Comparação Método Remoção MO Solo

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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
ABSTRACT termination of soil mineral properties requires complete
removal of organic matter without modification of the
We compare the performance of three most accepted reagents for
mineral phase. An incomplete removal of organic mat- organic matter removal: hydrogen peroxide (H
2
O
2
), sodiumhypochlo-
rite (NaOCl) and disodium peroxodisulfate (Na
2
S
2
O
8
). Removal of ter hampers the evaluation of phyllosilicate clay miner-
organic matter from soil is mostly incomplete with the efficiency of
alogy (Tributh and Lagaly, 1991), SSA determination
removal depending on reaction conditions and sample properties.
(de Jonge et al., 2000) and may also affect infrared (IR)
Generally, NaOCl and Na
2
S
2
O
8
are more effective in organic C re-
and differential thermal analysis (Mitchell and Farmer,
moval than H
2
O
2
. Alkaline conditions and additives favoring disper-
1962).
sion and/or desorption of organic matter, such as sodium pyrophos-
Hydrogen peroxide was introduced by Robinson
phate, seem to be crucial for C removal. Pyrophosphate and additives
(1922) for soil texture analysis and became the most
for pH control (bicarbonate) may irreversibly adsorb to mineral sur-
widely used chemical reagent for organic matter de-
faces. In soils with a large proportion of organic matter bound to the
struction. Some alternative reactants have been pro- mineral matrix, for example subsoils, or rich in clay-sized minerals
(Fe oxides, poorly crystalline Fe and Al phases, expandable phyllo- posed to increase C removal efficiency and to reduce
silicates), C removal can be little irrespective of the reagents used.
possible effects of H
2
O
2
on minerals. Sodium hypochlo-
Residual organic C seems to seems to represent largely refractory
rite (Anderson, 1963) and Na
2
S
2
O
8
(Meier and Mene-
organic matter, and comprises mainly pyrogenic materials and ali-
gatti, 1997) have emerged as reagents with the greatest
phatic compounds. If protected by close association with minerals,
potential to replace H
2
O
2
. These reagents have been
other organic constituents such as low-molecular weight carboxylic
recently applied to soils (Kaiser et al., 2002; Kiem and
acids, lignin-derived and N-containing compounds may escape chemi-
Ko gel-Knabner, 2002; Eusterhues et al., 2003) and sedi-
cal destruction. For determination of mineral phase properties, treat-
ments (Mayer, 1999). ment with H
2
O
2
should be avoided since it may promote organic-
assisted dissolution of poorly crystalline minerals at low pH, disinte- To date, there is a vast number of oxidation protocols
gration of expandable clay minerals, and transformation of vermiculite
and much uncertainty regarding the effects of oxidative
into mica-like products due to NH
4
fixation. Sodium hypochlorite

reagents on soil constituents. Athorough understanding
and Na
2
S
2
O
8
are less harmful for minerals than H
2
O
2
. While the NaOCl
of treatments for soil organic matter removal with oxi-
procedure (pH 9.5) may dissolve Al hydroxides, alkaline conditions
dants is the key to a correct interpretation of experimen-
favor the precipitation of metals released upon destruction of organic
tal results. Thus, our objective is to review and compare
matter. Prolonged heating to 40C during any treatment may trans-
the suitability of H
2
O
2
, NaOCl, and Na
2
S
2
O
8
for organic
form poorly crystalline minerals into more crystalline ones. Sodium
matter removal from soils, sediments, and minerals. hypochlorite can be used at 25C, thus preventing heat-induced min-
eral alteration. 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-
R
emoval of organic matter by chemical reagents is
moval efficiency and reasons for organic matter resis- a common pretreatment for analyses of the soil
tance, (iv) the effects of reactants on soil minerals and mineral phase such as particle-size distribution (Gee
(v) metal precipitation, and (vi) implications for the use and Bauder, 1986), mineral composition (Tributh and
Lagaly, 1991), cation exchange capacity (CEC), and spe- of chemical treatments for soil analysis.
cific surface area (SSA; Kahle et al., 2003). Chemical
destruction of organic matter is also used to uncover
PROCEDURES, REACTION CONDITIONS,
mineral surfaces for subsequent sorption experiments
AND APPLICATION
(Jardine et al., 1989; Kaiser and Zech, 2000; Pagel-Wieder
et al., 2004) and to assess organically bound metals (e.g.,
Removal of organic materials from soil by aqueous
Shuman, 1983). Other fields for the use of chemical degra-
reactants is controlled by multiple factors, including the
dation of soil organic matter include the isolation of
reaction conditions (pH, temperature, contact time,
refractory organic fractions (Balesdent, 1996; Righi et
chemical additives) and soil properties (mineralogy, or-
al., 1995; Eusterhues et al., 2003) and the exploration
ganic matter content, and quality). Attempts have been
of organic matter properties (Cuypers et al., 2002). De-
made to optimize reaction conditions to increase the
efficiency of organic C removal from soils. This resulted
Institut fu r Bodenkunde und Pflanzenerna hrung, Martin-Luther-Uni-
in a variety of treatment protocols compiled in Table 1,
versita t Halle-Wittenberg, Weidenplan 14, D-06108 Halle, Germany.
which will be briefly discussed here.
Received 18 May 2004. *Corresponding author (mikutta@landw.uni-
halle.de).
Abbreviations: Ac, acetate; CEC, cation exchange capacity; IR, infra- Published in Soil Sci. Soc. Am. J. 69:120135 (2005).
Soil Science Society of America red; PAH, polynuclear aromatic hydrocarbons; SSA, specific surface
area; XRD, x-ray diffraction. 677 S. Segoe Rd., Madison, WI 53711 USA
120
Published January, 2005
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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
mL % %
Hydrogen peroxide
2 g soil 15 30 heating organic matter content Jackson (1958)
I) 5 g soil 1 30 10 mL H
2
O, 6070C, 5 1177 effect on minerals Lavkulich and Wiens (1970)
15 min
II) 10 g soil 5 30 20 mL H
2
O, initially 2881 effect on minerals Lavkulich and Wiens (1970)
room temperature, then
heating to 6070C
10 g soil 20 30 80 mL H
2
O, initially 5694 surface area and charge Sequi and Aringhieri (1977)
heating to 7080C
10 g soil 20 30 80 mL Na
4
P
2
O
7
, initially 88100 surface area and charge Sequi and Aringhieri (1977)
heating to 7080C
10 g clay to 60 g sand 5 30 initially room temperature, particle size distribution Gee and Bauder (1986)
then heating to 90C
10 g soil 5 30 then 10 1020 mL H
2
O, initially clay mineralogy Kunze and Dixon (1986)
heating to 6570C
N.A. vermiculite N.A. 30 80C, 3 min and 20C, 24 h effect on clay properties Muromtsev et al. (1990)
1520 g clay 100 10 initially room temperature, clay mineralogy Tributh and Lagaly (1991)
then heating to 6070C
3 g size fraction 50 50 (vol. %) initially room temperature, 85 surface area Feller et al. (1992)
then heating to 50C
10 g soil 10 30 or 50 initially room temperature, particle size distribution Sheldrick and Wang (1993)
then heating to 90C
10 g clay 200 5 60C, 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 70C for 24 h
1 g soil 50 6 80C, five repetitions 6697 surface area Theng et al. (1999)
10 g decarbonated sediment 20 30 HNO
3
, 5090C, 100 optimization of Schultz et al. (1999)
three additions of H
2
O
2
, sequential metal
NH
4
OAc to prevent extraction
metal precipitation
20 g soil 10 initially room temperature, 234 (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, 8394 analysis of residual Leifeld and Ko gel-Knabner
diam. 20 m then heating to 70C, 13 d organic matter (2001)
Sodium hypochlorite
10 g soil 20 6 boiling, 3 15 min, pH 9.5 3296 clay mineralogy Anderson, (1963)
5 g soil 10 6 boiling, 3 15 min, pH 9.5 6983 comparison H
2
O
2
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 80C, 5 1 h 8894 B adsorption and Marzadori et al. (1991)
desorption
1 g soil 2 5.3 96C, 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)
11.5 g sediment 13 6080C, 6 h, pH 99.5 N.A. surface area Mayer (1999)
1 g sediment 20 N.A. 95 5C, 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, 2680 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, 4981 isolation of stable Mikutta et al. (2004)
pH 8 organic matter
Disodium peroxodisulfate
0.2 g clay 8 g NaHCO
3
buffer, 98C, 1 h, 7897 clay mineralogy Meier and Menegatti (1997)
pH 7.88.5
0.5 g clay minerals 20 g 22 g NaHCO
3
buffer, 80C, effect on clay minerals Menegatti et al. (1999)
1 h, pH 7.88.5
0.2 g of size fractions 8 g NaHCO
3
buffer, 80C, 16 h 93 surface area Kiem et al. (2002)
0.5 g clay 20 g 22 g NaHCO
3
buffer, 80C, 1699 isolation of stable Eusterhues et al. (2003)
2 d organic matter
Pretreated with Na
4
P
2
O
7
NaOH.
Diethylenetriaminepentaacetic acid chelator.
OC, organic C.
Ac, acetate.
# Not available.
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122 SOIL SCI. SOC. AM. J., VOL. 69, JANUARYFEBRUARY 2005
Hydrogen Peroxide Lack of visible frothing and bleached soil color indicate
a complete reaction, but frothing may continue due to
Most protocols for sample preparation before textural
the decomposition of excess H
2
O
2
at mineral surfaces
and mineralogical analysis propose the use of 30%(wt/wt)
(REACTION OF OXIDANTS WITH INORGANIC
H
2
O
2
but 10 and 50% (wt/wt) H
2
O
2
have been suggested
AND ORGANIC MATTER section).
as well (Table 1). McLean (1931b) found that doubl-
Sometimes H
2
O
2
is used in combination with acetate
ing the H
2
O
2
concentration from 6 to 12% resulted in
buffer (pH 5) to prevent acidic conditions resulting from
little increase in C removal from soils (Fig. 1). This
formation of acid oxidation products (Douglas and Fies-
suggests that the concentration of H
2
O
2
is not decisive
singer, 1971; Pennell et al., 1995). The pH of unbuffered
for C removal efficiency, probably because of the de-
soilH
2
O
2
suspensions may drop by up to three units
composition of H
2
O
2
(REACTION OF OXIDANTS
and final pH values between 2 and 4 have been reported
WITH INORGANIC AND ORGANIC MATTER sec-
(Douglas and Fiessinger, 1971; Lavkulich and Wiens,
tion), and the presence of chemically stable and mineral-
1971; Griffith and Schnitzer, 1977). Using acetate buffer,
protected organic compounds (EFFICIENCY OF OR-
H
2
O
2
is additionally consumed due to the oxidation of
GANIC CARBON REMOVAL DEPENDS ONSAM-
acetate. Acetate (Ac) may also adsorb to minerals (e.g.,
PLE PROPERTIES section).
van Hees et al., 2003) and thus contribute to residual
Typically, the treatments start at room temperature
C (1741% C; Pennell et al., 1995).
because of a strong initial reaction with easily decom-
There is little consistency in H
2
O
2
use before SSA
posable organic matter. If frothing subsides, the sample
determination of the mineral phase. Hydrogen peroxide
is commonly heated to 60 to 90C (Table 1). Increasing
concentrations vary from 6 to 30% (Sequi and Arin-
temperature accelerates the decomposition of H
2
O
2
but
ghieri, 1977; Theng et al., 1999) and reaction tempera-
shortens the reaction time necessary to oxidize organic
tures from 50 to 80C (Feller et al., 1992; Theng et al.,
matter (Schultz et al., 1999). At temperatures 70C,
1999) (Table 1). Similarly, H
2
O
2
concentration and con-
H
2
O
2
is rapidly consumed and additional H
2
O
2
is needed
tact time proposed for isolation of stable organic matter
to perpetuate organic matter destruction. At lower tem-
vary strongly (Righi et al., 1995; Theng et al., 1992).
peratures, the contact time needs to be extended (Schultz
These examples demonstrate little agreement on proto-
et al., 1999). In practice, removal of organic C from soils
cols to achieve given research objectives.
using H
2
O
2
often requires several days and no reliable
indicator exists showing completion of the reaction.
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
OFMINERALCONSTITUENTS 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 INDUCEMODIFICATIONS
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 H
2
O
2
. 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
Fig. 1. (a) Effect of added H
2
O
2
volume on the efficiency of organic
Meier and Menegatti (1997) proposed the use of C removal from Welsh carbonate-free Madryn soil (, 5.1% C)
and Bodrwyn soil (, 4.3% C) using 6%(wt/wt) H
2
O
2
. (b) Organic Na
2
S
2
O
8
to remove organic matter from mineral phases
C removal efficiency from bulk soils with increasing H
2
O
2
concen-
in one single step (Table 1). Thermal decomposition of
tration. Soils contained between 1.3 and 6.5% organic C. Sixty
Na
2
S
2
O
8
did not decrease C removal at temperatures
milliliters H
2
O
2
were added equivalent to 0.08 g C. The samples
80C. By using a NaHCO
3
buffer, the pH of reaction
were heated gently then boiled (data adopted from McLean,
1931a, 1931b). suspensions with clay minerals and soils can be kept
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between 7 and 8.5 (Menegatti et al., 1999; Kiem and ally decomposed into O
2
and H
2
O (Eq. [1]) via produc-
Ko gel-Knabner, 2002), thus preventing acid-mediated tion of odd-electron (radical) intermediates (Evans and
mineral dissolution. After treatment, Meier and Mene- Upton, 1985). Fenton-like chemistry has been applied
gatti (1997) applied a hot wash (98C, 1 min) with formic in remediation of soils (Watts et al., 2002; Kanel et al.,
acid to remove any traces of salts. However, SO
4
2
and 2003) and in wastewater treatment (Waite, 2002).
HCO
3
have a high affinity for hydroxyl-bearing mineral

