Transformation of rock phosphate during composting and the effect of humic acid

Summary Phosphorus from Mussoorie rock phosphate (MRP) was solubilized and transformed into available forms when MRP was incorporated during composting of organic wastes. Clusterbean and redgram utilized phosphorus efficiently from the phosphorus enriched compost containing 3.1% P when added in the soil of pH 7.6 to 7.8. The solubilization of phosphorus during composting has been attributed to the formation of humic substances.     

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.     

Hyphal growth and mycorrhiza formation by the arbuscular mycorrhizal fungus Glomus claroideum BEG 23 is stimulated by humic substances

Effects of humic substances (humic acid or fulvic soil extract) or saprophytic microorganisms (Paecilomyces lilacinus and an unidentified actinomycete) on growth of mycelium and mycorrhiza formation by Glomus claroideum BEG23 were studied in a hydroponic system. Humic substances stimulated root colonization and production of extraradical mycelium by the mycorrhizal fungus. Both humic and fulvic acids tended to decrease populations of culturable bacteria and fungi in the cultivation system, indicating a moderately antibiotic activity. The addition of saprophytic microorganisms able to use humic substances to the cultivation system further stimulated the development of the mycorrhizal fungus. However, stimulation of G. claroideum was also observed when the saprophytic microorganisms were heat-killed, suggesting that their effect was not linked to a specific action on humic substances. The results indicate that humic substances may represent a stimulatory component of the soil environment with respect to arbuscular mycorrhizal fungi.     

Water repellency of Casuarina windbreaks (Casuarina equisetifolia Forst.) caused by fungi in central Taiwan

The water repellent layer (WRL) in the Casuarina plantation near Taichung Harbor in central Taiwan is mainly due to the development of filamentous fungi. The hyphae of the isolated fungi and the metabolites of the TCHC-5 and TCHC-20 fungi are also significantly hydrophobic. In the soil layers, humic substances decrease the phosphorus fixation and contribute to the formation of WRL. The hydrophobic properties of humic substances are unfavorable for the nutrient cycling in this area. The water contact angles of fulvic acids and humic acids are pH-dependent. Increasing the solution pH value reduces the hydrophobic strength for fulvic acids and/or humic acids. TCHC-15 and TCHC-16 isolated fungi exude strong acidic metabolites (pH 2.7–3.0). This may result in polymerization and/or precipitation of fulvic acids and humic acids and increase the hydrophobic strength of the soil layers. Humic substances with aliphatic chains are the main components that form WRL in soils. Soil pH may be an indicator of the hydrophobic potential for organic matters.     

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.     

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     

A Study of the Decomposition of Reed (Phragmites australis ) as a Possible Source of Aquatic Humic Substances by Measuring the Natural Abundance of Stable Carbon Isotopes

The decomposition of leaf and steam litter of reed (P. australis) was measured both in the field and in the laboratory. The breakdown rates, the total carbon and the stable carbon isotope dynamics of reed litter were determined. The stable carbon isotope ratios of isolated humic substances (fulvic and humic acids) were also analysed. The δ¹³C value in reed remains increased from –26‰ to –24‰ for stems and from –27‰ to –26‰ for leaves. The dissolved fulvic and humic acids isolated from the experimental bottles (mean δ¹³C was –27.6‰) and the reservoir water were depleted in ¹³C (mean δ¹³C was –28.6‰) relative to the reed remains. The results show that reed litter is an important source of coloured aquatic humic substances. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of the maturity of wood waste compost on the structural features of humic acids

An analytical scheme for the separation of humic substances (HSs) and non-humic substances (non-HSs) was established to estimate the humification index (HI), which was defined as the ratio of HS carbon content to non-HS carbon content. The alkaline compost-extract contained a mixture of HSs and non-HSs, while acidification of the compost-extract resulted in precipitation of humic acid (HA). The acidified supernatant contained fulvic acid (FA) and non-HSs. In the present study, DAX-8 resin was used to separate FA and non-HSs. HI values, which were estimated to evaluate the maturity of wood waste compost, increased with composting duration. To determine the effects of compost maturity on HA structural features, correlations between HI and indicators of the degree of HA humification (atomic ratios, acidic functional group contents, spectroscopic parameters and molecular weight) were investigated. HI values were significantly related to the indicators of the extent of HA humification during composting.     

