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PubMed2003

Comparison of three sequential extraction procedures used to study trace metal distribution in an acidic sandy soil.

On an acid sandy soil contaminated with trace metals (Fe, Mn, Cu, Pb and Zn), three sequential extraction procedures were compared to determine the efficiency of the reagents used and the effects of the step order on the fractionation of metal species. In all cases, a magnesium nitrate solution (MgNIT) was previously used to extract exchangeable forms. In the first procedure (I), the next extraction step was performed with sodium acetate buffer (NaOAc), as used on calcareous soils, to dissolve active calcium carbonate. Then trace metals bound to different forms of oxi-hydroxides (NH(2)OH, TAMOx and TAMAs fractions) were extracted before organic matter/sulfide oxidation with hydrogen peroxide at pH 2.0 in nitric acid medium (OMHyd). Finally, residual bound metals (RESID) in each procedure were extracted with a nitric-hydrofluoric-perchloric acid mixture. The second procedure (II) was the same as I, but without the NaOAc step, because of the absence of carbonate in the study soil. In procedure III, the NaOAc step was omitted and the oxidizable organic/sulfide fraction was extracted with sodium hypochlorite at pH 8.5 (OMOCl) before the reducible fractions. This study first showed that NaOAc may remove considerable amounts of metals (especially Mn and Zn) in other forms than exchangeable ones. Procedures II and III give similar results for Fe, Mn and Zn forms, which were mainly found in fractions of inorganic soil components, but not for Cu and Pb. Copper distribution was affected by the position of the oxidation step in the sequence. In procedure II, where the oxidation step (OMHyd) ended the sequence, Cu was mainly recovered in the TAMOx fraction. However, in procedure III, where the oxidation step (OMOCl) preceded the NH(2)OH, TAMOx and TAMAs steps, Cu was found in both OMOCl and TAMOx fractions. Lead distribution varied with oxidation reagent: it was partly removed in the OMHyd fraction of procedures I and II, and to a much lower extent in the OMOCl fraction of procedure III, probably due to the alkaline pH of the reagent in the latter case.

Acids↗
PubMed2006

Al-Fe interactions and growth enhancement in Melastoma malabathricum and Miscanthus sinensis dominating acid sulphate soils.

Plants growing in acid sulphate soils are subject to high levels of Al availability, which may have effects on the growth and distribution of these species. Although Fe availability is also high in acid sulphate soils, little is known about the effect of Fe on the growth of native plants in these soils. Two species dominating this soil type in Asia, viz. Melastoma malabathricum and Miscanthus sinensis were grown hydroponically in a nutrient solution with different concentrations of Al and Fe. Melastoma malabathricum is found to be sensitive to Fe (40 and 100 microm). Application of 500 microm Al, however, completely ameliorates Fe toxicity and is associated with a decrease of Fe concentration in shoots and roots. The primary reason for the Al-induced growth enhancement of M. malabathricum is considered to be the Al-induced reduction of toxic Fe accumulation in roots and shoots. Therefore, Al is nearly essential for M. malabathricum when growing in acid sulphate soils. In contrast, application of both Fe and Al does not reduce the growth of M. sinensis, and Al application does not result in lower shoot concentrations of Fe, suggesting that this grass species has developed different mechanisms for adaptation to acid sulphate soils.

Acids↗
PubMedDate not supplied

[Weight distribution and optical characteristics of soil humic acids fractionated by gel chromatography and electrophoresis].

Combination of gel chromatography on Sephadex and polyacrylamide gel electrophoresis was used to obtain molecular weight- and electrophoretic mobility-uniform fractions of humic acids from soil of different types (chernozem, sod-podzol, grey forest, and red soils). Extinction and color (E4/E6) coefficients, as well as weight distribution (%) were studied for all humic acids and their fractions. The fractions differed by the weight distribution (%). Sod-podzol and red soils had twice the amount of high-molecular and half the amount of low molecular HA fractions as compared to chernozem and grey forest soil.

Chemical Fractionation↗
PubMed2002

Consequences of elevated CO2, augmented nitrogen-deposition and soil type on the soluble nitrogen and sulphur in the phloem of beech (Fagus sylvatica) and spruce (Picea abies) in a competitive situation.

