用高温石墨管原子吸收分光光度法测定土壤和污泥中的镉、铅、铜、镍、钴

Some soft and mud samples have been determined for eadmiun, lead, copper,nickel and cobalt by atomic absorption speetrophotometry with a high-temperature graphite tube, after their extraction with sodium diethylthiocarbonate into methy lisolutyl ketone. The tests of the effects of acidity on extraction and interference have been also carried out and the optimum conditions have been obtained. In addition, experiments on recoveries by this procedure have been performed for the elements in ppb amount. The recovery of the metals added to soil samples is made in the same manner and the precision values are given in this paper. This method is considered as to be applicable to the determination of soil and mud samples for the above-mentioned elements, of which the concentration is higher than 1 ppb.     

Separation and Precise Measurement of Lithium Isotopes in Three Reference Materials Using Multi Collector‐Inductively Coupled Plasma Mass Spectrometry

Lithium separation technique for three reference materials has been established together with precise determination of lithium isotope using a Neptune multi collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). The solutions of lithium element standard reference materials, potassium, calcium, sodium, magnesium and iron single element, were used to evaluate analytical methods applied. Three separate stages of ion-exchange chromatography were carried out using organic cation-exchange resin (AG 50W-X8). Lithium was enriched for the three stages using different eluants, which are 2.8 M HCl, 0.15 M HCl and 0.5 M HCl in 30% ethanol, respectively. The columns for the first and second stages are made of polypropylene, and those for the third stage are made of quartz. Total reagent volume for the entire chemical process was 35 mL for three reference materials. The recovery yielded for the three stages is 98.9–101.2% with an average of 100.0%, 97.6–101.9% with an average of 99.9%, and 99.8–103.3% with an average of 100.6%, respectively. The precision of this technique is conservatively estimated to be ±0.72–1.04‰ (2σ population), which is similar to the precision obtained by different authors in different laboratories with MC-ICP-MS. The δ7Li values (7Li/6Li relative to the IRMM-016 standard) determined for andesite (AGV-2) and basalt (BHVO-2) are 5.68‰ (n=18), 4.33‰ (n=18), respectively. The δ7Li value (7Li/6Li relative to the L-SVEC standard) determined for IRMM-016 is –0.01‰ (n=15). All these analytical results are in good agreement with those previously reported. In addition, the results for the same kinds of samples analyzed at the MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, are consistent with those obtained at the Plasma Laboratory, University of Maryland, within analytical uncertainty. According to these experiment results, it is concluded that this proposed procedure is a suitable method for determining the lithium isotopic composition of natural samples.     

β—Correction Spectrophotometric Determination of Cadmium with Cadion

Cadmium has been determined by β-correction spectrophotometry with cadion,p-nitrobenzenediazoaminoaz-obenzone,and a non-ionic surfactant,tuiton X-100.The real absorbance of a Cd-cadion chelate in the colored solution can be accurately determined and the complex-ratio of cadion with Cd(II) has been worked out to be 2.Beer‘s law is obeyed over the concentration range of 0-0.20mg/1 cadmium and the detec-tion limit for cadmium is only 0.003mg/1.Satisfactory experimental results are presented with respect to the determination of trace cadmium in wastewaters.     

Measurements of Sulfur Isotope Composition on Ultrasmall (80 Nanomole) Sulfide and Sulfate Samples by a Modified EA-IRMS

The traditional method for sulfur isotope measurement using EA-IRMS commonly requires sulfur content greater than 2 μmol. Such a large sample size limits its application to low-S materials, the size mainly being due to ineffective utilization of sample gas, almost 99.7% of which is discarded with carrier gas through the split port of the continuous-flow interface. A modified EA-IRMS system with a gas chromatographic (GC) column and a custom-built cryogenic concentration device is used in this study. We measured six reference materials to test the performance of this method. The results were consistent with those obtained through traditional EA-IRMS. Precisions ranging from ±0.24‰ to ±0.76‰ (1σ) can be obtained with samples equivalent to ~80 nmol sulfur, which were similar to results obtained from an alternative method using an absorption column. Our improved method is a powerful tool for sulfur isotope measurement in ultrasmall sulfide and sulfate samples, which can be further applied to carbon, nitrogen and oxygen isotope analyses of samples at about 100 nmol level.     

