Changes in the compound classes of dissolved organic matter along an estuarine transect: A study using FTIR and C NMR

In this work, we use Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) data to quantify the changes of major chemical compound classes (carboxylic acid, amide, ester, aliphatic, aromatic and carbohydrate) in high molecular weight (HMW, >1 kDa) dissolved organic matter (DOM) isolated along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that carboxylic acids and aromatic compounds are lost along the transect, while HMW DOC becomes enriched in carbohydrate moieties that could have a mid-transect source, perhaps the intensive red tide bloom (Choclodinium polykrikoides) which occurred during our sampling period. Taking the second derivative of the FTIR spectra resolved three pools of de-protonated carboxylic acids at our Dismal Swamp site (used to represent terrestrial organic matter in this area): one carboxylic acid pool, complexed with iron, seems to be lost between the Dismal Swamp and river sites; the second appears biogeochemically active throughout the riverine transect, disappearing in the coastal ocean sample; the third seems refractory, with the potential to be transported to and to accumulate within the open ocean. Five-member ring esters (γ-lactones) were the major ester form in the Dismal Swamp; aliphatic and acetate esters were the dominant esters in the estuary/marine DOM. No amide groups were detectable in Dismal Swamp DOM; secondary amides were present at the estuarine/marine sites. Coupling FTIR with ¹³C NMR provides new insights into the biogeochemical roles of carboxylic acid, amide and ester compounds in aquatic ecosystems.     

A new approach for molecular characterisation of sediments with Fourier transform ion cyclotron resonance mass spectrometry: Extraction optimisation

Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) can begin to tease apart the molecular character of sedimentary organic matter (SOM). We therefore tested five different solvents (aqueous base, CHCl₃, MeOH, pyridine and water) for their ability to extract a representative fraction from two organic rich lacustrine sediments, Mangrove Lake, Bermuda (MLB) and Mud Lake, Florida (MLF). Following comparison using liquid state nuclear magnetic resonance spectroscopy (NMR) and negative ion mode electrospray ionization mass spectrometry (FTICRMS) we found that pyridine was the optimal solvent, extracting a more diverse (10–100× greater integration for carbonyl, amide and amine groups) and a larger number of peaks on average (1375–1450 vs. 380–1450). Comparison of the pyridine extracts between MLB, MLF and two organic poor sediments from the Mississippi River Delta and Bayou Grande (Pensacola, FL) showed that only 4.9% of the molecular formulae were common to all four and that unique formulae made up the highest proportion of the assignments. The use of pyridine for extracting immature (Holocene) SOM for FTICRMS analysis can therefore be widely applied to immature sediments and produce representative spectra.     

Distribution of aliphatic,nonhydrolyzable biopolymers in marine microalgae

The recent discovery of several marine microalgal species which biosynthesize nonhydrolyzable, aliphatic biomacromolecules, termed algaenans, has provided new insights about the nature and origin of the organic matter preserved in marine sediments. This paper reports the examination of 12 new species of marine microalgae from five different classes; the results are discussed together with previous observations on marine algaenans. None of the diatoms and prymnesiophytes and only one of the dinoflagellates examined in the present study produced algaenan, whereas all the eustigmatophytes biosynthesize a very specific algaenan composed of polyether-linked long-chain alkyl units. Many of the chlorophytes investigated, as with their freshwater counterparts, also produce algaenan. The location of the algaenan in the algal cells and the resistance of these materials to chemical and bacterial attack are discussed with respect to their role as a potential sink of organic carbon in aquatic environments.     

柴达木盆地察尔汗湖区古湖相沉积物中含氮类分子化石的检出

利用气相色谱质谱联用仪(GC-MS)对青藏高原柴达木盆地察尔汗湖区贝壳堤剖面古湖相沉积物样品进行了系统地分析,检测出系列脂肪酸酰胺与脂肪腈类含氮类脂物分子化石.并对其在古湖相沉积物中的分布特征作了详细描述.对它们综合研究认为,早期成岩作用使来源于各种生物体的脂肪酸酰胺类分子化石部分地转化为脂肪腈类化合物.此外,不饱和脂肪酸酰胺与饱和脂肪酸酰胺的含量比值在剖面上并没有呈现明显下降的趋势,说明在降解过程中各种生物、物理及化学作用对它们不存在明显的选择性,指示有机质在沉积过程中可能处于一个偏氧化的环境.本文首次报道这两类物质,为更好地理解含氮类脂物分子化石在湖泊沉积物中的转化过程提供了一定的理论依据.     

