reasons for organic matter resis-
tance, (iv) the effects of reactants on soil minerals and
(v) metal precipitation, and (vi) implications for the use
of chemical treatments for soil analysis.
PROCEDURES, REACTION CONDITIONS,
AND APPLICATION
Removal of organic materials from soil by aqueous
reactants is controlled by multiple factors, including the
reaction conditions (pH, temperature, contact time,
chemical additives) and soil properties (mineralogy, or-
ganic matter content, and quality). Attempts have been
made to optimize reaction conditions to increase the
efficiency of organic C removal from soils. This resulted
in a variety of treatment protocols compiled in Table 1,
which will be briefly discussed here.
Abbreviations: Ac, acetate; CEC, cation exchange capacity; IR, infra-
red; PAH, polynuclear aromatic hydrocarbons; SSA, specific surface
area; XRD, x-ray diffraction.
 MIKUTTA ET AL.: REMOVAL OF ORGANIC MATTER FROM SOILS 121

Table 1. Methods for organic matter removal from soils, sediments, and minerals compiled from the literature.
OC§
removal
Material Volume Concentration Reaction conditions efficiency Determination Citation
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.

mL % %
Hydrogen peroxide
2 g soil ⬎15 30 heating – organic matter content Jackson (1958)
I) 5 g soil 1 30 10 mL H2O, 60–70ⴗC, 5 ⫻ 11–77 effect on minerals Lavkulich and Wiens (1970)
15 min
II) 10 g soil ⬎5 30 20 mL H2O, initially 28–81 effect on minerals Lavkulich and Wiens (1970)
room temperature, then
heating to 60–70ⴗC
10 g soil 20 30 80 mL H2O, initially 56–94 surface area and charge Sequi and Aringhieri (1977)
room temperature, then
heating to 70–80ⴗC
10 g soil 20 30 80 mL Na4P2O7, initially 88–100 surface area and charge Sequi and Aringhieri (1977)
room temperature, then
heating to 70–80ⴗC
10 g clay to 60 g sand ⬎5 ⬃30 initially room temperature, – particle size distribution Gee and Bauder (1986)
then heating to 90ⴗC
⬃10 g soil ⬎5 30 then 10 10–20 mL H2O, initially – clay mineralogy Kunze and Dixon (1986)
room temperature, then
heating to 65–70ⴗC
N.A. vermiculite N.A. 30 80ⴗC, 3 min and 20ⴗC, 24 h – effect on clay properties Muromtsev et al. (1990)
15–20 g clay ⬎100 10 initially room temperature, – clay mineralogy Tributh and Lagaly (1991)
then heating to 60–70ⴗC
3 g size fraction 50 50 (vol. %) initially room temperature, 85 surface area Feller et al. (1992)
then heating to 50ⴗC
10 g soil ⬎10 30 or 50 initially room temperature, – particle size distribution Sheldrick and Wang (1993)
then heating to 90ⴗC
10 g clay 200 5 60ⴗC, 5 d N.A.# investigation of clay- Righi et al. (1995)
humus complexes
0.9 g clay† 10 30 NaOAc buffer pH 5, 53 Cs adsorption Dumat et al. (1997)
1 h at room temperature,
then 70ⴗC for 24 h¶
1 g soil 50 6 80ⴗC, five repetitions 66–97 surface area Theng et al. (1999)
10 g decarbonated sediment 20 30 HNO3, 50–90ⴗC, 100 optimization of Schultz et al. (1999)
three additions of H2O2, sequential metal
NH4OAc to prevent extraction
metal precipitation
20 g soil – 10 initially room temperature, 2–34 (wt.) particle size Schmidt et al. (1999)
then boiling for 24 or 72 h fractionation
30 g soil, 500 15 then 30 initially room temperature, 83–94 analysis of residual Leifeld and Kögel-Knabner
diam. ⬍ 20 ␮m then heating to 70ⴗC, 1–3 d organic matter (2001)
Sodium hypochlorite
10 g soil 20 6 boiling, 3 ⫻ 15 min, pH 9.5 32–96 clay mineralogy Anderson, (1963)
5 g soil 10 6 boiling, 3 ⫻ 15 min, pH 9.5 69–83 comparison H2O2 vs. Omueti (1980)
NaOCl for textural
analysis
10 g soil 20 5.3 boiling, 3 ⫻ 15 or 30 min, N.A. sequential metal Shuman (1983)
DTPA‡, pH 8.5 extraction
5 g clay 50 5.25 boiling, 5 ⫻ 15 min, pH 9.5 N.A. charge and exchange Cavallaro and McBride (1984)
properties
20 g soil 100 7 80ⴗC, 5 ⫻ 1 h 88–94 B adsorption and Marzadori et al. (1991)
desorption
1 g soil 2 5.3 96ⴗC, 2 ⫻ 0.5 h, pH 8.5 N.A. sequential metal Qiang et al. (1994)
extraction
0.9 g clay‡ 2 6.6 boiling, 2 ⫻ 15 min, pH 8.5 76 Cs adsorption Dumat et al. (1997)
1–1.5 g sediment – 13 60–80ⴗC, 6 h, pH 9–9.5 N.A. surface area Mayer (1999)
1 g sediment 20 N.A. 95 ⫾ 5ⴗC, 3 ⫻ 1 h, pH 9.5 N.A. sequential metal La Force and Fendorf (2000)
extraction
10 g soil 30 6 room temperature, 3 ⫻ 16 h, 26–80 P adsorption and McDowell and Condron (2001)
pH 8.5 desorption
2 g soil 100 6 room temperature, 5 ⫻ 6 h, ⬎87 investigation of Kaiser et al. (2002)
pH 8 clay-humus complexes
4.5 g clay 250 6 room temperature, 6 ⫻ 6 h, 49–81 isolation of stable Mikutta et al. (2004)
pH 8 organic matter
Disodium peroxodisulfate
0.2 g clay – 8g NaHCO3 buffer, 98ⴗC, 1 h, 78–97 clay mineralogy Meier and Menegatti (1997)
pH 7.8–8.5
0.5 g clay minerals – 20 g 22 g NaHCO3 buffer, 80ⴗC, – effect on clay minerals Menegatti et al. (1999)
1 h, pH 7.8–8.5
0.2 g of size fractions – 8g NaHCO3 buffer, 80ⴗC, 16 h 93 surface area Kiem et al. (2002)
0.5 g clay – 20 g 22 g NaHCO3 buffer, 80ⴗC, 16–99 isolation of stable Eusterhues et al. (2003)
2d organic matter
† Pretreated with Na4P2O7 ⫹ NaOH.
‡ Diethylenetriaminepentaacetic acid ⫽ chelator.
§ OC, organic C.
¶ Ac, acetate.
# Not available.
 122 SOIL SCI. SOC. AM. J., VOL. 69, JANUARY–FEBRUARY 2005
Hydrogen Peroxide
Most protocols for sample preparation before textural
and mineralogical analysis propose the use of 30% (wt/wt)
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
H2O2 but 10 and 50% (wt/wt) H2O2 have been suggested
as well (Table 1). McLean (1931b) found that doubl-
ing the H2O2 concentration from 6 to 12% resulted in
little increase in C removal from soils (Fig. 1). This
suggests that the concentration of H2O2 is not decisive
for C removal efficiency, probably because of the de-
composition of H2O2 (REACTION OF OXIDANTS
WITH INORGANIC AND ORGANIC MATTER sec-
tion), and the presence of chemically stable and mineral-
protected organic compounds (EFFICIENCY OF OR-
GANIC CARBON REMOVAL DEPENDS ON SAM-
PLE PROPERTIES section).
Typically, the treatments start at room temperature
because of a strong initial reaction with easily decom-
posable organic matter. If frothing subsides, the sample
is commonly heated to 60 to 90⬚C (Table 1). Increasing
temperature accelerates the decomposition of H2O2 but
shortens the reaction time necessary to oxidize organic
matter (Schultz et al., 1999). At temperatures ⬎70⬚C,
H2O2 is rapidly consumed and additional H2O2 is needed
to perpetuate organic matter destruction. At lower tem-
peratures, the contact time needs to be extended (Schultz
et al., 1999). In practice, removal of organic C from soils
using H2O2 often requires several days and no reliable
indicator exists showing completion of the reaction.
