DEM simulations of methane hydrate exploitation by thermal recovery and depressurization methods

Methane hydrate (MH, also called fiery ice) exists in forms of pore filling, cementing and load-bearing skeleton in the methane hydrate bearing sediment (MHBS) and affects its mechanical behavior greatly. To study the changes of macro-scale and micro-scale mechanical behaviors of MHBS during exploitation by thermal recovery and depressurization methods, a novel 2D thermo-hydro-mechanical bonded contact model was proposed and implemented into a platform of distinct element method (DEM), PFC2D. MHBS samples were first biaxially compressed to different deviator stress levels to model different in-situ stress conditions. With the deviator stress maintained at constant, the temperature was then raised to simulate the thermal recovery process or the pore water pressure (i.e. confining pressure for MH bond) was decreased to simulate the depressurization process. DEM simulation results showed that: during exploitation, the axial strain increased with the increase of temperature (in the thermal recovery method) or decrease of pore water pressure (in the depressurization method); sample collapsed during MH dissociation if the deviator stress applied was larger than the compression strength of a pure host sand sample; sample experienced volume contraction but its void ratio was slightly larger than the pure host sand sample at the same axial strain throughout the test. By comparison with the laboratory test results, the new model was validated to be capable of reproducing the exploitation process by thermal recovery and depressurization methods. In addition, some micro-scale parameters, such as contact distribution, bond distribution, and averaged pure rotation rate, were also analyzed to investigate their relationships with the macroscopic responses.     

Iodine budget in surface waters from Atacama: Natural and anthropogenic iodine sources revealed by halogen geochemistry and iodine-129 isotopes

Iodine enrichment in the Atacama Desert of northern Chile is widespread and varies significantly between reservoirs, including nitrate-rich “caliche” soils, supergene Cu deposits and marine sedimentary rocks. Recent studies have suggested that groundwater has played a key role in the remobilization, transport and deposition of iodine in Atacama over scales of millions-of-years. However, and considering that natural waters are also anomalously enriched in iodine in the region, the relative source contributions of iodine in the waters and its extent of mixing remain unconstrained. In this study we provide new halogen data and isotopic ratios of iodine (¹²⁹I/I) in shallow seawater, rivers, salt lakes, cold and thermal spring water, rainwater and groundwater that help to constrain the relative influence of meteoric, marine and crustal sources in the Atacama waters. Iodine concentrations in surface and ground waters range between 0.35 μM and 26 μM in the Tarapacá region and between 0.25 μM and 48 μM in the Antofagasta region, and show strong enrichment when compared with seawater concentrations (I = ∼0.4 μM). In contrast, no bromine enrichment is detected (1.3–45.7 μM for Tarapacá and 1.7–87.4 μM for Antofagasta) relative to seawater (Br = ∼600 μM). These data, coupled to the high I/Cl and low Br/Cl ratios are indicative of an organic-rich sedimentary source (related with an “initial” fluid) that interacted with meteoric water to produce a mixed fluid, and preclude an exclusively seawater origin for iodine in Atacama natural waters. Iodine isotopic ratios (¹²⁹I/I) are consistent with halogen chemistry and confirm that most of the iodine present in natural waters derives from a deep initial fluid source (i.e., groundwater which has interacted with Jurassic marine basement), with variable influence of at least one atmospheric or meteoric source. Samples with the lowest isotopic ratios (¹²⁹I/I from ∼215 to ∼1000 × 10⁻¹⁵) strongly suggest mixing between the groundwater and iodine storage in organic-rich rocks (with variable influence of volcanic fluids) and pre-anthropogenic meteoric water, while samples with higher values (∼2000–93,700 × 10⁻¹⁵) indicate the input of anthropogenic meteoric fluid. Taking into account the geological, hydrologic and climatic features of the Atacama region, we propose that the mean contribution of anthropogenic ¹²⁹I is associated with ¹²⁹I releases during nuclear weapon tests carried out in the central Pacific Ocean until the mid 1990's (¹²⁹I/I = ∼12,000 × 10⁻¹⁵). This source reflects rapid redistribution of this radioisotope on a global scale. Our results support the notion of a long-lived continental iodine cycle in the hyperarid margin of western South America, which is driven by local hydrological and climate conditions, and confirm that groundwater was a key agent for iodine remobilization and formation of the extensive iodine-rich soils of Atacama.     

