Nitrogen functionality in “oil window” rank range vitrinite rich coals and chars

X-ray photoelectron spectroscopy (XPS) was used to characterize organic nitrogen species in coals and chars. The coals comprise a set of vitrinite-rich samples from the Penn State Coal Bank set, ranging from vitrinite reflectance (R_r) 0.42-1.60%. Chars were obtained after coal pyrolysis under an inert atmosphere at 800 °C and fast heating rate. In the coals, pyrrolic nitrogen was the predominant form, steadily decreasing with coal rank, while pyridinic and quaternary nitrogen showed pronounced variation with rank. In contrast to the coals, the chars show much less pyrrolic and pyridinic nitrogen, and more quaternary nitrogen. The chars were also characterized by having oxidized nitrogen and nitro sub-peaks, which were not observed for the coals. Apparently the occurrence of these forms is related to the decrease in the pyridinic nitrogen.     

Distribution of nitrogen forms in surface sediments of lakes from different regions,China

The characteristics of nitrogen fractions in the surface sediments of lakes from Eastern Plain Region, Yunnan-Guizhou Plateau Region, Northeast China Region, Qinghai-Tibet Plateau Region and Mongolia-Xinjiang Plateau Region were investigated and the differences of five lake regions on nitrogen fractionation were discussed. The results indicated that organic nitrogen (N_org) was the major nitrogen fraction accounting for 76.38–92.02 % of N_tot in sediments. The rank order of average N_org and N_tot of sediments in five lake regions was: Yunnan-Guizhou Plateau Region > Northeast China Region > Mongolia-Xinjiang Plateau Region > Qinghai-Tibet Plateau Region > Eastern Plain Region. The exchangeable nitrogen had a similar distribution as organic nitrogen in the studied sediments. NH₄ ⁺–N is the main exchangeable nitrogen of sediments in the studied lakes except in Lake Qinghai and Lake Yamdrok which contained higher nitrate concentrations than ammonium. Fixed ammonium (N_fix) in the sediments of studied lakes was irregularly distributed with the values ranging from 99.45 to 329.02 mg/kg. TOC was significantly and positively correlated with ammonium, nitrate, N_org and N_tot, while N_fix was negatively correlated with nitrate probably due to electrostatic attraction between N_fix and nitrate in layers of sediments.     

碳质物拉曼光谱变质温度计及其在造山带热结构重建与演化中的应用

变质沉积岩普遍含有碳质物,其源自沉积母岩中有机质。在变质过程中这些有机质逐渐转变为碳质物或石墨,且碳质物结晶程度可以作为变质等级的可靠指示标志。拉曼光谱是表征碳质物结晶度的有效工具,Beyssac et al.(2002a)基于碳质物拉曼光谱参数(R1=D1/G,D1和G为碳质物拉曼光谱峰强;R2=D1/(G+D1+D2),G、D1和D2为碳质物拉曼光谱峰面积)与寄主岩变质温度之间的线性关系构建了碳质物拉曼光谱温度计:T(℃)=-445(R2)+641,其简单且实用,并被应用到阿尔卑斯和喜马拉雅造山带热结构与折返机制研究中;随后,Rahl et al.(2005)对该变质温度计进行修订,修订后温度估算表达式为:T(℃)=737.3+320.9R1-1067R2-80.638R12,并将变质温度估算范围扩展为100~700℃。本文对碳质物拉曼光谱变质温度计的基本原理、方法、应用条件及其在造山带热结构重建与演化方面的研究进展进行了综述,并对碳质物拉曼光谱温度计与传统温度计估算的变质温度进行了系统的对比分析,结果表明碳质物拉曼光谱温度计代表峰期变质温度,不会受后期退变质影响,当传统温度计结果代表峰期变质温度时,二者计算结果一致。碳质物拉曼光谱温度计已被用于造山带热结构重建、折返过程的热演化,以及高应变带、流体相关热异常等研究。尽管变质过程的压力、变质持续时间、碳质物前体类型等因素对于碳质物拉曼光谱温度计的影响尚待研究,但与传统矿物组合温压计相结合,该方法可以有效评价峰期变质条件和造山多期热演化。     

