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.     

柿竹园矿床大理岩型锡矿石工艺矿物学研究

大理岩型锡矿石产于燕山早、中期千里山花岗岩与中、上泥盆统灰岩的外接触带。矿石呈细脉、网脉浸染状,锡矿物有:锡石、黄锡矿,富钛尼日利亚石、尼日利亚石和木锡矿,脉石矿物绿帘石、石榴石、电气石、萤石、方解石及磁黄铁矿等亦含锡,锡主要呈锡的浊立矿物存在,占总锡量的89.78％,其中锡石锡占总锡量的80.01％,其次有呈类质同象形式存在的锡,在绿帘石、石榴石、电气石等矿物中以Sn~(4+)取代Fe~(3+),这类锡占总量的8.33％。工艺矿物学研究表明,该类锡矿石以“贫”、“细”、“杂”为特征。锡不仅十分分散,而且品位偏低,矿石矿物组合及镶嵌关系复杂、相互包裹,紧密连生;锡矿物粒度微细,粒径一般为0.2～0.01mm,部分为<0.0l～0.002mm,是一种难选的锡矿石类型。通过锡的回收试验,采用选冶联合工艺流程,预测锡的最佳回收率可达50％以上。     

Occurrence and evolution of the Xiaotangshan hot spring in Beijing, China

Thermal groundwater occurs in bedrock aquifers consisting of the dolomite of the Wumishan Group of the Jixianin System and the Cambrian carbonate in the Xiaotangshan geothermal field near the northern margin of the North China Plain, China. The hot water in the geothermal field of basin-type discharges partly in the form of the Xiaotangshan hot spring under natural conditions. The hot water has TDS of less than 600 mg/L and is of Na·Ca-HCO₃ type. The geothermal water receives recharge from precipitation in the mountain area with elevation of about 500 m above sea level to the north of the spring. Thermal groundwater flows slowly south and southeast through a deep circulation with a residence time of 224 years estimated with the Ra–Rn method. The Xiaotangshan hot spring dried up in the middle of the 1980s owing to the increasing withdrawal of the hot water in the geothermal field in the past decades. The water level of the geothermal system still falls continually at an annual average rate of about 2 m, although water temperature changes very little, indicating that the recharge of such a geothermal system of basin-type is limited. Over-exploitation has a dramatic impact on the geothermal system, and reduction in exploitation and reinjection are required for the sustainable usage of the hot water.     

Application of MODFLOW and geographic information system to groundwater flow simulation in North China Plain, China

MODFLOW is a groundwater modeling program. It can be compiled and remedied according to the practical applications. Because of its structure and fixed data format, MODFLOW can be integrated with Geographic Information Systems (GIS) technology for water resource management. The North China Plain (NCP), which is the politic, economic and cultural center of China, is facing with water resources shortage and water pollution. Groundwater is the main water resource for industrial, agricultural and domestic usage. It is necessary to evaluate the groundwater resources of the NCP as an entire aquifer system. With the development of computer and internet information technology it is also necessary to integrate the groundwater model with the GIS technology. Because the geological and hydrogeological data in the NCP was mainly in MAPGIS format, the powerful function of GIS of disposing of and analyzing spatial data and computer languages such as Visual C and Visual Basic were used to define the relationship between the original data and model data. After analyzing the geological and hydrogeological conditions of the NCP, the groundwater flow numerical simulation modeling was constructed with MODFLOW. On the basis of GIS, a dynamic evaluation system for groundwater resources under the internet circumstance was completed. During the process of constructing the groundwater model, a water budget was analyzed, which showed a negative budget in the NCP. The simulation period was from 1 January 2002 to 31 December 2003. During this period, the total recharge of the groundwater system was 49,374 × 10⁶ m³ and the total discharge was 56,530 × 10⁶ m³ the budget deficit was −7,156 × 10⁶ m³. In this integrated system, the original data including graphs and attribution data could be stored in the database. When the process of evaluating and predicting groundwater flow was started, these data were transformed into files that the core program of MODFLOW could read. The calculated water level and drawdown could be displayed and reviewed online.     

