The contribution of trace elements from seawater to chimneys: a case study of the native sulfur chimneys in the sea area off Kueishantao, northeast of Taiwan Island

Hydrothermal fluid containing abundant matter erupts from seafloor, meets ambient cold seawater and forms chimneys. So the main matter origins of chimneys are seawater and matter which are taken by hydrothermal fluid from deep reservoir. However, because of seawater's little contribution to the forming of chimneys, it is usually covered by the abundant matter which is taken by hydrothermal fluid. Therefore, chimneys formed in ordinary deep seawater hydrothermal activity, containing complex elements, cannot be used to study the seawater's contribution to their formation. While the native sulfur chimneys, formed by hydrothermal activity near the sea area off Kueishantao, are single sulfur composition (over 99%), and within chimneys distinct layers are seen. Different layers were sampled for trace element determination, with Inductively Coupled Plasma Mass Spectrometry (ICP-MS). By analyzing the data, we consider C-layer (secondary inner-layer) as the framework layer of the chimney which formed early (Fig. 4), and its trace elements derive from hydrothermal fluid. While the trace elements within A, B, D layers have undergone later alteration. A, B layers are affected by seawater and D layer by hydrothermal fluid. The increase of trace elements of A and B layers was calculated using C layer as background. Based on the known typical volume of chimneys of the near sea area off Kueishantao, we calculated the volume of seawater that contributed trace element to chimneys formation to be about 6.37 x 10(4) L. This simple quantified estimate may help us better understand the seafloor hydrothermal activity and chimneys.

Determination of Total Arsenic and Arsenic Metabolites in Human Liver Hepatocytes

The effects of direct sampling and three digestion methods were investigated on the determination of arsenic in Chang liver hepatocytes after ultrasonic disintegration were investigated. The results showed that the efficiency of microwave digestion and obturator digestion was better than cold digestion and direct sampling. The day precision (present as RSD) of microwave digestion and obturator digestion were 2.1% and 1.2% the inter-day precision were 1.2% and 2.0%, respectively. The spike recovery for the total As in the sample is 95.7% - 108.1%. The As detection limits with these four sample treatment methods (including direct sampling) were 0.74 - 0.93 mu g/L. In addition, arsenic speciation in Chang liver hepatocytes was also analyzed using the hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma-mass spectrometry. The experimental results indicated that dimethylarsinic acid (DMA) and an intermediate metabolite of DMA were found lit Chang liver hepatocytes besides inorganic arsenic (As(III) and As(V)).

铂族元素分析方法研究及其在有关地质问题中的应用

Characterization of Platinum Group Elements (PGE) has been applied to earth, space and environmental sciences. However, all these applications are based on a basic prerequisite, i.e. their concentration or ratio in the research objects can be accurately and precisely determined. In fact, development in these related studies is a great challenge to the analytical chemistry of the PGE because their content in the geological sample (non-mineralized) is often extremely low, range from ppt (10~(-12)g/g) to ppt (10~(-9)g/g). Their distribution is highly heterogeneous, usually concentrating in single particle or phase. Therefore, the accurate determination of these elements remains a problem in analytical chemistry and it obstructs the research on geochemistry of PGE. A great effort has been made in scientific community to reliable determining of very low amounts of PGE, which has been focused on to reduce the level of background in used reagents and to solve probable heterogeneity of PGE in samples. Undoubtedly, the fire-assay method is one of the best ways for solving the heterogeneity, as a large amount of sample weight (10-50g) can be hold. This page is mainly aimed at development of the methodology on separation, concentration and determination of the ultra-trace PGE in the rock and peat samples, and then they are applied to study the trace of PGE in ophiolite suite, in Kudi, West Kunlun and Tunguska explosion in 1908. The achievements of the study are summarized as follows: 1. A PGE lab is established in the Laboratory of Lithosphere Tectonic Evolution, IGG, CAS. 2. A modified method of determination of PGE in geological samples using NiS Fire-Assay with inductively coupled plasma-mass spectrometry (ICP-MS) is set up. The technical improvements are made as following: (1) investigating the level of background in used reagents, and finding the contents of Au, Pt and Pd in carbonyl nickel powder are 30, 0.6 and 0.6ng/g, respectively and 0.35, 7.5 and 6.4ng, respectively in other flux, and the contents of Ru, Rh, Os in whole reagents used are very low (below or near the detection limits of ICP-MS); (2) measuring the recoveries of PGE using different collector (Ni+S) and finding 1.5g of carbonyl nickel is effective for recovering the PGE for 15g samples (recoveries are more than 90%), reducing the inherent blank value due to impurities reagents; (3) direct dissolving nickel button in Teflon bomb and using Te-precipitation, so reducing the loss of PGE during preconcentration process and improving the recoveries of PGE (above 60% for Os and 93.6-106.3% for other PGE, using 2g carbonyl nickel); (4) simplifying the procedure of analyzing Osmium; (5)method detection limits are 8.6, 4.8, 43, 2.4, 82pg/g for 15g sample size ofRu, Rh, Pd, Ir, Pt, respectively. 3. An analytical method is set up to determine the content of ultra-trace PGE in peat samples. The method detection limits are 0.06, 0.1, 0.001, 0.001 and 0.002ng/mL for Ru, Rh, Pd, Ir and Pt, respectively. 4. Distinct anomaly of Pd and Os are firstly found in the peat sampling near the Tunguska explosion site, using the analytical method. 5. Applying the method to the study on the origin of Tunguska explosion and making the following conclusions: (1) these excess elements were likely resulted from the Tunguska Cosmic Body (TCB) explosion of 1908. (2) The Tunguska explosive body was composed of materials (solid components) similar to C1 chondrite, and, most probably, a cometary object, which weighed more than 10~7 tons and had a radius of more than 126 m. 6. The analysis method about ultra-trace PGE in rock samples is successfully used in the study on the characteristic of PGE in Kudi ophiolite suite and the following conclusions are made: (1) The difference of the mantle normalization of PGE patterns between dunite, harzburgite and lherzolite in Kudi indicates that they are residual of multi-stage partial melt of the mantle. Their depletion of Ir at a similar degree probably indicates the existence of an upper mantle depleted Ir. (2) With the evolution of the magma produced by the partial melt of the mantle, strong differentiation has been shown between IPGE and PPGE; and the differentiation from pyroxenite to basalt would have been more and more distinct. (3) The magma forming ophiolite in Kudi probably suffered S-saturation process.

