湿热水解法测定岩矿中的氯

In this paper, a procedure of pyrohydrolysis-spectrophotometric determination has been estahlished for chlorine in ores and rocks.The catalyst selection and its required quantity,the time and temperature of sample decomposition and the influence of interferring elements and others are also discussed in detail. Because samples are usually fused with alkali, higher blank is an insurmountable problem. However, with our procedure, the above-mentloned drawback can be effectively overcome, and the determination of trace chlorine either in large or in minor quantities of samples also is rather ideal. The determined results indicate that the relative standard deviation in the former is 8.7%, and 4.5% in the latter case. This procedure is simple, rapid and well reproduceable. The detection limit of the method is 10ppm. The results obtained by our procedure are in good agreement with the proposed values from two reference samples in China (DZ∑-1 and DZ∑-2) and one international geochemical reference sample (RGM-1). This method has been proved to be reliable.     

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.     

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.     

Structural Setting and Kinematic Analysis of the Halaban Region,Eastern Arabian Shield,Saudi Arabia

The vorticity analysis technique was applied to measure the different lithological units,such as schist,metagranite and metavolcano-sedimentary rocks,which are present in the Halaban region.This work aims to interpret the relationship between the different lithologies and the tectonic setting,in order to elucidate the nature of kinematic analysis in the Halaban region.The kinematic analyses were applied to feldspar porphyroclasts,quartz and hornblende for twentysix samples.The kinematic vorticity number (W_m) for deformed rocks in the study area ranged from～0.6 to 0.9.The direction of the long axes for finite strain data (X axes) revealed a WNW trend with shallow dipping.The direction of the short axes for finite strain data (Z axes) were represented by vertical with associated horizontal foliation.The results of the kinematic vorticity and strain analyses are characterized by simple shear with different degrees of deformation in the Halaban region.Furthermore,our finite strain data shows no significant volume change during deformation.The subhorizontal foliation was synchronized with thrusting and deformation.Furthermore,throughout the overlying nappes,the same attitudes of tectonic contacts are observable,the nappes in the orogens being formed from simple shear deformation.     

Geochemical behavior of rare-earth elements and other major and minor elements in soundproducing and silent beach sands in Japan

The major element composition of sound-producing sand is reported together with rare-earth elements (REE) and other selected elements for the first time. Rare-earth element concentrations in beach sands from Miyagi and Tottori in Japan were determined by induction-coupled, argon-plasma spectrometry (ICP-MS) to characterize the REE of sound-producing and silent sands relative to the parental rocks. Sound-producing sand beaches are very common and all over in Japan: five beaches in Miyagi and 2 in Tottori are selected with other silent sand beaches in the areas. Both sound-producing sand and silent sand samples from Miyagi and Tottori contain more than 60wt% of SiO2 and are composed mainly of quartz and feldspar. Miyagi sand samples are characterized by light REE enrichment and flat chondrite-normalized patterns that are similar to those of local source sandstone. However, all sand samples from Miyatojima in Miyagi show positive Eu anomalies, a characteristic feature not shown in other sand samples from Miyagi. Tottori sand samples also are characterized by high REE contents and remarkable positive Eu anomalies. The sands containing lower REE contents are due to high quartz and feldspar contents. Miyatojima sand samples and Tottori sand samples have high REE contents and show remarkable positive Eu anomalies due to the presence of feldspar. The best results are obtained using all of the geological methods and the Principal Component Analysis (PCA) as a measure of the similarity between sound-producing sand and silent sand. The difference between sound-producing sand and silent sand is obtained from the PCA results.     

某些低对称矿物中二价铜离子晶场光谱的计算

Reported in this paper are the expressions for the crystal field potential energy and perturbation matrix elements for the symmetry of C4v, D2h and Ci, by which the crystal field spectra of Cu^2 ions in the minerals such as metatorbernite, conichalcite and turquoise have been calculated. In our calculation, the values uf (r^3) and (r^4)are determined by the empirical radial-wave function cited from reference [1]. The results obtained are essentially consistent with the experimental data.     

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.     

Assessment of Rock-Eval Tmax Data in Bambra-2 Well of Barrow Sub-basin, North West Shelf of Australia： A Case Study of Contaminated Rock-Eval Data

The contamination of cuttings and side-wall core (SWC) samples in the Bambra-2 well by drilling-mud additives and natural hydrocarbons may cause Ruek-Eval Tmax (℃) data to be suspect, and affect its utility in the assessment of thermal maturity. The Rock-Eval results of 284 cuttings samples, 31 side-wall core samples and conventional core samples from the Jurassic-Cretaceous sedimentary sequences in the Bambra-2 well are presented in this paper. Significantly lower Tmax values from cuttings samples compared with Tmax values from conventional core samples and solvent extracted SWC samples, from the deeper and higher maturity interval, are thought to have been caused by contamination by diesel and other drilling-mud additives. The cuttings samples in the Barrow Group of Cretaceous may be contaminated by natural hydrocarbons, resulting their Tmax values to be 2-10℃ lower than a regularly increased Tmax trend from core samples. This study indicates that more reliable Rock-Eval Tmax data are obtained from the conventional core samples and solvent extracted SWC samples. This study also indicates that the Tmax values from some SWC samples were also affected by free hydrocarbons, due to the use of diesel as a mud additive as well.     

