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1.
A theoretical model has been developed in order to test the hypothesis that simple organic acids are the chief agents of trace metal solubility in H2S-rich marine waters. The model utilizes stability constant given by Sillen and Martell (1964, 1971) and assumes that the free cation activity of each metal is controlled by simple solubility products. Typical values of pH, pS and Eh are employed in the calculations. The results indicate that free amino acids and hydrocarboxylic acids probably are not effective but that bisulfide and polysulfide complexes may be the chief agents of trace metal solubility. To the extent that it is present, the effect of dissolved organic matter on trace metal solubility probably resides in highly polymerized substances (e.g. humic acids).  相似文献   

2.
Minerals might act as important sorbents of sedimentary organic matter and reduce biodegradation, which favors the formation of hydrocarbon source rocks in the earth's history. Since most organic matter is degraded during the sinking process, at ambient temperature, it is important to investigate the adsorption capacity of different minerals during this process, to assess the organic loss from primary productivity to sedimentary organic matter. In this study, montmorillonite and calcite have been selected to study the impact of different minerals on the release, adsorption, and deposition of cyanobacterial (Synechococcus elonpata) fatty acids (FAs) at ambient temperature. Gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) have been utilized to detect the variation in fatty acids. Primary results suggest that minerals have a different impact on dissolved organic matter. Montmorillonite can specifically enhance the release of fatty acids from cyanobacterial cells by lowering the pH values of the solution. The adsorption of the dissolved organic matter by montmorillonite will also be enhanced under a lower pH value. Conjunction of fatty acids with montmorillonite to form a complex will favor the sinking and preservation of these organics. Selective adsorption is observed among fatty acids with different carbon numbers. In contrast, calcite does not show any impact on the release and adsorption of organic matter even though it is reportedly capable of acting as a catalyst during the transformation of organic matter at high temperature. The primary data bridge a link between primary productivity and sedimentary organic matter, suggesting the relative importance of claystones in the formation of hydrocarbon source rocks in the earth's history.  相似文献   

3.
烃源岩中的有机酸来源于有机质,但有机质具有不同的赋存形式,有机酸具有不同性质,这将影响有机酸与不同赋存有机质的关系,进而影响分离和检测方法。文章在总结前人对有机质赋存形式和有机酸性质等特征的基础上,提出烃源岩中的有机酸并以非单一的形式存在,具有水溶性、脂溶性和难溶性有机酸三种类型,游离有机质中存在水溶性和脂溶性有机酸,而结合有机质中存在水溶性、脂溶性和难溶性有机酸。因此在检测方法上需采取分步分离的方法,且根据有机酸的性质选取合适的检测方法,即水溶性有机酸利用离子色谱检测,索氏抽提得到的脂溶性有机酸利用气相色谱—质谱检测,通过酸解抽提残渣得到的难溶性有机酸利用红外光谱检测,全面系统地认识烃源岩中有机酸含量和类型等特征。这对进一步探讨烃源岩各种类型有机酸特征和演化规律,深化烃源岩有机质生烃以及有机—无机相互作用等机理都具有重要意义。  相似文献   

4.
The photodegradation of organo-mineral complexes in natural conditions was studied using samples of soil and swamp waters to study the effect of sunlight on the composition and properties of organic matter and metal forms dissolved in natural waters. The total contents of certain aliphatic and aromatic carboxylic acids increased in the samples after irradiation. Photodegradation of organic matter of the natural waters with the high Fe content is accompanied by the formation of colloidal particles (Fe hydroxides). The number of negatively-charged complexes of Ni, Cu, Zn, and Cd increased under insolation in swamp waters and decreased in soil waters.  相似文献   

5.
A review with 227 references of the title subject is presented. It is divided into two main sections, viz., nature and properties of humic matter, and water—metal—sediment interactions.The first section deals with the essential properties of organic matter which occurs naturally in drainage sediments and waters. Discussion of the basic molecular structure of humic and fulvic acids is followed by some details of the chemical nature of functional groups within these structures which are important in metal-ion adsorption and complexing reactions which these materials can undergo. Information is also presented for colloidal and polyelectrolyte properties, complexation properties, and finally a summary discussion of metal-ion—humic-acid, metal-ion—fulvic-acid stability constants for both single ligand and mixed ligand systems completes the section.The second section comprises discussions of some specific aspects of interactions between metals, sediments and waters, including metal and organic speciation studies; sorption interactions between organic matter, clays and humic acids; chemical reaction between humic acids, heavy-metal minerals, clays and other silicate minerals; metal-ion adsorption—desorption studies, oxidation—reduction reactions between metal ions and humic acids; effects of sulphide ion on some of the above interactions and finally a summary of some relevant field geochemical dispersion studies.This second section describes both laboratory and field studies for each aspect.  相似文献   

6.

