Characterisation of dispersed organic matter from lower Palaeozoic metasedimentary rocks by organic petrography, X-ray diffraction and micro-Raman spectroscopy analyses

Dispersed organic matter (DOM) concentrates of C-rich rocks from areas with different metamorphic characteristics were studied by organic petrography, X-ray diffraction (XRD) and micro-Raman spectroscopy analysis. The concentrates contain several types of DOM with different morphologies, reflectance, X-ray diffraction and micro-Raman characteristics.Four different morphological types were identified in the two studied areas. The different types have different distributions and their reflectance is quite variable in the four types, with a dominance of the highest reflectance values in the DOM from the area with the highest metamorphic grade.XRD analyses of samples from the areas reveal the presence of fine graphite together with non-graphitised carbons.The Raman spectral profiles show the usual bands G (1582 cm⁻¹) and D1 (1350 cm⁻¹), on the first-order Raman spectrum, and S1 (2700 cm⁻¹) on the second-order spectrum. Additional weaker bands, D2 (1620 cm⁻¹), and more rarely D3 (1500 cm⁻¹) and S2 (2900 cm⁻¹), are present. These are characteristic for disordered carbons in the different types of DOM and in both studied areas. However, the Raman parameters (D1/G intensity area ratio and the frequency and width of G band) indicate variable degrees of organisation in all DOM types.The existence of different types of DOM with different degrees of ordering in the same lithologies and metamorphic grade seems to be related to different organic precursors, as they are graphitised to different extents under the same metamorphic conditions. However, in the same lithologies and metamorphic grade, the existence of various stages of graphitisation within the same type of DOM can only be explained though the interaction of DOM with the metamorphic fluids present in the rocks. The ordering graphitisation process may be due to the existence of metamorphic fluid circulation events with a variety of compositions.     

A role for organic petrology in integrated studies of mudrocks: examples from Devonian black shales of the eastern US

Over the years, the study of mudrocks has lagged far behind that of other lithologies, a circumstance that is in part due to their fine-grained nature, and in part due to economic realities. Yet, within petroleum systems mudstones are usually the main source of hydrocarbons and typically are also important as hydrocarbon seals. Recent work on Late Devonian mudstones from the eastern US shows that much progress can be made through an integration of outcrop study, macro- and micropaleontology, ichnofossils, gamma ray spectroscopy, microscopic examination of thin sections in transmitted and reflected light, electron microscopy (SEM, BSE), electron microprobe, carbon and sulfur isotopes, and organic geochemistry.Erosion surfaces within this black shale succession have been traced over large distances and provide the foundation for a sequence stratigraphic re-interpretation of these rocks. Evidence of storm wave reworking of the seabed, as well as the realization that benthic colonization was much more widespread than previously believed, suggest that anoxic conditions in the water column were not a controlling factor in the accumulation of the large quantities of organic matter found in these shales.These distal Devonian shales accumulated slowly and allowed accumulation of large proportions of organic matter. In modern settings of abundant organic matter accumulation, the original material is broken down by bacteria within a matter of months into a mass of largely unidentifiable organic particles and extracellular bacterial slime. Although one can still find identifiable material within this mass, slime and amorphous material strongly dominate. After burial and maturation this material turns into the various organic macerals that organic petrologists are accustomed to describe. One might wonder in this context, how much information about the origin of a given mudstone unit can we hope to extract through organic petrology?In order to illustrate how organic petrology of mudrocks can contribute to their better understanding, Late Devonian black shales of the eastern US will be examined from a sedimentological perspective. Combining sedimentologic and geochemical data with basic observations on organic petrology, illustrates how the latter can contribute to more realistic scenarios of black shale genesis.     

