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1.
Calorimetric and potentiometric titrations have been used to evaluate direct and indirect methods of analysis for the carboxyl content of aquatic humic substances. The effects of cation binding, base strength, and removal of humic reaction products on carboxyl content values have been examined. The results suggest that the most appropriate analytical method for determination of an operationally defined carboxyl content would utilize a weak base that does not contain a polyvalent cation in an indirect titration on a reaction mixture from which all humic reaction products have been removed prior to titration. Titration data have been analyzed in terms of a formation function (δnOH) and in terms of operationally defined ‘mass action quotients’ (K?). The dependence of K? on pH is more readily and realistically described if no artificial differentiation of carboxyl groups into two or more sub-groups is imposed upon the data.  相似文献   

2.
Excitation-emission matrix fluorescence spectroscopy (EEM) has been widely used to elucidate the origin and structure of humic substances in natural environments. Due to its high sensitivity, good selectivity and non-destructive advantage, the EEM was applied to characterizing a commercial Fluka humic acid (FHA). The results showed that the EEMs of FHA has several Ex/Em peaks. Ionic strength (0-0.05 moL/L KClO4 ) exerted little effect on the fluorescence properties of FHA, while the concentrations (5-100mg/L) of FHA and pH (2-12 ) had significant effects. A red shift in the longer wavelength peak region was observed when the coneentrations or pH values increased. The fluorescence intensity increased with increasing pH, but slightly decreased in the case of pH = 5.0. The protonation constants ( lgK^ HL ) of peak B were calculated to be 3.57 and 3.13, indicating that peak B was due to carboxyl groups. The r(A/B) values range from 0.61 to 2.59. A strong linear relationship between r(A/B) and pH was also observed. This indicates that the fluorescence peaks A and B posses similar inherent fluorescence characteristics.  相似文献   

3.
利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.  相似文献   

4.
Aqueous solutions of increasing pH (7.0, 10.6 and 12.6) were used to extract exhaustively the organic matter (OM) from a pelo-stagnogley (heavy clay) soil in long term cultivation. OM yield was 1.7 times greater when the extracts were processed using an XAD-8 and XAD-4 resin-in-tandem procedure than that from the procedure of the International Humic Substances Society (IHSS). The substantial difference can be attributed to the amount retained by the XAD-4 resin, which is lost in the IHSS process. Elemental, δ13C, δ15N, cation exchange capacity, neutral sugars, amino acids and solid state CPMAS 13C NMR analyses indicated significant, but rational similarities and differences between the various fractions isolated. There was strong NMR evidence for material derived from lignin in all the humic and fulvic acid isolates. The signals were attenuated in the more transformed/oxidized fractions isolated at lower pH. Novel humic acid fractions enriched in carbohydrate/peptide functionalities were isolated from the more hydrophobic extracts at pH 10.6 and 12.6. Isolates from XAD-4, of microbial origin, were enriched in neutral sugars but not in amino acids, and had minimal aromaticity. Components isolated from the cultivated soil were broadly similar to those from a comparable soil in long term grassland. The compositions of fractions isolated from the drainage water were similar to those extracted from the soil but had higher carboxyl content. The amount and composition of the various organic fractions in grassland and the continuously cropped soil are discussed in terms of their potential to contribute to carbon sequestration by soil under similar management regimes.  相似文献   