内陆湖沼相和近海沼泽相沉积环境煤中微量元素和矿物的对比研究—以辽宁北票、江西建新和桥头煤研究为例

Using knowledge of geology, geochemistry, coal petrology, mineralogy, by means of a variety of advanced measuring methods such as inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRD), scanning electron microscopy with energy-dispersive spectrometer(SEM-EDS), sequential chemical extract and density fractions, the characteristics of trace elements and minerals in Jurassic Beipiao coal mine under inland limnetic sedimentary environment and in late Permian Jianxin and Qiaotou coal mines under paralic swamp sedimentary environment were studied. Compared with the average concentration in the world bituminous coals, the Beipiao coal was characterized by relatively high contents of Sc, Ti, Cr, Co, Ni, Zn, Se, Sr, Zr, Y, Ba, REE and Th, and lower contents of V, Rb, Cd, Sn, Pb, Bi and U; while the Jianxin coal was relatively enriched in Li, Sc, Ga, Sr, Y, Nb, Sb, Th and U, with low concentration of Be, Co, Ni, Cu, Ge, Zr, Mo, Cd, Cs, Ba, Pb and Bi; and the Qiaotou coal was enriched in Li, Sc, Sr, Nb, Ta, Zr, REE, Hf, Th and U, with low concentration of Be, V, Co, Ni, Cu, Ge, Mo, Cd, Cs, Ba, Tl, Pb and Bi. The concentrations of Ca, Mg and K in Beipiao coal are higher than those in Jianxin coal and Qiaotou coal, while Fe, S and Ti in Beipiao coal are lower than those in Jianxin coal and Qiaotou coal. The proximate analysis of coal samples was carried out, which indicated that Beipiao coal was medium- to high- ash (5.92-60.68%) with low sulphur coal, and Jianxin coal and Qiaotou coal was medium to high ash (8.85-46.33%) with high sulphur. The reflectivity was measured, which explained that Beipiao coal belonged to high volatile bituminous coal, Jianxin coal was low volatile bituminous coal and Qiaotou coal was low volatile anthracite. Quantitative maceral analyses were studied. The characteristics of rare earth elements (REE) were investigated, which showed that the total contents of REE were higher than that of the world's average content. With the increase of coal's metamorphic grade, the total contents of REE decreased from 98.5 X 10"6 of Beipiao coal to 94.2 X 10"6 of Jianxin coal, and to 75.9 X 10"6 of Qiaotou coal, and 5Eu reduced which indicated that the element Eu depleted. The characteristics of REE was controlled by the metamorphic grade of coal. And REE were mainly absorbed in clay minerals in Beipiao coal samples, while in Jianxin and Qiaotou coal mines, REE were primarily related to clay mineral and pyrite. The variation of trace elements in vertical direction of coal seams was studied, and the results showed that different trace elements differed greatly. The correlation between trace elements and ash were determined. Four major trace elements (aluminium-silicates, sulphide, carbonate and phosphate) accounted for the occurrence and distribution of most elements studied were determined. Coal samples were separated by density fraction, which showed that Cr, Cu, Mo and Pb were closely related to inorganic matters mainly distributed in P >2.6 and dropped remarkably in the density fractions P <2.3 . The occurrences of Co, Cr, Ni, As, Se, Mo, U were studied directly and quantitatively using sequential chemical extract with six steps, which showed that Co. Ni, Mo and U were mainly in the form of mineral, and As, Se chiefly in the form of organic state, while Cr mostly in the form of organic state and mineral. Major mineral phases presented in the Beipiao coal were Kaolinite, illite, quartz, calcite, and small amount of siderite, barite. While major mineral phases in Jianxin and Qiaotou coal were pyrite, kaolinite, and small amount of marcasite, rutile, sphalerite. This is the first time that the chromite in the coal was discovered in China, which indicates that Cr occurrence appeared in the form of chromite. The ratio of Sr/Ba, Sr/Ca and V/Ni in Beipiao coal mine under inland limnetic is smaller than that of in Jianxin and Qiaotou coal mines under paralic swamp. The ratio of K/Na and Th/U of Beipiao coal mine is higher than that of Jianxin and Qiaotou coal mine, which proved that Beipiao coal was not affected by sea water and Jianxin and Qiaotou coal were affected by sea water. Trace elements such as Cr, Ni, Mo in minerals were analyzed by SEM-EDS. The factors controlling the enrichment of trace elements can be divided into syngenetic stage factors and epigenetic stage factors.