Dispersed Organic Matter in Riphean Carbonate–terrigenous Sediments of the Kuzha Complex (Bashkirian Uplift, Southern Urals)

Regularities of the localization of dispersed organic matter in rhythmitic and carbonate members of the upper sequence of the Biktimir Formation were revealed by studying sections of the Middle Riphean sediments within the eastern limb of the Yurmatau Anticlinorium. This work presents the quantitative estimation of C_org content in lithological rock types and morphostructural features of carbonaceous inclusions and sulfide mineralization. The sedimentogenic–biogenic nature of organic matter and indications of gold mineralization in the host sedimentary rocks were revealed.     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

Carbon isotopes of organic matter from the upper Jurassic oil shales from the Volgian-Pechora shale province and its accumulation mechanisms

The isotopic composition of carbon from the organic matter of late Jurassic oil shales from the Volgian-Pechora shale province is studied. The existence of a dependence between C_org content in the rock and the isotopic composition of kerogen carbon is ascertained. The content of the heavy carbon isotope increases with increasing C_org. This dependence is accounted for by the progressive accumulation of isotopically heavy hydrocarbons of the initial organic matter due to sulfurization. The data on the isotopic composition of individual n-alkanes of bitumen in the rocks and the data on the absence of isotopic fractionation between thermobitumen and the residual kerogen from oil shales from the Volgian-Pechora shale province obtained by treating shale in an autoclave in the presence of water are presented first in this paper.     

Composition and genesis of the organic matter in the bottom sediments of the East Siberian Sea

The chemical composition of organic matter (C_org, N_org, δ¹³C, δ¹⁵N, and n-alkanes) was studied in the top layer of bottom sediments of the East Siberian Sea. Possible ways were proposed to estimate the amount of the terrigenous component in their organic matter (OM). The fraction of terrigenous OM estimated by the combined use of genetic indicators varied from 15% in the eastern part of the sea, near the Long Strait, to 95% in the estuaries of the Indigirka and Kolyma rivers, averaging 62% over the sea area.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased C_org/N_tot and δ¹³C_org (up to −17‰) were driven by generally nitrogen-poor but ¹³C-enriched terrigenous plant debris and SOM from C₄/C₃ vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C₃/C₄ vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower C_org/N_tot and δ¹³C_org (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and ¹²C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of C_org/N_tot and δ¹³C_org for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO₂.     

四川里伍黑牛洞铜矿床成矿流体特征及矿床成因研究

黑牛洞铜矿床经历了早期韧性变形-变质作用和成矿期的韧-脆性变形作用。早期韧性变形-变质作用过程中围岩可能分异出含CO2流体,并形成顺片理发育的磁黄铁矿、黄铜矿等矿化。成矿期为伴随江浪穹窿隆升的韧-脆性变形期,含矿石英脉中流体包裹体主要以富液相流体包裹体为主,次为纯气相流体包裹体。流体包裹体成分测试结果显示,富液相流体包裹体主要成分为水,含少量CO2和甲烷等烃类碳质流体;纯气相流体包裹体主要为甲烷,表明成矿流体为富水含炭质流体。流体包裹体氢、氧同位素测试结果表明,黑牛洞矿床含矿流体中的水主要来源于围岩中的变质水。燕山期花岗岩侵位,江浪穹窿隆升,韧-脆性变形形成系列滑脱断层。在此减压、降温过程中,成矿流体被活化并聚集、填充到滑脱断层内。     

Nitrogen isotope fractionations during progressive metamorphism: A case study from the Paleozoic Cooma metasedimentary complex, southeastern Australia