5.
The acid-base properties of 14 standard and reference materials from the International Humic Substances Society (IHSS) were investigated by potentiometric titration. Titrations were conducted in 0.1 M NaCl under a nitrogen atmosphere, averaging 30 min from start to finish. Concentrations of carboxyl groups and phenolic groups were estimated directly from titration curves. Titration data were also fit to a modified Henderson-Hasselbalch model for two classes of proton-binding sites to obtain “best fit” parameters that describe proton-binding curves for the samples. The model was chosen for its simplicity, its ease of implementation in computer spreadsheets, and its excellent ability to describe the shapes of the titration curves. The carboxyl contents of the IHSS samples are in the general order: terrestrial fulvic acids > aquatic fulvic acids > Suwannee River natural organic matter (NOM) > aquatic humic acids > terrestrial humic acids. Overall, fulvic acids and humic acids have similar phenolic contents; however, all of the aquatically derived samples have higher phenolic contents than the terrestrially derived samples. The acid-base properties of reference Suwannee River NOM are surprisingly similar to those of standard Suwannee River humic acid. Results from titrations in this study were compared with other published results from both direct and indirect titrations. Typically, carboxyl contents for the IHSS samples were in agreement with the results from both methods of titration. Phenolic contents for the IHSS samples were comparable to those determined by direct titrations, but were significantly less than estimates of phenolic content that were based on indirect titrations with Ba(OH)2 and Ca(OAc)2. The average phenolic-to-carboxylic ratio of the IHSS samples is approximately 1:4. Models that assume a 1:2 ratio of phenolic-to-carboxylic groups may overestimate the relative contribution of phenolic groups to the acid-base chemistry of humic substances.  相似文献   

6.
The main objective of this study is to investigate the possibility of powdered eggshell used as an adsorbent material for removal of humic acid from peat water. The influences of contact time, dose of eggshells, pH, and temperature were the factors considered in the removal processes of humic acid from peat water. In addition, adsorption isotherms of humic acid onto the powdered eggshell were also evaluated with the Langmuir and Freundlich approximations. Our results showed that the equilibrium of the process was eventually established after 60 min of the contact time, and also found that using 5 g of the powdered eggshell nearly 95 % of humic acid has been successfully removed from the peat water. The removal of humic acid gave better result when it was conducted at low pH, and it was almost unaffected the temperatures variation. The data was well fitted to Freundlich isotherm with the correlation coefficient of not <0.999, and could uptake the humic acid about 126.58 mg/g at pH 4.01, estimated from the Langmuir model. The kinetic experimental data proportionally correlated with the pseudo-second-order kinetic model with a rate constant in the range of 0.016–0.112 g mg?1 min?1, while intra-particle-diffusion were the main rate determining step in the humic acid removal process. The powdered eggshell investigated in this study, thus, exhibited as a high potential adsorbent for the removal of humic acid from peat water.  相似文献   

7.
Amino acids comprise from 15 to 36% by weight of humic substances from carbonate and non-carbonate sediments. Humic and fulvic acids extracted from carbonate sediments are characterized by an amino acid composition consisting primarily of the acidic amino acids, aspartic and glutamic acid. Humic substances from non-carbonate sediments have a distinctly different amino acid composition consisting primarily of glycine and alanine. Amino acid analyses of various molecular weight fractions of fulvic acids extracted from carbonates show that lower molecular weight fractions have appreciably higher relative abundances of the acidic amino acids compared to higher molecular weight fractions. Based on typical values for carboxyl group content in humic substances, acidic amino acids may be a significant contributor of these functional groups. Carbonate surfaces appear to selectively adsorb aspartic acid-enriched organic matter while non-carbonates do not have this property.  相似文献   

8.
In a comprehensive study of the distribution of organic and inorganic constituents in natural waters, the chemical compositions of several rivers flowing through the Coastal Plain of southeast Georgia (the Satilla River, in particular) have been investigated. These streams are generally characterized by low suspended load, low ionic strength, low pH values, and a predominance of organic over inorganic constituents. The dominance of sodium and chloride among inorganic ions indicates that rainfall is a major factor in determining the distribution of major elements in these waters. The low pH values and the relatively high concentrations of iron and aluminum appear to result from the high concentrations of organic matter. Chemical analysis (total acidity, carboxyl groups, amino acid residues, and CHN analysis) and spectroscopic analysis (i.r. and NMR) indicate that river water organic matter is chemically similar to soil fulvic acids.The dominance of organic matter over inorganic constituents and the resultant low pH values of these waters are in direct contrast with the chemical compositions of most of the rivers of the world which have been previously studied. Many large tributaries draining from the low relief tropical basins of the Amazon and other tropical rivers are expected to show similar characteristics; however, none of these has been studied extensively.  相似文献   

9.