Mixed spruce-beech plantations grown in large open-top chambers (OTC) were used to study consequences of elevated CO2, nitrogen-deposition and soil type on plant internal nitrogen and sulphur cycling of juvenile beech (Fagus sylvatica L.) and spruce (Picea abies Karst.) in a competitive situation. Processes of re-cycling as a consequence of protein turnover during leaf senescence in autumn were of further interest. For this purpose, phloem sap was collected in September 1998 and analysed for the composition and concentrations of organic and inorganic nitrogen and sulphur compounds. The phloem exudate of spruce showed higher total soluble non-protein nitrogen (TSNN) concentration on calcareous soil than on acidic soil, independent of the treatment. N-fertilization increased the N-concentration of phloem exudate significantly on both soil types, mainly by an increase of Arg and Gln concentrations. Elevated CO2 slightly increased TSNN on calcareous, but not on acidic soil. The combination of elevated CO2 and augmented N-deposition induced a further increase of TSNN on calcareous soil, but caused a lower N-effect on TSNN on acidic soil. Arg, the main TSNN component in phloem exudate, mediated this effect. Since Arg is considered to be a major nitrogen storage compound, it is concluded that in autumn elevated CO2 and augmented N-deposition, influence storage of N rather than N-supply of spruce. An effect of elevated CO2 and augmented N-deposition on GSH and sulphate concentrations in phloem exudate of spruce was not observed on acidic soil. On calcareous soil augmented N-deposition enhanced, elevated CO2 decreased phloem exudate GSH contents. In combination, elevated CO2 compensated the positive effect of N-deposition. The effects of elevated CO2 and augmented N-deposition on phloem sap N- and S-contents described above were not observed for beech trees. Apparently, elevated CO2 and augmented N-deposition did not affect plants internal S and N cycling of beech grown in spruce-beech plantations.

Journal Article↗
PubMed1992

Gene probe analysis of soil microbial populations selected by amendment with 2,4-dichlorophenoxyacetic acid.

Soils with a history of 2,4-dichlorophenoxyacetic acid (2,4-D) treatment at field application rates and control soils with no prior exposure to 2,4-D were amended with 2,4-D in the laboratory. Before and during these treatments, the populations of 2,4-D-degrading bacteria were monitored by most-probable-number (MPN) enumeration and hybridization analyses, using probes for the tfd genes of plasmid pJP4, which encode enzymes for 2,4-D degradation. Data obtained by these alternate methods were compared. Several months after the most recent field application of 2,4-D (approximately 1 ppm), soils with a 42-year history of 2,4-D treatment did not have significantly higher numbers of 2,4-D-degrading organisms than did control soils with no prior history of treatment. In response to laboratory amendments with 2,4-D, both the previously treated soils and those with no prior history of exposure exhibited a dramatic increase in the number of 2,4-D-metabolizing organisms. The MPN data indicate a 4- to 5-log population increase after one amendment with 250 ppm of 2,4-D and ultimately a 6- to 7-log increase after four additional amendments, each with 400 ppm of 2,4-D. Similarly, when total bacterial DNA from the soil microbial community of these samples was analyzed by using a probe for the tfdA gene (2,4-D monoxygenase) or the tfdB gene (2,4-dichlorophenol hydroxylase) a dramatic increase in the level of hybridization was observed in both soils.(ABSTRACT TRUNCATED AT 250 WORDS)

2,4-Dichlorophenoxyacetic Acid↗
PubMed2003

Accumulating behaviour of Lupinus albus L. growing in a normal and a decalcified calcic luvisol polluted with Zn.

