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1.
This work has investigated the possible formation of humic and fulvic acids, particularly high molecular weight moieties, in degrading diatom debris. The diatom debris was collected, freshly sedimented, from a well characterized natural field diatom population and allowed to degrade under conditions similar to those found at the sediment-water interface of many marine, organic-rich sediments.Samples of the detritus and overlying water were taken regularly over a period of 4 months and analysed for the presence of humic compounds. In the case of the detrital material, a sequential series of extractions were used. Molecular weight fractionation of the extracted humic material was carried out using Diaflow Ultrafiltration Membranes and two different fractionation methods have been compared. It appears that the choice of method may have an important effect on the determined distribution of the humic material, particularly when humic acid concentrations are low.High molecular weight (> 300 000- > 100 000) humic and fulvic acids were found in all the detrital samples, the content increasing with the period of decomposition. No evidence of any humic material was found in extracts of the living diatoms, the conclusion being that this material had been formed in situ during the degradation of the diatom debris. Most (65–90%) of the humic material was extracted from the detritus using a mild 0·05 m NaOH extraction at room temperature. Fulvic acids comprised approximately 90% of the total 0·05 m NaOH extraction, being composed mainly of either low molecular weight compounds (40–50% < 10000) or high molecular weight compounds (38–48% > 100000). Levels of humic acids were much lower and included a wide range of molecular weight fractions.The relevance of these findings to the possible origin of humic material in certain marine sediments is discussed.  相似文献   

2.
Two humic acids, HAL and HAN, isolated from marine sediments (Adriatic and Norwegian Sea) and humic (HAM) and fulvic (FAM) acids isolated from an estuarine sediment (Mahakam, Borneo) were characterized.The following characteristics: carbon content, hydrophobicity, degree of condensation and the content of aliphatic groups, are most pronounced for HAN, less pronounced for HAL and the least pronounced for HAM. The abundance of trace metals in the humic acids decreases in the following order: Al > Cu > Zn > Pb > Cd.Fulvic acid (FAM) has a lower carbon and a higher oxygen content than humic acids. It is hydrophilic and hardly any aliphatic groups were recorded. At pH 7 the predominant fraction of FAM has the apparent molecular weight of 20 000 daltons while the humic acids are of higher molecular weight.  相似文献   

3.
Vertical distributions of carbohydrates in humic and fulvic acids isolated from coastal sediments in Suo sound were investigated by gas chromatography and Sephadex gel chromatography. Humate carbohydrates were composed of fulvic acid carbohydrates (70 to 95%). Apparent molecular weight distribution of fulvic acid carbohydrates in vertical direction of sediments was 3·5 to 7·4% below molecular weight (M.W.) 1000, 32 to 42% for M.W. 1000 to 5000, 7·4 to 24% for M.W. 5000 to 10 000, 11·5 to 15·5% for M.W. 10 000 to 25 000, and 28 to 34% for M.W. over 25 000, respectively. Humic acid carbohydrates are present in high molecular weight over 25 000. Fulvic acid carbohydrates decreased with increasing depth. A decrease of humate carbohydrates occurred between the surface layers to 20 cm depth, below 20 cm vertical change of carbohydrates was not observed.  相似文献   

4.
In this paper the chemical characteristics of humic substances (humic acid and fulvic acid) from East China Sea surficial sediment are studied through combination of chemical and physical methods. Results show that humic acids have less aromatic hydrocarbon and more alkane structure.The contents of amino acids from hydrolyzate of humic substances are different. The amount of various amino acids (such as acidic, neutral or basic amino aicd) of fulvic acid is higher than that of humic acid. The distribution order of amino acid abundance in various kinds of sediments is neutral amino acid>aromatic amino acid> basic amino acid.In addition, mathematical statistic method is also used to study their distribution. All samples show similar regularities, i. e., the contents of glycine, alanine, aspartic and glutamic are very high and those of cystine and methionine are very low or even disappear.The above results further confirm that humic acid and fulvic acid have similar composition and structure.  相似文献   

5.
Molecular weight and trace metal distributions of fulvic and humic acid fractions of marine sediments from the Seto Inland Sea were investigated by using a gel filtration technique in combination with atomic absorption and emission spectrometries. A binary molecular weight distribution was found both in the fulvic acid fraction and in the humic acid fraction. The fulvic acid fractions with molecular weights of less than 1.5×103 and of 5×103?104 accounted for 38–57 % and 25–41 % of the total fulvic acids, respectively, and the humic acid fractions with molecular weights of 102?104 and of over 2×105 accounted for 58–73 % and 16–27 % of the total humic acids, respectively. The components with molecular weights of over 1.5×103 contained 54 %, on average, of the Fe, Zn and Cu in the fulvic acid fraction, and the components with molecular weights of over 104 contained 58 %, on average, of these metals in the humic acid fraction.  相似文献   

