Carbohydrates in humic and fulvic acids from Hiroshima Bay sediments

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.     

Deuterium content of humic acids from marine and non-marine environments

Deuterium values obtained for humic acids isolated from marine sediments from the NE Pacific are in the range of $\text{δ}\text{D}\text{= (?105 ± 5)‰}$, corresponding to values obtained for marine plankton from the same area. Soil humic acids have a much broader range of δD values (?57 to ?97‰), depending on the isotopic values of the precipitation and the isotopic composition of the parent plant precursor.Data obtained on hydrogen isotope distribution confirms previous hypotheses based on chemical analysis and on carbon isotopes, which indicated the authigenic nature of marine humates.     

Carbohydrates in humic and fulvic acids from sediments of Suo sound, Japan

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.     

Comparison of the structures of humic acids from marine sediments and degraded field diatoms by 13C- and 1H-NMR spectroscopy

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.     

13C NMR spectra and Cu(II) formation constants for humic acids from fluvial,estuarine and marine sediments

Humic acids extracted from fluvial, estuarine and marine sediments from the eastern coast of Florida were studied by CP/MAS ¹³C nuclear magnetic resonance. The freshwater humic acid contained a large percentage of lignin-derived aromatic carbon whereas the offshore marine samples contained large amounts of aliphatic carbon. The aliphatic carbon of the marine humic acids was more highly branched than that found for freshwater and estuarine sediments. Despite significant differences in the relative amounts and types of carbon present, conditional formation constants for Cu(II)-humic acid were very similar.     

Characterization of humic and fulvic acids isolated from marine sediments of Sagami and Suruga Bays with C-13 and proton nuclear magnetic resonance

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.     

Metal binding by humic acids in recent sediments from the SW Iberian coastal area

The concentrations of Cu, Zn, Cr, Ni, Pb, As, Mn and Co were determined by Inductively Coupled Plasma–Mass Spectrometry both in recent sediments from different locations of the Huelva littoral (SW Iberian Peninsula) and in their humic acid (HA) fractions in order to evaluate distribution and binding capacity of those trace elements to HAs. In addition, elemental composition (C, N, S) and δ¹³C values were determined to appraise the sources of organic matter in the area. This study involved the comparison of selected samples taken from different environments including the estuary of the Guadiana River, the main fluvial system of the region, the Tinto and Odiel estuary system and the proximal shelf. Significant positive correlations were found among Cu, Zn, As and Pb in bulk sediments, suggesting a common origin of all of those elements: the mining activities and pyrite deposits located hinterland. On the other hand, results for Cr, Co and Ni pointed to the basic rocks from the low basin of the Guadiana River as their main source. Elemental (C, N) and isotopic (δ¹³C) composition of sediments indicated a significant contribution of autochthonous plankton in coastal shelf sediments, whereas estuarine and riverine sediments showed a major contribution of terrestrial biomass. Geochemical values for their corresponding HAs suggested a greater terrestrial contribution in the sedimentary OM of the coastal shelf sediments than in bulk sediments, which evidenced the influence of coastal currents and sediment fluxes. Humic acids sequester considerable amounts of Cu and Zn contributing to reduce the bioavailability of these contaminants.     

The chemical forms of transition elements in marine sediments

The chemical forms of transition metals in marine sediments are discussed on the basis of differential chemical leaching.A large part of hydrogenous transition metals in the near-shore sediments is leached with dilute acetic acid, whereas hydrogenous transition metals in the deep-sea sediments are slightly leached with the acid solution and mostly leached with the reducing agent solution. This difference is attributed to the different forms of hydrogenous iron and manganese between the near-shore and deep-sea sediments.The chemical behavior of hydrogenous transition metals in the deep-sea sediments for the acid and reducing agent leaching solutions is similar to that in ferromanganese nodules. This similarity indicates that the major parts of hydrogenous transition metals in deep-sea sediments are associated with iron-manganese oxide minerals dispersed in or coated on the sediments.     

Measurement of volatile fatty acids in pore water from marine sediments by HPLC

Lower molecular weight volatile fatty acids are important intermediates in the anaerobic degradation of organic matter in marine sediments. The analysis of these compounds at the low in situ concentrations, however, still presents difficulties. A new derivatization procedure for the analysis of these compounds, coupled with high-performance liquid chromatography, has been modified for the analysis of volatile fatty acids in marine pore water to cover a linear calibration range from 0·5 μm to 10 mm. The modifications resulted in the detection of concentrations 40 times lower than in the original method and in good recoveries of fatty acid standards added to pore water (mean 101%). This modified procedure was then used to analyse fatty acids in pore water from sediments along a gradient of organic enrichment. The relative ratios of the individual acids were 1:0·1:0·02:0·01:0·02:0·01 for acetate, propionate, n-butyrate 2-methylbutyrate, iso-valerate and n-valerate. There was a tendency for the concentration of the more reduced acids to increase (propionate and n-butyrate) as organic enrichment increased. Several fatty acids were found that have not commonly been reported in marine pore water. These include 2-methylbutyrate, which is a specific anaerobic degradation product of iso-leucine, which, to the authors' knowledge, has not been previously found in marine pore water.     

