Characteristics of soil organic matter (SOM) extracted using base with subsequent pH lowering and sequential pH extraction

Humic substances from eight soils of varying properties were extracted by two different methods: (1) the traditional NaOH-extraction with subsequent acidification to different pH (approximately 1 to approximately 12) and sequential extractions using 0.01 M NaNO(3) at incremental pH (approximately 1 to approximately 11). Cumulative organic matter (OM) in the sequential extractions showed properties that were consistent with NaOH-extracted OM. The release of Al and Fe in the sequential extractions was closely related with the release of organic carbon (OC). The ratio of OC associated with humic acid (HA) and fulvic acid (FA) (the HA:FA ratio) varied widely among the soils indicating heterogeneity in their OM composition. However, a significant correlation between this HA:FA ratio and the NaOH extractable %OC content of the soils is indicative of the possible relationship between them. Between pH 5 and 7, which is a typical soil solution pH, a significant amount of HA-associated OC was soluble. In modeling metal speciation in soil solutions, it has been assumed that all dissolved organic carbon (DOC) that is active toward metal binding is associated with FA. The results of this study indicate that the validity of these assumptions based on model sensitivity alone is questionable.     

Modelling the role of humic acid in radiocaesium distribution in a British upland peat soil

The significance of exchange sites on organic matter in the retention of radiocaesium in highly organic soils remains unclear. To quantify this retention, we measured the binding of 134Cs to a humic acid isolated from a British upland peat soil, under a range of chemical conditions. We interpreted our results using Humic Ion Binding Model V, a model of humic substance chemistry which simulates ion exchange by non-specific accumulation of cations adjacent to the humic molecules. Model V could simulate the humic acid-solution partitioning of Cs under all the solution conditions used. The model was used to estimate the contribution of organic matter to Cs sorption by the whole soil composite. An estimate of Cs sorption by illite frayed edge sites was also made. These simulations show that organic matter may play only a minor role in binding Cs. even in highly organic soils.     

The effect of fire on soil organic matter--a review

The extent of the soil organic carbon pool doubles that present in the atmosphere and is about two to three times greater than that accumulated in living organisms in all Earth's terrestrial ecosystems. In such a scenario, one of the several ecological and environmental impacts of fires is that biomass burning is a significant source of greenhouse gases responsible for global warming. Nevertheless, the oxidation of biomass is usually incomplete and a range of pyrolysis compounds and particulate organic matter (OM) in aerosols are produced simultaneously to the thermal modification of pre-existing C forms in soil. These changes lead to the evolution of the OM to "pyromorphic humus", composed by rearranged macromolecular substances of weak colloidal properties and an enhanced resistance against chemical and biological degradation. Hence the occurrence of fires in both undisturbed and agricultural ecosystems may produce long-lasting effects on soils' OM composition and dynamics. Due to the large extent of the C pool in soils, small deviations in the different C forms may also have a significant effect in the global C balance and consequently on climate change. This paper reviews the effect of forest fires on the quantity and quality of soils' OM. It is focused mainly on the most stable pool of soil C; i.e., that having a large residence time, composed of free lipids, colloidal fractions, including humic acids (HA) and fulvic acids (FA), and other resilient forms. The main transformations exerted by fire on soil humus include the accumulation of new particulate C forms highly resistant to oxidation and biological degradation including the so-called "black carbon" (BC). Controversial environmental implications of such processes, specifically in the stabilisation of C in soil and their bearing on the global C cycle are discussed.     

