Effect of climate continentality on humus formation and elemental composition of humic acids of automorphic soils of Siberia

Humus formation and the elemental composition of macromolecules of humic acids of automorphic Siberian soils (gray forest soils, chernozems, and chestnut soils) have been considered in comparison with those of the analogous soils of the European part of Russia. It has been found that an increase in the continentality of climate leads to significant changes in the structure of humic acids in soils of similar origin in the meridional direction.     

Study of humic substance transformation in phosphatic soil in terms of nucleophilicity and electrophilicity

The applicability of the nucleophilicity/electrophilicity concept to the explanation of mechanisms of formation and transformation of humic substances was considered. Sequential time changes in the structure and properties of humic substances in phosphatic soil have been revealed. Different elemental composition of humic and fulvic acids at different stages of humus transformation was due to different patterns of electron density distribution in phosphorus-modified fragments of humic molecules. The important role of metals and phosphorus in realization of different pathways of humic substance transformation was demonstrated.     

Structural changes in lipid-free humic acids during composting of sewage sludge

Structural changes in humic acids (HAs), extracted after lipid removal from sewage sludge during composting, were investigated using various chemical methods (elemental analysis, Fourier transform infrared spectroscopy and ¹³C-nuclear magnetic resonance (NMR) spectroscopy). Compared to non-purified HAs, lipid-free HAs (LFHAs) exhibit higher C and N contents and high absorbance around 1652, 1540 and 1230 cm⁻¹, which indicates the intensity of the etherified aromatic structures and nitrogen-containing components. Less absorbance around 2920, 1600, 1414 and 1100 cm⁻¹ could be assigned to their low level of aliphatic compounds, mainly those with a carboxyl group. According to ¹³C-NMR spectroscopy, almost 45% of aliphatic structures are removed by lipid extraction and these correspond mainly to long-chain fatty acids. During composting, significant decomposition of non-substituted alkyl structures and N-containing components occurred, increasing the relative intensity of etherified aromatic structures.     

Effects of olive mill wastewater addition in composting of agroindustrial and urban wastes

In order to study the suitability of olive mill wastewater (OMW) for composting, thisliquid waste was added to two different mixtures of agroindustrial and urban wastesand the composting process was compared with two other piles of similar composition,but without OMW. These four piles were studied in a pilot plant using the Rutgers staticpile system. The addition of OMW produced a greater proportion of degradable organic matter or a higher degradation rate, higher electrical conductivity values, greater losses of total N and lower nitrification than in piles without OMW. Its addition also restricted the increase of the cation exchange capacity and provoked the appearance of phytotoxicity or a longer persistence of phytotoxicity. However, in general, all the composts showed increases in the cation exchange capacity, the percentage of humic acid-like carbon, the polymerisation ratio of these humic substances (which revealed that the organic matter had been humified during composting) and the germination index, the latter indicating the reduction of phytotoxicity during the process.     

Humic substances change during the co-composting process of municipal solid wastes and sewage sludge

The change of the degree of stability of compost during the composting process was a kind of guideline for our study. This stability was estimated by monitoring the chemical fractionation (extraction of humic and fulvic acids, and humin) during two cycles of composting. Change of humin (H), humic-like acid carbon (CHA) and fulvic-like acid carbon (CFA) fractions during the composting process of municipal solid wastes were investigated using two windrows W1 (100% of municipal solid wastes) and W2 (60% of municipal solid wastes and 40% of dried sewage sludge). Humin and fulvic acid fractions in the two windrows decreased since the start of composting process and tend to stabilize. At the end of composting process, humic acid fraction is more important in the windrow without sludge (W1) than the one with sludge (W2). The humification indexes used in this study showed that the humic-like acid carbon fraction production takes place largely during the phase of temperature increase (thermophilic phase), and it appeared very active in the windrow W2. At the end of composting process, the E₄/E₆ ratio value indicated that the compost of W1 is more mature than the compost of W2. The humification ratio (HR) allowed a correct estimation of compost organic matter stabilization level.     

