Comparison of the structural,spectroscopic and phenanthrene binding characteristics of humic acids from soils and lake sediments

The structural, spectroscopic and phenanthrene binding characteristics were compared for humic acids (HA) extracted from two different sources: eight soils and six lake sediments. The elemental analysis revealed that HA from sediments had higher H/C, N/C, and (N + O)/C ratios compared to HA from soils, reflecting a lower degree of humification and more autochthonous organic input upon the formation of the HA for lake sediments versus soil environments. HA from soils exhibited a higher content of aromatic carbon structures than the sediment HA based on ¹³C NMR results. The source of HA was easily distinguished by comparing the synchronous fluorescence spectra of each HA group. The presence of a protein like fluorescence was prominent for the HA from sediment while it was minor for the HA from soil. Irrespective of the HA source, however, humification index (HIX) exhibited a common positive correlation with the aromatic content, and a negative correlation with O-alkyl carbon structures of the HA. The correlations were consistent with the general structural trends of humification processes, suggesting that HIX may serve as a source independent predictor to describe the structural information and humification degree of terrigenous HA. Aromatic carbon structures did contribute to enhancing the phenanthrene binding for both sources of HA. However, the primary structures associated with non-ideal phenanthrene binding (i.e., non-linear sorption isotherm) appear to differ by the HA source because the opposed correlations were obtained between aromaticity and the isotherm linearity for the two HA groups. Our results suggest that the HA structural function associated with specific non-linear sorption for hydrophobic organic contaminants (HOCs) may be more strongly governed by the HA source than by the apparent physico-chemical properties.     

Racemization of amino acids in marine sediments determined by gas chromatography

Ratios of d- to l-amino acids in acid hydrolysates from foraminifera of two deep-sea cores from the Caribbean Sea and Atlantic Ocean increase with depth and consequently with age over a span from 40,000 to 2,000,000 yr. The changing ratios do not seem to follow first-order reversible rate laws. Valine, leucine and glutamic acid apparently racemize (isoleucine epimerizes) at slower rates than do phenylalanine, alanine, aspartic acid and proline. The general relative order for rates of racemization of total (free and bound) amino acids may depend on the electron-withdrawing capacity of the R substituents of the amino acids and on the rates with which the amino acids are naturally hydrolyzed. In contrast to the total amino acids, the free amino acids in these samples are more extensively racemized, probably as a result of various catalytic and hydrolytic reactions.Previous related work based on ion-exchange chromatography has considered only ratios of alloisoleucine to isoleucine. With the gas chromatographic method used here, d/l ratios of all common asymmetric amino acids can be estimated. Measurement of the extent of racemization of amino acids in marine sediments seems to provide the basis for a geochronological tool covering the last few million years.     

Dissolved free amino acids in interstitial waters of Georgia salt marsh soils

The patterns of concentration of dissolved free amino acids (DFAA) are different and more variable in pore water of soils from a Georgia salt marsh than in most surface waters. Elevated concentrations of DFAA (up to 8850 nmoles liter^?1) and high relative levels of alanine and glutamic acid suggest that bacteria may produce these amino acids. In addition to the common protein amino acids, an unidentified compound was present and was the dominant free amino acid in some sections. This compound appeared to be specific to pore waters as it was not observed in surface waters or in hydrolysates of sediments, bacteria or plants from the marsk.     

Sorption of radium-226 from oil-production brine by sediments and soils

The sorption of²²⁶Ra from oil-production brine by soils and sediments was investigated. Sorption was rapid, and the percentage sorbed increased with brine dilution. Greatest removals of²²⁶Ra from sediments in the laboratory occurred with alkaline DTPA, HCl, and BaCl₂, with lesser removals using CaCl₂ and NaCl solutions. Digestion of sediments with NaOCl indicates that most of the native and sorbed²²⁶Ra is associated with the mineral rather than organic fraction of the sediments. Correlation analysis based on 14 soils indicates that the retention of²²⁶Ra may involve precipitation reactions associated with sulfate-bearing minerals, as well as ion-exchange reactions with the clay mineral fractions of surficial earth materials. Oceanographer, Naval Ocean Research and Development Activity, Code 334; NSTL Station, Mississippi 39529 NORDA Contribution #83:334:01.     

