Molecular composition and possible transformations of labile soil organic matter fractions in Mediterranean arable soils: Relevance and implications.

With the increased global interest in sequestering carbon in soil, it is necessary to understand the composition of different pools of soil organic matter (SOM) that cycle over suitably short timeframes. To explore in detail the chemical composition of agroecologically relevant yet distinct fractions of SOM, the light fraction of SOM (LFOM), the 53-µm particulate organic matter (POM), and the mobile humic acid (MHA) fractions were sequentially extracted from agricultural soils and characterized using both 13C cross polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy and also Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The NMR results showed a decrease in the O-alkyl C region assigned to carbohydrates (51-110 ppm) and an increase in the aromatic region (111-161 ppm) proceeding from the LFOM to the POM and then to the MHA fraction. Similarly, based on the thousands of molecular formulae assigned to the peaks detected by FT-ICR-MS, condensed hydrocarbons were dominant only in the MHA, while aliphatic formulae were abundant in the POM and LFOM fractions. The molecular formulae of the LFOM and POM were mainly grouped in the high H/C lipid-like and aliphatic space, whereas a portion of the MHA compounds showed an extremely high (17-33, average of 25) double bond equivalent (DBE) values, corresponding to low H/C values of 0.3-0.6, representative of condensed hydrocarbons. The labile components appeared most pronounced in the POM (93% of formulae have H/C ≥ 1.5) similar to the LFOM (89% of formulae have H/C ≥ 1.5) but in contrast to the MHA (74% of formulae have H/C ≥ 1.5). The presence of both labile and recalcitrant components in the MHA fraction suggests that the stability and persistence of soil organic matter is influenced by a complex interaction of physical, chemical, and biological factors in soil. Understanding the composition and distribution of different SOM fractions can provide valuable insights into the processes that govern carbon cycling in soils, which can help inform strategies for sustainable land management and climate change mitigation.

Maize Growth and Grain Yield Responses to a Micronized Humic Product Across Soil Types and Annual Weather Patterns in Central Iowa, United States.

Despite growing interest in humic products as crop amendments, very few field evaluations have considered environmental factors of humic product efficacy. We determined the spatial and temporal variability in the efficacy of a micronized humic product on maize (Zea mays L.) growth and grain yield in two rainfed fields supporting a maize-soybean [Glycine max (L.) Merr.] rotation in 2012-2014, and 2016 in central Iowa, U.S. Crop management in both fields otherwise followed conventional farmer practices. In two dry growing seasons, mechanized combine measurements of grain yield increased significantly (P < 0.10) with humic product application on an eroded hilltop soil, amounting for two application rates to 930 and 1,600 kg ha-1 (11 and 19% of the control grain yield) in 2012, the droughtiest season, and 700 kg ha-1 (7% of the control) for the higher application rate in the somewhat droughty 2013 season. On a fertile side slope soil in the 2012 field, though, only a faint numeric response occurred in 2012, while on a toe slope soil the sole significant increase was in 2012, 870 kg ha-1 (14% increase above the control) for one application rate. With favorable rainfall in 2014 and 2016, significant grain yield increases with product application were small in the upland soil of 2014 and absent in 2016. Yield components analysis on 1-m row lengths of hand-collected samples attributed these yield boosts primarily to increased ear length, especially of the shorter ears. Combine grain yields, yield components, and total leaf area all demonstrated numerically slightly greater values for humic product treatments compared to the control in the vast majority of comparisons across years and soil types, with better distinction in the upland transects. Statistical significance, though, was reached only in the droughtier settings. The humic product had no consistent effects on nutrient concentrations of the grain, stover, or young leaves. Grain quality parameters showed a slight shift from protein to carbohydrates in the droughtier settings. Fifteen soil properties showed no response to the humic product. This humic product demonstrated the capability to improve maize growth in rainfed conditions in a high-yielding region, and its efficacy varied predictably with environmental conditions. This finding provides one potential explanation for inconsistent reports elsewhere of crop responses to humic products.

Maize Growth Responses to a Humic Product in Iowa Production Fields: An Extensive Approach.

