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.     

Nutrient attenuation in a shallow,gravel-bed river. II. Spatial and temporal changes in nitrogen dynamics and community metabolism

ABSTRACT

Instream processes alter the concentration and bioavailability of nutrients as they are transported downstream. By relating primary production and periphyton composition to changes in nutrient concentration in a gravel-bed river this study made inferences about recycling and attenuation. Where dissolved inorganic nitrogen (DIN) was abundant, concentrations decreased linearly with distance but by less than required to meet the nitrogen demand of primary production. Where DIN was barely measurable photosynthesis was reduced but only by 50%. We infer that recycling sustained primary production even when DIN concentrations were negligibly small. One implication is that DIN removal underestimates attenuation. Further experimental research on recycling and improved modelling is required to better quantify the length of streams adversely affected by nutrients.     

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。     

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。     

Attenuation of aqueous metal transport at two natural acid rock drainage occurrences in the Yukon Territory, Canada

Naturally acidic drainage associated with pyritic black shale has been observed in many locations in the Yukon Territory. While not necessarily linked to known mineral deposits, most of these natural acid rock drainage occurrences show elevated dissolved concentrations of trace elements, especially zinc, nickel, copper, cadmium and arsenic. Based on field observations, microbial investigation, chemical analyses and geochemical modeling, the fate and transport of potentially deleterious elements at two natural acid drainage occurrences with slightly different settings are examined. The Macintosh Creek is a small, acidic stream （pH 2.98-3.40）, 2 km long, located in the Macmillan Pass area of east-central Yukon amidst known sedimentary exhalative massive sulfide mineralization but remains undisturbed by exploration activities. Its trace metal content is apparently derived from groundwater discharges, which gave as much as 5.0, 2.5, 0.7, 0.13 and 0.03 mg/L ofZn, Ni, Cu and As, respectively. Interaction and sorption reactions with algal mats, biofilms and iron oxyhydroxides appear to be the dominant mechanisms attenuating aqueous contaminant transport along the stream. Cryogenic precipitation further consolidates the ferricrete formation and reduces the mobility of the sorbed metals. The tributaries of the Engineering Creek along the Dempster Highway in northern Yukon drain through a series of dolomite, phyllite, argillite, limestone, black shale, sandstone and conglomerate with no known concentration of mineralization. In this area, the water chemistry fully reflects the local geology with acidic streams invariably associated with black shale occurrences. Groundwater seeps in the headwaters area of the km-180 Creek completely enclosed in black shale gave pH 3.0 and as much as 148, 39, 2.9 and 9.1 mg/L of Zn, Ni, Cu and As, respectively. Sorption with iron oxyhydroxide and organic matter appear to dominate the attenuation of contaminant transport along the stream. However, once entered into carbonate-dominated terrains, secondary carbonate minerals exercise additional geochemical control on the local water chemistry as a result of neutralization.     

Modes of raising northeastern Tibet probed by explosion seismology

New wide-angle reflection and refraction seismic data provide constraints on the structure of the upper lithosphere, and test models of its evolution to raise the northeastern part of the Tibetan Plateau. Amplitudes observed for reflections from the crust-mantle boundary are sufficiently large to suggest that there is no significant partial melt in the deep crust. The data show an increase of the crustal thickness between terranes from north of the Kun Lun Fault into the Qang Tang of central Tibet, and a contrast among their intracrustal images and compositions. In the north, P and S velocities are consistent with a dominantly felsic composition and show that only the upper crust thickened. South of the Kun Lun Fault a thicker crust made of two layers could result from the superposition of the originally thin crust of the Bayan Har terrane on the lower part of the crust of the domain to the north, which upper crust it shoved and thickened. Different modes of crustal thickening, either by thickening of individual layers or superpositions and imbrication among them appear to work jointly to raise the topography.