Soil Biology & Biochemistry 44 (2012) 130e142

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Soil Biology & Biochemistry

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Biogeochemical factors related with organic matter degradation and C storage

in agricultural volcanic ash soils
Z. Hernández*, G. Almendros
Spanish National Research Council (CSIC), Serrano 115B, 28006 Madrid, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Laboratory incubation experiments in addition to physicochemical analyses of volcanic ash soils were
Received 26 February 2011 carried out in order to identify biogeochemical factors related with soil organic C (SOC) stabilization in the
Received in revised form long term and with the potential for C sequestration of agroecosystems. Up to 24 vineyard plots under
15 July 2011
similar subtropical conditions in Tenerife Island (Spain) were sampled. Soil samples were incubated for 30
Accepted 18 August 2011
days in laboratory conditions (27
C and 66% water holding capacity) and the CO2 released was periodically
Available online 12 September 2011
measured to plot C mineralization curves. Soil organic matter (SOM) with special emphasis paid on the
humic acid (HA) was characterized by elemental composition, spectroscopic techniques: visible, infrared
Keywords:
C mineralization
(IR) and 13C nuclear magnetic resonance (13C NMR) and analytical pyrolysisegas chromatography/mass
Laboratory incubation spectrometry (GC/MS). The dependent variables examined were either the total mineralization coefficient
Selective preservation (TMC, g C $ kg C soil1 day1) in laboratory incubations, or the SOC. A very significant negative correlation
Humic acid was found between SOC and TMC, i.e., in our soils, the higher the biodegradation rates under laboratory
Vineyards conditions, the lower the soil C sequestered in the corresponding plots. In it was also observed that the
Allophanic soils concentration of amorphous minerals (Alo þ ½ Feo index) and the water holding capacity at 0.033 MPa were
associated with lower CO2 release; the latter could suggest microanaerobic conditions hampering biodeg-
radation in these thixotropic soils. Conversely, no correlation was found between SOC or TMC and typical soil
physical and chemical factors, such as granulometric fractions or exchangeable calcium. The molecular
characteristics of the HAs showed also predictive potential as regards SOC resilience, reflecting the
comparatively fast biodegradation of SOM composed mainly of biomass constituents (prominent lignin
signature and O-alkyl 13C NMR region). The poor correlation between total aromaticity of the HAs and SOM
resistance against biodegradation could be explained by a dual origin of aromatic structures in HAs, either
consisting of methoxyl-containing non-decomposed lignin structures or condensed black carbon-like
polyaromatic structures. The results suggested the possibility of predicting the vulnerability of SOC to
biodegradation from laboratory incubation experiments, which results of interest for modeling global
change scenarios.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction the main reason of C resilience was the extremely aromatic nature
of the SOM, further studies (Shindo et al., 1986a, 1986b, 2004;
Andosols have been traditionally described as active C sinks, Golchin et al., 1997) have pointed out that such aromaticity could
with high potential to stabilize SOC (Dahlgren et al., 1993; Eswaran also be an effect of local biomass burning (e.g. charred grass of
et al., 1993). The strong organomineral and organometallic inter- Miscanthus sinensis) then, SOM in other volcanic ash soils could also
actions in andic soils, in addition to the toxicity of exchangeable be strongly aliphatic as a consequence of hydromorphic conditions
aluminum have been considered main causes of the low C miner- in soil microcompartments (Naafs, 2004; Buurman et al., 2007;
alization rates (Zunino et al., 1982; Boudot et al., 1988, 1989). González-Pérez et al., 2007; Nierop and Buurman, 2007).
Although early studies in Japanese Andosols have suggested that There are few experimental data concerning factors responsible
for the stability of SOM (Almendros and Dorado, 1999) and, in
particular, there is no sufficient literature available and controver-
* Corresponding author. Tel.: þ34 917822091; fax: þ34 915640800.
sial results exist about the possible effect of global temperature in
E-mail addresses: [email protected], [email protected] increasing the SOM decomposition (Lomander et al., 1998; Leirós
(Z. Hernández). et al., 1999; Giardina and Ryan, 2000), so as the usefulness of

0038-0717/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.soilbio.2011.08.009
 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142 131