The distribution and nature of amino acids and other nitrogen-containing compounds in Lake Ontario surface sediments

Five surface sediment samples (0–3 cm), two suspended sediment samples and a zooplankton sample from Lake Ontario were analysed for nitrogen-containing compounds. Amino acids, amino sugars, ethanolamine and urea were separated and characterized by ion-exchange chromatography. Free amino acids and soluble combined amino acids and amino sugars accounted for less than 0–25 per cent of the total nitrogen in the sediments. Insoluble combined amino acids and amino sugars were the most abundant nitrogen fraction in the sediments, making up from 49 to 55 per cent of the total nitrogen. Evidence is presented that asparagine, glutamine and citrulline are present in the interstitial waters and may make up part of the sediment organic nitrogen that was not characterized.The free amino acids released by the proteolytic enzyme, pronase, from the interstitial waters and sediment humic and fulvic acid extracts were determined. Pronase released 65 per cent of the soluble combined amino acids and 34 per cent of the fulvic acid amino acids as free amino acids. Enzyme activity was inhibited in the presence of the humic acid extract. The results indicate that the combined amino acids in the interstitial waters and fulvic acid extracts are intermediates between the primary aquatic detritus and the sediment humic acids. The enzyme experiments and infra-red data indicate that part of the sediment amino acids are combined through peptide linkages.     

Interaction of Cr(III) with the humus acids of soil,water, and bottom sediments

The interaction of Cr(III) with humus acids [fulvic (FA) and humic (HA) acids] was studied in the systems Cr(III)-FA, Cr(III)-HA, and Cr(III)-FA-HA. Chromium(III) reacts with FA extracted from the headwaters of the Moscow River and from the Krapivenka River (a tributary of Lake Seliger) to form a highly soluble high-molecular-weight Cr(III)-hydroxofulvate complexes with \(\bar \beta _{11} \) = 1.93 × 10⁶ and 5.70 × 10⁶, respectively. Humic acids extracted from peat in the Tver area and the sapropel of Lake Seliger behave as complexing sorbents with conditional affinity constants logβ = 3.78 and 3.23 for Cr(III) sorption at HA sites in the peat and sapropel, respectively. In the three-component system Cr(III)-FA-HA, the Cr(III) distribution coefficient between solution and precipitate is controlled by the pH value and FA content in the solution and decreases by 1–1.5 orders of magnitude with increasing fulvic acid content.     

Chemical characterization of fractionated humic acids from lake and marine sediments

Humic acids from Recent lacustrine and marine sediments were divided into five components by extractions with organic solvents and characterized by elementary composition, ultraviolet, visible and infrared absorption spectra and n.m.r. spectra. The results suggest that sedimentary humic acids have a cyclic structure (40–50% of the total carbon), which is considered to be alicyclic rather than aromatic. No marked differences except for an absorption near 410 mμ were observed between humic acids from lake and marine sediments.     

Bacteriohopanepolyols in tropical soils and sediments from the Congo River catchment area

The Congo River basin drains the second largest area of tropical rainforest in the world, including a large proportion of pristine wetlands. We present the bacteriohopanepolyol (BHP) inventory of a suite of tropical soils and, from comparison with published data, propose some initial ideas on BHP distribution controls. Strong taxonomic controls on BHP production are evident in wetland sediments. Dominant within the suite were 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol) and 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), indicating aerobic methanotrophy. A narrow range and low mean relative abundance of 30-(5′-adenosyl)hopane (adenosylhopane) and related compounds, collectively termed “soil marker” BHPs, were observed in Congo soils (mean 17%, range 7.9–36% of total BHPs, n = 22) compared with literature data from temperate surface soils and Arctic surface soils (mean 36%, range 0–66% of total BHPs, n = 28) suggesting a greater rate of conversion of these BHP precursors to other structures.     