Lupinus albus L. is a leguminous plant that is starting to generate interest for the phytoremediation soils showing intermediate metal pollution. Among these metals, Zn causes major phytotoxicity problems and is common in polluted soils of central Spain. The purpose of this study was to explore the nutritional behaviour of this plant species towards increasing Zn concentrations in two calcic luvisol soils: a normal basic soil and a decalcified acid soil. For this purpose the effects of different Zn concentrations on mineral nutrition, growth, nodulation and nitrogenase activity of nodulated Lupinus albus cv. Multolupa plants has been investigated. A 12-week trial was performed in pots under greenhouse conditions. In each soil, four replicate pots were set up per treatment (100, 150, 300, 500 and 700 ppm Zn). Seeds were inoculated with a Bradyrhizobium sp. (Lupinus) strain ISLU-16. Statistical analysis of data revealed significant effects of soil Zn on grown, plant mineral composition and nodulation. Lupin growth was better in acid soil than in basic soil with the low dose of Zn applied, although plant growth in acid soil was severely affected from 300 ppm Zn, where the pH of the soil was 4.7. Zn application produce nutritional imbalances, especially with the higher dose added. Most of Zn accumulation occurred in the roots in both types of soils. In acid soil, lupin absorbs high amounts of Zn in both root (4650 ppm) and aerial part (3605 ppm), when the doses of Zn applied was 300 ppm. This feature permits Lupinus albus cv. Multolupa to be considered as potential phytoremediator and also for the revegetation of degraded landfill areas with slightly acid or neutral soils polluted with Zn.

Adaptation, Physiological↗
PubMed1986

Influence of ingestion of aluminum, citric acid and soil on mineral metabolism of lactating beef cows.

Lactating beef cows (16 Hereford and 34 Angus, 430 kg average body weight, aged 8 to 10 yr) were fed a basal diet containing 200 micrograms/g Al alone or supplemented with Al-citrate, citric acid, soil or soil plus citric acid for 56 d. Diets containing Al-citrate, soil and soil plus citric acid contained 1,730, 1,870 and 1,935 micrograms/g Al, dry-basis, respectively. Adding soil to the diet also increased Mg and Fe content of the diet. Aluminum values in ruminal contents of beef cows fed the basal alone or supplemented with citric acid, Al-citrate, soil or soil plus citric acid were 800, 990, 2,930, 3,410 and 2,910 micrograms/g, air-dry basis, respectively. Serum Mg and inorganic P declined (P less than .01) and urinary Ca concentration increased (P less than .01) for cows fed Al-citrate. By d 56, serum Mg was 1.5 and 2.2 mg/dl, and serum P was 3.8 and 6.8 mg/dl, for cows fed Al-citrate and basal diets, respectively. Calcium concentrations in urine were 281 and 11 micrograms/g for cows fed Al-citrate and basal diets, respectively. Citric acid, soil and soil plus citric acid had no detrimental effects on serum Mg and inorganic P, or urinary Ca concentration. By d 56, serum Ca was higher (P less than .06) in cows fed Al-citrate, compared with cows on the other four diets. Bone Ca, P, Zn and percent ash were not significantly affected by treatment but bone Mg tended to be slightly lower (P less than .07) for cows fed Al-citrate.(ABSTRACT TRUNCATED AT 250 WORDS)

Aluminum↗
PubMed2001

Sorption of weak organic acids in soils: clofencet, 2,4-D and salicylic acid.

The sorption behaviour of a new wheat hybridising agent (clofencet, 2-4-(chlorophenyl)-3-ethyl-2,5-dihydro-5-oxopyridazine-4-carboxylic acid) was investigated in batch equilibrium experiments and compared to that of two other organic acids (2,4-D and salicylic acid). Sorption coefficients Kd for the three compounds were determined in 18 Cambisols and Ferralsols. Kd values for clofencet were 0.3-9.4 l/kg for Cambisols and 2.1-68 l/kg for Ferralsols. Sorption of clofencet was strongly related statistically to that of salicylic acid. Sorption of clofencet and salicylic acid decreased exponentially with increasing solution pH in Cambisols whereas a bell-shaped curve was obtained for the sorption of salicylic acid in Ferralsols. Sorption of 2,4-D (2,4-dichlorophenoxyacetic acid) was not statistically related to the pH of the different soils. Positively charged oxide surfaces were shown to play a significant role in the sorption of clofencet and salicylic acid. The use of simple correlation and multiple linear regressions suggested that the main sorption mechanisms of clofencet in soils were likely to be ligand exchange on oxide surfaces and, to a lesser extent, cation bridging. Differences in the sorption behaviour of clofencet/salicylic acid and 2,4-D might be attributed to the possibility of the two former compounds forming bidentate complexes with metals.