α谱法测定低微量铀、钍含量的研究

Alpha-spectrometric technique is described as an independent method of determining micro-content of U^233 and Th^233. This method is based on the comparison of U^234 and Th^233 alpha spectral activity in geological samples with U^232 and Th^233 spectral activity contributed by the spike of known concentration. The experiment procedure consists in dissolving fine powdered sample with acid and adding a given amount of U^232-Th^223 spike. The uranium and thorium are then separated by ion exchange. After purification each fraction is mounted on a separate stainless steel disk for measurement by alpha spectrometer which consist essentially of a surface barrier deterctor and a low noise amplification system connected to a multichannel analyser. After correcting for background, tail and other factors, the desired U^232 and Th^232 concentrations can be calculated. The data obtained by the alpha-spectrometric method using U^232-Th^223 spike are compared with colorimetric determination. Excellent agreement is obtained between the two sets of results. The coefficient of correlation is about 0.98 for U^234 and 0.97 for Th^232. The accuracy of uranium and thorium analyses by this method depends primarily upon the counting statistics of U^233, U^232, Th^233 and Th^223 and, to a lesser extent, upon the calibration of U^233-Th^238 spike. Errors of uranium and thorium concentration by this method are generally 2 to 5 per cent.     

国际地球化学标准参考样品分析

The analytical procedures used for many years in our institute for rock analysis are tested against 18 international geochemical reference samples provided by CRPG, ANRT and USGS. The validity of our method and its suitability for widely different samples are substantiated by the good agreement between our results and the recommended values.     

Ge（Li）γ谱仪测量^135U的丰度

In this paper a technique for determining ^235U abundance is described. After chemical separation, uranium-rich ore (a compound of uranium with chemical and radioactive pure)is made into U3O8 by burning at 850℃, and then the U3O8 is prepared as the radioactive measuring source with a definite weight and shape. The measurement is carried out of the net area of 185.7 keV γ -ray peak of ^235U by Ge (Li) γ -ray spectrometer, with the mixture of a number of primary uranium ores as normal abundance standard. Parallel analysis and counting are performed on the standard and samples with the same method. The abundance of ^235U will be known by comparing their net areas of 185.7 keV γ ray peaks of ^235U both in the samples and the standard. Two samples of uranium ore from China which are suspected to be anomalous in U abundance and one sample from Oklo natural reactor have been determined. The precision of the method is better than 1%.     

Determination of total selenium in geological samples by HG-AFS after concentration with thiol cotton fiber

Standard reference material and different geological samples were dissolved by system A （the mixture of nitric and perchloric acids） and system B （mixture of nitric, perchloric and hydrofluoric acids）, and total Se in all samples was measured by hydride-generation atomic fluorescence spectrometry （HG-AFS） after concentration with thiol cotton fiber （TCF）. The analytical results obtained by the two digestion method are in good agreement （within the limit of errors） for most of the samples, particularly for those having recommended values. The Se concentrations determined by the two methods are of no difference, and the correlation coefficient is 0.9986; the relative standard deviation （RSD） for the determination of 0.04 μg/g Se is 10.2%. The recovery rates of systems A and B by the standard-addition method were 96%-106% and 99%-104%, respectively.     

旋针主折射率计算法的改进及其误差的讨论

Several simplified equations are presented for the spindle-calculation method in measuring the refractive indices of minerals. By two (uniaxial) or three (biaxlal)measurements in two different immersion media, the principal indices of refraction of a mineral can be calculated according to the I.R. of immersion media and the oricntational angles of the nonprincipal refractive incices which I. R. are equivalent to that of immersion media. This method will he applicable also for measurements in solid immersion media. Precision of this spindle-calculation method has been discussed. In general, it sprecision can be compared with traditional immersion method. The author suggests that the major factors effecting the precision of this method are birefringence of the determined minerals and errors in measurements. A table is given of permissible deviation angles for extinction position determination.     