Field evaluations of commercial humic products have seldom involved replication across location or year. To evaluate the consistency of humic product efficacy in field conditions, we determined the effects of a humic product on maize (Zea mays L.) growth in high-yielding Midwestern (US) fields through the following two extensive approaches: (i) replicated strip plots in five site-year combinations from 2010 to 2013; and (ii) demonstration strips in 30-35 production fields annually from 2009 to 2011 that covered major areas of Iowa. Mechanized combine measurements of grain yield showed increases of 0.2-0.4 Mg ha-1 (1-4%) with humic product application for all five site-year combinations of the replicated strip plots. Six of 10 humic treatments within the fields responded positively (P < 0.07), and the positive responses of two more treatments approached significance at the benchmark of P = 0.10. In the demonstration strips, maize grain weight in hand-collected samples increased significantly (P < 0.004) with humic product application in each of the three growing seasons, and across all the three seasons by 6.5% (P < 0.001). Grain weight increased numerically for 76 of the 98 demonstration strips. Yield component analysis for both the replicated strip plots and the demonstration strips attributed the yield boosts largely to increased ear length, especially of the shorter ears. Humic product application caused significantly (P < 0.10) greater total leaf area in all eight field treatments at three site-year combinations. Humic product application did not consistently affect nutrient concentrations of the grain or stover or any measured soil property. These results represent among the widest geographic evaluations published on field efficacy of a humic product. They demonstrate the capability of a humic product to improve maize growth in high-yielding conditions.

Formation of Char-Like, Fused-Ring Aromatic Structures from a Nonpyrogenic Pathway during Decomposition of Wheat Straw.

Fused-ring aromatics, important skeletal components of black carbon (BC), contribute to long-term carbon (C) sequestration in nature. They have previously been thought to be primarily formed by incomplete combustion of organic materials, whereas the nonpyrogenic origins are negligible. Using advanced solid-state 13C nuclear magnetic resonance (NMR), including recoupled long-range C-H dipolar dephasing, exchange with protonated and nonprotonated spectral editing (EXPANSE), and dipolar-dephased double-quantum/single-quantum (DQ/SQ) spectroscopy, we for the first time identify fused-ring aromatics that formed during the decomposition of wheat (Triticum sp.) straw in soil under aerobic, but not anaerobic conditions. The observed formation of polyaromatic units as plant litter decomposes provides direct evidence for humification. Moreover, the estimation of the annual flux of such nonpyrogenic BC could be equivalent to 3-12% of pyrogenic BC added to soils from all other sources. Our findings significantly extend the understanding of potential sources of fused-ring aromatic C and BC in soils as well as the global C cycle.

Maximum soil organic carbon storage in Midwest U.S. cropping systems when crops are optimally nitrogen-fertilized.

Nitrogen fertilization is critical to optimize short-term crop yield, but its long-term effect on soil organic C (SOC) is uncertain. Here, we clarify the impact of N fertilization on SOC in typical maize-based (Zea mays L.) Midwest U.S. cropping systems by accounting for site-to-site variability in maize yield response to N fertilization. Within continuous maize and maize-soybean [Glycine max (L.) Merr.] systems at four Iowa locations, we evaluated changes in surface SOC over 14 to 16 years across a range of N fertilizer rates empirically determined to be insufficient, optimum, or excessive for maximum maize yield. Soil organic C balances were negative where no N was applied but neutral (maize-soybean) or positive (continuous maize) at the agronomic optimum N rate (AONR). For continuous maize, the rate of SOC storage increased with increasing N rate, reaching a maximum at the AONR and decreasing above the AONR. Greater SOC storage in the optimally fertilized continuous maize system than in the optimally fertilized maize-soybean system was attributed to greater crop residue production and greater SOC storage efficiency in the continuous maize system. Mean annual crop residue production at the AONR was 22% greater in the continuous maize system than in the maize-soybean system and the rate of SOC storage per unit residue C input was 58% greater in the monocrop system. Our results demonstrate that agronomic optimum N fertilization is critical to maintain or increase SOC of Midwest U.S. cropland.