6.
In seawater and lake water the complexation of several heavy metals, present in the dissolved state at relevant trace levels, with humic substances isolated from two marine and an estuarine sediment has been studied by differential pulse anodic stripping voltammetry (DPASV) at a hanging mercury drop electrode (HMDE). Taking Zn(II) as an example, the aim of this study was to gain direct information on the general level of importance of humic substances for the speciation of certain heavy metals in fresh and saline waters.In seawater humic acids originating from different sediments have very similar complexing properties for Zn(II), decreasing slightly in the order HAN > HAL > HAM. In lake water HAL is most efficient for complexing Zn(II), followed by HAN and HAM.In both types of natural waters, the sedimentary fulvic acid is less efficient in complexing Zn(II) than the respective humic acid from the same site. In general, the complexing efficiency decreases in the order EDTA > NTA > humic acids > fulvic acid.The problem of humic acid adsorption at the electrode, which somewhat limits the investigation of Pb(II) and Cd(II), and the impact of pH on the amount of complexed Zn(II) are also discussed.The findings provide further direct evidence for the conclusion previously drawn from existing complexation data that because of the rather low levels of dissolved humics in large parts of the oceans, the complexation efficiency of humics for Cd, Pb and Zn is too low to affect the speciation pattern of these three heavy metals.  相似文献   

7.
In order to improve the understanding of structural and reactive features of sediment organic matter from mangrove swamp as well as evaluate the relationship between such features and the impact from different sources (marine and terrestrial), humic and fulvic acids were isolated from two mangrove swamp sediments located in the Qinglan harbors on Hainan Island, China. One is a forest surface sediment site (WWM2), and the other is an estuary subaqueous sediment site (BMW). The humic and fulvic acids were characterized and compared using chemical and spectroscopic methods, including elemental analysis, thermogravimetric analysis (TGA), Fourier Transformed Infrared Spectroscopy (FTIR), 13C nuclear magnetic resonance (13C NMR) and potentiometric titrations. The results indicated that there were less aliphatic compounds but more aromatic compounds and oxygen-containing functional groups in fulvic acids. Humic acids contained more long-chain hydrocarbons and nitrogen compounds. Comparison of the C/N ratios and δ13C values for the humic substances at both sites indicated a larger marine and/or microbial contribution to the BMW site. Humic substances at the WWM2 site have more acidic functional groups than those of the BMW site. Compared to the literature, more phenolic groups existed in the samples of both sites, which may be due to the autochthonous contribution of mangrove plants.  相似文献   

8.
A core of 75 cm length from Hiroshima Bay, Seto Inland Sea in Japan, has been analyzed for the carbohydrate content of the humic and fulvic acids. These carbohydrates were found by gel filtration to be in the high molecular weight range. Carbohydrates were more abundant in fulvic acids than in humic acids. A comparison of carbohydrates in humic acids with those in fulvic acids showed that the former did not undergo diagenetic loss any faster than the latter. Identification of most alditol acetate in monosaccharides is based on the comparison of gas chromatographic retention indices and mass spectrometric fragmentation with those of authentic standard compounds. However, the compositional differences between carbohydrates in humic and fulvic acids were greater in the top section of 0–20 cm than in the 50–70 cm section. The processes which produce the humic-acid carbohydrates are operative either prior to or shortly after deposition.  相似文献   

9.
The C-13 and proton NMR spectra of marine humic and fulvic acids isolated from sediments of Sagami and Suruga Bays and Aldrich humic acid were obtained using pulse Fourier transform mode. The C-13 and proton NMR spectra, which clarified the differences in chemical characteristics among the various humic substances, showed that the marine humic acids had more aliphatic and less aromatic character than the Aldrich humic acid, and the marine fulvic acids had polysaccharide-like character. The C-13 NMR spectra of the marine humic substances, in particular, had many relatively well-resolved peaks with significant intensities, indicating the presence of variously bonded carbon atoms in them.  相似文献   

10.
泥炭样品^14C年龄可靠性初步研究   总被引：4，自引：1，他引：4  
本文通过对泥炭中分离出的碱不溶物、胡敏酸、富里酸等有机组分样品及未经组分分离的泥炭原样的~(14)C年龄测定,探讨了泥炭样品~(14)C年龄可靠性问题。初步认为:低灰分、低分解的泥炭,同一层位的各组分样品的~(14)C年龄,具有较明显的一致性,低灰分泥炭碱不溶物的~(14)C年龄,大多偏老于其它组分,表明其年龄是可靠的,但高灰分泥炭的碱不溶物,其年龄往往偏年轻,而胡敏酸组分的年龄则具有相对的可靠性;富里酸是最年轻的不稳定的组分,其~(14)C年龄明显年轻而不可靠,是现代碳污染的主要来源。  相似文献   

