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Soil organic carbon (SOC) associated with minerals is considered to be one of the most fundamental long-term SOC storage strategies, but little research has integrated the organo-mineral complexes regulated by long-term fertilization. Here, soil samples under three fertilization treatments (Control, no fertilization; NPK, chemical nitrogen, phosphorus and potassium fertilization; NPKM, NPK plus manure) from four 23-34 years long-term field experiment sites across China were examined. Chemical analyses indicated that vigorous iron (Fe) mobilization could be regulated by long-term fertilization regimes. Meanwhile, Fe K-edge X-ray absorption near-edge fine structure (XANES) demonstrated that compared to NPK treated soils, NPKM treated soils contained significantly higher concentration of poorly crystalline ferrihydrite. Results from both the Fourier transform infrared combined with two-dimensional correlation spectroscopy analyses (FTIR-2DCOS) and C 1 s X-ray photoelectron spectroscopy (XPS) revealed that aliphatic carbohydrate might play an important role in binding exogenous Fe(III) in all tested four soils. In addition, greater amounts of aromatic C (the most resistant soil C fraction) were under long-term treated NPKM than NPK soils. Furthermore, multiple regression analyses showed a significantly positive relationship between poorly crystalline Fe minerals and SOC or aromatic C. Such relationships indicated that aromatic functional groups had been attached to the poorly crystalline Fe minerals, which could also be protected from being transformed to the crystalline counterpart. In conclusion, results from our integrated spectroscopic analyses have evidenced greater improvement of both poorly crystalline Fe minerals and aromatic C in organically fertilized than in chemically fertilized soils., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Understanding the binding characteristics of copper (Cu) to different functional groups in soil dissolved organic matter (DOM) is important to explore Cu toxicity, bioavailability and ultimate fate in the environment. However, the methods used to explore such binding characteristics are still limited. Here, two-dimensional correlation spectroscopy (2DCOS) integrated with Fourier transform infrared (FTIR), 29 Si nuclear magnetic resonance (NMR), 27 Al NMR, and synchrotron-radiation-based FTIR spectromicroscopy were used to explore the binding characteristics of Cu to soil DOM as part of a long-term (23 years) fertilization experiment. Compared with no fertilization and inorganic fertilization (NPK), long-term pig manure fertilization (M) treatment significantly increased the concentration of total and bioavailable Cu in soils. Furthermore, hetero-spectral 2DCOS analyses demonstrated that the binding characteristics of Cu onto functional groups in soil DOM were modified by fertilization regimes. In the NPK treatment, Cu was bound to aliphatic C, whereas in the manure treatment SiO groups had higher affinity toward Cu than aliphatic C. Also, the sequence of binding of functional groups to Cu was modified by the fertilization treatments. Moreover, synchrotron-radiation-based FTIR spectromicroscopy showed that Cu, clay minerals and sesquioxides, and C functional groups were heterogeneously distributed at the micro-scale. Specifically, clay-OH as well as mineral elements had a distribution pattern similar to Cu, but certain (but not all) C forms showed a distribution pattern inconsistent with that of Cu. The combination of synchrotron radiation spectromicroscopy and 2DCOS is a useful tool in exploring the interactions among heavy metals, minerals and organic components in soils., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

To investigate potential interactions between the soil ionome and enzyme activities affected by fertilization with or without organic fertilizer, soil samples were collected from four long-term experiments over China. Irrespective of variable interactions, fertilization type was the major factor impacting soil ionomic behavior and accounted for 15.14% of the overall impact. Sampling site was the major factor affecting soil enzymatic profile and accounted for 34.25% of the overall impact. The availabilities of Pb, La, Ni, Co, Fe and Al were significantly higher in soil with only chemical fertilizer than the soil with organic amendment. Most of the soil enzyme activities, including α-glucosidase activity, were significantly activated by organic amendment. Network analysis between the soil ionome and the soil enzyme activities was more complex in the organic-amended soils than in the chemical fertilized soils, whereas the network analysis among the soil ions was less complex with organic amendment. Moreover, α-glucosidase was revealed to generally harbor more corrections with the soil ionic availabilities in network. We concluded that some of the soil enzymes activated by organic input can make the soil more vigorous and stable and that the α-glucosidase revealed by this analysis might help stabilize the soil ion availability.