Fig. 1. (a) Effect of added H2O2 volume on the efficiency of organic
C removal from Welsh carbonate-free Madryn soil (䊉, 5.1% C)
and Bodrwyn soil (䊊, 4.3% C) using 6%(wt/wt) H2O2. (b) Organic
C removal efficiency from bulk soils with increasing H2O2 concen-
tration. Soils contained between 1.3 and 6.5% organic C. Sixty
milliliters H2O2 were added equivalent to 0.08 g C. The samples
were heated gently then boiled (data adopted from McLean,
1931a, 1931b).
Lack of visible frothing and bleached soil color indicate
a complete reaction, but frothing may continue due to
the decomposition of excess H2O2 at mineral surfaces
(REACTION OF OXIDANTS WITH INORGANIC
AND ORGANIC MATTER section).
Sometimes H2O2 is used in combination with acetate
buffer (pH 5) to prevent acidic conditions resulting from
formation of acid oxidation products (Douglas and Fies-
singer, 1971; Pennell et al., 1995). The pH of unbuffered
soil–H2O2 suspensions may drop by up to three units
and final pH values between 2 and 4 have been reported
(Douglas and Fiessinger, 1971; Lavkulich and Wiens,
1971; Griffith and Schnitzer, 1977). Using acetate buffer,
H2O2 is additionally consumed due to the oxidation of
acetate. Acetate (Ac) may also adsorb to minerals (e.g.,
van Hees et al., 2003) and thus contribute to residual
C (17–41% C; Pennell et al., 1995).
There is little consistency in H2O2 use before SSA
determination of the mineral phase. Hydrogen peroxide
concentrations vary from 6 to 30% (Sequi and Arin-
ghieri, 1977; Theng et al., 1999) and reaction tempera-
tures from 50 to 80⬚C (Feller et al., 1992; Theng et al.,
1999) (Table 1). Similarly, H2O2 concentration and con-
tact time proposed for isolation of stable organic matter
vary strongly (Righi et al., 1995; Theng et al., 1992).
These examples demonstrate little agreement on proto-
cols to achieve given research objectives.
Sodium Hypochlorite
The use of NaOCl for organic matter removal was
first proposed by Anderson (1963) for mineralogical
analysis of clays (Table 1). The method utilizes 6%
(wt/wt) NaOCl at pH 9.5 and three consecutive cycles
including boiling for each 15 min. The restriction of
reaction time to 15 min is due to the fast decomposition
of NaOCl at high temperatures. Heat-induced mineral
changes (TREATMENTS INDUCE MODIFICATIONS
OF MINERAL CONSTITUENTS section) can be mini-
mized at room temperature, which requires extended
contact times (Table 1; Kaiser et al., 2002). If applied
at pH 9.5, NaOCl may partly dissolve Al secondary
phases (TREATMENTS INDUCE MODIFICATIONS
OF MINERAL CONSTITUENTS section). To avoid
this, NaOCl can be used at lower pH (Table 1). Treating
soils with NaOCl avoids vigorous frothing and boiling
over as often experienced when using H2O2. Modified
NaOCl protocols have been used for multiple purposes
such as for metal extraction from soil organic matter
(Shuman, 1983), before metal sorption studies (McDow-
ell and Condron, 2001), and to investigate stabilization
of organic C by mineral phases (Kaiser et al., 2002)
(Table 1).
Disodium Peroxodisulfate
Meier and Menegatti (1997) proposed the use of
Na2S2O8 to remove organic matter from mineral phases
in one single step (Table 1). Thermal decomposition of
Na2S2O8 did not decrease C removal at temperatures
⬎80⬚C. By using a NaHCO3 buffer, the pH of reaction
suspensions with clay minerals and soils can be kept
 MIKUTTA ET AL.: REMOVAL OF ORGANIC MATTER FROM SOILS
between 7 and 8.5 (Menegatti et al., 1999; Kiem and
Kögel-Knabner, 2002), thus preventing acid-mediated
mineral dissolution. After treatment, Meier and Mene-
gatti (1997) applied a hot wash (98⬚C, 1 min) with formic
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
acid to remove any traces of salts. However, SO42⫺ and
HCO3⫺ have a high affinity for hydroxyl-bearing mineral
surfaces (Ali and Dzombak, 1996; Su and Suarez, 1997)
and are likely to become attached to minerals such as
Fe and Al oxides or short range order minerals when
applied in high amounts (Table 1). Peroxodisulfate oxi-
dation was employed for predicting the bioavailability
of polynuclear aromatic hydrocarbons (PAH) in soils
and sediments since both, oxidation and biodegradation,
removed similar portions of PAH (Cuypers et al., 2000).
Recently, the Na2S2O8 procedure has been adopted to
soils to isolate stable organic matter and to study the
influence of mineral surfaces on organic matter storage
(Kiem and Kögel-Knabner, 2002; Eusterhues et al.,
2003).
REACTION OF OXIDANTS WITH
INORGANIC AND ORGANIC MATTER
In theory, CO2 and H2O are the end products of oxida-
tive organic matter destruction but a variety of by-prod-
ucts form during the chemical treatments. Intermediate
degradation products adsorb to mineral surfaces, form
precipitates (Martin, 1954), complex trace metals, and
thus hinder their redistribution to solid phases (Hoff-
man and Fletcher, 1981) and have the potential to pro-
mote mineral dissolution at low pH (Cornell and Schwert-
mann, 1996; Zhang and Bloom, 1999). The interaction
of oxidants with organic matter involves complex reac-
tions, depending on either one of the following factors:
(i) reaction conditions (pH, temperature), (ii) the pres-
ence of inorganic catalysts that are capable to transform
reagents into more reactive forms, and, in case of H2O2,
(iii) the presence of enzymes that reduce the oxidant’s re-
activity.
Hydrogen Peroxide
Hydrogen peroxide is thermodynamically unstable
and decomposes into O2 and H2O according to Eq. [1]
(Pardieck et al., 1992). Decomposition of H2O2 increases
with pH, being maximal close to the reagent’s pKa at
11.6 (Xiang and Lee, 2000).
H2O2 ⫹ H2O2 → 2H2O ⫹ O2 (log k ⫽ 36.12) [1]
When present in soils, reduced metal species can cata-
lyze the decomposition of H2O2 and thereby produce
OH radicals that are much more powerful oxidants than
H2O2 (Strukul, 1992). The Fe2⫹–catalyzed decomposi-
tion of H2O2 into OH species according to Eq. [2] resem-
bles the classical Fenton reaction. Surface sites of oxides
and montmorillonite (Fe2⫹ or Fe3⫹) may similarly pro-
duce OH radicals by Fenton-like reactions (Huang et
al., 2001; Gournis et al., 2002; Kwan and Voelker, 2002;
Petigara et al., 2002). Equations [2] through [6] repre-
sent the metal-catalyzed Haber-Weiss mechanism, where
the metal (M) is cycled between a lower [M(II)] and
higher [M(III)] oxidation state and where H2O2 is gradu-
123
ally decomposed into O2 and H2O (Eq. [1]) via produc-
tion of odd-electron (radical) intermediates (Evans and
Upton, 1985). Fenton-like chemistry has been applied
in remediation of soils (Watts et al., 2002; Kanel et al.,
2003) and in wastewater treatment (Waite, 2002).
⫺M2⫹ ⫹ H2O2 → ⫺M3⫹ ⫹ •OH ⫹ OH⫺
(Fenton reaction) [2]
3⫹ 2⫹
⫺M ⫹ H2O2 → ⫺M ⫹ HO2• ⫹ H⫹ [3]
2⫹ 3⫹
⫺M ⫹ •OH → ⫺M ⫹ OH⫺ [4]
•OH ⫹ H2O2 → H2O ⫹ HO2• [5]
3⫹ 2⫺ 2⫹
⫺M ⫹ O • → ⫺M ⫹ O2 [6]
Hydrogen peroxide can also be consumed by catalase-
positive bacteria, which are common members of the
microbial community in soil environments (Pardieck et
al., 1992). Catalase decomposes H2O2 into O2 and H2O
without formation of OH radicals (k ⬇ 4 ⫻ 107 M s⫺1;
Pardieck et al., 1992). Manganese oxides can also induce
the catalase-type reaction resulting in reduced efficiency
of organic C removal in Mn-containing soils. When the
soil reaction is acid, protonation of H2O2 may yield elec-
trophilic OH cations (Eq. [7]) while at alkaline condi-
tions nucleophilic perhydroxyl ions (HOO–) form
(Eq. [8]).
