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1.
Stream-water samples were collected during a 4-year-period in twosmall streams, one whose catchment was ditched for forestry halfway through the sampling period and another nearby reference stream whose catchment was not ditched during this period. The main aim was to study the impact of forest ditching on stream-water quality. Whereas the artificial drainage did not change the hydrograph pattern, it had a large effect on stream hydrochemistry: the concentrations of suspended material, Mn, Ca, Mg and Al increased, theconcentrations of total organic carbon decreased, and pH increased by approximately one unit, from an average of 4.4 to 5.4. The increase in suspended material, Mn and Al concentrations is explainedby the physical mobilisation of mineral particulates/colloids from mineral soils (till) exposed on the ditch slopes beneath the peat layer, while the increase in Ca and Mg loads is explained by the release of Ca2+ and Mg2+ in exchange reactions in this same soil layer. The increase in pH and decrease in TOC concentrations after ditching are related to changes in hydrological flow paths in the catchments, and most likely to immobilisation of both hydrogen ions and humic substances in the near neutral till horizon exposed beneath the peat layer. Only the aquatic abundance of Fewas not significantly affected by the ditching.  相似文献   

2.
The topsoil temperature in arid areas of Xinjiang, China can be up to about 80°C in summer. This may significantly affect the chemical properties of soil humic substances. However, the effects of high temperature on characteristics of soil humic substances and their complexation with toxic metals are still poorly known. In the present study, binding of Hg(II) to unheated soil humic substances and heated soil humic substances from sandy soils was comparatively investigated using three-dimensional excitation?Cemission matrix (EEM) fluorescence spectroscopy. Two fluorescent peaks (peak I at Ex/Em?=?365?C370/470?C474?nm; peak II at Ex/Em?=?270?C275/468?C472?nm) identified as humic-like fluorescence were observed in the EEM spectra of humic substances. Both peaks were clearly quenched by Hg(II), indicating the strong interaction of humic-like substances with Hg(II), and showed blue shifts after heat treatment. Heat treatment caused an increase of the fraction of accessible fluorophore (f a), binding sites number (n) and effective quenching constants (logK a), indicating that more binding sites in humic substances could bind Hg(II) and form more stable humic substances?CHg(II) complexes after heat treatment. However, a decrease of binding constants (logK b) suggested that heat treatment would reduce the binding capacity of each binding site of humic substances to Hg(II). This study implies the transport of Hg(II) may be affected by high temperature in the arid zone due to the modification of the physicochemical properties of humic substances in soil.  相似文献   

3.
土壤腐殖质提取和分组综述   总被引：4，自引：0，他引：4  
土壤腐殖质的定量提取、分离与纯化是深入研究土壤腐殖质的重要前提。本文详细综述了国内外腐殖质提取和分组的实验手段和研究进展;以国际腐殖质协会提供的标准方法为参考,对比论述了提取剂种类,提取次数、提取剂用量等的选择;对比讨论了两种主要的土壤腐殖质的分组方法。超滤分离和体积排阻色谱是腐殖质物理化学表征研究中的两种新兴技术,笔者认为组合使用两种实验手段对土壤腐殖质进行细致的分离与分组研究有助于深化理解土壤腐殖质的化学性质和分子结构。  相似文献   

4.
Metal concentrations from stream waters in two geological blocks in Northern Ireland were compared to determine the contributions of catchment characteristics and in-stream conditions. One block is composed of metamorphosed schist and unconsolidated glacial drift with peat or peaty podzol (mainly humic) soils, while the other block consists of tertiary basalt with brown earth and gley soils. Water samples were collected from 52 stream sites and analysed for iron (Fe), manganese (Mn) and aluminium (Al) as well as a range of other chemical determinands known to affect metal solubility. Densities of metal-rich ochre deposit were determined for stream bed stone samples. Higher conductivities and concentrations of bicarbonate, alkalinity, calcium and magnesium occurred on basalt than on schist. Despite higher Fe and Mn oxide concentrations in basalt-derived non-humic soils, stream water concentrations were much lower and ochre deposit densities only one-third of those on schist overlain by humic soils. Neither rock nor soil type predicted Al concentrations, but pH and dissolved oxygen did. Peat-generated acidity and the limited acid neutralising capacity of base-poor metamorphosed schist have resulted in elevated concentrations of metals and ochre deposit in surface waters.  相似文献   

