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1.
The nature and origins of diester phosphates in soils: a 31P-NMR study   总被引:2,自引:0,他引:2  
Makarov  M.  Haumaier  L.  Zech  W. 《Biology and Fertility of Soils》2002,35(2):136-146
Soils of two climosequences in Russia were investigated by 31P-NMR spectroscopy. They comprised Dystric Podzoluvisols, Haplic Greyzems, Calcic Chernozems, and Gypsic Kastanozems, which are located along temperature and precipitation gradients of the Russian Plain. Another sequence of soils included forest Humic Cambisols and Umbric Leptosols of subalpine and alpine meadows, which are formed in different climatic conditions along a climosequence of the Mt. Malaya Khatipara (northern Caucasus). The results showed that accumulation of DNA was high in the cold, wet, and acid soils (Dystric Podzoluvisol, alpine Umbric Leptosol), while phospholipids and teichoic acids mainly accumulated in the more microbially active soils. We performed a laboratory incubation experiment to test the relationship between microbial biomass P and P species identified in soil extracts. The proportions of P compounds resonating at 0.5-3.0 ppm in the NaHCO3 and H2SO4 extracts from the incubated Humic Cambisol increased. The amounts of phosphate diesters resonating at 0 ppm in the same extracts and in the subsequent NaOH extracts decreased after incubation. Based on the results of 31P-NMR spectroscopy of native soils and of the laboratory incubation experiment we concluded that signals at 0 ppm in spectra of soil alkaline extracts belong to DNA P which is mainly stabilised in soil organic matter outside microbial cells (at least in soils with relatively low microbial activity). Phospholipids-teichoic acids P extracted with 0.5 M NaHCO3 seems to be derived from soil microbial biomass, and its proportion can reflect the microbial activity in the soil.  相似文献   
2.
The relationship between organic P status of 4 soils, 20 microorganisms isolated from these soils (2 bacteria and 3 fungi for each soil) and 13 dominant plant species of typical natural ecosystems of these soils was evaluated. The soils used were represented by two pairs with different ratios of monoester and diester P, and of DNA and other diester P. A Dystric Podzoluvisol and an alpine Umbric Leptosol were characterized by a relatively high proportion of diester P including much DNA P, while a Calcic Chernozem and subalpine Umbric Leptosol had lower proportion of diesters containing relatively less DNA P. The proportions of P compounds in bacteria and plants were very similar on average, based on the monoester to diester P ratio and on the proportions of different diesters in alkaline extract, whereas fungi contained considerably higher proportions of monoesters and polyphosphates, and a higher proportion of phospholipids in the diester fraction. The results showed that the Porg composition of NaOH extracts from different soils was more similar to the composition of extracts from different groups of microorganisms. There was no clear correspondence between soil and microbial diester P proportion and composition. A high proportion of polyphosphate P including pyrophosphate P in soil extracts indicates a significant contribution of fungal P compounds in the soil while the monoester to diester P ratio, and DNA to non-DNA P ratio should be used with caution to interpret the origins of soil Porg. The relative contributions of microorganisms and plants to monoester and diester P in soils is only partially understood.  相似文献   
3.
The chemical composition of waste-material-derived dissolved organic matter (DOM) was characterized by chemolytic analyses and 1H, 13C and 31P nuclear magnetic resonance (NMR) spectroscopy. Dissolved organic matter was extracted by water from an aerobic fermented urban waste compost, a sewage sludge and a pig slurry and then fractionated using the XAD-8 method. The amount of water-extractable dissolved organic carbon (DOC) ranged from 3% in the sewage sludge to 22% in the pig slurry. Dissolved organic matter isolated from pig slurry was equally distributed between hydrophilic and hydrophobic DOC, whereas in the sewage-sludge-derived material the hydrophobic fraction was predominant. Dissolved organic C from the urban waste compost was mainly within the hydrophilic fraction. Wet-chemical analysis and 1H- and 13C-NMR spectra showed that both DOM fractions from the urban waste compost were low in neutral, acidic and amino sugars as well as in lignin-derived compounds. In turn, the materials were rich in low-molecular-weight aliphatic compounds. The chemical structure of both fractions is probably the result of the intensive transformation of urban waste compost during its fermentation. The hydrophilic fractions of DOM from sewage sludge and pig slurry contained considerable amounts of carbohydrates but were also rich in low-molecular-weight aliphatics. The respective hydrophobic fractions had the largest contents of CuO-extractable phenols which may in part derive from sources other than lignin. By contrast with the other materials, the hydrophobic fraction from the pig slurry seemed to contain polymeric rather than low-molecular-weight material. The 31P-NMR spectrum of the hydrophilic DOM fraction from urban waste compost did not show signals of inorganic or organic P compounds while the spectrum of the hydrophobic fraction revealed traces of monoester P, diester P, and orthophosphate. 31P-NMR spectroscopy suggested that both the hydrophobic and hydrophilic fractions from pig slurry did not contain organic P. The hydrophilic DOM fraction from sewage sludge contained orthophosphate, organic monoester P and a little pyrophosphate. The hydrophobic fraction contained mainly organic diester P and smaller amounts of teichoic acids and organic monoester P. Considering that water-soluble fractions of urban waste compost contained no easily plant-available P and a low content of labile organics, we conclude that this material contains less labile nutrients and is more refractory than the soluble constituents of pig slurry and sewage sludge.  相似文献   
4.
