Chemical characterization and decomposition of organic matter from two contrasting grassland soil profiles

Particle size fractions of soils from the surface 6 cm of two adjacent grassland plots which, as a result of different fertilizer treatments since 1897, have either a mor or a mull humus form were analysed using solid-state ¹³C nuclear magnetic resonance spectroscopy and fractionation of organic N by steam distillation. In the mor humus soil, which had received 180 kg (NH⁴)²SO⁴ ha^?1 annually and was pH 4.3, there was more C and N in the larger particle size fractions than in the mull humus soil (pH 5.8). The NMR spectra of correspondingly sized soil fractions were similar for both soils. The intensities of NMR signals between 0 and 40 ppm (alkyl-C) and between 160 and 200 ppm (carbonyl-C) increased with decreasing particle size. The intensities of the NMR signals between 60 and 90 ppm (0-alkyl-C) and between 90 and 110 ppm (acetal- and ketal-C) decreased with increasing particle size. Comparison of the NMR spectra of the >2000 um fractions from both soils with those of dried grass litter from the same plots indicated the exclusive plant origin of the C in the largest size fraction of the soils. NMR resonances between 40 and 60 ppm were attributed to alkyl-amino-C because their intensities agreed with the amino-N determinations obtained during organic N fractionation. During incubation in soil microcosms, the larger sized fractions decomposed more rapidly than the smaller fractions. However, all the correspondingly sized particle fractions from the two soils decomposed at the same rate except the >2000 pm fractions. The largest size fraction from the mor humus soil decomposed faster than that from the mull humus soil. This difference in decomposition rate could not be attributed to differences in the chemical composition of the >2000 pm fraction.     

Transformation of organic matter from maize residues into labile and humic fractions of three European soils as revealed by 13C distribution and CPMAS-NMR spectra

The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by ¹³C‐dilution analysis and CPMAS‐¹³C‐NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year‐long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ¹³C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS‐¹³C‐NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic‐rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of ¹³C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.     

A Comprehensive Study of Deep Catalytic Oxidation of Benzene, Toluene, Ethyl Acetate, and their Mixtures over Pd/ZSM-5 Catalyst: Mutual Effects and Kinetics

Reaction behaviors and kinetics of catalytic oxidation of benzene, toluene, and ethyl acetate with feed concentrations in the range of 700–5,000 ppm over Pd/ZSM-5 catalyst were investigated. Results for single components show that ethyl acetate (T ₅₀?=?190–200°C) is more easily oxidized than benzene (T ₅₀?=?215–225°C) and toluene (T ₅₀?=?225–235°C). The conversion of ethyl acetate was increased with the increase of its feeding concentration, while the opposite behaviors were observed for benzene and toluene as their conversion rates were decreased with the increase of the inlet concentration. Different behaviors were observed in catalytic oxidation of volatile organic compound (VOC) multi-components, the presence of benzene or toluene inhibits the conversion of ethyl acetate, and the aromatic hydrocarbons inhibit each other in all cases. Ethyl acetate possesses obvious inhibitory effect on benzene oxidation, while it is interesting to note that ethyl acetate has a promotion effect on toluene conversion. The kinetic data were fitted by the Power-law and Mars–van Krevelen kinetic models. The fitting result shows that the Power-law model is more suitable for predicting the conversion of benzene than the other VOCs, and the Mars–van Krevelen model can accurately express the reaction rate of all investigated VOCs.     

A comparison of water soluble organic substances in acid soils under beech and spruce in NE-Bavaria

Water soluble organic substances extracted from the L, O_f, O_h, A, and B horizons of acid soils under Beech (Fagus sylvatica) and Spruce (Picea abies) were fractionated on Sephadex G-25 (medium). Infrared, ¹H NMR and ¹³C NMR spectra of the fractionated components were obtained and comparisons were made among fractions, among horizons, and between forest types. Usually, the spectra indicated that carbohydrates dominated the water soluble fractions. Substances originated from spruce exhibited more undissociated carboxylic acid character than the beech derived material. Despite many similarities, principal differences in the carbohydrate components were found among fractions, among horizons, and between vegetation types.     