冻融环境下亚高山森林凋落叶添加对土壤腐殖质动态的影响

亚高山森林土壤形成过程中,胡敏酸、富里酸等腐殖物质的累积是维持土壤肥力及物质循环的重要途径,它受到土壤基质质量、凋落叶和环境因素的调控.本研究以川西亚高山典型的针叶林、针阔混交林和阔叶林土壤为对象,采用室内培养控制冻融环境和凋落叶添加的方法,研究冻融环境下凋落叶添加对土壤腐殖物质累积的影响.结果表明:冻融循环环境下针叶林土壤腐殖质含量升高,而针阔混交林和阔叶林土壤腐殖质含量降低,且凋落叶对土壤腐殖质含量无显著影响.培养前期冻融环境下3种林型土壤胡敏酸净累积,净累积量大小为针阔混交林>针叶林>阔叶林,富里酸含量下降,下降程度为阔叶林>针阔混交林>针叶林,且凋落叶对土壤胡敏酸和富里酸含量无显著影响.随培养时间的延长,3种林型土壤胡敏酸及富里酸含量均下降.这表明,凋落叶对土壤腐殖质含量的影响与土壤基质质量存在密切关系,且受到冬季土壤冻融时间长短的影响.     

Effects of humic and fulvic acids on growth of tobacco

Summary Organic matter was extracted with a mixture of 0.1M Na₄P₂O₇ and 0.1M NaOH from soil and a commercial organic matter product, Aqua Humus, and separated into humic and fulvic acids according to their solubility in acid and alkaline solutions. They were purified by passage through a cation exchange resin, freeze-dried, and used for characterization and seedling growth studies. The CEC increased with pH for both humic and fulvic acids. Data from tobacco seedling studies show that humic and fulvic acids from both sources increased root number and length at low concentrations while at high concentrations, humic acids inhibited length and number of roots but fulvic acids had no effect. The results support the proposition that fractions of organic matter referred to as humic and fulvic acids affect root development by means other than as a source of nutrients.     

UV spectroscopy: a tool for monitoring humification and for proposing an index of the maturity of compost

Composting organic matter is an interesting way to valorize waste. Compost is a product obtained after a humification process. The humification of organic matter during composting was studied by the quantification and monitoring of the evolution of humic substances. The final objective was to be able to evaluate the state of humification based on a spectrum of total humic substances using the method of UV spectral deconvolution. This study presented a new index obtained by UV spectroscopy using the deconvolution of an unknown spectrum of compost with 3 reference spectra. This index was compared to the maturity indices usually used, such as total extraction of humic substances (rate of extraction), IP (index of polymerization) or the humic acid to fulvic acid ratio. This new parameter, which was easy and quick to determine, gave precise information about the quality of the compost. It made it possible to disregard the values of aberrant concentrations caused by the classical protocol of extraction. Compared to the humic acid to fulvic acid ratio, the new index obtained by UV spectral deconvolution showed more representative results: the humic acid to fulvic acid ratio for an apparently non-mature compost was abnormally high, suggesting that the compost was mature, whereas the UV index proposed showed that the compost was really young and not yet humified.     

UPTAKE OF CADMIUM BY FRESHWATER GREEN ALGAE: EFFECTS OF PH AND AQUATIC HUMIC SUBSTANCES1

The effects of humic substances and low pH on short‐term Cd uptake by Pseudokirchneriella subcapitata (Korshikov) Hindak and Chlamydomonas reinhardtii Dang were investigated under defined exposure conditions. The uptake experiments were run in the presence of either a synthetic organic ligand (nitrilotriacetate) or natural organic ligands (Suwannee River fulvic or humic acid). An ion‐exchange method was used to measure the free Cd²⁺ concentrations in the exposure solutions. At pH 5, measured free Cd²⁺ concentrations agreed with estimations made using the geochemical equilibrium model WHAM, but at pH 7 the model overestimated complexation by both Suwannee River fulvic and humic acids compared with the ion‐exchange measurements. Consistent with the metal internalization step being rate limiting for overall short‐term uptake, intracellular Cd uptake was linear for exposure times less than 20 min at pH 5 or pH 7 for both algal species. After taking into account complexation of Cd in solution, Suwannee River humic substances had no additional effects on cadmium uptake at pH 7, as would be predicted by the free ion model. This absence of effects other than complexation persisted at pH 5, where the tendency of humic substances to adsorb to the algal cell surface is favored. Changes in pH strongly influenced Cd uptake, with the intracellular flux of Cd being at least 20 times lower at pH 5 than at pH 7 for P. subcapitata. Our results support models such as the free ion model or the biotic ligand model, in which humic substances act indirectly on Cd uptake by reducing the bioavailability of Cd by complexation in solution.     

