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1.
The reduction in light emission of the marine bacterium Vibrio fischeri used in the standard Microtox® bioassay was measured for the metals copper and mercury. The concentration at which the light emission was reduced by 50% (EC50) was determined to be (3.43 ± 0.83) μmol/L for Cu2+ and (0.66 ± 0.01) μmol/L for Hg2+. The reduction of the toxicity of these metals by humic and fulvic acids were studied using IHSS Standard and Reference Materials. Copper toxicity was reduced 17...20% by the soil and peat fulvic acids and 9...20% by the aquatic fulvic acids. While there appeared to be little difference in the reduction of Cu toxicity by fulvic acids from soils, peats, or aquatic systems, Hg toxicity was reduced 3.6...7.3% by the soils and peats, while aquatic fulvic acids reduced Hg toxicity 14...16%. Soil fulvic acids appear to have significantly less capacity to reduce Hg toxicity than Cu toxicity. Humic acids had much higher reductions of Cu toxicity (44...124%) compared to the fulvic acids, with little difference between aquatic and soil or peat humic acids, 44...124% and 67...100%, respectively. However, humic and fulvic acids, regardless of origin, had approximately the same effect on Hg toxicity with 3.5...16% reduction by fulvic acids and 8...20% reduction by humic acids. Unlike the fulvic acids, no clear trend was observed relative to origin of the humic acids. There was no correlation between percent reduction of Cu or Hg toxicity by the organic compounds and copper binding capacity (CuBC), C/N ratio, or carboxyl content of the materials. Examination of natural organic matter (NOM) isolated by reverse osmosis techniques from three water sources had reductions of both Cu and Hg toxicity that were most similar to the Suwannee River and Nordic fulvic acids.  相似文献   

2.
The distribution of halogens in various fractions of humic substances (HS), separated by their molecular weight, was found to be different for the different halogens. This was demonstrated for chlorine, bromine, and iodine in sewage and brown water samples by applying inductively coupled plasma mass spectrometry coupled with size‐exclusion chromatography. Quantification of the different fractions of iodinated humic substances was obtained by quadrupole mass spectrometry in connection with the isotope dilution technique using an 129I‐enriched spike solution. Quantitative analysis was not possible for the corresponding chlorine and bromine species because of spectrometric interferences in the quadrupole instrument. The ageing of HS/halogen species was followed with respect to possible transformations of these species in a ground and sewage water sample up to eight weeks. Even if a distinct structural variation of the humic substance was observed with time by measuring the UV absorption, chlorine remained in the same molecular weight fraction and only a small change was found for the HS/bromine species after eight weeks. In contrast to these findings a substantial transformation of HS/iodine compounds took place, which demonstrated that the transfer probability of halogens from one to another HS fraction is increased with decreasing strength of the halogen bond to carbon. By comparing the results of an original sewage water sample with a filtered one and with another one which was enriched by microorganisms cultivated from the same original sample, a strong microbiological influence on the transformation of HS/iodine species was found. A quantitative balance of the corresponding HS/iodine fractions was calculated for an ageing period of eight weeks showing that iodine was preferably transferred to newly formed UV active HS substances of high molecular weight. In total, no iodine was released from the humic substances.  相似文献   

3.
Three‐dimensional fluorescence spectra of water samples from an eucalyptus bleached kraft pulp mill and from a river, upstream and downstream of the discharge of the effluent, revealed the existence of a peak at δexc = 280 nm and δem = 340 nm Δδ = 60 nm), characteristic of effluentπs organic matter. Humic substances were isolated from the effluent by sequential adsorption onto resins XAD‐8 and XAD‐4 in series. Their synchronous fluorescence spectra with Δδ = 60 nm do also exhibit an intense signal at δexc = 280 nm (≈ 300 nm in the humic acid fraction). The peak is absent in the spectra of humic substances isolated from a non‐polluted site of the river, but it is clearly seen in the spectra of the humic substances from a site downstream of the discharge of the effluent. Synchronous fluorescence spectra (Δδ = 60 nm) of water samples from the river and its lagoon were recorded and revealed to be an easy and fast way of tracing the organic contamination from the effluent.  相似文献   