Sources and composition of soil organic matter fractions between and within soil aggregates

It is generally accepted that particulate organic matter derives from plants. In contrast, the enriched labile fraction is thought by many to derive from microbes, especially fungi. However, no detailed chemical characterization of these fractions has been done. In this study, we wanted to assess the sources (plants or microbes; fungi or bacteria) and degree of microbial alteration of (i) three particulate organic matter fractions – namely the free light fraction (1.85 g cm^?3), the coarse (250–2000 μm) and the fine (53–250 μm) intra‐aggregate particulate organic matter fractions – and of (ii) three density fractions of fine‐silt associated carbon – namely < 2.0, 2.0–2.2 (i.e. enriched labile fraction) and > 2.2 g cm^?3– by analysing the amino sugars, by CuO oxidation analyses, and by ¹³C‐, ¹H‐ and ³¹P‐NMR analyses. Macroaggregates (250–2000 μm) were separated by wet‐sieving from a former grassland soil now under a no‐tillage arable regime. The three particulate organic matter fractions and the three density fractions were isolated from the macroaggregates by a combination of density flotation, sonication and sieving techniques. Proton NMR spectroscopy on alkaline extracts showed that the enriched labile fraction is not of microbial origin but is strongly degraded plant material that is enriched in aliphatic moieties partly bound to aromatics. In addition, the enriched labile fraction had a glucosamine content less than the whole soil, indicating that it is not enriched in carbon derived from fungi. Decreasing yields of phenolic CuO oxidation products and increasing side‐chain oxidation in the order coarse intra‐aggregate particulate organic matter < fine inter‐aggregate particulate organic matter < fine‐silt fractions indicate progressive alteration of lignin as particle size decreases. The light fraction was more decomposed than the coarse inter‐aggregate particulate organic matter, as indicated by (i) its larger ratio of acid‐to‐aldehyde of the vanillyl units released by CuO oxidation, (ii) the smaller contribution of H in carbohydrates to total extractable H as estimated by ¹H‐NMR spectroscopy, and (iii) a larger contribution of monoester P to total extractable P in the ³¹P‐NMR spectra. In conclusion, the four fractions are derived predominantly from plants, but microbial alteration increased as follows: coarse inter‐aggregate particulate organic matter < light fraction ≈ fine inter‐aggregate particulate organic matter < enriched labile fraction.     

Evaluation of different fractions of the organic matter of peat on tetracycline retention in environmental conditions: in vitro studies

Purpose

Due to the modernization of the agro-industrial sector, compounds with different toxicity and effects on human health and animal have been used and consequently affecting the environment. Among them, tetracycline (TC) stands out as one of the antibiotics most commonly used worldwide. This study evaluated the TC interaction with different fractions of peat in natura and humic substances, humic acid, fulvic acid, and humin.

Materials and methods

The different fractions of the organic matter were characterized by organic matter content, elemental analysis, spectroscopic analysis (E₄/E₆), and nuclear magnetic resonance of carbon 13 (NMR ¹³C), and the interaction between TC and different fractions of organic matter was made by fluorescence spectrometry. We used the tangential ultra-filtration system for determining the complexation capability of humic substances (HSs), fulvic acids (FA), humic acids (HA), and humin (HUM) from peat with TC. Finally, we evaluated sorption kinetic experiments between TC and peat in natura.

Results and discussion

The peat samples, humic substances, FAs, HAs, and HUM were characterized by organic matter (OM), atomic ratio (H/C and C/O) calculated from elemental analysis data, functional groups quantified by NMR ¹³C data, and E₄/E₆ ratio, and the results show significant differences in the structural characteristics of the fractions of OM influenced by the type of microorganisms and environmental factors associated with this decomposition. Data analysis revealed the strongest interaction between HUM and TC (59.19 mg g^?1), followed by interaction between HS and TC (43.36 mg g^?1 HS). In the sorption studies, these conditions showed the best model to describe the system under consideration using the Freundlich model.

Conclusions

The results showed that the different fractions of the OM extracted from peat show different contributions that affect the bioavailability of contaminants to the environment.

