Thermodynamic and Kinetic Properties of Natural Brines

The physical chemistry of natural brines made up of mostly NaCl has been studied over the years. In this article, the work on the thermodynamics and kinetics of processes in NaCl brines will be examined. The importance of ionic interactions of the processes will be stressed. This will include the pressure–volume–temperature and physical–chemical properties of NaCl and other brine salts from 0 to 6 m, 0 to 200°C, and 0 to 1,000 bar applied pressures. Acid–base, gas–liquid, solid–liquid, and ion–complex formation processes in NaCl are examined. Equations that can be used to estimate the equilibria in NaCl are given. Pitzer models are discussed that can be used to estimate ionic equilibria in brines. The oxidation of Fe(II) and Cu(I) with O₂ and H₂O₂ and the reduction of Cu(II) with H₂O₂ in NaCl are examined in terms of ionic complexes of metals with OH^? and CO₃ ^2?. The oxidation of H₂S with O₂ and H₂O₂ is also examined in NaCl media. Equations are given that can be used to estimate the effect of ionic interactions on kinetic processes in NaCl.     

异常地层压力的综合预测方法及其在营尔凹陷的应用

预测异常地层压力的方法主要有以测井资料为主的平衡深度法、以地震资料为主的地震层速度法、以实测压力为主的经验关系法和数值模拟法,单独使用某一类方法预测地层压力都具有一定的局限性.提出了一种综合预测地层压力的方法,该方法将现有的测井、地震资料预测地层压力的方法进行了综合与改进,预测过程充分利用了营尔凹陷的测井资料、地震资料和压力测试资料,预测的地层压力与实测压力具有较好的一致性,证明用该方法来研究异常地层压力是有效的.研究发现营尔凹陷异常地层压力十分发育,纵向上,从浅至深可以依次划分为具有不同压力特征的4个压力带:常压带、浅层超压带、压力过渡带和深层超压带.通过测井、地震资料预测压力剖面的综合对比发现,各压力带的分布主要受地层层位和岩性控制.     

Contributions and unrealized potential contributions of cosmogenic-nuclide exposure dating to glacier chronology, 1990–2010

This paper reviews the application of cosmogenic-nuclide exposure dating to glacier chronology. Exposure dating of glacial landforms has made an outsize impact on this field because the technique filled an obvious need that had already been recognized by glacial geologists. By now, hundreds of studies have used cosmogenic-nuclide exposure dating to date glacial deposits, and in fact it is rare to find a study of glacial geology or glacier chronology, or any paleoclimate synthesis that makes use of such studies, that does not involve exposure dating. These developments have resulted in major contributions to glacier chronology and paleoclimate, in particular i) reconstructing Antarctic ice sheet change, ii) establishing the chronology of late Pleistocene and Holocene glacier change in mountain regions where it was previously unknown; iii) establishing the broad chronological outlines of mountain glaciations prior to the Last Glacial Maximum; and iv) gaining insight into subglacial erosional processes through the observation that many glaciated surfaces preserve cosmogenic-nuclide inventories from long past ice-free periods as well as the present one. An important potential future contribution will be the application of the large data set of exposure-dated glacier chronologies to better understand global and regional climate dynamics during Lateglacial and Holocene millennial-scale climate changes. However, this contribution cannot be realized without significant progress in two areas: i) understanding and accounting for geologic processes that cause apparent exposure ages on glacial landforms to differ from the true age of the landform, and ii) minimizing systematic uncertainties in exposure ages that stem from cosmogenic-nuclide production-rate estimates and scaling schemes. At present there exists an enormous data set of exposure ages on glacial deposits, but these data cannot be used to their full potential in paleoclimate syntheses due to an inadequate understanding of geologic scatter and production-rate uncertainties. The intent of this paper is to highlight this situation and suggest some strategies for realizing this potential.     

