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.     

Early diagenesis of fatty acids in lacustrine sediments—I. Identification and distribution of fatty acids in recent sediment from a freshwater lake

Fatty acids have been isolated and quantitatively determined from a 1.5 m sediment core of Lake Suwa, a eutrophic lake in the central districts of Japan.The fatty acids identified by combined gas chromatography-mass spectrometry were straight-chain saturated (C₁₂ to C₃₄), monounsaturated with even carbon number (C₁₆ to C₂₄) and branched-chain (iso, anteiso, 10-methyloctadecanoic) acids. The concentrations of the higher molecular weight (? C₂₀) saturated fatty acids remained nearly constant throughout the core, suggesting a high degree of preservation of those acids, whereas the monounsaturated and the lower molecular weight saturated fatty acids indicated a great decrease in concentration with depth to an approximately 20cm level. It is suggested that the microbial activity in sediments causes a significant reconstruction of the fatty acid distribution during early diagenesis.     

Biogeochemistry of fatty acids in recent sediments from Narragansett Bay,Rhode Island

The fatty acid composition of sediments from Narragansett Bay show significant variation between certain areas of the Bay. Both the organic carbon and fatty acid concentrations decrease with increasing distance from the Providence River area—an area which received municipal sewage and industrial effluents. The ratio of the fatty acid concentration to organic carbon concentration is fairly constant for all stations sampled. The variations in the relative abundance of fatty acids may reflect either the influence of fatty acids discharged to the river area by sewage effluents or the synthesis of fatty acids by microbial populations which probably differ for the areas compared. Temporal variations in fatty acid composition and fatty acid concentration are minimal. Lipolytic activity has been demonstrated and probably acts on glycerides deposited to the sediments releasing free fatty acids shortly after deposition. A model for the diagenesis of fatty acids in Recent sediments is proposed based upon the above findings and upon earlier reports by the authors and by other investigators.     

Compositional similarities of non-solvent extractable fatty acids from recent marine sediments deposited in differing environments

Five recent sediment samples from a variety of North American continental shelves were analyzed for fatty acids (FAs) in the solvent-extractable (SOLEX) lipids as well as four types of non-solvent extractable (NONEX) lipids. The NONEX lipids were operationally defined by the succession of extraction procedure required to recover them. The complete procedure included (i) very mild acid treatment, (ii) HF digestion and (iii) saponification of the sediment residue following exhaustive solvent extraction.The distribution pattern and various compositional parameters of SOLEX FAs in the five sediments were divided into three different groups, indicating the difference of biological sources and also diagenetic factors and processes among the three groups of samples. Nevertheless, the compositions of the corresponding NONEX FAs after acid treatment were surprisingly very similar. This was also true for the remaining NONEX FA groups in the five sediment samples.The findings implied that most of the NONEX FAs reported here are derived directly from living organisms. It is also concluded that a large part of NONEX FAs are much more resistant to biodegradation than we have thought, so that they can form the large percentage of total lipids with increasing depth of water and sediments.     

Hydrocarbons and fatty acids in two cores of Lake Huron sediments

Compositions of aliphatic hydrocarbons and of fatty acids were analyzed in two half-meter cores of postglacial Lake Huron sediment. One core represents a continuous record of the past 450 yr of sediment accumulation; the other consists of a surficial layer of modern sediment overlying 40 cm of 11,000–12,000 yr-old sediment. Concentrations of hydrocarbons are higher in the younger core than in the older one. Based upon n-alkane distributions, this reflects a smaller input of terrigenous material to Lake Huron 11,000 yr ago rather than diagenetic losses. Most of the hydrocarbons present in the 450 yr-old core are allochthonous while half are autochthonous in the older core. Fatty acids are primarily of aquatic character in both cores, and their concentrations decrease rapidly with depth. Unsaturated acids disappear more quickly than do their saturated analogs. Fatty acid degradation occurs mostly in the biologically active zone of these sediments, and little further alteration of fatty acids appears to happen over times as long as 12,000 yr.     