Transformation of organic matter during co-composting of pig manure with sawdust

Co-composting of pig manure with sawdust was studied in order to characterize the organic transformation during the process, using both chemical and spectroscopic methods. Humic acids (HA) and fulvic acids (FA) were fractionated from immature and mature pig manure compost, and characterized. After 63 days of composting, the ratio of total organic carbon and soluble organic carbon decreased to a satisfactory low level and the solid and soluble C/N ratios decreased rapidly for the first 35 days before attaining a constant value, indicating compost maturity. Humification could be responsible for the increase in humic acid proportion during composting. The increase in the aromatic bonds after composting, as indicated by the reduction of C/H and C/O ratios of HA and FA, resulted in a more stabilized product. A substantial increase in high molecular weight compounds along with a small increase in low molecular weight compounds was found in mature compost. Moreover the HA also had more complex organic compounds at this stage. Fluorescence spectral analysis showed an increase in the maximum wavelength of HA associated with the contents of aromatic structures in solution. A decrease in relative absorbance of HA at 1160 cm(-1), 2950 cm(-1) and 2850 cm(-1) was seen in the FTIR spectra indicating the decomposition of complex organic constituents, into simpler ones. Increase in the aromatic compounds with higher stability could account for the relative increase in the absorbance of HA at 1650 cm(-1) and 1250 cm(-1) of the mature compost. The composition of FA was not much altered, indicating most of the degradation of organic matter occurred in HA. Data from organic carbon, C/N ratio, elemental analysis, E(4)/E(6) ratio, gel chromatography, fluorescence and FTIR spectra indicated an increase in polycondensed structures and the presence of more stable organic matter in the mature compost.     

Microbial succession during a composting process as evaluated by denaturing gradient gel electrophoresis analysis

Microbial succession during a laboratory-scale composting process of garbage was analysed by denaturing gradient gel electrophoresis (DGGE) combined with measurement of physicochemical parameters such as temperature, pH, organic acids, total dissolved organic carbon and water-soluble humic substance. From the temperature changes, a rapid increase from 25 to 58 degrees C and then a gradual decrease, four phases were recognized in the process as follows; mesophilic (S), thermophilic (T), cooling (C) and maturing (M). The polymerase chain reaction-amplified 16S rDNA fragments with universal (907R) and eubacterial (341F with GC clamp) primers were subjected to DGGE analysis. Consequently, the DGGE band pattern changed during the composting process. The direct sequences from DGGE bands were related to those of known genera in the DNA database. The microbial succession determined by DGGE was summarized as follows: in the S phase some fermenting bacteria, such as lactobacillus, were present with the existing organic acids; in the T phase thermophilic bacillus appeared and, after the C phase, bacterial populations were more complex than in previous phases and the phylogenetic positions of those populations were relatively distant from strains so far in the DNA database. Thus, the DGGE method is useful to reveal microbial succession during a composting process.     

Anaerobic digestion of alcohol sulfate (anionic surfactant) rich wastewater--batch experiments. Part II: influence of the hydrophobic chain length

The mineralisation and the humification of organic matter (OM) in sterile horticultural plant wastes inoculated with Coriolus versicolor or Phanerochaete flavido-alba was investigated under different aeration rates in order to determine their efficacy as potential inoculants for composting. The change in elemental composition, lignin content and OM fractions was analysed during a 90-day incubation. Both fungi degraded 30% of lignin at low aeration rates. Different aeration rates led to significant changes in OM mineralisation induced by C. versicolor, but did not have noticeable effect on P. flavido-alba activity. The mineralisation was more effectively carried out by P. flavido-alba than by C. versicolor. Lignin degradation and the linked humification process were equally achieved by the two fungi and were enhanced in aerated conditions. The fungi analysed may facilitate the composting of lignocellulosic wastes by means of an increase in substrate bioavailability and OM humification.     

Spectroscopic properties of dissolved humic substances - a reflection of land use history in a fen area

The elemental composition and spectroscopic properties of dissolved fulvic acids isolated from different sampling media (topsoil, ground and surface water) of a natural fen area (high portion of organic soils) were examined to reveal the effects of land use history. These effects need to be known if dissolved humic substances are to be a major factor in identifying the impact of present and future changes in land use. Dissolved fulvic acids (topsoil, groundwater) from highly degraded peatlands (due to a long-term agricultural use) exhibit lower C/N ratios, higher absorption in the UV spectra, and higher absorption at 1,620 cm^–1 in the FTIR spectra compared with fulvic acids from relatively intact peatlands. These properties illustrate that long-term agricultural use with high inputs results in increased aromatic structures and a further humification of dissolved fulvic acids due to very strong peat decomposition compared with relatively intact peatlands. Synchronous fluorescence spectra also indicate the higher level of aromatic structures within fulvic acids isolated from sites with long-term agricultural use (high peat decomposition) compared with a land use history resulting in a lower peat decomposition. The different sources of fulvic acids in surface water (precipitation, runoff, interflow, groundwater) are the main reason for these effects not being detected in fulvic acids isolated from surface water. Short-term changes in land use characterized by a transition from crop farming to an unimproved grassland were found not to affect the spectroscopic properties of dissolved fulvic acids. A humification index deduced from the synchronous fluorescence spectra is proposed. We have strong evidence that dissolved humic substances indicate changes in the environmental conditions (both anthropogenic and natural) of wetlands with a high proportion of organic soils.     