laboratory incubation in the assessment of the resistance against tillage, application of organic or mineral amendments, use of plant
biodegradation of the SOM (Reichstein et al., 2000, 2005; Abril cover and pumice mulchings (Macías Hernández, 2005).
et al., 2001). The studied areas (Table 1) could be defined as: i) recent soil
An essential characteristic of Andosols is the dominance of non- formations with allophanic characteristics (U1, plots G1eG4) and
crystalline minerals (Torn et al., 1997) or Al-humus complexes soils with high-fertility volcanic materials transported by farmers
(Inoue and Higashi, 1988), which has been described to protect from mid-altitude sites to coastal plots, referred to as transportic
SOM from microbial decomposition, contributing to its stability soils (U4, plots M1eM4), ii) aluandic soils with dominance of
(Kögel, 1986; Takahashi et al., 1995). The factors involved in C Al-humus complexes (U2, plots O1eO4), iii) non-andic soils
sequestration are still very imperfectly known (Jambu, 1968; Oades, (U3, plots S1eS4), where non-tillage, permanent plant cover, liming
1988; Spaccini et al., 2000; Ashman et al., 2003). These factors are and occasional inputs from fly ash produced by wildfires could
often classified between extrinsic and intrinsic factors. Intrinsic improve the nutrient availability to crops, iv) poorly developed soils
factors would depend on the chemical composition of the SOM, formed from pumices which are classified as vitrandic soils in the
whereas extrinsic factors would depend on interactions between coastal level (U5, plots H1eH3) and at higher altitude (U6, plots
soil constituents (Almendros, 2008). F1eF3), and finally, vi) non-andic soils above 1000 m a.s.l. under
Several studies have suggested that SOM resilience is a major high daily thermal oscillation (U7, plots V1eV3).
consequence of intrinsic factors, such as chaotic, three-dimensional Soil samples were collected by triplicate in 100 m2 square plots,
structure with large amounts of disorderedly arranged aromatic from the upper 20 cm of the Ap soil horizons. The samples were air-
“building blocks” resistant to microbial attack (Oades, 1988; dried, sieved through 2 mm and gravel (>2 mm) was weighed and
Baldock and Skjemstad, 2000; Marschner et al., 2008). Apart from discarded.
specific molecular features of the SOM, a series of extrinsic factors
may also play a key influence on the retention of organic C in soil 2.2. Laboratory analyses
(Jastrow et al., 2007). This is the case with encapsulation of organic
particles into soil aggregates or the effect of Al3þ on soil microbial 2.2.1. Physical and chemical soil properties
activity (Carballas et al., 1979; Baldock and Nelson, 2000; A set of diagnostic soil features were determined (Soil Survey
Marschner et al., 2008). In general, these factors are related with Staff, 2006). The bulk density was estimated in 700-cm3 undis-
micro-compartmentalization of the humus fractions, physical turbed core samples and the porosity was calculated (Blake and
occlusion of the SOM in micro-aggregates or specific surface Hartge, 1986). Particle-size analysis (clay, silt and sand) was
interactions with clays or amorphous oxides protecting SOM carried out with the hydrometer method after sieving and disper-
(Baldock and Skjemstad, 2000). Recently, some authors have sion in a 0.5N solution of sodium hexametaphosphate and sodium
described that the complex fractal structure in allophane particles carbonate for 16 h (Soil Survey Staff, 2004). The weight percentage
makes SOM less available to microbes and enzymes (Woignier et al., of water-stable aggregates (>0.05 mm) was estimated following
2007; Chevallier et al., 2010). the method by Feodoroff (1960) after removing SOM by perox-
On the other hand, it is known that SOM content tend to decline idation. Saturation water holding capacity (WHC) at field capacity
when soils are cultivated intensively (Lal, 2004). This progressive C moisture content (at 0.033 MPa) and at the permanent wilting
loss is due to biodegradation-enhancing factors (Rasmussen and point (at 1.5 MPa) were determined (Guitián and Carballas, 1976).
Collins, 1991). Tillage also disrupts soil aggregates, exposing Soil pH and electric conductivity (EC) were measured in soilewater
embedded SOM to decomposition (Chen, 1986; Baldock and Nelson, suspensions (1:2.5 w:w). The SOC was determined by wet oxidation
2000; Devevre and Horwathm, 2000). Nevertheless, in andic soils with 1N potassium dichromate (Nelson and Sommers, 1982) and total
under agricultural management, an increase of aggregate stability nitrogen (N) by the Kjeldahl method (Piper, 1950). The exchangeable
has been observed (Hernández and Almendros, 2010), possibly due bases (Na, K, Ca and Mg) were extracted with ammonium acetate
to periodic desiccation of amorphous minerals (allophane and (pH ¼ 7) (Juo et al., 1976) and determined by atomic absorption
imogolite-type) and the increase of silica in the soil solution, which spectroscopy and the total cation exchange capacity (CEC) was
enhance organomineral interactions (Nanzyo et al., 1993) and the measured with selective ion electrodes. Soil microelements (Fe, Mn,
soil aggregate hierarchy (Tisdall and Oades, 1982). Zn, Cu) were extracted with EDTA (pH ¼ 4.5) (Lakanen and Ervio,1971)
Assuming the above considerations, this research aims to and measured by inductively coupled plasma atomic emission spec-
identify intrinsic and extrinsic factors controlling C stabilization in troscopy. Available phosphate (P2O5) was determined following to
volcanic ash soils subjected to agricultural practices. This could lead Burriel and Hernando (1950).
to explain the spatial variability of the physicochemical properties The andic character of the soils was evaluated according to
of the SOM developed under similar plant biomass (vineyard) and different indices such as the content of amorphous minerals
the same climatic conditions (Canary Islands, subtropical environ- (Alo þ ½ Feo), the Al-humus complexes, or the P retention following
ment). Apart from its theoretical interest, this study could be to Blakemore et al. (1987). Acid oxalate-extractable iron, aluminum
helpful in establishing scientific criteria to improve environmen- and silica (Feo, Alo, Sio) and pyrophosphate-extractable iron,
tally friendly agricultural practices. aluminum and silica (Fep, Alp, Sip) were determined by inductively
coupled plasma emission spectroscopy after extracting the soil
2. Materials and methods with 0.2M ammonium oxalate (pH ¼ 3) and 0.1M sodium pyro-
phosphate, respectively. The Alo value is a measure of all active Al
2.1. Field study compounds, including non-crystalline minerals (e.g. allophane and
imogolite) and Al-humus complexes, whereas Alp informs mainly
Sampling was carried out in 24 contrasting vineyard plots in on the forms of Al linked to SOM, so high values of Alp-to-Alo ratio
Tenerife Island (Spain 28
280 N and 16
290 W), including basaltic (>0.5) indicate dominance of inorganic forms of amorphous Al
(predominant), trachyphonolitic and pumitic volcanic materials (Van Reeuwijk, 1993).
(Table 1). In the sampling zones, the mean annual soil temperature
varies slightly with the altitude, ranging from isothermic 2.2.2. Incubation experiment
(15e22
C) to isomesic (8e15
C). Vineyards have been managed Soil samples of 20 g (<2 mm) were aerobically incubated by
for five centuries following agricultural practices of minimum triplicate in Erlenmeyer flasks closed with rubber stoppers with
 132
Table 1
Characteristics of soils in volcanic ash plots in Tenerife Island (Spain).

Units Plot Latitude/ Longitude/ Mountain Altitude/ Geological Annual Annual mean Soil Soil Soil type Agricultural management practicesb
UTMa UTM side (Teide m asl substrate mean precipitation/ horizon moisture (Soil Survey

Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142

SR L PB AT PC PPC AM AMF DI
volcano) T/
C mm regime Staff, 2006)
U1 G1 337878 3140530 North 351 Trachyphonolithic 18 460 Ap Ustic Haplic Ustarent    þ    þ þ
G2 337845 3140451 North 357 Trachyphonolithic 18 460 Ap Ustic Haplic Ustarent    þ    þ þ
G3 337871 3140440 North 359 Trachyphonolithic 18 460 Ap Ustic Haplic Ustarent    þ    þ þ
U2 O1 348681 3140620 North 364 Basaltic 18 470 Ap Ustic Typic Haplanthrept þ   þ    þ þ
O2 348654 3140577 North 364 Basaltic 18 470 Ap Ustic Typic Haplanthrept þ   þ    þ þ
O3 348713 3140688 North 355 Basaltic 18 470 Ap Ustic Typic Haplanthrept þ   þ    þ þ
O4 348688 3140683 North 357 Basaltic 18 470 Ap Ustic Typic Haplanthrept þ   þ    þ þ
U3 S1 360303 3149937 North 540 Basaltic 16 600 Ap/Bw Ustic Typic Haplanthrept þ þ þ   þ  þ þ
S2 360128 3149940 North 553 Basaltic 16 600 Ap/Bw Ustic Typic Haplanthrept þ þ þ  e þ e þ þ
S3 360219 3150100 North 542 Basaltic 16 600 Ap/Bw Ustic Typic Haplanthrept þ þ þ e e þ e þ þ
S4 360473 3149794 North 612 Basaltic 16 630 Ap/Bw Ustic Typic Haplanthrept þ þ þ e  þ  þ þ
U4 M1 354128 3146359 North 168 Basaltic 20 300 Ap Xeric Typic Ustorthent þ   þ    þ þ
M2 354093 3146412 North 168 Basaltic 20 300 Ap Xeric Typic Ustorthent þ   þ    þ þ
M3 354090 3146434 North 166 Basaltic 20 300 Ap Xeric Typic Ustorthent þ   þ    þ þ
M4 354104 3146524 North 158 Basaltic 20 300 Ap Xeric Typic Ustivitrand þ   þ    þ þ
U5 H1 363188 3134412 South 190 Pumitic 19 330 Ap Aridic Vitrandic Torriorthent þ   þ þ   þ þ
H2 363240 3134389 South 185 Pumitic 19 330 Ap Aridic Vitrandic Torriorthent þ   þ þ   þ þ
H3 363287 3134386 South 180 Pumitic 19 330 Ap Aridic Vitrandic Torriorthent þ   þ þ   þ þ
U6 F1 355509 3124313 South 890 Pumitic 14 286 Ap Udic Vitrandic Ustorthent þ   þ þ  þ  þ
F2 355526 3124303 South 880 Pumitic 14 286 Ap Udic Vitrandic Ustorthent þ   þ þ  þ  þ
F3 355535 3124292 South 875 Pumitic 14 286 Ap Udic Vitrandic Ustorthent þ   þ þ  þ  þ
U7 V1 337043 3113810 South 1256 Basaltic 12 537 Ap/Bw Xeric Typic Haplanthrept    þ     
V2 337063 3113819 South 1257 Basaltic 12 537 Ap/Bw Xeric Typic Haplanthrept    þ     
V3 337078 3113814 South 1257 Basaltic 12 537 Ap/Bw Xeric Typic Haplanthrept    þ   e  
a
Universal transverse mercator.
b
Agricultural management practices: SR: Stone removal; L: Liming; PB: Possible burning; AT: Annual tillage; PC: Pumicecover (0e50 cm); PPC: Permanent plant cover; AM: Application of manure, AMF: Annual mineral
fertilizer; DI: Drip irrigation.
 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142 133

polyethylene inlet and outlet tubes. The flasks with the soil samples

2.7 4.1 0.075

0.203

6.6 4.4 0.136

1.5 0.8 0.039
6.5 7.2 0.053
4.3 4.4 0.033

29.7 0.4 0.159

12.4 10.8 0.575
0.9 6.1 0.296
36.9 3.3 1.143

13.8 2.7 0.893

2.1 0.6 0.107
3.1 2.3 0.017
0.1 0.1 0.003
2.6 1.3 0.820
Fe/ Mn/ Zn/ Cu/ P2O5/

kg1 kg1 kg1 kg1 kg1

were kept for 30 days with a moisture content of 60% w:w into an
incubation oven at 27  0.1
C. The atmosphere in the flasks was

