UNIVERSIDAD DE CHILE MAGISTER EN MANEJO DE SUELOS Y AGUAS SEMINARIO DE MEMORIA

Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3-4100 kyr), Hawaiian Islands
Mikuta, R., Schaumann, G.E., Gildemeister, D., Bonneville, S., Kramer, M., Chorover, J., Chadwick, O.A. and G. Guggenberger

Ignacio Fuentes San Romn

Introduccin
El carbono orgnico ligado a minerales es considerado como relativamente estable y controla a largo plazo el secuestro de MO.

Estructuras aromticas son las ms resistentes a la biodegradacin. Cronosecuencia - Deriva mineralgica CO almacenado. MO es sorbida selectivamente a minerales por fraccionamiento de tamao molecular y qumico.

 Experimentos de Calorimetra de escaneado diferencial (DSC) dan cuenta de una disminucin en la movilidad segmental de la MO con el tiempo. Cambios mineralgicos afectan interaccin mineralorgnica por: Desarrollo de superficies reactivas; cambios en la MO sorbida; fraccionamiento sortibo de la MO. Investigacin de la naturaleza de las asociaciones minerales-orgnicas durante la meteorizacin progresiva de basalto (0.3-4100 kyr/PliocenoHoloceno) en el archipilago hawaiano.

Objetivo
Examinar la formacin cronodependiente y las caractersticas de las asociaciones mineralesorgnicas y las consecuencias de las propiedades fsicas y qumicas de MOM.

Hiptesis
Las transformaciones cronodependientes de los silicatos primarios que dominan en la lava basltica juvenil en minerales secundarios mas maduros es acompaada por cambios distintivos en las propiedades quimico-fsicas de la MOM.

Materiales y mtodos

1: Thaptic Udivitrand 2-4:Aquic Hydrudand 5: Aquic Hapludand 6: Plinthic Kandiudox MOAs se aislaron densiometricamente y se examinaron segn: Cambios en composicin mineral, rea superficial y porosidad mediante extraccin selectiva, espectroscopia fotoelectrnica de rayos X (XPS) adsorcin gaseosa y microscopa de transmisin electrnica (TEM) acoplada con espectroscopa de energa dispersiva. Transformaciones qumicas de la MO en MOAs mediante XPS y anlisis de biomarcadores moleculares (fenoles de lignina, carbohidratos no celulsicos). Alteracin del estado fsico de la MO en MOAs por el tiempo se investig mediante calorimetra de escaneo diferencial (DSC).

Tabla 1 Edad del suelo, origen, profundidad de muestreo y pH, adems de algunas propiedades bsicas de las asociaciones mineral-orgnicas (MOAs) de horizontes A y B en cronosecuencia.
Site age kyr
A horizons Thurston Laupahoehoe Kohala Pololu Kolekole Kokee B horizons Thurston Laupahoehoe Kohala Pololu Kolekole

Resultados y discusin
MOC MNa mg/g 2.3 9.9 13.2 19.4 9.7 2.8 2.5 5.6 4.4 3.6 8 18 14 15 13 14 9 20 27 23 C/N
b NaOH

Island

Absolut Soil density pH Depth (MOA) MOCa (H2O) cm g/cm3 mg/g

29 010 07 010

XA D-8c Fedithd % mg/g 5 153.6 46.9 43.7 40.1 241.3 11.5 100.8 15.4 124.1

Feoxd mg/g 4.3 84.2 37.4 40 15.4 4.4 10.7 77.9 16.9 56.6

Feox/ Fedith Aloxd mg/g 0.9 0.5 0.8 0.9 0.4 0 0.9 0.8 1.1 0.5 2.6 3.3 18.5 7.6 4.2 0.4 8.1 113.5 137.8 50.5

AlCue mg/g 1.5 0.9 11.1 6.1 1.9 0.2 1.5 7.6 15.9 9.2

Sioxd mg/g

Clay mineral compositionf

% 70 47 63 66 60 74 46 86 92 88

0.3 Hawaii 20 Hawaii 150 Hawaii 400 Hawaii

5.5 4.1 3.9 3.9 4.2 4.8 6.1 5.3 4 4.9

2.9 2.4 2.1 1.8 2.3 3.2 2.8 2.3 2.1 2.5

18.7 177.5 187.6 290.4 131.1 40.0 23.2 113.6 120.6 81.3

56 66 68 81 65 49 51 46 37 46

0.8 P, F, a 0.3 F, A, m, q 0.8 A, F, v, hiv, q 0.1 A, F, v, hiv, k, q 0.1 K, Gi, F, he, q 0.0 K, Gi, Go, he 4.1 P, F, a 29.5 F, A, m, q 44.7 A, F, hiv, q 4.9 A, F, v, hiv, k, q K, Gi, F, he, q, 2.0 m