Enhanced trapping of molybdenum by sulfurized marine organic matter of marine origin in Mesozoic limestones and shales

There have been many studies devoted to trace metals and their value in assessing the paleoredox conditions of ancient marine deposition. Among them, molybdenum (Mo) is frequently cited as an effective proxy for sediments and sedimentary rocks. Recently, Helz et al. (Helz, G.R., Miller, C.V., Charnock, J.M., Mosselmans, J.L.W., Pattrick, R.A.D., Garner, C.D., Vaughan, D.J., 1996. Mechanisms of molybdenum removal from the sea and its concentration in black shales: EXAFS evidences. Geochim. Cosmochim. Acta, 60, 3631-3642) and Adelson et al. (Adelson, J. M., Helz, G. R., Miller, C. V., 2001. Reconstructing the rise of recent coastal anoxia; molybdenum in Chesapeake Bay sediments. Geochim. Cosmochim. Acta, 65, 237-252.) suggested that Mo does not behave conservatively in the water column when H₂S reaches a threshold concentration. Above this concentration, a “switch” operates, and Mo is scavenged by forming bonds with metal-rich (notably iron) particles, sulfur-rich organic molecules and pyrite. In this paper, Mo-trapping by sulfur-rich organic matter (OM) in ancient marine deposits is emphasized. The following Mesozoic geological formations were selected for study because of their relatively high concentration of sulfurized OM: the Akkuyu Formation (Turkey), the Calcaires d'Orbagnoux (France) and Kimmeridge Clay (UK) and its timeequivalent in Boulonnais (France), the Kashpir oil shales (Russia), and the La Luna Formation (Venezuela). The sulfur-rich OM is identified by either measured organic-S abundance or kerogen microscope observation. Our results show that Mo is systematically more enriched relative to the other redox-sensitive/sulfide-forming elements studied (U, V, Ni, Cu, Zn, Cr), and Mo enrichment is positively correlated with the amount of sulfurized OM but not with pyrite abundance. These results illuminate the role played by sulfurized OM in geologic-scale Mo capture and retention, but they also underline the role played by reactive iron. Significant OM sulfurization is only possible when reactive iron is limited. Nevertheless, pyrite formation, though limited, could act as an initial Mo trap, prior to Mo uptake by OM that is sulfurized after the pyritization step. In future paleoenvironmental reconstructions, attention must be paid to this enhanced Mo enrichment in the presence of sulfurized organic matter. In such cases, the use of Mo could lead to overestimation of the reducing conditions of the depositional environment.     

Pb-Pb dating of black shales from the Lower Cambrian and Neoproterozoic strata, South China

Black shales occur widely in the Lower Cambrian and Neoproterozoic strata on the Yangtze Platform, South China. In this study, Lower Cambrian black shales from Xiuning section and Late Neoproterozoic black shales from Weng’an section were studied and Pb isotopic compositions were analyzed following a stepwise acid-leaching technique. The ²⁰⁶Pb/²⁰⁴Pb ratios in both sections show large variations, from 18.906 to 43.737 in the Weng’an section and from 24.811 to 38.110 in the Xiuning section. In contrast, the ranges for ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values in both sections are relatively smaller from 15.649 to 17.126 and 37.744-38.199 in the Weng’an section, and from 16.034 to 16.783 and 38.602-39.391 in the Xiuning section, respectively. These data yielded two Pb isotope isochron ages of 536±39 and 572±36 Ma, respectively. These ages well accord with other published data and we suggest that they represent the depositional ages for the Lower Cambrian Hetang Formation and the upper Neoproterozoic Doushantuo Formation in South China.     

Organic matter geochemistry and petrography of Late Cretaceous (Cenomanian-Turonian) organic-rich shales from the Belle Fourche and Second White Specks formations,west-central Alberta,Canada

Organic-rich mudstones with up to 10 wt% TOC from the upper portion of the Belle Fourche Formation and the lower part of the Second White Specks Formation in the Western Canada Sedimentary Basin were evaluated as source rocks. Both geochemistry and organic petrography indicate an open marine paleoenvironment with deposition of Type II kerogen based on the predominance of marine alginite and amorphous organic matter (OM), limited amounts of terrigenous vitrinite and inertinite macerals, the presence of marine fossils, and the low ratio of TOC to total sulfur (∼1.26). The prevalence of short-chain n-alkanes (n-C₁₃ to n-C₁₉), a predominance of C₂₈ αββ(H)-20S steranes, and small concentrations of oleanane confirm the dominantly algal and planktonic origin of OM. Alternating oxic to anoxic paleoenvironmental sedimentary conditions are proposed based on common bioturbation, abundant inoceramid prisms, and good organic richness. Biomarker distributions are consistent with intermittent anoxia, without unequivocal evidence for water column stratification or hypersalinity. The thermal maturity measured in seven sediment cores by different methods consistently indicates a westward increase in maturity according to vitrinite reflectance, T_max, and hopane and sterane biomarkers. Two cores are thermally immature (∼0.42 %Ro), one is early mature (∼0.65 %Ro), and four cores are within the oil window (∼0.78 to 0.89 %Ro). All thermally mature cores retain good to very good hydrocarbon potential (248 mg HC/g rock) and are dominantly oil-prone and minor gas-prone based on their maceral compositions. The upper Belle Fourche and lower Second White Specks Formations represent potential targets for unconventional light shale oil production.     

