Carbon isotopic fractionation by desorption of shale gases

Geochemical studies of shale gas and conventional reservoirs within the Triassic Yanchang Formation of Xiasiwan and Yongning Field, Ordos Basin show that methane is isotopically depleted in ¹³C as compared to δ¹³C₁ calculated by the Ro based on the relationship between δ¹³C₁ and Ro. Geochemical fractionation during the adsorption/desorption process of shale system may play a significant part in influencing δ¹³C₁ values of shale gas. Two shale core samples from confined coring of the Yanchang Formation were adopted segmented desorption experiments to examine this phenomenon. The results show that the δ¹³C₁ of desorbed gas changes little in the first few phases of the experiments at low desorption levels, but become less negative rapidly when the fraction of desorbed methane exceeds 85%. The desorption process for the last 15% fraction of the methane from the shale samples shows a wide variation in δ¹³C₁ from −49‰ to −33.9‰. Moreover, δ¹³C₁ of all desorbed methane from the shale samples is substantially depleted in ¹³C than that calculated by Ro, according to Stahl and Carey's δ¹³C₁–Ro equation for natural gas generated from sapropelic organic matter. This shows some gases with isotopically enriched in ¹³C cannot be desorbed under the temperature and pressure conditions of the desorption experiments. This observation may be the real reason for the δ¹³C₁ of shale gases and conventional reservoirs becomes more negative in Xiasiwan and Yongning Fields, Ordos Basin. The magnitude of the deviation between the δ¹³C₁ of shale gas and that calculated by Ro may be related to the adsorption capacity of shale or the proportion of absorbed gases. In this way, we may be able to evaluate the relative adsorption capacity of shale in geological conditions by δ¹³C₁ of the shale gas, or by δ¹³C₁ of conventional gas which generated by the shale with certainty. The δ¹³C₁ of conventional gas in Dingbian and Yingwang Fields have no deviation because the TOC value of the hydrocarbon source rock is relatively low.     

孔隙压力对煤岩基质解吸变形影响的试验研究

煤层气开采过程中,伴随着煤层气不断地吸附、解吸和渗流,煤体产生变形,极易导致煤和瓦斯突出事故。以晋城天地王坡煤矿为例,通过实验室内试验,模拟煤层气在复杂地层漫长的形成和逐渐开采过程,得到了孔隙压力与解吸量、应变的变化关系,并拟合得出其相应关系表达式,揭示了一些新的规律:(1)初期解吸速度较快,解吸量随时间的增长而不断增加,后期解吸速度减缓,解吸量逐渐趋于稳定;(2)孔隙压力与解吸量、应变呈现抛物线曲线关系,随孔隙压力的升高,吸附和膨胀变形占主导,其值均在增大;(3)存在最小孔隙压力值,随孔隙压力的增大,解吸时间增长,孔隙压力越小,吸附解吸规律越不明显,对于晋城天地王坡煤矿3#煤样,该值在1.0MPa左右;(4)不同加载方式对解吸量和变形量影响较大,先部分加载吸附后全部载荷解吸结果同比加全部载荷吸附解吸结果高13%～77%。试验结果可为煤层气(CBM)抽放安全和煤与瓦斯突出防治提供理论依据。     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

13X分子筛活化及其对氧气转移时吸附/解吸过程中氧同位素分馏效应的研究

在激光BrF5法分析硅酸盐和氧化物矿物的真空提取流程中,通常采用氧气作为工作气体来测定样品的氧同位素组成。这需要使用分子筛吸附并转移氧气到质谱进样系统,而分子筛的活化对于有效吸附和解吸氧气至关重要,否则会引起分析过程中的氧同位素分馏。通过采用13X分子筛进行多组实验分析,笔者发现用不同活化程度或中毒失活分子筛沸石转移时可能存在氧同位素分馏。在低温下分子筛是不能够活化的(或活化不完全),吸附能力很低,所测定的δ18O值是波动的。在200℃马弗炉中预加热24h,然后迅速转移到温度为100℃、真空度为10-3Pa系统中加热12h的分子筛,对氧气吸附能力很强,氧同位素分析的绝对误差为±0.05‰(1σ),能够满足地球化学氧同位素分析的要求。如果分子筛受BrF5污染,其吸附能力大为降低,测定的δ18O值呈下降趋势,氧同位素分馏高达0.7‰。如果分子筛受水汽污染,质谱接受电压不断地降低,存在解吸温度下的再吸附过程,测定δ18O值呈上升趋势。因此,分子筛在使用前要在适当条件下的活化,在发现污染或测量值发生波动变化时要及时更换,否则难以保证氧同位素分析数据的可靠性。     

