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1.
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。  相似文献   

2.
铁是海洋沉积物中重要的氧化还原敏感性元素之一,是早期成岩过程中地球化学循环变化的重要动力因素。早期成岩过程中,表层沉积物中铁氧化物的赋存形态主要可分无定形(弱晶型)铁氧化物和晶型铁氧化物,且前者的含量主要决定着沉积物中铁氧化物的还原活性;铁氧化物可以通过与硫酸盐还原产生的硫化物反应进行还原,还能在铁还原菌的参与下被表层沉积物中的有机质还原,沉积物中活性铁含量、有机质含量、沉积速率、植物根系导氧作用及底栖生物的扰动均能对铁还原率造成影响。早期成岩过程中可以形成黄铁矿,形成机理主要有:1)沉积物中先前形成的硫复铁矿(Fe_3S_4)等前体物质通过加硫反应形成;2)硫过饱和的球粒胶体通过脱水、成核、结晶以及聚合作用而成单个草莓状黄铁矿或初始自行黄铁矿微晶成核、生长、聚集、固化的小型黄铁矿微球团并入更大的胶体状黄铁矿结核、草莓状黄铁矿分组,从而形成黄铁矿集合体;黄铁矿化度(DOP)可作为区分古海洋氧化还原环境的指标。对铁同位素的研究表明,异化还原作用(DIR)过程中产生的铁同位素值偏低;页岩中黄铁矿的铁同位素在2.3Ga附近发生的突变反映了第一次大气氧气增高事件。磁学参数对铁相变化具有良好的反应,环境磁学在早期成岩过程研究中的应用,有助于快速划分铁还原带、研究环境中重金属循环行为。  相似文献   

3.
钱家店铀矿田主要赋矿层位为青山口组、姚家组原生红杂色岩系,目前关于其内部灰色砂体沉积期的原生氧化还原性仍存在较大分歧,直接影响了区内找矿部署,而草莓状黄铁矿对沉积岩形成的古环境具有重要指示作用。文章通过系统研究青山口组和姚家组灰色砂体内草莓状黄铁矿的赋存、硫同位素、粒径等特征,首次利用其粒径特征反演目标层位沉积-成岩期水体的古氧化还原条件,进而探讨其对铀成矿的意义。结果表明,钱家店铀矿田灰色砂体中草莓状黄铁矿主要形成于沉积-成岩期,全岩δ34S值为-37.5‰～-23.4‰,为低温微生物还原作用成因。姚家组、青山口组的草莓状黄铁矿粒径分布范围分别为1.6～28.0μm、0.8～52.0μm,平均粒径分别为8.0μm、9.3μm,最大粒径分别为28.0μm、52.0μm,粒径大于10μm的颗粒分别占21.8%、28.3%,表现出姚家组草莓状黄铁矿粒径整体较青山口组小,青山口组具较广的分布范围,但两者具有相似的粒径统计学分布规律。综合草莓状黄铁矿平均粒径对标准偏差和偏态系数二元图解表明,含矿目标层沉积时古水体为次氧化环境,这是目前含矿层不发育翼部矿体和具有“两红夹一灰”纵向氧化还原分带的主...  相似文献   

4.
【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。  相似文献   

5.
沉积过程对自生黄铁矿硫同位素的约束   总被引：6，自引：3，他引：3  
自生黄铁矿是海洋沉积物中还原态硫的主要赋存形式,其形成过程与有机质矿化相关,影响全球的C-S-Fe生物地球化学循环。自生黄铁矿硫同位素分馏主要受微生物硫酸盐还原的控制,但近期的研究成果表明局部沉积环境的改变也可以影响黄铁矿硫同位素的组成,特别是在浅海环境。在浅海非稳态沉积环境内,物理再改造和生物扰动作用,导致硫酸盐还原带内生成的硫化物被再氧化,进而影响黄铁矿的硫同位素值。浅海沉积过程容易受到古气候和海平面变化的影响,引起沉积速率的剧烈波动,导致有机质和活性铁输入的不稳定,进而影响成岩系统的开放性和硫酸盐还原速率,最终影响黄铁矿的硫同位素值。另外,沉积速率的改变还影响硫酸盐—甲烷转换带的迁移,造成有机质和甲烷厌氧氧化硫酸盐还原的相互转化,产生不同的硫同位素信号。东海内陆架泥质区为研究沉积过程对自生黄铁矿的形成及其硫同位素组成的约束机制提供了很好的研究材料。该区域有很好的沉积学研究基础,自生黄铁矿丰富、并且个别层位有生物气（甲烷为主）存在,是研究边缘海C-S-Fe循环的理想场所。  相似文献   