The well-studied Paleozoic Cooma metamorphic complex in southeastern Australia is characterized by a uniform siliciclastic protolith, of uniform age, with a continuous range of metamorphic grade from subgreenschist- to upper amphibolite-facies, and migmatite-grade in an annular pattern around the Cooma granodiorite. Those conditions are optimal for investigating variations of N concentrations and δ¹⁵N values during progressive metamorphism. Nitrogen concentrations decrease and δ¹⁵N increases with increasing metamorphic grade (sub-chlorite zone: 120 ppm N, δ¹⁵N = 2.3‰; chlorite zone: 110 ppm N, δ¹⁵N = 3.0‰; biotite and andalusite zone: 85 ppm N, δ¹⁵N = 3.8 ‰; sillimanite and migmatite zones: 40 ppm N, δ¹⁵N = 10.7‰). Covariation of K and N contents is consistent with N substituting for K as NH₄⁺ in micas. Observed trends of increasing δ¹⁵N values with decreasing nitrogen concentrations can be explained by a continuous release of nitrogen depleted in ¹⁵N with progressive metamorphism, which causes an enrichment of ¹⁵N in the residual nitrogen of the rock. Equilibrium models for Rayleigh distillation and batch volatilisation for data of the greenschist and amphibolite facies metasedimentary rocks can be explained by N₂-NH₄⁺ exchange at temperatures of 300-600 °C, whereas observed large fractionations for the upper amphibolite-facies and melt products in the migmatite-grade samples may be interpreted as NH₃-NH₄⁺ exchanges at temperature of 650-730 °C. Lower values in the highest grade zones may also stem in part from input of ¹⁵N-depleted fluids from the granodiorite.The magnitude of isotope fractionation of nitrogen is about 1-2‰ during progressive metamorphism of metasedimentary rocks from sub-chlorite zone to biotite-andalusite zone, which is consistent with previous studies. Consequently, the large spread of δ¹⁵N values in Archean greenschist-facies metasedimentary rocks of −6‰ to 30‰ can be accounted for by variable mixtures of mantle plume-dominated volatiles with a δ¹⁵N of −5‰, and a ¹⁵N-enriched marine sedimentary kerogen component inherited from a CI chondrite veneer having δ¹⁵N of 30‰ to 42‰.     

古海洋研究中的地球化学新指标

有机地球化学与微量元素地球化学古环境指标及其相关的同位素指标已成为追溯古全球变化与古海洋生物地球化学演化的有力工具。从古环境替代指标的示踪原理和应用的角度，综述了有孔虫碳同位素、有机地球化学整体指标、生物标志化合物、单体有机分子同位素、微量元素等在古海洋古环境研究中的应用及相关的研究动态与进展。指出古海洋研究正从以恢复古海洋的物理参数（温度、盐度、古洋流等）为主，向着揭示古水团演化、古生产力、古营养状况、碳贮库及碳循环等古生物地球化学演化过程方向纵深发展。     

Organic matter in Silurian rocks from the Chernov uplift

This study presents data on the composition of organic matter from the Late Silurian sediments of the Chernov uplift. These sediments are characterized by low C_org contents, which may reach 1–3% in individual layers. A relatively high thermal maturity of organic matter is confirmed by polycyclic biomarker distributions and Rock-Eval pyrolyisis data. Despite its higher thermal maturity level (T _max = 456°C), kerogen in carbonaceous shales from the Padymeityvis River exhibits good preservation of long-chain n-alkyl structures, which are readily identified in the ¹³C NMR spectra and by the molecular analysis of the kerogen pyrolysis products.     

Evaluating the thermal metamorphism of CM chondrites by using the pyrolytic behavior of carbonaceous macromolecular matter

The degrees of thermal metamorphism of 10 CM chondrites and of the Allende CV3 chondrite were evaluated from the viewpoint of “graphitization” of the carbonaceous macromolecular matter by means of flash pyrolysis-gas chromatography (GC). The unheated chondrites, Yamato- (Y-) 791198, Murray and Cold Bokkeveld, yielded larger amounts and wider varieties of pyrolyzates than the chondrites strongly heated in the parent asteroids, Y-82054, Y-86695, and Belgica- (B-) 7904, and Asuka- (A-) 881334 (more strongly heated than Y-793321, which has been weakly heated, but lesser than the other strongly heated meteorites). The weakly heated chondrites, Y-793321 and A-881458, showed intermediate features. The data indicate that graphitization of the carbonaceous matter is most extreme in the strongly heated chondrites and that during graphitization, the matter has lost its labile portion, which can generate pyrolyzates such as naphthalene. In order to establish a new method for the evaluation of the degree of graphitization of chondritic carbonaceous matter, a diagram was developed to show the relationship between the total amounts of pyrolyzates with retention times later than 5 min (=S_RT>5) and the ratio of the amount of naphthalene, a pyrolysis product, to S_RT>5 (=S_N/S_RT>5). The diagram indicates a possible evolutionary pathway of graphitization of the carbonaceous matter in carbonaceous chondrites.     