C-to-N dS m1 cmolc cmolc cmolc cmolc cmolc saturation/ mg mg mg mg g

measured daily by connecting one tube to the suction of the CO2

6
analyzer (Carmhograph-12, Wösthoff) and the other tube of the

15
incubation flask to a column filled with soda-lime (Almendros et al.,
1990). The data of the C mineralization curves were expressed in

20
61

33
11
189
23

15

21
56
9

17
18
114

110

111
terms of the different C content of the soil samples (Chone et al.,
1973), i.e. as soil respiration rate (mg 100 g1 soil day1) and

24

10

56

41
80
16
83
15
15
217

256

142
13
128

137
TMC (mg kg1 C day1).

8.0

1.6
65.7

24.4
1.1
78.3
13.6
83.8
11.2

16.6
106.1

129.3
36.0
64.8
3.0
2.2.3. Isolation and purification of humic acids

Mg/ CECc/ Base

Standard procedures were employed for the isolation of the

%
different humus fractions (Duchaufour and Jacquin, 1975; Hayes

1

0.8

3.6

0.6

2.9
26.3

22.5
3.1
17.0
1.6
29.1

21.6

17.9
3.9
16.6
0.0
and Swift, 1990). The soil lipid content (g 100 g1) was deter-

kg
mined after Soxhlet extraction using dichloromethane:methanol

1

1.2
3.1

1.1
0.1
2.5
0.6
3.8
0.4
3.5
0.4
4.9
0.6
1.9
0.2
0.6
kg
(3:1 v:v) for 8 h. A previous physical separation of the partially
decomposed organic particles (flotation in 2M H3PO4 followed

1

1.1
10.9

3.3
0.6
8.1
1.9
16.2
2.2
15.1
1.1
9.7
0.7
6.3
0.6
1.4
Ca/
by CHBr3eCH3CH2OH (1.8 g cm3) to obtain two fractions of free

kg
organic matter, FOM) was carried out before extracting the

1

1.8
0.3
0.8
0.2
2.5
1.0
3.3
0.5
3.4
0.2
7.0
0.3
2.4
0.2
0.4
kg

x ¼ Average of soil samples in sampling units; sd ¼ Standard deviation between soil samples; LSD ¼ Least significant difference between plots (P < 0.05).
K/
alkali-soluble humic fractions by shaking the soil with 0.1M
Na4P2O7 and 0.1M NaOH. This humic extract was precipitated by

1
Na/

1.4
0.2
0.3
0.1
0.2
0.0
0.9
0.2
0.9
0.1
0.6
0.1
0.2
0.1
0.1
kg
adding 6M HCl to separate the acid-insoluble fraction (HA) from
the acid-soluble fraction (fulvic acids, FA). The alkali-insoluble

0.55
0.07
0.31
0.03
0.16
0.02
0.47
0.21
0.29
0.03
0.67
0.05
0.37
0.02
0.06
soil extraction residue was treated with 60 mM Na2S2O4 to

EC/
remove iron and aluminum oxides (oxide-associated insolubi-

ratio
lized humin, o-EIH), followed by 1M HFeHCl treatments to
Soil

1
17

14
1
12
1
11
1
13
1
12
1
12
1
1
cleave clayehumus complexes (clay-associated, insolubilized

1
humin, c-EIH). The final soil residue still contains the non-
g 100 g
g 100 g1 soil N/
extractable humin (NEH). The C in the different SOM fractions
Total

0.31
0.06
0.24
0.02
0.16
0.02
0.16
0.10
0.19
0.02
0.22
0.03
0.11
0.01
0.03
was determined by wet oxidation (Nelson and Sommers, 1982).
Purified HAs were prepared for further analyses: the HAs were
WHCa pH SOCb/

redissolved in 0.5M NaOH and centrifuged at 43,500 g to sedi-

5.1
0.9
3.3
0.4
1.9
0.3
1.7
1.2
2.5
0.4
2.5
0.3
1.3
0.1
0.5
ment clay-sized minerals, and reprecipitated with 6M HCl, dia-
Average values of physical and chemical properties of soil samples from agricultural plots (Tenerife Island).

lyzed in cellophane bags (ViskingÒ dialysis tubing, molecular

5.2
0.6
4.4
0.1
6.3
0.3
7.3
0.9
7.2
0.4
7.4
0.0
5.6
0.1
0.4
weight cut-off 18,000 D; pore diameter ca. 25 Å, Medicell) to
MPa/% MPa/%
g 100 g1 g 100 g1 g 100 g1 stability/% at 0.033 at 1.5

remove the salts and dried at 35
C.

0.5
12.1

12.4
1.3
9.8
0.9
11.6
0.6
12.1
1.4
13.1
0.8
10.8
0.8
0.9
2.2.4. Chemical characterization of humic acids
Aggregate WHCa

2.5
69.7

62.1
4.9
58.4
1.2
62.3
3.6
54.4
6.0
57.4
3.3
53.9
3.5
3.1
The elemental composition was determined with a Carlo-Erba
EA 1108 analyser. The H-to-C and O-to-C atomic ratios were
calculated from the ash free elementary data to monitor the stages
of diagenetic transformation of the HAs (Van Krevelen, 1950).
3
59

62
10
74
2
68
9
33
10
26
2
57
7
4

The optical density of HAs was measured at 465 nm (E4) and

665 nm (E6) from solutions of 0.2 mg C cm3 in 0.01M NaOH
Sand/

(Kononova, 1982). The optical density is often considered as

2
35

43
5
27
2
35
4
57
1
65
2
35
3
2

a surrogate descriptor of aromaticity (Traina et al., 1990) and the

E4-to-E6 ratio as an index of molecular size (Chen et al., 1977). The
second derivative of the visible spectra was obtained in order to
Silt/

1
35

33
5
26
3
32
1
27
1
24
1
35
1
1

detect and quantify weak spectroscopic peaks, which in HA

frequently correspond to green-coloured fungal pigments (dihy-
droxyperylenequinone-type, DHPQ) (Kumada and Hurst, 1967;
Clay/

1
27

28
2
48
3
33
3
17
1
10
1
29
1
3

Almendros et al., 1985).

1

For IR spectroscopy, a Bruker IFS 28 Fourier-transform spectro-

g 100 g
gravel/
Porosity/ Coarse

photometer was used. Resolution-enhanced IR spectroscopy was

applied for improved pattern recognition (Almendros and Sanz,
2
46

25
1
5
1
30
2
34
1
46
1
24
1
1

Cation exchange capacity.

1991; Fernández-Getino et al., 2010), such is identifying the

Water holding capacity.