高压下深海碳循环的过程及其对生命活动的影响

目前约25%化石燃料来源的CO2被海洋吸收,缓解了人类活动对气候变化的影响。海洋通过多个概念的碳泵将大气中的CO2输送到深海。深海高压和低温的特点有利于CO2溶解,目前已经储存了相当于大气含量50倍的无机碳,另外,深海沉积物中还储存有大量甲烷水合物。认识深海中的碳循环过程,对于保护海洋固碳能力、开发固碳潜力有重要意义。总结了国内外在海洋碳库、碳输送研究方面的进展,重点讨论了深海C元素转化循环的过程以及高压对生命活动的影响。微生物驱动了深海碳循环,大部分浮游植物所包含的有机碳在沉降过程中被微生物矿化成CO2以及转化为难降解的有机碳,使深海成为巨大的、长周转时间的有机碳库; 高压能提高古菌甲烷厌氧氧化的活性,提升屏蔽海底甲烷释放的能力,同时,高压下氧化甲烷的过程中不仅产生碳酸氢盐,还产生可支持异养生物的乙酸,因此,全球甲烷厌氧氧化的通量可能被低估; 高压下细胞代谢额外产生的氨,可作为氨氧化古菌固定无机碳的潜在能量来源。总之,研究现在以及未来的人类活动对深海碳循环过程的影响以及环境效应,评估应用深海作为地球工程技术平台封存CO2的可能性,都迫切需要加深对碳循环在内的深海元素循环的认识。     

岩石圈中的地压梯度

岩石圈中的地压梯度是一个极为重要的参数 ,直接影响着各种地质作用的解释。与地温梯度一样 ,岩石圈中的地压梯度在空间和时间上也应是复杂多变的。文中通过热压系数建立岩石圈中的地温梯度与地压梯度之间的关系式 ,以此为基础 ,研究受地温梯度的影响岩石圈中的地压梯度的变化规律 ,得到的初步认识是 :岩石圈中的地压梯度是非线性的 ,静岩压力梯度是岩石圈中地压梯度的最小值 ,受地温梯度的影响岩石圈中地压梯度明显增加 ,可达到静岩压力梯度的 2倍以上。     

Calculation of barometric efficiency in shallow piezometers using water levels, atmospheric and earth tide data

The variation in atmospheric pressure at Baldry in New South Wales, Australia (32^°52′ S, 148^°32′ E), has been determined using a 4-year record of hourly measurements. Fourier analysis of this data shows clear diurnal and semi-diurnal variation in atmospheric pressure caused by atmospheric tides. The semi-diurnal component of the tide changes little with the seasons and induces a barometric response in shallow confined piezometers. The piezometer response is shown to be contaminated by an earth-tide component that has to be removed before accurate barometric efficiencies can be calculated. Data from three piezometers installed in a region of fractured and weathered granite are described in this paper. The results show that piezometers installed in shallow bedrock can have barometric efficiencies of close to unity and that only a small quantity or thickness of lower permeability material is sufficient to cause confining conditions. This observation has important implications for the interpretation of recharge processes in shallow aquifers.     

多功能水合物沉积物三轴试验系统的研制与应用

研制了新型多功能水合物沉积物三轴试验系统,系统由供-排气模块、应力加载模块、温控模块、数据采集模块和辅助模块组成。利用泵驱动高压液体施加围压和轴压,加载方式有恒压、恒流、梯度增压、跟踪气压模式,可以实现不同条件下的水合物合成、三轴剪切。围压跟踪气压的功能使水合物生成过程中净围压不变,保证了试样初始条件一致性。根据围压液体积变化测量试样体积变形,通过设置回压泵压力变化方式控制水合物气压,可以模拟不同降压速率条件下的水合物沉积物分解变形。以泥质粉细砂和二氧化碳为材料制作了三轴试样,进行了水合物合成、三轴剪切和降压分解试验,检验了仪器的可靠性。     

Chemical and isotopic examination of produced waters from the BP-Wolf lake in situ combustion pilot