2,4-Dichlorophenoxyacetic Acid↗
PubMed1992

Comparative impacts of forest harvest and acid precipitation on soil and streamwater acidity.

Annual H+ budgets were calculated for a catchment with a 65-year-old spruce-fir forest, and for an adjacent catchment at three years after a whole-tree harvest. In the harvested catchment sinks for H+ due to weathering and mineralization reactions were 85% greater, and sources of H+ due to biomass uptake were 60% greater than in the undisturbed catchment. There was an overall net consumption of 550 eq H+ ha(-1) year(-1) at year 3 after harvest compared to a net generation of 520 eq H+ ha(-1) year(-1) for the 65-year-old forest. Soil pH increased by 0.2-0.4 units soon after harvest, but there was little change in pH of streamwater from the harvested watershed. The whole-tree harvest resulted in a total production of about 30,000 eq H+ ha(-1) due to biomass removal. In contrast, wet and dry deposition at rates measured in this study could add more than 50,000 eq H+ ha(-1) in the 65-year period before the next harvest. Reducing the intensity of harvest may lessen long-term impacts of these sources of H+ on acidification of soils and streams.

Journal Article↗
PubMed2000

[Aluminum forms in acid sulfate soils].

With the method of sequential extraction, the extractable noncrystalline aluminum in Acid Sulfate Soils was fractionized into exchangeable Al (ExAl), absorbed inorganic hydroxy-Al(HyAl), organic complexed Al(OrAl), Fe oxide bound Al (DCBAl), interlayered Al(InAl) and noncrystalline aluminosilicate(NcAl) with average of 1.79, 2.51, 4.17, 4.14, 4.31 and 8.66 g Al2O3.kg-1, respectively. In actual Acid Sulfate Soils, the amount of different forms Al followed the order of NcAl > OrAl > InAl > DCBAl > ExAl > HyAl, but in potential acid sulfate soils, NcAl > InAl > DCBAl > HyAl > OrAl > ExAl. The average of the total extractable noncrystalline Al was 35.57 g Al2O3.kg-1, which covered 25.04% of the total amount of Al in Acid Sulfate Soils. The characteristic of extractable noncrystalline Al in Acid Sulfate Soils was the high proportion of active aluminum, such as ExAl, HyAl and OrAl. All forms of Al were closely related to the corresponding properties and ecological characteristics of Acid Sulfate Soils. The strong acid environment of actual Acid Sulfate Soils induced over-released Al, which transformed to active Al and resulted in Al toxicity.

Aluminum↗
PubMed2000

Evaluation of different approaches for modeling effects of acid rain on soils in China.

Acid deposition is an environmental problem of increasing concern in China. Acidic soils are common in the southern part of the country and soil acidification caused by acid deposition is expected to occur. Here we test and apply two different approaches for modeling effects of acid deposition and compare results with observed data from sites throughout southern China. The dynamic model MAGIC indicates that, during the last few decades, soil acidification rates have increased considerably due to acid deposition. This acidification will continue if sulfur deposition is not reduced, and if reduced more rapidly than base cation deposition. With the Steady State Mass Balance model (SSMB), and assuming that a molar ratio of Ca2+/Al3+ < 1 in soil water is harmful to vegetation, we estimate a slight probability for exceedance of the critical load for present deposition rates. Results from both modeling approaches show a strong dependence with deposition of base cations as well as sulfur. Hence, according to the models, changes in emission control of alkaline particulate matter prior to sulfur dioxide will be detrimental to the environment. Model calculations are, however, uncertain, particularly because available data on base cation deposition fluxes are scarce, and that model formulation of aluminum chemistry does not fully reproduce observations. An effort should be made to improve our present knowledge regarding deposition fluxes. Improvements to the model are suggested. Our work indicates that the critical loads presented in the regional acid deposition assessment model RAINS-Asia are too stringent. We find weaknesses in the SSMB approach, developed for northern European conditions, when applying it to Chinese conditions. We suggest an improved effort to revise the risk parameters for use in critical load estimates in China.