Early diagenesis of fatty acids in lacustrine sediments—II. A statistical approach to changes in fatty acid composition from recent sediments and some source materials

The percentage composition and total amounts of fatty acids from plankton, live and dead plants (waterweeds and higher plants) and a forest soil, considered as possible origins of autochthonous and allochthonous organic materials in lacustrine sediments, have been determined by gas-liquid chromatography. Statistical analyses were carried out by computing distance index of the fatty acid composition between these source materials and the uppermost sediment from Lake Suwa, and the composition diversity index (CDI) of fatty acids in the recent sediments from Lake Suwa.The distance index indicated that the fatty acid composition in the uppermost sediment is similar to those in diatoms, Zooplankton and forest soil, and the values for dead leaves were smaller than for live ones. It suggests that the autolysis and/or decomposition processes prior to deposition onto the top sediment makes the fatty acid composition of organic debris similar to the uppermost sediment. The CPI in recent sediments varied irregularly, whereas the CDI increased during early diagenesis to yield a value comparable to ancient sediments.     

Polyunsaturated fatty acids in a lacustrine sediment as a possible indicator of paleoclimate

Polyunsaturated fatty acids (C_18:2 and C_18:3ω3 were analyzed in the upper 20m layer of a 200 m long sediment core taken from Lake Biwa. Concentration maxima occur in layers at depths of 0.2, 1–5, 11–12, and 16m. The vertical changes in the $\text{(C}{}_{\mathrm{18:2}}\text{C(C}{}_{\mathrm{18:0}}$ ratio appear to correlate with paleoclimatic condition suggested from palynological evidence. On the basis of $\text{C}{}_{\mathrm{18:2}}\text{C}{}_{\mathrm{18:0}}$ ratios, it was suggested that it has been colder at 200, 1000–4000, 15,000 and 20,000 yr BP than at other times.     

Early diagenesis of fatty acids and isoprenoid alcohols in estuarine and coastal sediments

Fatty acids and isoprenoid alcohols were analyzed in river, estuarine, and coastal sediment cores: (1) to investigate the distribution of these lipids among the unbound phase. those bound or closely associated with humic substances, and those bound or closely associated with the huminkerogen and clay mineral matrix. (2) to investigate the diagenetic changes of these lipids with depth in the sediments. and (3) to obtain information on the use of these compounds as organic tracers in marine sediments.Results confirm earlier observations that fatty acids are rapidly altered in marine sediments Both the total and the individual fatty acids decrease in concentration with depth in the sediments: unsaturated acids decrease faster than saturated acids and unbound acids decrease faster than bound acids Approximately 8–62% of the fatty acids were unbound. 2–22% were associated with humic substances. and 38–86% were associated with the residual organic-mineral matrix. Qualitative differences also exist between the fatty acids associated with the unbound, humic, and residual fractions. The ratio of trans/cis geometric isomers of the fatty acids generally increases downcore. with no rearrangement of the double bond positions within the molecules. Either the cis isomer is being preferentially degraded with depth in the sediments, or there is a low temperature, clay catalyzed conversion of the cis isomers to the trans isomers occurring down the cores.Phytol was the major alcohol present in the sediments and does not appear to be altered as rapidly as the fatty acids. Less than 10% of the total phytol (PHY) plus dihydrophytol (DHP) was present as DHP and no trend could be discerned between PHY and DHP with depth or with unbound, humic, and residual material in the cores. All of the isolated DHP appeared to be present as the RRR stereoisomer. Along with the absence of phytane in the cores, this observation suggests that the reduction of phytol to dihydrophytol is microbially mediated in the upper layer of the sediment.     

Positional isomer composition of monounsaturated fatty acids from a lacustrine sediment

From the surface sediment of a eutrophic lake (Japan), the double bond position in the monounsaturated fatty acids (C₁₅-C₂₆) has been determined by combined gas chromatography-mass spectrometry of the methoxylated derivatives. The relative abundance of 11-octadecenoic acid, suggested to be of bacterial origin, is higher in the chloroform-methanol extract than the extract by saponification.     