The chemical and isotopic compositions of co-produced waters can be used to monitor the processes that take place during in situ combustion. Anticipated processes include mixing of waters, production of CO₂, production of high concentrations of dissolved sulphate and variations in water chemistry associated with heated zones. Water sources include pore waters in oil-bearing strata, waters in overlying or underlying aquifers, water condensed from previously injected steam, and waters associated with combustion. Waters from all sources may mix during production and interpretation of the combustion process can be refined by an understanding of water sources. Produced fluids from the BP-Wolf Lake pilot site in Alberta have been examined to evaluate the effectiveness of the chemical composition of water and the isotopic compositions of aqueous species for monitoring in situ combustion.Produced waters do not show simple conservative mixing behaviour. This suggests that multiple sources of water and other processes, including water-rock reactions, act to modify water compositions. At least three sources of produced waters can be recognized and these are interpreted to be formation water, injected steam and waters that have low Cl and high HCO₃ due to combustion. It is not possible to distinguish waters in the oil-bearing formation from regional waters present in aquifers that underlie the stimulated intervals. Dissolved aqueous species, such as SiO₂, Na, K (as Na/K) and Cl can be used to monitor the approach of the combustion front. Sulphate has been suggested as an indicator of approaching combustion and, although sulphate concentrations rise as combustion approaches a producing well, this indicator is not reliable in all cases. The use of all the above chemical parameters is recommended for detection of combustion zones during operation.The isotope composition of produced waters confirms that there has been significant water-rock interaction during combustion. Carbon isotope compositions of HCO₃ that range from −8 to −25% δ¹³C show that oil oxidation is a major contributor of CO₂ at high temperatures, but CO₂ produced by carbonate mineral dissolution becomes more significant as temperature decreases. Sulphate concentrations in waters produced during combustion can be an order of magnitude higher than those observed during steam stimulation. Both the oil (bitumen) and pyrite (FeS₂) are significant sulphur sources. Typically, the sulphur in both phases is in a reduced state and is available through oxidation associated with combustion. The δ³⁴S of dissolved sulphate in produced waters does not unequivocally identify either of the two major sources of sulphur. However, the relatively depleted δ³⁴ values for SO₄ suggest that the high sulphate concentrations generally associated with the approach of the combustion front result from the oxidation of pyrite.     

Oxidation and Mineralization of Mn2+ Ions Mediated by Pseudomonas putida: Insights from an Experimental Study

The formation of manganese oxides in nature is commonly mediated by microorganisms.In this study,the mineralization of biogenic manganese oxidation mediated by Pseudomanas putida has been experimentally investigated by employing various characterization techniques,including SEM,FESEM,TEM,XRD,and STXM-NEXAFS.The results indicate that Mn~(2+) ions can be oxidized into Mn(Ⅳ) minerals(birnessite and pyrolusite) and Mn(Ⅲ) minerals(hausmannite and feitknechtite),successively.The primary products(birnessite and pyrolusite) further transformed into hausmannite and feitknechtite under Mn~(2+) ion-enriched conditions.However,birnessite and pyrolusite are the endproducts of the continuous microbial oxidation processes.These biogenic Mn oxides are poorly crystallized,which provides them with a high potential for usage in environmental restoration of contaminated soils and waters contaminated with heavy metals.The approaches employed in this study will also enrich genesis research of biological oxidation of Mn(Ⅱ) species in nature.     

强降雨条件下具有张裂缝边坡临界滑动场

降雨持时较长且雨强较大时,雨水的入渗不仅会增大孔隙水压力,且易使张裂缝充水形成静水压力,对边坡稳定不利。结合降雨条件下饱和-非饱和渗流分析,考虑降雨过程中的瞬态孔隙水压力场与瞬态强度场,并同时考虑张裂缝充水时的静水压力,对边坡临界滑动场法进行改进,提出降雨条件下具有张裂缝边坡临界滑动场数值模拟方法,且对其进行了验证。将该方法用于一个典型均质黏土边坡算例,结果表明,（1）文中方法可考虑张裂缝具体位置、深度及其充水状态下对边坡稳定性的影响,并能搜索出任意形状危险滑面,计算结果合理可靠;（2）降雨条件下张裂缝中静水压力对边坡稳定性及滑面形状有较大影响;（3）降雨条件下张裂缝位置对边坡稳定有较大影响,距坡肩越近,张裂缝对边坡稳定性影响越大;（4）张裂缝处在最不利位置且充水时存在一个最不利深度。     