6.
古海洋氧化还原地球化学指标研究新进展   总被引：1，自引：0，他引：1  
古海洋氧化还原条件的恢复一直是地学界的研究热点。许多指标可以用来指示古海洋沉积岩(物)的氧化还原条件。其中地球化学和矿物学方法历来是研究古海洋氧化还原条件的主要手段,前人工作主要集中在单个种类指标(沉积学、矿物学、地球化学等)的单方面研究,缺乏系统研究。但沉积物中的氧化还原指标受很多因素的影响,用单个指标来指示水体的氧化还原条件存在不确定性。主要通过主量元素(总有机碳TOC、有机碳和磷的摩尔比Corg∶P),氧化还原敏感的微量元素(U、V、Mo),黄铁矿类型和草莓状黄铁矿粒径分布以及同位素(黄铁矿硫同位素δ34Spyrite、钼同位素δ98 Mo、铀同位素δ238 U)等指标的综合运用来区分硫化、缺氧、次氧化以及氧化等水体条件。在硫化水体中,氧化还原敏感元素和TOC含量均大量富集,尤其是Mo的富集系数(MoEF)比U的富集系数(UEF)更大(MoEFUEF),有机碳和磷的摩尔比(Corg∶P)也呈现高值;黄铁矿几乎全部呈草莓状,很少出现自形晶,草莓状黄铁矿平均粒径小(常小于5μm)且变化不大,δ34Spyrite值偏负,δ98 Mo值和海水同位素值接近,约为+2.3‰,δ238 U值为+0.2‰,高于海水的同位素值(-0.41‰)。水体环境为氧化的条件下,氧化还原敏感的元素和TOC的量都很缺乏,有机碳和磷的摩尔比(Corg∶P)出现低值,黄铁矿很少,且主要以自形晶的形式出现,平均粒径很大,黄铁矿中的δ34Spyrite值偏正,δ98 Mo值偏负,为-0.7‰,δ238 U值为-0.65‰。在缺氧和次氧化水体环境中,各种指标介于硫化和氧化环境之间,氧化还原敏感元素和TOC含量适中,U相对比Mo富集(UEFMoEF),黄铁矿以草莓状为主,有部分的自形晶出现,黄铁矿平均粒径较大,而且变化范围较大,黄铁矿中的δ34Spyrite值、δ98 Mo值以及δ238 U值均介于氧化和硫化环境之间。最后,还提出在分析古海洋的氧化还原条件时,要综合考虑多种影响因素,清晰认识到每个指标的适用性和局限性,并指出了存在的问题和不足。  相似文献   

7.
海洋天然气水合物系统硫同位素研究进展   总被引：2，自引：2，他引：0  
在海洋天然气水合物的地质系统中,甲烷的渗漏作用形成了独特的地球化学微环境。渗漏的甲烷在硫酸根-甲烷氧化还原界面与硫酸根之间发生厌氧氧化反应,同时硫酸盐发生还原反应,形成具有特殊同位素组成的自生碳酸盐、硫化物（AVS、黄铁矿等）和硫酸盐（重晶石、石膏）等。反应过程中硫酸盐还原菌的作用使得产物中硫的同位素发生了强烈分馏,具体表现为低δ34S值的硫化物矿物和高δ34S值的硫酸盐矿物的形成。沉积物中这种独特的硫同位素特征与海洋天然气水合物系统中独特地球化学微环境有关,是硫酸盐还原反应过程中细菌控制的硫酸盐分馏和厌氧细菌对硫的歧化反应（disproportionation）的共同作用结果。  相似文献   