4.
采用荧光光谱区域体积积分法定量研究洱海沉积物有色可溶性有机物(CDOM)三维荧光空间分布特性,结果表明,洱海沉积物CDOM中类腐殖酸组分占比最高(44.5%~74.2%),其次为溶解性微生物代谢产物(10.7%~20.4%)和类富里酸物质(8.19%~19.7%),而类蛋白组分占比最低,类腐殖酸占比与H/C和N/C均呈显著负相关;南部湖心平台区域沉积物类富里酸和类蛋白组分占比较高,其CDOM自生源占比较高;北部水生植物分布区溶解性微生物代谢产物占比较高,CDOM陆源性较强;中部深水区及南北湖湾区域类腐殖酸占比较高,随水深增加沉积物CDOM自生源特征增强.随沉积物深度增加类腐殖酸和溶解性微生物代谢产物占比呈下降趋势,类富里酸占比呈上升趋势,CDOM自生源特征增强,脂肪化程度增高.随湖泊富营养化程度增加沉积物CDOM受微生物代谢产物影响增强,陆源性增加,而自生源性降低,湖泊沉积物CDOM具有富营养化指示意义.  相似文献   

5.
A method is described for the specific hydrolysis of amino acids from humic substances by using the proteolytic enzyme “Pronase E”. The amino acids are analyzed by a fluorescence detector after precolumn derivatization and HPLC-separation. The pattern and the concentration of amino acids after the enzymatic hydrolysis are set up for humic substances of different origin. Due to the results the enzymatic hydrolysis is suitable for the characterization of humic substances with a nitrogen content higher than 3%. As shown in a kinetic study of the hydrolysis of a fulvic acid the influence of humic substances on the enzyme activity increases in case of lower nitrogen content. Due to the specificity of the proteolytic enzyme the operationally defined method is limited as shown by a protein of a known amino acid content. The amino acids leucine, valine, tyrosine and histidine are released to the highest extent. The determined total extent for the hydrolysis of Insulin B is 26.34% and for Casein 38.37%. By comparison of the enzymatic hydrolysis with the classic acid hydrolysis the advantages of the biochemical method are the simple experimental handling and the mild reaction conditions. Amino acids which are very unstable like glutamine and asparagine can only be analyzed by the enzymatic hydrolysis.  相似文献   

6.
The spatial and temporal distribution of humic substances in aquatic ecosystems can have important effects on ecosystem productivity, negatively impacting primary productivity while positively impacting secondary productivity. In the present investigation, a large shallow lake ecosystem was studied to determine the spatial and seasonal variation of the composition and concentration of humic substances. Concentrations of total dissolved organic matter, humic acid, and fulvic acid were found to display significant spatial distributions (1.3…13.5 mg/L, DOM; 0.1…5.4 mg/L, HA). The distribution is described by using mapping techniques and the analysis of the spatial distribution of the lake. An analysis of the seasonal variations also indicated the dependence of the occurrence of these compounds on meteorological and hydrological conditions. To identify the potential sources of these organic materials, an analysis was made of the ratio of humic and fulvic acid fractions and total DOM. It was found that areas of high DOM concentration coincided with the areas of highest HA percentage of total DOM. Furthermore using the ratio of the normalised concentrations of HA, FA, and residual DOM (< 5000 g/mol) it was found that areas dominated by each are spatially distinct. This confirms the hypothesis that in these shallow lakes, photodegradation and bacterioplankton activity will create a residence time dependent zonation of each component of the total DOM.  相似文献   

7.
8.
A combination of sephadex gel-chromatography and polyacrylamide gel electrophoresis was used to obtain stable electrophoretic fractions with different molecular sizes from a preparation of humic substances isolated from river water by reverse osmosis. The photochemical activity of humic substances and their fractions was determined. For the first time it is shown that low-molecular fractions of aquatic humic substances, when irradiated by polychromatic light, can intensely fluoresce and initiate the formation of singlet O2, effectively destroying model compound furfural. The photochemical activity and intensity of fluorescence of high-molecular fractions is insignificant. The obtained data will help to extend the current knowledge in the field of natural water hydrochemistry about the ways of its natural self-purification from anthropogenic pollutants.  相似文献   

9.
Structural aspects of humic substances (HSs) in marine waters of Engaño Bay (Atlantic Ocean) and water from the Chubut River (Patagonia, Argentina) were compared. The HSs were isolated, purified, and analyzed using a multiple-method approach for structural characterization: elemental analysis, nuclear magnetic resonance (13C and 1H NMR), infrared spectroscopy (FTIR), UV-visible absorption and fluorescence. Similarities between the marine and freshwater components were evaluated on the basis of N and O contents, H/C and C/N atomic ratios, infrared bands from nitrogen-containing and carboxylic groups, percentage of functional groups obtained from NMR spectra, spectral slope coefficient of absorption spectra, absorbance ratios at 250 and 365 nm (E 2/E 3), aromaticity, excitation–emission matrices and fluorescence quantum yield. Both the Engaño Bay and Chubut River waters have HSs that are mainly composed of fulvic acids (FAs); although they are very similar, they may be distinguished from one another. Similarities include the predominance of aliphatic carbon content (low aromatic content); however, the water bodies differed in their content of proteins and carboxylic acids. The Engaño Bay FAs have mainly an aquatic origin; although the Chubut River FAs suggest a similar aquagenic origin, there is also evidence of contributions from pedogenic FAs.  相似文献   

