Excitation−emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the >10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation−emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation−emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (Φi,n). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet−visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 h...

Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter.

Biochar as a sorbent for contaminant management in soil and water: a review.

Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy

Climate change 2014 - Synthesis Report

Rapid turnover of organic matter leads to a low efficiency of organic fertilizers applied to increase and sequester C in soils of the humid tropics. Charcoal was reported to be responsible for high soil organic matter contents and soil fertility of anthropogenic soils (Terra Preta) found in central Amazonia. Therefore, we reviewed the available information about the physical and chemical properties of charcoal as affected by different combustion procedures, and the effects of its application in agricultural fields on nutrient retention and crop production. Higher nutrient retention and nutrient availability were found after charcoal additions to soil, related to higher exchange capacity, surface area and direct nutrient additions. Higher charring temperatures generally improved exchange properties and surface area of the charcoal. Additionally, charcoal is relatively recalcitrant and can therefore be used as a long-term sink for atmospheric CO2. Several aspects of a charcoal management system remain unclear, such as the role of microorganisms in oxidizing charcoal surfaces and releasing nutrients and the possibilities to improve charcoal properties during production under field conditions. Several research needs were identified, such as field testing of charcoal production in tropical agroecosystems, the investigation of surface properties of the carbonized materials in the soil environment, and the evaluation of the agronomic and economic effectiveness of soil management with charcoal.

http://www.css.cornell.edu/faculty/lehmann/publ/BiolFertSoils%2035,%20219-230,%202002%20Glaser.pdf

Ameliorating physical and chemical properties of highly weathered soils in the tropics with charcoal – a review

A spent mushroom substrate (SMS) was mixed with wheat straw (WS) in three proportions, C1 (2:1), C2 (4:1), and C3 (6:1), and composted for 90 days in static piles with periodic turning to ensure adequate aeration. Samples from each pile were collected periodically (after 0, 30, 60, and 90 days), and the humic acid-like fractions (HAs) were isolated to determine their elemental composition (C, H, N, S, and O), acidic functional group (carboxylic and phenolic) content, and structural and functional characteristics using spectroscopic methods including ultraviolet-visible, Fourier transform infrared (FTIR), and fluorescence. The results of elemental and functional group analyses show that, with increasing time of composting, the N, O, and acidic functional group contents of HAs increase, whereas their C and H contents and C/N ratio decrease. The analysis of FTIR and fluorescence spectra shows that, with increasing composting time, the presence of aliphatic and polysaccharide-like structures in HAs decreases, whereas oxygenation, polycondensation, and polymerization increase. These results suggest that the chemical and structural characteristics of the HA fractions in the final composts resemble those typical of native soil HAs, which indicate that an adequate degree of maturity and stability is achieved after the end of composting. The results of the present study confirm that composting is an appropriate treatment to transform fresh organic matter (OM) in SMS into humified forms, thus enhancing their quality, agronomic efficiency, and environmental safety as a soil OM resource for application as soil amendment.

Composition and Structural Characteristics of Humified Fractions during the Co-composting Process of Spent Mushroom Substrate and Wheat Straw

The acid−base properties of humic acids (HAs) are known to significantly affect the acid−base buffering capacity of soils, thus having a marked influence on the speciation of cations in the soil solid and liquid phases. Detailed information on the proton binding behavior of humic-like acids (HALs) from organic amendments and humic acids (HAs) from amended soils is, therefore, of intrinsic interest for the evaluation of the agronomic efficacy and environmental impact of soil amendment. In this work, the acid−base properties of HLAs isolated from sewage sludge (SS) and municipal solid waste compost (MSWC), and HAs isolated from soils amended with either SS or MSWC and the corresponding nonamended control soils were investigated by potentiometric titrations at various ionic strengths (0.01, 0.05, 0.1, and 0.3 M) over the pH range from 3.5 to 10.5. The nonideal competitive adsorption (NICA)-Donnan model that describes proton binding by two classes of binding sites with low and high proton affinity, i.e., carb...

Proton binding to humic acids from organic amendments and amended soils by the NICA-Donnan model.