Organic matter transformations and kinetics during sewage sludge composting in a two-stage system

The use of different proportions of rape straw and grass as amendments in the composting of dewatered sewage sludge from a municipal wastewater treatment plant was tested in a two-stage system (first stage, an aerated bioreactor and second stage, a periodically turned windrow). The composition of feedstock affected the temperature and organic matter degradation in the bioreactor and the formation of humic substances, especially humic acids (HA), during compost maturation in the windrow. The total HA content (the sum of labile and stable HA) increased according to first-order kinetics, whereas labile HA content was constant and did not exceed 12% of total HA. Δlog K of 1.0–1.1 indicated that HA was of R-type, indicating a low degree of humification. Temperature during composting was the main factor affecting polymerization of fulvic acids to HA and confirmed the value of the degree of polymerization, which increased only when thermophilic conditions were obtained.     

Characterization of natural organic matter (NOM) derived from sewage sludge compost. Part 1: chemical and spectroscopic properties

In this study changes in the properties of natural organic matter (NOM) were studied during composting of sewage sludge in a laboratory experiment using the pile method. Typical physicochemical parameters were measured during 53 days of composting including humic fractions. The effects of humification on the molecular properties of humic acids (HA) were investigated by 13C CP/MAS NMR spectroscopy. On the basis of chemical analyses, 53 days of composting sewage sludge with structural material can be divided into three phases: (i) domination of rapid decomposition of non-humic, easily biodegradable organic matter (two to three weeks), (ii) domination of organic matter humification and formation of polycondensed, humic-like substances (the next two weeks), (iii) stabilization of transformed organic material and weak microbial activity. Spectroscopic characterization (13C NMR) of compost humic acids reveals changes in their structures during maturation. The changes are highly correlated with the processes taking place in bulk compost.     

Microbial Community Growth and Utilization of Carbon Constituents During Thermophilic Composting at Different Oxygen Levels

Composting is characterized by dramatic changes in microbial community structure, to a high extent driven by changes in temperature and in the composition of the organic substrate. This study focuses on the interrelationships between decomposition of major classes in the organic material and dynamics in microbial populations during thermophilic composting of source-separated organic household waste. Experiments were performed in a 200-L laboratory reactor at 16, 2.5, and 1% O₂ in the compost atmosphere. Major classes of carbon constituents were analyzed by chemical methods, and the microbial biomass and community structure determined by fatty acid analyses with phospholipid fatty acids (PLFA) and total ester-linked fatty acids (EL) methods. At all three O₂ levels, the process was characterized by a rapid increase in microbial activity and biomass in the early thermophilic phase, although this period was delayed at the lower O₂ concentrations. Starch and fat were the main substrates utilized at all three O₂ levels during this period. The depletion of the starch fraction coincided with the beginning of a microbial biomass decrease, suggesting thatstarch is an important carbon substrate for the growth of thermophilic microorganisms during composting. Growth yields in the microbial community based on consumption of major carbon constituent classes in the high-activity period fell between 22 and 28%. Multivariate statistical analysis of changes in fatty acid composition revealed small, but statistically significant differences in the microbial community succession. At 16% O₂, 10Me fatty acids from Actinomycetes and cyclopropyl fatty acids (from Gram-negative bacteria) became more important with time, whereas 18:1ω7t was characteristic at 2.5 and 1% O₂, indicating a more stressed bacterial community at the lower O₂ concentrations. Although adequate composting was achieved at O₂ levels as low as 2.5 and 1%, it is not recommended to compost at such low levels in large-scale systems, because the heterogeneous gas transport through the material in these systems might lead to anaerobic conditions and inefficient composting.     