5.
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6.
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7.
Recent studies indicate that glassiness represents a characteristic feature of soil organic matter (SOM). It is however unknown, to which extent the transitions detected in humic substances and whole soil samples correspond to common models of synthetic polymers providing the theoretical basis for explaining their glass transition characteristics. Physical aging associated with structural relaxation of amorphous substances below their glass temperature is one fundamental basis for the glass transition behavior of synthetic polymers. According to the results of this study, aging processes also occur in SOM. In whole soil samples, this process can be observed by the shift of glass transition-like step transitions to higher temperatures within the time scale of years. Not only the structural relaxation of the macromolecular organic substances, but also interactions with water molecules, which may exhibit both plasticizing and antiplasticizing properties, influence the aging process of SOM. Especially under moistening or drying conditions, a differentiation between the effects of water and of alterations of the SOM structure in the course of time on the rigidity of the macromolecular network is difficult.  相似文献   

8.
Cross-linking of humic substances with organic bridging groups is thought to contribute to the humification of soil organic matter. Model cross-linked humic substances were prepared by cross-linking Amherst soil humic acid by a diepoxide and a polycarboxylic acid, applying procedures established for cross-linking of polymers and textile fabrics. Products of the cross-linking reactions were analyzed by FTIR and 13C CPMAS NMR. Physicochemical properties of the products were determined by solubility experiments and thermal analysis. The incorporation of the cross-linker into the matrix of the humic acid by covalent linkages was confirmed by both the disappearance of bands of the reactive functional groups of the cross-linker in the FTIR spectrum and the increase of signals related to the incorporation of the cross-linker into the matrix of the humic acid in the FTIR and 13C CPMAS NMR spectra. The formation of covalent ester and ether linkages by the cross-linking reaction was indicated. Water solubilities at pH 6.2 of the cross-linked samples as determined by UV/Vis spectrometry were reduced compared to controls. Fewer water molecule bridges were formed in the cross-linked samples, which was attributed to a lower number of available functional groups and increased distances between humic acid strands caused by the cross-linking molecules. Reduced reactivities of humic acid strands in the cross-linked samples further indicated successful cross-linking. The reactions investigated in this study can be regarded as models for reactions occurring in natural soils to test the significance of cross-linking reactions in the humification process of soil organic matter and the physico-chemical properties and ecological function of organic matter in geosolids.  相似文献   

9.
Lignite samples from two deposits located in the Megalopolis Basin, Southern Greece, were evaluated for their potential applicability as raw materials for the production of organomineral fertilizers. Fundamental chemical analyses were carried out to demonstrate high humic substances and metal contents. To determine their relative distribution in the Megalopolis lignite extract, eight elements, namely Na, K, Cd, Mn, Mg, Pb, Zn, and Cu, were studied both in H2O and in Na4P2O7/NaOH solutions. The behavior of these metals showed significant variations; Zn, Pb, Cd, and Cu associate mostly to the humic substances and proved scarce in the water extract. Contrarily, K and Mg gave a significantly low total yield in the Na4P2O7/NaOH solution, while Mn was classified among the least extracted elements. Further enrichment of Megalopolis humic substances in these metals was achieved; Pb and Mg proved the most and least retained metal, respectively. Decomplexation titration curves of humic matter saturated with these metal ions demonstrated that novel organomineral fertilizing materials may develop based on optimized metal ion and humate contents, which can retain metals in a soluble form within a wide pH range. Formation of complexes between humic substances and Zn, Cd, and Mg was clearly indicated.  相似文献   

10.
《Applied Geochemistry》1997,12(5):593-605
The impact of sediment type on stream water geochemistry was studied in a catchment in Finland affected by sulphidic fine-grained sediments. Stream water samples for general characterisation of water quality (pH, electrical conductivity) were taken at the basin outlet during various hydrological conditions, while samples for detailed geochemical analysis were collected at 119 sites in the catchment on one single occasion during high-water flow in autumn. The occurrence of sulphidic fine sediments was estimated based on data from an airborne electromagnetic survey carried out by the Geological Survey of Finland.Growing-symbol maps, which were prepared for each of the studied variables in water, and statistical calculations including factor analysis and Spearman correlations show that the concentrations of Al, Ga, U and Tl, all the lanthanides and several alkali and alkaline earth metals (K, Mg, Na, Li, Ca, Rb, Sr), transition metals (Cd, Co, Cu, Zn, Sc, Mn, Ni, Y, Hf) and non-metals (S, Br, I, Si) increase in water when the proportion of the catchment cover of sulphidic fine sediments increases. It is therefore argued that these elements are released and mobilised in considerable amounts by the oxidation and subsequent acidification and weathering of this type of sediment. Other elements are either slightly depleted in streams in areas of sulphidic fine sediments (V, Nb, Pb, Zr), have a distribution unrelated to sediment type (Fe, Cr, Cs, Mo), or are only weakly impacted by the occurrence of sulphidic sediments in the catchment (As, Ti, Ba). It is argued that these elements are not leached extensively from the oxidising sulphidic sediments, and that their distributions at least partly may be controlled by the contents of dissolved humic material and/or suspended organic and inorganic phases in the water.  相似文献   