Significance of sedimentological studies to man's use of transitory coastal areas

A beach-ridge complex is a migrating sediment body constructed and kept in motion by high-energy processes, and the same processes that construct these features will, in time, partially or completely destroy them. The beach-ridge complex along the shore of southwestern Lake Michigan serves as an example. This body of sediment, approximately 17 by 3 km has undergone considerable change in the last 3,000 years, moving about 13 km along the shore as a result of forces generated by the Lake Michigan system — erosion at the northern end, deposition of the displaced sediment at the southern end of the complex. Sedimentological analysis of the beach-ridge complex demonstrates that each major modern environment can be characterized by a unique range in grain sizes, which make it possible to determine the environment in which the subsurface sediments were deposited. Lateral and thickness distribution of textural types can then be predicted. Erosion has been an important natural geologic process in the development of the beach-ridge complex, but it has become a problem only since man has occupied the nearshore areas. It will continue to be a problem, particularly at times of high lake level. Man's attempts to protect these areas by trying to alter the natural processes frequently have upset the delicate natural balance, unintentionally accelerating destruction in other areas. Beach replenishment is one method that would adapt well to this coast because there is an adequate supply of sand in the subsurface of the beach ridge complex whose grain size matches that of the modern beach sand.     

Taphonomy and site formation on California's Channel Islands

Inhabited by humans for over 12,000 calendar years, California's Channel Islands contain thousands of archaeological sites, ranging from dense shell middens and villages to small lithic scatters and camps. Similar to many islands around the world, the Channel Islands have a dearth of burrowing animals and limited historical development leading to generally good preservation of archaeological constituents and relatively high stratigraphic integrity. Despite these favorable preservation conditions, numerous natural and cultural processes have impacted the island's archaeological record. Channel Islands archaeologists, however, have given relatively limited attention to the effects of taphonomic and formation processes. The authors provide an overview of taphonomic and formation processes affecting Channel Islands archaeology, illustrating the importance of regional taphonomic syntheses in the management, preservation, and interpretation of archaeological sites. These data also demonstrate the significance of detailing formation processes in islands and other areas where burrowing rodents and other disturbances are thought to be absent or limited. © 2006 Wiley Periodicals, Inc.     

Origin and significance of 13-hydroxychlorophyll derivatives in sediments

The authenticity of hydroxychlorophyll derivatives in sediments has been verified by subjecting pure chlorophyll preparations to the extraction method used for sediments. Model studies of chlorophyll autoxidation reveal hydroxychlorophyll as the major product formed in the presence of hydrogen peroxide. Its stability to further oxidation implies that hydroxychlorophyll derivatives are not precursors of aetioporphyrins and are more likely to produce cycloalkanoporphyrins via the processes of diagenesis. The occurrence of 13²-hydroxyphaeophytin a throughout a sediment core from Loch Ness confirms it to be a widespread chlorophyll oxidation product formed during early diagenesis. Profiles of hydroxychlorophyll derivatives in a sediment core from an Antarctic lake demonstrate their potential for use as markers of oxidation processes in palaeoenvironmental assessment.     