M
2
H
2
O
2
M
3
OH OH
surfaces (Ali and Dzombak, 1996; Su and Suarez, 1997)

and are likely to become attached to minerals such as
(Fenton reaction) [2]
Fe and Al oxides or short range order minerals when
M
3
H
2
O
2
M
2
HO
2
H
[3]
applied in high amounts (Table 1). Peroxodisulfate oxi-
dation was employed for predicting the bioavailability
M
2
OH M
3
OH
[4]
of polynuclear aromatic hydrocarbons (PAH) in soils
OH H
2
O
2
H
2
O HO
2
[5]
and sediments since both, oxidation and biodegradation,
removed similar portions of PAH (Cuypers et al., 2000). M
3
O
2
M
2
O
2
[6]
Recently, the Na
2
S
2
O
8
procedure has been adopted to
Hydrogen peroxide can also be consumed by catalase-
soils to isolate stable organic matter and to study the
positive bacteria, which are common members of the
influence of mineral surfaces on organic matter storage
microbial community in soil environments (Pardieck et
(Kiem and Ko gel-Knabner, 2002; Eusterhues et al.,
al., 1992). Catalase decomposes H
2
O
2
into O
2
and H
2
O
2003).
without formation of OH radicals (k 4 10
7
M s
1
;
Pardieck et al., 1992). Manganese oxides can also induce
REACTION OF OXIDANTS WITH
the catalase-type reaction resulting in reduced efficiency
INORGANIC AND ORGANIC MATTER
of organic C removal in Mn-containing soils. When the
In theory, CO
2
and H
2
Oare the end products of oxida- soil reaction is acid, protonation of H
2
O
2
may yield elec-
tive organic matter destruction but a variety of by-prod- trophilic OH cations (Eq. [7]) while at alkaline condi-
ucts form during the chemical treatments. Intermediate
tions nucleophilic perhydroxyl ions (HOO
) form
degradation products adsorb to mineral surfaces, form
(Eq. [8]).
precipitates (Martin, 1954), complex trace metals, and
H
2
O
2
H
H
2
OOH H
2
O OH
[7]
thus hinder their redistribution to solid phases (Hoff-
man and Fletcher, 1981) and have the potential to pro-
H
2
O
2
HO
H
2
O HOO
[8]
mote mineral dissolutionat lowpH(Cornell and Schwert-
The possible decomposition pathways of H
2
O
2
in soils
mann, 1996; Zhang and Bloom, 1999). The interaction
imply that several reactive H
2
O
2
species can interact
of oxidants with organic matter involves complex reac-
with organic matter. In the simplest case, H
2
O
2
directly
tions, depending on either one of the following factors:
oxidizes organic compounds in a peroxidic-type reaction
(i) reaction conditions (pH, temperature), (ii) the pres-
by a two-electron process without O
2
formation (Schumb
ence of inorganic catalysts that are capable to transform
et al., 1955). Reaction of organic matter with OH radi- reagents into more reactive forms, and, in case of H
2
O
2
,
cals are far more complex. Under laboratory conditions, (iii) the presence of enzymes that reduce the oxidants re-
OH radicals react with alkenes and aromatics at diffu- activity.
sion-controlled rates (Watts et al., 2002). Hydroxyl radi-
cals can also initiate radical reactions among organic Hydrogen Peroxide
radicals produced by hydrogen abstraction from CH
Hydrogen peroxide is thermodynamically unstable
bonds. There is evidence that OH radicals preferentially
and decomposes into O
2
and H
2
O according to Eq. [1]
attack aromatic compounds: Westerhoff et al. (1999)
(Pardieck et al., 1992). Decomposition of H
2
O
2
increases
noted that aliphatic structures of natural organic matter
with pH, being maximal close to the reagents pK
a
at
react slower with OH radicals than aromatic moieties.
11.6 (Xiang and Lee, 2000).
Xie and Barcelona (2003) reported a higher chemical
H
2
O
2
H
2
O
2
2H
2
O O
2
(log k 36.12) [1]
resistance of low-molecular weight aliphatic hydrocar-
bons (C5C8) compared with aromatic compounds in
When present in soils, reduced metal species can cata-
jet-fuel contaminated sediments treated with H
2
O
2
.
lyze the decomposition of H
2
O
2
and thereby produce
These results are consistent with the general order of
OH radicals that are much more powerful oxidants than
reactivity: aromatic CH
2
CO COOH (Pey-
H
2
O
2
(Strukul, 1992). The Fe
2
catalyzed decomposi-
ton, 1993) and may account for the enrichment of ali-
tion of H
2
O
2
into OH species according to Eq. [2] resem-
phatic compounds in H
2
O
2
treated soils (Schulten et al.,
bles the classical Fenton reaction. Surface sites of oxides
1996; Leifeld and Ko gel-Knabner, 2001; COMPOSI-
and montmorillonite (Fe
2
or Fe
3
) may similarly pro-
TION OF ORGANIC MATTER section).
duce OH radicals by Fenton-like reactions (Huang et
In addition, certain aromatic compounds may selec- al., 2001; Gournis et al., 2002; Kwan and Voelker, 2002;
tively be removed by H
2
O
2
. Andreozzi et al. (2002) Petigara et al., 2002). Equations [2] through [6] repre-
observed that phenols adsorbed to goethite containing sent the metal-catalyzed Haber-Weiss mechanism, where
two adjacent OH groups (or one OH and one NH
2
) the metal (M) is cycled between a lower [M(II)] and
higher [M(III)] oxidation state and where H
2
O
2
is gradu- were oxidized by H
2
O
2
while those containing two
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COOH groups or one COOH plus one OH group were phatic compounds in natural organic matter. Chakrabar-
tty et al. (1974) used 12% (wt/wt) NaOCl (pH 12) to not reactive toward H
2
O
2
.
Degradation of lignin strongly depends on the reac- investigate the structural composition of humic acids
extracted fromsoil and coal. They reported that reaction tion milieu. At alkaline pH, degradation of lignin is
more complete than at acid pH, possibly because of results in aliphatic carboxylic acids (malonic, succinic,
glutaric, and adipic acid) and aromatic polycarboxylic more reactive H
2
O
2
species present and larger lignin
solubility (Sun et al., 2000; Xiang and Lee, 2000). This acids (50% CO
2
, up to 32% non-volatile acids). Hypo-
chlorite is presumed to cleave all methine, methylene, suggests that under acid conditions lignin components
may contribute to residual organic C in H
2
O
2
treated and methyl goups activated by electron-withdrawing
heteroatoms without simultaneously disrupting aro- soil. Chemical degradation of humic substances, lignin,
and simple carbohydrates by H
2
O
2
yields a variety of matic systems.
water-soluble compounds such as mono- and dicarbox-
ylic low-molecular-weight organic acids (e.g., formic, Disodium Peroxodisulfate
acetic, oxalic, and malonic acid), phenols and benzene-
In alkaline to slightly acid solutions, S
2
O
8
2
reacts with
carboxylic acids (Craik, 1924; Ku chlein, 1932; Griffith
H
2
O according to Eq. [11] (Kolthoff and Miller, 1955)
and Schnitzer, 1977; Xiang and Lee, 2000; Goldstone et
to finally give SO
4
2
by dissociation of HSO
4
.
al., 2002). Martin (1954) estimated that in two soil clays
reacted with H
2
O
2
, 30 to 40% of the initial organic C 2S
2
O
2
8
2H
2
O 4HSO
4
O
2
[11]
was transformed into oxalate. Similarly, Harada and
When heated, S
2
O
2
8
undergoes thermal homolysis or
Inoko (1977) using redox titration have calculated that
reacts with reduced metals, for example, Fe
2
ions, to
100 g of soil yielded between 0.01 and 0.2 moles of
yield SO
4
radicals that can react with organic matter

oxalate during H
2
O
2
treatment.
(Edwards and Curci, 1992). Hydroxyl radicals can also
Less is known about the interaction of H
2
O
2
with
form when SO
4
radicals react with H

2
O and with OH
N-containing compounds. Herriott (1947) reported that

ions at alkaline conditions (Eq. [12] and [13]). Reaction
at room temperature 5% (wt/wt) H
2
O
2
caused a loss of
[12] becomes negligible at dissolved organic C concen-
60% of amino-N from virus protein. Harada and Inoko
trations 1 mg L
1
, where organic compounds are the
(1977) showed that after treating soils with H
2
O
2
, resid-
major sink for SO
4
radicals (Peyton, 1993).

ual N was mainly water-soluble (60100%) and domi-
nated by inorganic N species (70%). Ammonia is a SO
4
H
2
O H
SO
2
4
OH [12]
product of the oxidative deamination of amino acids
SO
4
OH
SO
2
4
OH [13]
(Schnitzer and Hindl, 1980) and has been found after
Like OH radicals, SO
4
radicals have a similar reactiv- oxidation of humic acid (14 mg NH

3
out of 46 mg total
ity toward organic structures (Peyton, 1993). Larger, N) (Miles et al., 1985).
more resistant phenolic compounds may be synthesized
by coupling of phenols during radical reactions induced
Sodium Hypochlorite
by SO
4
radicals.
In aqueous solution, NaOCl principally exists in the
following equilibria (Eq. [9] and [10]).
EFFICIENCY OF ORGANIC
MATTER REMOVAL
OCl
H
2
O HOCl OH
[9]
Organic matter cannot completely be removed from
and
soils by wet oxidative treatments (Fig. 1). Early work
HOCl OCl
[10] took advantage of this fact by using H