Stratigraphic Division and Correlation of the Nihewan Beds by Multivariate Statistical Analysis

Described in paper is the principle of optimal partitioning method for stratigraphic division and correlation.The Nihewan Beds are taken for example to show how to apply this approach in stratigraphic division and correlation.The semiquantitative spectral analysis data on aggregate trace elements in 324 samples taken from the nine sections in the Nihewan Basin are treated with multivariate statistical method for stratigraphic division and correlation.First ,the data from all the sections are respectively calculated by the optimal partitioning method to establish the stratigraphic boundaries.The optimal partitioning method has proved itself to be applicable to stratigraphic division and correlation. In our practice the Nihewan Beds are divided into five zones (I-V).Zone I includes subzones Ia and Ib,Zones Ia,Ib,II and III are considered to be corresponding to the Pliocene(N2),the early Early Pleistocene,the late Early Pleistocene,and the Middle Pleistocene,respectively .Zones IV and V are probably Late Pleistocene in age.This indicated that sediments deposited con-temporaneous in the sections of the same basin are similar in geochemical characteristics,although dif-ferent in geographical location.However,the sediments also show some variations ,with a transitional relationship from one section to another .For example ,in Zone II,the sediments of the Xiaodukou section show not only the characteristics of the Nangou-Hongya and Hutouliang sections,but also those of the Xiashagou,Shixiaxi,Shixiadong and Wulitai sections.It can be seen from the above that the zones can be characteristically correlated with one another.In addition the feasibility of the optimal partitioning method is also described in the present paper.     

Application of grouped detrital zircon analyses to determine provenance and closely approximate true depositional age: Early Cretaceous McMurray-Clearwater succession,Canada

In the Lower CretaceousMcMurray-Clearwater succession of the intracontinental Alberta Foreland Basin,Canada,detrital zircon U-Pb geochronology samples(referred to herein as DZ samples)have been used to interpret the strata as representing a paleo-continental-scale drainage system.However,the majority of DZ samples are relatively small(n≈90–100),and syndepositional DZ(i.e.,crystallization age<5 Ma older than depositional age)are rare.This has forced a reliance on dinocysts with long stratigraphic ranges to chronostratigraphically subdivide the McMurray-Clearwater succession rather than employing maximum depositional ages(MDAs)derived from DZ samples.Herein,43 DZ samples(taken from20 subsurface cores)are assigned to 1 of 5 stratigraphic intervals,and in each stratigraphic interval all associated DZ samples are combined to produce a grouped DZ sample.Analysis and comparison of individual and grouped DZ samples are used to(1)assess variability in provenance through time and space,and(2)assess the accuracy of chronostratigraphically subdividing the succession using MDAs.Along the main paleo-drainage axis,a comparison of dissimilarity between DZ samples from the same stratigraphic interval,as well as between stratigraphic intervals,reveals increasing average dissimilarity between individual DZ samples and their respective grouped DZ samplewith increasing spatial separation of samples.These data indicate that in the McMurray Depocenter some sediment is sourced from local tributaries,leading to geographical provenance variability.CalculatedMDAs for all 43 DZ samples and groupedMDAs(gMDAs)for the 5 grouped DZ samples are compared to an ash-derived absolute age and existing biostratigraphy.In theMcMurray Formation,comparison of MDAs to gMDAs shows that in basins with rare syndepositional DZ,the gMDA method improved depositional age estimates by transforming low-confidence MDAs(e.g.,youngest single grains)into high-confidence(multi-grain)gMDAs.In the Clearwater Formationwhere syndepositional DZ are plentiful(i.e.,>5%of the total DZ population),calculating maximumlikelihood ages fromgrouped DZ samples avoids negatively biased(i.e.,too young)MDAs.We suggest grouped DZ samples and the gMDA method be used in systems with multiple DZ samples from a well-defined stratigraphic interval as a means of assessing variability in provenancewithin a depositional system and for improving estimates of depositional ages using DZ.     

