No abstract

Sorptive stabilization of organic matter by amorphous Al hydroxideSchneider, M.P.W.; Scheel, Th.; Mikutta, R.; van Hees, P.; Kaiser, K.; Kalbitz, K. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. ) with OM extracted from organic horizons under a Norway spruce and a European beech forest. The stabilization of OM by sorption was analyzed by comparing the CO 2 mineralized during the incubation of sorbed and non-sorbed OM. The mineralization of OM was evaluated based in terms of (i) the availability of the am-Al(OH) 3 , thus surface OM loadings, (ii) spectral properties of OM, and (iii) the presence of phosphate as a competitor for OM. This was done by varying the solid-to-solution ratio (SSR = 0.02-1.2 g L À1 ) during sorption. At low SSRs, hence limited am-Al(OH) 3 availability, only small portions of dissolved OM were sorbed; for OM from Oa horizons, the mineralization of the sorbed fraction exceeded that of the original dissolved OM. The likely reason is competition with phosphate for sorption sites favouring the formation of weak mineral-organic bindings and the surface accumulation of N-rich, less aromatic and less complex OM. This small fraction controlled the mineralization of sorbed OM even at higher SSRs. At higher SSRs, i.e., with am-Al(OH) 3 more available, competition of phosphate decreased and aromatic compounds were sorbed selectively, which resulted in pronounced resistance of sorbed OM against decay. The combined OC mineralization of sorbed and non-sorbed OM was 12-65% less than that of the original DOM. Sorbed OM contributed only little to the overall OC mineralization. Stabilization of OC increased in direct proportion to am-Al(OH) 3 availability, despite constant aromatic C ($30%). The strong stabilization at higher mineral availability is primarily governed by strong Al-OM bonds formed under less competitive conditions. Due to these strong bonds and the resulting strong stabilization, the surface loading, a proxy for the mineral's occupation by OM, was not a factor in the mineralization of sorbed OM over a wide range of C sorption (0.2-1.1 mg C m À2). This study demonstrates that sorption to am-Al(OH) 3 results in stabilization of OM. The mineral availability as well as the inorganic solution chemistry control sorptive interactions, thereby th...

No abstract

Carbon mineralization in acidic forest soils can be retarded by large concentrations of aluminium (Al). However, it is still unclear whether Al reduces C mineralization by direct toxicity to microorganisms or by decreased bioavailability of organic matter (OM) because dissolved organic matter (DOM) is precipitated by Al. We conducted an incubation experiment (6 weeks) with two DOM solutions (40 mg C litre À1 ) derived from two acidic forests and possessing large differences in composition. Aluminium was added to the solutions in realistic ranges for acidic soils (1.6-24 mg Al litre À1 ) at pHs of 3.8 and 4.5, to achieve differences in Al speciation. We determined different Al species, including the potentially toxic Al 3þ , by Diffusive Gradients in Thin Films (DGT) to evaluate toxic effects on microorganisms. Precipitation of OM increased with larger amounts of added Al and higher pH, and we measured a larger fraction of dissolved 'free' Al at pH 3.8 than at pH 4.5. Organic matter degradation decreased significantly with Al addition, and we found more organic matter degraded at pH 3.8 than at pH 4.5 for the respective Al additions. Consequently, the observed reduction in OM degradation (i.e. stabilization) cannot be explained by toxic effects of 'free' Al. However, C stabilization correlated significantly with C precipitation. The pH did not influence C stabilization directly, but determined the amount of C being precipitated. Phosphorus was removed along with OM by precipitation, which possibly also affected C stabilization. We conclude that C stabilization upon Al addition did not result from toxic effects, but was caused by reduced bioavailability of OM after its precipitation. The reduction in OM degradation by 65% is of great relevance for the overall C stabilization in acidic forest soils. Increasing pH and decreasing Al concentrations upon recovery from acidic deposition should therefore not result in decreased stabilization of precipitated OM.

Dissolved organic matter (DOM) is often neglected as a factor in the formation of stable soil organic matter (OM). Precipitation of DOM by dissolved Al could contribute substantially to C retention in acidic forest soils; however, no information is available on the stability of precipitated OM against microbial decay. We investigated the stability of Al–OM precipitates against microbial decay as related to (i) DOM composition, (ii) Al speciation, and (iii) the dissolved Al/C ratio. We produced Al–OM precipitates by adding AlCl3 (molar Al/C ratios: 0.05–0.3) at pH values of 3.8 and 4.5 to DOM solutions derived from Oi and Oa horizons, from either beech (Fagus sylvatica L) or spruce [Picea abies (L.) Karst.] litter. Between 13 and 84% of the C was precipitated, depending on pH, Al/C ratio, and the type of DOM. Precipitates were found to be enriched in aromatic C and mostly depleted in N when compared with DOM. Only 0.5 to 7.7% of precipitated C was mineralized during 7 wk of incubation. Mineralization of Al–OM precipitates was up to 28 times less than that of the respective DOM solutions. The extent of mineralization of Al–OM precipitates formed at pH 3.8 was reduced by 50 to 75% when compared with those formed at pH 4.5. The stability of precipitates against microbial decay increased with larger aromatic C content and larger C/N ratios. Our study clearly demonstrated that a large fraction of DOM can be precipitated and is thereby substantially stabilized against microbial decay.

The precipitation of dissolved organic matter (DOM) by aluminum (Al) results in a stable soil organic matter (OM) fraction. Extracellular enzymes can also be removed from soil solution by sorption or precipitation, but whether this affects their activity and their importance for carbon (C) mineralization is largely unknown. We studied the activity of eight extracellular enzymes, precipitated by Al together with DOM, in relation to C mineralization of the precipitated OM. Dissolved OM was obtained from the Oi and Oa horizon of two forest soils and precipitated at different Al : C ratios and pH values to achieve a large variation in composition and C mineralization of precipitated OM. All eight enzymes were present in a functional state in precipitated OM. On average 53% of DOM was precipitated, containing on average 17%–41% of the enzyme activity (EA) involved in C degradation (chitinase, cellobiohydrolase, β‐glucosidase, glucuronidase, lacasse, and xylosidase) previously present in soil solution. In contrast, on average only 4%–7% of leucine‐aminopeptidase and acid‐phosphatase activity was found in precipitated OM. The EA found in precipitates significantly increased the percentage of C mineralized of precipitated OM, with a stronger influence of C‐degrading enzymes than enzymes involved in N and P cycling. However, after 8 weeks of incubation the correlations between EA and C mineralization disappeared, despite substantial EA being still present and only 0.5%–7.7% of C mineralized. Thus, degradation of precipitated OM seems to be governed by EA during the first degradation phase, but the long‐term stability of precipitated OM is probably related to its chemical properties.