10.
野上佑作  福原富 《湖泊科学》1998,10(S1):241-246
Humic compounds are one of the major substances that affect the COD value of the surface water of Lake Kojima. The humic compounds in the lake water were studied with a spectrofluorophotometer. The 3-dimensional fluorescence spectrum suggests that two kinds of fluorescent substances exist in the lake water. One shows an fluorescence excitation maxim (Ex) at about 240 nm and an emission maxim (Em) at 413 nm. The other has an Ex at 330 nm and an Em at 418 nm. The former peaks are associated with humic acid and the latter peaks are associated with fulvic acid. These peak intensities are proportional to the COD values. The fulvic acid in the lake water may be enriched by the effluent from domestic water treatment plants.  相似文献   

11.
Recycling the large amounts of organic wastes produced by agriculture, forestry, urban and industrial activities as soil, organic amendments are the most popular and efficient option for avoiding their dispersion in the environment and restoring, maintaining, and/or improving the content of soil organic matter. Chemical stability and biological maturity are two important factors for the successful use of organic wastes in agriculture with limited risk for the surrounding environment. Stabilization and maturation of raw organic wastes inherently imply the achievement of an extensive humification, that is, a wide conversion of easily degradable organic matter to refractory organic compounds that resemble native soil humic substances (HS). Soil HS are the most important components of soil organic matter responsible of several soil functions and processes. As a consequence, the amount and quality of HS‐like fractions in any organic amendment are believed to be of primary importance for its agronomic efficacy, environmental safety and economic value. The first part of this review focuses on the chemical and physico‐chemical changes occurring in the humic substances (HS) ‐like fractions of organic wastes of various nature and sources subjected to common treatment processes aimed at producing environmentally‐safe soil amendments with beneficial agronomic properties. The second part discusses the composition, structure, and chemical reactivity of the HS‐like components in organic amendments of various origins and nature, and their effects on native soil HS. The review concludes by highlighting the need for innovative research targeted mainly to achieve a better fundamental understanding of the molecular structure and reactivity of soil HS and HS‐like fractions in organic amendments, the mechanisms of HS formation and transformations in the natural environment and during the treatment processes of raw organic wastes, the interactions with metals and organic xenobiotics, and the direct physiological effects that HS may exert on plants.  相似文献   

12.
Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.  相似文献   

13.
A natural decay of plant and animal biomass in aquatic environments results in the release of different simple structured organic substances into water. In our laboratory experiments we investigated whether some of them, e.g., starch or peptone, and also a complex yeast biomass can be transformed into humic-like substances by natural assemblages and some pure cultures of aquatic microorganisms. After a 6 months incubation most of the cultural media enriched with those natural organic substrates turned dark in color and humic-like substances (HS) could be isolated. However, the original substrate organic carbon was mainly mineralized in microbial cultures, and only about 3 % C was converted into HS. Total yields of HS differed in dependence of the individual substrate used (peptone > yeast > starch), the origin of inoculum (river > lake > groundwater), and the incubation temperature (20°C > 10°C). According to their elemental composition, and their spectroscopical and electrophoretic characteristics the microbially formed HS resembled natural aquatic humic matter, but were higher in aliphatic constituents (carbohydrates, peptides) and lower in aromatic structures. HS-like substances were also obtained from pure cultures of a bacterium Bacillus sphaericus and a fungus Cladosporium cladosporioides. The 13C and 15N isotopic contents of the microbially produced HS differed in dependence on the microbial inoculum and the type of organic substrates used, but in general they indicated anabolic processes to be mainly responsible for the humification of the simple organic substrates used in our experiments.  相似文献   

14.
Complex formation reactions with the interaction of fulvic and humic acids with zinc and iron ions in a model aqueous system. The complexing ability of humic acids was experimentally proved to be much higher than that of fulvic acids. The complexing ability of fulvic acids is found to decrease over time. The dependence of the complexing ability of heavy metals on the types of ion and humic substances and the proportions of components in the solution is examined. The obtained experimental results on the occurrence forms of heavy metals were compared with their theoretical estimates calculated for natural water bodies.  相似文献   