“lignin fingerprint”, which includes characteristic bands at

1330 cm1 (syringyl-type, S) and 1260 cm1 (guaiacyl-type, G), in
Soil organic carbon.
5
55

43
6
41
2
45
2
53
1
56
7
35
3
4
density/ %

addition to bands coinciding with those in lignins at ca. 2920, 1720,

3

1620, 1640, 1540, 1510, 1460, 1330, 1270 and 1030 cm1 (Farmer and
kg m

8
795

920
64
964
29
955
16
854
18
853
49

42
40
1056
Bulk

Morrison, 1964). In order to facilitate the interpretation of the large

LSD

set of IR spectra, a lignin gradient was established ordering (1e30)

sd

sd

sd

sd

sd

sd

sd
Table 2

U1 x

U2 x

U3 x

U4 x

U5 x

U6 x

U7 x
Plots

the HA samples, in terms of the more or less smoothed lignin

c
a
b

pattern with the progress of the humification, i.e., low values

134 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142

Table 3
Average values of soil carbon mineralization indices and andic characteristics in volcanic ash soils (Tenerife Island).

Plot Soil respiration measurements/g CO2 kg C soil1 day1 Silandic and aluandic properties/g kg1 Alp-to-Alo P retention
ratio g 100 g1
TMC MC1 MC2 MC3 Alo Feo Sio Alp Fep Sip Alo þ 1/2 Feo
U1 x 44 26 27 46 11.0 9.3 4.8 2.7 0.7 1.0 15.6 0.2 41
sd 12 8 5 13 1.8 1.1 0.8 1.5 0.8 0.9 1.3 0.1 1
U2 x 61 29 30 41 5.3 10.5 1.7 3.8 2.2 2.9 10.6 0.7 34
sd 3 4 4 6 1.8 2.1 0.5 1.0 0.4 0.8 2.8 0.1 7
U3 x 111 47 31 22 4.7 8.8 1.4 1.8 1.0 1.5 9.2 0.4 34
sd 26 20 6 16 0.7 0.8 0.3 0.7 0.3 0.4 1.0 0.1 4
U4 x 77 35 29 36 6.4 7.3 3.7 1.0 0.5 1.8 10.1 0.2 23
sd 12 1 2 3 6.9 6.3 3.9 0.9 0.4 0.3 10.1 0.0 24
U5 x 98 33 28 39 6.0 5.8 3.0 0.8 0.8 1.2 8.9 0.1 16
sd 22 7 6 13 1.5 1.1 0.3 0.4 0.4 0.3 2.1 0.0 3
U6 x 105 28 31 41 2.6 2.1 1.4 0.2 0.2 2.1 3.6 0.1 0
sd 40 3 1 4 0.3 0.0 0.1 0.1 0.0 0.0 0.3 0.0 0
U7 x 129 27 33 39 3.9 5.1 1.5 0.9 0.3 0.8 6.5 0.2 31
sd 22 7 2 6 0.6 0.7 0.0 0.1 0.0 0.4 0.2 0.1 5
LSD 24 11 5 8 0.9 0.9 0.3 0.4 0.2 0.4 0.9 0.1 5

TMC ¼ Total mineralization carbon/g CO2 kg C soil1 day1. MC1 to MC3 ¼ Partial mineralization coefficient (1 ¼ 0e3 days; 2 ¼ 4e10 days. 3 ¼ 11e30 days). Alo. Feo. Sio. Alp. Fep.
Sip ¼ Acid oxalate and sodium pyrophosphate-extractable aluminum. Iron and silica. respectively (g kg1). P retention/g 100 g1. x ¼ Average of soil samples in sampling units;
sd ¼ standard deviation between soil samples; LSD ¼ least significant difference between field plots with a P value < 0.05.

indicated low humification stages and high contribution of lignin to (intrinsic factors) and its interaction with soil mineralogical and
the total IR spectra. environmental constraints (extrinsic factors).
The 13C NMR was used to quantify different C types: alkyl, Multivariate, non-linear statistical models (Kruskal, 1964) were
O-alkyl, aromatic and carbonyl (González-Vila et al., 1983; Chen and applied to identify readily the HAs’ characteristics more closely
Chiu, 2003). associated with accumulation of SOC and TCM, using the 1-Pearson
Analytical pyrolysis was carried out with a Pyrojector unit (SGE correlation index as affinity index. This numerical taxonomy
instruments) connected to a GC/MS system Agilent 6890 with an approach was also applied to the soil samples set, in order to shed
HP-1 capillary column (30 m  250 mm). The compounds corre- some light on the impact of the agricultural practices on volcanic
sponding to the chromatographic peaks were identified from their ash soils.
mass spectra (i.e., fragmentometry, comparisons with standards and Principal component analysis (PCA) was used to obtain
library searching), grouped into five families and their cumulative criteria to reduce the number of relevant physical and
abundances were calculated: i) carbohydrate-derived compounds, chemical descriptors in new axes (principal components)
ii) lignin-derived compounds (methoxyphenols), iii) alkyl compounds explaining most of the variability between the soil plots under
derived from lipids or aliphatic biomacromolecules; iv) N-containing study.
compounds and v) methoxyl-lacking aromatic compounds (Saiz-
Jiménez and de Leeuw, 1986). 3. Results

2.2.5. Statistical analyses 3.1. Soil characteristics and incubation experiment

Simple regression models were used to examine the extent to
which SOC and TMC (dependent variables) varied in response to Tables 2 and 3 summarize the main physical, chemical and
the chemical composition and structural characteristics of the HAs mineralogical characteristics of the soils studied and Tables 4 and 5

Table 4
Average values of soil organic matter fractions and elementary composition of humic acids from volcanic ash soils (Tenerife Island).

Plot Soil organic matter fractions/g C kg1 C soil HA/FA Elementary composition (g 100g 1
) and atomic ratios of humic acids

Lipid FOM HA FA o-EIH c-EIH NEH C H N C-to-N Atomic Atomic

H-to-C O-to-C
U1 x 1.0 1.4 31 11 1.2 2.2 53 2.8 54 5 5 11 1.1 0.5
sd 0.2 0.3 6 1 0.1 0.5 6 0.4 0.4 0.2 0.3 0.6 0.05 0.01
U2 x 1.2 1.8 28 19 0.9 3.5 47 1.6 54 5 5 10 1.2 0.5
sd 0.7 0.8 3 6 0.3 0.5 5 0.6 1.6 0.5 0.2 0.6 0.12 0.02
U3 x 0.4 1.2 32 17 1.5 6.4 42 2.6 55 4 4 12 0.8 0.5
sd 0.1 0.4 8 6 0.5 1.7 4 2.2 0.6 0.3 0.1 0.3 0.07 0.01
U4 x 0.3 0.4 40 10 3.1 9.5 37 4.5 50 5 4 11 1.2 0.6
sd 0.1 0.1 9 3 0.6 1.4 9 2.2 4.2 0.2 0.3 0.8 0.11 0.12
U5 x 0.7 1.9 25 26 1.3 5.2 41 1.0 52 5 5 11 1.2 0.5
sd 0.1 0.6 3 3 0.6 1.8 5 0.2 0.8 0.1 0.2 0.3 0.01 0.02
U6 x 0.5 3.1 17 21 1.2 4.1 54 0.8 53 6 6 9 1.4 0.5
sd 0.1 1.0 2 5 0.2 0.8 5 0.3 0.8 0.3 0.1 0.3 0.09 0.01
U7 x 0.4 4.2 40 13 2.4 7.9 33 3.3 57 5 5 13 1.1 0.5
sd 0.1 1.4 4 2 0.2 1.0 2 0.9 1.4 0.1 0.3 1.0 0.04 0.02
LSD 3.5 0.8 7 5 0.4 1.3 5 1.5 2.4 0.5 0.4 2.5 0.12 0.07

FOM ¼ Free organic matter. HA ¼ Humic acid. FA ¼ Fulvic acid. o-EIH ¼ oxides-Associated insolubilized humin. c-EIH ¼ clays-associated insolubilized humin. NEH ¼ Non-
extractable humin. x ¼ Average of soil samples in sampling units; sd ¼ Standard deviation between soil samples; LSD ¼ Least significant difference between field plots with a P
value < 0.05.
 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142 135