H2O2 ⫹ H⫹ ↔ H2⫹OOH ↔ H2O ⫹ OH⫹ [7]
H2O2 ⫹ HO⫺ → H2O ⫹ HOO⫺ [8]
The possible decomposition pathways of H2O2 in soils
imply that several reactive H2O2 species can interact
with organic matter. In the simplest case, H2O2 directly
oxidizes organic compounds in a peroxidic-type reaction
by a two-electron process without O2 formation (Schumb
et al., 1955). Reaction of organic matter with OH radi-
cals are far more complex. Under laboratory conditions,
OH radicals react with alkenes and aromatics at diffu-
sion-controlled rates (Watts et al., 2002). Hydroxyl radi-
cals can also initiate radical reactions among organic
radicals produced by hydrogen abstraction from C–H
bonds. There is evidence that OH radicals preferentially
attack aromatic compounds: Westerhoff et al. (1999)
noted that aliphatic structures of natural organic matter
react slower with OH radicals than aromatic moieties.
Xie and Barcelona (2003) reported a higher chemical
resistance of low-molecular weight aliphatic hydrocar-
bons (C5–C8) compared with aromatic compounds in
jet-fuel contaminated sediments treated with H2O2.
These results are consistent with the general order of
reactivity: aromatic ⬎ –CH2– ⬎ –CO– ⬎ –COOH (Pey-
ton, 1993) and may account for the enrichment of ali-
phatic compounds in H2O2–treated soils (Schulten et al.,
1996; Leifeld and Kögel-Knabner, 2001; COMPOSI-
TION OF ORGANIC MATTER section).
In addition, certain aromatic compounds may selec-
tively be removed by H2O2. Andreozzi et al. (2002)
observed that phenols adsorbed to goethite containing
two adjacent OH groups (or one OH and one NH2)
were oxidized by H2O2 while those containing two
 124 SOIL SCI. SOC. AM. J., VOL. 69, JANUARY–FEBRUARY 2005
COOH groups or one COOH plus one OH group were
not reactive toward H2O2.
Degradation of lignin strongly depends on the reac-
tion milieu. At alkaline pH, degradation of lignin is
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
more complete than at acid pH, possibly because of
more reactive H2O2 species present and larger lignin
solubility (Sun et al., 2000; Xiang and Lee, 2000). This
suggests that under acid conditions lignin components
may contribute to residual organic C in H2O2–treated
soil. Chemical degradation of humic substances, lignin,
and simple carbohydrates by H2O2 yields a variety of
water-soluble compounds such as mono- and dicarbox-
ylic low-molecular-weight organic acids (e.g., formic,
acetic, oxalic, and malonic acid), phenols and benzene-
carboxylic acids (Craik, 1924; Küchlein, 1932; Griffith
and Schnitzer, 1977; Xiang and Lee, 2000; Goldstone et
al., 2002). Martin (1954) estimated that in two soil clays
reacted with H2O2, 30 to 40% of the initial organic C
was transformed into oxalate. Similarly, Harada and
Inoko (1977) using redox titration have calculated that
100 g of soil yielded between 0.01 and 0.2 moles of
oxalate during H2O2 treatment.
Less is known about the interaction of H2O2 with
N-containing compounds. Herriott (1947) reported that
at room temperature 5% (wt/wt) H2O2 caused a loss of
60% of amino-N from virus protein. Harada and Inoko
(1977) showed that after treating soils with H2O2, resid-
ual N was mainly water-soluble (60–100%) and domi-
nated by inorganic N species (⬎70%). Ammonia is a
product of the oxidative deamination of amino acids
(Schnitzer and Hindl, 1980) and has been found after
oxidation of humic acid (14 mg NH3 out of 46 mg total
N) (Miles et al., 1985).
Sodium Hypochlorite
In aqueous solution, NaOCl principally exists in the
following equilibria (Eq. [9] and [10]).
OCl⫺ ⫹ H2O ↔ HOCl ⫹ OH⫺ [9]
and
HOCl ↔ OCl⫺ ⫹ H⫹ [10]
When natural organic matter is treated with hypo-
chlorite species (HOCl, OCl⫺), high-molecular-weight
chlorinated compounds form in a first step that is fol-
lowed by the cleavage of benzene rings into trihalometh-
anes and haloacetic acids (Jimenez et al., 1993; Li et al.,
2000; Pomes et al., 2000). Sodium hypochlorite-treated
humic acid yielded more chloroform than treated fulvic
acid (Peters et al., 1980). Trihalomethane and haloacetic
acids likely derive from 3,5-dihydroxybenzene structures.
In accordance, Norwood et al. (1987) noted that chlorina-
tion of aquatic fulvic acid produced chlorinated aliphatics
and resulted in preferential removal of lignin phenols.
Chlorinated phenols were also found after reaction of
hypochlorite with humic and fulvic acid (Quimby et al.,
1980), substituted benzoic acids (Larson and Rockwell,
1979), and after chlorination of lignin (Rajan et al., 1996).
Westerhoff et al. (2004) observed a higher reactivity of
aqueous chlorine for aromatic compounds than for ali-
phatic compounds in natural organic matter. Chakrabar-
tty et al. (1974) used 12% (wt/wt) NaOCl (pH 12) to
investigate the structural composition of humic acids
extracted from soil and coal. They reported that reaction
results in aliphatic carboxylic acids (malonic, succinic,
glutaric, and adipic acid) and aromatic polycarboxylic
acids (⬎50% CO2, up to 32% non-volatile acids). Hypo-
chlorite is presumed to cleave all methine, methylene,
and methyl goups activated by electron-withdrawing
heteroatoms without simultaneously disrupting aro-
matic systems.
Disodium Peroxodisulfate
In alkaline to slightly acid solutions, S2O82⫺ reacts with
H2O according to Eq. [11] (Kolthoff and Miller, 1955)
to finally give SO42⫺ by dissociation of HSO4⫺.
2S2O28⫺ ⫹ 2H2O → 4HSO4⫺ ⫹ O2 [11]
2⫺
When heated, S2O undergoes thermal homolysis or
8
reacts with reduced metals, for example, Fe2⫹ ions, to
yield SO4⫺ radicals that can react with organic matter
(Edwards and Curci, 1992). Hydroxyl radicals can also
form when SO4⫺ radicals react with H2O and with OH⫺
ions at alkaline conditions (Eq. [12] and [13]). Reaction
[12] becomes negligible at dissolved organic C concen-
trations ⬎1 mg L⫺1, where organic compounds are the
major sink for SO4⫺ radicals (Peyton, 1993).
SO4⫺• ⫹ H2O → H⫹ ⫹ SO24⫺ ⫹ OH• [12]
SO⫺•
4 ⫹ OH⫺ → SO 2⫺
4 ⫹ OH• [13]
⫺
Like OH radicals, SO4 radicals have a similar reactiv-
ity toward organic structures (Peyton, 1993). Larger,
more resistant phenolic compounds may be synthesized
by coupling of phenols during radical reactions induced
by SO4⫺ radicals.
EFFICIENCY OF ORGANIC
MATTER REMOVAL
Organic matter cannot completely be removed from
soils by wet oxidative treatments (Fig. 1). Early work
took advantage of this fact by using H2O2 for determina-
tion of the degree of humification in soils (Robinson
and Jones, 1925) and to gain information about the
composition of organic matter (McLean, 1931a, 1931b).
Progressing research revealed a number of factors re-
sponsible for incomplete C removal such as soil reaction,
presence of carbonates, chemically resistant organic
compounds, and protection of organic matter by min-
eral surfaces.
Hydrogen Peroxide
The extent of organic C removal by H2O2 varies with
soils and particle-size separates, ranging from ⬍20%
(Bartlett et al., 1937) to ⬎93% (Kahle et al., 2003).
Typical efficiencies of C removal are listed in Table 1.
Hosking (1932) noted for a number of calcareous Aus-
tralian Black soils that 20% (wt/wt) H2O2 removed only
5 to 20% of organic matter when the soil reaction was
alkaline (pH 9–10) while 50 to 90% were removed when
 MIKUTTA ET AL.: REMOVAL OF ORGANIC MATTER FROM SOILS
the soil pH was between 6 and 7.5. In soils containing
Mn oxides, only ⬍30% of organic matter was removed
because of rapid H2O2 decomposition. Hosking (1932)
and Anderson (1963) increased the C removal by re-
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
moving carbonates first, using HCl (pH 2–3) or a Na
acetate buffer (pH 5). In calcareous soils, carbonate
coatings favor occlusion and thus physical protection of
organic matter against destruction. Oxalate, which is a
common product of organic matter destruction (HY-
DROGEN PEROXIDE under section REACTION OF
OXIDANTS WITH INORGANIC AND ORGANIC
MATTER), can form insoluble complexes with Ca2⫹,
thus leaving a residual organic C fraction behind after
H2O2 treatment. Moreover, HCO3⫺ and CO23⫺ ions are
known to inhibit organic matter degradation during wa-
ter purification by scavenging OH radicals (Wang et al.,
2001). The same may hold true for H2O2 treatment of
calcareous soils where carbonates likely dissolve due to
the production of organic acids.