Equilibrium-kinetic modeling allows investigating metal behavior in the water–rock-organic matter system with time to evaluate anthropogenic effects on the environment. In the article, the interactions of stagnant mine drainage water of the flooded mine “Arsenic” with ore and gangue minerals were simulated using different organic matter incorporation approaches. If the model is closed to humic substances (no additional organic matter input), most fulvic acids are bound in the Fe fulvate complex. While under the removal of Fe fulvate from the model, the Cu fulvate becomes prevalent, the contribution of the fulvate complexes with Zn, Mg, and Ca also increases. This scenario simulates the organo-mineral complexes behavior well and allows identifying the sequence of metal binding to organic ligands as follows Fe?>?Cu?>?Zn?>?Mg?>?Ca. The second scenario imitates the constant input of organic matter to the model (open system regarding humic substances). The dissolved metal concentrations in the model solution are extremely high in comparison to the mine drainage water. This scenario demonstrates that excessive input of organic matter leads to the accumulation of the metals in a dissolved form and blocks the secondary mineral formation despite the faster dissolution of the primary minerals under a more acidic pH than in the first scenario. However, despite the differences between the model solution and the mine drainage water, this scenario is useful to address specific issues associated with changes in natural and anthropogenic conditions. Both scenarios show the importance of organic matter incorporation to the equilibrium-kinetic models.

  相似文献   

7.
The sedimentary humic acid or its acid-hydrolysate, consisting of various amino acids, was found effective in dissolving unusually large quantities of metals (up to 682 mg/g of organic matter) from their insoluble salts. The presence of humic acid in the reaction media which had favorable conditions for the precipitation of metals as carbonates, hydroxides or sulfides, prevented the formation of insoluble metal salts. Infrared analysis suggests that the metals added to various anionic systems and humic acid do not react with the anion. The most likely mechanism of reaction appears to be a complex formation between metals and organic matter which keeps the metal in solution.The enhanced solubility and consequent decrease in precipitation of metals under the influence of humic compounds, as evidenced in these studies should play a leading role in the accumulation of metals in sedimentary deposits.  相似文献   

8.
汞等重金属元素在黄浦江中迁移富集研究   总被引:1,自引:0,他引:1       下载免费PDF全文
为了探讨生物膜对重金属元素的富集,以及生物膜在水-沉积物交换过程中的影响和贡献,研究了生物膜和沉积物对于汞等重金属的吸附以及吸附前后汞形态的变化.结果表明沉积物中的汞和大部分重金属元素以残渣态为主,可交换态、有机质结合态、碳酸盐结合态百分含量相对较少.生物膜中有机质含量很高,生长时间,光照,季节都是影响生物膜中重金属元素含量的重要因素.可以推断,光照越强,温度越高,生长时间越长,生物膜中重金属元素含量越高.  相似文献   

9.
张玉龙  冉勇 《地球化学》2014,(2):114-121
从东江到珠江口采集了悬浮颗粒物,通过测定总有机质的元素(TOC、TN)、同位素(δ13C、δ15N)组成以及生物标志物(氨基酸、木质素)等地球化学性质,来揭示颗粒有机质的来源和组成。结果表明,浮游生物(13%-52%)和土壤(45%-77%)是珠江颗粒有机质的主要来源,植物(0%-11%)对颗粒物的贡献较小。颗粒有机质含有高比例的氨基酸碳(TAAC),说明浮游生物对颗粒物的重要性。氨基酸的降解指数(DI)在-0.51到0.79之间,说明这些水生来源有机质的降解程度比较小。木质素的降解参数(Ad/Al、3,5-BD/V)较大,表明珠江颗粒有机碳的陆源来源主要是土壤。在颗粒物中检测到了少量的二氨基庚二酸(Dapa),说明细菌对颗粒有机碳也有所贡献。不同环境中颗粒物的木质素组成主要与颗粒物丰度和粒径有关:(1)相对于河流,水库颗粒物中的木质素含量显著偏低,降解程度更高;(2)相对于中游,下游颗粒物丰度较高,木质素含量较高。  相似文献   