Acid-base characteristics of organic carbon in the HUMEX lake Skjervatjern

The Humic Lake Acidification Experiment (HUMEX) was launched in 1988 to study the role of humic substances in the acidification of surface waters and the impacts of acidic deposition on the chemical and biological properties of humic substances. This subproject was designed to determine the contribution of organic acids to the acidity of Lake Skjervatjern (the HUMEX Lake) and the impacts of the acidification on the characteristics of organic carbon. In order to get an empirical measure for organic acidity, dissolved organic carbon (DOC) was fractionated, isolated, and base-titrated from each half of Lake Skjervatjern. Hydrophobic acids were the dominant organic carbon fraction; the total organic acid content was generally greater than 80% of the DOC. The reliability of the fractionation procedure was tested with synthetic acids and the Nordic Fulvic acid. The DOC fractions did not show high variation over the 1.5-y acidification period. Hydrophilic acids had consistently greater exchange acidities compared to hydrophobic acids, averaging 12.9 μeq/mg DOC vs. 10.9 μeq/mg DOC, respectively. The dissociation of organic acids during acid-base titrations clearly increased with increasing pH. The high organic anion contribution to the ion balances indicates that humic matter is an important acidity source in Lake Skjervatjern. There are slight signs that the contribution of organic acids to overall lake acidity has decreased since acidification was initiated.     

Correlation of the partitioning of dissolved organic matter fractions with the desorption of Cd,Cu, Ni,Pb and Zn from 18 Dutch soils

Eighteen Dutch soils were extracted in aqueous solutions at varying pH. Extracts were analyzed for Cd, Cu, Ni, Pb and Zn by ICP-AES. Extract dissolved organic carbon (DOC) was also concentrated onto a macroreticular resin and fractionation into three operationally defined fractions: hydrophilic acids (Hyd), humic acids (HA) and fulvic acids (FA). In this manner, change in absolute solution concentration and relative percentage for each fraction could be calculated as a function of extraction equilibrium pH. The soils were also analyzed for solid phase total organic carbon and total recoverable metals (EPA Method 3051). Partitioning coefficients were calculated for the metals and organic carbon (OC) based on solid phase concentrations (less the metal or OC removed by the extraction) divided by solution concentrations. Cu and Pb concentrations in solution as a function of extract equilibrium pH are greatest at low and high pH resulting in parabolic desorption/dissolution curves. While processes such as proton competition and proton promoted dissolution can account for high solution metal concentrations at low pH, these processes cannot account for higher Cu and Pb concentrations at high pH. DOC increases with increasing pH, concurrently with the increase in Cu and Pb solution concentrations. While the absolute concentrations of FA and HA generally increase with increasing pH, the relative proportional increase is greatest for HA . Variation in HA concentrations spans three orders of magnitude while FA concentrations vary an order of magnitude over the pH range examined. Correlation analysis strongly suggests that HA plays a major role in increasing the concentration of solution Cu and Pb with increasing pH in the 18 soils studied. The percentage of the OC that was due to FA was nearly constant over a wide pH range although the FA concentration increased with increasing pH and its concentration was greater than that of the HA fraction at lower pH values (pH = 3-5). Thus, in more acidic environments, FA may play a larger role than HA in governing organo-metallic interactions. For Cd, Ni, and Zn, the desorption/dissolution pattern shows high metal solution concentrations at low pH with slight increases in solution concentrations at extremely high pH values (pH>10). The results presented here suggest that the effects of dissolved organic carbon on the mobilization of Cd, Ni, and Zn may only occur in systems governed by very high pH. At high pH, it is difficult to distinguish in this study whether the slightly increased solution-phase concentrations of these cations is due to DOC or hydrolysis reactions. These high pH environments would rarely occur in natural settings.     

Effect of shelterbelt on two kinds of soils on the transformation of organic matter

The changes of the total nitrogen, average yearly concentration of ammonia, nitrate ions, urease activity, total amount of amino acids in humic acids (HA) and the structure of humic acids were monitored in relation to the effect of shelterbelt as biogeochemical barrier located on a mineral and mineral-organic soil. The transformation of different forms of nitrogen in the soil under shelterbelt was strongly connected with the humification process and the molecular structure of humic acids.     