Using Na4P2O7 as a dispersing agent in the H2O2 treat-
ment, organic C removal is more complete than by
applying H2O2 alone (Simon et al., 1992). Sequi and
Aringhieri (1977) increased the average organic matter
removal by using H2O2–Na4P2O7 from 79 to 96%, likely
by disruption of aggregates, thereby releasing occluded
organic matter, and by displacing sorbed organic com-
pounds from mineral surfaces. Pyrophosphate and also
PO34⫺ sorb strongly and hysteretically to soil minerals
(Varadachari et al., 1995; Celi et al., 2000). Hence, when
carrying out a sorption experiment with soil treated with
a mixture of H2O2 and Na4P2O7, occupation of reactive
sorption sites by pyrophosphate needs to be considered.
Furthermore, organo–mineral complexes and chemi-
cally stable compounds contribute to the resistance of
organic matter (EFFICIENCY OF ORGANIC CAR-
BON REMOVAL DEPENDS ON SAMPLE PROP-
ERTIES section).
Sodium Hypochlorite
According to Anderson (1963), the C removal effi-
ciency of 6% (wt/wt) NaOCl at pH 9.5 was less affected
by the presence of carbonates (up to 9% CaCO3) than
when using 30% (wt/wt) H2O2. Several studies revealed
that 6% (wt/wt) NaOCl at pH 9.5 removed more C from
bulk soils and clays than 30% (wt/wt) H2O2 (Anderson,
1963; Omueti, 1980; Cheshire et al., 2000). The NaOCl
treatment does not require additional dispersing re-
agents because of dispersion by NaOCl itself. In spite
of a higher electric potential of NaOCl with decreasing
pH, C removal efficiency is maximal at pH 9.5 (Lavkul-
ich and Wiens, 1970). This indicates that desorption
from mineral surfaces under alkaline conditions is deci-
sive for the removal of organic compounds. Desorption
may be of similar importance for organic matter removal
as the oxidative breakdown of organic compounds, sug-
gesting the term “wet oxidation” to be misleading. Kai-
ser and Guggenberger (2003) tested a modified NaOCl
treatment (pH 8, room temperature, five repetitions)
on 196 heavy soil fractions (density ⬎1.6 g cm⫺3) and
found that between 77 to 95% of the initial organic C
125
could be removed by this procedure. Reduction of the
number of repetitive treatments may decrease the re-
moval of organic matter in soils rich in poorly crystalline
Fe and Al phases (Siregar et al., 2004).
Disodium Peroxodisulfate
The efficiency of Na2S2O8 to remove organic matter
has been proposed to be superior to H2O2 and NaOCl
(Meier and Menegatti, 1997; Table 1). When the authors
tested NaH2PO4 as buffer, C removal was less than when
using NaHCO3 buffer. This can be attributed to the
lower pH (drop from approximately 8 to 5) in case of
the Na2S2O8–NaH2PO4 mixture, which disfavors desorp-
tion of mineral-bound organic matter. Kiem and Kögel-
Knabner (2002) applied Na2S2O8 to particle-size frac-
tions of loamy and sandy surface soils and found a
contact time of 16 h sufficient to reduce organic C con-
centrations by about 93% (Table 1). Oxidative destruc-
tion of humic acid (Martin et al., 1981) and organic
matter from aquifer sediments (Powell et al., 1989),
however, not exceeded 50%. Thus, desorption of or-
ganic matter by HCO3⫺ or SO24⫺ is likely the key step
in removal of organic C from soils. In contrast, Eust-
erhues et al. (2003) found that in some cases even 2 d
of reaction time were insufficient to destroy organic C
in acid soils rich in secondary minerals (Table 1). This
indicates that either chemically stable compounds repre-
sented a major organic fraction (not tested) or strong
interactions with mineral surfaces limited desorption of
organic matter (PROTECTION OF ORGANIC MAT-
TER BY SOIL MINERALS section under EFFI-
CIENCY OF ORGANIC CARBON REMOVAL DE-
PENDS ON SAMPLE PROPERTIES).
EFFICIENCY OF ORGANIC CARBON
REMOVAL DEPENDS ON
SAMPLE PROPERTIES
Sample-specific properties like the presence of chemi-
cally stable organic compounds and protective mineral
phases are also crucial for organic C removal efficiency.
Composition of Organic Matter
Pyrogenic materials (black carbon) represent a group
of chemically resistant compounds in soils. They com-
prise randomly oriented condensed aromatic rings lo-
cated in graphite-like structures (Schmidt and Noack,
2000). Such materials can make up a significant portion
of organic matter in soils, especially in soils adjacent to
coal-processing industries (Schmidt et al., 1999) or in
soils from technogenic materials (Zikeli et al., 2004).
Hydrogen peroxide is ineffective to degrade graphite,
anthracite, lignite, charcoal, and ash (Robinson, 1927;
Schmidt et al., 1999).
Low-molecular-weight organic acids produced during
oxidative treatments are relatively resistant against fur-
ther degradation (Luft and Stöffler, 1998) and thus be-
come enriched during oxidative treatments. Analyzing
H2O2–treated clay and bulk soil fractions by differential
thermal and infrared analysis, Farmer and Mitchell
 126 SOIL SCI. SOC. AM. J., VOL. 69, JANUARY–FEBRUARY 2005
(1963) and Harada and Inoko (1977) found no evidence
for resistant organic compounds other than oxalate. For-
mation of insoluble calcium oxalates is favored under
alkaline conditions, while in acidic soils adsorption of
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
oxalate to variable charge minerals is more likely.
Farmer and Mitchell (1963) noted that in some cases
complexed oxalate couldn’t be extracted by H2O but by
5% ethylenediaminetetraacetate. In contrast, Escudey
et al. (1999) suggested extensive washing with H2O after
the H2O2 treatment to remove oxalate from soils com-
pletely but did not quantify their results.
Several studies confirmed that organic compounds
other than black carbon and oxalate could survive oxida-
tive treatments (Righi et al., 1995; Schulten et al., 1996;
Cuypers et al., 2002). Aliphatic compounds are a signifi-
cant portion of chemically resistant organic matter. Grif-
fith and Schnitzer (1977) estimated that n-alkanes and
n-fatty acids accounted for up to 40% of the H2O2–resis-
tant organic matter, while a substantial fraction of resid-
ual C could not be extracted by organic solvents. Study-
ing the H2O2–resistant organic matter in mica–beidellite
interstratified clay by Py-FIMS, Schulten et al. (1996)
found it to be enriched in N-containing compounds,
n-C22–C26 carboxylic acids, n-alkanes, n-diols and alkyl-
substituted aromatic esters. Leifeld and Kögel-Knabner
(2001) showed by CPMAS 13C-NMR analysis that H2O2
preferentially removed sugars (O-alkyl C) and lignin
compounds (mainly aromatic C) from ⬍20-␮m particle-
size separates of agricultural soils leaving an aliphatic
residue behind. In accordance, persulfate treatment evi-
denced the presence of aliphatic biopolymers in sedi-
mentary and terrestrial humic acids (Saiz-Jimenez, 1992).
Martin et al. (1981) found that n-C16–C18 fatty acids were
the most abundant compounds after reaction of humic
acid with acid K2S2O8. However, a variety of benzenecar-
boxylic and phenolic acids were also detected. Cuypers
et al. (2002) reported that persulfate preferentially re-
moved labile and more amorphous organic matter while
the residuum was enriched with long-chain aliphatics.
The resistant organic matter was proposed to have a
more condensed structure, a higher affinity for hydro-
phobic compounds and being more thermostable than
amorphous organic matter.
Lower C/N ratios of H2O2–resistant organic matter
indicate a higher chemical stability of some N com-
pounds. Cheshire et al. (2000) found that some amino
acids were protected against degradation possibly within
microaggregates or by interaction with mineral surfaces.
Interpretation of C/N ratios after organic matter re-
moval is, however, questionable since mineral-bound
NH4⫹ or NH4⫹ produced during organic matter degrada-
tion and subsequently fixed to minerals can also affect
C/N ratios (Miles et al., 1985; Leifeld and Kögel-Knab-
ner, 2001).