10.
A coal-based thermal power plant is situated on the bank of the Pandu River, which is a tributary to the Ganges near Kanpur. River sediments downstream from the ash pond outfall are contaminated by fly ash. In order to establish the role of soils and sediments in retaining fly ash-derived heavy metals, copper was investigated as a model metal. A maximum concentration of 70 ppm Cu could be leached from the fly ash, confirming that it is a major source of this metal. Soil samples and river sediments were examined for Cu adsorption in the natural state as well as after treatment with H2O2, EDTA, and H2O2 followed by EDTA. The organic fraction of the samples was determined, and it had a major control on removal of Cu from a solution with 10–4 M initial concentration. Further characterization of organic matter indicated that with reference to natural samples, the humic acid fraction had a copper enrichment factor in the range 9.1–15.1. The factor for fulvic acids, in contrast, was between 3.5 and 5.5. This leads to the conclusion that river deposits rich in humic acids would withstand relatively high metal loads. Only when the metal input exceeds the maximum retention potential, would the metal be fractionated into the aqueous phase and act as a potential biocide.  相似文献   

11.
Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pKMHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pKMHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl, F, OH, SO42−, CO32−, PO43−), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln3+) and sulfate complexes (LnSO4+) dominate, whereas in alkaline waters, carbonate complexes (LnCO3+ + Ln[CO3]2) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.  相似文献   

12.
Muddy carbonate deposits near the Dry Tortugas, Florida, are characterized by high organic carbon remineralization rates. However, approximately half of the total sedimentary organic matter potentially supporting remineralization is occluded in CaCO3 minerals (intracrystalline). While a portion of nonintracrystalline organic matter appears to cycle rapidly, intracrystalline organic matter has an approximately constant concentration with depth, suggesting that as long as its protective mineral matrix is intact, it is not readily remineralized. Organic matter in excess of intracrystalline organic matter that is preserved may have a variety of mineral associations (e.g., intercrystalline, adsorbed or detrital). In surface sediment, aspartic acid contributed ∼22 mole % and ∼50 mole % to nonintracrystalline and intracrystalline pools, respectively. In deeper sediment (1.6-1.7m), the composition of hydrolyzable amino acids in both pools was similar (aspartic acid ∼40 mole %). Like amino acids, intracrystalline and nonintracrystalline fatty acids have different compositions in surface sediments, but are indistinguishable at depth. These data suggest that preserved organic matter in the nonintracrystalline pool is stabilized by its interactions with CaCO3. Neutral lipids are present in very low abundances in the intracrystalline pool and are extensively degraded in both the intracrystalline and nonintracrystalline pools, suggesting that mineral interactions do not protect these compounds from degradation. The presence of chlorophyll-a, but absence of phytol, in the intracrystalline lipid pool demonstrates that chloropigments are present only in the nonintracrystalline pool. Sedimentary chloropigments decrease with depth at similar rates in Dry Tortugas sediments as found in alumino-silicate sediments from the Long Island Sound, suggesting that chloropigment degradation is largely unaffected by mineral interactions. Overall, however, inclusion and protection of organic matter by biominerals is a major pathway for organic matter preservation in this low-organic carbon, biomineral-rich regime.  相似文献   

13.
In order to study the ‘in vitro’ fixation of metal ion species on algal and bacterial sedimentary organic matter, two algal mat samples have been studied. The main interest of this organic matter is its specific cyanobacterial origin. After isolation and purification, the organic matter was characterized by elemental and functional analysis, infrared spectroscopy. carbohydrates and amino-acid titration. These analyses indicate the richness of this type of organic matter in amino acids and carbohydrates, its poverty in aromatic structures, and to ascertain the types of bacteriological and chemical transformations undergone by the original biological compounds in the first steps of the diagenesis.  相似文献   

