Ancient paddy soils from the Neolithic age in China's Yangtze River Delta.

Identifying prehistoric irrigated rice fields and characterizing the beginning of paddy soil development are important for a better understanding of human development and agricultural history. In 2003, paddy soils and irrigated rice fields buried at a depth of 100-130 cm were excavated at Chuo-dun-shan in the Yangtze River Delta, close to Suzhou, China. The fields of sizes between 1.4 and 16 m(2) were surrounded with ridges that were connected to ditches/ponds via outlets to control the water level within the fields. Many carbonized and partly carbonized rice grains with an age of 3,903 B.C. (measured (14)C age 5,129+/-45 a BP) were recovered. The surface layers of these buried paddy fields showed a high content of soil organic matter and a considerable high density of rice opals. The latter were identified to derive from Oryza spp. Solid-state (13)C nuclear magnetic resonance spectroscopy revealed aromatic carbon (C) as the predominant organic C form in the fossil surface layer. This is expected, if the major source represents burnt rice and straw. In summary, our data are in agreement with new evidences indicating that in China, paddy soils and irrigated rice cultivation were initiated and developed more than 6,000 years ago.

Formation of heteroaromatic nitrogen after prolonged humification of vascular plant remains as revealed by nuclear magnetic resonance spectroscopy.

In the search for the mechanisms involved in the immobilization of organic nitrogen in humified remains of vascular plants, the efforts of the present investigation were directed toward the examination of the transformation of nitrogenous compounds during the peat and coal stage by means of solid-state nuclear magnetic resonance (NMR) spectroscopy. While accumulation of heteroaromatic-N is not detected in most of the studied peat layers, a clear shoulder in the chemical shift region of pyrrole- or indole-N is observed in the solid-state 15N NMR spectrum of material from the deepest (and thus oldest) peat layer underlying the sapropel from Mangrove Lake, Bermuda (10000 years). This points to the assumption that transformation of nitrogen occurs between an advanced stage of peatification and an early stage of coalification. The observed sudden alteration in nitrogen functionality indicates that continuous accumulation of newly synthesized or selectively preserved biogenic structures is not responsible for the presence of heteroaromatic-N in these fossilized deposits. It seems rather likely that abiotic conditions, occurring during advanced sediment maturation, have an effect on the observed N transformation. With increasing coalification, pyrrole-type-N becomes the dominant form in the macromolecular coal network. Pyridine-type-N was only detected in a coal of anthracite rank.

Solid-state 13C NMR spectroscopic, chemolytic and biological assessment of pretreated municipal solid waste.

In Central Europe, composting and anaerobic digestion of municipal solid waste (MSW) is used as pretreatment before landfilling to reduce landfill emissions. MSW samples were analyzed before, during, and after pretreatment to assess the stability of the organic matter. Chemolytic, nuclear magnetic resonance (NMR) spectroscopic, and respiration parameters were correlated to evaluate a substitution of the time-consuming respiration analysis by chemical parameters. 13C cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed a preferential biodegradation of O-alkyl carbon (carbohydrates) and a selective accumulation of plastics during all pretreatments, confirming findings from chemolytic analyses. Principal component analysis exhibited a strong association between the respiration rate, the carbohydrate content, and the O-alkyl C content, corroborating that carbohydrates are the most important compounds of MSW with regard to the emission potential. Rank correlation (Spearman) also showed strong relationships between the respiration rate and the content of carbohydrates (r = 0.75) and of O-alkyl C (r = 0.72).

Solid-state (13)C NMR spectroscopic, chemolytic and biological assessment of pretreated municipal solid waste.

In Central Europe, composting and anaerobic digestion of municipal solid waste (MSW) is used as pretreatment before landfilling to reduce landfill emissions. MSW samples were analyzed before, during, and after pretreatment to assess the stability of the organic matter. Chemolytic, nuclear magnetic resonance (NMR) spectroscopic, and respiration parameters were correlated to evaluate a substitution of the time-consuming respiration analysis by chemical parameters. (13)C cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed a preferential biodegradation of O-alkyl carbon (carbohydrates) and a selective accumulation of plastics during all pretreatments, confirming findings from chemolytic analyses. Principal component analysis exhibited a strong association between the respiration rate, the carbohydrate content, and the O-alkyl C content, corroborating that carbohydrates are the most important compounds of MSW with regard to the emission potential. Rank correlation (Spearman) also showed strong relationships between the respiration rate and the content of carbohydrates (r=0.75) and of O-alkyl C (r=0.72).

Solid-state nitrogen-15 nuclear magnetic resonance analysis of biologically reduced 2,4,6-trinitrotoluene in a soil slurry remediation.

Soil contaminated with 2,4,6-trinitrotoluene (TNT) and spiked with [14C]- and [15N3]-TNT was subjected to an anaerobic-aerobic soil slurry treatment and subsequently analyzed by radiocounting and solid-state 15N nuclear magnetic resonance (NMR) spectroscopy. This treatment led to a complete disappearance of extractable radioactivity originating from TNT and almost all of the radioactivity was recovered in the insoluble soil fraction. As revealed by solid-state 15N NMR, a major fraction of partially reduced metabolites of TNT was immobilized into the soil during the early stage of the anaerobic treatment, although some of the compounds (i.e., aminodinitrotoluenes and azoxy compounds) were extractable by methanol. Considerable 15N intensity was assigned to condensation products of TNT metabolites. A smaller signal indicated the formation of azoxy N. This signal and the signal for nitro groups were not observed at the end of the anaerobic phase, revealing further reduction and/or transformation of their corresponding compounds. An increase of the relative proportion of the condensation products occurred with increasing anaerobic incubation. Aerobic incubation resulted in a further decrease of aromatic amines, presumably due to oxidative transformations or their involvement in further condensation reactions. The results of the study demonstrate that the anaerobic-aerobic soil slurry treatment represents an efficient strategy for immobilizing reduced TNT in soils.

Analysis of 13C and 15N CPMAS NMR-spectra of soil organic matter and composts.

15N and 13C CPMAS spectra of composted plants are presented. The plants (L. rigidium and Zea mays) were grown in 15N enriched medium and fermented for several months until an approx. 80% of the dry matter was lost. In all 15N spectra the secondary amide/peptide peaks at 87 ppm contributes more than 80% of the total intensity. No new 15N peaks are formed during the fermentation process. Older attempts to assign a significant fraction of humic acid nitrogen to heteroaromatic structures formed in the fermentation process are thus most probably wrong.