Protection of Organic Matter by Soil Minerals
Hosking (1932) recognized that more organic matter
resisted the H2O2 treatment in soils with higher clay
content. This suggests that organic matter can be pro-
tected against oxidative treatments by interaction with
soil minerals. Contemporary work distinguishes be-
tween the mechanisms of intercalation and sorptive pro-
tection.
Intercalation includes replacement of hydrated in-
organic interlayer cations of expandable 2:1 phyllosili-
cate clay minerals by organic molecules. This requires
either cationic or neutral organics and a strongly acidic
soil reaction. Theng et al. (1992) and Righi et al. (1995)
assumed that organic matter intercalated in expandable
clay minerals is hardly decomposable by H2O2 due to
a limited accessibility toward the reagent. In contrast,
Kodama and Schnitzer (1971) found no evidence that
organic matter sorbed into the interlayer regions of mica-
vermiculite-montmorillonite-interstratified clay resisted
15% (wt/wt) H2O2.
Eusterhues et al. (2003) observed that the concentra-
tion of Na2S2O8–resistant organic matter related posi-
tively to the clay content (r ⫽ 0.93) in twelve horizons
from two acid soil profiles (Typic Haplorthod and Typic
Dystrochrept). In the Spodosol, a significant relationship
of residual organic C to dithionite–citrate–bicarbonate-
extractable Fe (r ⫽ 0.90) suggests that the resistant
organic matter was likely associated with Fe (hydr)-
oxides (sorptive protection). Similar results were re-
ported by Mikutta et al. (2004) for NaOCl-resistant
organic matter in clay subfractions from subsurface hori-
zons of smectitic, vermiculitic, illitic, kaolinitic, and chlo-
ritic soils (Table 1). Despite the heterogeneous sample
set, the concentration of residual organic C correlated
well with oxalate-extractable Fe (Feo) and Al (Alo) (Fig.
2a). Acid oxalate primarily extracts Fe and Al from
poorly crystalline aluminosilicates, ferrihydrite and Fe
and Al humus complexes (Wada, 1989).
The efficiency of poorly crystalline minerals to protect
organic matter against oxidative destruction was con-
firmed in batch experiments. Singer and Huang (1993)
and Huang (1995) showed that humic, tannic, and citric
acid associated with non-crystalline Al hydroxide were
only partly destructible by H2O2 and NaOCl, while tan-
nic and citric acid were completely oxidized in the ab-
sence of Al hydroxide. The higher resistance of mineral-
associated organic compounds was explained by incor-
poration of organic compounds by coprecipitation or
by formation of strong surface complexes.
Mikutta et al. (2004) showed that the capability of
minerals in clay subfractions to protect organic matter
decreases as more organic C is associated with mineral
surfaces. The C removal efficiency related closely to
the initial organic C concentration normalized to the
mineral SSA (C loading; Fig. 2b). This result is consis-
tent with the finding that at small C loadings, organic
matter occupies a larger surface area with more func-
tional groups involved in multiple-site attachments with
mineral surfaces (Kaiser and Guggenberger, 2003). Or-
ganic matter in direct contact to the mineral surface
thus appears less susceptible to chemical destruction.
Eusterhues et al. (2003) provided further evidence that
the C removal efficiency depends on the protective ca-
pability of mineral surfaces. They observed that C re-
moval by Na2S2O8 decreased with soil depth. Nearly all
organic C was removed from A and EA horizons (⬎98%)
 MIKUTTA ET AL.: REMOVAL OF ORGANIC MATTER FROM SOILS 127

while in the deeper B and C horizons 9 to 84% of the

initial organic C resisted Na2S2O8. This effect can be
explained by larger amounts of mineral-bound organic
matter and by stronger association of organic matter
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.

with mineral surfaces with increasing soil depth. In sur-

face horizons, there is much unprotected, particulate
organic matter and binding sites at mineral surfaces
may already be occupied by organic matter resulting in
weaker bindings. In deeper horizons where less of the
mineral surface area is covered by organic compounds
(small C loading), organic matter may sorb in a more
spread-out, uncoiled conformation with more ligands
involved in direct contact with the mineral surface (Kai-
ser and Guggenberger, 2003). As a result, desorption
of organic matter from mineral surfaces during oxidative
treatments is more difficult in subsoils than in topsoils.

TREATMENTS INDUCE MODIFICATIONS

OF MINERAL CONSTITUENTS
The use of chemical destruction of organic matter is
based on the supposition that minerals are unaffected by
the treatments. Here we summarize reports on mineral
changes likely induced by the treatments.

Thermal Effect on Minerals
Most treatments are conducted under elevated tem-
peratures (60–100⬚C) (Table 1). Kaiser and Guggen-
berger (2003) showed that temperatures ⬎40⬚C lasting
several hours can transform moist amorphous Al hy-
droxide into gibbsite while temperatures ⬎80⬚C con-
verted ferrihydrite into hematite. The total SSA of both
mineral phases decreased on heating by about 90%,
partly due to the entire loss of microporosity (⬍2 nm).
So even moderate heating can alter oxide surface prop-
erties and thus gives rise to artifacts, at least in soils rich
in poorly crystalline components. The only procedure
reported to be efficient under ambient temperature is
the modified NaOCl treatment proposed by Kaiser et
al. (2002) (Table 1). However, the method is time-con-
suming and laborious.
Hydrogen Peroxide
Phyllosilicates
Many studies on the effects of H2O2 on individual
minerals were conducted outside the field of soil re-
search (Hayashi and Oinuma, 1964; Muromtsev et al.,
1990; Üçgül and Girgin, 2002). The use of unweathered
minerals and the variety of procedures applied, compli-
cates the transferability to soil systems. Despite this,
some general remarks can be made.
Drosdoff and Miles (1938) first noted destruction of
mica and some vermiculite samples when treated with
6 and 30% (wt/wt) H2O2. Mineral exfoliation resulted
from catalytic decomposition of H2O2 by Mn oxides
located in mineral interlayers. Amonette et al. (1985)
showed that H2O2 penetrates biotite interlayer spaces
expanded by tetraphenylborate and oxidizes 85% of the
structural Fe2⫹ ions within 24 h. Also, H2O2 diffuses into
Fig. 2. (a) Relation between the concentrations of residual organic
C and oxalate-extractable Fe plus Al in fine (䊉, ⬍0.2 ␮m) and
coarse clay (䊊, 0.2–2 ␮m) fractions of 12 acid subsoil samples with
different mineralogy after treatment with 6% (wt/wt) NaOCl. (b)
Relationship between the organic C loading of mineral surfaces and
the amount of removable organic C (data adopted from Mikutta et
al., 2004).
the interlayer spaces of phlogopite (mica with low Fe
content) and vermiculite via exchange with H2O and
cations and decomposes into O2 and H2O (Üçgül and
Girgin, 2002; Obut and Girgin, 2002). The gas evolved
can disrupt individual silicate layers. Increasing thick-
ness of the minerals (80–120 fold) was noted with in-
creasing H2O2 concentration (1–50%), temperature (40–
60⬚C), and contact time (1–30 h). Above 60⬚C, phlogopite
started to exfoliate as described by Drosdoff and Miles
(1938), possibly because of accelerated decomposition
of H2O2 with increasing temperature. However, treat-
ment with 30% (wt/wt) H2O2 (60⬚C, 70 min) caused no
phase change of phlogopite according to x-ray diffrac-
tion (XRD) (Üçgül and Girgin, 2002).
Douglas and Fiessinger (1971) showed by XRD that
the (001) signals of smectite and vermiculite decreased
after reaction with H2O2 in presence of large amounts
of sucrose (168 g C kg⫺1 clay) while little effect was
observed without sucrose or in presence of sodium ace-
tate buffer (pH 5). They inferred that both minerals,
especially vermiculite, were partly destroyed due to the
low pH (pH 1.8–3) induced by incomplete oxidation of
sucrose. However, decreasing (001) basal peak reflec-
tions following H2O2 treatment may also result from
residual organic matter producing less than perfect ori-
entation of clay specimen (Dohrmann, 2003).
Miles et al. (1985) observed NH4⫹ produced during
organic matter degradation to sorb to exchange sites of
vermiculite, inducing collapse of the 1.48-nm spacings to
 128 SOIL SCI. SOC. AM. J., VOL. 69, JANUARY–FEBRUARY 2005
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
Fig. 3. (a) Scanning electron microscope (SEM) image of oxide-free
(dithionite–citrate-treated) Prassa-Kimolos bentonite (Greece),
(b) oxide-free bentonite treated with 30% (wt/wt) H2O2 (6 h, 80ⴗC)
in the presence of 230 mg L–1 dissolved organic C. Bars represent
100 ␮m.
the 1.03-nm position characteristic for mica-like phases.