14.
The New York Bight is a sector of the Middle Atlantic continental shelf. The Bight consists of a part of the Atlantic Ocean offshore of the New York and New Jersey metropolitan area. This area includes the most populated coastal setting in North America. The Atlantic shelf and its estuaries are used for waste disposal, dredging, commercial fishing, and recreation; activities that contribute to the contamination of associated bottom sediments. Existing data for toxicants are still inadequate. Improvements in sediment and water quality will require a more detailed knowledge and understanding of sediments and water in the Bight. Eleven coring stations were established in New York Bight. Decreases in pH and Eh both above and below the water/sediment interface are attributed to the activity of anaerobic bacteria. Sulfate reduction is one of the important processes in lowering pH. Low Eh values of up to −443 can be related to sulfate-reducing bacteria. The highest negative Eh generally occurs with the highest organic carbon concentration. Core samples yielded up to 4.00% organic carbon compared to 0.8 to 1.2% in sediments of the natural nearshore environment. Twenty-seven different aliphatic hydrocarbons, fourteen PAHs, five cyclic hydrocarbons, and eight dicarboxylic acids were identified in the Bight pore waters. Sediment located deeper in the Hudson Shelf Valley has a greater abundance of aliphatic hydrocarbons as adsorbed pollution on clay and silt. The presence of dicarboxylic acids leached from plastic came from anthropogenic activities (mostly sewage). PAHs have two sources: coal ash (observed in sediments) and petroleum (part of the sewage, run-offs, and oil spills). The rest of the hydrocarbons have a petroleum or biogenic origin. The high amount of organic carbon may be the result of sewage sludge or originated from natural sources. The main sources of contaminants are dumpsites, emergency releases after heavy rainstorms from sewage-treatment plants, tanker washing, storage transfer spills, run-off, and air-borne pollution. The relatively high accumulation of organic matter causes oxygen depletion, which creates anaerobic conditions. The presence of hydrogen sulfide makes the environment toxic for most of the biota. Detected hydrocarbons, especially PAHs easily enter the food chain and may cause cancer and mutagenic reactions of biota and humans. Organic petrology of six organic-rich sediments from New York Harbor illustrates a diverse population of anthropogenic and natural organic components. Three core samples (V-2, AC-4, and HV-3) contain coarse-textured organic matter. A slim majority of those components are anthropogenic. They are derived mainly from coal combustion by-products. The other two core samples (AC-6 and T-1) contain mainly very fine-grained organic matter. A majority of them are amorphous organic matter (AOM) that is derived from bacterial degradation of modern organic matter. Radionuclide dating (137Cs, K-40, Pb-210) shows post-1950 components for the shallowest intervals in the cores (<30 cm). The post-1950 sediment, distributed in the tops of core, is recycled material from the dumpsites. The underlying sediment has isotopic signatures that suggest dates before active dumping.  相似文献   

15.
铀有机地球化学研究进展   总被引:5,自引:0,他引:5       下载免费PDF全文
与负矿有密切关系的有机质主要是腐殖酸(HAS),富里酸(FAS),微生物及细菌,腐殖酸与铀酰存在着强烈的吸附,络合及还原关系。微生物和细菌在铀矿形成过程中也起到很微妙的作用。在研究手段上包括试验,计算,热解分析,X-线分析,烈变径迹分析,电子探针,红外光谱,紫外光谱,荧光光谱,顺磁共振,色谱质谱联用的方法。  相似文献   

16.
Despite of the importance of the aquatic ecosystems as organic matter pools within the global carbon cycle, specific studies in river sediments are still insufficient. This study was carried out in an Atlantic basin where nine sites were selected in the lowest middle stretch of the River. The analyses include total organic carbon, C/N ratios, humus composition (humic, fulvic and humin), A2/A4 and A4/A6 ratios, biologically active organic matter (BAOM), water soluble organic matter (WSOC) and coloured water soluble organic carbon (CWSOC). The results suggested a predominance of allochthonous sources to the organic matter, highly influenced by the land uses together with the river hydrodynamics, namely urban and forest at sites 1, 2 and 9, and agricultural at sites 7 and 8. The 38% of the total organic matter was humic and fulvic acids. The biologically active organic matter, which may act as a proxy of microbial activity, showed a mean value of 0.9% of the total organic matter, showing the lowest values at sites with the highest organic matter total, soluble or coloured. This coloured organic matter represented an average of 3.60% of the total organic matter, and showed the highest visible light absorption at those sites more affected by human activities, close to centres of population (1, 2 and 9). This coloured fraction showed also a high degree of photostability. C/N ratios were less effective to discriminate between allochthonous or autochthonous sources, whereas A4/A6 ratios were effective to estimate variations of autochthonous sources, as it measures the variations of phytopigments of the river bed sediments.  相似文献   

17.
塑料容器是降水中生物有机酸研究的常用样品储集器,极地冰芯和粒雪样品钻取中也常用聚乙烯塑料袋盛装,且常常采用双封口方式保存。这种样品保存方式和样品暴露于大气一样,都会造成样品中有机酸含量的污染。定量研究一述污染是准确分析降水中有机酸含量的前提和基础。以超水为主要实验样品,对聚乙烯塑料顺和空气的甲酸,乙酸污染的研究表明,甲酸、乙酸的污染主要来自聚乙烯塑料代的热塑封口过程,而聚乙烯塑料桶的影响不明显。塑  相似文献   