Isolation of humic acid from the brown algaPilayella littoralis

A standard humic acid extraction procedure has been used to isolate dark brown organic residues from samples of the macroscopic marine brown algaPilayella littoralis. The residues are insoluble in water, but soluble at high pH, and are similar in elemental composition, ash content, UV-visible, IR, PMR and X-Ray fluorescence spectra, X-Ray diffractograms and scanning electron micrographs to residues of a humic acid isolated from municipal compost. These results indicate thatPilayella produces humic acids.Author for correspondence     

The influence of topography on the nature of humic substances in soil organic matter at a site in the Atlantic Coastal Plain of South Carolina

The effect of topography on the nature of humic substances, isolated as water soluble organic carbon (WSOC), fulvic acid (FA), and humic acid (HA) was evaluated by comparing relative proportion and chemical characteristics of these fractions in upland and bottomland Coastal Plain soils in South Carolina. The fractions were characterized by elemental analysis and¹³C cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy. The majority of humic substances occur as humic acids, with bottomland soils having higher HA/FA ratios when compared to upland soils. We found no significant differences between upland and bottomland humic substances with respect to yields of WSOC and fulvic acids, and in the C and N content of humic and fulvic acids. Carbon-13 CPMAS NMR spectroscopy revealed that the WSOC and fulvic acid fractions were composed largely of O-alkyl-C structures with bottomland soils having higher amounts of these groups. Humic acid C distribution was similar between upland and bottomland soils and was largely composed of aromatic groups. Our results demonstrate that topography influences the formation of humic acid and the structural and chemical properties of the various humic fractions.requests for offprints     

Py-GC/MS analysis of sediments from Lake Biwa,Japan: characterization and sources of humic acids

Humic substances extracted and purified from bottom sediments of northern Lake Biwa, Japan, in November 2012 and 2013 were characterized using elemental analysis, Fourier-transform infrared spectroscopy, hydrogen-1 nuclear magnetic resonance (¹H NMR) analysis, and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). The infrared (IR) bands in the spectra of humic acids showed the presence of amide linkages and polysaccharides. Results of ¹H NMR analysis showed that the humic acids contained approximately twice the number of aliphatic protons as those in the Japanese soil standards used for comparison. Results of the Py-GC/MS analysis, which evaluates pyrolysis temperature dependency of the amount of pyrolysis products, showed that the generation of pyrolysis products in humic acids also differed from that in Japanese soil standards but was similar to that of phytoplankton in Lake Biwa. This analysis method is the first to provide extensive information about the chemical structure of humic substances; conventional Py-GC/MS provides limited information for a single temperature. Data suggest that humic acids in lake sediments are related to chemical characteristics of phytoplankton. Results shed new light on the origins of humic substances in deep-water-lake sediments and provide insights into material recycling in such sediments.     

Emission of Climate-Relevant Trace Gases and Succession of Microbial Communities during Open-Windrow Composting

Determination of different indicators of microbial biomass, community structure, and bioactivity by the fumigation extraction method, as well as determination of phospholipid fatty acids (PLFAs) and their subfractions and the measurement of trace gases, respectively, provides valuable information about microbial succession in composting processes. The emission rates of carbon dioxide (CO(inf2)), methane (CH(inf4)), and nitrous oxide (N(inf2)O) increased successively during compost maturation: initially in the presence of easily degradable nutrients, during high temperature, and after the temperature had cooled down, respectively. The emission rate patterns of these trace gases corresponded to the concentrations of PLFAs and their particular subfractions. (i) Similar to the CO(inf2) emission rates, microbial biomass estimations by fumigation extraction and by determination of the amount of total PLFAs showed a discontinuous decrease during the composting process, with a slight increase at the end of the observation period. (ii) An increase in ether lipids, indicating the enhanced presence of archaean methanogens, and an elevated CH(inf4) emission were observed at the same time. (iii) The period of enhanced N(inf2)O emission corresponded to the increase in beta and omega hydroxy fatty acids derived from the outer membrane. Additionally, the continuous increase in branched-chain fatty acids suggested an increase in gram-positive bacteria and actinomycetes, and the decrease in polyunsaturated fatty acids indicated a decrease in eukaryotic cells during the composting.     

