Sulfur Isotopes of Framboidal Pyrite in the Permian-Triassic Boundary Clay at Meishan Section

Pyrite framboids were found in the Permian-Triassic boundary at Meishan Section, while their sulfur isotopes were determined. The majority of framboids is less than 5 μm in diameter, with some large-sized framboids. Also, euhedral gypsums were observed in the boundary clay. The authors suppose that most of the pyrite framboids formed just below the redox boundary and stopped growing after entering the lower water column. The result indicates that it was probably lower dysoxia condition in the temporal ocean. Moreover, the authors also presume that some pyrite was oxidated to sulfates accompanying the fluctuation of redox condition, which would probably be the origin of the negative sulfur isotopes of gypsum and CAS reported before. In addition, sulfur isotope of framboidal pyrite suggests that sulfur is originated from bacterial sulfate reduction in anoxic condition. Therefore, this study confirms that the ocean was widely anoxic during the Permian-Triassic transitional period. However, the redox condition in temporal ocean was probably not stable, with short-term fluctuations.     

沉积物成岩蚀变过程中的Mn、Cd和Mo元素活动特征:以ODP 1148站钻孔沉积物记录为例

通过对南海北部的ODP 1148站岩芯600 mcd以上(约30 Ma以来)的沉积物中自生富集Mn、Cd和Mo等过渡金属元素的含量变化的研究,并结合相关的化学组成结果,探讨了岩芯内部氧化-还原条件的变化以及相关元素的活动特征,反演了相应沉积时期的环境演变.结果显示,岩芯387 mcd以上,自生Mn富集明显,代表氧化的环境;387～485 mcd之间,自生Cd含量明显富集,Mn含量显著降低,代表少氧的环境;485 mcd以下,Mn和Cd含量极低,自生Mo明显富集,代表缺氧的环境.随氧化-还原条件的变化,Mo存在明显的向下迁移并在缺氧界面的缺氧一方达到最大值的趋势,而Cd在少氧环境形成的固相态则可能在缺氧环境下不稳定,溶解态的Cd有向上迁移的趋势,并且在少氧/缺氧界面的少氧一方富集.这些过渡金属元素记录的氧化-还原条件的变化,反映出ODP 1148站所在海区的沉积环境变化:早期有较丰富的陆源输入,表层海水生产力较高,随着南海不断扩张以及全球海平面上升,该海区表层海水生产力逐渐降低.     

沉积地层中草莓状黄铁矿分析方法及其在古海洋学上的应用

草莓状黄铁矿是黄铁矿的特殊形态,其定义为由相近大小、相似形态的黄铁矿微晶颗粒组成的球形、亚球形聚合体。草莓状黄铁矿粒径分析已广泛应用于各个地质历史时期的古海洋环境恢复研究中,但其形成机理、判别标准与实验方法仍存在分歧。因此对沉积地层中草莓状黄铁矿的形成机理、在古海洋环境恢复中的指示意义及判别标准、实验与数据分析方法等进行总结阐述,有助于理解草莓状黄铁矿的粒径大小与形态对氧化还原条件的指示意义。草莓状黄铁矿在不同氧化还原环境下的形成机理存在差异,其粒径大小、数量以及分布范围可综合反映沉积时水体的氧化还原条件;而草莓状黄铁矿微晶几何形态及整体形貌特征也与古海洋氧化还原环境密切相关。此外,虽然有学者指出该方法可能存在一些问题,但只要在分析过程中结合沉积特征、古生态特征、地球化学指标等多方面证据对环境进行综合判别,甄别特殊条件下沉积的草莓状黄铁矿,则可有效避免这些问题。最后,针对后期氧化作用对草莓状黄铁矿粒径分布的影响进行了评价,结果显示经过后期氧化作用的草莓状黄铁矿粒径变化很小,不会对其在恢复古海洋氧化还原环境的应用上产生影响。     

Authigenic Gypsum in Gas-Hydrate Associated Sediments from the East Coast of India (Bay of Bengal)