     

Thermal oxidation does not fractionate soil organic carbon with differing biological stabilities

Thermal analysis techniques have been used to differentiate soil organic carbon (SOC) pools with differing thermal stability. A correlation between thermal and biological stability has been indicated in some studies, while others reported inconsistent relationships. Despite these controversial findings and no standardized method, several recently published studies used thermal analysis techniques to determine the biological stability and quality of SOC in mineral soils. This study examined whether thermal oxidation at temperature levels between 200°C and 400°C, combined with evolving gas analysis and isotope ratio mass spectrometry, is capable of identifying SOC pools with differing biological stability in mineral soils. Soil samples from three sites being under Miscanthus (C₄‐plant) cultivation for more than 17 years following former agricultural cropland (only C₃‐plant) cultivation were used. Due to natural shifts in ¹³C content, young and labile Miscanthus‐derived SOC could be distinguished from stable and old C₃‐plant‐derived SOC. The proportion of Miscanthus‐derived SOC increased significantly with increasing temperatures up to 350°C in bulk soil samples, indicating increasing oxidation of labile and young SOC with increasing temperatures. Use of density fractions to validate the thermally oxidized SOC from bulk soil samples revealed that the thermal oxidation patterns did not reflect the biological stability of SOC. The suggested biologically labile particulate organic carbon (light fraction from density fractionation) was clearly enriched in Miscanthus‐derived young SOC. The thermal oxidation patterns, however, revealed preferential oxidation of these biologically labile fractions not at low temperatures, but rather at higher temperatures. The reverse was found for the biologically stable mineral‐associated density fraction (heavy fraction). Based on different soil types, it was concluded that the thermal stability of SOC between 200°C and 400°C is not a suitable indicator of the biological stability of SOC and, thus, thermal oxidation is not capable of fractionating SOC pools with differing biological stability.     

Quantification of long‐chain fatty acids in dissolved organic matter and soils

The objective was to develop and adapt a versatile analytical method for the quantification of solvent extractable, saturated long‐chain fatty acids in aquatic and terrestrial environments. Fulvic (FA) and humic (HA) acids, dissolved organic matter (DOM) in water, as well as organic matter in whole soils (SOM) of different horizons were investigated. The proposed methodology comprised extraction by dichloromethane/acetone and derivatization with tetramethylammonium hydroxide (TMAH) followed by gas chromatography/mass spectrometry (GC/MS) and library searches. The C_10:0 to C_34:0 methyl esters of n‐alkyl fatty acids were used as external standards for calibration. The total concentrations of C_14:0 to C_28:0 n‐alkyl fatty acids were determined in DOM obtained by reverse‐osmosis of Suwannee river water (309.3 μg g^—1), in freeze‐dried brown lake water (180.6 μg g^—1), its DOM concentrate (93.0 μg g^—1), humic acid (43.1 μg g^—1), and fulvic acid (42.5 μg g^—1). The concentrations of the methylated fatty acids (n‐C_16:0 to n‐C_28:0) were significantly (r² = 0.9999) correlated with the proportions of marker signals (% total ion intensity (TII), m/z 256 to m/z 508) in the corresponding pyrolysis‐field ionization (FI) mass spectra. The concentrations of terrestrial C_10:0 to C_34:0 n‐alkyl fatty acids from four soil samples ranged from 0.02 μg g^—1 to 11 μg g^—1. The total concentrations of the extractable fatty acids were quantified from a Podzol Bh horizon (26.2 μg g^—1), Phaeozem Ap unfertilized (48.1 μg g^—1), Phaeozem Ap fertilized (57.7 μg g^—1), and Gleysol Ap (66.7 μg g^—1). Our results demonstrate that the method is well suited to investigate the role of long‐chain fatty acids in humic fractions, whole soils and their particle‐size fractions and can be serve for the differentiation of plant growth and soil management.     

Relation between carbon and nitrogen turnover in soil organic fractions of microbial origin