内蒙古东升庙矿床岩浆热液叠加成矿作用——来自地质与矿物包裹体测温的证据

The Dongshengmiao Pb-Zn deposit located in the Mesoproterozoic aulacogen in a passive continental margin in the north- west margin of the North-China Craton is widely considered to be a untypical SEDEX deposit.Recently,new types of mineralization such as chalcopyrite veins and re-crystallized sphalerite ores with visible hydrothermal alteration have been found in the deposit at depth.In this paper we report the decrepitation temperatures of fluid inclusions in chalcopyrite,sphalerite and quartz from these new types of ores.The decrepitation temperatures of fluid inclusions in chalcopyrite(4 samples),sphalerite(2 samples)and quartz(5 samples)are 303～456℃,97～497℃,146～350℃and 350～556℃,respectively.The decrepitation temperatures of fluid inclusions in the vein-type chalcopyrite are similar to the decrepitation temperatures of fluid inclusions in chalcopyrite from the Hercynian Oubulage porphyry Cu-Au deposit(313～514℃)and the Chehugou porphyry Cu-Mo deposit(277～485℃),supporting our interpretation that the Dongshengmiao deposit was overprinted by magmatic hydrothermal mineralization.The decrepitation temperatures of fluid inclusions in re-crystallized sphalerite from the Dongshengmiao deposit are characterized by two peaks,97～358℃and 358～497℃.The decrepitation temperatures of fluid inclusions in quartz in ehalcopyrite veins from the Dongshengmiao deposit are also characterized by two peaks,146～350℃and 350～556℃.The lower and higher temperature peaks in both cases are considered to represent two separate mineralization events,original SEDEX mineralization and magmatic hydrothermal overprinting,respectively.The higher decrepitation temperatures of fluid inclusions in quartz and sphalerite from the Dongshengmiao deposit are similar to the decrepitation temperatures(340～526℃)of fluid inclusions in sphalerite from the Baiyinnuoer skarn-type Pb-Zn deposit in the region. Replacement of pyrite by sphalerite and overgrowth of chalcopyrite on pyrite in the Dongshengmiao support our interpretation that the original SEDEX mineralization was overprinted by magmatic hydrothermal activity in the deposit.Our results suggest that there may be separate porphyry and skarn-type deposits related to Hercynian magmatism and associated hydrothermal activities in the Langshan area, which are potential exploration targets in the future.     

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+.     

Mineralogy,M-type tetrad effect and radioactivity of altered granites at the G. Abu Garadi shear zone,central Eastern Desert,Egypt

The G. Abu Garadi area is covered mainly by metasediments, alkali feldspar granites and stream sediments. The alkali feldspar granite is traversed by a major strike-slip fault trending in an N-S direction as well as two subordinate sets of faults trending NW to WNW for the first one and NE for the second one. These faults represent the shear zones affected by magmatic (syngenetic) as well as hydrothermal (epigenetic) activities causing alteration of the granitic rocks. The most common alteration features are albitization, greisenization and koalinitization. The mass balance calculations of the studied altered samples show enrichments in Zr, Y, Ni, U, Th and Ga and depletions in Zn, Sr, Nb, Ba, Pb, Cu and V. Only the greisenized samples exhibit a significant enrichment in Nb, ∑REE budget and pronounced lanthanide tetrad effect (M-type), especially TE1,4, while weakly expressed tetrad effects are for the other albitized and koalinitized samples. Mineralogically, the common accessory minerals in the altered samples include samarskite-(Y), betafite, uranothorite, zircon, fluorite and cassiterite. The greisenized granites contain high eU and eTh than the other altered types, where they are characterized by an assemblage of the radioactive minerals; samarskite-(Y), betafite, uranothorite in addition to zircon. The inter-element relationships between U and Th and also their ratios illustrate that the radioelement distribution in these granites is mainly governed by magmatic processes, in addition to post-magmatic ones. The distribution of chemical elements and the fractionation of some isovalents within the shear zone are largely controlled by the newly formed mineral phases. With respect to uranium mobilization, uranium migrated from the host alkali feldspar granites of G. Abu Garadi, while the shear zones acted as traps for the migrated uranium. Moreover, U migrated in the shear zone during greisenization and albitization, and migrated out during koalinitization.     