Acid Rain↗
PubMed2004

Effects of adding organic materials to an acid sulfate soil on the growth of cocoa (Theobroma cacao L.) seedlings.

Acid sulfate soils having a pH of less than 3.5 are widespread in Malaysia. Some of these soils are planted to cocoa, but the yield is reported to be low due to soil infertility related to Al toxicity. Cocoa growth is sensitive to the presence of Al in the soil. To a certain extent, Al toxicity in soils can be reduced by organic matter application and to a greater extent in iron-poor acid sulfate soil. A study was conducted to determine the efficacy of various types of organic materials easily available in the country to ameliorate acid sulfate soil infertility for growing cocoa seedlings. The treatments were control (nil), lime (3 t/ha), peat (10% w/w), peat plus green manure (10% w/w), peat plus rice straw (10% w/w), peat plus chicken dung (10% w/w) and peat plus POMS (Palm oil mill sludge) (10% w/w). The growth of cocoa seedlings was affected significantly by the presence of Al in the cocoa tissues. As the amount of Al in the leaves increased, the relative top dry weight of cocoa seedlings decreased. Likewise, the relative plant height was negatively correlated with Al in the leaves. Peat as well as peat in combination with green manure, rice straw, chicken dung or palm oil mill sludge was able to reduce Al toxicity in acid sulfate soil; the highest top dry weight of cocoa seedlings were obtained in the peat plus green manure treatment. The best cocoa seedlings root growth was found for the peat treatment alone. The relative top dry weight of cocoa seedlings was negatively correlated with Al(3+) as well as Al(3+)+Al(OH)(2+)+Al(OH)(2)(+) activity in the soil solution. The critical values for Al(3+) and the combination of Al(3+)+Al(OH)(2+)+Al(OH)(2)(+) activity in the soil solution were 10 microM and 15 microM, respectively.

Aluminum↗
PubMed1975

Ecology of soil arthrobacters in clarion-webster toposequences of iowa.

Toposequence variations in soil properties were characterized and related to variations in populations of total isolatable bacteria and arthrobacters. Increases in soil NO(3)-N, available phosphorous, NO(3)-N-producing power, Arthrobacter counts, and the percentage of the total counts represented by arthrobacters were correlated with decreases in soil acidity. The total bacterial counts were not correlated with soil acidity but were associated with percentage of soil organic matter and percentage of clay. The percentage of the total counts represented by arthrobacters was lowest at the summit position and increased downslope to the highest value in the toeslope position. Factor analysis of the data revealed that 67 to 81% of the total variance exhibited by all variables per site-sampling period could be accounted for by soil acidity, soil structure, soil fertility, soil moisture, and bacterial factors. A selective medium was developed for soil arthrobacters and tested on a wide variety of central Iowa soils to determine its potential as a medium for enumeration as well as isolation. The medium developed in this study was found to be superior to the other available direct-isolation media for soil arthrobacters.

Journal Article↗
PubMed1992

Biodegradation of soil humic acids by Streptomyces viridosporus.

Biodegradation of soil humic acids by Streptomyces viridosporus ATCC 39115 growing in a mineral salts--glucose medium was demonstrated. This biodegradation accompanies bacterial growth and is, therefore, presumed to be a primary metabolic activity, but humic acids were not used as the sole source of carbon. This bacterial activity was enhanced when cells were shaken and within a pH range of 6.5-8.5. In further experiments, the relative abilities of S. viridosporus to mineralized [14C]melanoidin, used as synthetic humic acid, were also established. In contrast to the white rot fungus Phanerochaete chrysosporium, another microorganism exhibiting humic acid degrading activity at acidic pH, poor extracellular activities were found in culture medium of S. viridosporus, and veratryl alcohol does not result in increased humic acid degradation. In spite of some peroxidase activity measured in culture filtrates and analyzed by polyacrylamide gel electrophoresis, the humic acid degrading system of S. viridosporus, in these experimental conditions, seems to be cell associated.