8.
金龙山金矿是产于南秦岭镇安－旬阳晚古生代沉积盆地细碎屑岩－碳酸盐建造中的微细浸染型金矿,主要载金矿物毒砂,黄铁矿,粒度多为10－100um,约为次显微状金颗粒直径的1000倍左右,黄铁矿为含砷铁矿,并常作为原生沉积成因草莓状,球菌状黄铁矿的增生环带,因而常规方法无法分出原生沉积因黄铁矿热液阶段黄铁矿,毒砂,用于单矿物化学分析,同位素,热电性测定的黄铁矿样品多为热液改造后多段黄铁矿与热液阶段黄铁矿,毒砂,用于单矿物化学分析,同位素,热电性测煊的黄铁矿样品多为热液造后多阶段黄铁矿的混合样品,毒砂的含金性比黄铁矿更好,成岩期黄铁矿无砷很低,金矿成矿阶段黄铁矿亏硫,毒砂亏砷,金、砷最大可能是含矿热液带入的,成岩期黄铁矿可能提供了部分硫,黄铁矿的热电系数范围较大,毒砂亏砷,金,砷最大可能是含矿热液带入的,成岩期黄铁矿可能提供了部分硫,黄铁矿的热电系数范围较大,空穴导型,电子导型均有,以空穴型为主,矿带内化物的硫同位素呈多垛状产出,但主要集中于6‰－17‰之间,铅同位素反映了造山带特征,与汞锑矿石的铅同位素相近,金锑成矿与深大断裂的活动有关。  相似文献   

9.
研究所用样品由“海洋四号”船于2005年8月在三亚市SEE方向约150km处采取。XRD和扫描电镜观察表明样品普遍存在自生碳酸盐、硫酸盐和草莓状（framboidal）黄铁矿。自生矿物组合和显微结构特征与冷泉沉积物类似，属微生物成因。孔隙水中Mg^2＋、Ca^2＋和硫酸根的浓度均有随深度增加而降低的趋势，说明这些组分在成因过程中被消耗。成岩反应过程中的溶解二氧化碳可能来自甲烷的厌氧氧化。样品中硫酸根的消耗主要和硫酸盐矿物沉淀有关，而非硫酸根还原。这意味着造成沉积物中黄铁矿大量沉淀的还原态硫并非来自采样深度，它和甲烷及Ba^2＋一样，均来自地层更深处。  相似文献   

10.
草莓状黄铁矿是指由等粒度的亚微米级黄铁矿晶体或微晶体紧密堆积而成,形似草莓的黄铁矿球形集合体.它们在氧化和缺氧海洋环境中形成的机理不同,沉积岩中草莓状黄铁矿的粒径分布特征是恢复古海洋的氧化还原状态行之有效的方法之一.然而,草莓状黄铁矿粒径统计仅能区分出氧化和缺氧硫化的环境,不能进一步区分缺氧程度及状态(如次氧化、缺氧含...  相似文献   

11.
In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.  相似文献   

12.
The Ediacaran-Cambrian transition is characterized by numerous events such as the emergence of large multi-cellular metazoans and surface environmental disturbances.Based on geological evidence,it has been proposed that this transition coincided with the increase in the atmospheric oxygen level that was key to the evolution of life.Even though ancient redox conditions can be inferred from the composition of sedimentary iron mineral species,this method is not necessarily applicable to all rocks.In the Earth system,the cycling of iron is of considerable interest owing to its sensitivity to redox conditions.Information regarding the paleo-oceanic iron cycle is revealed in the iron isotopic composition of ironbearing minerals.Unfortunately,only limited iron isotopic data exists for Ediacaran-to Cambrianperiod oceans.To circumvent this deficiency,we drilled a fossiliferous Ediacaran to Early Cambrian sedimentary succession in the Three Gorges region,South China.We analyzed the iron isotope ratios(δ~(56/54)Fe)of pyrite grains in the drill cores using laser ablation multi collector inductively coupled plasma mass spectrometry.The results demonstrate large variations inδ~(56/54)Fe,from-1.6 to 1.6‰,and positive iron isotope ratios are observed in many successions.The presence of positiveδ~(56/54)Fe in pyrite indicates that the ferrous iron in the seawater was partially oxidized,suggesting that seawater at Three Gorges was ferruginous during the Ediacaran and Early Cambrian periods.However,aggregated pyrite grains in organic carbon-rich black shales at Member 4 of the Doushantuo Formation and the base of the Shuijingtuo Formation yield near-zeroδ~(56/54)Fe values;this suggests that the ocean was transiently dominated by sulfidic conditions during these periods.Notably negativeδ~(56/54)Fe values,lower than-1‰,can be interpreted as a signature of DIR.The DIR also might contribute in part to the re-mineralization of organic matter during the largest negative carbon isotope anomaly in the Ediacaran.  相似文献   