Technical note: Examining the use of ethylenediaminetetraacetic acid for humic extraction of ancient bone

We examined the efficacy of ethylenediaminetetraacetic acid (EDTA) for removing humic contaminants from collagen extracted from ancient bone. Humic contaminants must be removed to obtain reliable stable isotope values from ancient bone collagen, given that humic acids have consistently lower δ¹³C values than collagen. The purpose of our research was to examine if EDTA treatment could effectively remove humic contaminants from bone collagen and thus serve as an alternative to the commonly implemented sodium hydroxide (NaOH) treatment, which may be associated with large collagen losses in poorly preserved samples. We compared the isotopic and elemental composition of ancient samples treated with EDTA alone, samples demineralized in hydrochloric acid (HCl) and rinsed in EDTA, samples treated with HCl alone, and samples demineralized in HCl and rinsed with NaOH. The samples used in the analyses were selected because they presented evidence of substantial humic contamination. We found that NaOH was the most effective agent for reducing humic contaminants as evidenced by the samples treated with this agent having higher δ¹³C values and lower C:N ratios relative to other treatments. The results from samples treated with EDTA suggest that this chemical cannot effectively remove humic contaminants given that these samples had significantly higher C:N ratios and lower δ¹³C and δ¹⁵N values relative to the HCl/NaOH treatment. Our results demonstrate that when performing stable isotope analysis of ancient bone collagen suspected to be contaminated with humic acids, NaOH is the most effective chemical agent to remove humic contaminants, while EDTA cannot perform this task.     

Nitrogen uptake in barley after spring incorporation of 15N-labelled Italian ryegrass into sandy soils

A 5-month laboratory incubation experiment was conducted to study the immobilization-mineralization of N in soil to which dried or composted ¹⁵N labelled ryegrass (Lolium italicum L.) had been added. Cellulose was added to dried ryegrass to give a C/N ratio similar to that of composted ryegrass. Exchangeable NH₄ ⁺ and NO₃ ^–, HCl-hydrolyzable N forms, microbial biomass N, NaOH-soluble and insoluble N were monitored during incubation. Dried ryegrass brought about a significant increase in total and labelled exchangeable NH₄ ⁺, while a rapid immobilization and a subsequent slow release of exchangeable NH₄ ⁺ was observed in soil with composted ryegrass, together with a resistance to degradation of the labelled humic substances. Compounds synthesized during the composting process and resistant to microbial decomposition probably caused an increase in the amino-acid fraction of soil. These findings suggest that composting can reduce the risk of N losses.     

The effects of humic substances within the Ah horizon of a Calcic Luvisol on morphological changes related to invertase and peroxidase activities in wheat roots

The chemical and biological characteristics of humus within the Ah horizon (Calcic-Luvisol) have been studied. Attention was paid to variation in the NMR spectra of humic fractions and ¹³C values and to how these changes are related to different biological humic fraction activities.The chemical changes in particular involve the decrease of the aromatic component and the increase of the non-aromatic component within the horizon and the different ¹³C value not only within the horizon but also among the humic fractions distinctive of different molecular sizes.An attempt has been made to explain the vertical chemical changes in terms of processes affecting the biological characteristics of the high and low molecular size humic fractions. The main conclusions are that the low molecular size humic fractions, in the upper part of the horizon, are of greater importance with respect to the other humic fractions in influencing the enzyme activities linked to growth metabolism. The biological role of the high molecular size humic fractions characterised by a relevant content of peptidic- and carbohydratic-C is also presented.     

Characterization of different decomposition stages of biowaste using FT-IR spectroscopy and pyrolysis-field ionization mass spectrometry

The decomposition stage and stabilization of organic matter in biowaste (mixture of yard waste and kitchen waste), originating from an open windrow process, were investigated using Fourier transform infrared (FT-IR) spectroscopy and pyrolysis-field ionization mass spectrometry (Py-FIMS). These investigations provided detailed information about chemical constituents and their behavior during the composting process. The chemical compounds were classified by their molecular signals in Py-FIMS. Multivariate statistical analysis revealed, that during the composting process, the group containing lipids, fatty acids and other chemical compounds with aliphatic skeletons changed the most. Corresponding with Py-FIMS findings changes were observed in absorbance bands of infrared spectra that reflect this group of organic compounds: the aliphatic methylene bands at 2925 and 2850cm^-1, the band of C=O vibrations of carboxylates at 1640cm^-1, the O=H in-plane bend of carboxylic acids, the CO₂ stretch of carboxylates and the CH₂ group of alkanes at around 1430cm^-1. During decomposition these bands decreased up to a steady level that indicated stabilization. The band at 1260–1240cm^-1 that can be assigned to the C=O stretch of carboxylic acids or to the C=N stretch of amides and the band of aromatic amines at 1320cm^-1 disappeared completely. The nitrate band at 1384cm^-1 appeared at a later stage of the composting process. The relative increase of chemical compounds like moieties of lignin, humic acids and tannins in the composted material contributed to the aromatic C=C band at around 1640cm^-1.