Authigenic gypsum crystals, along with pyrite and carbonate mineralization, predominantly calcites were noticed in distinct intervals in a 32 m long piston core, collected in the gas hydrate- bearing sediments in the northern portion of the Krishna-Godavari basin, eastern continental margin of India at a water depth of 1691 m. X-ray diffraction and energy dispersive spectrum studies confirm presence of pyrite, gypsum, calcite, and other mineral aggregates. The occurrence of gypsum in such deep sea environment is intriguing, because gypsum is a classical evaporite mineral and is under saturated with respect to sea water. Sedimentological, geochemical evidences point to diagenetic formation of the gypsum due to oxidation of sulphide minerals (i.e. pyrite). Euhedral, transparent gypsum crystals, with pyrite inclusions are cemented with authigenic carbonates, possibly indicating that they were formed authigenically in situ in the gas hydrate-influenced environment due to late burial diagenesis involving sulphate reduction and anaerobic oxidation of methane (AOM). Therefore, the authigenic gypsums found in sediments of the Krishna-Godavari and Mahanadi offshore regions could be seen as one of the parameters to imply the presence of high methane flux possibly from gas hydrate at depth.     

Oxygenation in carbonate microbialites and associated facies after the end-Permian mass extinction:Problems and potential solutions

Carbonate sediments deposited in normally-oxygenated shallow ocean waters of the latest Permian period, immediately prior to the end-Permian mass extinction, contain well-developed diverse shelly faunas. After the extinction of these skeletal metazoans, the sediments commonly comprise microbialites(regarded by most authors as benthic) and associated facies bearing evidence interpreted by many authors to indicate reduced oxygenation of the shallow ocean waters. However, the evidence of oxygenation state is inconsistent and the sequences have gaps, indicated in the following 5 points:1) Shelly fossils occur commonly in post-extinction shallow marine limestones, and likely to have been aerated in contact with the atmosphere. Nevertheless, although the largest mass extinction in Earth history may have caused reduced body size in shelly organisms, such reduction is arguably due to environmental stress of lowered oxygenation. Discriminating between these controls remains a challenge.2) Abundant pyrite framboids in many post-extinction limestones are interpreted by several authors as indicating dysoxic contemporaneous waters, so the organisms that lived there, now shelly fossils, were dysaerobic. However, verification is problematic because pyrite framboids scattered amongst shelly fossils cannot have formed amongst living organisms, which need at least some oxygen; synsedimentary framboid formation requires anoxic conditions in the redox boundary where sulphate-reducing processes work. Thus, framboids and shelly fossils found together means taphonomic mixing of sediments, destroying original depositional relationships so that it is not possible to determine whether the shells were aerobic or dysaerobic prior to sediment mixing. Furthermore, diagenetic growth of framboids is possible, as is import of previously-formed framboids from deeper water during upwelling. Thus, there is no proof of an environmental link between framboid size and occurrence, and contemporaneous oxygenation in these post-extinction shallow water facies, so we question the validity of this model in those facies, but consider that the model is valid for deeper water facies.3) Some publications provide evidence of oxygenation, from redox-sensitive elements in post-extinction limestones, while others indicate low oxygen conditions. Redox-sensitive geochemistry requires further work to explore this issue at higher resolution of sampling than has been so far applied.4) Biomarkers recorded in some post-extinction facies contain evidence of anoxic conditions(including green sulphur bacteria) but other examples lack these, which may be indicate fluctuations of water oxygenation. However, a key issue that has not yet been resolved is determination of whether biomarkers were imported into the sites of deposition, for example by upwelling currents, or formed where they are found.Thus, there is currently no verification that biomarkers of low oxygen organisms in shallow water settings actually formed in the places where they are sampled.5) The common occurrence of small erosion surfaces and stylolites represents loss of evidence, and must be accounted for in future studies.The oxygenation state of post-end-Permian extinction shallow marine facies continues to present a challenge of interpretation, and requires high-resolution sampling and careful attention to small-scale changes, as well as loss of rock through pressure solution, as the next step to resolve the issue.     