2
O
2
for determina-
tion of the degree of humification in soils (Robinson
When natural organic matter is treated with hypo-
and Jones, 1925) and to gain information about the
chlorite species (HOCl, OCl
), high-molecular-weight
composition of organic matter (McLean, 1931a, 1931b).
chlorinated compounds form in a first step that is fol-
Progressing research revealed a number of factors re-
lowed by the cleavage of benzene rings into trihalometh-
sponsible for incomplete Cremoval such as soil reaction,
anes and haloacetic acids (Jimenez et al., 1993; Li et al.,
presence of carbonates, chemically resistant organic
2000; Pomes et al., 2000). Sodium hypochlorite-treated
compounds, and protection of organic matter by min-
humic acid yielded more chloroform than treated fulvic
eral surfaces.
acid (Peters et al., 1980). Trihalomethane and haloacetic
acids likely derive from 3,5-dihydroxybenzene structures.
Hydrogen Peroxide
In accordance, Norwood et al. (1987) noted that chlorina-
tion of aquatic fulvic acid produced chlorinated aliphatics The extent of organic C removal by H
2
O
2
varies with
soils and particle-size separates, ranging from 20% and resulted in preferential removal of lignin phenols.
Chlorinated phenols were also found after reaction of (Bartlett et al., 1937) to 93% (Kahle et al., 2003).
Typical efficiencies of C removal are listed in Table 1. hypochlorite with humic and fulvic acid (Quimby et al.,
1980), substituted benzoic acids (Larson and Rockwell, Hosking (1932) noted for a number of calcareous Aus-
tralian Black soils that 20% (wt/wt) H
2
O
2
removed only 1979), and after chlorination of lignin (Rajan et al., 1996).
Westerhoff et al. (2004) observed a higher reactivity of 5 to 20% of organic matter when the soil reaction was
alkaline (pH 910) while 50 to 90% were removed when aqueous chlorine for aromatic compounds than for ali-
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the soil pH was between 6 and 7.5. In soils containing could be removed by this procedure. Reduction of the
number of repetitive treatments may decrease the re- Mn oxides, only 30% of organic matter was removed
because of rapid H
2
O
2
decomposition. Hosking (1932) moval of organic matter in soils rich in poorly crystalline
Fe and Al phases (Siregar et al., 2004). and Anderson (1963) increased the C removal by re-
moving carbonates first, using HCl (pH 23) or a Na
acetate buffer (pH 5). In calcareous soils, carbonate
Disodium Peroxodisulfate
coatings favor occlusion and thus physical protection of
The efficiency of Na
2
S
2
O
8
to remove organic matter
organic matter against destruction. Oxalate, which is a
has been proposed to be superior to H
2
O
2
and NaOCl
common product of organic matter destruction (HY-
(Meier and Menegatti, 1997; Table 1). When the authors
DROGENPEROXIDEunder section REACTIONOF
tested NaH
2
PO
4
as buffer, Cremoval was less than when
OXIDANTS WITH INORGANIC AND ORGANIC
using NaHCO
3
buffer. This can be attributed to the
MATTER), can form insoluble complexes with Ca
2
,
lower pH (drop from approximately 8 to 5) in case of
thus leaving a residual organic C fraction behind after
the Na
2
S
2
O
8
NaH
2
PO
4
mixture, which disfavors desorp-
H
2
O
2
treatment. Moreover, HCO
3
and CO
2
3
ions are
tion of mineral-bound organic matter. Kiem and Ko gel-
known to inhibit organic matter degradation during wa-
Knabner (2002) applied Na
2
S
2
O
8
to particle-size frac-
ter purification by scavenging OH radicals (Wang et al.,
tions of loamy and sandy surface soils and found a
2001). The same may hold true for H
2
O
2
treatment of
contact time of 16 h sufficient to reduce organic C con-
calcareous soils where carbonates likely dissolve due to
centrations by about 93% (Table 1). Oxidative destruc-
the production of organic acids.
tion of humic acid (Martin et al., 1981) and organic
Using Na
4
P
2
O
7
as a dispersing agent in the H
2
O
2
treat-
matter from aquifer sediments (Powell et al., 1989),
ment, organic C removal is more complete than by
however, not exceeded 50%. Thus, desorption of or-
applying H
2
O
2
alone (Simon et al., 1992). Sequi and
ganic matter by HCO
3
or SO
2
4
is likely the key step
Aringhieri (1977) increased the average organic matter
in removal of organic C from soils. In contrast, Eust-
removal by using H
2
O
2
Na
4
P
2
O
7
from 79 to 96%, likely
erhues et al. (2003) found that in some cases even 2 d
by disruption of aggregates, thereby releasing occluded
of reaction time were insufficient to destroy organic C
organic matter, and by displacing sorbed organic com-
in acid soils rich in secondary minerals (Table 1). This
pounds from mineral surfaces. Pyrophosphate and also
indicates that either chemically stable compounds repre-
PO
3
4
sorb strongly and hysteretically to soil minerals
sented a major organic fraction (not tested) or strong
(Varadachari et al., 1995; Celi et al., 2000). Hence, when
interactions with mineral surfaces limited desorption of
carrying out a sorption experiment with soil treated with
organic matter (PROTECTION OF ORGANIC MAT-
a mixture of H
2
O
2
and Na
4
P
2
O
7
, occupation of reactive
TER BY SOIL MINERALS section under EFFI-
sorption sites by pyrophosphate needs to be considered.
CIENCY OF ORGANIC CARBON REMOVAL DE-
Furthermore, organomineral complexes and chemi-
PENDS ON SAMPLE PROPERTIES).
cally stable compounds contribute to the resistance of
organic matter (EFFICIENCY OF ORGANIC CAR-
EFFICIENCY OF ORGANIC CARBON BON REMOVAL DEPENDS ON SAMPLE PROP-
REMOVAL DEPENDS ON
ERTIES section).
SAMPLE PROPERTIES
Sodium Hypochlorite Sample-specific properties like the presence of chemi-
cally stable organic compounds and protective mineral
According to Anderson (1963), the C removal effi-
phases are also crucial for organic C removal efficiency.
ciency of 6% (wt/wt) NaOCl at pH 9.5 was less affected
by the presence of carbonates (up to 9% CaCO
3
) than
Composition of Organic Matter
when using 30% (wt/wt) H
2
O
2
. Several studies revealed
that 6% (wt/wt) NaOCl at pH 9.5 removed more C from
Pyrogenic materials (black carbon) represent a group
bulk soils and clays than 30% (wt/wt) H
2
O
2
(Anderson,
of chemically resistant compounds in soils. They com-
1963; Omueti, 1980; Cheshire et al., 2000). The NaOCl
prise randomly oriented condensed aromatic rings lo-
treatment does not require additional dispersing re-
cated in graphite-like structures (Schmidt and Noack,
agents because of dispersion by NaOCl itself. In spite
2000). Such materials can make up a significant portion
of a higher electric potential of NaOCl with decreasing
of organic matter in soils, especially in soils adjacent to
pH, C removal efficiency is maximal at pH 9.5 (Lavkul- coal-processing industries (Schmidt et al., 1999) or in
ich and Wiens, 1970). This indicates that desorption soils from technogenic materials (Zikeli et al., 2004).
from mineral surfaces under alkaline conditions is deci- Hydrogen peroxide is ineffective to degrade graphite,
sive for the removal of organic compounds. Desorption anthracite, lignite, charcoal, and ash (Robinson, 1927;
may be of similar importance for organic matter removal Schmidt et al., 1999).
as the oxidative breakdown of organic compounds, sug- Low-molecular-weight organic acids produced during
gesting the term wet oxidation to be misleading. Kai- oxidative treatments are relatively resistant against fur-
ser and Guggenberger (2003) tested a modified NaOCl ther degradation (Luft and Sto ffler, 1998) and thus be-
treatment (pH 8, room temperature, five repetitions) come enriched during oxidative treatments. Analyzing
on 196 heavy soil fractions (density 1.6 g cm
3
) and H
2
O
2
treated clay and bulk soil fractions by differential
thermal and infrared analysis, Farmer and Mitchell found that between 77 to 95% of the initial organic C
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(1963) and Harada and Inoko (1977) found no evidence soil minerals. Contemporary work distinguishes be-
tween the mechanisms of intercalation and sorptive pro- for resistant organic compounds other than oxalate. For-
mation of insoluble calcium oxalates is favored under tection.
Intercalation includes replacement of hydrated in- alkaline conditions, while in acidic soils adsorption of
oxalate to variable charge minerals is more likely. organic interlayer cations of expandable 2:1 phyllosili-