11.
 Spatial variations in the density and velocity fields have been observed in the Gareloch (Scotland) during surveys in 1987–1988 and 1993–1994. The variation of the density field has been analyzed on a variety of time scales from semidiurnal to seasonal in order to quantify effects caused by the forcing factors of tidal mixing, freshwater input, and wind. Initial results indicate that water density in the loch is controlled (to a major degree) by the freshwater input from runoff from the local catchment area and from freshwater entering on the flood tide from the Clyde Estuary. It is estimated that during winter periods the high freshwater flows from the rivers Leven and Clyde into the Clyde Estuary account for up to 75% of the freshwater creating the density structure in the loch. Analysis of long-term dissolved oxygen data reveals that major bottom water renewals occurred between July and January in the years 1987–1994. Major bottom water dissolved oxygen renewals have a general trend but during the year sporadic renewals can take place due to abnormal dry spells increasing the density of the water entering from the Clyde, or consistently strong winds from the north reducing stratification in the loch and producing better mixed conditions. Velocities vary spatially, with the highest velocities of up to 0.6 m s–1 being associated with the velocity jet effect at the constriction at the sill of the loch. Observed near-surface mid-loch velocities increased as the vertical density gradients in the upper layers increased. This indicates for the observed conditions that increased stratification in the upper layers inhibits the entrainment rate and hence rate of gain of thickness of the wind-driven surface layer, resulting in increased surface velocities for a given wind speed and direction. The main flow is concentrated in the upper 10 m and velocities below 10 m are low. Observed mean spring tide surface velocities are on average 30% greater than mean neap tide surface velocities. Received: 22 May 1995 · Accepted: 23 August 1995  相似文献   

12.
Shu Tao 《GeoJournal》1996,40(1-2):213-217
Total organic carbon in unpolluted water from Yinluan River, Tianjin, China was fractionated into five operational defined fractions of particulate organic carbon, hydrophobic compounds, humic substances, non-humic anions, and other hydrophilic compounds using a multi-step filtration and adsorption scheme. The organic carbon contents and the trihalomethane formation potential of these fractions were determined. It was demonstrated that about half of the dissolved organic carbon in the sample is humic substances which is quite active in term of chlorination reaction. Particulate organic carbon is also an important precursor of the volatile halogenated hydrocarbons. All other fractions, which account for another half of the dissolved organic carbon, contribute to a relatively small percentage of the trihalomethanes produced during the chlorination experiment. It was concluded that humic substances, dissolved or suspended, are the most important precursor of halogenated hydrocarbons during chlorination, owing to their high abundance and trihalomethane formation potential.This study was supported by the National Excellent Young Scientist Fund of China.  相似文献   

13.
Particulate matter plays an important role in the removal of metal ions from water in natural aquifers. Some of the most important of these materials consist of associations of inorganic particles (clay minerals, oxides) with humic substances, associations that can form readily in such an environment due to the strong affinity between inorganic particles and humic substances. These associations are referred to in this paper as organic-inorganic hybrids. However, it is not clear whether the sorbed species of metal ions in such organic-inorganic hybrids are organic or inorganic species because of the complexity of such hybrids and the lack of appropriate methods for characterizing the trace metal ions incorporated in them. In this study, laser-induced fluorescence spectroscopy (LIF) was used successfully to characterize the Cm(III) species on an FA(fulvic acid)-montmorillonite hybrid, an example of such organic-inorganic hybrids. The LIF clearly showed that Cm(III) can be sorbed as Cm(III)-fulvate complex in the FA-montmorillonite hybrid. These results were consistent with those of experiments of solid-water partitioning of Cm(III) (or Eu(III) used as an analogue) and speciation calculations based on the stability constants of Cm(III)-fulvate complexes determined in this study. The results of LIF and the partitioning experiments showed that the solid-water distribution of humic substances governed that of Cm(III) under our experimental conditions. The Cm(III) preference for forming Cm(III)-fulvate complexes was also evident under a condition that would be found in a natural aquifer with a fairly low concentration of organic matter in freshwater (dissolved organic carbon: 2 mg/dm3), as determined by our speciation calculations. These findings on the importance of humic substances in the migration of Cm(III) indicate that the clarification of the environmental behavior of humic substances is necessary to understand fully the behavior of Cm(III), or actinide(III) and lanthanide(III) ions, in natural aquifers.  相似文献   