15.
16.
This paper deals with the influence of different humic substances (HS) on the enzyme activity (EA) of the proteolytic enzyme pronase E. The EA was determined by analyzing the concentration of the amino acid valine hydrolyzed from caseine. For amino acid analysis, a flourescence detector was used after precolumn derivatization and HPLC-separation of the hydrolysis products. The data show that the presence of HS has no adverse effects on amino acid analysis. Based on this result, a decrease of EA was observed in the presence of HS acting as enzyme inhibitors. Clear inhibition effects could be seen for different fulvic acids (HO3 FA, FBR FA and FBR 1.0 FA) at concentrations of 150 mg/L. In case of FBI-2 FA, higher concentrations were necessary to decrease the EA significantly. At an inhibitor concentration of 1500 mg/L the EA was mostly found to be less than 50%. The standard deviations of the results don't allow a differentiation between the HS of different origin and treatment. Specifying HS according to their influence on EA has to remain uncertain. As shown in a kinetic study of the hydrolysis of L-Leucine-2-naphthylamide-hydrochloride, the inhibitor HO3 FA decreases the maximum velocity of the reaction but has no effect on the Michaelis constant. These results indicate that this HS acts as a noncompetitive inhibitor.  相似文献   

17.
A characterization method for AOX in surface water samples was developed and tested. The method involves fractionation using a hydrophobic C18 resin and a weak anionic exchange resin and allows the fractionation of the AOX pool of surface water samples into four fractions: (1) hydrophilic acidic, (2) hydrophilic non‐acidic, (3) hydrophobic acidic, and (4) hydrophobic non‐acidic. The adsorption analysis was verified with AOX‐relevant model compounds and was applied to characterize the AOX pool of a stream sample from the Moskva river (Russia). In addition to the fractionation analysis, size‐exclusion chromatography was used to characterize the AOX pool of the sample studied. Hydrophilic acids made up the major fraction of the AOX pool (55 %). Among this fraction chlorinated high‐molecular acids (humic substances) made up the main fraction (35 %).  相似文献   

18.
The degradation of dissolved organic matter (DOM) was studied in alkaline solution. The products were characterised using UV/vis spectroscopy, size‐exclusion chromatography (SEC), and by the analysis of low‐molecular‐weight organic acids (LMWOA). The degradation experiments were performed with water from a brown water lake or its isolated fulvic acid fraction and sodium hydroxide at different reaction times and temperatures. Depending on the wavelength and the reaction time, the UV/vis absorbance between 230 nm and 600 nm increased or decreased. The behaviour of model compounds during reactions in alkaline media was compared to the UV/vis spectroscopic behaviour of DOM. The release of LMWOA was described by kinetic data and compared to the data of model reactions. Evidence was given for the carboxylic esters playing a significant role in the release of LMWOA only during the beginning of the alkaline degradation. The results gained by SEC with on‐line UV and DOC detection showed that the average size of DOM was decreasing, and that a major part of the degradation products consisted of low‐molecular‐weight mono‐ and dicarboxylic acids.  相似文献   

19.
乌梁素海沉积物腐殖质的组成及分布特征   总被引:4,自引:2,他引:2  
以乌梁素海为研究对象,应用化学方法对乌梁素海湖泊表层沉积物有机质含量、腐殖质组成、影响腐殖质的环境因子及腐殖化程度进行了研究,结果表明:乌梁素海表层沉积物有机质含量变化范围为1.06%~5.38%.有机质分布特征与表层沉积物所处的水力条件、水生植物分布、人为活动有关;腐殖质组成中,胡敏酸含量为0.65~2.78 g/kg,富里酸含量为2.19~8.72 g/kg,胡敏素是主体,含量在3.28~20.92 g/kg之间;腐殖质与环境因子的相关性分析中,各组分含量与有机质含量呈极显著相关.pH值与胡敏素含量呈显著负相关.溶解氧与富里酸、胡敏素含量分别呈极显著正相关、显著正相关.腐殖化程度分析中,随着有机质含量的上升,可提取腐殖质的相对含量下降.PQ值介于9.50%~27.06%之间,平均值为21.47%,变异较大,且腐殖化程度较低.  相似文献   

20.
The electroendosmotic flow (EOF), generated by the migration of solvated ions near the charged capillary surface, is an important factor in determining the capillary electrophoretic behaviour of humic substances (HS). We investigated the electrophoretic mobilities of HS fractions of reduced molecular-weight polydispersity extracted from peat and from a spodosol either in the presence or after suppression of the EOF. When the EOF was not suppressed, HS migrated to the cathode in spite of their negative charge. Fractionation of HS according to molecular size was achieved in polyacrylamide-coated capillaries filled with 0.05 M tris-phosphate buffer. In uncoated capillaries filled with the same buffer, all fractions had very close mobilities. Addition of polyethylene glycol MW 4000 at concentrations above its entanglement threshold caused the migration times of larger molecules to increase more than those of smaller molecules. The separation was a linear function of molecular size up to 75000 g mol–1 for peat HS and to 50000 g mol–1 for HS extracted from the spodosol.  相似文献   

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