Background  

The dispersion-aggregation behaviors of suspended colloids in rivers and estuaries are affected by the compositions of suspended materials (i.e., clay minerals vs. organic macromolecules) and salinity. Laboratory experiments were conducted to investigate the dispersion and aggregation mechanisms of suspended particles under simulated river and estuarine conditions. The average hydrodynamic diameters of suspended particles (representing degree of aggregation) and zeta potential (representing the electrokinetic properties of suspended colloids and aggregates) were determined for systems containing suspended montmorillonite, humic acid, and/or chitin at the circumneutral pH over a range of salinity (0 – 7.2 psu).  相似文献   

10.
中国东部主要入海河流As元素分布、来源及影响因素分析   总被引：4，自引：2，他引：2  
为查明中国河流中As等重金属元素的分布规律,于2007—2008年分丰水期和枯水期对中国东部30余条入海河流水体、悬浮物统一进行采样分析。结果表明:东部河流中As元素溶解态含量均值为3.1μg/L,同世界河流相比,明显偏高;且频率分布直方图具有多个峰值,反映出明显的人为污染。利用富集系数的研究表明,悬浮物同样受到较明显的人为污染。As在河水中的迁移形式以溶解态为主,pH值和温度对As的迁移形式有明显影响。流域内岩石类型对河流中As含量影响显著,火山岩、火山碎屑岩类广泛分布的流域河水中As含量明显偏高,花岗岩及中、深变质岩广泛分布的流域河流中As含量则偏小。利用生活、工业污水作为As元素人为来源端元,对海河、黄河、长江、珠江等河流人为源进行了估算,分别为46.7%、18.7%、13.5%、8.3%。  相似文献   

11.
以广西武鸣县典型的碳酸盐岩成土剖面和陆源碎屑岩成土剖面为研究对象,研究了不同成土母质在成土过程中Se元素与其形态在垂向上的迁移变化规律及其影响因素。结果表明：碳酸盐岩和陆源碎屑岩在成土过程中,土壤Se含量均继承了成土母质的特点,且前者在表层明显富集,而后者相对较稳定,算术平均值分别为0.55 mg/kg和1.43 mg/kg。前者的水溶性总硒含量高于后者,平均含量分别为3.48 μg/kg和1.81 μg/kg,但均以硒酸态硒为主,其次是亚硒酸态硒和腐殖酸结合态硒。成土剖面上,土壤Se含量及其形态影响因素研究表明,碳酸盐岩成土剖面上,Se的含量与形态主要受土壤TOC含量和pH值影响;陆源碎屑岩成土剖面上,影响Se的含量及其形态的因素较多,土壤pH值、TOC、Al2O3和Fe2O3含量以及土壤质地等均对其有不同程度的影响。  相似文献   

12.
陆架边缘海是“河口—陆架”体系重要的碳汇,黏土矿物作为主要载体将有机质与金属元素吸附于表面或层间,通常表现为粒度、有机质和金属元素含量之间高度正相关。本文通过分析南黄海中部沉积物粒度、总有机碳、主微量元素,探讨三者之间分布特征和相互关系,进一步开展金属元素、有机质与黏土矿物吸附模拟实验,结果表明,酸性条件（pH=4）下适量的金属离子（Zn2+、Ni2+、Pb2+）明显促进伊利石对腐殖酸（有机质主要组成部分）吸附,腐殖酸吸附量达到20.06 mg/g,其中金属离子加入使腐殖酸吸附量提高6.25%;同时碱性条件（pH=8）下金属离子也能够促进伊利石对腐殖酸吸附,腐殖酸吸附量达到15.7 mg/g,金属离子加入使腐殖酸吸附量提高38.9%。金属离子的阳离子键桥作用促进伊利石吸附腐殖酸,且酸性环境下腐殖酸的吸附量高于碱性环境。证实了陆架边缘海背下金属元素的参与对黏土矿物吸附腐殖酸具有明显促进作用,有利于在全球碳循环过程形成边缘海“碳库”,同时海洋酸化可能造成海洋溶解有机质降低和重金属离子浓度升高,对陆架边缘海海洋生态系统平衡构成威胁。  相似文献   