Innovation of experimental methodology for adsorbed gases on hydrocarbon-source rocks

As compared to the device developed by our predecessors, the newly developed adsorbed gas degasification-collection device has a series of advantages such as wide sample application range, large sample inlet, high vacuum, short-time sample smashing, low crushing temperature and water-free gas collection, which ensure the geochemical characteristics of acquired adsorbed gas samples to be the same as those of the adsorbed gases on corresponding hydrocarbon-source rocks. The results showed that the acquired adsorbed gases are composed mainly of hydrocarbon gas and carbon dioxide gas, with the hydrocarbon gas accounting for more than 80%, and can be measured reliably for their δ13C1-δ13C3 data, even δ13C4-δ13C5 data. The results of carbon isotope test and analysis satisfy the needs for the geochemical study and application of adsorbed gases. The above new techniques of experimental geochemistry are helpful for establishing the new direct natural gas-source correlation method, proving that the previous usual method of indirect natural gas-source correlation is scientific and authentic, thus providing the experimental basis for the study and application of adsorbed gases on hydrocarbon-source rocks.     

Isotopic composition of dissolved boron and its geochemical behavior in a freshwater-seawater mixture at the estuary of the Changjiang （Yangtze） River

The isotopic composition of dissolved boron, in combination with the elemental concentrations of B, Cl and salinities in freshwater-seawater mixed samples taken from the estuary of the Changjiang River, the largest one in China, was investigated in detail in this study. Brackish water and seawater samples from the estuary of the Changjiang River were collected during low water season in November, 1998. Boron isotopic compositions were determined by the Cs2BO^＋2-graphite technique with a analytical uncertainty of 0.2‰ for NIST SRM 951 and an average analytical uncertainty of 0.8‰ for the samples. The isotopic compositions of boron, expressed in δ^11B, and boron concentrations in the Changjiang River at Nanjing and seawater from the open marine East Sea, China, are characterized by δ^11B values of -5.4‰ and 40.0‰, as well as 0.0272 and 4.43 mg B/L, respectively. Well-defined correlations between δ^11B values, B concentrations and Cl concentrations are interpreted in terms of binary mixing between fiver input water and East Sea seawater by a process of straightforward dilution. The offsets of δ^11B values are not related to the contents of clastic sediment and to the addition of boron. These relationships favor a conservative behavior of boron at the estuarine of the Changjiang River.     

Characterizing the Micropores in Lacustrine Shales of the Late Cretaceous Qingshankou Formation of Southern Songliao Basin, NE China

Micropores of shale are significant to the gas content and production potential of shale, which has been verified in the research of marine shale gas; while, few studies have been conducted on lacustrine shales. This study collected 42 samples from three wells in the Late Cretaceous Qingshankou Formation of the southern Songliao Basin, NE China, and investigated these samples by the focused ion beam-scanning electron microscope (FIB–SEM) and nitrogen adsorption analysis techniques. Four types of micropores were identified in the samples, i.e., intergranular pore, intracellular pore, organic matter pore and microfracture. The pore structure type is characterized by open slit pores and “ink type” pores which are mainly 1.5–5 nm in diameter with mesopores as the main pores. The mesopores account for 74.01% of the pore volume and 54.68% of the pore surface area. Compared with the lacustrine shales from the Triassic Yanchang Formation in the Ordos Basin and Xujiahe Formation in the Sichuan Basin, the intergranular clay mineral interlayer pores are considered to be the main reservoir space for shale gas storage in the study area, followed by intraparticle pores, organic matter pores and microfractures. Maturity and micropore are the key controlling factors which affect the shale gas content of the Qingshankou Formation in southern Songliao Basin.     

The Hizeh-Jan Kaolin Deposit of NW Iran:the TetradEffect in REE Distribution Patterns

The Hizeh-Jan kaolin deposit(northwest of Varzeghan, East-Azarbaidjan Province, NW Iran) is a product of the alteration of Eocene andesitic rocks. Based on mineralogical examinations, kaolinite, quartz, smectite, pyrophyllite, muscovite-illite, alunite, calcite, diaspore, goethite and hematite are the most abundant mineral phases in this deposit. The geochemical indicators, such as Y/Ho and Zr/Hf, indicate the non-CHARAC(non-Charge-radius control) behavior of these pairs, which are likely to be due to the occurrence of the tetrad effect phenomenon in this deposit. Simultaneous concave and convex shapes in the chondrite-normalized REE distribution patterns are a remarkable feature of the kaolin samples. Bivariate diagrams of the size of the third tetrad effect(T_3) versus geochemical parameters such as Y/Ho, Nb/Ta and Zr/Hf ratios display two distinct populations for the kaolin samples. The first population is characterized by high T_3 values(>0.13), which are near or on the fault zone. The second population is characterized by low T_3 values(<0.13), and are farther from the fault zone. The obtained results from the geochemical data have furnished compelling evidence that fluidrock interaction, overprint of hypogene processes by supergene ones, and structural control, are key controlling factors for the occurrence of tetrad effects in REE distribution patterns in the Hizeh-Jan kaolin deposit.     