14.
The paper presents data on the specifics of the distributions of chemical elements in natural waters of the Kola North depending on the landscape–geochemical characteristics of the water catchment areas and aerotechnogenic pollution. The territory is subdivided into seven zones with different dominant rock types and typical landscapes. Lakes in the Kola region generally contain elevated concentrations of Cu, Ni, Co, Cr, V, Mo, U, Sb, Bi, Al, Fe, Mn, Sr, Li, Rb, Pb, Zn, Cd, La, and Ce. The waters of lakes in the influence zones of Cu–Ni mines are enriched in La, Ce, Sm, Gd, Pr, and Nd. In waterlogged landscapes, waters are enriched in certain trace elements because of their migration with humic acids. Technogenic acidic precipitation is proved to result in leaching of several elements, first of all Cd, Zn, and As (as well as other elements contained in rocks composing the water catchment areas) and their transfer into the waters.  相似文献   

15.
This study deals with the weathering processes operating at the scale of a small catchment (Nsimi-Zoetele, Cameroon) and is focused on the role of organic colloids on mineral weathering and transport of elements in natural waters. Samples of river, spring and groundwaters from Nsimi-Zoetele were filtered through membranes of decreasing pore size (0.22 μm, 0.025 μm, or: 300,000 Da, 5000 Da) to separate colloidal fractions from the truly dissolved one. Major and trace elements and dissolved organic carbon (DOC) were analysed in each fraction. Two kinds of waters can be distinguished in the catchment: clear and coloured waters. Clear waters exhibit low concentrations of major and trace elements and DOC. Elements are carried in these solutions in a true dissolved form except Al and rare earth elements (REEs). By contrast, the higher abundances of Al, Fe and trace elements in coloured waters are controlled by the colloidal fraction. Thermodynamic equilibrium calculations show that clear waters are in equilibrium with kaolinite and iron oxi-hydroxide which are major minerals in the weathered soil. For coloured waters, the aqueous speciation of Ca, Mg, Cu, Fe, Al, La and Th was calculated taking into account the complexes with humic acids. Speciation calculations for Cu, Fe, Al, La, Th show a strong complexation with humic acids, in good agreement with the results of the filtration experiments. By contrast, although filtration experiments show a strong control of major cations by organic matter (for example 75% for Ca), speciation calculations reveal that their complexes with humic ligands do not exceed a few percent of total dissolved elements. This discrepancy is explained as an artefact induced by the organic colloids and occurring during the filtration procedure. Finally, both filtration experiments and speciation calculations show that organic matter plays an important role in natural DOC-rich waters. Organic acids increase significantly the dissolution rates of silicates and oxi-hydroxides and thus the amounts of solutes and of complexed elements leaving the catchment.  相似文献   

16.
The early diagenetic environment of intertidal sandy sediments (sands) and muddy sediments (muds) is described and compared from two cores taken from an unpolluted part of the Manukau Harbour, New Zealand. Extraction techniques characterized the form of the trace elements (Fe, Mn, S, C, Pb, Zn, Cu) at different depths in the sediment. Dissolved forms of Fe, Mn, and S were measured in interstitial water. Nonresidual metal concentrations, humic acid, FeS, and FeS2 are an order of magnitude higher in the muds than in the sands because of dilution by unreactive sand particles. Muds contain a larger proportion of metals in the mobile fractions; exchangeable (Mn), carbonate (Mn, Fe, Zn), and easily-reducible oxide (Fe, Mn, Zn, Pb). This is due to greater surface area (for Mn adsorption); the favorable conditions for MnCO3, FeCO3, and FeS precipitation; and higher concentrations of easily reducible iron oxide and humic acid. Therefore, compared to the sands, muds are more important as reservoirs for toxic metals, both in terms of quantity and availability. At either site there was very little difference between the forms of Zn, Pb or Cu identified by sequential extraction as sediments changed from oxic to anoxic conditions. One reason for this is that the amounts and proportions of some of the important components that bind metals, viz., amorphous iron hydrous oxides, humic acids, and FeS2, do not change much. Other components that do change with redox conditions, for example, manganese phases and FeS, are only minor components of the sediment. Redox conditions, then, have relatively little effect on trace-metal partitioning in the sediment matrix of these unpolluted sediments.  相似文献   