Study of Ni adsorption on NKF-6 zeolite

The adsorption of ⁶³Ni from aqueous solutions using NKF-6 zeolite was investigated by a batch technique under ambient conditions. The adsorption was investigated as a function of contact time, pH, ionic strength, foreign ions, humic substances (FA/HA) and temperature. The kinetic adsorption was well described by the pseudo-second-order rate equation. The adsorption of ⁶³Ni on NKF-6 zeolite was strongly dependent on pH and ionic strength, and the adsorption of ⁶³Ni increased with increasing NKF-6 zeolite content. At low pH values, the presence of FA enhanced the adsorption of ⁶³Ni on NKF-6 zeolite, but the presence of HA had no drastic effect. At high pH values, the presence of FA or HA decreased the adsorption of ⁶³Ni on NKF-6 zeolite. The adsorption isotherms were well represented by the Langmuir model. The thermodynamic parameters (i.e., ΔH⁰, ΔS⁰and ΔG⁰) for the adsorption of ⁶³Ni were determined from the temperature dependent isotherms at 293.15, 313.15 and 333.15 °K, respectively, and the results indicate that the adsorption reaction was favored at high temperature. The results suggest that the adsorption process of ⁶³Ni on NKF-6 zeolite is spontaneous and endothermic.     

Impact of water quality parameters on the sorption of U(VI) onto hematite

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH < 6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH > 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.     

The molecular properties of humic substances isolated from a UK upland peat system: a temporal investigation.

The study concerns the possible changes in the molecular characteristics of humic materials isolated from the same source as a function of time. A great deal of data has been reported concerning the contrast in molecular characteristics of humic substances isolated from different environments. This has primarily been an attempt to identify source-specific molecular characteristics. However, data presented in this paper suggests that humic substances isolated from a single catchment have significant changes in molecular characteristics over time. Two naturally occurring peat pools (X and Y) situated upon a small organic catchment on Great Dun Fell, Cumbria, UK were sampled monthly between November 1994 and November 1996. Dissolved organic matter (DOM) from the pool water samples was fractionated using macroporous nonionic resins (XAD8 and 4), and the humic, fulvic and hydrophilic acids were collected. These fractions were analysed for elemental composition (C, H and N), weight average molecular weight, functional group content and adsorption (340 nm) of a 1 g l(-1) solution measured in a 1-cm spectrophotometer cell. The molecular characteristics were compared to those of natural DOM described by Scott et al. (1998). Scott et al. reported that drought conditions and seasonal climatic changes could have appreciable effects upon molecular characteristics of natural DOM. Results showed that the atomic H/C ratio of the humic substances increased immediately after strong drought conditions experienced in the summer of 1995. This change was temporary with atomic H/C ratio decreasing gradually over the following months. A similar decrease was observed in the carboxyl group content of the isolated compounds. The data set suggested that atomic H/C ratio in the fulvic and hydrophilic fractions exhibited seasonal characteristics of higher ratios during the late summer/early autumn months. This was not observed in the humic fraction. Humic acids exhibited a seasonal pattern of higher weight average molecular weight during the summer months. These trends were explained in terms of summer production of DOM in the catchment soils, their sequestering in the soil due to limited soil water movement during the summer months and their relative ease of dissolution when rainfall and soil water movement increased during the late summer/early autumn period. The results were found to support seasonal and long-term patterns observed in natural DOM as reported by Scott et al. (1998).     