Biodegradation, Environmental↗
PubMed2000

Clostridium akagii sp. nov. and Clostridium acidisoli sp. nov.: acid-tolerant, N2-fixing clostridia isolated from acidic forest soil and litter.

Two anaerobic acid-tolerant bacteria, CK58T and CK74T, were isolated from acidic beech litter and acidic peat-bog soil, respectively. Both bacteria were spore-forming, motile rods with peritrichous flagella. The capacity to sporulate decreased with prolonged cultivation. Cells of CK58T formed chains or aggregates and were linked by a connecting filament that consisted of a core and a surrounding sheath. Cellobiose, glucose, xylose, arabinose, maltose, mannose and salicin supported growth of CK58T. These substrates, as well as mannitol, lactose, sucrose, glycerol, melezitose, raffinose and rhamnose, supported growth of CK74T. Sorbitol, trehalose, H2/CO2, CO/CO2, vanillate, Casamino acids, peptone, and various purines and pyrimidines did not support the growth of either organism. Growth of CK58T and CK74T on glucose yielded butyrate, lactate, acetate, formate, H2 and CO2 as end products. Growth of CK58T and CK74T was observed at pH 3.7-7.1 and 3.6-6.9, respectively. CK58T and CK74T grew in nitrogen-free medium at pH 3.7 under an N2 atmosphere and reduced acetylene at rates approximating 1 nmol min-1 (mg protein)-1. CK58T and CK74T did not contain carbon monoxide dehydrogenase or cytochromes, produce methane, or dissimilate nitrate or sulfate. Thus, CK58T and CK74T were characterized as nonacetogenic, N2-fixing, fermentative chemo-organotrophs. The G + C contents of CK58T and CK74T were 31.4 and 30.7 mol%, respectively. CK58T and CK74T were phylogenetically most closely related to Clostridium pasteurianum. The 16S rRNA gene sequence similarity values of CK58T and CK74T to C. pasteurianum and each other did not exceed 96.5%, and it is proposed that strains CK58T and CK74T be named Clostridium akagii CK58T (DSM 12554T) and Clostridium acidisoli CK74T (DSM 12555T), respectively. These results suggest that previously uncharacterized clostridial species reside and might fix N2 in the annoxic microzones of acidic forest soil and litter.

Anaerobiosis↗
PubMed2004

The contribution of alkali soluble (humic acid-like) and unhydrolyzed-alkali soluble (core-humic acid-like) fractions extracted from maize plant to the formation of soil humic acid.

Alkali soluble (humic acid-like material) (HA-like) (yield of 132 gkgdm(-1)) and the unhydrolized-alkali soluble (core-humic acid-like material) (core-HA-like) (yield of 33.4 gkgdm(-1)) fractions were extracted from maize plants and characterized by C and N determinations, DRIFT, and 1H and 13C-NMR spectroscopy. Fresh plants were subsequently incubated for 6 months in an artificial mineral soil, and the HA-like and core-HA-like trends were monitored quantitatively (C fraction content) and qualitatively (spectroscopic approach) in order to study their contribution to the formation of soil humic acid. During incubation the HAC-like partially degraded (loss of 320 gkgHAC(-1)) and partially formed new fulvic-like acids (160 gkgHAC(-1)). On the contrary, the stable fraction of HAC, the core-HAC-like, was maintained (loss of 153 kgcore-HAC(-1)), representing, after incubation, 846 gkg(-1) of the initial core-HAC-like content. The core-HA-like fraction is composed of lignin residues, polysaccharides, lipids and proteins, probably structured into a well-defined network, i.e. the plant cell wall.

Alkalies↗
PubMed2001

Interaction of imidazolinone herbicides with soil humic acids. Experimental results and molecular modeling.