Opportunity costs seriously limit the large-scale production of bio-organic fertilizers (BOFs) both in China and internationally. This study addresses the utilization of amino acids resulting from the acidic hydrolysis of pig corpses as organic nitrogen sources to increase the density of TrichodermaharzianumT-E5 (a typical plant growth-promoting fungi, PGPF). This results in a novel, economical, highly efficient and environmentally friendly BOF product. Fluorescence excitation-emission matrix (EEM) spectroscopy combined with fluorescence regional integration (FRI) was employed to monitor compost maturity levels, while pot experiments were utilized to test the effects of this novel BOF on plant growth. An optimization experiment, based on response surface methodologies (RSMs), showed that a maximum T-E5 population (3.72 × 108 ITS copies g-1) was obtained from a mixture of 65.17% cattle manure compost (W/W), 19.33% maggot manure (W/W), 15.50% (V/W)hydrolytic amino acid solution and 4.69% (V/W) inoculum at 28.7°C after a 14 day secondary solid fermentation. Spectroscopy analysis revealed that the compost transformation process involved the degradation of protein-like substances and the formation of fulvic-like and humic-like substances. FRI parameters (PI, n, PII, n, PIII, n and PV, n) were used to characterize the degree of compost maturity. The BOF resulted in significantly higher increased chlorophyll content, shoot length, and shoot and root dry weights of three vegetables (cucumber, tomato and pepper) by 9.9%~22.4%, 22.9%~58.5%, 31.0%~84.9%, and 24.2%~34.1%, respectively. In summary, this study presents an operational means of increasing PGPF T-E5 populations in BOF to promote plant growth with a concomitant reduction in production cost. In addition, a BOF compost maturity assessment using fluorescence EEM spectroscopy and FRI ensured its safe field application.

The binding characteristics of organic ligands and minerals in fulvic acids (FAs) with Al are essential for understanding soil C sequestration, remain poorly understood. In this study, Fourier transform infrared (FTIR) spectroscopy combined with two-dimensional correlation spectroscopy (2DCOS) analysis was applied for the first time to explore the binding of Al with organic ligands and minerals in soil FAs. For these analyses, two contrasting treatments were selected from a long-term (i.e., 22-year) fertilization experiment: chemical (NPK) fertilization and swine manure (SM) fertilization. The results showed that the long-term application of organic and inorganic fertilizers to soils had little effect on the compositions of the fluorescent substances and organic ligands in the soil FAs. However, long-term SM fertilization increased the weathered Al and Si concentrations in the soil FAs compared with long-term chemical fertilization. Furthermore, organic ligands in the soil FAs were mainly bound with Al in the NPK treatment, whereas both organic ligands and minerals (Al-O-Si, Si-O) were bound with Al under the M fertilization conditions. Both transmission electron microscopy (TEM) images and X-ray diffraction spectra demonstrated that amorphous and short-range-ordered nanominerals were abundant in the soil FAs from the SM plot in contrast to the soil FAs from the NPK plot. This result illustrates the role nanominerals play in the preservation of soil FAs by during long-term organic fertilization. In summary, the combination of FTIR and 2D correlation spectroscopy is a promising approach for the characterization of the binding capability between soil FAs and Al, and a better understanding FA-Al binding capability will greatly contribute to global C cycling.

The composting industry has been growing rapidly in China because of a boom in the animal industry. Therefore, a rapid and accurate assessment of the quality of commercial organic fertilizers is of the utmost importance. In this study, a novel technique that combines near infrared (NIR) spectroscopy with partial least squares (PLS) analysis is developed for rapidly and accurately assessing commercial organic fertilizers quality. A total of 104 commercial organic fertilizers were collected from full-scale compost factories in Jiangsu Province, east China. In general, the NIR-PLS technique showed accurate predictions of the total organic matter, water soluble organic nitrogen, pH, and germination index; less accurate results of the moisture, total nitrogen, and electrical conductivity; and the least accurate results for water soluble organic carbon. Our results suggested the combined NIR-PLS technique could be applied as a valuable tool to rapidly and accurately assess the quality of commercial organic fertilizers.

Particle-size soils were fractionated for evaluating changes in the composition of bacterial community and enzyme activity in response to 13 years of fertilization. This study focused on Mollisol and its particle-size fractions of 200-2,000 μm (coarse sand sized), 63 to 200 μm (fine sand sized), 2 to 63 μm (silt sized), and 0.1 to 2 to μm (clay-sized). Long-term chemical fertilization lowered the pH of all particle fractions, whereas organic fertilizer application mitigated soil acidification. Nutrient concentrations depended on both fertilizer treatment and particle fractions and enzymes were unevenly active throughout the soil. Generally, the highest enzyme activities were observed in the silt and clay fractions of control soil and the soil treated with chemical fertilizer (N, P, and K (NPK)) and in the sand-sized fraction of soil treated with manure and chemical fertilizer (MNPK). Except for acid phosphomonoesterase, the other tested enzyme activities in coarse-sized fractions of MNPK soil were significantly higher than those of the control and NPK soils. Fertilization and soil fraction interactively ( p < 0.05) affected the enzyme activity. Denaturing gradient gel electrophoresis analysis showed that the bacterial community structure significantly differed in different particle sizes with a higher bacterial diversity in small-sized than in coarse-sized fractions. Dominant bands were excised and sequenced. We have found the following bacterial groups: Actinobacteria, γ-proteobacteria, and Acidobacteria. In addition, enrichment of organic matter in coarser fractions was related to greater bacterial diversity than any other treatment. Principal component analysis showed a smaller variability among fractions of the organic amended treatment. Redundancy analysis showed that the tested properties significantly affected the composition of bacterial community with the exception of C/N and available P. No significant correlation between enzyme activity and bacterial community composition was detected, whereas positive correlations between other soil properties and enzyme activities were observed to various extents. Probably, enzyme activities might be affected by specific functional bacterial communities rather than by the overall bacterial community. We concluded that the long-term application of organic manures contributed to the increase of soil organic matter content of particles higher than 200 mm, with higher bacterial diversity and increases in most of the enzyme activities. [ABSTRACT FROM AUTHOR]

