Variable humic product effects on maize structural biochemistry across annual weather patterns and soil types in two Iowa (U.S.A.) production fields.

Agronomic benefits of humic product application to crops are receiving increasing attention, though underlying biochemical changes remain unexplored, especially in field settings. In this study, maize (Zea mays L.) concentrations of 11 phenol and five carbohydrate monomers were determined in whole plant stover (four growing seasons) and roots (two growing seasons) at physiological maturity for two rainfed fields in Iowa (USA) having humic product applications. Stover and root tissues tended toward greater phenol concentrations in a drier upland transect but greater carbohydrate concentrations in a wetter lowland transect. Two humic treatments further accentuated these trends in upland roots. Their phenol content increased significantly with humic application in the droughtier season of root sampling (2013). Phenol increases above the unamended control averaged 20% for each monomer. Total phenols increased above the control by 12% and 19% for the two humic treatments. Five carbohydrate monomers in the upland roots did not respond to humic application. In the second year of root sampling (2014), which had abundant rainfall, upland root phenols did not respond substantively to humic application, but root carbohydrates increased on average by 11 or 20% for the two humic treatments compared to the control, reaching significance (P< 0.10) in 7 of 10 cases. Upland stover phenol concentrations responded differently to humic product application in each of four years, ranging from numeric increases in the droughtiest year (2012) to significant decreases with abundant rainfall (2014). In the lowland transect, root phenols and carbohydrates and stover phenols responded inconsistently to humic application in four years. Stover carbohydrates did not respond consistently to humic application in either transect. The phenols that were more responsive to humic application or to droughtier conditions included p-coumaric acid and syringaldehyde, which are heavily involved in late-season maize lignification. In summary, humic product application further promoted root lignification, a natural response to drought. Yet under non-drought conditions it promoted root carbohydrate production. Carbohydrate production might be the intrinsic plant response to humic product application in stress-free conditions. These results indicate complex interactions in field conditions between plant biochemistry, environmental signals, and the humic product.

Environmental and Agricultural Relevance of Humic Fractions Extracted by Alkali from Soils and Natural Waters.

To study the structure and function of soil organic matter, soil scientists have performed alkali extractions for soil humic acid (HA) and fulvic acid (FA) fractions for more than 200 years. Over the last few decades aquatic scientists have used similar fractions of dissolved organic matter, extracted by resin adsorption followed by alkali desorption. Critics have claimed that alkali-extractable fractions are laboratory artifacts, hence unsuitable for studying natural organic matter structure and function in field conditions. In response, this review first addresses specific conceptual concerns about humic fractions. Then we discuss several case studies in which HA and FA were extracted from soils, waters, and organic materials to address meaningful problems across diverse research settings. Specifically, one case study demonstrated the importance of humic substances for understanding transport and bioavailability of persistent organic pollutants. An understanding of metal binding sites in FA and HA proved essential to accurately model metal ion behavior in soil and water. In landscape-based studies, pesticides were preferentially bound to HA, reducing their mobility. Compost maturity and acceptability of other organic waste for land application were well evaluated by properties of HA extracted from these materials. A young humic fraction helped understand N cycling in paddy rice ( L.) soils, leading to improved rice management. The HA and FA fractions accurately represent natural organic matter across multiple environments, source materials, and research objectives. Studying them can help resolve important scientific and practical issues.

Abundant and stable char residues in soils: implications for soil fertility and carbon sequestration.

Large-scale soil application of biochar may enhance soil fertility, increasing crop production for the growing human population, while also sequestering atmospheric carbon. But reaching these beneficial outcomes requires an understanding of the relationships among biochar's structure, stability, and contribution to soil fertility. Using quantitative (13)C nuclear magnetic resonance (NMR) spectroscopy, we show that Terra Preta soils (fertile anthropogenic dark earths in Amazonia that were enriched with char >800 years ago) consist predominantly of char residues composed of ~6 fused aromatic rings substituted by COO(-) groups that significantly increase the soils' cation-exchange capacity and thus the retention of plant nutrients. We also show that highly productive, grassland-derived soils in the U.S. (Mollisols) contain char (generated by presettlement fires) that is structurally comparable to char in the Terra Preta soils and much more abundant than previously thought (~40-50% of organic C). Our findings indicate that these oxidized char residues represent a particularly stable, abundant, and fertility-enhancing form of soil organic matter.

Nitrogen-bonded aromatics in soil organic matter and their implications for a yield decline in intensive rice cropping.

Previous research has shown that long-term intensive cropping of irrigated lowland rice has led to significant grain-yield declines in field trials. The yield decline was attributed to decreased availability of soil nitrogen, which is held mostly in the soil organic matter. By advanced solid-state NMR spectroscopy, we have detected significant amounts of amide nitrogen directly bonded to aromatic rings in a humic acid fraction extracted from a continually submerged, triple-cropped rice soil. Because nitrogen bonded to aromatics is not readily plant-available, this observation can explain the yield decline. Quantitative (13)C NMR combined with advanced spectral editing showed that this humic acid is rich in lignin derivatives (>45% of all carbon), whereas the corresponding humic acid fraction extracted from an aerobic, single-cropped rice soil contains less lignin and less nitrogen bonded to aromatics.

Multinuclear magnetic resonance analysis of two humic acid fractions from lowland rice soils.

To determine the effects of intensive cropping of tropical lowland rice (Oryza sativa L.) and the associated long-term soil submergence on chemical properties of soil organic matter, we used solid-state 13C and 15N and solution 31P nuclear magnetic resonance (NMR) spectroscopy to analyze the labile mobile humic acid (MHA) and the more recalcitrant calcium humate (CaHA) fractions extracted from a series of soils supporting several long-term field experiments in the Philippines. The soils varied mainly in degree of submergence and cropping intensity, ranging from a rainfed rice field without soil submergence to irrigated double- and triple-cropped fields in which soil remains submerged almost all year long. As reported previously, all analyses associated increasing intensity of rice cropping with larger proportions of less humified material in the MHA and CaHA, such as diester phosphorus (P), amide nitrogen (N), and phenolic carbon (C). We established significant correlations between proportions of various spectral areas as well as between some spectral areas and other humic acid (HA) properties such as visible light absorption and free radical concentration (positive indices of humification) and hydrogen (H) concentration (negative index of humification). For example, spectral proportions of heterocyclic N were positively, and proportions of amide N and phenolic C negatively, correlated with visible light absorption and free radical concentration, and each of these spectral proportions had an opposite sign when correlated with H concentration. The correlations of N-alkyl C proportions were the strongest with these properties and with other functional group proportions.