Seasonal changes in the concentration and colour of humic substances in some aquatic environments

SUMMARY. 1. Between February and September 1974, concentrations of fulvic and humic acids in waters from a cryoboreal region of the Precambrian Shield in Quebec varied between 0.5–6.1 mg 1⁻¹ and 0.1–6.5 mg 1⁻¹ respectively. Whereas the fulvic acids usually remained relatively constant during this period, humic acids showed appreciable increases.
2. The number and weight average molecular weights of the fulvic acids (∼5000 and ∼22,000 daltons respectively) were lower than those of the humic acids (∼20,000 and ∼75,000 daltons respectively). The average molecular weight of the aquatic humic matter often decreased during late summer and early autumn. During spring floods the molecular weight of fulvic acids increased and that of humic acids declined.
3. Because the aquatic humic acids were more intensely coloured than fulvic acids, they contributed more than 30% of the colour of the water even though they accounted for only 15% of the concentration of humic matter. The colour intensity of both fulvic and humic acids generally appeared to increase during the latter part of the summer, when there was normally a decrease in the value of the colour quotient (E₄/E₆ ratio), indicating the accumulation in the waters of more humified material.     

Changes in the Structure and Properties of Alkali-Soluble Humic Substances in Phosphorus-Enriched Gray Forest Soil

The dynamics of spectral and kinetic properties of alkali-soluble humic substances in the gray forest soil were studied in the course of its incubation with NH₄H₂PO₄ (44.5 mg P per 100 g soil) for seven days, one year, and three years. The results provided evidence for consistent changes in the energy state of electrons in the functional groups of humic molecules extracted from the phosphorus-enriched soil. The structure of these molecules markedly changed by the end of the experiment, which was manifested in the increased number of coupled chromophores (due to the formation of additional C=C bonds) and the accumulation of new strongly polar functional groups (P=O). These changes provided for an increased solubility of soil humus in 0.1 N NaOH, higher saturation of dissolved humic substances with metals, and a different pattern of the distribution of carbon, metals, and phosphorus between the fractions of humic and fulvic acids.     

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.     

Removal of Humic Substances from Aqueous Solution by Fungal Pellets

The removal of humic substances from aqueous solution at pH=4.8 and 6.0 and 25 °C by pure culture of Aspergillus niger has been examined. The removal of humic substances from aqueous phase was monitored by following the decrease in absorbance at 370 nm. COD and fungal growth were also measured. The initial concentration of humic and fulvic acids, pH and diameter of fungal pellets were found to be the most important parameters. The results suggested that decolorization of batch culture was a consequence of several processes. In the first 5 hours for pellets with diameter 1-3 mm and 10 hours for pellets with diameter 2-5 mm adsorption of humic substances was dominant. Afterwards, desorption of slightly bound humic substances and their degradation, as well as degradation of remaining humic substances in the solution, continued simultaneously through the period of 10 days.     

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.     

川西亚高山森林凋落物去除对土壤腐殖质动态的影响

森林凋落物作为森林土壤腐殖质的主要来源, 在土壤腐殖质的形成中发挥着重要作用, 但不同森林类型凋落物因其含量、组成等的不同, 对土壤腐殖质的影响也不同。该研究以川西亚高山针叶林、阔叶林和针阔混交林3种不同森林类型为对象, 采用凋落物原位控制实验, 对比研究不同关键期凋落物去除对土壤可提取腐殖质、胡敏酸和富里酸含量及胡敏酸/富里酸、胡敏酸/可提取腐殖质的影响。主要结果: (1)土壤可提取腐殖质、胡敏酸和富里酸含量在不同森林类型中差异显著。土壤可提取腐殖质含量总体表现为针叶林>针阔混交林>阔叶林, 胡敏酸含量总体表现为针阔混交林>针叶林>阔叶林, 而富里酸含量则表现为针叶林>阔叶林>针阔混交林, 其中3种林型中土壤腐殖质的主要成分为富里酸, 总体均表现为富里酸型。不同采样时期也显著影响了土壤可提取腐殖质、胡敏酸和富里酸含量, 总体均表现为先升高后下降的趋势。除个别采样时期外, 凋落物去除总体降低了土壤可提取腐殖质、胡敏酸和富里酸的含量。(2)胡敏酸/富里酸和胡敏酸/可提取腐殖质的结果显示3种林型土壤总体腐殖化程度均较低, 整体表现为针阔混交林>阔叶林>针叶林, 凋落物去除在一定程度上有利于提高阔叶林与针阔混交林的腐殖质品质。(3)相关分析表明不同凋落物处理间土壤可提取腐殖质与土壤有机碳含量、全氮含量和土壤含水量呈显著正相关关系, 与温度呈显著负相关关系。综上所述, 短期的凋落物去除会降低土壤腐殖物质的含量, 但不同林型间由于凋落物类型差异会导致土壤腐殖质的不同变化, 说明土壤腐殖质的动态变化受凋落物类型以及环境因素的综合调控。因此, 关于凋落物变化对土壤腐殖质的影响还需进一步的长期研究。     