Labelled ¹⁴C-acetate and ¹⁵N-(NH₄)₂SO₄ were added to a clay soil in the laboratory to follow transformations of microbial C and N, A fungal population developed initially, reaching a maximum by day 5, then rapidly declined and was replaced by a population dominated by bacteria and actinomycetes. Soil samples containing doubly-labelled microorganisms and their metabolites were extracted by Na₄P₂O₇, and the extracted material further separated with phenol.The highly labelled acid-soluble (fulvic acid) fraction of the Na₄P₂O₇ extract contained extracellular metabolites of low molecular weight which were rapidly attacked and converted to new microbial biomass, metabolites, mineral N or CO₂. Na₄P₂O₇ also removed an acid-insoluble (humic acid) fraction of which up to 70 per cent of the labelled C and N could be removed by phenol. Attack of these recently synthesized extracellular materials was indicated by a rapid decline of Na₄P₂O₇ extractable C and N during the growth of bacteria and actinomycetes.Following Na₄P₂O₇ extraction, the residue was sonicated and peptized in water and the components of the microbial biomass were partitioned into sedimentation fractions by centrifugation. The components concentrated in the > 0.2 μm fraction, which were hypothesized as being cell wall components, were more resistant to attack than materials in the < 0.04 μm fraction. The materials in the latter fraction were thought to originate from cytoplasmic constituents. The labelled materials in the < 0.04 μm sized fraction, which accumulated as the fungal population developed, were utilized less rapidly by the developing bacterial population.Decomposition of the microbial population resulted in transfer of C and N through various sediment fractions. The organic fraction (considered to be cytoplasmic material and adsorbed extracellular metabolites) which became labelled as the bacterial population developed, was utilized less rapidly by the developing bacterial population than components removable by Na₄P₂O₇. Evolution of ¹⁴CO₂, production of microbial material and immobilization of N closely paralleled the incorporation and release of these elements from the fractions. The similarity of the behavior patterns of these elements suggested they were intimately associated within the soil microbial system studied. This demonstrated that N transformations were highly dependent on C transformations.     

The effect of organic amendments on mineral phosphate fractions in calcareous soils

Organic amendments considerably affect nutrient balance and interfraction mobility of nutrients by influencing the chemical, physical, and biological environment in soils. In this study, the effects of five amendments including: two composts, farmyard manure, packaging‐industry by‐product, and olive‐mill waste on time‐dependent interfraction mobility of P among mineral P fractions in two semiarid‐region soils differing in carbonate content and texture were investigated. Organic materials were applied at the rate of 0, 25, 50, and 100 g (kg soil)^–1 soil thoroughly mixed and incubated at 27°C ± 2°C for 110 d. Phosphorus fractions were sequentially extracted by 0.1 M NaOH + 1 M NaCl (NaOH‐P), citrate‐bicarbonate‐dithionite (CBD‐P), and 0.5 M HCl (Ca‐P). Results showed that organic amendments especially farmyard manure significantly influenced NaOH‐P, CBD‐P, and Ca‐P. In addition, higher application rates of organic residues increased NaOH‐P fraction. NaOH‐P and CBD‐P fractions were increased after addition of organic residues and then converted to Ca‐P fraction within the end of incubation period. Increasing application rate of organic residues allowed P to be retained in more labile fractions for a longer period. The amount of Ca‐P was found to be related with carbonate content of soils. It can be concluded that organic residues applied to calcareous soils may enhance P nutrition of agricultural plants.     

<Superscript>13</Superscript>C-NMR analysis of components of chernozem humic acids and their fractions with different molecular sizes and electrophoretic mobilities

Tandem size-exclusion chromatography and polyacrylamide gel electrophoresis were used for obtaining stable fractions of different molecular sizes and electrophoretic mobilities from chernozem humic acids (HAs). The obtained fractions were analyzed using solid-phase ¹³C NMR. The tendencies of the changes in the aromatic and aliphatic components of the HA fractions with different molecular sizes and electrophoretic mobilities were experimentally revealed. The aromatic-to-aliphatic carbon ratio C_arom (165–108 ppm)/C_aliph (108-0 ppm) was used for comparing the degrees of aliphaticity and aromaticity of the HA macromolecules. This ratio increased by more than five times when going from the high-molecular-weight to the low-molecular-weight fractions and largely determined their hydrophilic properties. The obtained results can be useful for the interpretation of the structural organization and the ecological functions of soil HAs and their fractions.     

Fractionation of dissolved organic matter on the XAD resin

Analytical fractionation conditions on the resin XAD-7H of organic substances from gravitational soil moisture influence the proportion and the yield of the extracted fractions. Increasing the column capacity factor k’ is accompanied by a decreased yield of hydrophobic fraction and the change in its composition. The sorption column capacity factor of k’ = 30 is sufficient for the extraction of all hydrophobic components from a soil solution with a concentration of C_DOM of ～25 mg/L.     