Adsorption and desorption isotherms of the herbicides imazapyr, imazethapyr and imazaquin on a soil humic acid have been performed at pH 2.8 and 4.0 (below and above the pKa of the herbicides). At both pH, adsorption increased according to the lipophilic character of the molecules (imazapyr < imazethapyr << imazaquin). The extent of adsorption was higher at pH 2.8 than at pH 4.0 because of the partial ionization of the carboxylic groups of both herbicides and humic acids at increasing pH. Desorption of imazapyr and imazethapyr was nearly complete at pH 4 and higher than 60% at pH 2.8 while desorption of imazaquin was 45 and 8% at pH 4 and 2.8, respectively. No differences between adsorption isotherms at 10 degrees C and 25 degrees C were observed a pH 4.0 indicating that adsorption involved very weak bonds while at pH 2.8, adsorption was higher at 10 degrees C than at 25 degrees C indicating an exothermic process. The isosteric enthalpy of adsorption of each herbicide was low (about -1 kJoule mole(-1)) suggesting that low energetic bonds were involved. Adsorption on different humic acids has indicated that for each herbicide, the extent of adsorption expressed as Kd was correlated with the amount of carboxylic and aromatic groups of humic acids suggesting that hydrogen bonding and/or charge-transfer complexes formation could take place. Molecular modeling and geometry optimization of humic acid and soil organic matter (SOM) herbicide complexes were also performed. The results obtained with this theoretical approach gave a consistent chemical interpretation of the experimental results. To the best of our knowledge this is the first report to contribute to a better understanding of site-specific bonding of herbicides in SOM complexes by nanochemical modeling and distinct energy descriptors.

Adsorption↗
PubMed2004

Long term changes in the distribution and delta(15)N values of individual soil amino acids in the absence of plant and fertiliser inputs.

The long-term 'biodegradation' on soil amino acids was examined in the control plots of '42 parcelles' experiment, established in 1928 at INRA, Versailles (France). None of the plots is cultivated, but is kept free of weeds, and mixed to a depth of 25 cm twice yearly. Topsoil (0-10 cm depth) samples collected in 1929, 1963 and 1997 were subjected to acid hydrolysis (6 N HCl) for comparison. The distribution and delta(15)N natural abundance of 20 individual amino acids in the soils were determined, using ion chromatography (IC) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). The total N and amino acid-N (AA-N), respectively, decreased by 54 % and 73 % in the period from 1929 to 1997. The average N loss was comparable for 1929-1963 (period 1) and 1963-1997 (period 2), but AA-N loss was three times faster in the former period. This significant reduction in total AA-N content was mirrored in the individual amino acids, which decreased by 74 % +/- 1 % (ranging 58-89 %) between 1929 and 1997. The bulk delta(15)N values generally increased from 1929 to 1997, mainly associated with comparable or even higher increase of delta(15)N of the non-AA-N in the soil. The residence time (t(1/2), time in which half of N was lost from a specific soil pool) was ca. 65 +/- 5 years for the bulk soil, and comparable for periods 1 and 2. However, between periods 1 and 2 it decreased from 128 to 41 years in the non-AA pool, but increased from 59 to 92 years in the AA-N pool. Proline and amino acids that appear early in soil microbial metabolic pathways (e.g. glutamic acid, alanine, aspartic acid and valine) had relatively high delta(15)N values. Phenylalanine, threonine, glycine and leucine had relatively depleted delta(15)N values. The average delta(15)N value of the individual amino acids (IAAs) increased by 1delta unit from 1929 to 1997, associated with a similar rise from 1929 to 1963, and no change thereafter till 1997. However, the delta(15)N values of phenylalanine decreased by more than 7delta(15)N units between 1929 and 1997. The delta(15)N shift of IAAs from 1929 to 1963 and from 1929 to 1997 was not influenced by the relative amount of N remaining compared with the 1929 soil concentrations. The only exception was phenylalanine which showed decreasing delta(15)N associated with its decreasing concentration in the soil. We conclude therefore that in the absence of plant and fertiliser inputs, no change in the delta(15)N value of individual soil amino acids occurs, hence the original delta(15)N values are preserved and diagnostic information on past soil N (cycling) is retained. The exception was phenylalanine, its delta(15)N decreased with decreasing concentration from 1929 to 1997, hence it acted as a 'potential' marker for the land use changes (i.e. arable cropping to a fallow). The long term biological processing and reworking of residual amino acids resulted in a (partial) stabilisation in the soil, evidenced by reduced N loss and increased residence time of amino acid N during the period 1963-1997.

Amino Acids↗