Stratigraphy, sedimentology and bulk organic geochemistry of black shales from the Proterozoic Vindhyan Supergroup (central India)

Four organic-rich shale units of the Proterozoic Vindhyan sedimentary succession have been scanned to reveal their origin and hydrocarbon potential. The wavy-crinkly nature of the carbonaceous laminae is suggestive of a microbial mat origin of the shales. These shales are thus different from Phanerozoic black shales which typically exhibit planar laminae. The hydrocarbon potential of the black shale units has been evaluated by Rock-Eval pyrolysis. Total organic carbon content of many of the shales exceeds 1%. The meanT _max for the black shales translate to a vitrinite reflectance range of 2.05-2.40% Rm based on standard conversion techniques. These shales have reached the catagenetic stage near the beginning of anthracite formation.     

Calcareous nannofossils from late Jurassic sediments of the Volga Basin (Russian Platform): evidence for productivity-controlled black shale deposition

The Jurassic/Cretaceous boundary interval in the northern hemisphere is characterized by the widespread occurrence of black shales. About 60% of all petroleum source rocks comprise sediments of late Jurassic and early Cretaceous age with the origin of such black shales still under discussion. In order to better understand the factors that controlled black shale sedimentation, 78 samples were analyzed for calcareous nannofossils from two sections (Gorodische, Kashpir) of the Volga Basin (NE Russia). Calcareous nannofossils are ideal proxies for deciphering nutrient, temperature and salinity fluctuations. Additionally 58 samples from both sections were also analyzed for clay mineralogy, ¹³C_org , TOC and CaCO₃ composition. Both sections contain calcareous claystones and intercalated organic rich shales overlain by phosphorite beds. The presence of the calcareous nannofossil species Stephanolithion atmetros throughout both successions allows a biostratigraphic assignment to the S. atmetros Nannofossil Biozone (NJ 17), which corresponds to the Dorsoplanites panderi Ammonite Biozone of the Middle Volgian. The marlstones of the Kashpir section yield a well-preserved rich and diverse nannoflora, whereas all black shale beds are essentially barren of calcareous nannofossils. Only the uppermost black shale layers yield an impoverished assemblage of low diversity and abundance. Geochemical data suggest an early diagenetic nannofossil dissolution in the black shales of the Kashpir section. This is supported by the occurrence of coccoliths in black shale horizons of the Gorodische section. The assemblages in both sections are dominated by coccoliths of the Watznaueriaceae group (Watznaueria barnesae, Watznaueria fossacincta, Watznaueria britannica, Watznaueria communis), Biscutum constans and Zeugrhabdotus erectus. In Kashpir rare specimens of Crucibiscutum salebrosum occur in the higher part of the section. These taxa indicate boreal affinities. B. constans and Z. erectus are considered to be taxa indicative of a higher productive environment, while C. salebrosum is a cool-water species. From base to top of the Kashpir section, consecutive mass occurrences of different taxa/groups were observed: W. barnesae–W. fossacincta acme, W. britannica–W. communis acme, Z. erectus acme, B. constans acme (including sparse occurrences of C. salebrosum).The observed distribution patterns have been interpreted as characterizing a transition from a low productive, oligotrophic setting with high abundances of K-selected cosmopolitan species (Watznaueriaceae) and predominating marlstone sedimentation to a higher productive, mesotrophic setting. Cooler water temperatures marked by r-selection and acmes of opportunistic species (Z. erectus, B. constans) are coincident with the deposition of black shales and phosphorites in the higher part of the section. Interpretation of clay mineral distribution indicates that black shale deposition occurred under semi-arid hinterland climatic conditions concomitant with a sea level rise. This induced dysoxic conditions in the deeper parts of the Volga Basin, favoring the preservation of organic matter. The cause of the nutrient enrichment in the surface water is still unclear, but possible river water input from the continents does not seem to have been the controlling factor under a semi-arid climate. The occurrence of phosphorites in the upper part of both sections presumably indicates that enhanced productivity may be better explained by the upwelling of nutrient-rich bottom water and thereby causing the recycling of nutrients from oxidized phytoplankton back into the photic zone. This recycling effect finally may have led to an intensified phytoplankton growth which seemed to be a sufficient source for the enrichment of organic matter. This is well correlated with the increase in black shale horizons in the upper part of the Kashpir section.     