Influences of ore formation on biomarkers in the Kupferschiefer from the Lubin mine, Poland

Molecular biomarkers are the important maturity parameters for sedimentary organic matter.They have also been widely used for determining the maturity of organic matter in ore deposits. However,during the study of organic matter in the Kupferschiefer from the Lubin mine, it had been found that the biomarkers were influenced by sulfide formation. In order to probe into the degree of influence on biomarkers, seven samples collected from a Kupferschiefer section from the Lubin mine were analyzed by various geochemical methods. The results indicated that in the samples with higher copper contents, the values of biomarkers are lower than in the samples with lower copper contents. In highly mineralized samples, hydrogen donation for thermochemical sulfate reduction (TSR) occurred in alkylated phenanthrenes and naphthalenes, leading to the decrease of 12 biomarker parameters during the Kupferschiefer mineralization.     

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%.     

A Preliminary Study on Paleomagnetism and Rock Magnetism of Eclogite from the Maobei Area

A preliminary study of paleomagnetism and rock magnetism has been done on 55 eclogite samples collected from the Chinese Continental Scientific Drilling (CCSD) site at the Maobei (毛北) area, Donghai (东海) County, Jiangsu (江苏) Province. Also the isothermal remanence, hysteresis loop, magnetic fabric, thermal susceptibility were measured, and analyses were made by electron-probe and scanning electric microscope on some samples synchronously. The result indicates that there are two groups of stable remanence, the normal and reversed magnetization. The remanence orientations are: D=94.3o, I=-29.1o and D=273.7o, I=15.4o, respectively. The magnetization intensity and the density of the samples which carry the normal magnetization are very different from those bearing reversed magnetization. The magnetic anisotropy is weak, and the minimum axis is hardly determined. The isothermal remanence and the hysteresis loop show that the magnetic carriers of the eclogite are likely SD (single domain) and PSD (pseudo-single domain) magnetite. According to the magnetic property, the cause of formation of magnetic carriers, the mechanism of the remanence, and the significance for the tectonics are discussed.     

Composition of Kerogen in Kupferschiefer from Southwest Poland

Thirty-seven Kupferschiefer samples from southwestern Poland were analyzed by microscopy, Rock-Eval approach and instrumental neutron activation analysis to understand the geochemical and morphological characteristics of kerogen present in the samples. The analytical results indicate that there are two different types of kerogens. One type was only subjected to thermal alteration processes, and the other was further oxidized after deposition of the sediment.In the oxidized samples migrabitumen was transformed into pyrobitumen. Rock-Eval analyses show a significant decrease in HI values in the oxidized samples and an increase in OI values in relation to the samples that were not influenced by oxidation. Variations in S2 versus Corg contents indicate a change in kerogen from Type II to Type III with progressing oxidation. The presence of pyrobitumen and the depletion of hydrogen in the altered kerogen allow one to conclude that the kerogen was used as hydrogen donor for thermochemical sulfate reduction(TSR).     

Identifying the Hydrochemical Characteristics, Genetic Mechanisms and Potential Human Health Risks of Fluoride and Nitrate Enriched Groundwater in the Tongzhou District, Beijing, North China

Fluoride and nitrate enriched groundwater are potential threats to the safety of the groundwater supply that may cause significant effects on human health and public safety, especially in aggregated population areas and economic hubs. This study focuses on the high F? and NO3? concentration groundwater in Tongzhou District, Beijing, North China. A total of 36 groundwater samples were collected to analyze the hydrochemical characteristics, elucidate genetic mechanisms and evaluate the potential human health risks. The results of the analysis indicate: Firstly, most of the groundwater samples are characterized by Mg-HCO3 and Na-HCO3 with the pH ranging from 7.19 to 8.28 and TDS with a large variation across the range 471–2337 mg/L. The NO3? concentration in 38.89% groundwater samples and the F? concentration in 66.67% groundwater samples exceed the permissible limited value. Secondly, F? in groundwater originates predominantly from water-rock interactions and the fluorite dissolution, which is also regulated by cation exchange, competitive adsorption of HCO3? and an alkaline environment. Thirdly, the effect of sewage disposal and agricultural activities have a significant effect on high NO3– concentration, while the high F? concentration is less influenced by anthropogenic activity. The alkaline environment favors nitrification, thus being conducive to the production of NO3?. Finally, the health risk assessment is evaluated for different population groups. The results indicate that high NO3? and F? concentration in groundwater would have the largest threat to children’s health. The findings of this study could contribute to the provision of a scientific basis for groundwater supply policy formulation relating to public health in Tongzhou District.