Intensive organic vegetable production increases soil organic carbon but with a lower carbon conversion efficiency than integrated management

Intensive vegetable production in greenhouses has rapidly expanded in China since the 1990s and increased to 1.3 million ha of farmland by 2016, which is the highest in the world. We conducted an 11‐year greenhouse vegetable production experiment from 2002 to 2013 to observe soil organic carbon (SOC) dynamics under three management systems, i.e., conventional (CON), integrated (ING), and intensive organic (ORG) farming. Soil samples (0–20 and 20–40 cm depth) were collected in 2002 and 2013 and separated into four particle‐size fractions, i.e., coarse sand (> 250 µm), fine sand (250–53 µm), silt (53–2 µm), and clay (< 2 µm). The SOC contents and δ¹³C values of the whole soil and the four particle‐size fractions were analyzed. After 11 years of vegetable farming, ORG and ING significantly increased SOC stocks (0–20 cm) by 4008 ± 36.6 and 2880 ± 365 kg C ha^?1 y^?1, respectively, 8.1‐ and 5.8‐times that of CON (494 ± 42.6 kg C ha^?1 y^?1). The SOC stock increase in ORG at 20–40 cm depth was 245 ± 66.4 kg C ha^?1 y^?1, significantly higher than in ING (66 ± 13.4 kg C ha^?1 y^?1) and CON (109 ± 44.8 kg C ha^?1 y^?1). Analyses of ¹³C revealed a significant increase in newly produced SOC in both soil layers in ORG. However, the carbon conversion efficiency (CE: increased organic carbon in soil divided by organic carbon input) was lower in ORG (14.4%–21.7%) than in ING (18.2%–27.4%). Among the four particle‐sizes in the 0–20 cm layer, the silt fraction exhibited the largest proportion of increase in SOC content (57.8% and 55.4% of the SOC increase in ORG and ING, respectively). A similar trend was detected in the 20–40 cm soil layer. Over all, intensive organic (ORG) vegetable production increases soil organic carbon but with a lower carbon conversion efficiency than integrated (ING) management.     

New qualitative approach in the characterization of antioxidants in white wines by antioxidant free radical scavenging and NMR techniques

The aim of this study was to obtain new information on antioxidant compounds in white wines. For this purpose, white wine degradation was promoted by a forced aged protocol, and six normally aged white wines from different vintages were analyzed. Both normal and forced aged wines were sequentially extracted using hexane and ethyl acetate. Apolar antioxidants were removed using hexane, and polar antioxidants were extracted with ethyl acetate. This last residue was subject to partial re-extraction with hexane and acetone. The antioxidant capacity of the wines and of each fraction was evaluated by two free radical methods, ABTS and DPPH. Normal aging provides a decrease in the total antioxidant capacity of wines. The antioxidant activity of ethyl acetate/acetone extracts was approximately 95% higher than that found for the hexane extracts. Concerning the forced aged wines, results showed that the wine submitted to a temperature of 60 degrees C for 21 days had higher antioxidant activity than that submitted to a temperature of 20 degrees C. With regard to the ethyl acetate/acetone extracts, oxygen and temperature treatment leads to a decrease in their antioxidant activity. NMR analysis was performed in the highest antioxidant capacity organic fractions (ethyl acetate/acetone extracts) and in the aqueous fraction of the control wine (T = 20 degrees C), in order to attempt the characterization of species involved in oxygen protection. Possible structures of antioxidant compounds in white wines were proposed. Two of these are tyrosol-like structures. This molecule is a well-known phenolic compound in wine, and it is reported to have antioxidative effects.     

Effects of urease and nitrification inhibitors on the efficient use of urea for pastoral systems

Abstract

The humic substances contained in an animal organic waste were extracted and the total extract separated into three humic fractions with different molecular weights (low, F₁ <10³; medium, F₂, with molecular weights ranging from 10³ to 10⁴; and high, F₃ >10⁴). The C content was highest in F₂, the same fraction also showing the lowest N content. The molecular weight of the humic fractions influenced the electrical conductivity, the highest molecular weight resulting in the lowest degree of electrical conductivity. Membrane-controlled ultrafiltra-tion (the method used to separate the various fractions from the whole extract) was also suitable for purifying such enzymes as phosphatase and β-glucosidase: the total activity obtained from the three fractions was considerably greater than that determined in the whole extract, Pyrolysis-gas chromatography (Py-GC) applied to the whole extract and humic fractions showed that in the F₃ fraction (highest molecular weight) benzene was the major fragment while furfural was the major fragment of F₁ (lowest molecular weight). For this reason, the humification index benzene/toluene indicates that the fraction with the highest molecular weight was the most humified while the furfural/pyrrole ratio indicates that the fraction with the lowest molecular weight was the most degradable. The whole extract and the fraction F₁ had a negative effect on seed germination when the concentration was equivalent to 100 mg kg^?1 of C, while the germination index was higher than that of the control when only 10 mg kg^?1 were used. The F₂ fraction had a positive effect on germination regardless of the concentration used. When 10 mg kg^?1 of C of the humic substances studied were added to the nutrient solution for growth experiments with maize plants, F₃ led to increases in root weight and F₂ led to increases in shoot weight. An inhibitor effect was observed for fraction F₁.     

