粉煤灰基地质聚合物水热原位转化NaP型沸石分子筛的研究

以固体废弃物粉煤灰基地质聚合物为基本骨架,通过水热合成法将其原位转化为自支撑Na P型沸石分子筛型体,并研究了水热过程中碱液浓度、碱液体积、水热温度和水热时间对NaP型沸石分子筛结晶程度、形貌和机械强度的影响,得到粉煤灰基地质聚合物原位转化Na P型沸石分子筛型体的适宜条件为水热温度100℃、NaOH浓度2.0mol/L、NaOH体积50 m L、水热时间24 h。所得Na P型沸石分子筛型体的抗压强度为23.21 MPa,BET比表面积为50.46 m~2/g,已达到工业生产P型沸石的水平。该法工艺简单,环境友好,可控成型。在此方法的基础上通过改变原料配比和反应条件,可以合成其他类型的沸石分子筛型体。     

Investigation of gas content of organic-rich shale:A case study from Lower Permian shale in southern North China Basin,central China

Measuring gas content is an essential step in estimating the commerciality of gas reserves. In this study,eight shale core samples from the Mouye-1 well were measured using a homemade patented gas desorption apparatus to determine their gas contents. Due to the air contamination that is introduced into the desorption canister, a mathematical method was devised to correct the gas quantity and quality.Compared to the chemical compositions of desorbed gas, the chemical compositions of residual gas are somewhat different. In residual gas, carbon dioxide and nitrogen record a slight increase, and propane is first observed. This phenomenon may be related to the exposure time during the transportation of shale samples from the drilling site to the laboratory, as well as the differences in the mass, size and adsorptivity of different gas molecules. In addition to a series of conventional methods, including the USBM direct method and the Amoco Curve Fit(ACF) method, which were used here for lost gas content estimation, a Modified Curve Fit(MCF) method, based on the 'bidisperse' diffusion model, was established to estimate lost gas content. By fitting the ACF and MCF models to gas desorption data, we determined that the MCF method could reasonably describe the gas desorption data over the entire time period, whereas the ACF method failed. The failure of the ACF method to describe the gas desorption process may be related to its restrictive assumption of a single pore size within shale samples. In comparison to the indirect method, this study demonstrates that none of the three methods studied in this investigation(USBM, ACF and MCF) could individually estimate the lost gas contents of all shale samples and that the proportion of free gas relative to total gas has a significant effect on the estimation accuracy of the selected method. When the ratio of free gas to total gas is lower than 45%, the USBM method is the best for estimating the lost gas content, whereas when the ratio ranges from 45% to 75% or is more than 75%, the ACF and MCF methods, are the best options respectively.     

Occurrence and Chemical Compositions of Amphiboles in Altered Dioritic Rocks of Laiwu Skarn‐Type Iron Deposit in West Shandong Area,China

The Laiwu Fe deposit is the largest skarn‐type deposit in West Shandong in China, with an estimated reserve of 290 Mt of iron ore. Here, we investigate the occurrence and chemical composition of amphiboles in altered dioritic rocks of this deposit. Three generations of amphibole group minerals were identified in these rocks. The first type (Type 1) is a hornblende with a generally euhedral crystal shape, 150–500 μm in size, and dominantly occurs in the host monzonite. The second type (Type 2) of hornblende occurs as fine grains (<100 μm) or concentric rims, less than 50 μm in thickness, around the Type 1 hornblende. The third type (Type 3) of amphibole is anhedral actinolite occurring along the boundary or the cracks of the Type 1 or 2 hornblende grains. The Type 1 hornblende has higher FeO (12.5–15.6 wt.%) and lower MgO contents (11.2–14.6 wt.%) than the Type 2 hornblende, which has an FeO content ranging from 8.8 to 10.5 wt.% and MgO content ranging from 14.2 to 17.1 wt.%. The Type 3 actinolite shows the lowest FeO (4.6–6.4 wt.%) and highest MgO (19.8–21.2 wt.%) contents. We infer that the Type 2 hornblende formed from Fe‐rich hydrothermal fluids released during rapid upwelling of the crystallizing magma. The fluids were relatively reduced and enriched in Fe. The Type 3 actinolite formed by coupled dissolution and reprecipitation, and its formation is one of the features denoting Fe‐enrichment events. Our study of these types of amphibole provides insights into the ore formation process.     

Automated Extraction of a Five‐Year LA‐ICP‐MS Trace Element Data Set of Ten Common Glass and Carbonate Reference Materials: Long‐Term Data Quality,Optimisation and Laser Cell Homogeneity

LA‐ICP‐MS is increasingly applied to obtain quantitative multi‐element data with minimal sample preparation, usually achieved by calibration using reference materials (RMs). However, some ubiquitous RMs, for example the NIST SRM 61× series glasses, suffer from reported value uncertainties for certain elements. Moreover, no long‐term data set of analyses conducted over a range of ablation and tuning conditions exists. Thus, there has been little rigorous examination of the extent to which offsets between measured and reported values are the result of error in these values rather than analytically induced fractionation. We present new software (‘LA‐MINE’), capable of extracting LA‐ICP‐MS data with no user input, and apply this to our system, yielding over 5 years of data (~ 5700 analyses of ten glass and carbonate RMs). We examine the relative importance of systematic analytical bias and possible error in reported values through a mass‐specific breakdown of fourteen of the most commonly determined elements. Furthermore, these data, obtained under a wide range of different ablation conditions, enable specific recommendations of how data quality may be improved, for example the role of diatomic gas, the effect of differential inter‐glass fractionation factors and choice of transport tubing material. Finally, these data demonstrate that the two‐volume Laurin ablation cell is characterised by no discernible spatial heterogeneity in measured trace element ratios.     