Role of the fungal mycelium in the retention of radiocaesium in forest soils

The aim of this work was to study possible binding of 137Cs to various organic components in the soil and fungi, by using various sequential extraction procedures. The retention and binding of 137Cs has been studied in two horizons Of/Oh and Ah/B of a Ukrainian forest soil. The exchangeable fractions 137Cs from soil (sum of H2O and 1 M NH4OAc fraction) were found to be 12% in the organic-rich layer (range 11-14%) and 23% in the organic-poor (range 20-29%). The hydrolysis with 10% H2SO4 resulted in an additional release of 30% of 137Cs from the organic-rich soil (range 30-35%) and 38% from the organic-poor soil horizon (range 27-53%). Extraction with 30% H2O2 released 11 and 15% of the 137Cs activity from organic-rich and organic-poor soil horizons. The corresponding values for treatment with 98.8% NaOCl were about 27% in both types of soil. About 11% of the total 137Cs activity was found in the humic acid fraction, about 5% in the fulvic fraction and 46% in the residue fraction. Relatively high level of 137Cs activity in soil (ca. 50%) was thus still left unsolved in the residue fraction. About 29% of 137Cs activity concentration in fungal mycelia was found as water soluble with a range of 11 to 41%. Additionally 24% of the 137Cs activity from mycelia was released by 1 M ammonium acetate extraction. Together, water and 1 M ammonium acetate extraction released about 53% of the total 137Cs activity in the mycelia. In fruit bodies of mycorrhizal fungi, 68% of the total 137Cs inventory was found to be water soluble at room temperature and 93% at 80 degrees C.     

Partition of iodine (¹²⁹I and ¹²⁷I) isotopes in soils and marine sediments

Natural organic matter, such as humic and fulvic acids and humin, plays a key role in determining the fate and mobility of radioiodine in soil and sediments. The radioisotope ¹²⁹I is continuously produced and released from nuclear fuel reprocessing plants, and as a biophilic element, its environmental mobility is strongly linked to organic matter.Due to its long half-life (15.7 million years), ¹²⁹I builds up in the environment and can be traced since the beginning of the nuclear era in reservoirs such as soils and marine sediments. Nevertheless, partition of the isotope between the different types of organic matter in soil and sediment is rarely explored. Here we present a sequential extraction of ¹²⁹I and ¹²⁷I chemical forms encountered in a Danish soil, a soil reference material (IAEA-375), an anoxic marine sediment from Southern Norway and an oxic sediment from the Barents Sea. The different forms of iodine are related to water soluble, exchangeable, carbonates, oxides as well as iodine bound to humic acid, fulvic acid and to humin and minerals. This is the first study to identify ¹²⁹I in humic and fulvic acid and humin. The results show that 30-56% of the total ¹²⁷I and 42-60% of the total ¹²⁹I are associated with organic matter in soil and sediment samples. At a soil/sediment pH below 5.0-5.5, ¹²⁷I and ¹²⁹I in the organic fraction associate primarily with the humic acid while at soil/sediment pH > 6 ¹²⁹I was mostly found to be bound to fulvic acid. Anoxic conditions seem to increase the mobility and availability of iodine compared to oxic, while subaerial conditions (soils) reduces the availability of water soluble fraction compared to subaqueous (marine) conditions.     

The volatilisation and sorption of (129)I in coniferous forest,grassland and frozen soils

129I is a potentially important radionuclide in safety assessments of proposed deep geological radioactive waste repositories due to its radiotoxicity, high mobility and long physical half-life (15.7 million years). In soils, iodine is present both in an inorganic form and in organohalide complexes, some of which are volatile under natural environmental conditions.This study has examined volatilisation, sorption and the effect of freezing on sorption and loss of (125)I (physical half-life 60.2 days), as a surrogate for (129)I, within coniferous forest and grassland soils. The results do not suggest that volatilisation from these soils is a significant pathway for the transport of (129)I. Strong and specific sorption of iodine to humic substances has been demonstrated, which is reduced at freezing temperatures. It is hypothesised that rapid sorption to soil humic substances can significantly reduce volatilisation rates. The effect of freezing conditions on iodine extractability from soils suggests a microbially mediated sorption process.     