高渗压小水力梯度岩石渗透性测试

对低渗透岩石的渗透性测试一般采用瞬时压力脉冲法,但该方法不能真实模拟野外高孔隙水压力、小水力梯度的现场实际条件,而且试验存在较大误差。为此开发研制了一套新型高压渗透仪,在渗透出水端安装了管路过滤器、调速阀两种器械元件,可手动任意调控流量大小,而流量大小采用精确测量渗出水体积变化量表示。试验只要保证进水端水压不变,当调控的水流量与试样的渗流量达到平衡时,则会在出水端形成一个稳定的水压值。该套试验设备不但可对圆柱体试样进行渗透性、力学特性测试,而且还可以对方柱体试样进行渗透性测试,实现了对岩石实际所处应力、高孔隙水压力环境的真实模拟。实测检验理论技术可行,达到了满意的试验效果。     

Subsurface Airflow Induced by Natural Forcings

Subsurface airflow can be induced by natural processes,such as atmospheric or barometric pressure changes, water table fluctuations,topographic effects,and rainfall infiltration．Barometric pressure fluctuations are the most common cause of subsurface airflow,which can be significant under favourable geological conditions．This process has been studied most extensively because of its application to passive soil vapor extraction．Soil airflow induced by water table fluctuations can be significant,particularly where the fluctuations are of high frequency,for example,in tidal-influenced coastal areas．Top-ographic effects can lead to strong subsoil airflow in areas with great elevation differences．Rainfall infiltration usually produces only weak airflow.Air flow induced by these natural processes has important environmental and engineering implications．Among the different processes,airflow induced by tidal fluctuations has been studied the least,although it has exciting applications to coastal engineering projects and environmental remediation．     

岩溶塌陷机理研究进展

岩溶塌陷机理是开展岩溶塌陷监测、预警、防控及治理工作的基础。长期以来,岩溶塌陷机理研究都是以事后调查的定性推测为主,缺乏必要的科学观测数据支持,导致目前的岩溶塌陷机理仍然处于假设阶段,并成为岩溶塌陷灾害监测预警与防治方面的理论瓶颈问题。文章总结了近年来国内外岩溶塌陷机理的最新研究进展,提出目前的岩溶塌陷机理都可以归结为土岩体的渗透变形,但其临界或破坏指标还需进一步探讨,此外指出随着高频采样的水压力、 加速度计及声波等传感器的实用化,塌陷机理研究将面临着从静水压力到动水压力方面的挑战,并且压力脉动造成的气蚀破坏、共振破坏也将是下步探究的重点。     

考虑孔压积累-消散耦合的等效有限元方法

交通荷载往复作用下饱和软土路基会发生显著的工后沉降,并引起不均匀沉降。采用基于室内循环三轴或空心圆柱扭转试验建立的经验显式模型与等效有限元相结合方式,在预测路基长期沉降方面取得了较好的效果。然而,其采用的瞬时积累、逐步消散的孔压模型与实际工程中孔压积累与消散同时进行有着明显的差异。忽略这种差异将会使得计算结果低于实际值。采用能反映自然排水条件下震动孔压长消规律的解析公式,对以上的不足作出改进,并用改进的孔压模型计算了上海浦东国际机场第一跑道的长期运营沉降。分析表明,与瞬时积累、逐步消散的孔压模型相比,考虑孔压积累与消散耦合效应的孔压模型,计算结果更接近实测资料。     

Origin of Basalt Magmas: An Experimental Study of Natural and Synthetic Rock Systems