A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.     

Defining the Potential of Nanoscale Re‐Os Isotope Systematics Using Atom Probe Microscopy

Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm³). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS ¹⁸⁷Os/¹⁸⁹Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM ¹⁸⁷Os/¹⁸⁹Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.     

Effect of 2D spatial variability on slope reliability: A simplified FORM analysis

To meet the high demand for reliability based design of slopes, we present in this paper a simplified HLRF(Hasofere Linde Rackwitze Fiessler) iterative algorithm for first-order reliability method(FORM). It is simply formulated in x-space and requires neither transformation of correlated random variables nor optimization tools. The solution can be easily improved by iteratively adjusting the step length. The algorithm is particularly useful to practicing engineers for geotechnical reliability analysis where standalone(deterministic) numerical packages are used. Based on the proposed algorithm and through direct perturbation analysis of random variables, we conducted a case study of earth slope reliability with complete consideration of soil uncertainty and spatial variability.     

庐枞火山岩盆地南部拔茅山铜矿深部找矿潜力分析

位于庐枞火山岩盆地南部的拔茅山铜矿,是细脉带蚀变岩型脉状铜矿的代表。研究表明,其深部具有斑岩型铜矿的勘探潜力。为了进一步明确其深部找矿潜力,针对研究区斑岩型、热液型铜多金属矿的岩体、断裂、接触带等主要控矿因素,利用高精度磁法和可控源音频大地电磁测深(CSAMT)成果,分别对拔茅山岩体的分布、产状和深部形态及其与围岩的接触带特征进行了剖析。在此基础上,通过与沙溪斑岩铜矿地质、物探异常特征的类比,指明了研究区的找矿方向和有利找矿部位,为进一步找矿提供了思路和依据。     

Multi-factor sensitivity analysis on the stability of submarine hydrate-bearing slope

There are many factors affecting the instability of the submarine hydrate-bearing slope (SHBS), and the interaction with hydrate is very complicated. In this paper, the mechanical mechanism of the static liquefaction and instability of submarine slope caused by the dissociation of natural gas hydrate (NGH) resulting in the rapid increase of pore pressure of gas hydrate-bearing sediments (GHBS) and the decrease of effective stress are analyzed based on the time series and type of SHBS. Then, taking the typical submarine slope in the northern South China Sea as an example, four important factors affecting the stability of SHBS are selected, such as the degree of hydrate dissociation, the depth of hydrate burial, the thickness of hydrate, and the depth of seawater. According to the principle of orthogonal method, 25 orthogonal test schemes with 4 factors and 5 levels are designed and the safety factors of submarine slope stability of each scheme are calculated by using the strength reduction finite element method. By means of the orthogonal design range analysis and the variance analysis, sensitivity of influential factors on stability of SHBS are obtained. The results show that the degree of hydrate dissociation is the most sensitive, followed by hydrate burial depth, the thickness of hydrate and the depth of seawater. Finally, the concept of gas hydrate critical burial depth is put forward according to the influence law of gas hydrate burial depth, and the numerical simulation for specific submarine slope is carried out, which indicates the existence of critical burial depth.     

Down‐slope facies variability within deep‐water channel systems: Insights from the Upper Cretaceous Cerro Toro Formation,southern Patagonia

In southern Patagonia, outcrops of the Upper Cretaceous Cerro Toro Formation preserve a >150 km long deep‐water axial channel belt in the Magallanes–Austral Basin, providing a unique opportunity to investigate longitudinal variations in the depositional characteristics of a deep‐water channel system. This study documents sedimentological, stratigraphical and geochronological data from the Cerro Toro Formation in the Argentine sector of the basin. New results are integrated with previous work from the Chilean basin sector to conduct a basin‐scale comparison of the timing of deposition, provenance and lithofacies proportions. The Cerro Toro channel belt includes a nearly 1000 m thick section characterized by high‐density turbidites and mass‐wasting deposits. Two ash beds from the base of the section yield U–Pb zircon ages of 90·4 ± 2 Ma and 88·0 ± 3 Ma, indicating similar initiation ages as documented in the Chilean sector. The U–Pb detrital zircon age spectra from samples in the study area reveal similar provenance trends to samples from the Chilean basin sector, with peak age populations at 310 to 260 Ma, 160 to 135 Ma and 110 to 82 Ma. The maximum depositional age of the channel belt in the Argentine sector is 87·8 ± 1·5 Ma and all new geochronology data corroborate an 86 to 80 Ma depositional age for the main Cerro Toro channel belt. Statistical analyses of 7370 beds from nearly 8000 m of new and previously published stratigraphic sections along the entire outcrop belt suggest progressive variations in the down‐system proportion of lithofacies. In the up‐slope region, lithofacies representing mass wasting processes (for example, debris‐flow and mass‐transport deposits) account for ca 29% of the stratigraphic thickness, as opposed to 5% in the down‐slope region of the channel belt, where turbidity current deposits are more prevalent. The proportion of beds >1 m thick also decreases systematically down slope, particularly for conglomeratic turbidite deposits. This work highlights that: (i) the proportion of thick beds and distribution of lithofacies are key down‐system changes in the stratigraphic fill of this deep‐water channel belt; (ii) detrital zircon trends suggest a relatively well‐mixed longitudinal depositional system; and (iii) geochronology of the main Cerro Toro outcrop belt supports but does not necessitate the model of a single, roughly age‐equivalent, channel system. This study has implications for understanding the downslope variability in depositional processes, stratigraphic architecture and reservoir quality of submarine channel systems.