Influence of humic, fulvic and hydrophilic acids on the growth, photosynthesis and respiration of the dinoflagellate Prorocentrum minimum (Pavillard) Schiller

Blooms of the dinoflagellate Prorocentrum minimum often occur in coastal regions characterized by variable salinity and elevated concentrations of terrestrially derived dissolved organic carbon (DOC). Humic, fulvic and hydrophilic acid fractions of DOC were isolated from runoff entering lower Narragansett Bay immediately after a rainfall event and the influence of these fractions upon P. minimum growth, cell yield, photosynthesis and respiration was examined. All organic fractions stimulated growth rates and cell yields compared with controls (no organic additions), but the extent of stimulation varied with the fraction and its molecular weight. Greatest stimulations were observed with humic and fulvic acids additions; cell yields were more than 2.5 and 3.5 times higher than with hydrophilic acid additions while growth rates were 21 and 44% higher, respectively. Responses to additions of different molecular weight fractions of each DOC fraction suggest that growth rate effects were attributable to specific molecular weight fractions: the >10,000 fraction of humic acids, both the >10,000 and <500 fractions of fulvic acids and the <10,000 fraction of hydrophilic acids. The form and concentration of nitrogen (as NO₃⁻ or NH₄⁺) present also influenced P. minimum response to DOC; 10–20 μg ml⁻¹ additions of fulvic acid had no effect upon growth rates in the presence of NH₄⁺ but significantly increased growth rates in the presence of NO₃⁻, a relationship probably related to fulvic acid effects upon trace metal bioavailability and subsequent regulation of the biosynthesis of enzymes required for NO₃⁻ assimilation. The influence of DOC additions on P. minimum respiration and production rates also varied with the organic fraction and its concentration. Production rates ranged from 1.1 to 3.4 pg O₂ cell⁻¹ h⁻¹, with highest rates observed upon exposure to fulvic and hydrophilic acid concentrations of >10 μm ml⁻¹. Low concentrations (5–10 μg ml⁻¹) of humic acid had no statistically significant effect upon production, but exposure to concentrations >25 μg ml⁻¹ resulted in a 30% decrease in O₂ evolution, probably due to light attenuation by the highly colored humic acid fraction. Respiration rates ranged from 1.2 to 2.7 pg O₂ cell⁻¹ h⁻¹ and were elevated upon exposure to both fulvic and hydrophilic acids, but not to humic acid. These results demonstrate that terrestrially derived DOC fractions play an active role in stimulation of P. minimum growth via direct effects upon growth, yield and photosynthesis as well as via indirect influences such as interactions with nitrogen and effects upon light attenuation.     

Novel speciation analysis of copper in river water: observation of soluble anionic copper–ligand complexes

In natural water, copper is believed to be complexed with organic materials such as humic and fulvic acids, as well as anthropogenic substances such as ethylenediaminetetraacetic acid (EDTA). The nature of the complexes is known to be a main factor in determining copper toxicity to aquatic biota, as well as its geochemical transport. In this study, organically chelated copper species in river water were revealed to be classified into hydrophobic and anionic components using column cartridge separation techniques based on C18 and anion exchange. The amounts of anionic ligated copper species in the tested water samples ranged from 0 to 46 nM, and the average contribution of the anionic ligated copper to the total dissolved copper concentration was around 30 %. Several water samples contained discharged sewage effluents with high contents of EDTA, which may be the main chelating agent responsible for copper retention on the anionic ion exchange cartridge column. However, most of the river water samples were not contaminated with EDTA, and therefore, fulvic substances are expected to be responsible for retention. As this is the first observation of anionic copper species in the natural aquatic environment, further geochemical and biological studies of these substances should be undertaken.