鄱阳湖生态区长期施肥对稻田土壤碳汇效应与固碳潜力的影响

在施肥条件下确定平衡状态时,土壤有机碳含量水平对于正确评价土壤的固碳潜力和制定合理的有机物质分配措施具有重要意义。分析了前人研究的江西省有机碳储量数据并采用Jenny模型对长期不同施肥下有机碳动态数据进行模拟。结果表明,鄱阳湖生态区有机碳储量占全省的46%,以鹰潭地区最高,九江地区最低。施肥明显增强了土壤的碳汇作用,单施有机肥或有机无机肥配施（70F+30M、50F+50M、30F+70M、NPKM、NPK+S、NPK+P和NPK+C）处理的土壤有机碳含量明显高于施化肥处理,以南昌县的30F+70M、进贤县的NPKM和余江县的NPK+P处理最高,其平衡时有机碳含量和固碳潜力分别较施化肥处理提高了3061%和6115%、3017%和5496%、3826%和7479%。因此,提高鄱阳湖生态区农田有机碳密度和固碳潜力最有效方法是有机无机肥配施,其配施方式以猪粪配施化肥相对最好,配施比例以70%有机肥配施30%化肥为宜     

Changes of AhR-mediated activity of humic substances after irradiation

Humic substances (HS) and natural organic matter (NOM) are natural organic compounds ubiquitous in the environment. However, some studies indicate that both HS and NOM can act as xenobiotics, e.g. induce hormone-like effects in fish, amphibians and invertebrates. Molecules of these substances contain a number of aromatic rings and conjugated double bonds--the so called chromophores. Irradiation of dissolved HS and NOM can lead to a series of photochemical reactions which can act on these substances itself, or on other substances present in aquatic environment along with HS and NOM such as e.g. xenobiotics. In our previous study, we have found significant interactions of five humic acids (HA) with cytosolic aryl hydrocarbon receptor (AhR) in an in vitro bioassay based on H4IIE-luc cells. In the present study, we have studied the changes in AhR-mediated activities both of HS and NOM after irradiation that simulated natural solar light. Nine different HS and two NOM samples were irradiated in Pyrex tubes with a medium-pressure mercury lamp for a duration of 0 to 52 h (which corresponds to 0-52 d natural solar radiation). Original concentrations of the samples were 50 mg L(-1), and the greatest concentration of HS and NOM photoproducts subsequently tested in the bioassay was 17 mg L(-1), which is an environmentally relevant concentration. After irradiation the absorbances of all the samples were less than the original materials. The AhR-mediated activity of the HA-Fluka and HA Sodium Salt were partially decreased by irradiation. The activities of other HS and NOM, that were either AhR-active or -inactive were not changed by irradiation. The results of the study demonstrate that AhR-mediated activities of two active HA is caused by both photo-stable and photo-labile AhR activators, while the other three active HA contain only photo-stable AhR activators. Potential mechanisms of the observed irradiation-induced changes in AhR-mediated activities are discussed.     

Effects of soil amendments on lead uptake by two vegetable crops from a lead-contaminated soil from Anhui, China

Previous studies have documented that phosphate compounds of lead (Pb) [e.g., pyromorphite Pb5(PO4)3-(X), where X=OH, F or Cl] are comparatively insoluble, and their formation in Pb-contaminated soil may be a means of reducing the bioavailability and chemical lability of Pb in soil. In this study, the effect of phosphate compound amendments on the bioavailability of Pb in a polluted alkaline soil was examined. A Pb-contaminated soil was treated with hydroxyapatite (HA), phosphate rock (PR), water-soluble P fertilizer (single superphosphate, SSP) and the combination of HA with SSP. The bioavailability of Pb was determined in plant uptake studies with vegetables (Brassica campetris L. var. communis, BC) and Brassica oleracea L. var. acephala, BO) and sequential extraction. The results indicated that the Pb concentrations in both shoots and roots of two vegetable plants decreased with increasing quantities of added P compound, and the HA treatment had the best effect at the level of 5000 mg of P kg(-1)as compared with other treatments in which the Pb concentrations in shoots of BO and BC decreased 51.9% and 65.5%, respectively, and the Pb concentrations in roots of BO and BC decreased 67.3% and 57.2%, respectively, as compared with the control treatment. The SSP treatment had little effect on the Pb concentrations in plant tissues. Sequential extraction results indicated that the addition of soil amendments transform soil Pb from nonresidual fractions to residual fraction substantially. The effect of treatments followed this order at the equivalent P addition: HA>PR>HA+SSP>SSP. The results suggested that HA amendments can lower the bioavailability and increase the geochemical stability of soil Pb, so it has the potential for in situ remediation in Pb-contaminated soils.     