Natural basalts and eclogites were investigated experimentallyat a series of temperatures in the pressure range 1 atm to 40kb and with water pressures 1 to 10 kb. Some runs were alsomade on related synthetic systems at 10 and 33 kb. The two principal magma types recognized by field investigators—tholeiiteand alkali basalt types-appear to be separated by equilibriumthermal divides at 1 atm. The principal divides were found byexperiment at elevated pressures to give way to a new set ofequilibrium thermal divides resulting from a new mineralogy.The change of the equilibrium thermal divides with pressureleads to the derivation of the two principal magma trends fromthe same bulk composition. The melting behavior of basalts and eclogites indicates thatboth are the partial melting products of a more primitive rock(e.g. garnet peridotite). In the region of magma generation(below 60 km) the parental material, presumed to be garnet peridotite,yields an eclogitic magma and its fractionation depends on thegarnet and omphacite of the eclogite, not on plagioclase andclinopyroxene of a basaltic magma. Increase of the garnet constituentsin the magma at high pressure by effective removal of omphaciteor shift of the garnet-omphacite boundary ‘surface’will give rise to a tholeiite-type magma at low pressure. Similarly,increase of the omphacite constituents in the magma at highpressure by physical or physicochemical means will give riseto an alkali basalt-type magma at low pressure. In general,alkali basalt-type magmas are to be expected to be generatedat greater depths than tholeiite-type magmas from the same primarysource rock. Establishment of the two major basalt series takes place inthe region of generation; additional minor diversification ofeach series may come about after emplacement in or on the crustby crystal settling, oxidation or reduction, gas fluxing, contamination,and other processes. The derivative magmas are greatly restrictedby the course of liquid thermal descent imposed at generation. Pressure-temperature limits established experimentally suggestthat the basalt-eclogite transformation may be responsible forthe Mohorovii discontinuity under the continents, but not underthe oceans. The field of stability of basalt is drastically reduced in thepresence of water, and amphibolite is produced. The meltingof amphibolite takes place over a much greater range of temperaturethan basalt. At 10 kb water pressure the beginning of meltingof amphibolite closely approaches that of granite. Partial meltingof amphibolite may yield anorthositic liquids having a relativelylow anorthite content at exceptionally low temperatures. Eclogiteitself is not stable in the presence of water and gives placeto amphibolite or pyroxene hornblendite. Magmas which crystallizeto basalt, gabbro, or eclogite must have had a low water-contentat the time of crystallization. Fifteen rock and twenty-three mineral analyses as well as numerouspartial chemical analyses of experimental products were madeby J. H. Scoon in the course of the investigation. These chemicalanalyses bear on many mineralogical and petrological problems.     

An analytical assessment on the impact of covers on the onset of air convection in mine wastes

If a mine waste pile is left open, an active chemical reaction of oxidation is often found due to the commonly high content of pyritic materials. The oxidation of pyrites is an exothermic process and the released heat will promote the flow of fresh oxygen from the surrounding atmosphere into the waste dump. As a result, oxidation reaction will accelerate and temperature within the dump can increase to as high as 60°C above the ambient temperature. The oxidation process also releases sulphuric acid and hydrogen ions into ground water to cause water contamination. Low‐permeability covers such as clay liners have been recently proposed to abate the oxidation process in mine wastes. The effectiveness of using low‐permeability materials to cover mine wastes in order to suppress the pyrite oxidation is examined. By conducting the theoretical analysis of the onset of convective air flow within waste rocks, the conditions under which soil gas flow is significant are identified. By comparing the results with previous field measurements and theoretical analysis for the uncovered conditions, it is shown that low‐permeability covers can effectively suppress soil gas flow and slow down the pyrite oxidation process in mine wastes. Copyright © 2001 John Wiley & Sons, Ltd.     

Calculated phase equilibria for a morb composition in a P–T range, 450–650 °C and 18–28 kbar: the stability of eclogite

Lower temperature eclogite (with T = 600 °C) represents a significant part of the occurrences of eclogite in orogenic belts. ‘True’ eclogite, with, for example, garnet + omphacite >70%, is well represented in such an occurrence. Calculated phase equilibria in Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO), for just one rock composition – that of a representative mid‐ocean ridge basalt, morb – are used to see under what circumstances ‘true’ eclogite is predicted to occur. The variables considered are not only pressure (P) and temperature (T) but also water content and oxidation state. The latter two variables are known to exert a significant control on mineral assemblage but are difficult to establish retrospectively from the observed rocks themselves. It is found that whereas oxidation state does have a strong effect on mineral assemblage, the key control on developing ‘true’ eclogite is shown to be temperature and water content. If temperature is established to be <600 °C, water content has to be low (less or much less than that for H₂O saturation) in order for ‘true’ eclogite to form. Moreover, unless pressure is at the high end in the range considered, lawsonite eclogite and ‘true’ eclogite will tend to be mutually exclusive, with the former requiring high water content at the lower temperature where it occurs, but the latter requiring low water content.