Paddy soils constitute the largest anthropogenic wetlands on earth, where microbial and non-microbial pathways jointly determine the fate of carbon from organic amendments. However, the specific mechanisms underlying these processes remain poorly understood. Here, we examined the influence of microbial anabolism versus catabolism and iron (Fe)-mediated soil organic carbon (SOC) protection versus decomposition on the topsoil carbon sequestration efficiency (CSE) of exogenous organic amendments in a rice-wheat cropping system subjected to nine years of no fertilizer (CT), chemical fertilizer (CF), 50% CF plus pig manure compost (CFM), 100% CF plus straw (CFS), 50% CF plus pig manure compost and straw (CFMS), and 87.5% CF plus pig manure compost (OICF) amendments. The CSE under CT and CFM was approximately 1.5- to 2.4-fold higher than that under the other four treatments. A structural equation model indicated that Fe-mediated free radical reactions and exogenous carbon inputs were negatively correlated with CSE, whereas soil microorganisms were positively correlated with CSE. Microbial biomass carbon and Fe-bound organic carbon were higher while the metabolic quotient, the ratio of microbial carbon-use efficiency to nitrogen-use efficiency and the percentage of Fe-bound organic carbon to SOC were lower under CFM and CFMS than under CF, CFS and OICF. The concentrations of ferrous Fe, oxalate-extractable Fe oxides, hydrogen peroxide and hydroxyl radicals were lower, but the activity of catalase was higher under CFM and CFMS than under CF, CFS and OICF. Therefore, partial substitution of chemical fertilizer with compost enhances topsoil CSE in three ways: directly through the input of refractory organic carbon, indirectly through improving the microbial substrate-use efficiency, and to a lesser extent through promoting the formation of organo-Fe complexes and accelerating the decay of hydrogen peroxide, thereby possibly serving as a management tool for attenuating terrestrial carbon-climate feedbacks. • Rice-wheat cropping displayed a positive feedback loop for carbon sequestration. • Soil microorganisms had a positive effect on carbon sequestration efficiency. • Iron-mediated free radical reactions had a negative effect on carbon sequestration efficiency. • Compost application improved microbial substrate-use efficiency. • Compost application enhanced iron-mediated organic carbon protection against decomposition. [ABSTRACT FROM AUTHOR]

Mineral protection regulates long-term global preservation of soil organic carbon (SOC), but little research has been conducted on the iron (Fe) oxide availability for carbon binding regulated by seasonal variation of wetting and drying and fertilization in paddy soils. The objective of this study was to explore the effects of five-year rice-wheat rotation and organic fertilization on the production of short-range-ordered (SRO) Fe oxides and SOC sequestration. Five fertilization treatments were examined: (1) no fertilizer control (CK), (2) chemical nitrogen, phosphorus and potassium (NPK), (3) 50% NPK plus manure (NPKM), (4) 100% NPK plus straw (NPKS), and (5) 30% NPK plus manure organic-inorganic compound fertilizer (NPKMOI). Soil samples were collected from 2013 to 2015 after each wheat and rice harvest. A split-plot analysis of variation was used to investigate the respective role of fertilizer treatments (main-plot) and crop seasons (sub-plot) in the transformation of SRO-Fe oxides. Variation partitioning analysis was used to quantify the contribution of SRO-Fe oxides to the accumulation of SOC. Five-year rice-wheat rotation without any fertilization (CK) increased the oxalate extractable Fe oxides (Feo) by 55.06% compared with the initial soil. The Feo concentration was higher (P < 0.05) in the NPKM, NPKS and NPKMOI treatments than in the NPK and CK treatments, and was higher after the rice harvest than after the wheat harvest. Furthermore, the Feo concentration was positively (P < 0.001) correlated with the SOC content and negatively correlated with the specific carbon mineralization rate (SCMR, rate per unit SOC). Moreover, the Feo could explain 52.57% and 40.5% of the variation in the SOC content and the SCMR, respectively. In addition, the partial humification coefficient (PHC, the percentage of SOC change per unit of exogenous carbon input) of the crop straw was 12.92% but amounted to 41.45% to 46.35% for different types of compost. These results indicate that the reductive dissolution and subsequent oxidative precipitation of Fe oxides induced by seasonal alternation of wetting and drying can be further promoted via organic fertilization possibly by forming organo-Fe complexes, which contribute to the accumulation of SRO-Fe oxides and the preservation of organic carbon in paddy soils. Unlabelled Image • Rice-wheat rotation contributed to the redox transformation of iron oxides. • Organic fertilization further improved the redox transformation of iron oxides. • Oxalate extractable iron oxides explained 52.57% of the variation in the soil organic carbon. • Oxalate extractable iron oxides explained 40.5% of the variation in the specific carbon mineralization rate. [ABSTRACT FROM AUTHOR]