A numerical study of mechanical behavior of a cement paste under mechanical loading and chemical leaching

Based on relevant experimental data of a petroleum cement paste under mechanical loading and chemical leaching, an elastic‐plastic model is first proposed by taking into account plastic shearing and pore collapse. The degradation of mechanical properties induced by the chemical leaching is characterized by a chemical damage variable which is defined as the increase of porosity. Both elastic and plastic properties of the cement paste are affected by the chemical damage. The proposed model is calibrated from and applied to describe mechanical responses in triaxial compression tests respectively on sound and fully leached samples. In the second part, a phenomenological chemical model is defined to establish the relationship between porosity change and calcium dissolution process. The dissolution kinetics is governed by a diffusion law taking into account the variation of diffusion coefficient with calcium concentration. The chemical model is coupled with the mechanical model, and both are applied to describe mechanical response of cement paste samples subjected to progressive chemical leaching and compressive stresses. Comparisons between experimental data and numerical results are presented.     

Using monazite and zircon petrochronology to constrain the P–T–t evolution of the middle crust in the Bhutan Himalaya

The growth and dissolution behaviour of accessory phases (and especially those of geochronological interest) in metamorphosed pelites depends on, among others, the bulk composition, the prograde metamorphic evolution and the cooling path. Monazite and zircon are arguably the most commonly used geochronometers for dating felsic metamorphic rocks, yet crystal growth mechanisms as a function of rock composition, pressure and temperature are still incompletely understood. Ages of different growth zones in zircon and monazite in a garnet‐bearing anatectic metapelite from the Greater Himalayan Sequence in NW Bhutan were investigated via a combination of thermodynamic modelling, microtextural data and interpretation of trace‐element chemical ‘fingerprint’ indicators in order to link them to the metamorphic stage at which they crystallized. Differences in the trace‐element composition (HREE, Y, Eu_N/Eu*_N) of different phases were used to track the growth/dissolution of major (e.g. plagioclase, garnet) and accessory phases (e.g. monazite, zircon, xenotime, allanite). Taken together, these data constrain multiple pressure–temperature–time (P–T–t) points from low temperature (<550 °C) to upper amphibolite facies (partial melting, >700 °C) conditions. The results suggest that the metapelite experienced a cryptic early metamorphic stage at c. 38 Ma at <550 °C, ≥0.85 GPa during which plagioclase was probably absent. This was followed by a prolonged high‐T, medium‐pressure (~600 °C, 0.55 GPa) evolution at 35–29 Ma during which the garnet grew, and subsequent partial melting at >690 °C and >18 Ma. Our data confirm that both geochronometers can crystallize independently at different times along the same P–T path and that neither monazite nor zircon necessarily provides timing constraints on ‘peak’ metamorphism. Therefore, collecting monazite and zircon ages as well as major and trace‐element data from major and accessory phases in the same sample is essential for reconstructing the most coherent metamorphic P–T–t evolution and thus for robustly constraining the rates and timescales of metamorphic cycles.     

Dissolved organic matter in surface runoff in the Loess Plateau of China: The role of rainfall events and land-use

Exploring the chemical characterization of dissolved organic matter (DOM) is important for understanding the fate of laterally transported organic matter in watersheds. We hypothesized that differences in water-extractable organic matter (WEOM) in soils of varying land uses and rainfall events may significantly affect the quality and the quantity of stream DOM. To test our hypotheses, characteristics of rainfall-runoff DOM and WEOM of source materials (topsoil from different land uses and gullies, as well as typical vegetation) were investigated at two adjacent catchments in the Loess Plateau of China, using ultraviolet–visible absorbance and excitation emission matrix fluorescence with parallel factor analysis (PARAFAC). Results indicated that land-use types may significantly affect the chemical composition of soil WEOM, including its aromaticity, molecular weight, and degree of humification. The PARAFAC analysis demonstrated that the soils and stream water were dominated by terrestrial/allochthonous humic-like substances and microbial transformable humic-like fluorophores. Shifts in the fluorescence properties of stream DOM suggested a pronounced change in the relative proportion of allochthonous versus autochthonous material under different rainfall patterns and land uses. For example, high proportions of forestland could provide more allochthonous DOM input. This study highlights the relevance of soils and hydrological dynamics on the composition and fluxes of DOM issuing from watersheds. The composition of DOM in soils was influenced by land-use type. Precipitation patterns influenced the proportion of terrestrial versus microbial origins of DOM in surface runoff. Contributions of allochthonous, terrestrially derived DOM inputs were highest from forested landscapes.     