Table 5
Spectroscopic characteristics of humic acids from volcanic ash soils (Tenerife Island)
13
Plot Visible spectroscopy (optical density) Intensity of diagnostic IR bands (normalized as absolute abundances) C NMR (percentage of the total
spectral area)

E4 E4-to-E6 DHPQb Lignin IR band IR band IR band IR band IR band IR band IR band IR band IR band Alkyl Cs O-Alkyl Aromatic
(465 nm)a ratio gradientc at 2920 at 1460 at 1720 at 1620 at 1510 at 1640 at 1540 at 1330 at 1270 Cs Cs
cm1 cm1 cm1 cm1 cm1 cm1 cm1 cm1 cm1
U1 x 1.4 3.9 25 19 27 49 61 38 4 17 18 8 15 23 22 35
sd 0.08 0.17 2.6 1.0 4.5 5.1 7.7 2.2 1.1 2.7 4.3 1.6 1.4 1.1 1.0 1.7
U2 x 1.0 3.5 16 24 32 70 53 24 11 26 25 6 17 25 24 32
sd 0.34 0.59 3.0 1.3 11.7 27.5 10.3 1.7 6.6 11.7 12.7 0.7 0.5 5.1 4.8 7.8
U3 x 1.4 4.0 17 29 19 42 78 37 6 7 8 10 18 18 18 42
sd 0.69 0.29 3.8 1.3 7.1 13.9 7.8 2.1 0.7 2.8 3.4 1.2 2.1 2.7 2.6 4.2
U4 x 1.0 4.2 17 13 39 55 51 23 7 16 16 8 12 26 26 29
sd 0.60 0.46 4.8 3.1 7.1 12.9 6.1 5.6 1.8 10.3 8.2 1.4 2.5 2.7 2.5 4.1
U5 x 0.9 6.3 12 7 29 63 52 29 9 19 20 6 13 26 25 30
sd 0.18 0.53 3.5 1.0 8.3 10.4 3.6 2.7 0.3 2.6 3.7 0.7 0.5 0.3 0.3 0.4
U6 x 0.5 4.9 5 3 47 97 39 17 18 38 37 4 10 30 29 23
sd 0.08 1.03 0.4 1.0 7.7 2.2 2.6 3.7 2.1 0.9 1.0 0.4 0.6 2.3 2.1 3.5
U7 x 1.1 3.9 16 15 51 74 73 39 8 24 20 9 19 25 25 31
sd 0.18 0.20 0.0 1.0 0.7 4.3 10.3 4.0 0.4 2.3 7.1 0.4 2.1 1.7 1.6 2.6
LSD 0.20 0.52 2.8 1.9 9.0 17.2 6.7 3.4 3.5 6.3 7.6 1.2 1.6 3.1 3.1 5.0
13
C NMR ¼ alkyl (0e46 ppm). O-alkyl (46e110 ppm) and aromatic (110e160 ppm) C-types. respectively; x ¼ Average of soil samples in sampling units; sd ¼ standard
deviation between soil samples; LSD¼ least significant difference between plots with a P value < 0.05.
a
E4 and E6 ¼ optical density at 465 and 665 nm (absorption units).
b
Sum of the intensity (absorption units  104) of the valleys at 468 and 622 nm in the 2nd derivative visible spectra. produced by fungal pigments (4,9-dihydroxyperylene-
3,10-quinone).
c
Lignin signature recognized in the IR profile of the humic acids (scaled between 1 ¼ maximum similarity with lignin to 30, almost completely smoothed lignin pattern).

show structural descriptors of the corresponding HAs (Hernández, either to rapid consumption of the most biodegradable compounds
2009) (Table 6). during the exponential growth of the soil microbial population and/
Fig. 1 shows mineralization curves of different soils, i.e., values of or to degradation of the SOM in external surfaces of soil aggregates
progressive CO2 release during the 30-day incubation experiment. (Almendros and Dorado, 1999). In fact, comparatively low CO2
Since the kinetics suggested broad successive stages (Riffaldi et al., emissions coincided with plots with high percentages of soil
1996), the curves were divided into three regions, corresponding to aggregates and short-range minerals (U1; U2) whereas plots
early (MC1, 0e3 days), intermediate (MC2, 4e10 days) and advanced with noticeable amount of clay-size minerals (U3) showed
(MC3, 11e30 days) stages, and expressed as percentages of the total high percentage of biodegradable C at this stage (MC1, Table 3)
amount of CO2 released in the course of the 30-day experiment (Fig. 1). The intermediate stage (MC2) could correspond to further
(Table 3). The sharp peak at the early stage (MC1) could correspond degradation of weakly biodegradable SOM fractions. Finally, the

Table 6
Average values of abundancesa of the main compounds released by analytical pyrolysis from humic acids from volcanic ash soils (Tenerife Island).

U1 U2 U3 U4 U5 U6 U7 LSD

x sd x sd x sd x sd x sd x sd x sd
Total carbohydrate-derived compounds
Furan derivatives 17 1.0 10 3.1 10 5.1 9 2.1 6 1.1 11 3.2 8 3.6 9.9
Acetic acid 17 2.9 10 5.5 24 17.8 13 2.8 16 2.9 9 2.1 10 2.9 14.3
Other carbohydrates 14 2.3 14 4.2 13 4.1 10 1.5 11 2.4 13 1.0 11 3.3 12.3
Lignin-derived compounds
Guaiacyl-type lignin 7 2.0 27 9.2 3 4.7 5 4.0 21 0.9 25 0.7 8 2.6 12.7
Siringyl-type lignin 0 0.2 3 2.0 1 0.6 1 0.9 2 0.4 10 1.9 1 0.3 2.1
Vinylphenol 0 0.1 1 0.3 0 0.0 0 0.3 1 0.4 2 0.5 0 0.3 0.6
G to S ratio 28 12.3 14 8.8 9 17.2 10 13.1 15 5.2 2 0.5 10 0.5 4.4
Total non methoxylated aromatics
Alkylphenols 7 2.7 9 4.2 10 3.3 3 1.7 15 0.6 9 2.0 5 0.9 8.3
Alkylnaphtalenes 0 0.3 0 0.0 0 0.3 0 0.2 0 0.2 0 0.0 0 0.3 0.4
Alkylbenzenes 14 3.2 9 5.5 13 4.1 8 2.4 8 3.9 6 1.2 10 1.2 9.5
Other aromatics 1 0.3 1 0.2 1 0.5 0 0.2 0 0.1 0 0.0 2 0.5 0.5
Total N-compounds
Pyrroles 7 2.9 4 1.9 8 4.9 4 0.9 5 1.2 5 1.5 4 0.8 5.0
Pyridines 3 1.8 2 0.4 3 1.4 2 1.0 2 0.6 1 0.9 2 1.2 2.1
Indoles 0 0.0 0 0.2 0 0.0 0 0.2 0 0.1 0 0.0 0 0.1 0.1
Other N-compounds 2 1.7 1 0.7 4 2.5 4 1.0 2 0.8 0 0.0 2 0.6 1.9
Total alkyl compounds
Alkanes 8 2.7 6 2.5 2 2.8 18 15.8 5 1.8 3 1.5 8 2.3 7.3
Alkanedienes 2 1.1 3 1.1 1 1.6 7 4.1 3 0.9 4 0.5 9 3.4 4.0
Fatty acids 1 1.6 3 2.9 7 5.6 16 8.1 3 1.2 1 2.2 20 13.0 8.9
Aliphatic 13 2.9 14 2.2 12 0.9 39 3.5 10 2.9 8 1.4 36 5.6 3.4
a
Percentage of total ion chromatographic area. x ¼ Average of soil samples in sampling units; sd ¼ Standard deviation between soil samples; LSD ¼ Least significant
difference between plots with a P value < 0.05.
136 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142

a b
1.4 1.4
Andic soils (G1–G3) Vitrandic soils (H1–H3)
1.2 1.2
MC1: 31.6 % MC1: 40.6 %
1.0 1.0
MC2: 22.0 % MC2: 20.7 %
0.8 0.8
MC3: 46.3 % MC3: 38.7 %
0.6 0.6