Early diagenesis of fatty acids in lacustrine sediments—III. Changes in fatty acid composition in the sediments from a brackish water lake

A 3-m sediment core taken from Lake Suigetsu, in which a shift from fresh to brackish water occurred about three hundred years ago, has been examined for variation with depth of organic carbon and fatty acids. From the difference in total amounts of sulphur between sediments under fresh and brackish water environments, the surface sediments above approximately 35 cm depth were deduced to be accumulated under a brackish water environment. The total contents of organic carbon and fatty acids, and percentage composition of fatty acids gave discontinuous profiles above and below the 35–40 cm sediment layer. At a depth of 12.5 cm, the distribution in chain length of the fatty acids changed from a unimodal (the predominance of C₁₂-C₁₈ over C₂₀-C₃₄) to a bimodal pattern, which was mirrored by the composition diversity index (CDI).Although the fatty acids in the surface sediments (0–40 cm) from Lake Suigetsu seemed to suffer milder degradation through microbial activity than those in a core (0–150 cm) from Lake Suwa, a freshwater eutrophic lake, both lacustrine sediments showed similar trends in the alteration of fatty acid composition with depth.     

Geophysical indicators of culturally emplaced soils and sediments

Archaeologists dealing with earthen forms must distinguish those constructed by humans from those with a natural origin. Geophysical techniques can help identify culturally loaded soils and sediments. We suggest that intrinsic changes in geophysical properties, due to cultural loading, can serve as fingerprints in determining whether a mound or other earthen form is natural or culturally constructed. Culturally emplaced soils might be identified through anomalous values in geophysical properties or through unusual spatial or stratigraphic complexity. The identification of this “lumpiness” in geophysical properties may involve geophysical techniques quite different from those employed in traditional archaeogeophysical surveys. Experiments at three prehistoric mound sites (the Cahokia Mounds State Historic Site, Effigy Mounds National Monument, and the Hopeton Earthwork) illustrate a number of these techniques including studies of the anisotropy (directionality) of geophysical properties, seismic Rayleigh (surface) waves, and magnetic susceptibility. © 2002 Wiley Periodicals, Inc.     

Elemental sulfur in drain sediments associated with acid sulfate soils

This paper reports the abundance of elemental S in drain sediments associated with acid sulfate soils. The sediments exhibited near-neutral pH (5.97–7.27), high concentrations of pore-water Fe²⁺ (1.37–15.9 mM) and abundant oxalate-extractable Fe (up to 4300 μmol g⁻¹). Maximum acid-volatile sulfide (AVS) concentrations in each sediment profile were high (118–1019 μmol g⁻¹), with AVS often exceeding pyrite-S. Elemental S occurred at concentrations of 13–396 μmol g⁻¹, with the higher concentrations exceeding previous concentrations reported for other sedimentary systems. Up to 62% of reduced inorganic S near the sediment/water interface was present as elemental S, due to reaction between AVS and oxidants such as O₂ and Fe(III). Significant correlation (r = 0.74; P < 0.05) between elemental S and oxalate-extractable Fe(III) is indicative of elemental S formation by in situ oxidation of AVS. The results indicate that AVS oxidation in near-surface sediments is dynamic in acidified coastal floodplain drains, causing elemental S to be a quantitatively important intermediate S fraction. Transformations of elemental S may therefore strongly influence water quality in ASS landscapes.     

An investigation into the selective dissolution of sulphide phases from stream sediments and soils

A leaching technique was investigated for the dissolution of sulphide and other mineral phases in geochemical exploration samples. Samples were leached with a mixture of H₂O₁ and ascorbic acid at room temperature and the insoluble residues were leached a second time with a warm solution of ammonium acetate. Sample solutions were analysed by atomic absorption spectrophotometry. Results obtained provide useful information for assessing the significance of anomalous geochemical exploration data.     

Oxygen isotopic ratios in fine quartz silt from sediments and soils of southern Africa

Fine quartz silt (1–10μm dia, important in aerosol dust) isolated from a large number of soils, as well as Phanerozoic shales, sandstones and recent sands of the southern African stratigraphie column (Carboniferous, Permian and Triassic) exhibits a mean δ¹⁸O of 12.2 ± 2.1%0. These values are similar to those reported for South Pacific pelagic sediments and adjacent land areas of similar latitude but are lower than those reported for this size fraction of 30 Mesozoic and Paleozoic shales (20.7 ± 1.8%.) and soils from mid-continental U.S.A., for aerosol quartz in the North Pacific pelagic sediments, and for eolian caps in high-elevation soils of Hawaii. The lower oxygen isotopic ratios in fine quartz silt of southern Africa reinforces the earlier indication that Southern Hemisphere detritai sedimentary reservoirs contain a higher proportion of igneous and metamorphic quartz (lower δ¹⁸O) and less lowtemperature authigenic quartz (higherδ¹⁸O) than Northern Hemisphere detritai sediments. The difference reflects climates, as continents drifted in latitude.     