Sources of the transuranic elements plutonium and neptunium in arctic marine sediments

We report here thermal ionization mass spectrometry measurements of ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu, ²⁴²Pu, and ²³⁷Np isolated from oceanic, estuarine, and riverine sediments from the Arctic Ocean Basin. ²³⁸Pu/^239+240Pu activity ratios are also reported for alpha spectrometric analyses undertaken on a subset of these samples. Our results indicate that the Pu in sediments on the Alaskan shelf and slope, as well as that in the deep basins (Amerasian and Eurasian) of the Arctic Ocean, has its origin in stratospheric and tropospheric fallout. Sediments from the Ob and Yenisei Rivers show isotopic Pu signatures that are distinctly different from those of northern-hemisphere stratospheric fallout and indicate the presence of weapons-grade Pu originating from nuclear fuel reprocessing wastes generated at Russian facilities within these river catchments. Consequently, sediments of the Eurasian Arctic Ocean, particularly those in the Barents and Kara Seas, probably contain a mixture of Pu from stratospheric fallout, tropospheric fallout, and fuel-reprocessing wastes of riverine origin. In particular, the ²⁴¹Pu/²³⁹Pu ratios observed in these sediments are inconsistent with significant contributions of Pu to the arctic sediments studied from western European reprocessing facilities, principally Sellafield in the UK. Several other potential sources of Pu to arctic sediments can also be excluded as significant based upon the transuranic isotope ratios presented.     

Molecular weight and trace metal distributions in fulvic and humic acid fractions of coastal marine sediments

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.     

Studies in seawater and lake water on interactions of trace metals with humic substances isolated from marine and estuarine sediments: I. Characterisation of humic substances

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.     

A comparison of non-hydrolytic methods for extracting amino acids and proteins from coastal marine sediments

Advances in analytical techniques now allow for the potential analysis of intact peptides and proteins isolated from marine sediments. However, there is no established technique for the extraction of macromolecular materials from marine sediments. Six different methods for extracting the amino acid component from coastal marine sediments were compared to the standard hot acid hydrolysis technique for their percent recovery and amino acid composition. The standard hot acid hydrolysis on dried, whole sediments released the greatest concentration of total amino acids (PS-THAA; 3.52 mg gdwt^− 1 ± 10% (SMD)), yet this only accounted for 22% of the total nitrogen in Puget Sound sediments (Washington, USA). Repeated hydrolysis of the same samples did not improve the recovery of nitrogen by more than an additional 10%. Base extraction (0.5 N NaOH) was the second best method for recovering amino acid nitrogen, releasing 60% of the Puget Sound total hydrolyzable amino acids (PS-THAA) (corresponding to 13% of the total sedimentary nitrogen), and has the advantage that it does not rely on peptide hydrolysis to free the nitrogenous component from the sediment matrix. The amino acid distribution of the 0.5 N NaOH extract was not significantly different than the initial THAA. Other non-hydrolyzing methods released lower yields of amino acids (Triton X-100 ≥ hot water > 50 mM NH₄HCO₃ > HF), but might prove to be of use to investigators interested in specific fractions of sedimentary organic nitrogen because these four methods had distinctly different amino acid compositions (enrichments in basic amino acids and depletions in acidic amino acids). Treatments with HF both before and after traditional hydrolysis and/or extractions with base did not release any more of the sedimentary nitrogen. Our results are consistent with the hypothesis that a large fraction of the sedimentary nitrogen (TN) is protected within an organic matrix.     

海洋沉积物含水率对部分碱金属及碱土金属元素含量的影响及意义

利用电感耦合等离子体光谱仪(ICP-AES)对海洋表层沉积物及上覆海水、海洋沉积物国家标准物质、陆地的水系沉积物及土壤国家标准物质进行检测以对比海洋沉积物含水率对部分碱金属及碱土金属元素分析结果所造成的影响。结果显示海洋沉积物含水率对钠离子影响最大,往往有超过50%的钠离子来自其中所含海水的贡献,而海洋沉积物含水率对钾、钙、镁的影响则较为微弱。因此,研究海洋沉积物化学组分时有必要考虑其所含海水对钠含量的贡献,以期达到不同海洋沉积物化学组分的可比性。     

粤西湛江港海底沉积物重金属的分布特征与来源

2004年9月23日至10月5日对湛江港海洋沉积物中金属元素的含量及分布进行了调查。共采集样品20个,采用王水-氢氟酸消解,电感耦合等离子体发射光谱法测定样品中的金属元素As、Cd、Co、Cr、Cu、Ni、Pb、Zn、Al、Ca、Fe、Mg和Mn。结果发现,湛江港大多数区域的沉积物未受污染,但霞山区港务局码头附近海域受到Cd、Cu和Pb的轻度污染,特呈岛养殖区也受到Cu的轻度污染。主成分分析结果表明,Al、Cd、Co、Cr、Cu、Fe、Ni、Pb和Zn主要通过陆源输入进入近岸水域的沉积相中,Ca、As、Mg和Mn主要通过海洋环境中水相和沉积相的相互作用进入沉积相中。结合其它调查结果认为,湛江港的Cd污染在水相、沉积相和生物相中均已存在,应引起有关部门的高度重视。     