Geochemistry of Paraná-Etendeka basalts from Misiones,Argentina: Some new insights into the petrogenesis of high-Ti continental flood basalts

The Early Cretaceous (∼135–131 Ma) Paraná-Etendeka continental flood basalts, preserved in bulk in the Paraná basin of southern Brazil and vicinity, have been divided into low-Ti and high-Ti types that govern the southern and northern halves of the basin, respectively. We have examined a new sample set from the southern margin of the northern high-Ti segment of Paraná basalts in Misiones, northeastern Argentina. These basalts are strongly to moderately enriched in TiO₂ (2–4 wt.%), have relatively high Ti/Y (300–500), low MgO (3.5–6.5 wt.%), and high Fe (FeO(tot) 12–14 wt.%) and belong to the Pitanga and Paranapanema magma types of Peate et al. (1992). Nd and Sr isotope compositions are quite unvarying with ε_Nd (at 133 Ma) values of −4.6 to −3.6 and initial ⁸⁷Sr/⁸⁶Sr of 0.7054–0.7059 and show no variation with fractionation. Compared to high-Ti lavas in the central and northern parts of the Paraná high-Ti basalt segment, the lavas from Misiones are similar to those in the northeastern magin of the basin but less radiogenic in initial Nd isotope composition than those in the central part. This variation probably reflects mixed EM1-EM2 source components in the sublithospheric mantle. A polybaric melt model of a sublithospheric mantle source at the garnet lherzolite-spinel lherzolite transition is compatible with the observed Ti budget of the Pitanga and Paranapanema lavas, regardless of the Nd isotope composition of their purported source.     

Geochemistry of rare-earth elements in shallow groundwater,northeastern Guangdong Province,China

Shallow groundwater and hot springs were collected from northeastern Guangdong Province, Southeast China, to determine the concentrations and fractionation patterns of rare-earth elements(REE). The results show that the La, Ce and Nd of REEs are abundant in groundwater and rock samples, and the ∑REE contents in groundwater and rock samples range from 126.5 to 2875.3 ng/L, and 79.44 to 385.85 mg/L, respectively. The shallow groundwater has slightly HREE-enriched PAAS-normalized patterns. However, the granitic rocks PAAS-normalized patterns, with remarkable negative Eu anomalies, are different from that of shallow groundwater. The enrichment of HREE is considered to be controlled by REE complexation and readsorption for most groundwater has Ce and Eu positive anomalies. The Ce and Eu anomalies in groundwater are controlled by redox conditions. Moreover, the Fe-contain sediments dissolution and/or the reduction of Fe oxyhydroxides are another factor contributing to Ce anomalies. The Eu anomalies in groundwater are controlled by the preferential mobilization of Eu2+ during water-rock interaction compared to Eu3+.     

太平洋富钴结壳中碲元素的地球化学特征及其富集机制探讨

文章通过对采自太平洋海域不同海山上68个结壳样品中Te元素地球化学特征的研究,探讨了富钴结壳中控制Te元素富集的古海洋氧化还原环境及其富集机制。分析表明,太平洋海域中大多数结壳的w（Te）变化于13.4×10^-6~115.8×10^-6,平均50×10^-6,是海水w（Te）的10⁹倍;结壳中w（Te）与Mn/Fe比值呈正相关,相关系数为0.51;与Fe呈负相关,相关系数为-0.61,显示结壳中Te与Co有类似的地球化学特征。古海水氧化还原环境的改变是控制结壳中Te元素含量变化的重要因素;能反映古海水氧化还原环境的Ce异常与结壳中Te含量基本呈同步变化趋势,Te含量具有随古海水氧化程度减弱而降低的特征。结壳中Te元素的富集主要受控于其内的Mn/Fe比值。Te元素的富集机制除被海水中带微弱正电荷的FeOOH胶体以库伦静电吸附外,还可能与δ-MnO₂表面上以一种表面络合物方式的富集机制有关。Te进入结壳的存在形式及其在不同古海洋环境中的富集机制还有待进一步研究和探讨。     

南天山拜城县波孜果尔A型花岗岩类锆石U-Pb定年及其Lu-Hf同位素组成

新疆拜城县波孜果尔A型花岗岩类岩体位于塔里木地台北缘及邻区的近东西向碱性侵入岩带上,主要岩石类型为霓石钠闪石英碱长正长岩、霓石钠闪碱长花岗岩、黑云母碱长正长岩。全岩SiO₂=68.97%~74.14%,Na₂O+K₂O=9.67%~11.19%,Al₂O₃=13.72%~15.26%,Fe₂O₃=0.18%~1.41%,FeO=0.91%~1.51%,CaO=0.35%~0.63%。稀土元素总量较高,ΣREE=298×10^-6~1286×10^-6,平均706×10^-6,轻稀土富集,重稀土亏损,强烈的Eu负异常,呈“右倾海鸥型”的稀土元素配分模式。富Nb、Ta、Zr、Hf等高场强元素,亏损Ba、K、Sr等大离子亲石元素,Zr+Nb+Ce+Y=936×10^-6~3684×10^-6,平均1813×10^-6。为A1型花岗岩。岩体形成于早二叠纪。锆石LA-ICP-MS U-Pb年龄为287.7~291.6Ma,平均289.8Ma,岩体形成后,在279.1~282Ma左右经历了后期热液流体的改造。锆石ε_Hf（t）值为-6.3~9.0,两阶段模式年龄（t_DM2）跨越古元古代晚期-新元古代中期,主要集中在中元古代。岩浆平均温度832~839℃,形成于非造山的板内构造环境,且具高温、无水、低氧逸度的成岩特点。该岩体具有壳幔混源的特点。     