Infrared spectroscopy confirmed NH4⫹ fixation by the
treated vermiculite. Therefore, the H2O2 treatment is
not suitable for XRD-based identification of vermiculite
in soils.
Van Langeveld et al. (1978) inferred from reduced
XRD reflections that montmorillonite (6% organic C)
was structurally altered during H2O2 treatment. Figure
3a and 3b display the transformation of bentonite on
treatment with 30% (wt/wt) H2O2 at 80⬚C for 6 h in pres-
ence of dissolved organic matter. Compared with un-
treated particles, the treated ones show distinctively
frayed structures suggesting corrosion likely caused by
decomposing H2O2 and acidic organic matter degrada-
tion products.
In contrast, Hayashi and Oinuma (1964) found no
indications for major alterations of repository clays (ver-
miculite, montmorillonite, illite, chlorite) treated with
30% (wt/wt) H2O2 at 80 to 90⬚C over several days. Mu-
romtsev et al. (1990) recognized no structural alteration
of pure vermiculite treated with 30% (wt/wt) H2O2 by
applying XRD analysis, nevertheless the CEC doubled
because of layer expansion. Rosenberg and Hooper
Fig. 4. X-ray diffractograms of Mg-saturated, glycerated, and oriented
Fithian illite (I) (⬍2 ␮m) before and after treatment with 10%
(wt/wt) H2O2 (Fithian illite: 85% illite, 15% mixed layers, kaolinite,
quartz). The treatment was conducted in the presence of straw and
manure (S, M, diam. 0.1 mm). Before treatment, organo–mineral
associations (5% organic matter) were prepared by three drying
and wetting cycles. Treatments: (a) no, (b) I ⫹ H2O2, (c) I ⫹ H2O2 ⫹
S, and (d) I ⫹ H2O2 ⫹ M.
(1997) showed that deposit illites were not attacked by
H2O2. We studied illite treated with 10% (wt/wt) H2O2
(80⬚C, 120 h) in the presence and absence of organic
matter. Before treatment, clay specimens were sub-
jected to drying–wetting cycles in the presence of ma-
nure and straw (0.1 mm) to facilitate the formation of
clay–organic associations. Using XRD, we observed no
structural change of illite induced by H2O2 treatment
(Fig. 4).
The results compiled above indicate that the alter-
ation of phyllosilicates by H2O2 depends on (i) the pres-
ence of catalyzing materials, (ii) the existence of accessi-
ble interlayer mineral surfaces, and (iii) the abundance
of organic matter. The results imply that pure depository
minerals not weathered in the soil environment and thus
lacking structural modifications such as cracks, microfis-
sures, and expansion zones as well as sorbed organic
matter are little affected by treatment with H2O2.
Carbonates, Oxides, and Sulfides
In calcareous soils, H2O2 treatment may cause dissolu-
tion and corrosion of carbonate minerals because of the
low pH of H2O2 (Pingitore et al., 1993). Typically, Mn
oxides are destroyed during the H2O2 treatment (Shu-
man, 1983; Papp et al., 1991; Table 2). Manganese (III,
IV) oxides are affected by reduction to Mn2⫹, which is
 MIKUTTA ET AL.: REMOVAL OF ORGANIC MATTER FROM SOILS
Table 2. Destruction of Mn oxide and sulfide minerals by oxidative treatments (data adopted from Papp et al., 1991).
Mn and Fe extracted, %
Pyrite Pyrrhotite
Treatment MnO2 FeS2 FeS
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
H 2O2† 97 92 46
H2O2 and Na4P2O7‡ 98 41 21
NaOCl¶ 1.7 0.8 0.9
† 1 g sample ⫹ 8 mL of 3:2 mixture of 30% (wt/wt) H2O2 and 0.025 M HNO3.
‡ Conducted at pH 6.5 according to Sequi and Aringhieri (1977); Table 1.
¶ Modified from Lavkulich and Wiens (1970); followed by acid wash.
subsequently oxidized to yield MnOOH (Pardieck et
al., 1992), Mn3O4 (Jackson, 1958), or a mixture of differ-
ent Mn oxides (Moon et al., 1999). Sulfide minerals are
readily dissolved by reaction with H2O2 (Mukherjee et
al., 2001). Papp et al. (1991) showed that H2O2 dissolved
21 to 99% of the total metals present in sulfides
(Table 2). Consequently, H2O2 should not be used to
estimate organically bound metals when sulfide miner-
als are present, for example in acid sulfate soils from
coastal lowlands (Shamshuddin et al., 2004).
Iron and Al (hydr)oxides may be affected during the
H2O2 treatment by heat-induced transformation into
more crystalline forms and by organic-assisted disso-
lution at low pH. At alkaline pH, for example, in cal-
careous soils or when using H2O2 in combination with
Na4P2O7, oxides remain unaltered (Marzadori et al., 1991).
At low pH (pH 2–4), large concentration of oxalate,
and high temperature, the H2O2 treatment is comparable
or even more aggressive than the acid-oxalate method
(pH 3, room temperature, darkness, 4 h) designed for
extraction of poorly crystalline minerals and Fe and Al
bound to organic matter (Blakemore et al., 1987). For
acid soils treated with 30% (wt/wt) H2O2, Lavkulich
and Wiens (1970) reported that the amount of oxalate-
extractable Fe and Al decreased by 34 to 80% and 1 to
90% (II–H2O2 treatment, Table 3). They assumed that in-
organic Fe and Al phases dissolved during the H2O2
treatment. However, mass balance calculations utiliz-
ing selective extractions prior and after H2O2 treatment
suggest that dissolution of poorly crystalline Fe and Al
components alone does not entirely explain the smaller
Feo and Alo concentrations after H2O2 treatment (Table 3).
More likely, they result from heat-induced recrystalliza-
tion of poorly crystalline oxides. However, after mild
H2O2 treatment (I-H2O2 treatment; Table 3), the mass
balance was positive indicating higher extraction effi-
ciency of acid oxalate after the H2O2 treatment due to
disaggregation and removal of organic matter coatings
from oxide surfaces (Marzadori et al., 1991). When test-
ing the influence of 10% (wt/wt) H2O2 on six acid subsoil
samples, we found an average decrease of Feo and Alo
concentrations by approximately 90% (Table 3). Alumi-
num and Fe in reacted H2O2 solutions were little (Ta-
ble 3), suggesting the decrease in oxalate-extractable
components to be related to the transformation of min-
erals at high temperature (80⬚C).
Pyrophosphate, when used in conjunction with H2O2
as a dispersing reagent to enhance C removal, can cause
loss of peptized fine mineral particles, especially in pres-
ence of adsorbed organic matter, or dissolution of cer-
129
Cu and Zn extracted, %
Chalcopyrite Chalcocite Chalcopyrite Sphalerite
CuFeS2 Cu2S CuFeS2 ZnS
39 99 88 80
75 99 97 93
8.7 4.2 2.3 1.9
tain mineral constituents like amorphous Al(OH)3 (Par-
fitt and Childs, 1988; Kaiser and Zech, 1996). In addition,
pyrophosphate may induce precipitation of Ca phos-
phates (Hawke et al., 1989; Celi et al., 2001) and Al
phosphates (e.g., poorly crystalline Al phosphate, tara-
nakite, wavellite) (Kim and Kirkpatrick, 2004).
Sodium Hypochlorite
In general, Mn oxides and sulfide minerals are dis-
solved to a lesser extent by NaOCl compared with H2O2
(Table 2). Lavkulich and Wiens (1970) found that, at
pH 9.5, NaOCl dissolved significantly less oxalate-extract-
able Fe and Al than H2O2 (Table 3). This can be ex-
plained by the alkaline pH of NaOCl, which prevents
acid-induced mineral dissolution and may probably sup-
port hydrolysis and precipitation of hydroxides (METAL
PRECIPITATION section). However, some Al can be
dissolved at pH 9.5, for example in the Alouette Ap
horizon (Table 3). Using the method of Lavkulich and
Wiens (1970), Osei and Singh (1999) reported that no
Fe was released from tropical surface soils by NaOCl
while extracted Al and Si accounted for up to 0.3 g kg⫺1.
