The contribution of bacteria to organic matter in coal-measure source rocks

On the basis of GC–MS analysis, a suite of nine coal-measure source rocks (Ro 0.51%–0.63%) from the southern margin of Junggar basin was found to contain many biomarkers for bacterially-generated hydrocarbons: hopane, sesquiterpene, C₂₃+ monomethyl alkanes (even carbon predominance), and C₂₄+ alkyl cyclohexane. Rock–eval and microscope analysis indicate that vitrinite (especially desmocollinite and homocollinite) plays a significant role in the generation of hydrocarbons in coal-measure source rocks. Vitrinite performs this role by absorbing ultramicroscopic organic matter, generally in the form of resins or bacterial plastids. C₂₃+ monomethyl alkanes (even carbon predominance) and C₂₄+ alkyl cyclohexane series compounds are derived from bacterial metabolites of higher plants. The ultramicro organic matter adsorbed by vitrinite source rocks in the study area is probably ultramicro bacterial plastids. Because the organic matter of higher plants with low hydrogen content has been transformed into organic matter rich in hydrogen by bacteria, the hydrocarbon generation capacity of source rocks is greatly improved. In other words, in coal-measure source rocks, bacteria play an important role in hydrocarbon generation.

     

Assessment of lacustrine/fluvial clays as liners for waste disposal (Lake Van Basin, Turkey)

Potential use of lacustrine/fluvial type clays in Lake Van Basin (Turkey) as liner material is investigated by studying their chemical, mineralogical and technological properties. The results show dominant clay minerals being Ca-smectite along with illite, swelling chlorite, and chlorite. Na-smectite, palygorskite, and kaolin group minerals with lesser quantities are also determined in some samples. Cation exchange capacities of samples are between 12 and 23?meq/100?g; plasticity index is between 13 and 39%; calculated hydraulic conductivity is between 2.7?×?10^?9 and 4.5?×?10^?11; volumetric swelling capacity is between 6 and 10%. It is concluded that clays in the basin have suitable properties to be used as liner materials, with some localities having better clays as liner materials than the others. The results also indicate economical potential of fluvial/lacustrine clays and highlight their important role in sustainable development of environmentally sensitive areas, among them the Lake Van Basin itself.     

Structural determination of purpurin-18 (as methyl ester) from sedimentary organic matter

We report the isolation and structural determination (RP-18 HPLC, UV–VIS, MS, ¹H NMR and two-dimensional ¹H NMR (COSY and ROESY)) of purpurin-18 (as methyl ester) from geological samples. Existing data suggest that purpurins-18 are derived from chlorophyll or its transformation products by postdepositional, microbially mediated processes in sediments. Diagenetic transformations of purpurins-18 can lead through fossilization to pyrroporphyrins and some ETIO porphyrins isolated from sediments.     

Immunological studies on microbial mats from Solar Lake (Sinai)— A contribution to the organic geochemistry of sediments

Immunological and biochemical techniques were used to investigate organic matter in microbial mats from Solar Lake (Sinai, Egypt). Antibodies, elicited in rabbits against samples taken at different depths from a core of these mats, were used for the detection of immunological determinants preserved in these samples. Special attention was given to an antiserum directed against a top mat fraction (3–10 mm depth) and an antiserum against a fraction from a lower section of the core (380–390 mm depth). Both antisera, tested in a dot-blot immunobinding assay, were found to give positive reactions with organic matter from different depths of the sediment. An immunohistochemical experiment with the antisera points to antigenic determinants on Recent and subfossil sheaths of Microcoleus. In addition, extracts of sediment samples were submitted to electrophoresis in polyacrylamide gels in order to characterize the separated macromolecules by immunological means. The results showed a rapid decrease in the number of antigenic determinants from Recent to subfossil samples. However, even in the deepest layers of the sediment (690–700 mm depth) intact biopolymers were detected.     

Morphotectonics of lacustrine basins: The Baikal rift zone as an example

Formation mechanisms and development of numerous and morphologically diverse lacustrine basins of the Baikal rift zone are considered in terms of morphotectonics. All the representative lake species are characterized, and their regional morphotectonic classification is suggested.     