Organic Carbon Distribution in the Bazhenov Horizon Rocks of the Western Siberian Megabasin

The distribution of organic carbon in the Bazhenov horizon rocks of the western Siberian sedimentary basin is investigated. The organic carbon concentration in rocks is estimated by the results of core analyses (4094 core analyses) and by the calculations of the core-log data correlations (48 500 measurements) according to the data of radiation and electrical loggings. The average content of organic carbon in the rocks of the Bazhenov and Tutleim (lower subformation) formation is 7.7%. The map of organic carbon concentrations in the sedimentary rocks of the basin is constructed. In the basin, C_org is distributed asymmetrically. The region of maximum C_org concentrations occupies the southwestern part of the internal area of the sedimentary basin. Silicites and biogene silica-enriched mixtites are enriched with organic matter most of all.     

Palaeoceanographic controls on geochemical characteristics of organic-rich Exshaw mudrocks: role of enhanced primary production

Organic-rich source rocks have generally been attributed to enhanced preservation of organic matter under anoxic bottom waters. Here, geochemical analysis of kerogen and whole rock samples of organic-rich (lithofacies B₁) and organic-lean (lithofacies B₂) laminated mudrocks of the Devonian–Carboniferous Exshaw Formation, Alberta, highlight the importance of primary production in governing the quantity and quality of organic matter. Lower Si/Al, K/Al, Ti/Al and quartz/clay ratios in lithofacies B₂, similar maceral types and the laminated fabric of the two lithofacies indicate that the quality and quantity of organic matter are not related to grain size, redox or organic matter source changes. High Total Organic Carbon (TOC) and Hydrogen Index (HI), low Oxidation Index (Ox.I. ratio of oxygen functional groups to aliphatic groups derived by FTIR), lighter δ¹⁵N_tot and heavier δ¹³C_org isotopes indicate that kerogen of lithofacies B₁ accumulated during periods of high organic-carbon production and delivery of relatively fresh, labile, well-preserved organic matter to the sea floor. In contrast, low TOC, HI, high Ox.I., heavier δ¹⁵N_tot and lighter δ¹³C_org isotopes indicate low primary productivity and delivery, high recycling and poor preservation of organic matter during accumulation of lithofacies B₂.     

SPORE-POLLEN COMPLEXES OF UPPER DEVONIAN OF THE RUSSIAN PLATFORM

Carbonaceous units commonly host or are closely related to lode-gold mineralization in the mesothermal Fazenda Maria Preta (FMP) and Fazenda Canto (FC) deposits of the Paleoproterozoic Rio Itapicuru greenstone belt of northeastern Brazil. In these deposits, the carbonaceous matter occurs mainly as: (1) straight to anastomosing seams (Type I) along or transecting the rock fabric, or as stylolitic structures in quartz veins; (2) single grains composed of an agglomerate of highly anisotropic subgrains (Type II); or (3) single grains with a homogeneous internal texture (Type III), which are either enclosed in Type-I carbonaceous seams or disseminated in the rock matrix. Type-I carbonaceous matter commonly hosts or is overgrown by the gold-related sulfide paragenesis, particularly arsenopyrite, whereas both Type I and Type II enclose crystals of arsenopyrite or occur as inclusions and in sharp contact with the sulfide phases.

The three morphological types of carbonaceous matter exhibit similar Raman spectral characteristics, with distinct D and O peaks at wave numbers between 1351 cm^?1 and 1357 cm^?1, and 1585 cm^?1 and 1598 cm^?1, respectively. In contrast to the FMP deposit, the carbonaceous matter of the FC deposit shows D peaks of higher intensities than the O peaks. The O peaks are accompanied by an additional disorder-induced band on the high wave number side (≈ 1622 cm^?1), and the O/D peak intensity ratios are higher and the half-height O-peak widths smaller. These spectral parameters indicate that the carbonaceous matter in both deposits corresponds to some form of microcrystalline disordered graphitic material and defines a graphitization trend from the FMP to the FC deposit.