Sample preparation for isotopic determination of boron in clay sediments

The procedures of sample preparation for isotopic determination of boron in clay sediments is very cumbersome, by far, there haven’t been relevant reports on that. In order to establish an effective method for sample preparation, a series of experiments were carried out. In this paper, boron in clay sediments was extracted with HCl solution and purified by two-step ion exchange method. Extracted HCl solution should be adjusted to alkalescency before passing through the Amberlite IRA 743 resin column due to the fact that Amberlite IRA 743 resin absorbs boron only from alkalescent solution. However, a mass of hydroxides of Al and Fe will be precipitated when the extracted HCl solution becomes alkalescent. Hydroxides of Al and Fe have a strong adsorption capacity for boron, which can cause boron isotope fractionation. To treat precipitated hydroxides of Al and Fe, four procedures, namely direct ion exchange (DRIE), decationizing ion exchange (DCIE), once sedimentation ion exchange (OSIE) and repeated sedimentation ion exchange (RSIE) were used and assessed. The influences of the four procedures on separation and extraction and isotopic composition of boron in experimental solutions and clay sediments were also discussed. According to the results, the DRIE, DCIE and OSIE are improper. The result of sample determination indicates that when extracting boron via RSIE, with the increase of precipitation times, there’s an obvious decrease in boron content in the precipitated hydroxides while a sharp increase in recovery of boron and it is favorable for weakening the influence of boron isotope fractionation. But the process of RSIE is time consuming and it may introduce boron. It needs further research to establish a more effective sample preparation method for isotopic deter- mination of boron in clay sediments.     

Efficiency of a re-usable Carius tube for determination of platinum group elements in ultramafic rocks

Digestion with aqua regia in Carius tube is commonly employed for determination of PGEs in geological samples. However, silicates cannot be completely dissolved by aqua regia and PGEs might partially remain in silicate residue. In this study, an ultramafic reference material was used to investigate the efficiencies of a new re-usable Carius tube after digestion at 220 and 240℃, and an autoclave-lined Carius tube at 260 and 280℃. The results show that about 10% of PGEs retained in the silicate residues at 220 and 5% still r℃ emains even digestion temperature increases to 280℃. These results agree with previous works that increasing the digestion pressure and temperature can achieve more effective dissolution. Thus, a modified digestion procedure for determination of PGEs in ultramafic rocks by the re-usable Carius tube was proposed in this study.     

An Effective Method for Free Vibration of Plate on Elastic Half Space

The vibration analysis of a plate on an elastic foundation is an important problem in engineering. It is the interaction of a plate with the three-dimensional half space and the plate is usually loaded from both the upper and lower surfaces. The contact pressure from the soil can not be predefined. According to Lambs solution for a single oscillating force acting on a point on the surface of an elastic half space, and the relevant approximation formulae, a relation between the local pressure and the deflection of the plate has been proposed. Based on this analysis, the reaction of the soil can be represented as the deformation of the plate. Therefore, the plate can be separated from the soil and only needs to be divided by a number of elements in the analysis. The following procedure is the same as the standard finite element method. This is a semi-analytical and semi-numerical method. It has been applied to the dynamic analysis of circular or rectangular plates on the elastic half space, at low or high frequency vibration, and on rigid, soft or flexible foundations. The results show that this method is versatile and highly accurate.     

Thermogravimetry-differential thermal analysis coupled with chromatography as a thermal simulation experimental method and its application to gaseous hydrocarbons from different source rocks