皖南二叠纪海相暗色岩系成因及有机质富集模式

皖南二叠系已成为页岩气勘探的重要目标层位,暗色岩系的硅质来源长期存在争议,有机质富集堆积机理尚不清楚。本文通过皖南地区二叠纪海相栖霞组、孤峰组和大隆组暗色岩系的岩石学特征、古生物群落、沉积特征、有机质丰度和元素地球化学特征分析,探讨其沉积背景、硅质来源和有机质富集模式。研究表明：栖霞组硅质主要来源于热液;孤峰组硅质主要来源于生物和热液;大隆组硅质主要来源于生物和热液,少量来源于生物。二叠纪属热带—亚热带温暖潮湿气候,暗色岩系沉积于具缓慢沉积速率的厌氧—贫氧的100～300 m水体环境中,有机质含量高。栖霞组和孤峰组富有机质暗色岩系的形成除受控于局限滞留的缺氧环境外,还和海底热液活动提供生物繁盛的营养元素与矿物质和上升流的作用有较为密切的关系。大隆组富有机质暗色岩系的形成与长兴期多期火山喷发带入大量营养元素和微量元素,导致初级生产力提高,生物消亡—繁盛—再消亡—再繁盛—消亡,生烃母质快速堆积,且与缺氧环境密不可分。     

Enrichment and Origin of Some Trace Elements in Black Shales from the Early Cambrian in Eastern Guizhou Province

The analysis is based on the elemental geochemistry, ¹³C, ¹⁸O isotope and lithology combination of the black shale, a set assemblage mud and carbon of lithology , in East Guizhou. The coordinated change in spider diagrams of race elements suggests those elements have the same source. The ¹³C, ¹⁸O isotopes, mode of REE partition and characteristic enrichment of elements assemblage in carbonaceous shale show that the deep thermal fluid is added, and the shelf sea basin edge with distribution of hydrothermal activity is propitious to precipitation of ore elements. Evidence from the ³⁴S isotope and redox-sensitive elements show that the hydrostatic hypoxia environment is also conducive to precipitation of elements. The lithologic features (phosphorus, coal-bearing layers) and high content of organic carbon indicate that the deposits are influenced by the upwelling ocean current.     

Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes

Subaerial exposure and oxidation of organic carbon (C_org)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial C_org oxidation are expected to shift new biomass δ¹³C_org composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ¹³C_org at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C_org-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, C_org-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of C_org without producing a δ¹³C shift between acid rock drainage precipitates and shale. Moreover, ¹³C enrichment in inorganic carbon of precipitates does not support microbial C_org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ³⁴S = δ³⁴S_shale − δ³⁴S_precipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ¹⁵N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of C_org, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.     

Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

湘西震旦—寒武纪黑色岩系的有机岩石学特征及其形成条件

湘西上震旦统、下寒武统黑色岩系主要由富碳硅质页岩、石煤、硅质页岩、硅质岩、磷块岩和重晶石岩等组成。有机质属于腐泥型, 无形态组分是黑色岩系的主要显微组分类型, 微粒体、细粒状体呈密集状组成岩石的基质。有形态组分总体含量较低, 多为藻类体, 零星分布于基质中, 表明一方面有机质受热演化程度较高, 另一方面表明有机质来源于浅水台地边缘。湘西黑色岩系中有机质主要来源于藻、菌类生物, 台缘斜坡带是有机质聚集的有利场所, 缺氧环境 （事件） 主要起因于藻类的大量发育与有机质降解的耗氧过程, 为有机质得以保存、转化提供了必要条件。     

Subaqueous early eruptive phase of the late Aptian Rajmahal volcanism,India: Evidence from volcaniclastic rocks,bentonite, black shales,and oolite