渤海中南部沉积物中生源要素的分布特征

从化学结合形式出发,对渤海中南部海区沉积物中OC、N、P、BSi等生源要素的含量进行调查分析,讨论了各生源要素的分布及其影响因素。结果表明:受陆源输入的影响,表层沉积物中各形态氮、磷及有机碳均呈现"近岸高,远岸低"的分布趋势,生物硅的含量分布则与海区浮游硅藻的分布趋势相一致;可交换态氮是总氮中较活跃的部分,占总氮的比例约为3.7%;固定态铵是总氮的主要组成部分,约占总氮的38.4%,其主要与有机质含量及黏土矿物组成有关;渤海表层沉积物中OC/BSi、ON/BSi以及OP/BSi的比值分别为2.38、0.19、0.03,低于Redfield比值,说明有机质优先于生物硅分解;OC/ON平均值在6.0~14.0之间,判断渤海沉积物中有机质受陆源输入和海洋自生共同影响;其中,有机碳主要以陆源输入为主,而有机氮在沉积物表层主要以陆源输入为主,在沉积物下层则主要来源于海洋自生。     

Distribution pattern and geochemical analysis of rare earth elements in deep-ocean sediments

The content and distribution pattern of rare earth elements(REEs)in surface sediments from the Eastern and Western Pacifi c Ocean,the Northern and Southern Atlantic Ocean,and the Southwestern Indian Ocean were explored and the resources and geochemical characteristics of REEs in deep-ocean sediments from diff erent oceans were studied.The total REE abundances(ΣREE)in the diff erent oceans ranged as follows:Eastern Pacifi c,56.88–500.02μg/g;Western Pacifi c,290.68–439.94μg/g;Northern Atlantic,55.33–154.90μg/g;Southern Atlantic,40.83–69.30μg/g;and Southwestern Indian Ocean,20.24–64.76μg/g.Their corresponding LREE(La-Eu)/HREE(Gd-Lu)average values were 5.18,5.86,9.01,5.21,and 4.59,which indicated that the light REEs were all evidently enriched.δEu andδCe showed slight Eu-negative anomalies and signifi cant Ce-positive anomalies in all sediments.Although the contents of REEs in the sediments varied among the diff erent oceans,the distribution patterns of REEs were similar,and the correlation coeffi cient was greater than 0.9290.In the Eastern Pacifi c sediments,ΣREE showed a signifi cantly positive correlation with Co,Cu,Zn,Mn,Mo and a weak correlation with Fe.In the Western Pacifi c and Southern Atlantic sediments,ΣREE presented no obvious correlation and a weakly negative correlation with Co,Cu,Zn,Mn,Mo and Fe,respectively.ΣREE in the Southwestern Indian Ocean sediments positively correlated with Cu,Zn,Mn,Mo,Fe,and had a weakly negative correlation with Co.     

Distribution of free gas in marine sediments: a global overview

To quantify the global distribution of free gas in shallow marine sediments, we have identified and indexed over 100 documented cases in the scientific and engineering literature. Our survey confirms previous assumptions, primarily that gas bubbles are ubiquitous in the organic-rich muds of coastal waters and shallow adjacent seas. Acoustic turbidity, as recorded during seismo-acoustic surveys, is the most frequently cited evidence used to infer the presence of seafloor gas. Biogenic methane predominates within these shallow subbottom deposits. Because of their global prevalence, growing interest in gassy marine sediments is understandable, as their presence can have profound scientific, engineering and environmental significance.     

海洋沉积物微量元素地球化学特征对天然气水合物勘探的指示意义

天然气水合物与资源和全球环境变化等重大科学问题密切相关。前期关于甲烷渗漏区地球化学特征的研究主要集中于浅表层沉积物（＜20 m）,而浅层沉积物（＞20 m）地球化学特征知之甚少。为探讨海洋浅层沉积物微量元素特征与天然气水合物勘探的相关关系,对南海神狐海域沉积物进行了4个站位的钻探取样,分析了样品主、微量元素和有机碳地球化学特征,并采用氧化还原状态以及Mo与TOC相关关系的分析方法进行探讨。结果显示,沉积物主量元素特征主要受到陆源碎屑物质输入的主导,与天然气水合物富集无明显关系。水合物赋存段及附近沉积物中Ba和Mo元素高度富集,存在明显的“Ba峰”和“Mo峰”,主要是由于天然气水合物分解释放大量甲烷产生的硫化环境所导致。因此,沉积物中的Ba和Mo富集特征可作为识别可能存在天然气水合物分布的重要地球化学指标。