In this paper a thermogravimetry-differential thermal analysis method coupled with chromatography （TG-DTA-GC） has been adopted to simulate the generation of gaseous hydrocarbons from different hydrocarbon source rocks such as coals, mudstones, and carbonate rocks with different maturities. The temperature programming for thermal simulation experiment is 20℃/min from ambient temperature to 700℃. As viewed from the quantities and composition of generated gaseous hydrocarbons at different temperatures, it is shown that low-mature coal has experienced the strongest exothermic reaction and the highest loss of weight in which the first exothermic peak is relatively low. Low-mature coal samples have stronger capability of generating gaseous hydrocarbons than high-mature samples. The amounts and composition of gaseous hydrocarbons generated are closely related not only to the abundance of organic carbon in source rocks, but also to the type of kerogen in the source rocks, and their thermal maturity. In the present highly mature and over-mature rock samples organic carbon, probably, has already been exhausted, so the production of gaseous hydrocarbons in large amounts is impossible. The contents of heavy components in gaseous hydrocarbons from the source rocks containing type- Ⅰ and - Ⅱ kerogens are generally high ; those of light components such as methane and ethane in gaseous hydrocarbons from the source rocks with Ⅲ-type kerogens are high as well. In the course of thermal simulation of carbonate rock samples, large amounts of gaseous hydrocarbons were produced in a high temperature range.     

我国台湾浅滩海底沉积物稀土元素地球化学

REE geochemistry of sea-floor sediments from the Taiwan Shallow has been studied.∑ REE of 76 samples from the Taiwan Shallow was determined by chemical extraetion-spectrophotometry, of which 7 samples were analyzed for 15 rare earth elements by XRF. The analytical results show that ,∑ REE of the samples increases gradually with a decrease in grain size. The average REE contents are 60 ppm for coarse-grained sediments,82 ppm for medium-coarse-grained ones, 145 ppm for fine-grained ones, and 211 ppm for silt. The REE content of the samples is controlled mainly by the grain size and mineralogical composition of sediments. The ehondrite-normalized REE distribution patterns in sediments from the Taiwan Shallow are similar to those in granites in Fujian Province, China, which show a negative Eu anomaly and a positive Ce anomaly. The distribution curves are negative in slope. It is considered that based on REE geochemical characteristics, mineralogical composition and related oceanographic information, the Taiwan Shallow sediments seem to be largely residual deposits of ancient littoral facies from various types of continental rocks during Pleistocene glacial period. These sediments have also been reworked by modern sedimentatoion.     

Permeability Heterogeneity in a Fractured Sandstone–Mudstone Rock Mass in Xiaolangdi Dam Site, Central China

Abstract: Heterogeneity of permeability in fractured media is a hot research topic in hydrogeology. Numerous approaches have been proposed to characterize heterogeneity in the last several decades. However, little attention has been paid to correlate permeability heterogeneity with geological information. In the present study, several causes of permeability heterogeneity, that is, lithology, tectonism, and depth, are identified. The unit absorption values (denoted as ω), which are results obtained from the packer test, are employed to represent permeability. The variability of permeability in sandstone–mudstone is so significant that the value of unit absorptions span 3–4 orders of magnitude at any depth with several test sections. By declustering, it has been found that under a similar tectonic history, the means of permeability differ greatly at different formations as a result of different mudrock contents. It has also been found that in the same formation, permeability can be significantly increased as a result of faulting. The well-known phenomenon, the decrease in permeability with depth, is found to be caused by the fractures in the rock mass, and the relationship between permeability and depth can be established in the form of logω–logd. After subtracting the trend of ω with absolute depth, the mean of the residual value at each relative depth can be well correlated with the distribution of mudstone. The methods proposed in this paper can be utilized to research in similar study areas.     

Source and Enrichment Mechanism of Lithium in the Triassic Argillaceous Marine Sediments from Huangjinkou, Sichuan, China

In the Triassic marine sediments, an obvious enrichment of lithium has been found. The source and enrichment mechanism of lithium is unknown. Here, we report trace and rare earth element and isotope analyses for Triassic sedimentary samples from core ZK601, recovered from the Huangjinkou anticline in the Xuanhan basin. Lithium concentrations from the Leikoupo and Jialingjiang formations are much higher than the average concentrations in the crust of eastern China and in other marine sediments. Lithium concentrations are highest at depths of 3300–3360 m (in argillaceous marine sediments), and Li is positively correlated with Rb, Ga, Zr, Nb and other trace elements. The range of δ7Li values in our samples is consistent with that in other Triassic marine carbonate rocks. Lithium concentrations and isotope ratios are negatively correlated in the argillaceous dolomite samples at depths of 3300–3360 m. We compared the results in this study with trace and rare earth elements in the clay from Sichuan and Chongqing, and propose that the clay in the argillaceous marine evaporites from Huangjinkou formed via the hydrolysis of volcanic ash during Early–Middle Triassic volcanic eruptions into brine basins, during which clay adsorbed Li from the brine and formed Li-rich argillaceous dolomites. The addition and hydrolysis of volcanic ash in the evaporative brine is also related to the formation of a new type of polyhalite.     