Selective extraction of organically bound gold in soils, lake sediments and stream sediments

The extraction of organically bound gold from surficial materials is accomplished by using a solution of 5% sodium hypochlorite. A 10-g sample is digested at least twice with 50 mL of hypochlorite solution. The recovery of gold from the organic phase is nearly quantitative for lake sediments and stream sediments high in organic content. For stream sediments and soils low in organics, the recovery of gold is complicated by the sorption of released gold onto inorganic sample components. For these materials, recoveries as low as 70% of the organically bound gold are possible. For a stream sediment sample containing 53.4 ppb gold, the precision of the method is approximately 6% for a 10-g sample and 14% when a 5-g sample of stream sediment is used. The results obtained for all materials tested indicate that a substantial fraction of the gold found in sediments and soils exists as organically bound gold.     

Determination of molybdenum in soils and sediments with a modified zinc dithiol procedure

Molybdenum determination, in soils and sediments, by dithiol (Stanton, 1966) is difficult when an emulsified organic layer forms and interferes with the colorimetric analysis. Addition of small quantities of acetone is suggested for clarification of the organic phase.     

Comparison of binding abilities of fulvic and humic acids extracted from recent marine sediments with UO22+

Potentiometric titrations were used to measure conditional stability constants of UO₂²⁺-fulvic acid and UO₂²⁺-humic acid complexes. Both 2:1 and 1:1 COO^-:UO₂²⁺ binding were observed. With decreasing metal concentration (2.5·10⁻⁴-6.25·10⁻⁵ M) increasing amounts of UO₂²⁺ were in the form of 1:1 humate complexes and 2:1 fulvate complexes. Despite the high nitrogen content and the low acidic OH group content, the successive stability constant values were similar to those determined for divalent cations associated with fulvic and humic compounds isolated from soils. Stability constant values increase simultaneously with increasing ionization of the humic (or fulvic) acid polyelectrolytes and with decreasing metal concentration.     

水体富营养化与水体沉积物释放营养盐

水体富营养化已经成为世界水环境面临的最为重要的问题.简要介绍了中国水体富营养化的现状和水体富营养化的成因.着重阐述了在截断外源污染后,水体沉积物对营养盐的释放及其主要影响因素,并提出了目前存在的问题和未来的发展方向,为水体富营养化的研究、预防和治理工作提供了系统、科学的理论依据.     

Organic matter in small mesopores in sediments and soils

The three-way correlation among organic matter concentrations, specific surface area and small mesopores observed for many soils and sediments led to the hypothesis that enclosure within the pores might explain the apparent protection of organic matter by minerals. We test this hypothesis by examining whether the bulk of organic matter resides within small mesopores. Pore volumes as a function of pore width were measured before and after organic matter removal, and the volume differences ascribed to organic matter filling of pores. Minor changes in small mesopore size distributions upon treatments such as centrifugation and muffling indicate the robustness of the mineral matrices that form these pores. We developed an additional method to assess organic matter densities using high-resolution pycnometry, and used these densities to convert pore volumes to organic matter contents. Although smaller mesopores are shown to have sufficient volumes to contain significant fractions of the total organic matter, only small fractions of total organic matter were found to reside in them. These results are consistent with preferential association between organic matter and aluminous clay particle edges, rather than the largely siliceous clay faces that contribute most surface area and form pore walls. While simple enclosure within smaller mesopores cannot, therefore, explain protection, network effects working at larger size scales may account for exclusion of digestive agents and hence organic matter protection.     

Rapid sampling of organic matter in flooded soils and sediments

Estuaries and Coasts - A coring system using a compressed air supply and a sediment shaking procedure using a soil dispersant are described which greatly simplify and shorten the task of...