The effect of organic matter and oxygen on the degradation of bacterial membrane lipids in marine sediments

The biodegradation of purified radiolabelled membrane lipids from a methanogenic bacterium and a pseudomonad were investigated in mangrove, beach and high marsh marine sediments under aerobic and anaerobic conditions. The effect of organic matter on the amount and rate of degradation was also examined by supplementing beach sediments with humic acids. In aerobic sediments, CO₂ was the major product of lipid degradation while under anaerobic conditions both CO₂ and CH₄ were major end products and the overall rates were reduced (up to 40%) relative to aerobic conditions. Total bacterial numbers increased during all incubations with the largest increases occurring in anaerobic sediments supplemented with humic acids. No lipid degradation occurred in aerobic or anaerobic sediments treated with formaldehyde or autoclaving. In low organic beach sediments, the ester-linked phospholipid of the pseudomonad was degraded much more rapidly than the diphytanyl glycerol diether of the methanogen with 69% of the phospholipid degraded in 96 hours versus only 4% of the methanogen lipid. Lipid degradation in both aerobic and anaerobic sediments was highly correlated to organic matter content with increasing amounts of organic matter inhibiting degradation. Long incubations (75 days) of the diphytanyl glycerol ether resulted in 51% degraded to CO₂ in low (0.5%) organic mangrove sediments while only 9% was mineralized in high (10.8%) organic marsh sediments. Physicochemical sorption of membrane lipids to the organic matrix is proposed as a mechanism which protects membrane lipids from microbial attack and degradation.     

Molecular composition of sedimentary humic acids from South West Iberian Peninsula: A multi-proxy approach

The molecular structural features of humic acid (HA) fractions isolated from recent sediments from the estuaries and continental platform along the Huelva littoral (SW Iberian Peninsula, Spain) were studied using complementary analytical tools. The approach included elemental analysis, solid state, ¹³C cross polarisation magic angle spinning nuclear magnetic resonance spectroscopy (¹³C CP-MAS NMR), pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) and stable C and N isotopic composition (δ¹³C, δ¹⁵N). The results point to the presence of vascular plant matter contributing to all the HAs, even those far from the coastal area. A contribution of lignocellulose material was detected from ¹³C NMR signals at 152 ppm (O-aryl C), 55 ppm (methoxyl C) and 33 ppm (alkyl chain) and confirmed by the presence of lignin derived structures (methoxy phenols) in the pyrolysis chromatograms. Nevertheless, the HAs from the westernmost part of the continental platform had the lowest aromatic and the highest C-alkyl abundance (¹³C NMR spectroscopy). These data, combined with low C/N and high H/C values, a relative enrichment in δ¹³C and the presence in the pyrolysates of conspicuous n-alkyl nitrile and amide series, together with n-alkane/ene homologues, pointed towards a relevant marine (autochthonous) contribution to this sedimentary organic matter (OM). In contrast, HAs from sediments collected from the Tinto-Odiel River mouth and Guadiana Estuary areas revealed a major input of terrestrial OM. In general, the data support the idea that the HAs still contain valuable information about the signature of aliphatic and aromatic biomacromolecules contributing to the deposited OM.     

Molecular characterization of dissolved organic matter in pore water of continental shelf sediments