Pyrite in ammonite-bearing shales from the Jurassic of England and Germany

Pyrite occurs both in normal clays and shales with a benthic fauna (Oxford Clay, England, and Lias ε, Germany) and in highly bituminous shales (Lias ε, Germany). In normal shales it is present in small quantities as early framboids, but more conspicuously as internal moulds of fossils, especially ammonites. The pyrite in these is petrographically varied; several types of internal sediments and chamber linings are described and illustrated by reflected-light and scanning electron microscopy. Most striking are pyrite stalactites, suspended from the roofs of ammonite chambers, which were later filled by calcite or baryte. Pyrite formed in reducing micro-environments, while the sediment generally was not wholly anoxic. Most pyrite pre-dates compaction of sediment, breakage of fossils and solution of shell aragonite. Variable rates and conditions of reduction of sea water sulphate are reflected in δ³⁴S values ranging from ?55 to +44. Stalactites probably started to form when the ammonite chambers were partially gas-filled. In the bituminous Lias ε shales pyrite occurs abundantly as early framboids and micro-nodules. Larger nodules show a variety of forms, some of which post-date compaction of the sediment. Pyrite is not associated with the abundant flattened ammonites. δ³⁴S values in shales are grouped about a mode near ?20. Pyrite formed over a long time-span, and throughout the sediment, not just in protected cavities. Contrasts in pyrite types can be related to differing depositional environments and organic contents of the shales. Pyrite is an important mineral in diagenetic mineral parageneses which can be deduced by studying fossil void-fillings and concretions, and which help define the diagenetic history of a shale.     

Interplay of S and As in Mekong Delta sediments during redox oscillations

The cumulative effects of periodic redox cycling on the mobility of As,Fe,and S from alluvial sediment to groundwater were investigated in bioreactor experiments.Two particular sediments from the alluvial floodplain of the Mekong Delta River were investigated:Matrix A(14 m deep)had a higher pyrite concentration than matrix B(7 m deep)sediments.Gypsum was present in matrix B but absent in matrix A.In the reactors,the sediment suspensions were supplemented with As(Ⅲ)and SO_4~(2-),and were subjected to three full-redox cycles entailing phases of nitrogen/CO_2,compressed air sparging,and cellobiose addition.Major differences in As concentration and speciation were observed upon redox cycling.Evidences support the fact that initial sediment composition is the main factor controlling arsenic release and its speciation during the redox cycles.Indeed,a high pyrite content associated with a low SO_4~(2-)content resulted in an increase in dissolved As concentrations,mainly in the form of As(Ⅲ),after anoxic half-cycles;whereas a decrease in As concentrations mainly in the form of As(Ⅴ),was instead observed after oxic half-cycles.In addition,oxic conditions were found to be responsible for pyrite and arsenian pyrite oxidation,increasing the As pool available for mobilization.The same processes seem to occur in sediment with the presence of gypsum,but,in this case,dissolved As were sequestered by biotic or abiotic redox reactions occurring in the Fe—S system,and by specific physico-chemical condition(e.g.pH).The contrasting results obtained for two sediments sampled from the same core show that many complexes and entangled factors are at work,and further refinement is needed to explain the spatial and temporal variability of As release to groundwater of the Mekong River Delta(Vietnam).     

Early diagenesis of redox-sensitive trace metals in the Peru upwelling area - response to ENSO-related oxygen fluctuations in the water column

Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ∼0 to 93 μM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Niño Southern Oscillation (ENSO).Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ precipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions.Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record.     