Fate of microbial biomass-derived amino acids in soil and their contribution to soil organic matter

Soil organic matter (SOM) is important for soil fertility and for the global C cycle. Previous studies have shown that during SOM formation no new compound classes are formed and that it consists basically of plant- and microorganism-derived materials. However, little data on the contribution from microbial sources are available. Therefore, we investigated previously in a model study the fate of C from ¹³C-labelled Gram-negative bacteria in soil (Kindler, R., Miltner, A. Richnow, H.H., Kästner, M., 2006. Fate of gram negative bacterial biomass in soil – mineralization and contribution to SOM. Soil Biology and Biochemistry 38, 2860–2870) and showed that 44% of the bulk ¹³C remained in the soil. Here we present the corresponding data on the fate of amino acids hydrolysed from proteins, which are the most abundant components of microbial biomass. After 224 days incubation, the label in the total amino acids in the soil amended with ¹³C-labelled cells decreased only to >95%. The total amino acids therefore clearly showed a lower turnover than the bulk ¹³C and a surprisingly stable concentration. Proteins therefore have to be considered as being stabilised in soil in dead, non-extractable biomass or cell fragments by known general stabilisation mechanisms. The label in the amino acids in a fraction highly enriched in living microbial biomass decreased to a greater extent, i.e. to 25% of the initially added amount. The amino acids removed from this fraction were redistributed via the microbial food web to non-living SOM. All amino acids in the microbial biomass were degraded at similar rates without a change in isotopic signature. The nuclear magnetic resonance (NMR) spectra of the soils were very similar and indicate that the residues of the degraded microbial biomass were very similar to those of the SOM and are a significant source for the formation of the SOM.     

Origin and formation pathways of kerogen-like organic matter in recent sediments off the Danube delta (northwestern Black Sea)

The chemical structure, source(s), and formation pathway(s) of kerogen-like organic matter (KL) were investigated in recent sediments from the northwestern Black Sea, off the Danube delta. Three sections from a sediment core collected at the mouth of the Sulina branch of the delta, under an oxic water column, were examined: S₀ (0–0.5 cm bsf), S₁₀ (10–13 cm bsf), and S₂₀ (20–25 cm bsf). The bulk geochemical features of these sediments (total organic carbon, organic C/N atomic ratio, δ¹³C_org) were determined. Thereafter, KL was isolated from the samples, as the insoluble residue obtained after HF/HCl treatment. KL chemical composition was investigated via spectroscopic (FTIR, solid state ¹³C and ¹⁵N NMR) and pyrolytic (Curie point pyrolysis–gas chromatography–mass spectrometry) methods, and the morphological features were examined by scanning and transmission electron microscopy. Similar morphological features and chemical composition were observed for the three KLs and they suggested that the selective preservation of land-plant derived material as well as of resistant aliphatic biomacromolecules (probably derived from cell walls of freshwater microalgae) was the main process involved in KL formation. Besides, some melanoidin-type macromolecules (formed via the degradation-recondensation of products mainly derived from proteinaceous material) and/or some encapsulated proteins also contributed to the KL chemical structure.     

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5–116 hr) and temperatures (150°–410°C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid <1%. Whereas n-alkanes produced from lipid show a CPI > 1.0, those produced by thermal alteration of kerogen display a CPI < 1.0. The volatiles produced by heating the lipid and humic acid fractions were largely CO₂ and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C₂–C₄ hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.     

Fate of bacterial biomass derived fatty acids in soil and their contribution to soil organic matter

Soil organic matter (SOM) is a major pool of the global C cycle and determines soil fertility. The stability of SOM strongly depends on the molecular precursors and structures. Plant residues have been regarded as the dominant precursors, but recent results showed a major contribution of microbial biomass. The fate of microbial biomass constituents has not yet been explored; therefore, we investigated the fate of fatty acids (FA) from ¹³C labeled Gram-negative bacteria (Escherichia coli) in a model soil study [Kindler, R., Miltner, A., Richnow, H.H., Kästner, M., 2006. Fate of gram negative bacterial biomass in soil—mineralization and contribution to SOM. Soil Biology & Biochemistry 38, 2860–2870]. After 224 days of incubation, the label in the total fatty acids (t-FA) in the soil decreased to 24% and in the phospholipid fatty acids (PLFA) of living microbes to 11% of the initially added amount. Since the bulk C decreased only to 44% in this period, the turnover of FA is clearly higher indicating that other compounds must have a lower turnover. The ¹³C label in the t-FA reached a stable level after 50 days but the label of the PLFA of the living microbial biomass declined until the end of the experiment. The isotopic enrichment of individual PLFA shows that the biomass derived C was spread across the microbial food web. Modelling of the C fluxes in this experiment indicated that microbial biomass is continuously mineralized after cell death and recycled by other organisms down to the 10% level, whereas the majority of biomass derived residual bulk C (～33%) was stabilized in the non-living SOM pool.     