The late Aptian(118-115 Ma) continental flood basalts of the Rajmahal Volcanic Province(RVP) are part of the Kerguelen Large Igneous Province,and constitute the uppermost part of the Gondwana Supergroup on the eastern Indian shield margin.The lower one-third of the Rajmahal volcanic succession contains thin layers of plant fossil-rich inter-trappean sedimentary rocks with pyroclasts,bentonite,grey and black shale/mudstone and oolite,whereas the upper two-thirds consist of sub-aerial fine-grained aphyric basalts with no inter-trappean material.At the eastern margin and the north-central sector of the RVP,the volcanics in the lower part include rhyolites and dacites overlain by enstatite-bearing basalts and enstatite-andesites.The pyroclastic rocks are largely felsic in composition,and comprise ignimbrite as well as coarse-grained tuff with lithic clasts,and tuff breccia with bombs,lapilli and ash that indicate explosive eruption of viscous rhyolitic magma.The rhyolites/dacites(68 wt.%) are separated from the andesites( 60 wt.%) by a gap in silica content indicating their formation through upper crustal anatexis with only heat supplied by the basaltic magma.On the other hand,partially melted siltstone xenoliths in enstatite-bearing basalts suggest that the enstatite-andesites originated through mixing of the upper crust with basaltic magma,crystallizing orthopyroxene at a pressure-temperature of ~3 kb/1150℃.In contrast,the northwestern sector of the RVP is devoid of felsic-intermediate rocks,and the volcaniclastic rocks are predominantly mafic(basaltic) in composition.Here,the presence of fine-grained tuffs,tuff breccia containing sideromelane shards and quenched texture,welded tuff breccia,peperite,shale/mudstone and oolite substantiates a subaqueous environment.Based on these observations,we conclude that the early phase of Rajmahal volcanism occurred under predominantly subaqueous conditions.The presence of grey and black shale/mudstone in the lower one-third of the succession across the entire Rajmahal basin provides unequivocal evidence of a shallow-marine continental shelf-type environment.Alignment of the Rajmahal eruptive centers with a major N—S mid-Neoproterozoic lineament and the presence of a gravity high on the RVP suggest a tectonic control for the eruption of melts associated with the Kerguelen plume that was active in a post-Gondwana rift between India and Australia-Antarctica.     

Comparative study by infrared spectroscopy of the organic matter of phosphate-rich (Oulad Abdoun basin) and black shale (Timahdit basin) series (Morocco)

Fourier transform infrared spectroscopy has been used to get quantitative information on the oxidation state of the organic matter of stable residues extracted from strata of the phosphate-rich basin of Oulad Abdoun and from oil shales of the Timahdit basin, Morocco.Throughout the respective filling of both basins the redox conditions have been more oxidizing in the top part of the sediments in Oulad Abdoun basin than in the Timahdit basin. This is interpreted as the result of the sedictural evolution of the basin Oulad Abdoun basin having evolved in stable platform conditions while the Timahdit basin evolved in subsiding ones.The phosphate-rich beds contain the more oxidized organic stable residues. Sedimentological evidence shows that the oxidation was associated reworking processes. These processes are responsible for the progressive concentration of the phosphatic grains and prove to be necessary for the P₂O₅ content to become higher than 10% this value being the highest encountered in the sediment within which the phosphatic grains form.     

鄂西地区上二叠乐平统大隆组硅质岩成因及有机质富集机理

晚二叠世是古生代环境、生物演化的关键时期,发育广泛的富有机质沉积,并成为南方重要的烃源岩层位。为了解该时期的富有机质堆积机理,我们选择了鄂西台内盆地晚二叠世大隆组富有机质硅质岩(TOC平均值为5.8%,峰值为18%)作为研究对象。硅质岩中常量元素Al/Fe均值为0.79,Mn/Ti均值为0.21,显示为大陆边缘环境下的生物成因,即非热水成因。∑REE值与Al2O3含量有着良好的正相关关系,表明当时陆源物质的输入对硅质岩的形成有很大影响。微量元素U/Th、V/(V+Ni)均说明硅质岩沉积环境为缺氧水体环境。通过对草莓状黄铁矿粒径的统计表明,大多数(64%～89%)的草莓状黄铁矿粒径小于5μm,反映缺氧甚至硫化的环境。而且,U、V、Mo的富集以及Ni、Cu元素的亏损说明水体的缺氧主要是由于海水分层,水体循环受阻造成的。TOC与氧化还原参数的变化步调基本一致,两者有着较好的正相关关系,而与生产力指标Ba/Al相关性很差,说明有机质富集主要是由水体的缺氧而不是初级生产力控制的。     