Holocene Refreshening and Reoxygenation of a Bothnian Sea Estuary Led to Enhanced Phosphorus Burial

Salinity variations in restricted basins like the Baltic Sea can alter their vulnerability to hypoxia (i.e., bottom water oxygen concentrations <2 mg/l) and can affect the burial of phosphorus (P), a key nutrient for marine organisms. We combine porewater and solid-phase geochemistry, micro-analysis of sieved sediments (including XRD and synchrotron-based XAS), and foraminiferal δ¹⁸O and δ¹³C analyses to reconstruct the bottom water salinity, redox conditions, and P burial in the Ångermanälven estuary, Bothnian Sea. Our sediment records were retrieved during the Integrated Ocean Drilling Program (IODP) Baltic Sea Paleoenvironment Expedition 347 in 2013. We demonstrate that bottom waters in the Ångermanälven estuary became anoxic upon the intrusion of seawater in the early Holocene, like in the central Bothnian Sea. The subsequent refreshening and reoxygenation, which was caused by gradual isostatic uplift, promoted P burial in the sediment in the form of Mn-rich vivianite. Vivianite authigenesis in the surface sediments of the more isolated part of the estuary ultimately ceased, likely due to continued refreshening and an associated decline in productivity and P supply to the sediment. The observed shifts in environmental conditions also created conditions for post-depositional formation of authigenic vivianite, and possibly apatite formation, at ～8 m composite depth. These salinity-related changes in redox conditions and P burial are highly relevant in light of current climate change. The results specifically highlight that increased freshwater input linked to global warming may enhance coastal P retention, thereby contributing to oligotrophication in both coastal and adjacent open waters.     

Quantitative micro‐X‐ray fluorescence scanning spectroscopy of wet sediment based on the X‐ray absorption and emission theories: Its application to freshwater lake sedimentary sequences

Micro‐X‐ray fluorescence scanning spectroscopy of marine and lake sedimentary sequences can provide detailed palaeoenvironmental records through element intensity proxy data. However, problems with the effects of interstitial pore water on the micro‐X‐ray fluorescence intensities have been pointed out. This is because the X‐ray fluorescence intensities are measured directly at the surfaces of split wet sediment core samples. This study developed a new method for correcting X‐ray fluorescence data to compensate for the effects of pore water using a scanning X‐ray analytical microscope. This involved simultaneous use of micro‐X‐ray fluorescence scanning spectroscopy and an X‐ray transmission detector. To evaluate the interstitial pore water content from the X‐ray transmission intensities, a fine‐grained sediment core retrieved from Lake Baikal (VER99‐G12) was used to prepare resin‐embedded samples with smooth surfaces and uniform thickness. Simple linear regression between the linear absorption coefficients of the samples and their porosity, based on the Lambert–Beer law, enabled calculation of the interstitial pore spaces and their resin content with high reproducibility. The X‐ray fluorescence intensities of resin‐embedded samples were reduced compared with those of dry sediment samples because of: (i) the X‐ray fluorescence absorption of resin within sediment; and (ii) the sediment dilution effects by resin. An improved micro‐X‐ray fluorescence correction equation based on X‐ray fluorescence emission theory considers the instrument's sensitivity to each element, which provides a reasonable explanation of these two effects. The resin‐corrected X‐ray fluorescence intensity was then successfully converted to elemental concentrations using simple linear regression between the data from micro‐X‐ray fluorescence scanning spectroscopy and from the conventional analyzer. In particular, the calculated concentration of SiO₂ over the depth of the core, reflecting diatom/biogenic silica concentration, was significantly changed by the calibrations, from a progressively decreasing trend to an increasing trend towards the top of the core.     

Diagenetic formation of gypsum and dolomite in a cold‐water coral mound in the Porcupine Seabight,off Ireland

Authigenic gypsum was found in a gravity core, retrieved from the top of Mound Perseverance, a giant cold‐water coral mound in the Porcupine Basin, off Ireland. The occurrence of gypsum in such an environment is intriguing, because gypsum, a classic evaporitic mineral, is undersaturated with respect to sea water. Sedimentological, petrographic and isotopic evidence point to diagenetic formation of the gypsum, tied to oxidation of sedimentary sulphide minerals (i.e. pyrite). This oxidation is attributed to a phase of increased bottom currents which caused erosion and enhanced inflow of oxidizing fluids into the mound sediments. The oxidation of pyrite produced acidity, causing carbonate dissolution and subsequently leading to pore‐water oversaturation with respect to gypsum and dolomite. Calculations based on the isotopic compositions of gypsum and pyrite reveal that between 21·6% and 28·6% of the sulphate incorporated into the gypsum derived from pyrite oxidation. The dissolution of carbonate increased the porosity in the affected sediment layer but promoted lithification of the sediments at the sediment‐water interface. Thus, authigenic gypsum can serve as a signature for diagenetic oxidation events in carbonate‐rich sediments. These observations demonstrate that fluid flow, steered by environmental factors, has an important effect on the diagenesis of coral mounds.     