13.
Sedimentary pyrites in black shales contain abundant trace elements that provide information on the chemistry of the seawater at the time of sedimentation. This study focuses on the Barney Creek Formation (~ 1640 Ma) in the McArthur Basin in the Northern Territory of Australia, which is host to one of the world's largest SEDEX Zn-Pb-Ag deposits, and several smaller deposits. Fine-grained sedimentary pyrite has been sampled from three drill holes through the Barney Creek Formation at various distances from SEDEX mineralisation. Samples were selected through the stratigraphy of each hole and analysed by LA-ICPMS for a suite of 14 trace elements. The data show that sedimentary pyrite at the base of the Barney Creek Formation, closest (within 1 km) to SEDEX mineralisation, is strongly enriched in Zn and Tl by one to two orders of magnitude compared to the global average for sedimentary pyrite. In contrast sedimentary pyrite from the hole furthest from SEDEX mineralisation (~ 60 km) contains mean Zn and Tl values equal to, or less than, the global average. Based on the three drill hole pyrite data sets it is concluded that trace elements that are contributed to the basin during hydrothermal exhalation, and adsorbed into contemporaneous sedimentary pyrite, are principally Zn, Tl, Cu, Pb, Ag and As. In contrast, trace elements that are adsorbed into sedimentary pyrite from background seawater are principally Mo, Ni, Co, Se and As. These differences have enabled the development of a SEDEX fertility diagram for sedimentary basins, based on the composition of sedimentary pyrite, that distinguish high Zn, but barren shales, from high zinc SEDEX-related shales. In parallel with the increase in Zn and Tl in sedimentary pyrite approaching mineralisation there is a decrease in Ni, Co and Mo. This means that the ratios Zn/Ni and Tl/Co are particularly good pyrite vectors to SEDEX mineralisation in the McArthur Basin, varying over 4 to 6 orders of magnitude from barren shales to mineralised shales. It is speculated that the reason for the reverse relationship between Ni, Co and Zn, Tl may be caused by hydrothermal exhalations into the water column that effect the ion-exchange pyrite surface complexation processes that alter the uptake of these elements into sedimentary pyrite.Another important conclusion of this study is that hydrothermal exhalations into a sedimentary basin may affect the redox sensitive trace element chemistry of sedimentary pyrite and therefore the trace element chemistry of pyritic black shales. Nickel, Co and Mo all decrease in proximity to hydrothermal vents that form SEDEX deposits, whereas Zn, Tl and Pb increase. Selenium and bismuth are the only redox sensitive trace elements that appear to be unaffected by hydrothermal activity in the McArthur Basin. This has implications on how trace element concentrations of black shales and pyrite are used to reflect past global ocean chemistry.  相似文献   

14.
The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ34S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ34S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ34S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ34Spyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe3+ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H2O, not O2. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.  相似文献   

15.
Sedimentary pyrite formation: An update   总被引：1，自引：0，他引：1  
Sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time. The amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter, dissolved sulfate, and reactive detrital iron minerals. Organic matter appears to be the major control on pyrite formation in normal (non-euxinic) terrigenous marine sediments where dissolved sulfate and iron minerals are abundant. By contrast, pyrite formation in non-marine, freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic-rich fresh water shales from marine shales. Under marine euxinic conditions sufficient H2S is produced that the dominant control on pyrite formation is the availability of reactive iron minerals.Calculations, based on a sulfur isotope model, indicate that over Phanerozoic time the worldwide average organic carbon-to-pyrite sulfur ratio of sedimentary rocks has varied considerably. High CS ratios during Permo-Carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time. Low CS ratios, compared to today, during the early Paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean. The latter could have been due to lower oceanic oxygen levels and/or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time.  相似文献   