Noble metals in black shales of the Sukhoi Log gold deposit (East Siberia): evidence from scintillation arc atomic-emission spectrometry

Scintillation arc atomic-emission spectrometry (SAES) is used to study noble metals (NM), including Au, Ag, Pt, Pd, Ir, Os, Rh, and Ru, in black shales of the Sukhoi Log gold deposit (Irkutsk Region, Russia), with a focus on NM total contents in samples and on the compositions and sizes of NM-bearing particles. The estimated sizes of gold particles and their distribution are confirmed by results of scanning electron microscopy combined with energy dispersive X-ray microanalysis (SEM-EDX). The SAES results are in satisfactory agreement with earlier SEM-EDX data on NM species but reveal a much greater number and diversity of element associations.     

Palynofacies and organic geochemistry studies of organic matter from a wetland system of southern Brazil influenced by different hydrological regimes in the Quaternary

The main goal of this study was to quantitatively and qualitatively characterize the sedimentary organic matter (OM) and demonstrate the usefulness of geochemistry and palynofacies analysis for obtaining paleoenvironmental data for the Holocene in southernmost Brazil. The results indicate that during the time interval from 10,586 cal yr BP to the present, the study area housed a wetland characterized by different hydrologic regimes. The basal peaty deposits correspond to a phase influenced mainly by the groundwater table, whereas the upper deposits composed of silty organic mud indicate fluvial influence related to river overflow events. In a similar manner, the TOC (total organic carbon) and TS (total sulfur) contents are higher in the basal portion of the profile, decreasing toward the top. These findings could be related to granulometry alterations that are linked to hydrologic regimes or anthropogenic interference in the landscape dynamics. Anomalous TS content observed in one of the samples might be due to an external source and perhaps related to the presence of thermal springs in the region. These types of areas have potential as a modern reference that can be applied in the reconstruction of past analogous environments such as coal deposits associated with fluvial paleoenvironments.     

Characterizing the molecular structure of organic matter from natural environments: An analytical challenge

Natural organic matter (OM) is widespread in terrestrial ecosystems and it plays a major role in the global carbon cycle. Despite this high environmental importance, its characterization at the molecular level remains unsatisfactory, especially when the macromolecular OM is concerned. Such a characterization is challenging because of the diversity and heterogeneity of OM, but it is of prime importance to derive OM reactivity and, more generally, to model environmental processes in which natural OM is involved. This awareness led to a wealth of analytical developments, which are described in the present review. They include improvements of existing techniques, but also new approaches and concern spectroscopic tools along with chemical and thermal degradations.     

银额盆地巴隆乌拉白垩系巴音戈壁组黑色页岩沉积环境及有机质富集模式

银额盆地早白垩世沉积的巴音戈壁组湖相页岩是一套重要的烃源岩。通过对巴隆乌拉剖面黑色页岩进行地球化学分析,研究其主量、微量和稀土元素特征,以及黑色页岩沉积的古环境及有机质富集模式。结果表明,Sr/Ba值为0.14~0.24,平均值为0.18,B/Ga值为3.89~6.51,平均值为5.03,相当B含量为230.88×10-6~375.99×10-6,平均值为294.95×10-6,古盐度为11.97‰~15.83‰,平均值为14.70‰;V/(V+Ni)值为0.67~0.84,平均值为0.74,Ceanom值为-0.113~0.018,平均值为-0.055;古气候指数(C)为0.80~1.34,平均值为1.06,化学蚀变指数(CIA)为75~81,平均值为79;古水深为4.16~88.04 m,平均值为33.40 m;P/Ti值为0.10~0.22,平均值为0.15,过剩钡(BaXS)为-46.5×10-6~144.5×10-6,平均值为38.85×10-6。综合各参数特征,研究区黑色页岩沉积于温暖、湿润、半咸水、缺氧的还原环境,沉积水体较深,具有低的古生产力条件。有机碳含量与沉积环境间相关性的研究表明,巴音戈壁组黑色页岩有机质富集是古盐度、氧化-还原条件、古气候、古生产力等因素共同作用的结果。研究结果可为银额盆地中生界沉积演化和油气资源评价提供理论支撑。