17.
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18.
River water (Water of Luce, Scotland) is used in laboratory experiments designed to investigate physical and chemical properties of Fe. Mn, Cu, Ni, Co, Cd and humic acids in riverine and estuarine systems. Using NaCl, MgCl2 and CaCl2 as coagulating agents, coagulation of dissolved (0.4 μm filtered) Fe, Cu, Ni, Cd and humic acids increases in a similar matter with increasing salt molarily: Ca2+ is the most dominant coagulating agent. Removal by coagulation with Ca2+ at seawater concentrations ranges from large (Fe-80%. HA-60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Cd, Mn-3%). Destabilization of colloids is the indicated mechanism. Solubility-pH measurements show that between a pH of 3 and 9, Fe, Cu, Ni, Mn, Co and Cd are being held in the dissolved phase by naturally occurring organic substances. Between pH of 2.2 and 1.2 a large proportion of dissolved Fe, Cu. Ni and Cd (72, 35,44 and 36% respectively) is precipitated along with the humic acids; in contrast, Mn and Co show little precipitation (3%). Adsorption-pH experiments, using unfiltered river water spiked with Cu, indicate that adsorption of Cu onto suspended particles is inhibited to a large extent by the formation of dissolved Cu-organic complexes.The experimental results demonstrate that solubilities and adsorption properties of certain trace metals in freshwaters can be opposite to those observed with artificial solutions or predicted with chemical models. Interaction with organic substances is a critical factor.  相似文献   

19.
Organic matter from an arable soil derived from base rich parent material was extracted by alkali and fractionated on the basis of solubility in 0.1 N HCl, hot water and hot 6 N HCl and by selective adsorption on charcoal. The distribution of associated metals was determined and Cu had the largest proportion, 15%, associated with the organic matter. Moderate proportions of the total Al, Co, Ni, and V (3–8%) but only small amounts (?1%) of the Mn, Fe, Ti, Cr, Ba and Sr were extracted from the soil by alkali. The Fe and Ti were concentrated mainly in the humic fraction whereas Mn and V were both found largely in the fulvic acid.Electron paramagnetic resonance spectra of the various fractions were examined and attempts made to relate the spectra to the forms of some of the metals present. In the humic acid fraction Cu was present partly as a copper porphyrin-type complex but in the fulvic acid it was in some other complexed form. VO2+ occurred in complexed forms in the fulvic acid which were more covalent than VO2+ humic acid complexes, whereas the Mn2+ components of the humic and fulvic acids all had a high degree of ionicity.  相似文献   

20.
The paper suggests an accurate approach to studying carbonate equilibrium in the water of the Razdol’naya River. The approach involves measuring pH by Pitzer’s scale, using a cell without liquid junction; measuring the total alkalinity by Bruevich’s technique; and using apparent constants of carbonate equilibrium with regard for the organic alkalinity. The Pitzer technique was employed to calculate the apparent constants of carbonate equilibrium in solution that models the riverine water: Ca(HCO3)2–NaCl–H2O within the range of alkalinity of 0–0.005 mol/kg and temperatures of 0–25°C. Carbonate equilibrium in the water of the Razdol’naya River was sampled for studying at eight sites during all four seasons. Although the contents of biogenic compounds in the water are high, they can merely insignificantly affect the acid–base equilibrium, which is controlled in the riverine water by carbonate equilibrium and the concentrations of humic substances, which play the greater role, the greater the discharge of the river. In addition to the production and destruction of organic matter, carbonate equilibrium in the river is also affected by the supply of humic substances with soil waters and total alkalinity with groundwaters. The fluxes of alkalinity and humic substances annually brought by the Razdol’naya River to Amur Bay are evaluated at 1.33 × 109 mol and 9.9 × 106 kgC, respectively. The carbon dioxide export with the Razdol’naya River is equal to the alkalinity flux and does not depend on the weathering mechanisms.  相似文献   

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