13.
Concentrations of Ca, Cd, Cu, Fe, and Pb and binding capacities for Cd, Cu, and Pb were determined for water samples collected from 12 lakes in southwestern Maine using atomic absorption and ion-selective electrodes, respectively. Surface waters in this area are soft and characterized by low pH. Some lakes were highly colored with refractory organics, whereas others had very low organic carbon concentrations. Both Cu and Pb concentrations were positively correlated with organic carbon content. Copper and Pb binding capacities were significantly correlated with organic carbon content, whereas Cd binding capacity was positively correlated with pH, but not with organic carbon. Surface water binding capacity for Pb was greater than that for Cu or Cd. More than 99% of the Ca from all waters studied was removed onto cationic exchange resins. Less than 1% of the total Cu existed as cationic species in highly humic waters, whereas as much as 65% existed as cationic species in less huic waters. Conversely, more than 99% of the Cd present in humic waters existed as cationic species, whereas as little as 50% existed as cationic species in less humic, more alkaline waters. These correlative studies indicate that binding by organic carbon is important for both Cu and Pb in this area and must be considered in models of trace metal speciation. However, Cd binding in the same waters is not correlated with organic carbon, which does not need to be considered in speciation models for Cd.  相似文献   

14.
Freshwater humic substances from Lake Celyn, Gwynedd, N. Wales have been investigated by 13C-NMR spectroscopy. Carboxyl, aromatic, o-alkyl and alkyl resonances can be recognised. Varying pulse delay from 0.43 s to 2.5 sec has little effect on the magnitude of the signal ascribed to aromatic carbon, but there is a small nuclear Overhauser effect (1.45 at a pulse delay of 0.8 sec).The results show-that 24% of the Lake Celyn humic acid carbon is carboxyl and 40% is aromatic. The high proportion of aromatic carbon suggests the Lake Celyn humic acid is largely formed from terrestrial humic substances from the surrounding peaty watershed.  相似文献   

15.
13C and 1H NMR spectra were obtained for humic acids isolated from marine sediments. NMR shows great promise in identifying structural components of humic acids as some new and interesting structural features are identified. Aliphatic structures were found to constitute a much larger fraction of humic acids than previously thought, and they appeared to be highly branched. Although the aromatic content of terrestrial humic acid was found to be lower than expected, the aromaticity appears to be a specific discriminator of terrestrial/aquatic source types. A humic acid isolated from an anoxic algal sapropel was found to be composed predominantly of polyuronic acids and different than other aquatic sedimentary humic substances.  相似文献   

