ALBERT

Description: Branched Glycerol Dialkyl Glycerol Tetraethers (GDGTs) are membrane spanning lipids synthesised by as yet unknown bacteria that thrive in soils and peat. In order to obtain more information on their ecological niche, the stable carbon isotopic composition of branched GDGT-derived alkanes, obtained upon ether bond cleavage, has been determined in various soils, i.e. peat, forest, grassland and cropland, covered by various vegetation types, i.e., C3- vs. C4-plant type. These δ13C values are compared with those of bulk organic matter and higher plant derived n-alkanes from the same soils. With average δ13C values of −28‰, branched GDGTs in C3 soils are only slightly depleted (ca. 1‰) relative to bulk organic carbon and on average 8.5‰ enriched relative to plant wax-derived long-chain n-alkanes (nC29–nC33). In an Australian soil covered with C4 type vegetation, the branched GDGTs have a δ13C value of −18‰, clearly higher than observed in soils with C3 type vegetation. As with C3 vegetated soils, branched GDGT δ13C values are slightly depleted (1‰) relative to bulk organic carbon and enriched (ca. 5‰) relative to n-alkanes in this soil. The δ13C values of branched GDGT lipids being similar to bulk organic carbon and their co-variation with those of bulk organic carbon and plant waxes, suggest a heterotrophic life style and assimilation of relatively heavy and likely labile substrates for the as yet unknown soil bacteria that synthesise the branched GDGT lipids. However, a chemoautotrophic lifestyle, i.e. consuming respired CO2, could not be fully excluded based on these data alone. Based on a natural labelling experiment of a C3/C4 crop change introduced on one of the soils 23 years before sampling and based on a free air CO2 enrichment experiment with labelled CO2 on another soil, a turnover time of ca. 17 years has been estimated for branched GDGTs in these arable soils.

Description: To maximize crop productivity fertilizer P is generally applied to arable soils, a significant proportion of which becomes stabilized by mineral components and in part subsequently becomes unavailable to plants. However, little is known about the relative contributions of the different organic and inorganic P bound to Fe/Al oxides in the smaller soil particles. The alkaline (NaOH-Na2EDTA) extraction with solution 31P-nuclear magnetic resonance (31P-NMR) spectroscopy is considered as a reliable method for extracting and quantifying organic P and (some) inorganic P. However, any so-called residual P after the alkaline extraction has remained unidentified. Therefore, in the present study, the amorphous (a) and crystalline (c) Fe/Al oxide minerals and related P in soil aggregate-sized fractions (〉 20, 2–20, 0.45–2 and 〈 0.45 μm) were specifically extracted by oxalate (a-Fe/Al oxides) and dithionite (DCB, both a- and c-Fe/Al oxides). These soil aggregate-sized fractions with and without the oxalate and DCB pre-treatments were then sequentially extracted by alkaline extraction prior to solution 31P-NMR spectroscopy. This was done to quantify the various chemical P forms which were associated with a- and c-Fe/Al oxides both in alkaline extraction and in the residual P of different soil aggregate-sized fractions. The results showed that overall P contents increased with decreasing size of the soil aggregate-sized fractions. However, the relative distribution and speciation of varying P forms were found to be independent of soil aggregate-size. The majority of alkaline extractable P was in the a-Fe/Al oxide fraction (42–47 % of total P), most of which was orthophosphate (36–41 % of total P). Furthermore, still significant amounts of particularly monoester P were bound to the oxides. Intriguingly, however, Fe/Al oxides were not the main bonding sites for pyrophosphate. Residual P contained similar amounts of total P associated with both a- (10–13 % of total P) and c-Fe oxides (10–12 % of total P) in various aggregate-sized fractions, suggesting that it was likely occluded within the a- and c-Fe oxides in soil. This implies that with the dissolution of Fe oxides, these P may be released and thus available for plants and microbial communities.

Description: To maximize crop productivity fertilizer P is generally applied to arable soils, a significant proportion of which becomes stabilized by mineral components and in part subsequently becomes unavailable to plants. However, little is known about the relative contributions of the different organic and inorganic P bound to Fe/Al oxides in the smaller soil particles. Alkaline (NaOH–Na2EDTA) extraction with solution 31P-nuclear magnetic resonance (31P-NMR) spectroscopy is considered a reliable method for extracting and quantifying organic P and (some) inorganic P. However, any so-called residual P after the alkaline extraction has remained unidentified. Therefore, in the present study, the amorphous (a) and crystalline (c) Fe/Al oxide minerals and related P in soil aggregate-sized fractions (〉 20, 2–20, 0.45–2 and 〈 0.45 μm) were specifically extracted by oxalate (a-Fe/Al oxides) and dithionite–citrate–bicarbonate (DCB, both a- and c-Fe/Al oxides). These soil aggregate-sized fractions with and without the oxalate and DCB pre-treatments were then sequentially extracted by alkaline extraction prior to solution 31P-NMR spectroscopy. This was done to quantify the P associated with a- and c-Fe/Al oxides in both alkaline extraction and the residual P of different soil aggregate-sized fractions. The results showed that overall P contents increased with decreasing size of the soil aggregate-sized fractions. However, the relative distribution and speciation of varying P forms were found to be independent of soil aggregate-size. The majority of alkaline-extractable P was in the a-Fe/Al oxide fraction (42–47 % of total P), most of which was ortho-phosphate (36–41 % of total P). Furthermore, still significant amounts of particularly monoester P were bound to these oxides. Intriguingly, however, Fe/Al oxides were not the main bonding sites for pyrophosphate. Residual P contained similar amounts of total P associated with both a- (11–15 % of total P) and c-Fe oxides (7–13 % of total P) in various aggregate-sized fractions, suggesting that it was likely occluded within the a- and c-Fe oxides in soil. This implies that, with the dissolution of Fe oxides, this P may be released and thus available for plants and microbial communities.

Description: Branched Glycerol Dialkyl Glycerol Tetraethers (GDGTs) are membrane spanning lipids synthesised by as yet unknown bacteria that thrive in soils and peat. In order to obtain more information on their ecological niche, the stable carbon isotopic composition of branched GDGT-derived alkanes, obtained upon ether bond cleavage, has been determined in a peat and various soils, i.e. forest, grassland and cropland, covered by various vegetation types, i.e., C3- vs. C4-plant type. These δ13C values are compared with those of bulk organic matter and higher plant derived n-alkanes from the same soils. With average δ13C values of −28‰, branched GDGTs in C3 soils are only slightly depleted (ca. 1‰) relative to bulk organic carbon and on average 8.5‰ enriched relative to plant wax-derived long-chain n-alkanes ( nC29–nC33). In an Australian soil dominantly covered with C4 type vegetation, the branched GDGTs have a δ13C value of −18‰, clearly higher than observed in soils with C3 type vegetation. As with C3 vegetated soils, branched GDGT δ13C values are slightly depleted (1‰) relative to bulk organic carbon and enriched (ca. 5‰) relative to n-alkanes in this soil. The δ13C values of branched GDGT lipids being similar to bulk organic carbon and their co-variation with those of bulk organic carbon and plant waxes, suggest a heterotrophic life style and assimilation of relatively heavy and likely labile substrates for the as yet unknown soil bacteria that synthesise the branched GDGT lipids. However, a chemoautotrophic lifestyle, i.e. consuming respired CO2, could not be fully excluded based on these data alone. Based on a natural labelling experiment of a C3/C4 crop change introduced on one of the soils 23 years before sampling and based on a free-air CO2 enrichment experiment with labelled CO2 on another soil, a turnover time of ca. 18 years has been estimated for branched GDGTs in these arable soils.