Phospholipid fatty acids analysis of the vertical distribution of microbial communities in eutrophic lake sediments

Vertical distribution of microbial communities in a eutrophic lake sediments of Lake Xuanwu was quantified by phospholipid fatty acids analysis and multivariate statistical analysis was employed to interprete the data. Principle component analysis of sediment characteristics parameters, including total nitrogen, total phosphorus, organic matters and pH produced clustering of sampling sites for two distinct groups. These groups corresponded with the two sampling stations and the levels of nutrient enrichment. Total phospholipid fatty acids concentration, which is indicative of microbial biomass, reduced with depth, however, the relative percentage of anaerobic prokaryotes increased. To assess changes of microbial community along depth, phospholipid fatty acids compositions were analyzed by cluster analysis. Distinct clusters were observed in different sampling stations. Canonical correspondence analysis was carried out to infer the relationship between sediment characteristics and microbial communities. Phospholipid fatty acids samples collected at the same sampling site clustered together. Canonical correspondence analysis revealed that the environmental parameter with the greatest bearing on the phospholipid fatty acids profiles was pH. This study proved the successful application of phospholipid fatty acids and multivariate analysis to investigate the relationship between environment factors and microbial community composition.     

Nitrogen distribution as a function of radiocarbon age in Paleosol humic acids

Humic acids were extracted from six Paleosols (buried soils), ranging in radiocarbon ages from about 6000 to 29,000 yr. The N distribution (total N, amino acid-N, amino sugar-N, ammonia-N and “unknown” N) in each Paleosol humic acid was determined. After 6 M HCl hydrolysis, amino acid-N and ammonia-N decreased with increasing age but relative concentrations of “unknown” N increased. Aspartic acid, valine and serine were the most stable amino acids. Concentrations of amino sugars were very small, with concentrations of galactosamine exceeding those of glucosamine. The data showed that with increasing age, identifiable N components were converted to complex polymeric compounds whose identities still remain unknown. The different N-forms in HA's of geological times are valuable geochemical markers which provide useful information on the history of these soils.     

Phosphorus burial as a function of paleoproductivity and redox conditions in Arabian Sea sediments

In this study the response of sedimentary phosphorus (P) burial to changes in primary productivity and bottom water oxygen concentrations during the Late Quaternary is investigated, using two sediment cores from the Arabian Sea, one recovered from the continental slope and the other from the deep basin. The average solid-phase P speciation in both cores is similar, authigenic and biogenic (fish debris) apatite make up the bulk of the P inventory (ca. 70%);whereas P adsorbed to iron oxides, organic P, and detrital apatite constitute minor fractions. Postdepositional redistribution has not significantly altered the downcore distribution of total solid-phase P. Phosphorus burial efficiencies are generally lower during periods of increased paleoproductivity. This is caused by (a) partial decoupling of the P export flux, consisting primarily of particulate organic P, and the P burial flux, consisting primarily of biogenic and authigenic apatite; and (b) the lack of increased rates of authigenic CFA formation during periods of higher P deposition. In addition, fluctuations in bottom water oxygen concentrations may have affected P burial in continental slope sediments. The results of this study indicate that higher primary productivity induces more efficient P cycling. On time scales exceeding the oceanic P residence time, this process may induce higher surface water productivity, thus creating a positive feedback loop. In the Arabian Sea, this feedback mechanism may have contributed to changes in sea surface productivity on sub-Milankovitch time scales because P, regenerated on the continental slopes of the Oman and Somalian coastal upwelling zones, is reintroduced into the photic zone relatively fast.     

Molecular weight distribution of humic and fulvic acids of sediments from a north Florida estuary

The molecular weight distribution of the humic and fulvic acid fractions of two sediments was determined using Amicon ultrafiltrat ion techniques. All fractions of humic substances had a molecular weight range of less than 500 to greater than 300,000. The largest component of humic acids was in the greater than 300,000 molecular weight range, whereas, the largest percentages of fulvic acids were in the less than 500 molecular weight range and the 100,000–300,000 molecular weight range. From this preliminary investigation there appears to be a qualitative relationship between the molecular weight composition of the humic substances in the sediment and the salinity of the overlying water within an estuarine environment.     

Extraction of amino acids from soils and sediments with superheated water

A method of extraction for amino acids from soils and sediments involving superheated water has been investigated. About 75–97 per cent of the amino acids contained in four soils of a soil profile from Illinois were extracted by this method. Deep penetration of water into soil aggregates and partial hydrolysis of peptide bonds during this extraction by water at high temperature are likely mechanisms responsible for the release of amino acids from samples. This extraction method does not require subsequent desalting treatments when analyses are carried out with an ion-exchange amino acid analyzer.     