18.
As a kind of marine organic matter with important geochemical characteristics, amino sugars can effectively reflect the source, diagenetic state and mineralization process of organic matter by their concentration and composition in marine environment. This article systematically concluded the research progresses of amino sugars from the aspects of their source, composition and distribution characteristics in marine environment, and the role as a biomarker indicating source and diagenetic state of marine organic matter. The result showed that the macromolecular morphology, the oxygen and nutrient level and the sedimentary environment could affect the reactivity of amino sugars. The higher ratios of glucosamine to galactosamine (GlcN/GalN) and the Total Hydrolysable Amino Acids to Total Hydrolysable Amino Sugars (THAA/THAS) can reflect the fresh planktonic organic matter source and the lower ratios can reflect the conversion from planktonic to bacterial organic matter. The carbon and nitrogen normalized yield of total hydrolysable amino sugars, however, could give contradictory results depending on the relative contribution of the source and degradation degree of organic matter. Muramic acid is suitable to estimate the contribution of relatively fresh bacteria organic matter to particulate and sediment organic matter, but it is not suitable for applying in the dissolved organic matter because of its very low concentration leading from its rapid recycle. It is critical to enhance the research on the contribution of different microorganisms to amino sugars and differentiate the influence of organic matter source and degradation on amino sugars in marine environment. The research on the conversion and fate of amino sugars in marine environment is also needed.  相似文献   

19.
The Nepal Himalayas is the source of many glacial and spring-fed river systems crisscrossing the moun-tainous terrain.There is an increasing recognition of small mountain rivers(SMRs)to have a significant combined export of dissolved and particulate organic carbon to the global carbon flux.We analyzed flu-vial sediments from two SMRs and compared the results with two large mountain rivers(LMRs)in Nepal.We investigated the organic matter(OM),its compositional variability,and seasonal export using a suite of lipid biomarkers,namely n-alkanes,n-alkanoic acids,n-alkanols,and sterols.The SMRs indicated a similarity in lipid distribution and were affected by a strong seasonal variability.The LMRs showed a dis-tinct contrast in the distribution of lipids in suspended sediments.Bedload sediments in SMRs were derived from diverse sources with weak terrigenous dominance all-year-round compared to the sus-pended load.Functional lipids(n-alkanoic acids and n-alkanols)were the major constituents in SMR sed-iments,indicating better preservation.In contrast,n-alkane concentration dominated over other fractions in suspended sediments retrieved from LMRs.The biomarker trends differentiate SMRs from LMRs with lower transformed/degraded OM in SMRs.A common observation was the strong presence of even carbon compounds in short-chain n-alkanes in SMR bedload sediments and their predominance in suspended sediments in LMRs.Such an unusual trend is attributed to specific biomarker sources from the catchment and ongoing processes in fluvial systems.Topsoil colonized by fungal species under moist acidic condi-tions and autochthonous bacteria contributes to the organic matter pool in shallow SMRs.In LMRs,the contribution from thermally mature sedimentary hydrocarbons and the diagenetic reduction of n-alkanoic acids to n-alkanes are additional contributors to the allochthonous carbon pool.The differences in lipid concentrations,their distribution,seasonality,and the size of rivers suggest differential preserva-tion/degradation of the organic matter pool and their importance in contributing to the carbon budget.  相似文献   

20.
Effect of addition of municipal solid waste compost (MSWC) on two metals viz. copper (Cu) and zinc (Zn) contents of submerged rice paddies were studied. Experiments were conducted during the three consecutive wet seasons from 1997 to 1999 on rice grown under submergence, at the Experimental Farm of Calcutta University, India. A sequential extraction method was used to determine the metal (Cu and Zn) fractions in MSWC and cow dung manure (CDM). Both metals were significantly bound to the organic matter and Fe and Mn oxides in MSWC and CDM. Metal content in rice straw was higher than in rice grain. Metal bound with Fe and Mn oxides in MSWC and CDM best correlated with straw and grain metal followed by exchangeable and water soluble fractions. Carbonate, organic matter bound and residual fractions in MSWC and CDM did not significantly correlate with rice straw and grain metal. The MSWC would be a valuable resource for agriculture if it can be used safely, but long-term field experiments with MSWC are needed to assess by regular monitoring of the metal loads and accumulation in soil and plants.  相似文献   

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