A study of oxic/anoxic effects on degradation of sterols at the simulated sediment–water interface of coastal sediments

Laboratory incubation experiments were conducted to determine the behavior of sterols at the sediment–water interface in oxic and anoxic sediments. Both plankton and 4- -cholesterol were used as tracers. Cholesterol was rapidly degraded at the sediment–water interface: 55% of -cholesterol was lost from sediments under anoxic conditions and 78% under oxic conditions over three and one-half months. About 3% of initially-added free radiolabel was incorporated into a bound pool that was released only by saponification of solvent-extracted sediment. Less than 1% of initially-added radiolabel remained in pore waters after three and one-half months. Rate constants for degradation of cholesterol in oxic and anoxic surficial sediments were estimated by tracking variations in radioactivity and sterol concentration as a function of time. We discuss our results in terms of factors affecting sterol degradation in coastal marine sediments, including molecular structure, sediment matrix effect, and redox conditions.     

沉积地层中的黄铁矿形态及同位素特征初探——以华南埃迪卡拉纪深水相地层为例

地质历史时期新元古代大气氧含量普遍较低。在硫酸盐还原细菌作用下,作为海洋重要的氧化性离子,陆源硫酸根离子有效促进了深层海水的氧化进程。在此过程中,硫元素在硫酸根和黄铁矿之间发生显著同位素分馏,其分馏程度可反推当时古海洋的氧化还原状态。沉积地层中的黄铁矿普遍具有多种形态,不同形态黄铁矿的形成环境多有不同。如草莓状黄铁矿多形成于底层缺氧水体或沉积物的浅表面,而大颗粒单晶黄铁矿或脉状黄铁矿则多沉积于成岩早期的沉积物孔隙或形成于成岩后期的热液改造。与草莓状黄铁矿不同,大颗粒单晶或脉状黄铁矿的硫同位素组成并不能反映沉积时期的古海洋氧化还原条件。判定沉积地层中不同形态的黄铁矿及形成过程,是获得有效反映海洋沉积环境硫同位素组成特征的基本前提。简要总结了地质历史时期沉积地层中的黄铁矿类型及矿物形成过程,并以华南埃迪卡拉纪蓝田组岩芯样品为例,识别出各个样品中的黄铁矿形态组成特征,对比分析了全岩黄铁矿与样品中大颗粒黄铁矿硫同位素组成差异。研究结果表明:不同岩性样品中黄铁矿的形态种类及含量均存在差异。页岩样品保存有更好形态的自形晶以及草莓状黄铁矿;碳酸盐岩样品中具有较多自形晶以及他形晶黄铁矿,并且其中的少量草莓状黄铁矿遭受后期成岩作用而发生不同程度的晶体蚀变。样品中大颗粒黄铁矿的硫同位素值（δ34S_L-pyr）通常显著高于全岩黄铁矿的硫同位素值（δ34S_T-pyr）,最大差值可达48.5‰。在利用黄铁矿的硫同位素组成来反推当时古海洋环境时,需要区分不同形态黄铁矿,仔细剔除大颗粒黄铁矿,降低成岩期黄铁矿对样品中硫同位素组成的影响。更细致的微区黄铁矿硫同位素分析工作将依赖于SIMS分析测试手段进行。     

Pyritization of iron and trace metals in anoxic fjord sediments (Nordåsvannet fjord,western Norway)