0.4 0.4

0.2 0.2
1 2 3 1 2 3
0.0 0.0

1.4 1.4
Aluandic soil (O1–O4) Vitrandic soils (F1–F3)
1.2 1.2
MC1: 34.6 % MC1: 33.3 %
1.0 1.0
MC2: 25.0 % MC2: 22.7 %
0.8 0.8
MC3: 49.9 % MC3: 41.0 %
0.6 0.6
CO2 release / mg C · 100 g-1 day-1

0.4 0.4
0.2 0.2
1 2 3 1 2 3
0.0 0.0

1.4 1.4
Transportic soils (M1–M3) Non-andic soils (V1–V3)
1.2 1.2
MC1: 43.6 % MC1: 32.1 %
1.0 1.0
MC2: 20.8 % MC2: 22.1 %
0.8 0.8
MC3: 35.6 % MC3: 39.6 %
0.6 0.6
0.4 0.4
0.2 0.2
1 2 3 1 2
0.0 3
0.0
5 10 15 20 25 30
1.4
Non-andic soils (S1–S4) Time/days
1.2
MC1: 54.1 %
1.0
MC2: 24.3 %
0.8
MC3: 21.6 %
0.6

0.4
0.2
1 2 3
0.0
5 10 15 20 25 30
Time/days
Fig. 1. Average mineralization curves (error bars indicate least significant differences between spatial replicates) and percentages of total CO2 released (mg C 100 g1 day1), at
different stages of the laboratory experiments (MC1: early, MC2: intermediate and MC3: advanced) in cultivated volcanic soils on North (a) and South (b) side of the Teide volcano
(Tenerife Island). Numbers 1e3 indicate the different mineralization stages. Sample labels refer to Tables 1e3.

advanced stage (MC3) in which CO2 release tends to stabilize after most significant (P < 0.05) linear correlation coefficients between
30 days, could represent a virtually steady stage of soil respiration, TMC, the percentages of C mineralization in each stage (MC1, MC2
after the previous depletion of labile or physically exposed organic and MC3), the amount of SOC (dependent variables), and the set of
fractions. In general, the mineralization curves obtained showed soil abiotic variables in addition to the characteristics of HA
TMC values ranging between 8 and 18 mg C kg C soil1 day1, (independent variables).
similar to those reported in agricultural soils (López-Fando and A very significant negative correlation (P < 0.01, r2 ¼ 0.7)
Almendros, 1994) but lower that C mineralization rate from between TMC and the concentration of SOC in the different soils
a forest soil in Tenerife Island (Mora et al., 2007). was observed (Fig. 2, Table 7). The soil C biodegradation (TMC) also
decreased with soilewater saturation at field capacity and at the
3.2. Correlation study permanent wilting point (Table 7) (P < 0.01, r2 ¼ 0.76), which points
to an effect of water filled pore space on SOC accumulation.
A total of 102 variables corresponding to physical, chemical and The content of Alo and Alp, the P retention and the (Alo þ ½ Feo)
mineralogical soil characteristics including HA descriptors obtained index which have been used as indicators of the allophanic char-
by elemental analysis, spectroscopic and pyrolytic techniques were acter (Shoji et al., 1993), were positively correlated with the amount
processed versus respirometric data. Tables 7 and 8 showed the of SOC (Table 7). As expected, the correlation with P retention
 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142 137

Table 7 Table 8
Significant correlation indices (P < 0.05)a between humic acid characteristics and Significant correlation indices (P < 0.05)a between humic acid characteristics and
respiratory indexes reflecting their biodegradation in volcanic ash soils. respiratory indexes reflecting their biodegradation in volcanic ash soils

TMCb MC1 MC2 MC3 SOC TMCb MC1 MC2 MC3 SOC
(0e3 days)c (4e10 days)c (11e30 days)c (0e3 days)c (4e10 days)c (11e30 days)c
Soil respiration indices Optical density
MC1 0.47 0.92* E465 0.39
MC2 0.49 0.47 E4-to-E6 ratio
MC3 0.92* 0.78* 0.46 DHPQ 0.42 0.51 0.47
Soil physical and chemical properties IR spectroscopic parameters
1
Bulk density 0.59* 0.45 0.45 0.70* 2920 cm band 0.39
Coarse gravel 0.57* 0.44 0.46 0.52* 1460 cm1 band 0.40 0.48
1
Silt 0.48 0.43 1720 cm band 0.52*
WHC at 0.033 MPa 0.76* 0.51 0.35 0.73* 1330 cm1 band 0.40 0.45 0.45
WHC at 1.5 MPa 0.41 0.48 0.41 0.42 1270 cm1 band 0.40
pH 0.49 0.49 1270-to-1330 ratio 0.39 0.46
13
Electric 0.41 C NMR spectroscopy
conductivity Alkyl Cs 0.40 0.39 0.40
Exchangeable Na 0.47 0.58 0.41 O-alkyl Cs 0.37 0.39 0.40
Exchangeable K 0.50 0.38 Aromatic Cs 0.37 0.39 0.40
Cation exchange 0.65* 0.59* Elemental composition of the HA
capacity H 0.54* 0.44
Base saturation 0.47 N 0.42 0.46 0.45
Total Fe 0.70* 0.41 0.74* C-to-N atomic ratio 0.44 0.45 0.39
Total Mn 0.46 0.52* 0.52* 0.52* H-to-C atomic ratio 0.43 0.40
Soil organic 0.67* 0.43 0.50 0.50 1.00 Pyrolysis products
carbon Furan derivatives 0.50 0.50 0.40 0.43 0.60*
Total N 0.96* Guaiacyl (G)-type 0.40 0.38
Soil C-to-N ratio 0.39 0.45 0.43 0.85* compounds
Alo 0.50 0.51 0.42 0.72* G-to-S ratio 0.71*
Alp 0.53* Total 0.39
Alo þ1/2 Feo 0.53* 0.41 0.69* methoxyphenols
P retention 0.40 0.45 Alkylphenols 0.38 0.40
Soil organic matter fractions Alkylnaphthalenes
Lipid 0.44 0.51 0.37 0.51 0.55* Non methoxylated 0.39
HA 0.58 0.85* aromatics
FA 0.49 0.37 0.39 0.65* Benzothiazoles 0.69* 0.57*
o-EIH 0.64* Total N-compounds 0.48 0.37
c-EIH Alkanedienes 0.45 0.47
NEH 0.63* 0.49 0.47 0.42 0.92* Fatty acids 0.47
a Total aliphatic 0.52*
P < 0.01 indicated with an asterisk. Variable labels refer to Tables 2 and 4.
b
TMC ¼ Total mineralization coefficient (g C kg C soil1 day1). a
P < 0.01 indicated with an asterisk. Variable labels refer to Tables 2 and 4.
c
MC1 to MC3 ¼ Partial mineralization coefficients. Variables not displaying b
TMC ¼ Total mineralization coefficient (g C kg C soil1 day1).
c
significant (P < 0.05) correlation with soil respiratory indexes or SOC are not shown. MC1 to MC3 ¼ Partial mineralization coefficients. Variables not displaying
significant (P < 0.05) correlation with soil respiratory indexes or SOC are not shown.