16.
A diffusion-diagenesis model of the sulfur cycle is developed to calculate theoretical distributions of stable sulfur isotopes in marine sediments. The model describes the depth variation in δ34S of dissolved sulfate and H2S. and of pyrite. The effects of sulfate reduction, sulfate and H2S diffusion. and of sedimentation are considered as well as the bacterial isotope fractionation and the degree of pyrite formation. Under open system conditions of sulfur diagenesis the isotopic difference, ΔSO2?4 — H2S, tends to increase with depth being smaller than the bacterial fractionation factor near the sediment surface and larger in deeper layers. The two isotopes in SO2?4 or in H2S do not diffuse in the same proportion as they occur in the porewater. This explains why sulfur, which is incorporated from seawater sulfate by diffusion and precipitation as pyrite, can be enriched in 32S relative to the seawater sulfate. The model calculations demonstrate the importance of taking the whole dynamic sulfur cycle into account before drawing conclusions about sulfur diagenesis from the stable isotope distribution.  相似文献   

17.
南大西洋中脊的26°S热液区广泛发育多金属硫化物、底泥、枕状熔岩、非活动性烟囱体和活动性烟囱体。为了有效探索硫、铜等成矿物质的来源以及成矿作用过程,分别以玄武岩、烟囱体残片及块状多金属硫化物为研究对象,开展了熔融包裹体、硫同位素和铜同位素研究。结果显示：区内玄武岩新鲜未蚀变且斑晶中产出大量熔融包裹体;熔融包裹体气泡壁附着黄铜矿、黄铁矿及磁铁矿等子矿物,说明在岩浆作用过程中可从熔浆中分离出成矿所需的金属元素和硫,这些成矿元素随着岩浆去气作用进入挥发分中,并随着脱气作用迁移出来。通过对烟囱体残片及块状多金属硫化物中黄铁矿的硫同位素组成进行比对分析,发现26°S热液区内硫化物的硫同位素与大西洋各热液区硫化物的硫同位素变化范围相一致,但δ34SV-CDT值略低（3.0‰~3.9‰）。低的δ34SV-CDT值指示硫以岩浆硫源为主,海水硫酸盐还原硫占比低。黄铜矿呈现略微富铜重同位素特征且分馏程度较低,其δ65Cu值（0.171‰~0.477‰）趋近于大洋中脊玄武岩的铜同位素值（0）。综合硫同位素及铜同位素特征,表明热液流体经历了岩浆和海水的混合过程,成矿物质主要来自于岩浆热液,成矿作用过程中可能有少量海水混入。  相似文献   

18.
Upper Cretaceous Phosphorites from different localities in Egypt were analyzed for their rare earth elements (REEs) contents and sulfur and strontium isotopes to examine the effect of depositional conditions versus diagenesis on these parameters.The negative Ce and Eu anomalies of the study phosphorites suggest its formation under reducing conditions. However, chondrite-normalized REEs patterns show relative enrichments of LREEs over the HREEs, which is obviously different from the seawater REEs pattern suggesting post-depositional modifications on the REEs distributions during diagenesis. The difference in the REEs concentrations and Ce anomalies among the study localities as well as the similarity between the REEs patterns of these phosphorites and associated black shales might support this interpretation.The concentration of structural SO42− (0.6-3.7%) and their δ34S values (+0.5 to -20‰) in the upper Cretaceous phosphorites in Egypt suggest the formation of these phosphorites in the zone of sulfate reduction. On the other hand, the sulfur isotopes in the pyrite from the study phosphorites (δ34S = +4.6‰ − 23‰ with an average of −7.7‰) are attributed to the influence of seawater from which pyrite was formed during diagenesis. The difference between the δ34S values in the phosphorites (all are positive values) and those in the associated pyrite (mostly negative values) reflect an asymmetric sulfate and sulfide sulfur isotopic composition due to the formation of francolite (source of sulfate) and pyrite (source of sulfide) in different conditions and/or process.The 87Sr/86Sr values of the upper Cretaceous phosphorites in Egypt are very close to the marine values during the Campanian-Maastrichtian time and their average (0.707622) is more or less comparable to the average 87Sr/86Sr values of the Cretaceous-Eocene Tethyan phosphorites. This suggests no post-depositional alteration (i.e. diagenetic effect) on the Sr isotopic composition of these phosphorites.  相似文献   