Integrating plant litter quality, soil organic matter stabilization, and the carbon saturation concept.

Labile, 'high-quality', plant litters are hypothesized to promote soil organic matter (SOM) stabilization in mineral soil fractions that are physicochemically protected from rapid mineralization. However, the effect of litter quality on SOM stabilization is inconsistent. High-quality litters, characterized by high N concentrations, low C/N ratios, and low phenol/lignin concentrations, are not consistently stabilized in SOM with greater efficiency than 'low-quality' litters characterized by low N concentrations, high C/N ratios, and high phenol/lignin concentrations. Here, we attempt to resolve these inconsistent results by developing a new conceptual model that links litter quality to the soil C saturation concept. Our model builds on the Microbial Efficiency-Matrix Stabilization framework (Cotrufo et al., 2013) by suggesting the effect of litter quality on SOM stabilization is modulated by the extent of soil C saturation such that high-quality litters are not always stabilized in SOM with greater efficiency than low-quality litters.

A new standardized method for quantification of humic and fulvic acids in humic ores and commercial products.

Increased use of humic substances in agriculture has generated intense interest among producers, consumers, and regulators for an accurate and reliable method to quantify humic acid (HA) and fulvic acid (FA) in raw ores and products. Here we present a thoroughly validated method, the new standardized method for determination of HA and FA contents in raw humate ores and in solid and liquid products produced from them. The methods used for preparation of HA and FA were adapted according to the guidelines of the International Humic Substances Society involving alkaline extraction followed by acidification to separate HA from the fulvic fraction. This is followed by separation of FA from the fulvic fraction by adsorption on a nonionic macroporous acrylic ester resin at acid pH. It differs from previous methods in that it determines HA and FA concentrations gravimetrically on an ash-free basis. Critical steps in the method, e.g., initial test portion mass, test portion to extract volume ratio, extraction time, and acidification of alkaline extract, were optimized for maximum and consistent recovery of HA and FA. The method detection limits for HA and FA were 4.62 and 4.8 mg/L, respectively. The method quantitation limits for HA and FA were 14.7 and 15.3 mg/L, respectively.

Why phenolic acids are unlikely primary allelochemicals in rice.

Allelopathy in rice (Oryza sativa, L.) effective against weeds has been found in about 3.5% of tested rice germplasm in both laboratory and field experimentation. However, the allelochemicals responsible for growth inhibition of rice-associated weeds have not yet been identified. In the literature, phenolic acids are often mentioned as putative allelochemicals. If phenolic acids commonly reach growth inhibitory concentrations in rice ecosystems, it must be expected that the degree of tolerance to phenolic acids will vary among traditional rice cultivars or plant species adapted to rice environments having inherently different phenolic acid concentrations. Phenolic acids concentrations are normally greater in submerged than in aerobic soils. A dose-response study, however, showed that seedlings of rice cultivars adapted to submerged anaerobic soils did not have higher level of tolerance against p-hydroxybenzoic acid than did seedlings of varieties adapted to aerobic upland soils. Moreover, traditional rice cultivars had no greater tolerance than did improved cultivars that were recently bred for traits other than tolerance of phenolic acids. Similarly, there were no differences in tolerance of p-hydroxybenzoic acid between two Echinochloa weed species adapted to either anaerobic or aerobic growth conditions. Thus, neither the rice cultivars nor weed species had evolved different tolerance levels against the phenolic acid. However, all rice cultivars had significantly greater tolerance of p-hydroxybenzoic acid than did either weed species. In a second experiment, the rates at which rice plants released phenolic acids into solution cultures were measured for at least one month, the time period of greatest allelopathic activity following planting under field conditions. The maximum release rate of phenolic acids during the first month of growth was approximately 10 microg/plant/day. At a conventional plant density, the release rate of phenolic acids would be approximately 1 mg/m2/day. This order of release rate cannot provide concentrations remotely close to phytotoxic levels determined for these rice cultivars and weed species. The results presented in this paper do not preclude the possibility that phenolic acids might be one component in a mixture of chemicals that, when present simultaneously, are allelopathic.