(Table 7) was lower than with Alo content (P < 0.01, r2 ¼ 0.72), due
to periodic applications of phosphate fertilizer. In the case of easily
extractable Fe, there was negative correlation with TMC (P < 0.01, TMC (P < 0.05, r2 ¼ 0.40) (Fig. 2) as could correspond to the
r2 ¼ 0.70). intrinsic resistance to biodegradation expected for these recalci-
Negative correlations were found between TMC and the trant units. Conversely, there was positive correlation between TMC
percentage of HAs and NEH (P < 0.01, r2 ¼ 0.58 and r2 ¼ 0.63, and the concentration of O-alkyl and alkyl Cs (P < 0.05, r2 ¼ 0.4),
respectively), which was also the case with the amount of SOC expected from the comparatively biodegradable character of these
(P < 0.01, r2 ¼ 0.85 and r2 ¼ 0.92, respectively) (Table 7). structures.
To less significant levels, TMC was also negatively correlated The concentration of N in the HAs correlated negatively with the
with the optical density at 465 nm (E4) (Table 8) and with the TMC (P < 0.05, r2 ¼ 0.42) and positively with the yield of pyrolytic
intensity of the spectral valleys at 468 and 622 nm in the 2nd methoxyphenols indicating a possible lignoprotein origin (N-rich
derivative of the HAs (Fig. 2), attributed to DHPQ fungal pigments, HAs) in SOM from manure-amended plots with pumice covers.
suggesting that the higher the maturity or complexity of the SOM, Concerning other pyrolysis compounds, the yield of furan deriva-
the lower the SOC biodegradation. tives and the G-to-S ratio correlated positively with SOC (P < 0.01,
The TMC was also weakly correlated with the intensity of the IR r2 ¼ 0.60 and r2 ¼ 0.71, respectively), which indicated accumulation
aliphatic bands at 2920 and 1460 cm1 (Table 8), in general asso- of carbohydrate-derived compounds and high decomposition of
ciated to biodegradable plant and microbial components. On the lignin-derived compounds respectively, whereas there was nega-
other hand, the positive correlation between TMC and the intensity tive correlation between the total yield of aliphatic compounds and
of the IR band at 1720 cm1 (P < 0.05, r2 ¼ 0.52) (Fig. 2), which has SOC (P < 0.01, r2 ¼ 0.52). On the other hand, TMC showed weak
been associated to the presence of C]O stretching vibrations of positive correlation with the yield of alkanedienes, and negative
carboxyl groups (Almendros and Sanz, 1991), could be indicating an correlation with lignin-derived methoxyphenols and with the yield
increased of carboxylation in the SOM associated to C biodegrad- of carbohydrate-derived pyrolysis products (P < 0.05, r2 ¼ 0.49 and
ability in cultivated soils, as it has been described by other authors r2 ¼ 0.50, respectively).
(Tinoco et al., 2002; Hernández, 2009). Concerning CO2 release in the three successive stages: 0e3 days
As it was expected, the extent of the HA aromatic domain esti- (MC1), 4e9 (MC2) days and 10e30 days (MC3) (Fig. 1, Tables 7 and 8)
mated by 13C NMR (Ar region) was negatively correlated with the some positive correlations were found between CO2 evolved at
138 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142

Fig. 2. Significant linear regression plots between total mineralization coefficient (TMC, dependent variable) and several soil and humic acid characteristics in volcanic ash soils
subjected to agricultural practices. Sample labels refer to Tables 2e5. Inner and outer dotted lines indicated 95% confidence and prediction limits, respectively.

stage I (MC1) and the concentration of Mn in soil, the accumulation (mainly Al and Fe oxides and hydroxides), the lack of erosion in flat
of S-type structures (1330 cm1 band) and the pyrolytic yields of agricultural terraces and the similar time after clearing and culti-
N-compounds. The CO2 released in the last incubation stage, MC3 vation (ca. 5 centuries).
was negatively correlated with bulk density, concentration of Mn
and NEH, intensity of 1330 cm1 IR band, aromatic Cs in HAs and 4.2. Intrinsic and extrinsic factors influencing the amount of SOC
the yields of N- and S-compounds, i.e. with HA features suggesting
high SOC stabilization. Data in Table 7 confirm the significant role of the intense
organomineral interactions in C stabilization in volcanic ash soils
4. Discussion (Nanzyo et al., 1993; Torn et al., 1997; Baldock and Skjemstad, 2000;
Dahlgren et al., 2004). In fact, we found very significant negative
4.1. Soil carbon mineralization in laboratory and field conditions correlation between TMC and the occurrence of short-range
minerals suggesting physicochemical protective role on SOM. The
Recent papers have questioned that results from laboratory dominance of the mineralogical composition of the volcanic ash
incubation experiments could be representative of natural condi- soils contrast with the lack of correlation between soil C mineral-
tions. In such studies, it is considered that the SOC transformed into ization and some features a priori considered as primary drivers of
CO2 only accounts for a very small amount of the SOM and this soil C cycle, such as soil granulometric composition or Ca content
biodegradation would mainly occur at expenses of the organic (Baldock and Skjemstad, 2000).
coatings of soil aggregates, or simple water-soluble compounds As it has been described in the literature on Andosols, the
(Fang et al., 2005; Davidson and Janssens, 2006). Then, SOC accu- formation of Al-humus complexes is believed to protect soil humus
mulation would result from long-term natural processes not from microbial decomposition (Carballas et al., 1979; Kögel, 1986).
necessarily reflected in short laboratory incubations. In the present Our results point to at least two non-exclusive SOC stabilizing
study, the negative correlation between laboratory mineralization mechanisms. On the one hand, organomineral coatings could
rates and field SOC levels evidences that, in volcanic ash soils, the provide protection against microbial attack (i.e., encapsulation or
CO2 release under laboratory conditions could be of interest to physical entrapping in aggregates). On the other hand, the intense
establish soil resilience levels based on the susceptibility to sorption processes at the soil matrix level (HAs) in specific surfaces
mineralization of SOC forms. In this sense, the CO2 release repre- of short-range minerals could favor the protection of SOC fractions,
sented between 1.32  0.3 to 3.88  0.6 g CeCO2 kg C soil1 for as it has been described in other ecosystems (Jastrow et al., 2007).
a time of 30 days in andic and clayic soils, respectively. This fact Apart from this, the presumable effect of the water saturated
suggests that despite the low proportion of the total SOC which micropores over the organic matter biodegradation, also reflected
turns into CO2 in the 30-day experiment, the mineralization trends in the molecular characteristics of the HAs, such as the yield of
are kept in the long term (Fig. 1). This systematic behavior, despite carbohydrate-derived pyrolysis products and the content of soil N,
the contrasting agricultural management, could be attributed to the typical in hydromorphic soil environments (Huc et al., 1974;
stabilizing role of short-range minerals and amorphous oxides Almendros et al., 1996) could explain the fact that high WHC
 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142 139