Glacier change and glacier runoff variation in the Tuotuo River basin,the source region of Yangtze River in western China

Glaciers in the Tuotuo River basin, western China, have been monitored in recent decades by applying topographical maps and high-resolution satellite images. Results indicate that most of glaciers in the Tuotuo River basin have retreated in the period from 1968/1971 to 2001/2002, and their shrinkage area is 3.2% of the total area in the late 1960s. To assess the influence of glacier runoff on river runoff, a modified degree–day model including potential clear-sky direct solar radiation has been applied to the glaciated regions of the river basin over the period 1961–2004. It was found that glacier runoff has increased in the last 44 years, especially in the 1990s when a two-thirds increase in river runoff was derived from the increase in glacier runoff caused by loss of ice mass in the entire Tuotuo River basin.     

Coupled and complex: Human-environment interaction in the Greater Yellowstone Ecosystem, USA

Complexity theory has received considerable attention over the past decade from a wide variety of disciplines. Some who write on this topic suggest that complexity theory will lead to a unifying understanding of complex phenomena; others dismiss it as a passing and disruptive fad. We suggest that for the analysis of coupled natural/human systems, the truth emerges from the middle ground. As an approach focused as much on the connections among system elements as the elements themselves, we argue that complexity theory provides a useful conceptual framework for the study of coupled natural/human systems. It is, if nothing else, a framework that leads us to ask interesting questions about, for example, sustainability, resilience, threshold events, and predictability.In this paper we attempt to demystify the ongoing discussions on complexity theory by linking its evocative and overloaded terminology to real-world processes. We illustrate how a shift in focus from system elements to connections among elements can lead to meaningful insight into human-environment interactions that might otherwise be overlooked. We ground our discussion in ongoing interdisciplinary research surrounding Yellowstone National Park’s northern elk winter range; a tightly coupled natural/human system that has been the center of debate, conflict, and compromise for more than 135 years.     

运用3DEEMs及荧光偏振方法研究pH、离子强度及浓度效应对腐殖酸荧光光谱特性的影响

利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.     

中国-俄罗斯原油管道工程(漠河-大庆段)冻土工程地质考察与研究进展

在2005-2007年期间,先后3次对中国-俄罗斯原油管道漠河-大庆段沿线的冻土工程地质条件等进行科学考察,开展了冻土工程地质条件及其在气候变化和人类活动作用下的评价和预测研究.考察研究结果表明:管道沿线多年冻土在各类融区、季节冻土和水系等分隔作用下呈片状或岛状分布,沿线岛状、稀疏岛状及零星岛状占多年冻土区段的40%左右;管道沿线多年冻土随着气候的转暖和人类活动的影响不断退化.地形地貌单元、植被分布、地表水分条件的变化等局部因素对多年冻土的分布和地下冰的赋存产生重要的影响,管道沿线大约分布有50 km左右的沼泽湿地,其表层为腐殖质土及泥炭层,泥炭层下面分布着含土冰层或地下冰,是管道沿线最差的冻土工程地质地段;由于中俄原油管道沿线水系发育多,冻胀丘、冰椎和冰幔等不良冻土现象广泛分布.科学考察的成果为管道沿线冻土工程地质条件评价和预测、管道的稳定性影响分析以及后期的长期检测系统设置等研究奠定坚实的基础,进一步为即将开工的中俄原油管道漠河-大庆段工程的设计、施工提供科学依据.     

无机盐类对天然矿物低温催化混合酯生烃反应的影响

脂肪酸酯是一类重要的生烃母质。选择了十四烷酸甲酯、十六烷酸甲酯和十八烷酸甲酯的混合酯为模型反应物,以方解石、白云石、伊利石、钙蒙脱石和黄铁矿为催化剂,分别考察了氯化钾、氯化镁、氯化钠、硫酸钠以及混合盐对天然矿物低温催化混合酯生烃反应的影响。结果表明,无机盐类对矿物催化下混合酯的生烃反应均有不同程度的影响,硫酸钠具有反催化作用,其它盐类具有正催化作用。且在各无机盐存在下,不同的矿物表现出不同的催化活性。     

气举反循环采矿方法单井试验及应用探讨

湖南道县一个矿区,铁锰矿体储量约2200万t。由于复杂的水文地质和工程地质条件,从20世纪70年代发现后,一直没有开采。笔者通过多年大直径工程井的实践经验,查阅国内外资料后,提出了钻井-气举反循环法试开采的方法,并在现场进行了单孔开采试验,获得了比较满意的效果。以该矿体Ⅱ号矿为例,介绍了钻井-气举反循环法采矿的适用条件、工艺过程以及试采情况,并就以后大面积开采提出了若干技术措施。