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.     

Application of a linear unmixing algorithm to the normal alkane patterns from recent salt marsh sediments

Normalized gas chromatograms of the normal alkane fraction extracted from 22 surface sediment samples from a salt marsh near Georgetown, South Carolina were submitted to an unmixing algorithm. This algorithm identified four end-number contributors, three of which very closely resemble n-alkane patterns from dominant plant species. The fourth end-member is apparently a mixture. Proportioning of the n-alkane patterns of the sediments suggests that the patterns reflect contributions from living surface plant material and dead plant material brought in by tides. The successful unmixing of complex patterns of alkanes from marsh sediments suggests a valuable new technique for the interpretation of chromatographic data.     

The pollen complex from postglacial sediments of the Laptev Sea as a bioindicator

The first results of comparison of palynological analysis (pollen of terrestrial plants), SEM analysis of pollen morphology, and radiocarbon age dating (AMS14C) of sediments of the eastern shelf of the Laptev Sea show that the diverse taxonomic composition of pollen spectra provides an integrated idea of the vegetation and climate of the region over 11.2 calendar kiloyears. It is found that phases of the tree and shrub vegetation development (maxima of pollen of Betula sect. Nanae and Pinus s/g Haploxylon) correspond to the warm epochs in the Holocene. It is obvious that birch phytocoenoses first settled in the southern tundra subzone with increasing temperature, and then coniferous communities of forest tundra. An occurrence of pollen of shrubby birches (Nanae) suggests compliance of permafrost landscapes with cold climate conditions, i.e., with an annual average temperature of ?2°C and amount of precipitation of less than 500 mm. Owing to a progressive increase in summer temperatures, dwarf cedar and pine communities advanced toward the seashore. The SEM analysis results show that a significant proportion of regional coniferous pollen belongs to representatives of Pinus pumila (Pall.) and P. sylvestris L. In addition, the SEM study of the exine of Pinus sylvestris L. and P. pumila (Pall.) Regel pollen grains confirmed polymorphism in coniferous pollen. According to the inverse relationship between climate and vegetation, frequent climate fluctuations that are typical of progressive and differential postglacial transgression were revealed. An increase in arboreal pollen transfer onto the shelf later than 9.1 cal. ka coincides with the time of forest boundary migration to the north due to the warming of the Earth’s climate. At that time, the tundra vegetation was replaced by forest-tundra vegetation, the maximum stage of sea transgression began, and there appeared a trend of increasing temperature and moisture.     

陕西勉县后沟—大坪山锰矿床地质—地球化学特征及控矿因素

近年里在南秦岭磷.锰成矿带中-东段的后沟—大坪山一带发现3条锰-磷矿化带,并圈定出3个锰矿体.锰矿体均赋存于下寒武统塔南坡组碳泥质岩—碳酸盐岩内,属海相沉积变质+改造类型锰矿床.本文在初步总结该区锰矿成矿地质特征的基础上,对优质锰矿成矿条件和成矿控制作用进行了系统深入的探讨.研究表明：本区锰成矿元素沉积受扬子地台北缘具有准稳定性质的前震旦纪基底裂陷构造盆地的控制,具有磷-锰共存、低Co、低Co/Ni比以及相对较高富集系数的Ni、Pb、Zn和B等成矿地球化学特征,成矿物质具有多源性,主要与扬子地块前震旦纪基底的陆源风化迁移沉积有关.锰成矿作用具有明显的盆控性、层控性和岩性专属性.优质锰受磷、锰分离沉积控制,层位上具有下磷上锰分层成矿特点.基于上述研究,本文提出含锰灰岩（白云质灰岩）和含黄铁矿碳质千枚岩为本区锰矿找矿标志.     

Application of a continuous distribution model for proton binding by humic acids extracted from acidic lake sediments

The proton binding characteristics of humic acids extracted from the sediments of Cranberry Pond, an acidic water body located in the Adirondack Mountain region of New York State, were explored by the application of a multiligand distribution model. The model characterizes a class of proton binding sites by mean logK values and the standard deviations of logK values about the mean. Mean logK values and their relative abundances were determined directly from experimental titration data. The model accurately predicts the binding of protons by the humic acids for pH values in the range 3.5 to 10.0.