16.
The stability and structure of aqueous complexes formed by trivalent antimony (SbIII) with carboxylic acids (acetic, adipic, malonic, lactic, oxalic, tartaric, and citric acid), phenols (catechol), and amino acids (glycine) having O- and N-functional groups (carboxyl, alcoholic hydroxyl, phenolic hydroxyl and amine) typical of natural organic matter, were determined at 20 and 60 °C from solubility and X-ray absorption fine structure (XAFS) spectroscopy measurements. In organic-free aqueous solutions and in the presence of acetic, adipic, malonic acids and glycine, both spectroscopic and solubility data are consistent with the dominant formation of SbIII hydroxide species, , at strongly acid, acid-to-neutral and basic pH, respectively, demonstrating negligible complexing with mono-functional organic ligands (acetic) or those having non adjacent carboxylic groups (adipic, malonic). In contrast, in the presence of poly-functional carboxylic and hydroxy-carboxylic acids and catechol, SbIII forms stable 1:1 and 1:2 complexes with the studied organic ligands over a wide pH range typical of natural waters (3 < pH < 9). XAFS spectroscopy measurements show that in these species the central SbIII atom has a distorted pseudo-trigonal pyramidal geometry composed of the lone pair of 5s2 electrons of Sb and four oxygen atoms from two adjacent functional groups of the ligand (OC-OH and/or COH), forming a five-membered bidendate chelate cycle. Stability constants for these species, generated from Sb2O3 (rhomb.) solubility experiments, were used to model Sb complexing with natural humic acids possessing the same functional groups as those investigated in this study. Our predictions show that in an aqueous solution of pH between 2 and 10, containing 1 μg/L of Sb and 5 mg/L of dissolved organic carbon (DOC), up to 35% of total dissolved Sb binds to aqueous organic matter via carboxylic and hydroxy-carboxylic groups. This amount of complexed Sb for typical natural DOC concentrations is in agreement with that estimated from dialysis experiments performed with commercial humic acid in our work and those available in the literature for a range of standardized IHSS humic acids. Our results imply that a significant part of Sb is likely to be bound with humic acids via hydroxy-carboxylic moieties, in the form of bidendate complexes. However, following the strong chemical affinity of SbIII for reduced sulfur, some undefined fraction of SbIII might also be bound to the minor thiol-bearing moieties of humic acids; further studies are required to check this hypothesis.  相似文献   

17.
Carboxyls play an important role in the chemistry of natural organic molecules (NOM) in the environment, and their behavior is dependent on local structural environment within the macromolecule. We studied the structural environments of carboxyl groups in dissolved NOM from the Pine Barrens (New Jersey, USA), and IHSS NOM isolates from soils and river waters using attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. It is well established that the energies of the asymmetric stretching vibrations of the carboxylate anion (COO−) are sensitive to the structural environment of the carboxyl group. These energies were compiled from previous infrared studies on small organic acids for a wide variety of carboxyl structural environments and compared with the carboxyl spectral features of the NOM samples. We found that the asymmetric stretching peaks for all NOM samples occur within a narrow range centered at 1578 cm−1, suggesting that all NOM samples examined primarily contain very similar carboxyl structures, independent of sample source and isolation techniques employed. The small aliphatic acids containing hydroxyl (e.g., d-lactate, gluconate), ether/ester (methoxyacetate, acetoxyacetate), and carboxylate (malonate) substitutions on the α-carbon, and the aromatic acids salicylate (ortho-OH) and furancarboxylate (O-heterocycle), exhibit strong overlap with the NOM range, indicating that similar structures may be common in NOM. The width of the asymmetric peak suggests that the structural heterogeneity among the predominant carboxyl configurations in NOM is small. Changes in peak area with pH at energies distant from the peak at 1578 cm−1, however, may be indicative of a small fraction of other aromatic carboxyls and aliphatic structures lacking α-substitution. This information is important in understanding NOM-metal and mineral-surface complexation, and in building appropriate structural and mechanistic models of humic materials.  相似文献   

18.
The sorption of cadmium and humic acids from aqueous solutions using surface-modified nanozeolite A has been investigated under various examination conditions. The morphology of untreated and treated nanozeolite was studied under scanning electron microscope and transmission electron microscope. Isotherms of cadmium adsorption onto surface-modified nanozeolite A were studied at different pH, solid to liquid ratio, adsorbate concentration and interaction time. Kinetic and equilibrium studies were conducted and the equilibrium data have been analyzed using Langmuir and Freundlich isotherm models. The study revealed that experimental results were in agreement with the Freundlich model. The Langmuir monolayer adsorption capacity was found to be 1666.67 g cadmium and 6.75 g humic acid per gram of modified nanozeolite A, which is higher than that of reported value for other zeolites. The sorption ability was enhanced by surface modification and reduction in size and enabled the zeolite to adsorb cadmium. The adsorption of cadmium and humic acid on nanozeolite was found to be the highest at pH 6 and 3, respectively. Results showed that solid to liquid ratio and pH are the most important factors for cadmium and humic acid removal, respectively. Effect of competitive ions was studied and results showed that there is no competition between cadmium and humic acid sorption and presence of these ions.  相似文献   