From various manufacturers and distributors 48 fertilizer samples were collected and analyzed for contents of barium, rubidium and strontium by atomic absorption spectrophotometry. The investigated elements are almost always detectable in appreciable amounts in straight and compound fertilizers originated from natural rocks and salt deposits; whereas synthetic nitrogen fertilizers contain in every case low amounts of rubidium, no barium and appreciable quantities of strontium only in some cases. Potassium sulphate fertilizers appear to be the major source of rubidium and superphosphate and calciumcyanamide the source of barium, whilst the three of them supplied sensible amounts of strontium to fertilized soil to affect its average total content to a various degree.

Evaluation of barium, rubidium and strontium contents in commercial fertilizers

The effect of forest cover distribution and plant litter input on soil organic carbon were analyzed to better understand the dynamics of carbon cycling across ecosystems on the “Natural Oriented Reserve Bosco delle Pianelle”. Fluorescence spectroscopy represents a very useful tool to characterize soil organic matter properties, since it allows to directly monitor the molecular status of a fluorophore depending on its chemical environment, as well as on its structure, substituents of the aromatic moieties, and molecular weight. Here, fluorescence analysis was performed on humic acids isolated from four litters (HALs) and their underlying soils (HAs) at three depths. All samples were collected from a protected forest area, Southern Italy, under different plant covering: Quercus ilex L. (Q), mixed Carpinus betulus L. and Carpinus orientalis Mill. (CC), Pinus halepensis L. (P), and mixed Quercus trojana Webb. and Quercus ilex L. (QQ). Data obtained showed a fast decomposition process for P and QQ litters, with HAs in the underlying soils characterized by the presence of simple, highly fluorescent structural components also in the deepest layers. On the contrary, a slow decomposition process was observed for Q and CC litters, whose underlying soil HAs were characterized by an increasing aromatic polycondensation and humification degree from the surface to the deepest layers, as supported by low values of fluorescence intensity and high wavelength maxima. Results obtained indicate that P and QQ species promote C accumulation and stock in the underlying soils, thanks to a greater decomposition of their litter, and fluorescence spectroscopy is a very simple and suitable method to evaluate the influence of three species distribution on soil organic carbon pools.

Forest soil organic carbon dynamics as affected by plant species and their corresponding litters: a fluorescence spectroscopy approach

The knowledge of acid-base characteristics of humic acid (HA) and fulvic acid (FA) fractions of organic amendments and amended soils is of considerable importance for assessing their agronomic efficacy and environmental impact. In this work, the acid-base properties of HAs and FAs isolated from pig slurry, soils amended with either 90 or 150 m(3) ha(-1) yr(-1) of pig slurry for 3 yr, and the corresponding nonamended control soil were investigated by using a current potentiometric titration method. The nonideal competitive adsorption (NICA) model that describes proton binding by two classes of binding sites (carboxylic- and phenolic-type groups) was successfully fit to titration data. With respect to the control soil HA and FA, pig-slurry HA and FA were generally characterized by smaller carboxylic-type group contents, slightly smaller phenolic-type group contents, larger affinities for proton binding by the carboxylic-type groups, and much smaller, in the case of the HA fraction, or similar, in the case of the FA fraction, affinities for proton binding by the phenolic-type groups. Amendment with pig slurry determined a number of modifications in soil HAs and FAs, including decrease of acidic functional group contents, and slight increase of the proton affinity of the carboxylic-type groups. Further, a slight decrease of the affinities for proton binding by the phenolic-type groups of HAs was observed. These effects can have a large impact on the biological availability, mobilization, and transport of macro- and micronutrients, toxic metal ions, and xenobiotic organic cations in pig slurry-amended soils.

Nicola Senesi

Papers

Composition and Structural Characteristics of Humified Fractions during the Co-composting Process of Spent Mushroom Substrate and Wheat Straw

Proton binding to humic acids from organic amendments and amended soils by the NICA-Donnan model.

Evaluation of barium, rubidium and strontium contents in commercial fertilizers

Forest soil organic carbon dynamics as affected by plant species and their corresponding litters: a fluorescence spectroscopy approach

Proton binding by humic and fulvic acids from pig slurry and amended soils.