11.
The interactions in seawater of cadmium, copper, and zinc with natural levels of marine humus (fulvic and humic acids) were studied using differential pulse anodic stripping voltammetry (DPASV). Interactions with Cu were also examined by ultraviolet spectrophotometry. The degree of interaction relates to the structure of the particular fulvic or humic acid tested. Marine fulvic and humic acids with different equivalent weights and varying degrees of aromaticity and heteroatom substitution were tested to assess the relative importance of these fundamental structural features in determining the degree of interaction. An index of heteroatom substitution, derived from proton magnetic resonance spectra of these materials, when combined with equivalent weights correlated with the nature and degree of metal interaction. Both marine fulvic and humic acids appreciably interacted with Zn. In contrast, the extent of interaction of fulvic acids with Cu appears to be related to their structure while humic acids appear to interact with Cu regardless of structure. Cadmium interacts only with mature, highly crosslinked humic acids.  相似文献   

12.
本文采用元素分析、镜下观察、红外光谱、扫描电镜和热解分析等技术,分析了冲绳海槽柱状样中腐植酸、富里酸和干酪根的化学、物理特征,并探讨了它们之间的成因关系和干酪根类型。沉积物的产烃能力甚差,每吨沉积物仅能生成0.49～1.18kg烃类物质。  相似文献   

13.
The mixing behaviour of iron, manganese, phosphate and humic acid in a Delaware salt marsh creek was studied using field data, laboratory mixing experiments, and geochemical mass balance equations. Property-salinity diagrams for field data indicated that the removal of iron is 56–70% in the 0–10‰ salinity range. A proposed mechanism of removal is the flocculation of colloidal iron, perhaps with humic acid. Phosphate, however, undergoes 195% addition in the same low salinity region, which may be due to release of phosphate from resuspended sediments. Dissolved manganese is conserved, as is humic acid throughout the salt marsh mixing zone. Within the uncertainty of the data the maximum possible removal of humic acid is 23%.Laboratory mixing experiments that simulated salt marsh mixing along the same salinity gradient as observed in the field (5–25‰) showed only small-scale additions and removals compared to the field results. Such small-scale changes occurred largely at salinities >10‰ in the laboratory experiments, whereas most removals and additions occurred at salinities <10‰ in the field. Mixing studies also showed little difference between prefiltered and unfiltered mixes. The studies suggest that simple mixing of salt marsh waters, with or without suspended material, does not strongly influence the observed behaviour of dissolved constituents in salt marshes, and that other processes (e.g. sediment or intertidal exchange) must dominate their behaviour.  相似文献   

14.
Humic substances (HS) from salt marsh soils were characterized and the relationships among HS composition and some geochemical factors were analysed. For this, three salt marshes with the same vegetation cover (Juncus maritimus), but with different geochemical characteristics, were selected. The qualitative characterization of the soil humic acids and fulvic acids was carried out by elemental analysis, FTIR spectroscopy, fluorescence spectroscopy and VACP/MAS 13C NMR spectroscopy.HS from salt marsh soils under sea rush (Juncus maritimus) displayed some shared characteristics such as low degree of humification, low aromatic content and high proportion of labile compounds, mainly polysaccharides and proteins. However, although the three salt marsh soils under study were covered by the same type of vegetation, the HS showed some important differences. HS composition was found to be determined not only by the nature of the original organic material, but also by environmental factors such as soil texture, redox conditions and tidal influence. In general, an increase in the humification process appeared to be related to aerobic conditions and predominance of sand in the mineral fraction of the soil, while the preservation of labile organic compounds may be associated with low redox potential values and fine soil texture.  相似文献   

15.
Humic compounds were determined in sediments collected in an area of the Adriatic sea receiving fresh waters from the river Po. Sediment cores (10 cm) were sectioned into four layers which were analysed separately for redox potential (Eh), total phosphorus (TP), total organic carbon (TOC), humic (HA) and fulvic acid (FA) content. The structure of HA and FA was also investigated. The results showed that the TOC and TP content decreased from the coast to the open-sea stations. Humic and fulvic acid concentrations were also inversely correlated to the distance from the coast. Moreover, the humic and fulvic acids were closely correlated to the total organic content and to the total phosphorus content. The correlations found between humic substances (HS) and TOC and TP, respectively, could be explained both by an in situ formation due to the high content of nutrients and organic matter, and by a common source of HS, TOC and TP, namely the River Po discharge. The predominant presence of aliphatic carbon in the humic structures, the low degree of substitution and the high nitrogen content suggest that primarily humified compounds were formed in situ. Nevertheless, the River Po can act both as supplier of organic matter of which decomposition products lead to the formation of humic compound and as carrier of humified compounds.  相似文献   

