The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

鄂尔多斯盆地黄陵、东胜地区地温场对比

鄂尔多斯盆地黄陵、东胜铀矿区分别处于盆地南部渭北隆起的北侧边缘和盆地北部伊盟隆起的东部,赋矿层位都是中侏罗统直罗组。盆地南、北铀矿区在现今地温场及古地温场都存在明显差异,南部现今大地热值及热演化程度明显高于北部。对于下侏罗统延安组和石炭—二叠系煤层,黄陵地区镜质体反射率都高于东胜地区。通过镜质体反射率资料得出同一埋深的一套地层经历的最大古地温和对应的古地温梯度也有南部高于北部的现象。由于早白垩世后期盆地普遍整体抬升使得现今地温相对古地温降低,南部黄陵地区抬升剥蚀量大于北部东胜地区,导致古、今地温差异也大于后者。盆地南部庆阳—富县一带局部构造热运动,导致南部异常地温场的形成,使得南部热演化程度高于北部。     

焦作-郑州天然气输气管道工程地质灾害防治措施及防治建议

焦作-郑州天然气输气管道是较重要建设项目,输气管道起自焦作市博爱县磨头镇,南止郑州市惠济区古荥镇,该输气管道沿线地质环境条件复杂程度为简单-中等。地质灾害类型主要为崩塌、地裂缝、地面不均匀沉陷,黄土湿陷和沙土液化等地质灾害。工程建设有引发和加剧崩塌灾害的可能性,有遭受地质灾害的危险性。工程建设过程中应针对不同的灾害类型采取适当的预防或治理措施。     

Evolution of cool skin and direct air-sea gas transfer coefficient during daytime

Absorption of solar radiation within the thermal molecular sublayer of the ocean can modify the temperature difference across the cool skin as well as the air-sea gas transfer. Our model of renewal type is based on the assumption that the thermal and diffusive molecular sublayers below the ocean surface undergo cyclic growth and destruction, the heat and gas transfer between the successive burst events are performed by molecular diffusion. The model has been upgraded to include heating due to solar radiation. The renewal time is parameterized as a function of the surface Richardson number and the Keulegan number. A Rayleigh number criterion characterizes the convective instability of the cool skin under solar heating. Under low wind speed conditions, the solar heating can damp the convective instability, strongly increasing the renewal time and correspondingly decreasing the interfacial gas exchange. In the ocean, an additional convective instability caused by salinity flux due to evaporation becomes of importance in such cases. The new parameterization is compared with the cool skin data obtained in the western equatorial Pacific during the Tropical Ocean Global Atmosphere Coupled Ocean Atmosphere Response Experiment in February 1993. In combination with a model of the diurnal thermocline it describes main features of the field data both in nighttime and daytime. Under low wind speed conditions (< 5 m s^-1) diurnal variations of the sea surface temperature due to the formation of a diurnal thermocline were substantially larger than those across the cool skin. Under wind speeds > 5 m s^-1, diurnal variations of the surface temperature due to the variations of the thermal molecular sublayer become more important.     

“煤特征指数”与矿井瓦斯危险类型的关系

矿井瓦斯危险程度与煤层中瓦斯赋存状况及其泄出方式有关,并取决于多种地质条件和采掘工艺。其中,煤特征条件特别重要。本文分析了湖南省的5种矿井瓦斯危险类型以及相应的煤特征条件,提出了“煤特征指数(I_c)”这一概念。I_c是一项评价矿井瓦斯危险程度的综合指标。研究表明,矿井瓦斯危险愈严重,则其I_c值愈高。应用该项成果预测了16对矿井的瓦斯危险类型,取得了满意的效果。     

饱和软土压缩曲线的“反常”现象

饱和软土压缩试验时,经常出现压缩曲线“反常”、压缩系数“倒大”的现象。它是土的原始结构发生破坏前后的不同压缩性的客观反映。饱和软土的结构力很微弱,唯质量好的原状土才能见到这种“反常”。应从成孔、取样、测试及资料整理等多个环节保证其工程意义。     

库车坳陷侏罗系煤成气动力学模拟研究

应用黄金管—高压釜封闭体系热模拟实验与GC、GC-IRMS分析技术,结合KINETICS专用软件,对库车坳陷侏罗系煤成气进行了动力学模拟研究。库车坳陷侏罗系煤具有高的产气性,在高演化阶段主要产甲烷气;侏罗系煤热解气甲烷碳同位素为-36‰～-25‰,乙烷碳同位素为-28‰～-16‰;甲烷、C2-C5气态烃的生成活化能分别为(47～64k)calm/ol、(55～72k)calm/ol,频率因子各为5.265×1013s-1、5.388×1018s-1。在此基础上,进一步探讨了克拉2气田天然气的成因。研究认为,克拉2气田天然气属阶段捕获的煤成气,主要聚集了5～1Ma时期的天然气,其成熟度Ro分布范围为1.3%～2.5%。     

山西沁水盆地煤层气成藏的微观动力能条件研究

煤层气成藏的微观动力能条件主要包括煤储层的孔隙—裂隙系统、煤储层的生气作用和储气作用两个方面。以山西沁水盆地为例,深入剖析了煤储层的孔隙—裂隙系统及其发育历程、煤储层的生气作用与能量聚散,阐明了煤层气成藏的微观动力能对成藏效应的控制作用。结果表明:构造作用对储层渗透率具有明显的控制作用,成烃增压致使能量聚集,成为盖层突破作用的主要驱动力,而能量放散则主要是通过煤储层孔隙—裂隙系统的产生、发展。根据上述研究成果,沁水盆地煤层气成藏的地质区划结果为:盆地南部的有利区带为阳城和晋城的北部地区,包括潘庄、樊庄、郑庄等地区;盆地中部的有利区带为安泽—沁源地区,位于盆地西斜坡的中南部;盆地北部的可能有利区带为寿阳东南部地区,位于榆次东北部和阳泉西南部之间。