Black Mollisols are typically rich in charred organic matter, however, little is known about the zonal distribution of black C (BC) in steppe soils. In this study, we used benzene polycarboxylic acids (BPCA) as specific markers for BC in particle‐size fractions of depth profiles in several zonal soils (Greyzem, Phaeozem, Chernozem, Kastanozem) of the Russian steppe. In addition, liquid‐state 13C‐NMR spectra were obtained on the alkaline‐soluble soil organic matter (SOM). The results showed that both the content and depth distribution of BC varies in the different soil types; the concentration of BC in the bulk top soils being closely related to the aromaticity of the SOM (r2 = 0.98 for the native topsoils, 0.83 for top‐ and subsurface soils). Especially the Chernozems were rich in aromatic SOM, which partly contained more than 17% BC of total C, most of which being allocated in the mineral fractions. Long‐term arable cropping did not reduce the BC contents of the surface soil, though it did promote the enrichment of BC in the silt fractions. The same shift was detected as soil depth increased. We conclude that BC is not fully inert in these soils, but apparently can be preserved in the silt as decomposition of SOM increased, i.e., it accumulates exactly in that fraction, which has been formerly assigned to contain old, aromatic C.  相似文献   
5.
The solubility and forms of phosphorus (P) were investigated in manures from chicken and pigs, eight whole soil samples and clay-, silt-, and sand-size separates from an arable and a grassland soil. Total P (Pt) in liquid pig manure (16.2 g kg–1) and dry chicken manure (26.2 g kg–1) was distributed between residual P (39–41% Pt), H2SO4–P (17–27% Pt), labile resin- and NaHCO3–P (24–39% Pt), and NaOH-P (3–10% Pt). Most soils had larger proportions of NaOH-P and residual P, indicating reactions of manure-derived P compounds with pedogenic oxides and humic substances. Clay-size separates had the highest P-concentrations in all fractions and were particularly enriched in exchangeable and labile P forms. Solution 31P-nuclear magnetic resonance (NMR) spectra of 0.5 M NaOH extracts from manures and some soil samples showed greater signal intensities for orthophosphate and monoester P than 0.1 M NaOH extracts. This can be explained by alkaline hydrolysis phosphate diesters at higher NaOH concentrations and/or by preferential extraction of diesters at lower concentrations. The 31P-NMR spectra showed differences between the two manures and confirmed that increasing proportions of ester-P can be expected if they are spread to soils. The NaOH extracts of soil samples were characterized by large proportions of orthophosphate-P (mean 77% of assigned P compounds), which seemed to be slightly enriched in clay fractions whereas the extracts from silt contained more ester-P. Sequential extractions and 31P-NMR spectroscopy both showed that these excessively manured soils are likely to lose large amounts of P. Received: 15 July 1996  相似文献   
6.
It is generally accepted that particulate organic matter derives from plants. In contrast, the enriched labile fraction is thought by many to derive from microbes, especially fungi. However, no detailed chemical characterization of these fractions has been done. In this study, we wanted to assess the sources (plants or microbes; fungi or bacteria) and degree of microbial alteration of (i) three particulate organic matter fractions – namely the free light fraction (1.85 g cm?3), the coarse (250–2000 μm) and the fine (53–250 μm) intra‐aggregate particulate organic matter fractions – and of (ii) three density fractions of fine‐silt associated carbon – namely < 2.0, 2.0–2.2 (i.e. enriched labile fraction) and > 2.2 g cm?3– by analysing the amino sugars, by CuO oxidation analyses, and by 13C‐, 1H‐ and 31P‐NMR analyses. Macroaggregates (250–2000 μm) were separated by wet‐sieving from a former grassland soil now under a no‐tillage arable regime. The three particulate organic matter fractions and the three density fractions were isolated from the macroaggregates by a combination of density flotation, sonication and sieving techniques. Proton NMR spectroscopy on alkaline extracts showed that the enriched labile fraction is not of microbial origin but is strongly degraded plant material that is enriched in aliphatic moieties partly bound to aromatics. In addition, the enriched labile fraction had a glucosamine content less than the whole soil, indicating that it is not enriched in carbon derived from fungi. Decreasing yields of phenolic CuO oxidation products and increasing side‐chain oxidation in the order coarse intra‐aggregate particulate organic matter < fine inter‐aggregate particulate organic matter < fine‐silt fractions indicate progressive alteration of lignin as particle size decreases. The light fraction was more decomposed than the coarse inter‐aggregate particulate organic matter, as indicated by (i) its larger ratio of acid‐to‐aldehyde of the vanillyl units released by CuO oxidation, (ii) the smaller contribution of H in carbohydrates to total extractable H as estimated by 1H‐NMR spectroscopy, and (iii) a larger contribution of monoester P to total extractable P in the 31P‐NMR spectra. In conclusion, the four fractions are derived predominantly from plants, but microbial alteration increased as follows: coarse inter‐aggregate particulate organic matter < light fraction ≈ fine inter‐aggregate particulate organic matter < enriched labile fraction.  相似文献   
7.