Negligible amounts of Fe and Al were dissolved during
treatment of a Mollisol surface soil with 5.3% (wt/wt)
NaOCl (Qiang et al., 1994; Table 1). In soils rich in
poorly crystalline minerals, 6% (wt/wt) NaOCl at pH 8
(room temperature, three repetitions) dissolved no Fe
and ⬍3% of dithionite-citrate extractable Al and Si
(Siregar et al., 2004). These findings support the view
that crystalline oxides and silicates are not affected by
NaOCl.
However, NaOCl treatments at higher temperatures
may induce changes in extractable pedogenic Al and
Fe (e.g., Langley Ap; Table 3) due to transformation
into more crystalline forms. In contrast, Marzadori et
al. (1991) studying calcareous soils found an increase in
Feo and Alo after destruction of organic matter by 7%
(wt/wt) NaOCl despite heating to 80⬚C (Table 1). In that
case, the thermal transformation of a poorly crystalline
oxide fraction was probably overcompensated by an
increased extractability of poorly crystalline phases due
to the removal of organic coatings. Mayer (1999) found
an increased enthalpy for the adsorption of N2 on marine
sediments treated with 13% (wt/wt) NaOCl at pH 9 to
9.5. The change in adsorption enthalpy was attributed
to microtopographic or chemical changes of mineral
surfaces due to the highly alkaline reaction conditions.
This effect warrants further research.
 130 SOIL SCI. SOC. AM. J., VOL. 69, JANUARY–FEBRUARY 2005

Table 3. Effect of H2O2 and NaOCl treatment on oxalate-extractable Fe and Al fractions in acid bulk soils. Negative values in the ‘mass
balance’ column indicate that poorly crystalline components were transformed during heating into more crystalline forms. Data for
the H2O2 (30%) and the NaOCl treatment adapted from Lavkulich and Wiens (1970).
After treatment in After treatment in
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.

Initial residues extracts Mass balance†

Soil Horizon Feo Alo Feo Alo Fe Al Fe Al
g kg⫺1
30% (wt/wt) H2O2 (Treatment I; see ‘Material’ column in Table 1)
Abbotsfort Ap 7.6 10.0 6.3 8.6 0.06 1.9 ⫺1.2 0.5
Abbotsfort Bir 3.5 7.8 3.1 7.0 N.D.‡ 0.2 ⫺0.4 –0.6
Alouette Ap 7.8 10.2 7.7 3.6 1.2 3.1 1.1 –3.5
Cloverdale Ap 8.6 4.6 11.8 3.0 0.9 3.5 4.1 1.9
Cloverdale C 4.2 2.6 3.9 2.6 0.1 0.3 ⫺0.2 0.3
Langley Ap 15.0 12.0 17.9 6.6 0.7 3.6 3.6 –1.8
Whatcom Ap 9.9 6.7 11.6 4.5 0.5 2.8 2.2 0.6
Whatcom Bir 12.0 16.8 11.2 18.0 0.01 0.3 ⫺0.8 1.5
30% (wt/wt) H2O2 (Treatment II; see ‘Material’ column in Table 1)
Abbotsfort Ap 7.6 10.0 3.8 8.3 0.1 1.8 ⫺3.7 0.1
Abbotsfort Bir 3.5 7.8 2.3 7.7 0.02 0.6 ⫺1.2 0.5
Alouette Ap 7.8 10.2 1.6 1.1 7.2 11.5 1.0 2.4
Cloverdale Ap 8.6 4.6 5.3 2.7 1.7 4.0 ⫺1.6 2.1
Cloverdale C 4.2 2.6 1.9 2.3 0.04 0.1 ⫺2.3 –0.2
Langley Ap 15.0 12.0 8.9 6.2 1.9 8.0 ⫺4.2 2.2
Whatcom Ap 9.9 6.7 5.8 3.4 2.0 5.8 ⫺2.1 2.5
Whatcom Bir 12.0 16.8 6.0 14.5 0.2 1.2 ⫺5.8 –1.1
6% (wt/wt) NaOCl (according to Anderson, 1963; Table 1)
Abbotsfort Ap 7.6 10.0 7.3 9.7 0.03 0.1 –0.3 –0.2
Abbotsfort Bir 3.5 7.8 3.3 6.0 N.D. 0.1 –0.2 –1.7
Alouette Ap 7.8 10.2 4.9 5.7 0.7 1.7 –2.2 –2.8
Cloverdale Ap 8.6 4.6 8.7 4.4 0.1 0.2 0.2 0
Cloverdale C 4.2 2.6 4.7 3.0 N.D. 0.0 0.5 0.4
Langley Ap 15.0 12.0 11.1 7.0 0.2 0.5 –3.7 –4.5
Whatcom Ap 9.9 6.7 11.3 7.2 0.2 0.6 1.6 1.1
Whatcom Bir 12.0 16.8 12.2 16.0 0.01 0.02 0.2 –0.8
10% H2O2 (wt/wt) (according to Tributh and Lagaly, 1991; Table 1)
Rottleberode Bw 2.3 1.0 0.2 0.1 0.01 0.1 ⫺2.1 –0.8
Kyffhäuser E 1.1 1.5 0.1 0.1 0.3 0.7 ⫺0.7 –0.7
Kyffhäuser Bt 1.1 1.9 0.2 0.2 0.4 0.8 ⫺0.5 –0.9
Bährental Bw 2.9 2.5 0.3 0.2 0.4 1.2 ⫺2.2 –1.1
Hewenegg AB 8.9 3.4 0.9 0.4 0.3 0.2 ⫺7.7 –2.8
Köhlerwald Bt 13.4 13.3 1.4 1.2 N.D. 1.8 ⫺12.0 ⫺10.3
† Mass balance (Fe, Al) (g kg⫺1) ⫽ (Feo, Alo)residuum ⫹ (Fe, Al)extract ⫺ (Feo, Alo)initial.
‡ N.D. ⫽ not detected.

Disodium Peroxodisulfate phase properties and organically bound metal fractions.

Using XRD, IR spectroscopy and N2 adsorption,
Menegatti et al. (1999) found no structural alteration
of Na2S2O8–treated illite, kaolinite, and montmorillonite
reference minerals (⬍0.2 and ⬍2 ␮m). Minor losses of
Ca, K, and Mn were explained by partial removal of
fine-grained accessory minerals such as feldspars and
carbonates. The SSA of most treated samples remained
unaltered while the SSA of montmorillonite increased
by ⬎20 m2 g⫺1. This was attributed to the dispersion
of large aggregates. The CEC of the treated minerals
remained unchanged. However, HCO3⫺ as used for pH
control may partly be converted into CO23⫺ on heating,
which at 80⬚C, can extract Al from allophanes and hy-
droxides (Wada, 1989). Thus, if used for organic matter
removal from soils where these phases are abundant, for
example volcanic ash soils and Spodosols, this potential
defect requires further attention.
METAL PRECIPITATION
The question whether metal ions complexed with or-
ganic matter are released and precipitate during oxida-
tion is relevant for the reliable assessment of mineral
Sequi and Aringhieri (1977) noted that Fe and Al associ-
ated with organic matter are released during H2O2 oxi-
dation and subsequently precipitate as hydroxides on
inorganic and organic components. These precipitates
are assumed to alter SSA and charge of the mineral
phase and to protect organic matter against further deg-
radation. The formation of metal precipitates during the
H2O2 treatment was inferred from the increase in SSA
(N2–BET) and positive surface charge, and the concomi-
tant decrease of negative charge. However, it is more
likely that the alteration of surface charge derived from
the removal of organic matter carrying much negative
charges located in carboxylic groups and from exposure
of positively charges on oxide surfaces. Despite that,
precipitation of metals formerly complexed with organic
matter cannot be ruled out. Schultz et al. (1999) pre-
ferred H2O2 instead of alkaline NaOCl to assess organi-
cally bound metals in carbonate-free sediments to avoid
metal precipitation (Table 1). Addition of NH4 acetate
during the H2O2 treatment was intended to prevent re-
adsorption of metals to the solids. Hoffman and Fletcher
(1981) showed that NaOCl (6.5%, pH 9.5) induced little
precipitation of trace metals (Cu, Zn, Fe, Mn, Mo) when
 MIKUTTA ET AL.: REMOVAL OF ORGANIC MATTER FROM SOILS
inorganic precipitates from soils and sediments were
redissolved by acidified H2O. In spite of the alkaline
conditions, soluble organic compounds can effectively
scavenge metals released and thus hinder their precipi-
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
tation. In accordance, Shuman (1983) showed for six
bulk soils that 5% (wt/wt) NaOCl (pH 8.5) dissolved
similar amounts of metals (Cu, Fe, Zn) from the organic
fraction as 30% (wt/wt) H2O2 while H2O2 extracted sig-
nificantly more Mn. In summary, there is no consistent
perception on the degree of precipitation of organically
bound metals released during organic matter destruc-
tion and on the potential effects on mineral properties.