The accumulation and storage of trace metals in coastal sediments is an environmental concern. It is, therefore, important to understand better how these metals are bound or released under different redox conditions. This study of Fe and trace metal fixation under continuously anoxic conditions in the bottom sediments and the lower water column of the Nordåsvannet fjord in western Norway contributes further to such understanding. It allows investigation of both an end member redox state and one important mechanism of Fe and trace metal accumulation in sediments, the pyritization of Fe and trace metals. Pyrite formation occurs both in the water column and in the sediments of the Nordåsvannet fjord and favours the fixing of Fe and trace metals in the bottom sediments of the fjord. Thus, these sediments act as a continuous sink for Fe and trace metals. The DOP, and the degrees of trace metal pyritization for Mo, Ni and Cr correlate with organic matter content. While it is generally thought that Fe is the factor limiting pyrite formation in anoxic environments, this study found that degrees of pyritization of Fe (DOP) are clearly below 100%, and the availability of metabolizable organic matter is limiting pyrite formation. This is an important finding, because it indicates that increased supply of organic and mineral matter by higher runoff from land would further enhance the fixation of these metals in the fjord sediments, as would higher organic matter availability from increased productivity due to higher nutrient supply. The metals stored in the bottom sediments could be released into the biogeochemical cycle if redox conditions were to change from anoxic to suboxic or oxic. The fjord would then become a source rather than a sink for these metals.     

Neoproterozoic peritidal phosphorite from the Sete Lagoas Formation (Brazil) and the Precambrian phosphorus cycle

The Neoproterozoic Sete Lagoas Formation (ca 610 Ma) of the São Francisco Basin, Brazil, is a succession of siltstone, limestone and phosphorite. Phosphorite forms part of a previously unrecognized 150 to 200 m thick, unconformity bounded depositional sequence. Lithofacies stacking patterns indicate that deposition was punctuated by higher order fluctuations in base level that produced aggradational parasequences. These shallowing‐upward cycles record the progradation of phosphate‐rich intertidal flats over shallow subtidal deposits as accommodation filled. The presence of mudcracks, authigenic chert nodules, lack of coarse terrigenous clastics and the abundance of silt with fine, abraded quartz grains suggests accumulation along an arid coastline with significant aeolian input. Delivery of phosphorus adsorbed on aeolian Fe‐(oxyhydr)oxide and clay is interpreted as having stimulated phosphogenesis in peritidal environments. Lithofacies associations indicate that windblown phosphorus promoted the establishment of cyanobacterial communities along the coast, which produced photosynthetic oxygen and the suboxic conditions necessary for the precipitation of authigenic carbonate fluorapatite. As in other Precambrian phosphatic systems, nearshore oxygen oases were a prerequisite for phosphorite accumulation because redox sensitive phosphogenic processes were pushed into the sediment to concentrate phosphorus. In more distal, anoxic environments phosphorite could not form because these biotic and abiotic processes were suspended in the water column, which cycled phosphorus in sea water rather than at the sediment–water interface. Such shallow‐water phosphorite is unlike larger, younger Neoproterozoic–Phanerozoic phosphatic deposits inferred to have formed in deeper‐upwelling related environments. The increasing size of phosphatic deposits through the latest Precambrian is interpreted as reflecting the progressive ventilation of the oceans during the Neoproterozoic Oxygenation Event, and resultant expansion of phosphogenic environments into distal settings. The widespread cycling of bioavailable phosphorus at the sea floor not only produced the first true phosphorite giants, but may have also been an important precondition for the evolution of multicellular animals.     