cate clay minerals by organic molecules. This requires Farmer and Mitchell (1963) noted that in some cases
complexed oxalate couldnt be extracted by H
2
O but by either cationic or neutral organics and a strongly acidic
soil reaction. Theng et al. (1992) and Righi et al. (1995) 5% ethylenediaminetetraacetate. In contrast, Escudey
et al. (1999) suggested extensive washing with H
2
O after assumed that organic matter intercalated in expandable
clay minerals is hardly decomposable by H
2
O
2
due to the H
2
O
2
treatment to remove oxalate from soils com-
pletely but did not quantify their results. a limited accessibility toward the reagent. In contrast,
Kodama and Schnitzer (1971) found no evidence that Several studies confirmed that organic compounds
other than black carbon and oxalate could survive oxida- organic matter sorbed into the interlayer regions of mica-
vermiculite-montmorillonite-interstratified clay resisted tive treatments (Righi et al., 1995; Schulten et al., 1996;
Cuypers et al., 2002). Aliphatic compounds are a signifi- 15% (wt/wt) H
2
O
2
.
Eusterhues et al. (2003) observed that the concentra- cant portion of chemically resistant organic matter. Grif-
fith and Schnitzer (1977) estimated that n-alkanes and tion of Na
2
S
2
O
8
resistant organic matter related posi-
tively to the clay content (r 0.93) in twelve horizons n-fatty acids accounted for up to 40% of the H
2
O
2
resis-
tant organic matter, while a substantial fraction of resid- from two acid soil profiles (Typic Haplorthod and Typic
Dystrochrept). In the Spodosol, a significant relationship ual C could not be extracted by organic solvents. Study-
ing the H
2
O
2
resistant organic matter in micabeidellite of residual organic C to dithionitecitratebicarbonate-
extractable Fe (r 0.90) suggests that the resistant interstratified clay by Py-FIMS, Schulten et al. (1996)
organic matter was likely associated with Fe (hydr)- found it to be enriched in N-containing compounds,
oxides (sorptive protection). Similar results were re- n-C
22
C
26
carboxylic acids, n-alkanes, n-diols and alkyl-
ported by Mikutta et al. (2004) for NaOCl-resistant substituted aromatic esters. Leifeld and Ko gel-Knabner
organic matter in clay subfractions fromsubsurface hori- (2001) showed by CPMAS
13
C-NMR analysis that H
2
O
2
zons of smectitic, vermiculitic, illitic, kaolinitic, and chlo- preferentially removed sugars (O-alkyl C) and lignin
ritic soils (Table 1). Despite the heterogeneous sample compounds (mainly aromatic C) from20-m particle-
set, the concentration of residual organic C correlated size separates of agricultural soils leaving an aliphatic
well with oxalate-extractable Fe (Fe
o
) and Al (Al
o
) (Fig. residue behind. In accordance, persulfate treatment evi-
2a). Acid oxalate primarily extracts Fe and Al from denced the presence of aliphatic biopolymers in sedi-
poorly crystalline aluminosilicates, ferrihydrite and Fe mentary and terrestrial humic acids (Saiz-Jimenez, 1992).
and Al humus complexes (Wada, 1989).
Martin et al. (1981) found that n-C
16
C
18
fatty acids were
The efficiency of poorly crystalline minerals to protect
the most abundant compounds after reaction of humic
organic matter against oxidative destruction was con-
acid with acid K
2
S
2
O
8
. However, a variety of benzenecar-
firmed in batch experiments. Singer and Huang (1993)
boxylic and phenolic acids were also detected. Cuypers
and Huang (1995) showed that humic, tannic, and citric
et al. (2002) reported that persulfate preferentially re-
acid associated with non-crystalline Al hydroxide were
moved labile and more amorphous organic matter while
only partly destructible by H
2
O
2
and NaOCl, while tan-
the residuum was enriched with long-chain aliphatics.
nic and citric acid were completely oxidized in the ab-
The resistant organic matter was proposed to have a
sence of Al hydroxide. The higher resistance of mineral-
more condensed structure, a higher affinity for hydro-
associated organic compounds was explained by incor-
phobic compounds and being more thermostable than
poration of organic compounds by coprecipitation or
amorphous organic matter.
by formation of strong surface complexes.
Lower C/N ratios of H
2
O
2
resistant organic matter
Mikutta et al. (2004) showed that the capability of
indicate a higher chemical stability of some N com-
minerals in clay subfractions to protect organic matter
pounds. Cheshire et al. (2000) found that some amino
decreases as more organic C is associated with mineral
acids were protected against degradation possibly within
surfaces. The C removal efficiency related closely to
microaggregates or by interaction with mineral surfaces.
the initial organic C concentration normalized to the
Interpretation of C/N ratios after organic matter re-
mineral SSA (C loading; Fig. 2b). This result is consis-
moval is, however, questionable since mineral-bound
tent with the finding that at small C loadings, organic
NH
4
or NH
4
produced during organic matter degrada-
matter occupies a larger surface area with more func-
tion and subsequently fixed to minerals can also affect
tional groups involved in multiple-site attachments with
C/N ratios (Miles et al., 1985; Leifeld and Ko gel-Knab-
mineral surfaces (Kaiser and Guggenberger, 2003). Or-
ner, 2001).
ganic matter in direct contact to the mineral surface
thus appears less susceptible to chemical destruction.
Protection of Organic Matter by Soil Minerals
Eusterhues et al. (2003) provided further evidence that
the C removal efficiency depends on the protective ca- Hosking (1932) recognized that more organic matter
resisted the H
2
O
2
treatment in soils with higher clay pability of mineral surfaces. They observed that C re-
moval by Na
2
S
2
O
8
decreased with soil depth. Nearly all content. This suggests that organic matter can be pro-
tected against oxidative treatments by interaction with organic Cwas removedfromAand EAhorizons (98%)
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while in the deeper B and C horizons 9 to 84% of the
initial organic C resisted Na
2
S
2
O
8
. This effect can be
explained by larger amounts of mineral-bound organic
matter and by stronger association of organic matter
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 frommineral 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.
Fig. 2. (a) Relation between the concentrations of residual organic
Thermal Effect on Minerals
C and oxalate-extractable Fe plus Al in fine (, 0.2 m) and
coarse clay (, 0.22 m) fractions of 12 acid subsoil samples with Most treatments are conducted under elevated tem-
different mineralogy after treatment with 6% (wt/wt) NaOCl. (b)
peratures (60100C) (Table 1). Kaiser and Guggen-
Relationship between the organic Cloading of mineral surfaces and
berger (2003) showed that temperatures 40C lasting
the amount of removable organic C (data adopted from Mikutta et
several hours can transform moist amorphous Al hy-
al., 2004).
droxide into gibbsite while temperatures 80C con-
verted ferrihydrite into hematite. The total SSA of both
the interlayer spaces of phlogopite (mica with low Fe
mineral phases decreased on heating by about 90%,
content) and vermiculite via exchange with H
2
O and
partly due to the entire loss of microporosity (2 nm).
cations and decomposes into O
2
and H
2
O (U
cgu l and
So even moderate heating can alter oxide surface prop-
Girgin, 2002; Obut and Girgin, 2002). The gas evolved
erties and thus gives rise to artifacts, at least in soils rich
can disrupt individual silicate layers. Increasing thick-
in poorly crystalline components. The only procedure
ness of the minerals (80120 fold) was noted with in-
reported to be efficient under ambient temperature is
creasing H
2
O
2
concentration (150%), temperature (40
the modified NaOCl treatment proposed by Kaiser et
60C), and contact time (130 h). Above 60C, phlogopite
al. (2002) (Table 1). However, the method is time-con-
started to exfoliate as described by Drosdoff and Miles
suming and laborious.
(1938), possibly because of accelerated decomposition
of H
2
O
2
with increasing temperature. However, treat-
ment with 30% (wt/wt) H
2
O
2
(60C, 70 min) caused no Hydrogen Peroxide
phase change of phlogopite according to x-ray diffrac-
Phyllosilicates
tion (XRD) (U
cgu l and Girgin, 2002).