Water extracts from fresh wheat and barley straw, straw incubated with Pleurotus ostreatus, and straw compost were studied by IR, 1H NMR, and 13C NMR spectroscopy. During incubation lignin was degraded, water extractability increased, and water extracts were rich in polysaccharides. After composting solubility decreased and the water extracts were rich in aromatic, methoxyl, and carboxyl C, but poor in O-alkyl C indicating that during composting mainly polysaccharides had been mineralized. GPC revealed that water extracts from straw compost contained polysaccharides, peptides, C- and O-substituted aromatics, and alkyl compounds.  相似文献   
8.
Cattle dung contributes to hot‐spot inputs of nutrients to grassland systems, but not much is known about its organic P (Po) composition and fate in the grassland soils. We used 31Phosphorus (P)–Nuclear Magnetic–Resonance (NMR) spectroscopy of alkaline soil extracts to examine potentials for tracing of different functional Po forms into a temperate grassland soil amended with dung. The proportion of monoester, DNA‐diester, and phospholipid+teichoic acid P were comparable in dung extracts, but the soil was dominated by monoester P. The temporal trends in the DNA‐diester P–to–monoester P (DDNAM) and diester P–to–monoester P (DM) ratio of dung, native soil, and soil amended with dung were monitored in the 70 d field experiment. The DDNAM and DM ratio in the dung‐amended soil (0–1 and 1–5 cm depth) were always intermediate between the dung and (unamended) control soil. Clearly, extracted soil P was a mixture of incorporated dung‐derived P and native soil P. The dung‐P contribution in the 0–1 cm samples peaked at 47% of the total extracted P at day 70 and at 15% after 42 d in the 1–5 cm soil depth (based on the DM ratio). The proportions of dung‐derived P and C in the soil were positively correlated with: 1) topsoil, using the DDNAM ratio (r2 = 0.975), and 2) top‐ and subsoil, using the DM ratio (r2 = 0.656). We concluded that our DDNAM and DM‐P ratios approach (obtained from solution‐31P NMR) did trace successfully the short‐term dynamics and fate of dung Po in soil. It indicated that dung‐derived Po varied as rapidly in soil as the dung‐derived C.  相似文献   
9.
NaOH-extracts from different soils of the alpine and shrub zones at the Schneibstein (Nationalpark Berchtesgaden) between 1790–2275 m were studied using 31P NMR spectroscopy. NaOH (0.5 M) dissolved 29–49% of Pt. Orthophosphate monoesters were the dominant fraction (41–79%). Orthophosphate diesters comprised 10–20%. A higher diester content (36%) was found in a hydromorphic soil. Inorganic phosphate comprised 5–27%, depending on soil pH. So, in acid horizons (pH 4.45 and 5.05) 27 and 23% were detected, whereas in horizons with higher pH (> 6) only small amounts (5–8%) were found. Pyrophosphate and polyphosphates were found in traces. Phosphonates (ca. 6%) occurred mainly in acid soils.  相似文献   
10.
Black carbon (BC) occurs ubiquitously in the environment. Its oxidation in the laboratory yields a suite of benzene polycarboxylic acids (BPCAs), suggesting similar oxidation products in soils. Since only for a few soils the occurrence of BPCAs in the free form has been documented, screening for them in a broad range of contrasting soils was conducted. They were extracted from soil samples with 0.5 M NaOH and quantified using gas chromatography–mass spectrometry. As expected, BPCAs turned out to be as ubiquitous as BC. They were detected not only in every soil sample investigated so far, but also in samples from drill cores up to a depth of 10 m and in recently deposited calcareous tufa. The concentrations covered a range similar to that of some phenolic acids. The range exceeded those reported for low‐molecular‐weight aliphatic acids or simple sugars in soils. The distribution of BPCAs in soil profiles indicated a considerable potential of translocation within, and export from, soil, in particular of benzene hexacarboxylic (mellitic) acid. Mellitic acid may therefore be present in almost any geochemical sample affected by seepage water from soils. Its high water solubility and strong metal‐complexing ability suggest it may be involved in metal‐transport processes, at least on geological timescales.  相似文献   
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