Dissolved organic matter (DOM) in sediment pore water is a complex molecular mixture reflecting various sources and biogeochemical processes. In order to constrain those sources and processes, molecular variations of pore water DOM in surface sediments from the NW Iberian shelf were analyzed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and compared to river and marine water column DOM. Weighted average molecular element ratios of oxygen to carbon ((O/C)_wa) and hydrogen to carbon ((H/C)_wa) provided general information about DOM sources. DOM in local rivers was more oxygenated ((O/C)_wa 0.52) and contained less hydrogen ((H/C)_wa 1.15) than marine pore water DOM (mean (O/C)_wa 0.50, mean (H/C)_wa 1.26). The relative abundance of specific compound groups, such as highly oxygenated aromatic compounds or nitrogen-bearing compounds with low H/C ratios, correspond to a high concentration of lignin phenols (160 μg/g sediment dry weight) and a high TOC/TN ratio (13.3) in the sedimentary organic matter and were therefore assigned to terrestrial sources. The lower degree of unsaturation and a higher relative abundance of nitrogen-bearing compounds in the pore water DOM reflected microbial activity within the sediment. One sampling site on the shelf with a high sediment accumulation, and a humic-rich river sample showed a wide range of sulfur compounds in the DOM, accompanied by a higher abundance of lipid biomarkers for sulfate-reducing bacteria, probably indicating early diagenetic sulfurization of organic matter.     

An interpretation of carbon and sulfur relationships in Black Sea sediments as indicators of environments of deposition

Syngenetic iron sulfides in sediments are formed from dissolved sulfide resulting from sulfate reduction and catabolism of organic matter by anaerobic bacteria. It has been shown that in recent marine sediments deposited below oxygenated waters there is a constant relationship between reduced sulfur and organic carbon which is generally independent of the environment of deposition. Reexamination of data from recent sediments from euxinic marine environments (e.g., the Black Sea) also shows a linear relationship between carbon and sulfur, but the slope is variable and the line intercepts the S axis at a value between 1 and 2 percent S. It is proposed that the positive S intercept is due to watercolumn microbial reduction of sulfate using metabolizable small organic molecules and the sulfide formed is precipitated and accumulates at the sediment-water interface. The variation in slope and intercept of the C to S plots for several cores and for different stratigraphic zones for the Black Sea can be interpreted in relation to thickness of the aqueous sulfide layer or thinness of the oxygen containing layer and to deposition rate, but also may be influenced by availability of iron, and perhaps the type of organic matter (Leventhal, 1979).     

Organic geochemistry and pore water chemistry of sediments from Mangrove Lake,Bermuda

Mangrove Lake, Bermuda, is a small coastal, brackish-water lake that has accumulated 14 m of banded, gelatinous, sapropelic sediments in less than 10⁴ yr. Stratigraphic evidence indicates that Mangrove Lake's sedimentary environment has undergone three major depositional changes (peat, freshwater gel, brackish-water gel) as a result of sea level changes. The deposits were examined geochemically in an effort to delineate sedimentological and diagenetic changes. Gas and pore water studies include measurements of sulfides, ammonia, methane, nitrogen gas, calcium, magnesium, chloride, alkalinity, and pH. Results indicate that sulfate reduction is complete, and some evidence is presented for bacterial denitrification and metal sulfide precipitation. The organic-rich sapropel is predominantly algal in origin, composed mostly of carbohydrates and insoluble macromolecular organic matter called humin with minor amounts of proteins, lipids, and humic acids. Carbohydrates and proteins undergo hydrolysis with depth in the marine sapropel but tend to be preserved in the freshwater sapropel. The humin, which has a predominantly aliphatic structure, increases linearly with depth and composes the greatest fraction of the organic matter. Humic acids are minor components and are more like polysaccharides than typical marine humic acids. Fatty acid distributions reveal that the lipids are of an algal and/or terrestrial plant source. Normal alkanes with a total concentration of 75 ppm exhibit two distribution maxima. One is centered about n-C₂₂ with no odd/even predominance, suggestive of a degraded algal source. The other is centered at n-C₃₁ with a distinct odd/even predominance indicative of a vascular plant origin. Stratigraphic changes in the sediment correlate to observed changes in the gas and pore water chemistry and the organic geochemistry.     