湖相沉积物有机地球化学在古环境研究中的应用

湖相沉积物中的有机质蕴含着丰富的地球化学信息,是古环境研究中必要的基础资料之一。文章综述了近年来湖相沉积物有机地球化学在古环境研究中的应用,结果表明:1在应用有机地球化学信息探讨古环境时,首先要根据有机质组成特征区分其来源,不同来源的有机质,其地球化学特征存在差异;2有机质碳同位素(δ13Corg)是研究古气候变化的常用指标,在区分暖湿、暖干、冷湿、冷干气候类型时需结合沉积物中总有机质丰度(TOC)、总有机氮丰度(TN)、自生碳酸盐氧同位素(δ18O)等资料;3脂肪酸不饱和度可作为恢复古环境温度的定性指标,UK37和UK37'在定量恢复古湖水表层温度中有较好的应用效果,TEX86有望应用在古湖水表层温度的重建;4生物标志化合物可较好地区分沉积物中有机质的来源、沉积水体的盐度及氧化还原性。可见,有机地球化学是研究古环境常用且有效的技术手段,多项有机地球化学参数相互验证能够更精确地重建古环境并预测其演化趋势。     

Coupling between Pbex and organic matter in sediments of a nutrient-enriched lake: An example from Lake Chenghai, China

Sediment cores were collected from deep-water areas of Lake Chenghai, China in June 1997. The vertical profile of ¹³⁷Cs activity gives reliable geochronological results. The results also indicate that sediment accumulation rates in deep-water areas of Lake Chenghai were relatively constant in recent decades, averaging 0.43 g cm^− 2 y^− 1, despite a variable organic carbon influx. ²¹⁰Pb_eq (= ²²⁶Ra) activity was relatively constant also, with an average value of 54.3 ± 3.2 Bq kg^− 1. Vertical profiles of ²¹⁰Pb_ex (= ²¹⁰Pb_total − ²²⁶Ra) decreased exponentially, resulting in somewhat lower sediment accumulation rates (0.3 g cm^− 2 y^− 1). These lower rates are likely less reliable, as the relatively large fluctuations in ²¹⁰Pb_ex activities correlate closely to the organic carbon (C_org) content of the sediments. For example, the vertical profile of ²¹⁰Pb_ex activity displays peaks at mass depths of 3.7-4.7 g cm^− 2 (10-12 cm) and 10-11 g cm^− 2(25-28 cm), similar to the maxima in the vertical profile of C_org. This phenomenon must be related to the delivery of particulate organic matter (POM) from the water to the sediments, or to watershed soil erosion. Since the mean atomic ratios of H_org / C_org and C_org / N_org in Lake Chenghai sediments are 5.5 and 7.0, respectively, indicating that POM was predominantly derived from the remains of authigenic algae, this eliminates watershed erosion rates as a primary control on lake sedimentation rates as resolved by ²¹⁰Pb_ex. Sedimentation fluxes (F(C_org)) of particulate organic carbon since 1970 varied between 60 to 160 g m^− 2 y^− 1, and appeared to closely influence variations in ²¹⁰Pb_ex concentrations. For example, sedimentation fluxes of ²¹⁰Pb_ex (F(²¹⁰Pb_ex)) showed maxima in the years 1972-1974 and 1986-1989, likely reflecting historical variations of lake biological productivity or carbon preservation.     