16.
A simple method for the determination of dissolved humic acid based on carbon analysis is presented. This method was used to measure the distribution of dissolved humic acids in seven coastal plain estuaries located in the middle-Atlantic United States. Results indicate that 100% of the dissolved humic acid was removed during estuarine mixing, although concurrent measurements of dissolved organic carbon showed either production or conservative behavior in regions of the estuary where humic acid removal was observed. It is apparent from these observations that removal of dissolved humic acid is a minor part of the estuarine transport of dissolved organic carbon.Laboratory experiments carried out by mixing river water with sea water demonstrated that salt-induced removal of dissolved humic acid was insignificant in two of three estuaries studied. These results suggest in situ removal of dissolved humic acid may not be universally caused by increasing estuarine salinity.  相似文献   

17.
The elemental composition and oxygen-containing functional groups contents in the marine humic acids from the five sediment samples from Sagami Bay and Suruga Bay were determined. Kumada's method of classification of soil humic acids was applied to the marine humic acids. The carbon, nitrogen, hydrogen, oxygen and sulfur contents of the marine humic acids were, on average, 52.96, 5.12, 5.79, 34.99 and 1.13%, respectively, without wide variation. In comparison with terrestrial humic acids, the marine ones had relatively lower carbon content and higher hydrogen and nitrogen contents. It is suggested that the marine humic acids have more aliphatic and less aromatic character, as expected from their possible origins, e.g., phytoplankton. The total acidity, carboxyl, phenolic and alcoholic hydroxyl, carbonyl and methoxyl group contents in the marine humic acids were, on average, 5.80, 3.27, 2.53, 2.53, 3.09 and 0.41 milliequivalents per gram of dry ash-free humic acid (me g–1), respectively. From quantitative data on the elemental composition and functional groups of the average marine humic acid, its empirical formula was calculated to be C107H138O20(COOH)9(OH)7 phenolic (OH)7 alcoholic (CO)9(OCH)3N10S. The marine humic acids were similar to the so-called B type of soil humic acids with regard to the distribution of functional groups and spectroscopic properties.  相似文献   

18.
The interaction of chromium (III) with humic substances obtained from pond sediment was experimentally studied using electrophoresis combined with ultrafiltration. The results show that within the neutral pH range chromium (III) in the presence of humic substances and some organic acids forms uncharged and/or negatively charged organic complexes of various molecular weights. A part of the chromium(III)-humic or -fulvic acid complexes having a negative charge was of lower molecular weight. Chromium (III) spiked in fresh water exists as various soluble anionic and/or uncharged species, and the molecular weights of these anionic complexes correspond to those of chromium(III)-humic and -fulvic complexes. These complexes may remain as stable dissolved forms for 10 days. The significance of the occurrence of chromium(III)-organic complexes in natural water in the geochemical cycle of chromium in the hydrosphere is discussed.  相似文献   

19.
Humic acids isolated from marine sediments of the Peru continental shelf and from a degraded field diatom population dominated by the diatoms Skeletonema costatum, Nitzschia seviata and Thalassiosira sp. were characterized on the basis of infrared spectra and 13C- and proton-NMR spectra. Aliphatic structures were found to constitute the major fraction of humic acids and they appear to be highly branched. Carbohydrates and to a lesser extent aromatic materials, carbonyl-, ether-, alcohol- and amino groups are important contributors to the structure of marine humic acids. A close relationship was observed between the chemical structure of the sedimentary humic acid and the plankton humic acid.  相似文献   

20.
It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (<0.4 μm) were linearly related to salinity (10.8–36.6), suggesting that the distribution of these elements was mainly controlled by continuous mixing processes. Dissolved concentrations across the salinity gradient ranged for Cd: 87–187 pM; Cu: 1.4–18.3 nM; and Ni: 2.6–18.8 nM, with highest values near the Mississippi river mouth, and lowest concentrations in a warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (<10 kDa, 97 ± 1%) and cationic fraction (Chelex-100 extractable, 94 ± 4%). A novel observation across the estuarine mixing zone was that colloidal metal concentrations were identical to either inert (for Cu, Ni) or AMPG-labile anionic (Cu, Cd) fractions. The difference in behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal–organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were “inert” averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of ‘inert’ and ‘anionic’ metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.  相似文献   

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