19.
In order to asses the contribution of sorption by complexation to the concentration of noble metals at early stages of the formation of their deposits in black shales, the sorption of Au(III), Pt(IV), Rd(II), Rh(III), Ru(IV), and Os(IV) ions was studied on ash-free preparations of humic acids (HA) separated from peat of the Tver region and marine sediment samples taken on the Peruvian shelf. Data on the nature and protolytic characteristics of oxygen-containing HA functional groups were obtained. It has been shown that carboxyl groups and phenol oxygroups, which ensure the HA complexation with ions of noble metals, are present in the HA structure. The dissociation constant values for HA carboxyl groups (pKa) and the distribution function of these groups in their pKa values have been established. It has been revealed that the pKa value for both of the HA groups varies within two orders of magnitude: the average value is equal to 6.1 for HA from peat and 7.0 for HA from marine sediments. A fairly high and similar for both of the HA groups sorption capacity with respect to Au(III), Rd(II), Rh(III), Ru(IV), and Os(IV) ions was established in model experiments. It is equal to 320–350 mg g–1 for Au, 100–110 mg g–1 for Pd, 11–12 mg g–1 for Rh, 16–19 mg g–1 for Ru, and 23 mg g–1 for Os. The study of platinum(IV) sorption revealed that humic acids from peat and marine sediments do not virtually sorb Pt(IV), and this observation is important for understanding genetic features of the formation of noble metal deposits in black shales. Based on sorption isotherms for Au(III), Pd(II), Rh(III), and Ru(IV), the conditional affinity constant values for HA sorption centers with respect to ions of these metals were calculated by the method of quantitative physicochemical analysis. These values prove that complex compounds forming at the HA surface possess a high strength: the log values for the Au(III)–HA, Pd(II)–HA, Rh(III)–HA, and Ru(IV)–HA compounds are equal to 6.0, 5.0, 3.2, and 3.5, respectively.  相似文献   

20.
Water samples from eight major Texas rivers were collected at different times during 1997–1998 to determine the dissolved and particulate trace metal concentrations, expected to show differences in climate patterns, river discharge and other hydrochemical conditions, and human activities along the different rivers. Specifically, two eastern Texas rivers (Sabine, Neches) lie in a region with high vegetation, flat topography, and high rainfall rates, while four Central Texas rivers (Trinity, Brazos, Colorado, and San Antonio) flow through large population centers. Relatively high dissolved organic carbon (DOC) concentrations in the eastern Texas rivers and lower pH led to higher Fe and Mn concentrations in river waters. The rivers that flow through large population centers showed elevated trace metal (e.g., Cd, Pb, Zn) concentrations partly due to anthropogenically produced organic ligands such as ethylenediaminetetraacetic acid (EDTA) present in these rivers. Trace metal levels were reduced below dams/reservoirs along several Texas rivers. Statistical analysis revealed four major factors (suspended particulate matter [SPM], EDTA, pH, and DOC) that can explain most of the observed variability of trace metal concentrations in these rivers. SPM concentrations directly controlled particulate metal contents. Variation in pH correlated with changes of dissolved Co, Fe, Mn, and Ni, and particulate Mn concentrations, while DOC concentrations were significantly related to dissolved Fe concentrations. Most importantly, it was found that, more than pH, EDTA concentrations exerted a major control on dissolved concentrations of Cd and Zn, and, to a lesser extent, Cu, Ni, and Pb.  相似文献   

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