兴蒙造山带—华北克拉通地球化学走廊带沉积物主成分的含量与空间分布研究

选取兴蒙造山带—华北克拉通地球化学走廊带上沉积物的SiO_2、Al_2O_3、CaO、MgO、Na_2O、K_2O、TFe_2O_3、FeO、TiO_2、MnO、P_2O_5、CO_2、H_2O~+、pH十四个指标,研究其在不同二级构造单元、地理景观、土壤类型、降雨量等级下的含量与空间分布特征,并讨论该地球化学走廊带上化学蚀变指数。结果表明:在兴蒙造山带—华北克拉通地球化学走廊带上,作为沉积物主体的SiO_2、Al_2O_3两者含量为明显负相关而空间分布表现出此消彼长的特征;CaO、MgO、CO_2高含量分布区则与碳酸盐岩地层或含碳酸盐矿物的土壤有关,而MgO的高含量还与走廊带上镁铁质基性-超基性岩有一定关系,表明了这三个指标的高含量受特定岩性或矿物的影响较大;Na_2O、K_2O含量除了受继承的基岩影响外,还受到后期的风化作用和气候及自身地球化学性质等复杂因素综合影响,对Na_2O来说尤为如此;TFe_2O_3、MnO、TiO_2、P_2O_5相对于在地质背景复杂地段,经过冲积平原的沉积物混匀后,含量差异更小;相对干冷的内蒙古半干旱草原的气候条件有利于FeO存在,使得其相对燕山地区含量差异较TFe_2O_3要小,在章丘以南相对温暖湿润地区更易被氧化而导致其含量整体较低;北方干冷气候条件下,沉积物H_2O~+含量普遍较低,局部高含量位于碳酸盐岩地层或第四系分布区;走廊带上的pH值反映了沉积物偏碱性的特征,而在章丘以南的地区随着降雨量的增加,相对温暖湿润的气候条件,沉积物pH值表现为中性-偏弱酸性;兴蒙造山带—华北克拉通地球化学走廊带沉积物的CIA值反映出在寒冷、干燥气候条件下低等的化学风化程度,兴蒙造山带沉积物平均风化程度相对华北克拉通沉积物的平均风化程度差异变化相对要小,显示兴蒙造山带的降雨量与温度等风化影响因素变化较小。作为反映元素的地球化学亲和性的量化指标,离子电位可以更好地帮助理解沉积物元素的含量和空间分布差异。     

新疆博格达山北麓白杨河剖面页岩地球化学特征及其地质意义

通过博格达山北麓白杨河剖面芦草沟组页岩的地球化学特征的综合研究,讨论了芦草沟组页岩的元素富集特征和沉积环境以及源区物源特征和构造背景。结果表明:1研究区页岩P元素极为富集,这受控于页岩中凝灰质火山灰夹层的广泛发育;2对比于世界页岩微量元素分布,白杨河页岩相对富集Li、B、Pr、Tb、Dy、Ho、Er、Tm和Lu元素,其他元素相对亏损;3白杨河剖面页岩地化参数揭示芦草沟组自下而上气候由温湿向干热转变,进而引起水体由淡水向咸水的转变和还原程度的进一步加强;4物源区遭受低级-中等风化程度,物源类型主要为长英质火成岩,其次为铁镁质火成岩;5物源区大地构造背景以大陆岛弧-活动大陆边缘构造背景为主。     

云南磷铝石谱学特征研究

使用电子探针、X射线粉晶衍射仪、傅里叶变换红外光谱仪、激光拉曼光谱仪、紫外可见分光光度计等仪器,对最近在云南发现的一种达到宝石级别的磷铝石进行了化学成分、矿物组成、红外吸收光谱、拉曼光谱、紫外可见吸收光谱等方面的研究。化学成分分析结果表明,该磷铝石的主要化学成分为P和Al,并含有少量的Fe和V;X射线粉晶衍射结果显示,该磷铝石的矿物成分主要为磷铝石,杂质较少;红外光谱与拉曼光谱分析均检出磷酸根基团的特征峰,红外光谱分析还显示有结晶水与结构水的存在;紫外可见吸收光谱在300和420 nm附近的吸收归属于Fe3+,630 nm附近较宽缓的吸收带由Fe3+和V3+共同产生。并将磷铝石与绿松石进行了谱学方面的对比分析,以便更好地区分两者。     