Douglas and Fiessinger (1971) showed by XRD that Many studies on the effects of H
2
O
2
on individual
minerals were conducted outside the field of soil re- the (001) signals of smectite and vermiculite decreased
after reaction with H
2
O
2
in presence of large amounts search (Hayashi and Oinuma, 1964; Muromtsev et al.,
1990; U
cgu l and Girgin, 2002). The use of unweathered of sucrose (168 g C kg

1
clay) while little effect was
observed without sucrose or in presence of sodium ace- minerals and the variety of procedures applied, compli-
cates the transferability to soil systems. Despite this, tate buffer (pH 5). They inferred that both minerals,
especially vermiculite, were partly destroyed due to the some general remarks can be made.
Drosdoff and Miles (1938) first noted destruction of low pH (pH 1.83) induced by incomplete oxidation of
sucrose. However, decreasing (001) basal peak reflec- mica and some vermiculite samples when treated with
6 and 30% (wt/wt) H
2
O
2
. Mineral exfoliation resulted tions following H
2
O
2
treatment may also result from
residual organic matter producing less than perfect ori- from catalytic decomposition of H
2
O
2
by Mn oxides
located in mineral interlayers. Amonette et al. (1985) entation of clay specimen (Dohrmann, 2003).
Miles et al. (1985) observed NH
4
produced during showed that H