1400 Molokai 08 4100 Kauai 016 0.3 20 150 400

1523 4567 4160 4464

1400 4.9 2.6 19.9 2.0 10 100 29 53.3 14.4 0.3 14 2.4 3049 4100 5.2 3.1 12.1 1.6 7 75 21 143.9 2.3 0 2.1 0.4 0.1 K, Gi, Go, he, m Kokee 50100 a MOC and MN = mineral-associated organic C and N. b Fraction of the mineral-associated OC extractable in 0.1M NaOH. c Fraction of the NaOH-extractable OC that adsorbs to XAD-8 resin after acidification to pH 2. d Fedith = dithionite-extractable Fe; Feox, Alox, Siox = oxalate-extractable Fe, Al, Si. e AlCu = CuCl2-extractable Al. f Data compiled from Chorover et al. (2004): upper case letters indicate major constituents, lower case letters indicate minor constituents; P, plagioclase; A, short-rangeordered Al gels or aluminosilicates (e.g., allophane); F, ferrihydrite; Q, quartz; V, vermiculite; HIV, hydroxyl-interlayered vermiculite; K, kaolin minerals (kaolinite and/or halloysite); Gi, gibbsite; He, hematite; Go, goethite; M, magnetite.

 MOC y MN estrechamente relacionados a la deriva mineralgica. Media de 74 % OC y 88% Nt en MOAs. MOC-MN (r2 = 0.92). % MOC en B-MOAs liberado >A-MOAs. OC en A-MOAs s. aromticas/ B-MOAs menos hifrofbicos.

rea de superficie especfica y mesoporosidad

Specific surface area (SSA), CBET constant, net enthalpy of N2 adsorption (DHxs), pore volume data, surface enrichment of C and N, and the volumetric ratio of OM and minerals in mineralorganic associations from A and B horizons of the long substrate age gradient. Site Surface Volumetri VOM/ ,a b c d age SSA CBET DHx SSAcorr MIV MEV TPV enrichement c ratio Vmineral 210 1050 <200 rOM = 1.4 rOM = 1.7 N2 CO2 nm nm nm C N g/cm3 g/cm3 KJ/ (mm3/ (kyr) (m2/g) mol (m2/g) (mm3/g) g) A horizons Thurston 0.3 2.3 151 3.3 2.4 1 2.5 1 4.9 14.8 16.8 8.4 0.08 0.07 Laupahoehoe 20 54.4 141 3.2 84.4 23.5 25.3 32.5 44.7 146.9 1.6 1.3 1.54 0.99 Kohala 150 28.8 123 3.1 46 13 22 13.8 63.2 140.7 1.4 1.4 1.27 0.85 Pololu 400 19 72 2.7 45.3 7.5 21.4 20.4 63.7 150.9 1.3 1.2 2.87 1.57 Kolekole 1400 20.2 86 2.9 27.4 8.5 11 10.3 52.8 115.6 1.7 1.6 0.76 0.55 Kokee 4100 47.6 195 3.4 51.8 9.5 10.9 21.4 20 64.5 5.2 3.9 0.23 0.18 B horizons Thurston 0.3 9.3 206 3.4 9.8 4 6.8 4.3 8.8 19.7 9 5.5 0.1 0.08 Laupahoehoe 20 62.9 153 3.2 81.4 27 52.7 30 99.1 255 1.9 1.6 0.58 0.43 Kohala 150 55 153 3.2 72.4 23 55.5 36 98.8 194.7 1.7 1.8 0.56 0.42 Pololu 400 65.2 183 3.3 77.9 28 29.5 28.5 80 221.6 2.3 2.3 0.4 0.31 Kolekole 1400 64.8 179 3.3 67.4 7.5 15.3 33.5 84.4 219.8 5.7 2.3 0.08 0.06 Kokee 4100 70.9 145 3.2 72.7 3.5 7.9 39.4 141.7 265.6 7.2 1.3 0.06 0.05
a SSA

corrected for OM content (see Section 2.5). b Micropore volume (<2 nm). c Mesopore volume. d Total pore volume. e Surface enrichment = C or N (XPS)/C or N (elemental analysis). f Assumptions: mOM = 2 mOC, rOM = 1.4 or 1.7 g/cm3, VOM=mOM/rOM, Vmineral = VMOA VOM, where VMOA = 1000 g/rMOA, rMOA data

Fig. 3. Plot of the volumetric ratio of sorbed OM (VOM) versus mineral matter (Vmineral) in mineralorganic associations from A (A-MOA) and B horizons (B-MOA) of the long substrate age gradient.