5β-isomers of stanols and stanones as potential markers of sedimentary organic quality and depositional paleoenvironments

Organic molecules originating only from the in situ diagenesis of biogenic molecules are ideal geochemical fossils which may provide information essential for the characterization and reconstruction of depositional environments and subsequent chemical reactions during diagenesis. It is proposed herein that this is the case for the 5β-isomers of stanols and stanones produced during stenol hydrogenation in young aquatic sediments, if shown to be essentially free of any major anthropogenic pollution (particularly, sewage). In order to clarify the environmental factors controlling the production of the 5β-steroidal isomers from stenols in recent aquatic sediments, attempts were made to relate the occurrence of 5β-stanols to various environmental parameters. Positive correlations between elevated concentrations of 5β-stanols and the degree of autochthonous contribution to sedimentary organic matter were consistently found in various surface aquatic sediments from a wide variety of depositional environments and also in older sediments extending even to the late Pleistocene. According to this finding, it was concluded that the primary factor controlling the conversion of stenols to 5β-stanols through 5β-stanones in anaerobic aquatic sediments is probably the relative contribution of autochthonous organic matter suitable for microbial metabolism (i.e. metabolizable organic matter) to the sediments. Consequently, it is proposed that the 5β-isomers of stanols and stanones, at least in immature aquatic (marine and non-marine) sediments, can serve as primary markers for defining the quality of sedimentary organic matter (viz. the relative contribution of metabolizable organic materials to sedimentary organic matter) and as indicators for the types and rates of microbiological activities responsible for early diagenesis of organic matter in anaerobic sediments. It is also suggested that the combination of the 5β-steroidal isomers with organic source parameters will allow these compounds to assist in indicating oxic or anoxic depositional environments.     

Kinetics of microbial sulfate reduction in estuarine sediments

Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, K_m, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, R_max, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm⁻³ h⁻¹ at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of R_max in the brackish sediments were lower (3.7-7.6 nmol cm⁻³ h⁻¹ at 21 °C), probably due to less labile organic matter, as inferred from higher C_org/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher R_max values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.     

Chemical composition of the graphitic black carbon fraction in riverine and marine sediments at sub-micron scales using carbon X-ray spectromicroscopy

The chemical composition of the graphitic black carbon (GBC) fraction of marine organic matter was explored in several marine and freshwater sedimentary environments along the west coast of North America and the Pacific Ocean. Analysis by carbon X-ray absorption near-edge structure spectroscopy and scanning transmission X-ray microscopy shows the GBC fraction of Stillaguamish River surface sediments to be dominated by more highly ordered and impure forms of graphite, together forming about 80% of the GBC, with a smaller percent of an aliphatic carbon component. Eel River Margin surface sediments had very little highly ordered graphite, and were instead dominated by amorphous carbon and to a lesser extent, impure graphite. However, the GBC of surface sediments from the Washington State Slope and the Mexico Margin was composed almost solely of amorphous carbon. Pre-anthropogenic, highly oxidized deep-sea sediments from the open Equatorial Pacific Ocean contained over half their GBC in different forms of graphite as well as highly aliphatic carbon, low aromatic/highly acidic aliphatic carbon, low aromatic/highly aliphatic carbon, and amorphous forms of carbon. Our results clearly show the impact of graphite and amorphous C phases in the BC fraction in modern riverine sediments and nearby marine shelf deposits. The pre-anthropogenic Equatorial Pacific GBC fraction is remarkable in the existence of highly ordered graphite.     

Freshwater chlorophycean algae in recent marine sediments of the Beaufort, Laptev and Kara Seas (Arctic Ocean) as indicators of river runoff

Freshwater chlorophycean algae are characteristic organic-walled microfossils in recent coastal and shelf sediments from the Beaufort, Laptev and Kara seas (Arctic Ocean). The persistent occurrence of the chlorophycean algae Pediastrum spp. and Botryococcus cf. braunii in marine palynomorph assemblages is related to the discharge of freshwater and suspended matter from the large Siberian and North American rivers into the Arctic shelf seas. The distribution patterns of these algae in the marine environments reflect the predominant deposition of riverine sediments and organic matter along the salinity gradient from the outer estuaries and prodeltas to the shelf break. Sedimentary processes overprint the primary distribution of these algae. Resuspension of sediments by waves and bottom currents may transport sediments in the bottom nepheloid layer along the submarine channels to the shelf break. Bottom sediments and microfossils may be incorporated into sea ice during freeze-up in autumn and winter leading to an export from the shelves into the deep sea. The presence of these freshwater algae in sea-ice and bottom sediments in the central Arctic Ocean confirm that transport in sea ice is an important process which leads to a redistribution of shallow water microfossils.     