2
O
2
penetrates biotite interlayer spaces
expanded by tetraphenylborate and oxidizes 85% of the organic matter degradation to sorb to exchange sites of
vermiculite, inducing collapse of the 1.48-nmspacings to structural Fe
2
ions within 24 h. Also, H
2
O
2
diffuses into
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Fig. 4. X-ray diffractograms of Mg-saturated, glycerated, and oriented
Fithian illite (I) (2 m) before and after treatment with 10%
(wt/wt) H
2
O
2
(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, organomineral
associations (5% organic matter) were prepared by three drying
and wetting cycles. Treatments: (a) no, (b) I H
2
O
2
, (c) I H
2
O
2
S, and (d) I H
2
O
2
M.
Fig. 3. (a) Scanning electron microscope (SEM) image of oxide-free
(dithionitecitrate-treated) Prassa-Kimolos bentonite (Greece),
(1997) showed that deposit illites were not attacked by (b) oxide-free bentonite treated with 30% (wt/wt) H
2
O
2
(6 h, 80C)
in the presence of 230 mg L
1
dissolved organic C. Bars represent
H
2
O
2
. We studied illite treated with 10% (wt/wt) H
2
O
2
100 m.
(80C, 120 h) in the presence and absence of organic
matter. Before treatment, clay specimens were sub-
the 1.03-nm position characteristic for mica-like phases.
jected to dryingwetting cycles in the presence of ma-
Infrared spectroscopy confirmed NH
4
fixation by the
nure and straw (0.1 mm) to facilitate the formation of
treated vermiculite. Therefore, the H
2
O
2
treatment is
clayorganic associations. Using XRD, we observed no
not suitable for XRD-based identification of vermiculite
structural change of illite induced by H
2
O
2
treatment
in soils.
(Fig. 4).
Van Langeveld et al. (1978) inferred from reduced
The results compiled above indicate that the alter-
XRD reflections that montmorillonite (6% organic C)
ation of phyllosilicates by H
2
O
2
depends on (i) the pres-
was structurally altered during H
2
O
2
treatment. Figure
ence of catalyzing materials, (ii) the existence of accessi-
3a and 3b display the transformation of bentonite on
ble interlayer mineral surfaces, and (iii) the abundance
treatment with 30% (wt/wt) H
2
O
2
at 80C for 6 h in pres-
of organic matter. The results imply that pure depository
ence of dissolved organic matter. Compared with un-
minerals not weathered in the soil environment and thus
treated particles, the treated ones show distinctively
lacking structural modifications such as cracks, microfis-
frayed structures suggesting corrosion likely caused by
sures, and expansion zones as well as sorbed organic
decomposing H
2
O
2
and acidic organic matter degrada-
matter are little affected by treatment with H
2
O
2
.
tion products.
In contrast, Hayashi and Oinuma (1964) found no
Carbonates, Oxides, and Sulfides
indications for major alterations of repository clays (ver-
miculite, montmorillonite, illite, chlorite) treated with In calcareous soils, H
2
O
2
treatment may cause dissolu-
tion and corrosion of carbonate minerals because of the 30% (wt/wt) H
2
O
2
at 80 to 90C over several days. Mu-
romtsev et al. (1990) recognized no structural alteration low pH of H
2
O
2
(Pingitore et al., 1993). Typically, Mn
oxides are destroyed during the H
2
O
2
treatment (Shu- of pure vermiculite treated with 30% (wt/wt) H
2
O
2
by
applying XRD analysis, nevertheless the CEC doubled man, 1983; Papp et al., 1991; Table 2). Manganese (III,
IV) oxides are affected by reduction to Mn
2
, which is because of layer expansion. Rosenberg and Hooper
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Table 2. Destruction of Mn oxide and sulfide minerals by oxidative treatments (data adopted from Papp et al., 1991).
Mn and Fe extracted, % Cu and Zn extracted, %
Pyrite Pyrrhotite Chalcopyrite Chalcocite Chalcopyrite Sphalerite
Treatment MnO
2
FeS
2
FeS CuFeS
2
Cu
2
S CuFeS
2
ZnS
H
2
O
2
97 92 46 39 99 88 80
H
2
O
2
and Na
4
P
2
O
7
98 41 21 75 99 97 93
NaOCl 1.7 0.8 0.9 8.7 4.2 2.3 1.9
1 g sample 8 mL of 3:2 mixture of 30% (wt/wt) H
2
O
2
and 0.025 M HNO
3
.
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 tain mineral constituents like amorphous Al(OH)
3
(Par-
al., 1992), Mn
3
O
4
(Jackson, 1958), or a mixture of differ- fitt and Childs, 1988; Kaiser and Zech, 1996). In addition,
ent Mn oxides (Moon et al., 1999). Sulfide minerals are pyrophosphate may induce precipitation of Ca phos-
readily dissolved by reaction with H
2
O
2
(Mukherjee et phates (Hawke et al., 1989; Celi et al., 2001) and Al
al., 2001). Papp et al. (1991) showed that H
2
O
2
dissolved
phosphates (e.g., poorly crystalline Al phosphate, tara-
21 to 99% of the total metals present in sulfides
nakite, wavellite) (Kim and Kirkpatrick, 2004).
(Table 2). Consequently, H
2
O
2
should not be used to
estimate organically bound metals when sulfide miner-
Sodium Hypochlorite
als are present, for example in acid sulfate soils from
coastal lowlands (Shamshuddin et al., 2004). In general, Mn oxides and sulfide minerals are dis-
Iron and Al (hydr)oxides may be affected during the solved to a lesser extent by NaOCl compared with H
2
O
2
H
2
O
2
treatment by heat-induced transformation into
(Table 2). Lavkulich and Wiens (1970) found that, at
more crystalline forms and by organic-assisted disso-
pH 9.5, NaOCl dissolved significantly less oxalate-extract-
lution at low pH. At alkaline pH, for example, in cal-
able Fe and Al than H
2
O
2
(Table 3). This can be ex-
careous soils or when using H
2
O
2
in combination with
plained by the alkaline pH of NaOCl, which prevents
Na
4
P
2
O
7
, oxides remain unaltered (Marzadori et al., 1991).
acid-induced mineral dissolution and may probably sup-
At low pH (pH 24), large concentration of oxalate,
port hydrolysis and precipitation of hydroxides (METAL
and high temperature, the H
2
O
2
treatment is comparable
PRECIPITATION section). However, some Al can be
or even more aggressive than the acid-oxalate method
dissolved at pH 9.5, for example in the Alouette Ap
(pH 3, room temperature, darkness, 4 h) designed for
horizon (Table 3). Using the method of Lavkulich and
extraction of poorly crystalline minerals and Fe and Al
Wiens (1970), Osei and Singh (1999) reported that no
bound to organic matter (Blakemore et al., 1987). For
Fe was released from tropical surface soils by NaOCl
acid soils treated with 30% (wt/wt) H
2
O
2
, Lavkulich
while extracted Al and Si accounted for up to 0.3 g kg
1
.
and Wiens (1970) reported that the amount of oxalate-
Negligible amounts of Fe and Al were dissolved during
extractable Fe and Al decreased by 34 to 80% and 1 to
treatment of a Mollisol surface soil with 5.3% (wt/wt)
90%(IIH
2
O
2
treatment, Table 3). They assumed that in-
NaOCl (Qiang et al., 1994; Table 1). In soils rich in
organic Fe and Al phases dissolved during the H
2
O
2
poorly crystalline minerals, 6% (wt/wt) NaOCl at pH 8
treatment. However, mass balance calculations utiliz-
(room temperature, three repetitions) dissolved no Fe
ing selective extractions prior and after H
2
O
2
treatment
and 3% of dithionite-citrate extractable Al and Si
suggest that dissolution of poorly crystalline Fe and Al
(Siregar et al., 2004). These findings support the view
components alone does not entirely explain the smaller
that crystalline oxides and silicates are not affected by
Fe
o
and Al
o
concentrations after H
2
O
2
treatment (Table 3).
NaOCl.
More likely, they result from heat-induced recrystalliza-
However, NaOCl treatments at higher temperatures
tion of poorly crystalline oxides. However, after mild
may induce changes in extractable pedogenic Al and
H
2
O
2
treatment (I-H
2
O
2
treatment; Table 3), the mass
Fe (e.g., Langley Ap; Table 3) due to transformation
balance was positive indicating higher extraction effi-
into more crystalline forms. In contrast, Marzadori et
ciency of acid oxalate after the H
2
O
2
treatment due to
al. (1991) studying calcareous soils found an increase in
disaggregation and removal of organic matter coatings
Fe
o
and Al
o
after destruction of organic matter by 7%
from oxide surfaces (Marzadori et al., 1991). When test-
(wt/wt) NaOCl despite heating to 80C(Table 1). In that
ing the influence of 10%(wt/wt) H
2
O
2
on six acid subsoil
case, the thermal transformation of a poorly crystalline
samples, we found an average decrease of Fe
o
and Al
o
oxide fraction was probably overcompensated by an
concentrations by approximately 90%(Table 3). Alumi-
increased extractability of poorly crystalline phases due
num and Fe in reacted H
2
O
2
solutions were little (Ta-
to the removal of organic coatings. Mayer (1999) found
ble 3), suggesting the decrease in oxalate-extractable