草莓状黄铁矿的形成机制探讨及其对古氧化-还原环境的反演

【研究目的】草莓状黄铁矿广泛存在于现代沉积物和沉积岩中,其成因机制总体上分为有机成因和无机成因两种,尽管两种机制均有理论与实验的支撑,但尚未建立一种具有普遍意义的形成机制。【研究方法】本文对目前草莓状黄铁矿的形成机理、氧化还原环境的应用及后期环境变化的影响进行了系统的综合研究。【研究结果】不同氧化-还原环境下形成的草莓状黄铁矿在粒径、形态以及硫同位素之间均存在较大的差异,可做为反演古氧化-还原环境的指标。草莓状黄铁矿的微晶尽管与粒径具有一定的正相关性,但是两者在形态演化序列、生长模式、聚集因素等方面与古氧化-还原环境的关系尚不清楚。仅凭草莓状黄铁矿粒径与铬还原法测定的硫同位素反演古氧化-还原环境存在一定的局限性,需要其他指标综合判定,尚需进一步开展草莓状黄铁矿原位硫同位素值与粒径对古氧化-还原环境反演的研究。后期氧化可使草莓状黄铁矿表面化学成分发生变化,但粒径分布依然具有古氧化-还原环境的指示意义。【结论】草莓状黄铁矿的实验模拟、理论体系和多学科交叉的研究中仍存在一些问题,尚需进一步研究。     

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。     

Pyrite oxidation during sample storage determines phosphorus fractionation in carbonate-poor anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (∼94 Ma) and the Paleocene-Eocene thermal maximum (∼55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO₃ contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO₃ can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.     

Authigenic pyrite and gypsum in South West African continental slope sediments

An unusual association of authigenic pyrite and authigenic gypsum has been found in silty clays recovered from the South West African continental slope. Nannofossil content suggests that the sediments are Upper Miocene-Lower Pliocene in age. Pyrite occurs as (1) granular masses, (2) ‘worm’tubes, (3) foraminiferal infillings, and (4) framboids. Gypsum occurs as euhedral single or twinned crystals of selenite. ‘Worm’tubes and foraminiferal infillings of pyrite are partially or completely enclosed in some gypsum crystals. Electron microprobe analyses show a relatively high concentration of manganese in both the granular masses and tubes. Present-day waters off this coast are dominated by the upwelling of cold, nutrient-enriched waters (the Benguela Current). These rich waters support an enormous population of plankton. Death and decomposition of these plankton consume oxygen, thereby creating a belt of anaerobic sediments close to shore. An Upper Miocene-Lower Pliocene regression (Dingle & Scrutton, 1974) lowered sea level and shifted an older analogue of this upwelling zone seaward, eventually establishing an anaerobic environment in places on the present continental slope. Anaerobic bacteria thrived in these conditions. They reduced SO₄ dissolved in sea water, initiating the formation of H₂S. The H₂S reacted with iron minerals present in the sediment to form FeS. Addition of elemental sulphur produced pyrite. This strongly reducing, low pH, environment became saturated with calcium obtained by the dissolution of planktonic calcareous organisms. Gypsum was precipitated once the product of the concentrations of dissolved calcium and SO₄ exceeded the gypsum solubility product.     

Comparative geochemistry of cadmium, rhenium, uranium, and molybdenum in continental margin sediments

The concentrations of authigenic phases of Cd, Re, U, and Mo increase with depth in four 45-cm-long sediment box cores collected along the axis of the Laurentian Trough, Gulf of St. Lawrence. Average authigenic accumulation rates, estimated from element inventories, are similar to rates in other continental margin environments. Strong regional variations in sediment accumulation rate and sulfide concentration have little influence on the accumulation rates of Cd and Re. This suggests that slow precipitation kinetics controls the accumulation of Cd and Re in these sediments. The accumulation rate of authigenic U is more variable; it may be tied to the kinetics of microbially mediated U reduction and be controlled by the availability of reactive organic matter. Authigenic Mo is distinguished by a sharp subsurface concentration minimum, above which Mo cycles with manganese. Mo released to pore water upon reduction of Mn oxides diffuses downward and enriches the subsurface sediment. Mo accumulates most rapidly in the sediment with the highest sulfide content. Slow conversion of molybdate to thiomolybdate may explain the much slower Mo accumulation rate in the less sulfidic sediments. A component of authigenic Mo accumulates with pyrite in an approximately constant Mo:Fe ratio. The accumulation rate of pyrite and associated Mo is insensitive to AVS abundance. Pyrite formation may be limited by the reactivity of iron oxide minerals.