缅甸与莫桑比克红宝石的元素含量及紫外可见光谱学特征对比研究

采用镜下观察、激光剥蚀电感耦合等离子体质谱、紫外-可见吸收光谱等观察测试方法,对缅甸和莫桑比克红宝石的常规宝石学、包裹体、化学元素含量及紫外光谱特征进行了系统的对比研究。结果表明,缅甸红宝石在紫外荧光灯下呈现较强的红色荧光,内部含有互为60°夹角定向排列的短针状金红石、"糖浆状"构造等特征包裹体,具有低Fe、高V、高Ga的微量元素特征,紫外区吸收截止边小于320 nm,且694 nm处的荧光较强。莫桑比克红宝石在紫外荧光灯下荧光较弱,内部可见双晶面、无序排列的金红石和角闪石晶体等特征包裹体,具有高Fe、低V、低Ga的微量元素特征,紫外区吸收截止边在350 nm附近。上述性质可用作区分缅甸和莫桑比克红宝石的标志性识别特征。     

Geochemical constraints on the distribution of trace elements and volatiles in fluorapatite from the Panasqueira tin-tungsten deposit (Portugal)

A large, euhedral crystal of fluorapatite (ca. 19.5 × 20.0 mm) from the Panasqueira tin-tungsten deposit (Portugal) was investigated in terms of the distribution of trace elements by using several microanalytical techniques. The studied material represents almost pure fluorapatite with minor amounts of other cations (mainly Sr, Mn, REE and Fe), OH and Cl. Particular interest was given to the distribution of rare earth elements with respect to the crystallographic orientation. A broad range of analytical techniques were used, including optical microscopy coupled with cathodoluminescence imaging, electron probe microanalysis (EPMA), laser ablation – inductively coupled plasma mass spectrometry (LA-ICPMS), Raman microspectroscopy, and simultaneous thermal analysis coupled with mass spectrometry. The investigated crystal consists of the main crystal with a distinct core and rim (Ap_2core and Ap_2rim, respectively), which grew on a previous, euhedral crystal (Ap₁). The fluorapatite demonstrates various types of zoning: regular oscillatory, irregular, and internal sectoring, which is also reflected in trace elements concentrations. The rim Ap_2rim has lower concentrations of Mn, Sr and Fe, and significantly higher concentrations of REE compared to the core Ap_2core and older crystal Ap₁. Furthermore, the rim Ap_2rim is strongly depleted in Th, U and Pb. The entire crystal shows elevated Eu contents, expressed as a strong positive anomaly in chondrite-normalized REE patterns. With regards to the volatiles, F concentrations are constant in Ap₁, Ap_2core and Ap_2rim, whereas Cl is below the EPMA detection limit. The Ap_2rim was the only part of the investigated material containing OH and CO₃, which were observed in the Raman spectra. Furthermore, part of the crystal Ap_2core is extensively altered, likely due to fluid-induced metasomatic processes. LA-ICPMS U-Pb dating yielded highly discordant dates due to common Pb content. A lower intercept age of 297 ± 13 Ma (MSWD = 0.13) indicates the age of the fluorapatite crystallization. The overall analytical data constrain growth and post-growth processes, including crystallization of Ap₁ and Ap_2core, which both have typical hydrothermal Sn-W deposit characteristics, whereas Ap_2rim is related to a carbonate stage of the mineralization in the Panasqueira deposit.     

Comparative Study of Acid and Alkaline Stimulants with Granite in an Enhanced Geothermal System

The Enhanced Geothermal System (EGS) is an artificial geothermal system that aims to economically extract heat from hot dry rock (HDR) through the creation of an artificial geothermal reservoir. Chemical stimulation is thought to be an effective method to create fracture networks and open existing fractures in hot dry rocks by injecting chemical agents into the reservoir to dissolve the minerals. Granite is a common type of hot dry rock. In this paper, a series of chemical stimulation experiments were implemented using acid and alkaline agents under high temperature and pressure conditions that mimic the environment of formation. Granite rock samples used in the experiments are collected from the potential EGS reservoir in the Matouying area, Hebei, China. Laboratory experimental results show that the corrosion ratio per unit area of rock is 3.2% in static acid chemical experiments and 0.51% in static alkaline chemical experiments. The permeability of the core is increased by 1.62 times in dynamic acid chemical experiments and 2.45 times in dynamic alkaline chemical experiments. A scanning electron microscope analysis of the core illustrates that secondary minerals, such as chlorite, spherical silica, and montmorillonite, were formed, due to acid-rock interaction with plagioclase being precipitated by alkaline-rock interactions. Masking agents in alkaline chemical agents can slightly reduce the degree of plagioclase formation. A chemical simulation model was built using TOUGHREACT, the mineral dissolution and associated ion concentration variation being reproduced by this reactive transport model.