an increased enthalpy for the adsorption of N
2
on marine
components to be related to the transformation of min-
sediments treated with 13% (wt/wt) NaOCl at pH 9 to
erals at high temperature (80C).
9.5. The change in adsorption enthalpy was attributed Pyrophosphate, when used in conjunction with H
2
O
2
to microtopographic or chemical changes of mineral as a dispersing reagent to enhance C removal, can cause
surfaces due to the highly alkaline reaction conditions. loss of peptized fine mineral particles, especially in pres-
ence of adsorbed organic matter, or dissolution of cer- This effect warrants further research.
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Table 3. Effect of H
2
O
2
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 H
2
O
2
(30%) and the NaOCl treatment adapted from Lavkulich and Wiens (1970).
After treatment in After treatment in
Initial residues extracts Mass balance
Soil Horizon Fe
o
Al
o
Fe
o
Al
o
Fe Al Fe Al
g kg
1
30% (wt/wt) H
2
O
2
(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) H
2
O
2
(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% H
2
O
2
(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
Kyffha user E 1.1 1.5 0.1 0.1 0.3 0.7 0.7 0.7
Kyffha user Bt 1.1 1.9 0.2 0.2 0.4 0.8 0.5 0.9
Ba hrental 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
Ko hlerwald Bt 13.4 13.3 1.4 1.2 N.D. 1.8 12.0 10.3
Mass balance (Fe, Al) (g kg
1
) (Fe
o
, Al
o
)
residuum
(Fe, Al)
extract
(Fe
o
, Al
o
)
initial
.
N.D. not detected.
Disodium Peroxodisulfate phase properties and organically bound metal fractions.
Sequi and Aringhieri (1977) noted that Fe and Al associ-
Using XRD, IR spectroscopy and N
2
adsorption,
ated with organic matter are released during H
2
O
2
oxi-
Menegatti et al. (1999) found no structural alteration
dation and subsequently precipitate as hydroxides on
of Na
2
S
2
O
8
treated illite, kaolinite, and montmorillonite
inorganic and organic components. These precipitates
reference minerals (0.2 and 2 m). Minor losses of
are assumed to alter SSA and charge of the mineral
Ca, K, and Mn were explained by partial removal of
phase and to protect organic matter against further deg-
fine-grained accessory minerals such as feldspars and
radation. The formation of metal precipitates during the
carbonates. The SSA of most treated samples remained
H
2
O
2
treatment was inferred from the increase in SSA
unaltered while the SSA of montmorillonite increased
(N
2
BET) and positive surface charge, and the concomi-
by 20 m
2
g
1
. This was attributed to the dispersion
tant decrease of negative charge. However, it is more
of large aggregates. The CEC of the treated minerals
likely that the alteration of surface charge derived from
remained unchanged. However, HCO
3
as used for pH
the removal of organic matter carrying much negative
control may partly be converted into CO
2
3
on heating,
charges located in carboxylic groups and from exposure
which at 80C, can extract Al from allophanes and hy-
of positively charges on oxide surfaces. Despite that,
droxides (Wada, 1989). Thus, if used for organic matter
precipitation of metals formerly complexed with organic
removal from soils where these phases are abundant, for
matter cannot be ruled out. Schultz et al. (1999) pre-
example volcanic ash soils and Spodosols, this potential
ferred H
2
O
2
instead of alkaline NaOCl to assess organi-
defect requires further attention.
cally bound metals in carbonate-free sediments to avoid
metal precipitation (Table 1). Addition of NH
4
acetate
METAL PRECIPITATION
during the H
2
O
2
treatment was intended to prevent re-
adsorption of metals to the solids. Hoffman and Fletcher The question whether metal ions complexed with or-
(1981) showed that NaOCl (6.5%, pH 9.5) induced little ganic matter are released and precipitate during oxida-
tion is relevant for the reliable assessment of mineral precipitation of trace metals (Cu, Zn, Fe, Mn, Mo) when
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inorganic precipitates from soils and sediments were surface-controlled processes (e.g., adsorption, diffusion).
Hydrogen peroxide has been shown to disintegrate mi- redissolved by acidified H
2
O. In spite of the alkaline
conditions, soluble organic compounds can effectively cas, vermiculites, and smectites. Phyllosilicate disinte-
gration may become more significant with increasing scavenge metals released and thus hinder their precipi-
tation. In accordance, Shuman (1983) showed for six H
2
O
2
concentration, temperature and in the presence
of decomposable organic matter. In soils, destruction bulk soils that 5% (wt/wt) NaOCl (pH 8.5) dissolved
similar amounts of metals (Cu, Fe, Zn) from the organic of phyllosilicates might change the surface properties
but little experimental evidence has been given. For fraction as 30% (wt/wt) H
2
O
2
while H
2
O
2
extracted sig-
nificantly more Mn. In summary, there is no consistent example, Theng et al. (1999) hypothesized the SSA in-
crease of a smectitic soil following H
2
O
2
treatment to perception on the degree of precipitation of organically
bound metals released during organic matter destruc- result from destruction of smectite. Treatment with
NaOCl produced only a minor increase in SSA although tion and on the potential effects on mineral properties.
both reagents removed similar amounts of organic mat-
ter. Compared with H
2
O
2
, the effects of NaOCl or
SYNTHESIS
Na
2
S
2
O
8
on phyllosilicates seem negligible, but more
studies on soils are needed to confirm that. This review shows that a large number of protocols
Poorly crystalline constituents are most susceptible for removal of organic matter by H
2
O
2
, NaOCl, and
to alteration during treatments for organic matter re- Na
2
S
2
O
8
is available. Removal of soil organic matter
moval. In organic matter-rich soils treated with H
2
O
2
, is never complete and largely relies on the reaction
organic oxidation products like low-molecular-weight conditions chosen and the sample properties. Sodium
organic acids may assist mineral dissolution at low pH. hypochlorite and Na
2
S
2
O
8
are more effective in organic
During the alkaline NaOCl procedure (pH 9.5), Al from C removal than H
2
O
2
, especially in calcareous soils
hydrous oxides can dissolve. This effect can be avoided where oxidation-resistant Ca oxalates may form. Car-
by using NaOCl at lower pH. Moreover, temperatures bon removal efficiency can be increased by desorbing
40C applied during organic matter removal involves reagents such as NaHCO
3
and Na
4
P
2
O
7
, but those com-
the risk of recrystallization of poorly crystalline Al pounds strongly sorb to minerals, which needs to be
phases, while temperatures 80C may convert poorly considered in sorption experiments with treated sam-
crystalline into more crystalline Fe oxides. Since poorly ples. In soils with large portions of mineral-bound or-
crystalline phases significantly contribute to the physical ganic matter, Fe and Al (hydr)oxides and other poorly
and chemical properties of soils (Percival et al., 2000; crystalline constituents, even NaOCl and Na
2
S
2
O
8
fail
Kiem and Ko gel-Knabner, 2002), more effort should to reduce the organic Cconcentrations effectively. Clay-
be put on that question. At present, only the NaOCl sized Fe and Al phases provide large SSA and reactive
treatment has been shown to remain efficient at room hydroxyls favoring ligand exchange reactions with or-
temperature and thus avoids heat-induced transforma- ganic matter (Gu et al., 1995). The resulting mineral
tion of sensitive mineral phases. organic attachments are difficult to break, especially
Metals released during degradation of organic matter when a single molecule is attached to multiple mineral
may precipitate, and thereby possibly reduce the C re- surface sites, thus hampering desorption of organic mat-
moval efficiency and the amount of organically bound ter, which is an important prerequisite for organic mat-
trace metals in sequential extraction studies, and may ter removal. However, sorptive protection of organic
also affect surface properties of minerals. However, lit- matter by minerals is hardly discernable fromprotection
tle awareness exists of that problem. Hydrogen peroxide of organic matter due to occlusion in microaggregates
and NaOCl seem to induce similar metal precipitation, or coprecipitation with hydrous oxides. Since intercala-
with the degree of precipitation depending on the pH, tion is confined to expandable clay minerals and strongly