柴北缘鱼卡地区中侏罗统石门沟组含煤层段沉积有机相分析

柴达木盆地北缘鱼卡地区中侏罗统石门沟组含煤段中发育有油页岩、煤、碳质泥岩和泥岩等富有机质细粒沉积.为了研究其沉积有机相的类型及煤和油页岩形成的控制因素,本文通过岩心观察、工业分析结合有机地球化学测试分析等方法将含煤段细粒沉积物划分为了类型A(三角洲平原沉积环境)、B(三角洲前缘-浅湖沉积环境)、C1(湖沼非油页岩亚相)及C2(湖沼油页岩亚相)四种类型,其中类型C1沉积物中发育煤,类型C2中发育油页岩,且煤较油页岩具有更高的含油率、水分、挥发分以及发热量值.有机质类型特征方面,沉积有机相类型A、B及C1沉积物有机质类型均为Ⅱ2-Ⅲ型、有机质来源均以陆源和混合来源两种有机质来源为主,而类型C2中主要为Ⅱ2型,以混合有机质来源为主;类型A及C2其沉积物有机质均处于未成熟阶段,而类型B和C1中有机质均处于未成熟-低成熟阶段;有机质保存条件方面,类型A沉积物主要形成于缺氧的淡水环境,类型B主要形成于贫氧-缺氧的淡水-半咸水环境,类型C1形成于贫氧-缺氧的淡水-半咸水环境,而类型C2则主要形成于缺氧的淡水-半咸水环境.其中类型B较类型A,类型C2较类型C1,其沉积物均形成于更为还原且盐度更高的水体环境中.石门沟组含煤段是煤和油页岩的形成层位,稳定的沉积环境、丰富的湖泊有机质来源、良好的保存条件及较少的陆源碎屑的稀释共同促进了类型C2中油页岩的形成,而丰富的陆源植物供给及良好的保存条件则促进了类型C1中煤层的形成.     

青海湖底沉积物的矿物物相及有机质保存研究

盐湖沉积环境是烃源岩发育的重要地质环境。本文以青海湖湖底沉积物为例，根据有机质与粘土矿物含最及矿物表面积的关系，分析了矿物学因素对盐湖相富有机质沉积物中有机质保存的影响。研究发现：湖底沉积物中有机质丰富，为上层水中的浮游生物和南河流携带束的陆地高等植物两种来源。矿物物相分析发现沉积物中粘土矿物含量达到32．4％，以伊利石为主。沉积物经密度分离后测试发现，有机碳含量与粘土矿物含量及矿物表面积之间具有很好的正相关性，说明粘土矿物吸附是青海湖底沉积物中有机质的主要赋存形式。     

Marine Dissolved Organic Phosphorus Composition: Insights from Samples Recovered Using Combined Electrodialysis/Reverse Osmosis

The dominant phosphorus compound classes were characterized in marine samples using a new, high recovery method for isolating and concentrating bulk dissolved organic matter (DOM) called combined electrodialysis + reverse osmosis (ED/RO). In contrast to earlier studies that use ultrafiltration (UF) to recover only the high molecular weight DOM, ED/RO is capable of isolating both low molecular weight (LMW) and high molecular weight (HMW) DOM. Samples were collected from a broad range of marine environments: along a transect incorporating coastal and offshore waters off the Southeastern United States, in Effingham Inlet, a Pacific fjord located on Vancouver Island, British Columbia and in the Amundsen Sea, Antarctica. Results from phosphorus nuclear magnetic resonance (³¹P NMR) analysis reveal a similar abundance of P compound classes among samples, phosphate esters (80–85%), phosphonates (5–10%) and polyphosphates (8–13%). These samples contain significantly higher proportions of polyphosphate P and P esters and lower proportions of phosphonates than measured in previous studies using the UF method. The much higher levels of polyphosphate detected in our samples suggests that polyphosphate is present mainly in the LMW dissolved matter fraction. Polyphosphates in dissolved matter may be present as (or derived from) dissolved nucleotides or organismal polyphosphate bodies, or both. Low molecular weight P esters are possibly composed of phosphoamino acids and small carbohydrates, like simple sugar phosphates and/or dissolved nucleotides. Phosphonates in DOM are more prevalent as HMW phosphonate compounds, which suggests that LMW phosphonates are more readily utilized in marine ecosystems. Overall, the investigation of DOM across a size spectrum that includes both the HMW and the LMW fractions reveals a new picture of phosphorus distribution, cycling and bioavailability.     