Specific Features of the Population Ecology of Creeping Thistle, Cirsium arvense(L.) Scop. s. l.

Two populations of creeping thistle (Cirsium arvense) growing in a field uncultivated for many years and on the sloping bank of an artificial pond were studied with respect to the demographic and chemical composition. The results showed that the contents of some elements in plants depend on specific features of the soil and plant population parameters (abundance, biomass, and ontogenetic composition). Some indices of the content of mineral substances in the population and soil proved to be difficult to interpret unambiguously.     

成都平原土壤铅污染及其评价

采用随机布点方法在成都平原采集了0~20cm耕层土样及20~40cm的底层土样共98个。分析了成都平原土壤铅含量状况,同时用地质累积指数法进行了污染程度评价,并对污染土壤的分布规律以及铅在土壤中的迁移进行了探讨。结果表明：成都平原大多数农田土壤已经受到不同程度的铅污染。在86个耕层土样中,只有20个样点没有受到铅污染。受铅污染的样点中,污染级别为1~4级,以1、2级为主,属无污染到中污染的过渡状态和中度污染。其中1级污染有33个样点（占总样点数的38.4 %）,2级污染有30个样点（占总样点数的34.9 %）。个别样点已接近或达到了强度污染的水平。污染土壤的分布与污染源的位置关系密切,与土壤的理化性质也有一定的关系;铅主要累积在0~20cm的耕层土壤,同时也发生了一定的迁移,其数量与土壤理化性质有关。     

The Effect of Soil Cultivation on the Humus State of Gray Forest Soil in the Middle Urals

The results of studies on the humus state of soils in agrosystems of the Middle Urals (1984–1997) are described. It is shown that the change of agricultural technologies (crop rotation, doses of organic fertilizers, etc.) transforms environmental conditions and the direction of humus formation processes. Parameters such as the concentrations of humus and water-soluble carbon and soil potential for humus accumulation reliably characterize the humus state of arable soil and allow the mobility and migration rate of humic substances to be monitored.     

Interactions of secondary amines with bentonite clay and humic materials in dilute aqueous systems

The speciation of dimethylamine, diethylamine, dibutylamine, and diethanolamine on bentonite clay saturated with 1) Na and Ca cations, 2) dodecyltrimethylammonium cation, and 3) tannic acid, and on humic acid and peat, has been studied. Adsorption isotherms were determined and the effect of ionic strength and pH on the adsorption were studied. The results show that the amines react with the particulates by ion exchange mechanisms. Hydrogen bonding seems to also contribute to the binding of dibutylamine.     

Effects of dissolved organic matter on toxicity and bioavailability of copper for lettuce sprouts

It is well known that dissolved organic matter in soil solution may affect the toxicity or bioavailability of heavy metals to plants, but existing information on various organic substances is insufficient for treating problems with heavy metal-contaminated soils. To clarify how dissolved organic matter alters the toxicity and bioavailability of metals, we germinated lettuce seeds exposed to solutions containing Cu and several kinds of dissolved organic matters. Low molecular weight organic acids (citric, malic, and oxalic acids) increased the toxicity and bioavailability of Cu, but low concentrations of the synthetic chelators ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine penta-acetic acid (DTPA) decreased the toxicity and bioavailability of Cu. In contrast, humic acid appeared to be the most effective organic substance for detoxifying Cu, even though it did not significantly decrease the bioavailability of Cu. Consequently, the bioavailability and toxic effects of Cu in soil depend on the nature of coexisting organic substances in the soil solution.