metal content and the amount of organic matter. In- acid conditions, the relevance of protected organic com-
organic precipitates may probably become relevant for pounds in interlayer spaces is presumably small. Organic
soils and particle-size separates rich in organically com- matter resistant to oxidative treatment likely represents
plexed metals such as Andisols and Spodosols. 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
IMPLICATIONS
chemical and biological degradation suggests the treat-
ment with oxidative reagents to mimic biodegradation At present, the knowledge on oxidative removal of
soil organic matter is incomplete with respect to the ef- (Rihani et al., 1995; Cuypers et al., 2002). However,
selective degradation of certain structures of organic fects of oxidants on soil minerals. Therefore, systematic
studies on changes of mineral properties on oxidative matter by the three reagents (aromatics versus aliphat-
ics) and, in case of H
2
O
2
, the likely adsorption of organic removal of soil organic matter are required. These stud-
ies should involve pure minerals (poorly crystalline ox- intermediates deriving from labile organic matter (e.g.,
oxalate) to minerals needs to be considered. ides, expandable clay minerals), defined organomineral
complexes and soils with a wide range of properties (min- Based on the evidence shown, changes of mineral
phase properties when treated with oxidative reagents eral composition, pH, organic matter content). Conclu-
sions on the feasibility of a certain oxidant/protocol to seem inevitable. This attributes some ambiguity to stud-
ies concerned with soil mineralogical composition or remove organic Care possible only when several oxidants
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Table 4. Oxidative treatments in soil analysis. Advantages and drawbacks of reactants: () suitable, () not recommended,
(/) ambiguous.
Purpose Hydrogen peroxide Sodium hypochlorite Disodium peroxodisulfate
Textural analysis / uncertain for soils with high contents / little effect on silicates, / large reactant-soil and
of vermiculite, mica and smectite formation of haloorganics reactant-buffer ratio
Mineralogical analysis dissolution of carbonates little effect on silicates and no effect on reference phyllosilicate
and determination of destruction of smectitic, vermiculitic oxides (pH 8, 25C) clays
mineral properties and micaceous minerals dissolution of Al hydroxides / bicarbonate buffer may extract
transformation of vermiculites into (pH 9.5) allophan and hydroxides
mica-like minerals by NH
4
fixation heating may alter poorly heating may alter poorly crystalline
dissolution of poorly crystalline crystalline oxides (100C) oxides
oxides in acid soils (especially when
Na
4
P
2
O
7
is used as dispersant)
heating may alter poorly crystalline
oxides
Extraction of organically- dissolution of Mn oxides, sulfide little effect on Mn oxides, not used for this purpose
bound metals minerals, and poorly crystalline sulfides and poorly
oxides in acid soils crystalline minerals
/ alkaline pH may favor
metal precipitation (except
in soils rich in OM)
Amonette, J., F.T. Ismail, and A.D. Scott. 1985. Oxidation of iron in
are comparatively applied to the same sample collective.
biotite by different oxidizing solutions at room temperature. Soil
When modifying oxidation protocols, mineral alterations
Sci. Soc. Am. J. 49:772777.
should be elucidated by using combined methods like
Anderson, J.U. 1963. An improved pretreatment for mineralogical
XRD, IR spectroscopy, gas adsorption (e.g., N
2
, CO
2
), analysis of samples containing organic matter. Clays Clay Miner.
10:380388. and selective dissolution techniques.
Andreozzi, R., A. DApuzzo, and R. Marotta. 2002. Oxidation of
Table 4 may serve as a guide for the use of reagents
aromatic substrates in water/goethite slurry by means of hydrogen
for organic matter removal. For textural analysis, H
2
O
2
peroxide. Water Res. 36:46914698.
is adequate when the soil mineral phase is not domi-
Balesdent, J. 1996. The significance of organic separates to carbon
dynamics and its modelling in some cultivated soils. Eur. J. Soil nated by mica, vermiculite or smectites. This recommen-
Sci. 47:485493.
dation must be used with caution since the impact of
Bartlett, J.B., R.W. Rubble, and R.P. Thoma. 1937. The influence of
mineral disintegration on particle-size distribution has
hydrogenperoxide treatment onthe exchange capacity of Maryland
not yet been tested. Sodium hypochlorite is impractical
soils. Soil Sci. 44:123128.
for this purpose because of the formation of haloorgan- Blakemore, L.C., P.L. Searle, and B.K. Daly. 1987. Methods for chemi-
cal analysis of soils. New Zealand Soil Bureau. Scientific Rep. 80. ics that have to be disposed separately. Similarly, the
Dep. of Scientific and Industrial Research, Lower Hutt, New
large amounts of oxidant needed render the Na
2
S
2
O
8
Zealand.
procedure unsuitable for organic matter removal before
Cavallaro, N., and M.B. McBride. 1984. Effect of selective dissolution
textural analysis. For organic C removal before sorption
on charge and surface properties of an acid soil clay. Clays Clay
Miner. 32:283290. experiments and when surface properties of soils and
Celi, L., M. Presta, F. Ajmore-Marsan, and E. Barberis. 2001. Effects
minerals (SSA, CEC) are assessed, we recommend the
of pH and electrolytes on inositol hexaphosphate interaction with
use of NaOCl (pH 8, 25C) instead of 30% (wt/wt) H
2
O
2
goethite. Soil Sci. Soc. Am. J. 65:753760.
since phyllosilicate disintegration and heat-induced trans-
Celi, L., E. Barberis, and F.A. Marsan. 2000. Sorption of phosphate
formations of minerals are kept to a minimum. For quan- on goethite at high concentrations. Soil Sci. 165:657664.
Chakrabartty, S.K., H.O. Kretschmer, and S. Cherwonka. 1974. Hypo- tification of clay minerals, H
2
O
2
should be avoided
halite oxidation of humic acids. Soil Sci. 117:318322.
because of the transformation of vermiculites into mica-
Cheshire, M.V., C. Dumat, A.R. Fraser, S. Hiller, and S. Staunton.
like minerals by NH
4
fixation. The use of Na
2
S
2
O
8
is
2000. The interaction between soil organic matter and soil clay
appropriate for clay preparation before XRD analysis
minerals by selective removal and controlled addition of organic
matter. Eur. J. Soil Sci. 51:497509. since it seems not to alter the properties of reference
Cornell, R.M., and U. Schwertmann. 1996. The iron oxides. Structure,
clays. The application of NaOCl (pH 9.5) should be
properties, reactions, occurrences and uses. VCH, Weinheim.
avoided for soils containing interlayered Al and Al hy-
Craik, J. 1924. The mechanisms of the oxidation of typical carbohy-
droxides. Before further analysis, a test for the residues
drates. J. Soc. Chem. Ind. 43:171177.
of organic C and the reagents used is recommended.
Cuypers, C., T. Grotenhuis, J. Joziasse, and W. Rulkens. 2000. Rapid
persulfate oxidation predicts PAH bioavailability in soils and sedi-
ments. Environ. Sci. Technol. 34:20572063.
ACKNOWLEDGMENTS
Cuypers, C., T. Grotenhuis, K.G.J. Nierop, E.M. Franco, A. de Jager,
We are grateful to Christian Mikutta (Berlin University of
and W. Rulkens. 2002. Amorphous and condensed organic matter
Technology) and Adelina Siregar for comments and discus- domains: The effect of persulfate oxidation on the composition of
sion. Adelina Siregar provided the XRD diffractograms of soil/sediment organic matter. Chemosphere 48:919931.
De Jonge, H., L.W. de Jonge, and M.C. Mittelmeijer-Hazeleger. 2000. H
2
O
2
treated illite. This study was funded by the Deutsche
The microporous structure of organic and mineral soil materials.
Forschungsgemeinschaft priority program SPP. 1090 Soils as
Soil Sci. 165:99108.
sources and sinks for atmospheric CO
2
.
Dohrmann, R. 2003. The stability of clay minerals in acidic water
containing organic substances and XRD detection of clay modified
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R

fixation. Sodium hypochlorite

have a high affinity for hydroxyl-bearing mineral

surfaces (Ali and Dzombak, 1996; Su and Suarez, 1997)

radicals that can react with organic matter

radicals react with H

N-containing compounds. Herriott (1947) reported that

radicals (Peyton, 1993).

radicals have a similar reactiv- oxidation of humic acid (14 mg NH

[10] took advantage of this fact by using H

cgu l and Girgin, 2002).

cgu l and Girgin, 2002). The use of unweathered of sucrose (168 g C kg

produced during showed that H

cgu l, E., and I. Girgin. 2002. Chemical exfoliation characteristics

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