Phase Equilibrium and Phase Diagram of the Ternary System(MgCl_2 + MgB_2O_4 + H_2O) at 288 and 298 K

正1 Introduction The brines with high concentrations of magnesium and boron resources are widely distributed in the Qaidam Basin of the Qinghai-Tibet plateau,China(ZhengTang,1988).Although some works on the ternary system     

Suspended sediment and phosphorus in proglacial rivers: bioavailability and potential impacts upon the P status of ice‐marginal receiving waters

This paper adopts standard tests developed in temperate catchment research to determine the total phosphorus (TP) and the algal available (base‐extractable) phosphorus (NaOH–P) content of a wide range of glaciofluvial sediments from the Northern Hemisphere. We find that the TP content of these sediments is broadly similar to the P content of major rock types in Earth's crust (230–670 µgP/g) and so the TP yields of glacier basins may be high owing to the efficacy of suspended sediment evacuation by glacial meltwaters. We show that this is best achieved where subglacial drainage systems are present. The NaOH–P pool of the sediments is found to be low (1–23 µgP/g) relative to the TP pool and also to the NaOH–P pool of suspended sediments in temperate, non‐glacierized catchments. This most probably reflects the restricted duration of intimate contact between dilute meltwaters and glacial suspended sediments during the ablation season. Thus, despite the high surface‐area:volume ratio of glacial suspended sediments, the potential for P adsorption to mineral surfaces following release by dissolution is also low. Further, sorption experiments and sequential extraction tests conducted using glacial suspended sediments from two Svalbard catchments indicate that the generation of reactive secondary minerals (e.g. Fe‐ and other hydroxides) with a strong capacity to scavenge P from solution (and thereby promote the continued dissolution of P) may also be limited by the short residence times. Most P is therefore associated with poorly weathered, calcite/apatite‐rich mineral phases. However, we use examples from the Svalbard glacier basins (Austre Brøggerbreen and Midre Lovénbreen) to show that the high sediment yields of glaciers may result in appreciable NaOH–P loading of ice‐marginal receiving waters. Again, the importance of subglacial drainage is highlighted, as it produces a major, episodic release of NaOH–P at Midre Lovénbreen that results in a yield (8·2 kg NaOH–P/km²/year) more than one order of magnitude greater than that at Austre Brøggerbreen (where subglacial drainage is absent and the yield is 0·48 kg NaOH‐P/km²/year). Therefore, as since both detrimental and beneficial effects of sediment‐bound P loading in ice marginal receiving waters are possible (i.e. either reduced primary productivity owing to increased turbidity or P fertilization following desorption) there is a pressing need to assess the ambient P status of such environments and also the capacity for ice‐marginal ecosystems to adapt to such inputs. Copyright © 2004 John Wiley & Sons, Ltd.     

The magnetic properties of Quaternary and Tertiary sediments in the southern North Sea

Cores from boreholes penetrating late Quaternary, glacial, interglacial and postglacial sediments and the underlying late Cenozoic delta complex of the southern North Sea have been examined for their magnetic properties. A magnetic polarity stratigraphy has been established as an aid to biostratigraphic dating of the sediments; the Kaena-Gauss and Gauss—Matuyama transitions and the base and top of the Olduvai subchron have been identified. The strength and stability of laboratory-induced isothermal remanent magnetisation display clear magneto-petrological variations, which match lithostratigraphic changes in the cores. Principal component analysis has picked out a basin-wide and palaeoenvironmental consistency in the magnetic data. Large, multi-domain magnetite grains predominate in the post-deltaic and fluvio-deltaic sediments, whereas smaller greigite or titanomagnetite grains are concentrated in the intertidal and marine deltaic facies. Since heavy mineral analysis indicates that most of the deltaic detritus derived from common source areas, the differences in magnetic mineralogy have probably been caused by the sediment transport processes operating within the delta complex.     