F Representative transmission electron micrographs and X-ray electron dispersive spectra of mineralorganic associations from A horizons of the long substrate age gradient. Primary mineral particles at the 0.3-kyr site are partly covered with phases of poor crystallinity (A) while such poorly crystalline phases dominate the 20kyr (B), 150-kyr (C) and 400-kyr site (D). Note, the presence of film-like structures at the 400-kyr site (black arrow). At the 1400-kyr (E) and 4100-kyr (F) site, aggregates are composed to a much larger extent by secondary crystalline aluminosilicates and Fe (hydr)oxides, the latter particularly covering larger mineral particles at the 4100-kyr site.

Fig. 5. Examples of high-resolution XPS C1s spectra of mineralorganic associations from A horizons of the 0.3-kyr, 150-kyr, and 4100-kyr site of the long substrate age gradient. Numbers of deconvoluted sub-peaks refer to (1) unsubstituted aromatic carbon (ArA-C-C/Ar-C-H), (2) aliphatic carbon (C-C/C-H), (3) a-carbon (CC(O)O), (4) ether or alcohol carbon (C-O), (5) ketonic or aldehyde carbon (C=O), (6) amide carbon (C(O)N), (7) carboxylic carbon (C(O)O), and (8) p-p*-shake-up satellite from the aromatic structure.

Fig. 6. (AC) Regression plots of XPS-based carbon types with oxalate-extractable Fe, Al, and Si concentrations in mineralorganic associations from A (A-MOA) and B horizons (B-MOA). Note that the oxalate-extractable metal concentrations refer to bulk MOA samples whereas XPS data reveal the average composition of OM at particle surfaces.

Fig. 7. Change of the inorganic surface composition (Al, Si, Ti and Fe) and of C and N concentrations in mineralorganic associations from A horizons upon Ar+ sputtering. The data for C and N represent the percentage loss of C and N concentrations after 30 min of etching.

Fig. 10. (AF) Time-dependent change of lignin-derived phenol concentrations (K8) in organic layers and mineralorganic associations from A (A-MOA) and B horizons (B-MOA) (A); acid-to-aldehyde ratio of vanillyl (B) and syringyl units (C). The grey bands in B and C connote the acid-to-aldehyde ratios in collected plant source materials. Non-cellulosic carbohydrate concentrations (D); the GM/AX ratio (E) and RF/AX ratio (F). The GM/AX ratio refers to the mass quotient of (galactose + mannose)/(arabinose + xylose) and that of the RF/AX ratio to (rhamnose + fucose)/(arabinose + xylose).

Fig. 11. (AD) Time-dependent change of phenol concentrations (A = A horizon; B = B horizon) and non-cellulosic carbohydrate concentrations (C = A horizon; D = B horizon) normalized to mineral-associated OC (MOC). Abbreviations: K8, lignin phenols; BA, benzoic acid; 2H BA, 2-hydroxybenzoic acid; 3H BA, 3-hydroxybenzoic acid; 4H BA, 4-hydroxybenzoic acid; 3,5 diH BA, 3,5-dihydroxybenzoic acid; Xyl, xylose; Ara, arabinose; Rib, ribose; Rha, rhamnose; Fuc, fucose; Man, mannose; Gal, galactose; Glu, glucose; GluA, glucuronic acid; GalA, galacturonic acid.

Fig. 12. (AC) Plot of the syringyl-to-vanillyl ratio versus the cinnamyl-to-vanillyl ratio of source vegetation leaves, organic layers, and mineralorganic associations (A), MOC-normalized concentration of lignin phenols (K8) versus the ratio of benzenecarboxylic acids (BA) to lignin phenols (B), and the time-dependent change of the lignin-to-carbohydrate ratio in organic layers and mineralorganic associations (C).

Fig. 14. Time-dependent change of the DSC step transition temperature (T*) of organic matter in mineralorganic associations from A (AMOA) and B horizons (B-MOA). Marked samples did not show transitions in every replicate (*) or showed a weak, but reversing transition only (**).

Conclusiones
Transformaciones minerales a travs de la cronosecuencia causan un almacenamiento diferencial de la MO en MOAs. En horizontes superficiales ricos en MO, la pp en adicion a las reacciones de adsorcion estan involucradas en la formacion de MOAs. No existe completo recubriminto de las superficies minerales

Conclusiones
Evidencia del secuestro de C por suelos bien manejados. Estrategias clave son incrementar el tiempo del suelo vegetado, reducir o eliminar la labranza, estimular la produccin primaria e incrementar su retorno al suelo, aumentar el uso de vegetacin perene. Mayor capacidad de buscar incrementar el secuestro de C por pases industrializados y temperados y mayor informacin al respecto.