The carbonaceous matter of the FMP deposit is isotopically lighter (δ¹³C = ?23.3‰ to ?30.8‰; x = ?27.4 ± 1.8‰ relative to PDB) than the carbonaceous material of the FC (δ¹³C = ?18.5‰ to ?21.0‰, x = ?19.7 ± 0.9‰). These δ¹³C values, together with the geologic evidence, point toward a primarily biogenic organic origin for the carbonaceous matter. The marked differences in the Raman spectral parameters and the δ₁₃C values are interpreted as resulting from different degrees of thermal maturation of carbonaceous matter attained during the regional greenschist metamorphism and granite intrusions of the Rio Itapicuru greenstone belt.

The δ¹³C compositions of CO₂ resulting from the oxidation or hydrolysis of the carbonaceous matter, calculated by applying the equilibrium CO₂-graphite fractionation, fall within the range ?9.7‰ to ?18.8‰ at 360 to 420°C (FMP deposit) and ?6.0° to ?10.0° at 390 to 455°C (FC deposit). These calculated δ¹³C values are lower than those obtained from primary fluid-inclusion CO₂ in gold-bearing veins (?6.0° to ?10.2° for the FMP deposit; ?2.8° to ?4.9° for the FC deposit) and imply that the thermal maturation process of the carbonaceous matter contributed little to changes in the chemistry and isotopic composition of the ore fluid. The presence of the carbonaceous matter may have been an important factor in gold deposition during fluid-carbon interaction, acting: (1) as a chemical trap, by reducing the f(O₂) of the ore fluids or enhancing fluid immiscibility by adding small quantities of CH₄ and N₂ to the fluid phase; and/or (2) as a physical barrier, by adsorbing gold on its surface as activated carbon.     

Geochemistry and metal potential of triassic carbonaceous silicites in Sikhote Alin

In the Triassic siliceous formation of Sikhote Alin, carbonaceous silicites occur in the late Olenekian-middle Anisian member (4–20 m) of alternating cherts and clayey cherts (“phtanite member”) near the section base. The silicites are represented by radiolarian and spicule-radiolarian cherts alternating with clayey cherts. They contain up to 8.5% C_org. In the majority of sections, the rocks underwent structural and mineral transformation at the mesocatagenetic stage. The slightly oxidized organic (primarily, marine sapropelic) matter contains quinones, methyl, methylene, and ether groups. The content of neutral bitumens in rocks shows a wide variation range. The carbon isotopic composition in phtanites and clayey phtanites (δ¹³C from ?27.3 to ?30.2‰) is identical to that in many Paleozoic-Mesozoic bitumens and oils. As compared with other Mesozoic sedimentary rocks of Sikhote Alin, the carbonaceous silicites are enriched in V, B, Mo, Ni, Cu, and Ag. Anomalously high concentrations of Ba are recorded in phtanite rock sections at the Gornaya and Khor rivers and in the vicinity of Khabarovsk. Modal value of the Au content in phtanites and clayey phtanites is three or four times higher than the clarke value in carbonaceous silicites and reaches anomalous values in some sections (e.g., Ogorodnaya River section). Carbonaceous silicites of this section are also enriched in Pt. Positive Au-C_org correlation is recorded in clayey phtanites of the Ogorodnaya River section containing more than 0.5% C_org. In organic fractions, Au and Ag are concentrated in alcohol and alcohol-benzene bitumens, asphalt acids, and asphaltenes. Migration of bitumens from high-carbonaceous clayey phtanites to the pore-fissure space of cherts and phtanites also fostered the concentration of these metals in some low-carbonaceous layers of the member.     