长江三峡地区成冰纪-埃迪卡拉纪转换时期微量元素和稀土元素地球化学特征

通过微量元素和稀土元素地球化学分析,对长江三峡地区陡山沱组层型剖面--田家园子剖面成冰系南沱组顶部和埃迪卡拉系陡山沱组下部102个岩石样品进行了地球化学研究。重点分析了氧化还原敏感元素(Zn,Co,U,Mo,Ni,V)的富集特征,并探讨其可能成因机制以及三峡地区成冰纪-埃迪卡拉纪转换时期的水体特征。结果表明:在南沱组顶部仅Zn和Co富集;在盖帽白云岩下部,氧化还原敏感元素均富集,而在盖帽白云岩上部,除Zn和V外,其他氧化还原敏感元素均亏损;在陡山沱组Ⅱ段下部,氧化还原敏感元素由最初的亏损,逐渐变为较稳定的富集。在陡山沱组下部,出现2次明显的富集峰值,分别出现在剖面的0.4m处(盖帽白云岩中间)和6.5m处(陡山沱组Ⅱ段下部)。整个剖面大部分样品具有Eu的轻微正异常(Eu/Eu^*＜1.6), 而在剖面0.4m和6.5m处,Eu具有明显的正异常,结合稀土配分类型、Y/Ho值、La异常、Ce异常等指标,推测这2次异常均可能受到深海热液流的影响,而缺氧海水的上涌造成水体缺氧,导致这些元素出现富集峰值。U/Th、V/(V+Ni)以及稀土元素指标综合指示,三峡地区南沱组顶部冰碛岩应为氧化环境下的沉积物;随着冰川消融,冰融淡水注入古海洋,陡山沱组盖帽碳酸盐的沉积受冰融淡水的影响,深部缺氧海水的上涌使沉积水体经历氧化-缺氧-氧化的转变,海水的分层性较强;而陡山沱组Ⅱ段下部沉积环境以分层性较弱的弱氧化环境为主。     

西藏盐湖地区闪长玢岩锆石LA-ICP-MSU-Pb年龄及岩石成因

西藏盐湖地区的闪长玢岩体位于班公湖-怒江缝合带西段,其岩石的矿物组合为斜长石(45%~55%)、钾长石(20%~25%)、角闪石(10%~15%)、石英(5%~10%)和黑云母(5%)。锆石LA-ICP-MS U-Pb测年显示,该岩体的形成年龄介于117.6~121.3Ma,即早白垩世。岩石化学研究表明,盐湖地区的闪长玢岩具有I型花岗岩类的地球化学特征,其形成的构造背景为岛弧大陆挤压碰撞造山环境(IAG)。该闪长玢岩体的成因可能与向南俯冲的班公湖-怒江洋壳俯冲板片的断离导致的软流圈物质上涌和地壳重熔有关,即由下地壳基性岩类的部分熔融所形成。     

西藏岗巴晚白垩世锶同位素曲线的地层学意义及问题讨论

地质历史时期古海洋中的锶同位素组成具有全球基本一致的演化规律 ,并主要受全球性海平面变化影响。根据从西藏岗巴宗山上白垩统剖面中 6 3个海相碳酸盐样品获得的锶同位素测试数据建立了锶同位素演化曲线 ,与北美同时代锶同位素曲线进行了对比 ,证明晚白垩世有一次全球性海平面升降事件 ,在宗山剖面宗山组近底部的年龄值为 89.4 Ma,并讨论了西藏岗巴宗山地区晚白垩世地层划分对比中的一些问题。     

四川甲基卡伟晶岩型稀有金属矿床的成矿时代及其意义

青藏高原东部是中国仅次于新疆阿尔泰的伟晶岩集中产出的地区之一,也是世界上重要的伟晶岩型稀有金属矿产资源产地,其中的甲基卡矿床是中国最大的伟晶岩型锂多金属矿床.由于地处高原,交通不便,对于该矿床的成因及相关科学问题缺乏系统的研究.根据野外调查和同位素年代学研究,获得的甲基卡稀有金属矿床 134号脉和 104号脉的 Ar- Ar法坪年龄分别为 (195.7± 0.1) Ma和 (198.9± 0.4) Ma,等时线年龄分别为 (195.4± 2.2) Ma和 (199.4± 2.3) Ma.这说明青藏高原东部甘孜-理塘一带的伟晶岩矿床形成于印支运动之后的燕山早期,属于印支旋回强烈造山运动之后相对稳定阶段的产物,或者说甲基卡式的伟晶岩型矿床形成于印支旋回板块碰撞造山运动向燕山-喜马拉雅旋回陆内造山运动演化的过渡时期.这种特点与国内外类似的伟晶岩型稀有金属矿床具有相似性.