Amount and composition of clay-associated soil organic matter in a range of kaolinitic and smectitic soils

In the global carbon cycle, soil organic matter (SOM) is a major source/sink of atmospheric carbon. Clay minerals stabilize part of the SOM through mineral–organic matter binding. Stabilization of organic matter is essential for tropical soils. Since the climatic conditions of the tropics favor decomposition of organic matter, tropical soils would be very poor in organic matter without this stabilization process. This research aims at determining the effect of clay mineralogy on the amount and composition of organic matter that is bound to the mineral surface. We focused on organic matter that is associated with kaolinite and smectite. We characterized kaolinite- and smectite-associated SOM in soils from seven countries, employing ¹³C NMR spectroscopy and Py-GC/MS. The content of carbon in the total clay-size fraction showed no significant difference between kaolinitic and smectitic soils. This suggests that the total amount of organic carbon in the clay-size fraction is independent of the clay mineralogy. We first extracted the clay fraction with NaOH and thereafter with Na₄P₂O₇. About half of the kaolinite-associated SOM was extractable by NaOH. In the smectitic soils, pyrophosphate extracted more organic carbon than did NaOH. The Py-GC/MS and NMR results indicate that kaolinite-associated SOM is enriched in polysaccharide products, while smectite-associated organic matter contains many aromatic compounds. We suggest that different clay minerals use different binding mechanisms to complex SOM. As a result, the composition of clay-associated organic matter would be influenced by the type of clay that is dominantly present in the soil.     

The effect of copper applications on the movement of copper and other elements in organic soils

Copper concentrations should be maintained at 100 ppm (gg Cu g^?1 dry soil) in the surface layers of undecomposed peat soils, and 400 ppm in humified muck soils. The Cu supports plant nutrition, and inhibits enzymes that degrade the organic soils (Histosols). The required or extravagant applications of Cu may threaten groundwater quality if the Cu, or elements displaced by the Cu, moves downwards in the soils. To test this, powdered CUSO₄.5H₂O was applied to the top 15 cm of replicated microplots of organic soils to increase their Cu concentrations by 0, 150, 500, and 1500 ppm at field sites A (peat) and B (muck) in May 1978 and by 0, 100, 300, and 800 ppm at field site C (mucky peat) in 1979. Duplicate cores of up to 50 cm depth were taken in the spring of 1981 from each of the 56 microplots and analyzed. At all sites, none of the Cu additions caused significant displacement and downward movement of Ca, Mg, K, Fe, Mn, or Zn. There was a leaching of small fractions of the applied Cu down to 40 cm depth only when 1500 ppm of Cu was added to the humus-poor, acidic peat at site A. Some of the Cu applied at the 500 ppm rate at site A and 1500 ppm rate at site B was found in the 20 to 30 cm zone. At site C, none of the applied Cu moved from the top 20 cm (plow layer).     

Soil organic carbon in density fractions of tropical soils under forest – pasture – secondary forest land use changes

Our knowledge of effects of land use changes and soil types on the storage and stability of different soil organic carbon (SOC) fractions in the tropics is limited. We analysed the effect of land use (natural forest, pasture, secondary forest) on SOC storage (depth 0–0.1 m) in density fractions of soils developed on marine Tertiary sediments and on volcanic ashes in the humid tropics of northwest Ecuador. The origin of organic carbon stored in free light (< 1.6 g cm^?3) fractions, and in two light fractions (LF) occluded within aggregates of different stability, was determined by means of δ¹³C natural abundance. Light occluded organic matter was isolated in a first step after aggregate disruption by shaking aggregates with glass pearls (occluded I LF) and in a subsequent step by manual destruction of the most stable microaggregates that survived the first step (occluded II LF). SOC storage in LFs was greater in volcanic ash soils (7.6 ± 0.6 Mg C ha^?1) than in sedimentary soils (4.3 ± 0.3 Mg C ha^?1). The contribution of the LFs to SOC storage was greater in natural forest (19.2 ± 1.2%) and secondary forest (16.6 ± 1.0%) than in pasture soils (12.8 ± 1.0%), independent of soil parent material. The amount of SOC stored in the occluded I LF material increased with increasing silt + clay content (sedimentary soils, r = 0.73; volcanic ash soils, r = 0.58) and aggregation (sedimentary soils, r = 0.52; volcanic ash soils, r = 0.45). SOC associated with occluded I LF, had the smallest proportion of new, pasture‐derived carbon, indicating the stabilizing effect of aggregation. Fast turnover of the occluded II LF material, which was separated from highly stable microaggregates, strongly suggested that this fraction is important in the initial process of aggregate formation. No pasture‐derived carbon could be detected in any density fractions of volcanic ash soils under secondary forest, indicating fast turnover of these fractions in tropical volcanic ash soils.     