新疆罗北洼地湖相沉积物有机碳同位素的变化序列及其古环境意义

测定了新疆罗布泊地区湖相沉积物CK-2钻孔样品的总有机碳含量（TOC）及其同位素组成、碳酸盐含量和C/N比值等环境代用指标,以及石膏矿物的质谱-铀系年龄。测试结果表明,20～9kaB.P.期间沉积物δ¹³C_org.在-23.4‰～-16.1‰之间波动且阶段性明显,与TOC呈现良好的相关关系,整体变化趋势同南极Dome C冰芯中记录的全球大气CO₂浓度一致;C/N比值表明有机碳来源主要是陆生高等植物。因此大气CO₂浓度变化是影响20～9kaB.P.期间罗布泊湖相沉积物δ¹³C_org.值变化的主导因素,周围山体上C₃/C₄植物相对生物量的变化则是另一重要因素。依据δ¹³C_org.的变化序列将此时间段湖区古环境的演化分成6个阶段:20.0～14.1kaB.P.期间受到末次盛冰期的影响,气温偏低,湖水丰沛;14.1～13.3kaB.P.是一个气候不稳定期,冷暖波动较频繁,但以暖为趋势;13.3～12.8kaB.P.期间经历了一段冷期,于12.8kaB.P.结束了末次冰期,随后气候开始转暖至11.8kaB.P.;其后气温再次变冷并维持到10kaB.P.;最后从10kaB.P.进入全新世暖期。δ¹³C_org.序列明显向偏负方向变化,表明该地区变暖的趋势相当明显。罗布泊地区日益干旱化是全球气候变化的结果,尤其是受到全球CO₂浓度的不断升高所制约。     

A quantitative reconstruction of organic matter and nutrient diagenesis in Mediterranean Sea sediments over the Holocene

A multicomponent diagenetic model was developed and applied to reconstruct the conditions under which the most recent sapropel, S1, was deposited in the eastern Mediterranean Sea. Simulations demonstrate that bottom waters must have been anoxic and sulphidic during the formation of S1 and that organic matter deposition was approximately three times higher than at present. Nevertheless, most present day sediment and pore water profiles — with the exception of pyrite, iron oxyhydroxides, iron-bound phosphorus and phosphate — can be reproduced under a wide range of redox conditions during formation of S1 by varying the depositional flux of organic carbon. As a result, paleoredox indicators (e.g., C_org:S ratio, C_org:P_org ratio, trace metals) are needed when assessing the contribution of oxygen-depletion and enhanced primary production to the formation of organic-rich layers in the geological record. Furthermore, simulations show that the organic carbon concentration in sediments is a direct proxy for export production under anoxic bottom waters.The model is also used to examine the post-depositional alteration of the organic-rich layer focussing on nitrogen, phosphorus, and organic carbon dynamics. After sapropel formation, remineralisation is dominated by aerobic respiration at a rate that is inversely proportional to the time since bottom waters became oxic once again. A sensitivity analysis was undertaken to identify the most pertinent parameters in regulating the oxidation of sapropels, demonstrating that variations in sedimentation rate, depositional flux of organic carbon during sapropel formation, bottom water oxygen concentration, and porosity have the largest impact. Simulations reveal that sedimentary nutrient cycling was markedly different during the formation of S1, as well as after reoxygenation of bottom waters. Accumulation of organic nitrogen in sediments doubled during sapropel deposition, representing a significant nitrogen sink. Following reventilation of deep waters, N₂ production by denitrification was almost 12 times greater than present day values. Phosphorus cycling also exhibits a strong redox sensitivity. The benthic efflux of phosphate was up to 3.5 times higher during the formation of S1 than at present due to elevated depositional fluxes of organic matter coupled with enhanced remineralisation of organic phosphorus. Reoxygenation of bottom waters leads to a large phosphate pulse to the water column that declines rapidly with time due to rapid oxidation of organic material. The oxidation of pyrite at the redox front forms iron oxyhydroxides that bind phosphorus and, thus, attenuate the benthic phosphate efflux. These results underscore the contrasting effects of oxygen-depletion on sedimentary nitrogen and phosphorus cycling. The simulations also confirm that the current conceptual paradigm of sapropel formation and oxidation is valid and quantitatively coherent.