Research on the carbon isotopic composition of organic matter from Lake Chenghai and Caohai Lake sediments

The carbon isotopic composition of organic matter from lake sediments has been extensively used to infer variations in productivity. In this paper, based on the study of the contents and δ13C values of organic matter in different types of lakes, it has been found that δ13C values of organic matter have different responses to lake productivity in different lakes. As to the lakes dominated by aqutic macrophytes such as Lake Caohai, organic matter becomes enriched in 13C with increasing productivity. As to the lakes dominated by aquatic algae such as Lake Chenghai, δ13C values of organic matter decrease with increasing productivity, and the degradation of aquatic algae is the main factor leading to the decrease of δ13C values of organic matter with increasing productivity. Therefore, we should be cautious to use the carbon isotopic composition of organic matter to deduce lake productivity.     

Heavy metals in sediments as evidence for recent pollution and quasi-estuarine processes: an example from Lake Druzno,Poland

This article presents the results of a geochemical investigation of sediments from Lake Druzno (northern Poland), a reservoir fed by freshwater from the catchment, with periodic input of brackish water from Vistula Lagoon. This study analyzed the spatial variation in heavy metal content in surface sediments as well as the temporal changes in metal content in two sediment cores dated using the ²¹⁰Pb method. In the surface sediments, the highest metal concentrations were recorded in the northern part of the lake, with lower concentrations in the central and southern parts. Absolute values of metal concentrations in the cores were low, but normalization with respect to Al showed an increase during the second half of the 20th century. Mean enrichment factors (EF) in sediments from the second half of the 20th century ranged from insignificant (1–1.2) for Fe to (1.55–3.3) for Cu, Cd, Pb and Zn. The sediments deposited before 1950 had lower EF values (>1.5) and had low variability. Results from both the surface sediments and the cores indicate that the main source of lake pollution is brackish water intrusion from the Vistula Lagoon via the contaminated River Elbląg.     

Bacterial contribution to sedimentary organic matter; a comparative study of lipid moieties in bacteria and Recent sediments

A systematic study of the lipid composition of thirteen bacterial species and three Recent sediments (methanogenic sediment, cyanobacterial mat and evaporative gypsum crust) was undertaken in an attempt to recognize bacterial organic matter in sediments. A sequential method, which distinguishes between three different modes of occurrence of lipid moieties (free, OH⁻- and H⁺-labile), was applied. The acid-labile fractions are discussed.The three main groups of bacteria, archaebacteria, gram-positive eubacteria and gram-negative eubacteria, are easily distinguished. Methanogenic and extremely halophilic archaebacteria are characterized by the presence of diphytanyl glyceryl ether and the absence of fatty acids. The gram-positive eubacteria contain primarily iso- and anteiso-branched fatty acids whereas the gram-negative bacteria and sediments are dominated by β- and α-hydroxy fatty acids. A wide variety of H⁺-labile hydroxy fatty acids was observed which included several, as yet unknown, structures.β-Hydroxy fatty acids in this H⁺-labile mode of occurrence are exclusively present in bacteria. Their distribution patterns in sediments are considered “fingerprints” of past and present bacterial populations. The specific differences in β -hydroxy fatty acid compositions observed in the different bacteria and the three sediments investigated, suggest that amide-linked β-hydroxy fatty acid patterns are useful as markers of bacterial populations and therefore of environmental conditions.     

Fossil fuel compounds from fly dust in recent organic matter of southern Poland peats

Several samples of peat from 6 bogs located in southern Poland were investigated for occurrence and distribution types of biomarkers present in their extractable organic matter fraction. It was found that there are inputs from two different sources of organic compounds differing in their characteristics and origin: (1) recent immature peat organic matter deposited in situ which is the source of all polar functionalized compounds, most of n-alkanes, and acyclic isoprenoids, and (2) mature fossil fuels, most probably bituminous coals from the Upper Silesia Coal Basin of vitrinite reflectance equivalent values of 0.9–1.1%. The latter compounds were most probably transported with fly ash to bogs from nearby settlements utilizing such fuel in domestic ovens. This group includes pentacyclic triterpenoids (hopanes and moretanes), minor amounts of n-alkanes, and numerous alkyl naphthalenes and alkyl phenanthrenes. All these compounds show distributions and values of geochemical ratios characteristic for mature organic matter confirming there ex situ origin.     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10⁻¹³ to 7.16 × 10⁻¹² mol Hg (mg C)⁻¹ m⁻²s⁻¹. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R² = 0.88), aromaticity (R² = 0.80), and molecular weight (R² = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.