“天绘一号”卫星热控设计及飞行验证

本文介绍了“天绘一号”卫星的任务特点, 热控设计技术及关键问题的解决方法, 并对在轨飞行结果进行了详细分析。在轨飞行数据充分表明“天绘一号”卫星热控设计正确、合理。     

A Quantitative Evaluation of Shale Gas Content in Different Occurrence States of the Longmaxi Formation: A New Insight from Well JY-A in the Fuling Shale Gas Field,Sichuan Basin

Comprehensive quantitative evaluation of shale gas content and the controlling factors in different occurrence states is of great significance for accurately assessing gas-bearing capacity and providing effective well-production strategies. A total of 122 core samples from well JY-A in the Fuling shale gas field were studied to reveal the characteristics of S_1 l shale,15 of which were selected to further predict the shale gas content in different occurrence states, which are dependent on geological factors in the thermal evolution process. Geological parameters were researched by a number of laboratory programs, and the factors influential in controlling shale gas content were extracted by both PCA and GRA methods and prediction models were confirmed by the BE method using SPSS software. Results reveal that the adsorbed gas content is mainly controlled by TOC, Ro, SSA, PD and pyrite content, and the free gas content is mainly controlled by S_2, quartz content, gas saturation and formation pressure for S_1 l in well JY-A. Three methods, including the on-site gas desorption method, the empirical formula method, and the multiple regression analysis method were used in combination to evaluate the shale gas capacity of well JY-A, all of which show that the overall shale gas content of well JY-A is in the range of 2.0–5.0 m~3/t and that the free gas ratio is about 50%, lower than that of well JY-1. Cause analysis further confirms the tectonics and preservation conditions of S_1 l in the geological processes, especially the influence of eastern boundary faults on well JY-A, as the fundamental reasons for the differences in shale gas enrichment in the Jiaoshiba area.     

Role of coal type and rank on methane sorption characteristics of Bowen Basin, Australia coals

The effect of coal composition, particularly the organic fraction, upon gas sorption has been investigated for Bowen Basin and Sydney Basin, Australia coals. Maceral composition influences on gas retention and release were investigated using isorank pairs of hand-picked bright and dull coal in the rank range of high volatile bituminous (0.78% R_{o max}) to anthracite (3.01% R_{o max}). Adsorption isotherm results of dry coals indicated that Langmuir volume (V_L) for bright and dull coal types followed discrete, second-order polynomial trends with increasing rank. Bright coals had a minimum V_L at 1.72% R_{o max} and dull coals had a minimum V_L at 1.17% R_{o max}. At low rank, V_L was greater in bright coal by about 10 cm³/g, but as rank increased, the bright and dull trends converged and crossed at 1.65% R_{o max}. At ranks higher than 1.65% R_{o max}, both bright and dull coals followed similar trends. These competing trends mean that the importance of maceral composition on V_L varies according to rank. In high volatile bituminous coals, increases in vitrinite content are associated with increases in adsorption capacity. At ranks higher than medium to low volatile bituminous, changes in maceral composition may exert relatively little influence on adsorption capacity. The Langmuir pressure (P_L) showed a strong relationship of decreasing P_L with increasing rank, which was not related to coal type. It is suggested that the observed trend is related to a decrease in the heterogeneity of the pore surfaces, and subsequent increased coverage by the adsorbate, as coal rank increases. Desorption rate studies on crushed samples show that dull coals desorb more rapidly than bright coals and that desorption rate is also a function of rank. Coals of lower rank have higher effective diffusivities. Mineral matter was found to have no influence on desorption rate of these finely crushed samples. The evolution of the coal pore structure with changing rank is implicated in diffusion rate differences.