(up to 200 g kg1 at the permanent wilting point) and SOC are
a
associated negatively with TMC, as if some physical conditions
were indicating selective preservation of non-decomposed organic
fractions. In this sense, the role of the fractal structure of allophane
nanoparticles in the protection of SOC should not be ruled out
(Woignier et al., 2007; Chevallier et al., 2010).
Concerning humus fractions, the soils with SOM of compara-
tively less condensed organic fractions (i.e., high concentration of
FA, which coincide with soils after periodic application of com-
posted organic amendments) were more susceptible to C losses
than soils with SOM of higher maturity. A series of HA molecular
characteristics both concerning the C backbone and the peripheral
functional groups, which are associated to maturity and structural
condensation, were also found related with the resistance against
biodegradation.
Concerning the poor correlation between TMC and total
aromaticity of HAs in these agricultural soils, it could be explained
by the dual origin of the C structures: either from non-decomposed
lignified aromatic residues (Schubert, 1965; Schnitzer and Khan,
1972; Stevenson, 1982; Hempfling and Schulten, 1989) or from
b
black carbon-like fractions in soil (Piccolo, 1996; Hernández and
Almendros, 2010).
As regards plant lignin transformation in soil, it is described that
G-type lignins are more resistant to biodegradation than S-type
ones (Martínez et al., 1990) then the positive correlation between
TMC and S-type lignin units (IR band at 1330 cm1) would indicate
active degradation of plant debris. In this sense, G-to-S ratio
correlated with SOC, is compatible with the fact that residual lignin
was subjected to microbial reworking leading to HA-like structures
after demethoxylation and subsequent condensation of the
aromatic rings. This is the line with studies showing that selective
preservation of lignin should prevail during the early stages of
organic matter transformation whereas, at more advanced stages,
lignin biodegradation involving alkyl side-chain breakdown occurs
at the same or even higher rate as the overall litter decomposition
(Marschner et al., 2008). c
On the other hand, the resistance to biodegradation traditionally
ascribed to recalcitrant CeC units was also evident in these soils. As
it was suggested by the 13C NMR spectra (Hernández and
Almendros, 2010), some of these aromatic units could correspond
to constituents of black carbon (the most recalcitrant pyrogenic C
form) produced during fires in the past, which was classically
described in Japanese volcanic ash soils where SOM aromaticity is
just associated to charred plants fragments (Shindo et al., 2004).
When the CO2 release values are compared for the three
successive stages, it was observed that TMC in the early stages
coincides with prevalence of alkyl groups and of partially decom-
posed plant biomacromolecules (lignin-type) which is in the line of
the above-indicated early mineralization of recently incorporated
SOM (Davidson and Janssens, 2006).
The fact that the accumulation of SOC is very significantly corre-
lated with the N incorporated in the HA structure is compatible with
the fact that most N in HA is not readily available to soil biota, and also
Fig. 3. Soil and humic acid characteristics with a role on (a) C accumulation and
indicates that soil N is sequestered along with soil C (Almendros,
(b) C release as CO2 classified by multidimensional scaling using the 1-Pearson
2008). The correlation between some N forms in HAs (1540 and correlation index as similarity criterion. (c) Classification of plots from different
1640 cm1 IR band) and the yield of methoxyphenols highlighted sampling units using Euclidean distance as similarity index.
a lignoprotein pattern as postulated by Stevenson (1982).

4.3. Application of multivariate models to analyze factors related

with the levels of SOC correlation existing between them. In order to discuss factors
related to SOM biodegradability, it is interesting to discuss about
The results after processing the matrix of 1-Pearson correlation the variables clustering close to points representing C release as
indices between variables by multidimensional scaling (Kruskal, CO2 (TMC), or to its preservation in the soil pool (SOC). It is
1964; Fig. 3a) are shown in Fig. 3 where the distance in the plane observed that SOC was associated with descriptors such as the
between points (representing variables) is proportional to the content of amorphous minerals, the concentration of lipid, HA and
140 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142

humin, the WHC at field capacity, the N in HA, the DHPQs and the severe risk of C mineralization (U7: V1eV3, U4: M1eM3), iii) plots
pyrolytic yield of carbohydrate derivatives (Fig. 3a). with young SOM weakly protected to microbial attack (U6: F1eF3,
Conversely, other soil descriptors such as the bulk density, pH, U5: H1eH3) and iv) plots with physicochemical protection associ-
base saturation, yield of total aliphatic pyrolytic compounds, alkyl ated to abundance of amorphous minerals (U1: G1eG3, U2: O1eO3).
and O-alkyl Cs, and the intensity of the 2920 and 1460 cm1 IR In general, soil C mineralization rates were explained by the
aliphatic bands positively correlated with the TMC (Fig. 3b). levels of highly biodegradable organic matter of aliphatic character,
Figure 3c shows the ordination of plots after multidimensional i.e., showing characteristics in common with plant residues and
scaling applied to the soil data matrix with intrinsic and extrinsic microbial biomass. On the other side, multidimensional scaling
factors and using Euclidean distances as similarity index. This suggests that the occurrence of microanaerobic conditions in
allows knowing what plots are more similar each to other (i.e., a reactive organomineral matrix of volcanic materials could also be
lower distance in the plane after the dimensional reduction) illus- an important factor for soil C preservation.
trating the extent to which different agricultural practices controls
the levels of SOC. Whereas high mineralization rates were found in
vitrandic plots (U6: F1eF3, U5: H1eH3) and non-andic plots (U3: 5. Conclusions
S1eS3), consisting of soils with low SOC levels (<2%), the opposite
situation, indicating the progressive accumulation of SOC (>2%) Simple laboratory incubation experiments allowed forecasting
was found in silandic and aluandic plots (U1: G1eG3, U2: O1eO3). large variability of the amount of SOC in the case of volcanic ash
The scores for transportic soils (U4: M1eM3) lies near to vitrandic agricultural plots, which results of great interest for modeling
soils, indicating high similarity (i.e., lower distance in the plane) environmental change scenarios.
with these plots. The resistance of the SOM against biodegradation could be
Finally, PCA (Fig. 4) showed that up to 70% variance could be explained by intrinsic and extrinsic factors. In our volcanic ash soils,
explained by two principal components (PC1 and PC2). The first extrinsic factors connected with the intense sorption processes in
principal component (PC1) was mainly explained by the molecular specific surfaces of short-range minerals could favor the selective
composition of SOM (intrinsic factors), which provides a gradient preservation of the C in soil, e.g., content of amorphous minerals
of SOM maturity from plant biomacromolecules (as lignin) to (Alo þ ½ Feo), Al-humus complexes (Alo), aggregate stability and WHC
condensed chemical compounds (as methoxyl-lacking phenols), at the permanent wilting point (at 1.5 MPa). On the other hand,
whereas the second principal component (PC2) was a linear func- intrinsic SOM molecular characteristics both of its C backbone and its
tion of variables indicating physicochemical protection of SOM peripheral functional groups, suggest maturity and structural
(extrinsic factors). The sample scores in the space defined by the condensation in soils with comparatively low TMC. This is the case
first two components are distributed in four clusters corresponding with variables negatively correlated with TMC, such as the HA
to: i) plots with recalcitrant organic matter but without physico- concentration, non-extractable humin (irreversibly associated to
chemical protection, associated to the effect of liming or periodic mineral fractions), E4, quinone fungal pigments (DHPQs) and yields of
biomass burning (U3: S1eS3), ii) plots with low SOM content and specific pyrolysis compounds (furans and N-compounds).

a) TMC b)
6
PC 2: Soil C mineralization (25 % explained variance)

C-to-N
V1
IR 1720 cm-1
4 S1
V2 S4 N-compounds
pH V3 S3 OCH3-lacking
S2
M1 aromatics
2
IR 2920 cm-1 M2 M3 H3 Aromatic Cs
H2 E4
0 F1 DHPQ
IR 1460 cm-1 M4
F2 H1

O-Alkyl Cs F3 O3 O1
O4 O2
-2
Alkyl Cs
CEC G2
H-to-C
-4 Methoxyphenols c) G3 G1 d)
Alo + ½ Feo
HA
-6 Allophane SOC
Al-humus
nEIH
Clay
No complexes (pumices)
-8
-10 -8 -6 -4 -2 0 2 4 6 8 10
PC 1: Maturity and aromaticity of soil organic matter ( 45% explained variance)
Fig. 4. Principal component analysis (biplot showing variable loadings as lines pointing to the direction of increasing value for the variables, and sample scores as symbols),
showing: a) plots with severe risk to soil organic matter mineralization, b) plots with easily biodegradable soil organic matter, c) plots with high levels of young soil organic matter
and d) plots with high amount of non-decomposed SOM. Labels of samples and variables refer to Tables 2e5.
 Z. Hernández, G. Almendros / Soil Biology & Biochemistry 44 (2012) 130e142 141

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