19.
Large rounded pyrite grains (>1 mm), commonly referred to as “buckshot” pyrite grains, are a characteristic feature of the auriferous conglomerates (reefs) in the Witwatersrand and Ventersdorp supergroups, Kaapvaal Craton, South Africa. Detailed petrographic analyses of the reefs indicated that the vast majority of the buckshot pyrite grains are of reworked sedimentary origin, i.e., that the pyrite grains originally formed in the sedimentary environment during sedimentation and diagenesis. Forty-one of these reworked sedimentary pyrite grains from the Main, Vaal, Basal, Kalkoenkrans, Beatrix, and Ventersdorp Contact reefs were analyzed for their multiple sulfur isotope compositions (δ34S, Δ33S, and Δ36S) to determine the source of the pyrite sulfur. In addition, five epigenetic pyrite samples (pyrite formed after sedimentation and lithification) from the Middelvlei and the Ventersdorp Contact reefs were measured for comparison. The δ34S, Δ33S, and Δ36S values of all 41 reworked sedimentary pyrite grains indicate clear signatures of mass-dependent and mass-independent fractionation and range from ?6.8 to +13.8?‰, ?1.7 to +1.7?‰, and ?3.9 to +0.9?‰, respectively. In contrast, the five epigenetic pyrite samples display a very limited range of δ34S, Δ33S, and Δ36S values (+0.7 to +4.0?‰, ?0.3 to +0.0?‰. and ?0.3 to +0.1?‰, respectively). Despite the clear signatures of mass-independent sulfur isotope fractionation, very few data points plot along the primary Archean photochemical array suggesting a weak photolytic control over the data set. Instead, other factors command a greater degree of influence such as pyrite paragenesis, the prevailing depositional environment, and non-photolytic sulfur sources. In relation to pyrite paragenesis, reworked syngenetic sedimentary pyrite grains (pyrite originally precipitated along the sediment-water interface) are characterized by negative δ34S and Δ33S values, suggesting open system conditions with respect to sulfate supply and the presence of microbial sulfate reducers. On the contrary, most reworked diagenetic sedimentary pyrite grains (pyrite originally precipitated below the sediment-water interface) show positive δ34S and negative Δ33S values, suggesting closed system conditions. Negligible Δ33S anomalies from epigenetic pyrite suggest that the sulfur was sourced from a mass-dependent or isotopically homogenous metamorphic/hydrothermal fluid. Contrasting sulfur isotope compositions were also observed from different depositional environments, namely fluvial conglomerates and marine-modified fluvial conglomerates. The bulk of the pyrite grains from fluvial conglomerates are characterized by a wide range of δ34S values (?6.2 to +4.8?‰) and small Δ33S values (±0.3?‰). This signature likely represents a crustal sulfate reservoir derived from either volcanic degassing or from weathering of sulfide minerals in the hinterland. Reworked sedimentary pyrite grains from marine-modified fluvial conglomerates share similar isotope compositions, but also produce a positive Δ33S/δ34S array that overlaps with the composition of Archean barite, suggesting the introduction of marine sulfur. These results demonstrate the presence of multiple sources of sulfur, which include atmospheric, crustal, and marine reservoirs. The prevalence of the mass-dependent crustal sulfur isotope signature in fluvial conglomerates suggests that sulfate concentrations were probably much higher in terrestrial settings in comparison to marine environments, which were sulfate-deficient. However, the optimum conditions for forming terrestrial sedimentary pyrite were probably not during fluvial progradation but rather during the early phases of flooding of low angle unconformities, i.e., during retrogradational fluvial deposition, coupled in some cases with marine transgressions, immediately following inflection points of maximum rate of relative sea level fall.  相似文献   

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