Environmental changes in Saginaw Bay,Lake Huron recorded by geolipid contents of sediments deposited since 1800

Changes in organic materials preserved within sediments of Saginaw Bay deposited over the past two centuries record corresponding periods in the environmental history of this part of Lake Huron and its watershed. Sediments deposited since 1940 show an increasingly greater input of aquatic organic matter in response to accelerating cultural eutrophication of Saginaw Bay. Concentrations of fatty acids, sterols, fatty alcohols, and aliphatic hydrocarbons are higher in these modern sediments than in deeper ones. Molecular distributions of these geolipids reflect less aquatic material deeper in the sediments. Prior to 1875, sediment organic matter appears to be diluted by mineral matter from enhanced erosion caused by clearing of the watershed for farming and settlement. During this period there is better preservation of carbonate minerals due to quicker burial. Since 1875, petroleum components comprise over 90% of the total aliphatic hydrocarbon content of these sediments, reflecting the advent and continued existence of chronic, low-level petroleum contamination of this part of the Great Lakes.     

南四湖及主要入湖河流沉积物中磷的赋存形态研究

应用沉积物磷形态SMT提取方法,分析了南四湖及主要入湖河流丰水季节表层沉积物、独山湖及微山湖区沉积岩芯中磷的含量及形态组成变化,研究了磷的埋藏演化过程与人为污染特征.结果表明,老运河表层沉积物中磷的含量最高,为13068.3 mg/kg,以OP及NaOH-P为主,其富集系数分别为6.5和9.0,主要是与来自济宁市的废水污染有关.其余表层沉积物以HCl-P为主;受人为污染的影响,NaOH-P、OP产生一定程度的富集,其富集系数分别为1.0.3.7、1.3～6.0;部分沉积物中高含量的有机质加重了OP的富集.独山湖及微山湖沉积岩芯中以HCl-P和OP为主;20世纪60年代末期以来,随着湖泊生产力的提高及早期成岩过程中有机质的矿化分解,独山湖及微山湖沉积岩芯中TOC含量自下而上呈指数增加,这也导致了沉积物中OP的增加;独山湖及微山湖沉积岩芯6～0 cm和5～0 cm较高的OP及NaOH-P含量,指示了20世纪80年代中期以来磷的人为污染过程.     

Raman spectroscopy and biomarker analysis reveal multiple carbon inputs to a Precambrian glacial sediment

Extractable biomarkers can help elucidate the environment and biota of ancient glaciations, although the method must be applied with care, as glacial sediments have a potential for incorporation of older detrital carbon. In Phanerozoic glacial sediments, the distinct elemental, molecular and isotopic compositions of the terrestrial and marine biomass allow discrimination between primary marine and redeposited terrestrial organic matter. However, as the Proterozoic biosphere was largely microbial and marine, biomarker and isotopic analyses are insufficient for distinguishing primary organic matter from secondary reworked organic matter. Here, we report the combined application of Raman spectroscopy and biomarker analysis to Precambrian glacial sediments, which, together, allows discrimination between mixed pools of organic carbon and provides a promising new approach for rapidly screening Precambrian sediments for immature organic matter amenable to biomarker analysis.     

日本大沼湖沉积物碳氮比值、有机碳同位素特征及其近400年的古气候环境意义

通过对日本大沼湖沉积物样品总有机碳含量(TOC)及其稳定同位素、总氮含量(TN)和C/N 值的测定, 结合沉积岩芯火山灰和 14C 年代, 分析了大沼湖沉积物中有机质的来源, 探讨了沉积物有机碳同位素的主要影响因素。结果表明: 大沼湖沉积物中有机质主要来源于自生藻类, 受陆源输入的影响较小; 沉积物δ13C 值指示了夏季温度的变化。过去400年来, 大沼湖地区存在1660~1730年和1780~1860年两个明显的冷期, 与邻近地区冰芯、树轮和湖泊沉积物记录的冷期基本一致, 分别对应于Maunder和Dalton太阳黑子极小期。