SYNTHESIS
This review shows that a large number of protocols
for removal of organic matter by H2O2, NaOCl, and
Na2S2O8 is available. Removal of soil organic matter
is never complete and largely relies on the reaction
conditions chosen and the sample properties. Sodium
hypochlorite and Na2S2O8 are more effective in organic
C removal than H2O2, especially in calcareous soils
where oxidation-resistant Ca oxalates may form. Car-
bon removal efficiency can be increased by desorbing
reagents such as NaHCO3 and Na4P2O7, but those com-
pounds strongly sorb to minerals, which needs to be
considered in sorption experiments with treated sam-
ples. In soils with large portions of mineral-bound or-
ganic matter, Fe and Al (hydr)oxides and other poorly
crystalline constituents, even NaOCl and Na2S2O8 fail
to reduce the organic C concentrations effectively. Clay-
sized Fe and Al phases provide large SSA and reactive
hydroxyls favoring ligand exchange reactions with or-
ganic matter (Gu et al., 1995). The resulting mineral–
organic attachments are difficult to break, especially
when a single molecule is attached to multiple mineral
surface sites, thus hampering desorption of organic mat-
ter, which is an important prerequisite for organic mat-
ter removal. However, sorptive protection of organic
matter by minerals is hardly discernable from protection
of organic matter due to occlusion in microaggregates
or coprecipitation with hydrous oxides. Since intercala-
tion is confined to expandable clay minerals and strongly
acid conditions, the relevance of protected organic com-
pounds in interlayer spaces is presumably small. Organic
matter resistant to oxidative treatment likely represents
a refractory C pool since it seems to be older than bulk
organic matter before treatment (Theng et al., 1992).
Similar composition of residual organic matter after
chemical and biological degradation suggests the treat-
ment with oxidative reagents to mimic biodegradation
(Rihani et al., 1995; Cuypers et al., 2002). However,
selective degradation of certain structures of organic
matter by the three reagents (aromatics versus aliphat-
ics) and, in case of H2O2, the likely adsorption of organic
intermediates deriving from labile organic matter (e.g.,
oxalate) to minerals needs to be considered.
Based on the evidence shown, changes of mineral
phase properties when treated with oxidative reagents
seem inevitable. This attributes some ambiguity to stud-
ies concerned with soil mineralogical composition or
131
surface-controlled processes (e.g., adsorption, diffusion).
Hydrogen peroxide has been shown to disintegrate mi-
cas, vermiculites, and smectites. Phyllosilicate disinte-
gration may become more significant with increasing
H2O2 concentration, temperature and in the presence
of decomposable organic matter. In soils, destruction
of phyllosilicates might change the surface properties
but little experimental evidence has been given. For
example, Theng et al. (1999) hypothesized the SSA in-
crease of a smectitic soil following H2O2 treatment to
result from destruction of smectite. Treatment with
NaOCl produced only a minor increase in SSA although
both reagents removed similar amounts of organic mat-
ter. Compared with H2O2, the effects of NaOCl or
Na2S2O8 on phyllosilicates seem negligible, but more
studies on soils are needed to confirm that.
Poorly crystalline constituents are most susceptible
to alteration during treatments for organic matter re-
moval. In organic matter-rich soils treated with H2O2,
organic oxidation products like low-molecular-weight
organic acids may assist mineral dissolution at low pH.
During the alkaline NaOCl procedure (pH 9.5), Al from
hydrous oxides can dissolve. This effect can be avoided
by using NaOCl at lower pH. Moreover, temperatures
⬎40⬚C applied during organic matter removal involves
the risk of recrystallization of poorly crystalline Al
phases, while temperatures ⬎80⬚C may convert poorly
crystalline into more crystalline Fe oxides. Since poorly
crystalline phases significantly contribute to the physical
and chemical properties of soils (Percival et al., 2000;
Kiem and Kögel-Knabner, 2002), more effort should
be put on that question. At present, only the NaOCl
treatment has been shown to remain efficient at room
temperature and thus avoids heat-induced transforma-
tion of sensitive mineral phases.
Metals released during degradation of organic matter
may precipitate, and thereby possibly reduce the C re-
moval efficiency and the amount of organically bound
trace metals in sequential extraction studies, and may
also affect surface properties of minerals. However, lit-
tle awareness exists of that problem. Hydrogen peroxide
and NaOCl seem to induce similar metal precipitation,
with the degree of precipitation depending on the pH,
metal content and the amount of organic matter. In-
organic precipitates may probably become relevant for
soils and particle-size separates rich in organically com-
plexed metals such as Andisols and Spodosols.
IMPLICATIONS
At present, the knowledge on oxidative removal of
soil organic matter is incomplete with respect to the ef-
fects of oxidants on soil minerals. Therefore, systematic
studies on changes of mineral properties on oxidative
removal of soil organic matter are required. These stud-
ies should involve pure minerals (poorly crystalline ox-
ides, expandable clay minerals), defined organo–mineral
complexes and soils with a wide range of properties (min-
eral composition, pH, organic matter content). Conclu-
sions on the feasibility of a certain oxidant/protocol to
remove organic C are possible only when several oxidants
 132 SOIL SCI. SOC. AM. J., VOL. 69, JANUARY–FEBRUARY 2005
Table 4. Oxidative treatments in soil analysis. Advantages and drawbacks of reactants: (⫹) ⫽ suitable, (⫺) ⫽ not recommended,
(⫹/⫺) ⫽ ambiguous.
Purpose Hydrogen peroxide
Textural analysis ⫹/⫺ uncertain for soils with high contents
Reproduced from Soil Science Society of America Journal. Published by Soil Science Society of America. All copyrights reserved.
of vermiculite, mica and smectite
Mineralogical analysis ⫺ dissolution of carbonates
and determination of ⫺ destruction of smectitic, vermiculitic
mineral properties and micaceous minerals
⫺ transformation of vermiculites into
mica-like minerals by NH4ⴙ fixation
⫺ dissolution of poorly crystalline
oxides in acid soils (especially when
Na4P2O7 is used as dispersant)
⫺ heating may alter poorly crystalline
oxides
Extraction of organically- ⫺ dissolution of Mn oxides, sulfide
bound metals minerals, and poorly crystalline
oxides in acid soils
are comparatively applied to the same sample collective.
When modifying oxidation protocols, mineral alterations
should be elucidated by using combined methods like
XRD, IR spectroscopy, gas adsorption (e.g., N2, CO2),
and selective dissolution techniques.
Table 4 may serve as a guide for the use of reagents
for organic matter removal. For textural analysis, H2O2
is adequate when the soil mineral phase is not domi-
nated by mica, vermiculite or smectites. This recommen-
dation must be used with caution since the impact of
mineral disintegration on particle-size distribution has
not yet been tested. Sodium hypochlorite is impractical
for this purpose because of the formation of haloorgan-
ics that have to be disposed separately. Similarly, the
large amounts of oxidant needed render the Na2S2O8
procedure unsuitable for organic matter removal before
textural analysis. For organic C removal before sorption
experiments and when surface properties of soils and
minerals (SSA, CEC) are assessed, we recommend the
use of NaOCl (pH 8, 25⬚C) instead of 30% (wt/wt) H2O2
since phyllosilicate disintegration and heat-induced trans-
formations of minerals are kept to a minimum. For quan-
tification of clay minerals, H2O2 should be avoided
because of the transformation of vermiculites into mica-
like minerals by NH4⫹ fixation. The use of Na2S2O8 is
appropriate for clay preparation before XRD analysis
since it seems not to alter the properties of reference
clays. The application of NaOCl (pH 9.5) should be
avoided for soils containing interlayered Al and Al hy-
droxides. Before further analysis, a test for the residues
of organic C and the reagents used is recommended.
ACKNOWLEDGMENTS
We are grateful to Christian Mikutta (Berlin University of
Technology) and Adelina Siregar for comments and discus-
sion. Adelina Siregar provided the XRD diffractograms of
H2O2–treated illite. This study was funded by the Deutsche
Forschungsgemeinschaft priority program SPP. 1090 “Soils as
sources and sinks for atmospheric CO2”.
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