Etude des diphenol oxydases extraites d'une litiere de foret

Study of diphenol oxidases extracted from beech litter. Lyophilized neutral sterile extract from the fermentation (F) layer of beech litter (NALF Extract) exhibited the chemical characteristics of humic acids. It possessed diphenol oxidase activities. The specific activities (sp. act.), given in parentheses, are expressed in nmoles O₂ absorbed mg C^?1 min^?1: p-crcsol (19.5); catechol (0.6); dl-3(3,4-dihydroxyphenyl)alanine (5.7); d(+) catechine (4.8) and p-phenylenediamine (7.1). The NALF Extract was polydispersed by G100 Sephadex column chromatography. The firsi peak kd ~ 0.05 (fraction I), the intermediate band (fractions II + III) and the second peak k_d ~ 1.02 and 1.38 (fractions IV + V). Diphenol oxidases were localized in fractions I, II and III. Electrophoretic studies have shown that the fractions I, II and III are heterogeneous. Chromatography on DEAE cellulose of fraction I permitted the separation of 30 per cent of the laccase activity in a form which is free from humic material.     

Differences in the chemical composition of dissolved organic matter from waste material of different sources

The chemical composition of waste-material-derived dissolved organic matter (DOM) was characterized by chemolytic analyses and ¹H, ¹³C and ³¹P nuclear magnetic resonance (NMR) spectroscopy. Dissolved organic matter was extracted by water from an aerobic fermented urban waste compost, a sewage sludge and a pig slurry and then fractionated using the XAD-8 method. The amount of water-extractable dissolved organic carbon (DOC) ranged from 3% in the sewage sludge to 22% in the pig slurry. Dissolved organic matter isolated from pig slurry was equally distributed between hydrophilic and hydrophobic DOC, whereas in the sewage-sludge-derived material the hydrophobic fraction was predominant. Dissolved organic C from the urban waste compost was mainly within the hydrophilic fraction. Wet-chemical analysis and ¹H- and ¹³C-NMR spectra showed that both DOM fractions from the urban waste compost were low in neutral, acidic and amino sugars as well as in lignin-derived compounds. In turn, the materials were rich in low-molecular-weight aliphatic compounds. The chemical structure of both fractions is probably the result of the intensive transformation of urban waste compost during its fermentation. The hydrophilic fractions of DOM from sewage sludge and pig slurry contained considerable amounts of carbohydrates but were also rich in low-molecular-weight aliphatics. The respective hydrophobic fractions had the largest contents of CuO-extractable phenols which may in part derive from sources other than lignin. By contrast with the other materials, the hydrophobic fraction from the pig slurry seemed to contain polymeric rather than low-molecular-weight material. The ³¹P-NMR spectrum of the hydrophilic DOM fraction from urban waste compost did not show signals of inorganic or organic P compounds while the spectrum of the hydrophobic fraction revealed traces of monoester P, diester P, and orthophosphate. ³¹P-NMR spectroscopy suggested that both the hydrophobic and hydrophilic fractions from pig slurry did not contain organic P. The hydrophilic DOM fraction from sewage sludge contained orthophosphate, organic monoester P and a little pyrophosphate. The hydrophobic fraction contained mainly organic diester P and smaller amounts of teichoic acids and organic monoester P. Considering that water-soluble fractions of urban waste compost contained no easily plant-available P and a low content of labile organics, we conclude that this material contains less labile nutrients and is more refractory than the soluble constituents of pig slurry and sewage sludge.