Measurement and Analysis of Thermal Conductivity of Rocks in the Tarim Basin, Northwest China

: As a parameter that describes heat transmission properties of rocks, thermal conductivity is indispensable for studying the thermal regime of sedimentary basins, and retrieving high-quality data of thermal conductivity is the basis for geothermal related studies. The optical scanning method is used here to measure the thermal conductivity of 745 drill-core samples from the Tarim basin, the largest intermontane basin with abundant hydrocarbon potential in China, and water saturation correction is made for clastic rock samples that are of variable porosity. All the measured values, combined with previously published data in this area, are integrated to discuss the distribution characteristics and major controlling factors that affect the thermal conductivity of rocks in the basin. Our results show that the values of thermal conductivity of rocks generally range from 1.500 to 3.000 W/m·K with a mean of 2.304 W/m·K. Thermal conductivity differs considerably between lithological types: the value of a coal sample is found to be the lowest as being only 0.249 W/m·K, while the values for salt rock samples are the highest with a mean of 4.620 W/m·K. Additionally, it is also found that the thermal conductivity of the same or similar lithologic types shows considerable differences, suggesting that thermal conductivity cannot be used for distinguishing the rock types. The thermal conductivity values of mudstone and sandstone generally increase with increasing burial depth and geological age of the formation, reflecting the effect of porosity of rocks on thermal conductivity. In general, the mineral composition, fabric and porosity of rocks are the main factors that affect the thermal conductivity. The research also reveals that the obvious contrast in thermal conductivity of coal and salt rock with other common sedimentary rocks can induce subsurface temperature anomalies in the overlying and underlying formations, which can modify the thermal evolution and maturity of the source rocks concerned. This finding is very important for oil and gas resources assessment and exploration and needs further study in detail. The results reported here are representative of the latest and most complete dataset of thermal conductivity of rocks in the Tarim basin, and will provide a solid foundation for geothermal studies in future.     

Geochemical assessment of a siliceous limestone sample for cement making

A low grade siliceous limestone sample from the Jayantipuram mine of Andhra Pradesh, India, has been investigated for its suitability for cement making. Petrological as well as X-ray diffraction pattern studies indicated that the limestone sample was crystalline and dominantly composed of calcite and quartz. They are simple in mineralogy, and yet they have variable silica and lime contents. Geochemical analysis results of twenty five hand picked samples indicated that the limestone from the Jayantipuram mine shows a wide range of variations in LOI (29.94% to 40.64%), SiO2 (6.14% to 27.18%), CaO (37.93% to 50.78%), Al2O3 (0.49% to 2.27%) and Fe2O3 (0.28% to 2.4%). MgO, K2O, Na2O, TiO2 and MnO2 are present in traces. CaO with LOI shows a strong positive correlation where as CaO with SiO2 shows a strong negative correlation because of mineralogical factors. The chemical composition of the limestone reflects its mineralogical composition. The distribution of various elements in the acid-soluble fraction has been studied by the factor analysis method in order to interpret in terms of their mineralogy, sedimentary environment and diagenesis. Mineralogy, recrystallization and other diagenetic changes are the main factors affecting the distribution of the elements and their mutual relationships in the limestone. The aim of this paper is also to analyze how significantly the two parameters, silica modulus and lime saturation factor, influence this low grade siliceous limestone sample from the Jayantipuram mine of Andhra Pradesh, India, for the cement making process from the geochemical data.