电厂燃煤中主要有害元素的种类、迁移及潜在环境影响

Distributions of elements especially hazard trace elements in coals and their wastes from a coal fired power plant have been studied in detail using knowledge of Geology, Mineralogy, Geochemistry and Environmental chemistry. The key work is on the small particle sizes of fly ashes which escaped from electric precipitator and discharged into atmosphere. By means of X-ray powder diffraction (XRD) and scanning electron microscopy with energy-dispersive spectrometer (SEM-EDS), the characteristics of minerals and morphologies were studied. Different types of fly ash were formed in different stages and processes. More than 50% of small fly ashes belonged to inhalable particles (PM10). The very fine fly ashes preferred to attach on surface of bigger fly ash or conglutinate with each other and this decreased the environmental impact of tiny fly ashes. The trace elements in coal, fly ashes, slags and small particle sizes of fly ashes had been analysed by means of Neutron Activation Analysis (INAA), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma atomic emission spectrometry (ICP-AES). As particle sizes decreasing, distributions of most elements increased, but in contrary to most studies, this increasing trend was not very obviously because of the tendency of attachment of tiny fly ashes. The occurrence of 30 elements including hazard trace elements of Cd, Cr, Ni, Co, Pb, Zn, As, Se, Cu, V was studied by means of sequential chemical extract. The annual discharge of hazard trace elements of slag, fly ash, small fly ash (PM10), tiny fly ash (PM2.5) and air was calculated by mass balance. S, V, Cu, Pb, Se, Mo, Cd from power plant had potential impacts on environment. Hazard trace elements from the power plant had little effect on soil and aerosol comparing to those from other industrial sources and the effects were mostly on downwind direction. Both the high performance electric precipitator and high chimney made the hazard trace elements from power plant being transported far away but little environmental impacts.

大别（超）包产到户铁岩和阜新火山岩铂族元素斌存规律研究

The platinum-group elements (PGE), including Os, Ir, Ru, Rh, Pt and Pd, axe strongly siderophile and chalcophile. On the basis of melting temperature, the PGE may be divided into two groups: the Ir group (IPGE, >2000°C) consisting of Os, Ir and Ru, and the Pd group (PPGE, <20GO°C) consisting of Rh, Pt and Pd. Because of their unique geochemical properties, PGE provide critical information on global-scale differentiation processes, such as core-mantle segregation, late accretionary history, and core-mantle exchange. In addition, they may be used to identify magma source regions and unravel complex petrogenetic processes including partial melting, melt percolation and metasomatism in the mantle, magma mixing and crustal contamination in magma chambers and melt crystallization.Compared with other rocks, (ultra)mafic rocks have lower REE content but higher PGE content, so PGE have advantages in studying the petrogeneses and evolution of them. In this study, we selected (ultra)mafic rocks collected in Dabie Orogen and volcanic rocks from Fuxin Region. Based on the distribution and behaviour of platinum-group elements, combined with other elements, we speculate the magma evolution and source mantle of these (ultra)mafic rocks and volcanic rocks.Many (ultra)mafic rocks are widely distributed in Dabie Region. According to their deformation and metamorphism, we classed them into three types. One is intrusive (ultra)mafic rocks, which are generally undeformed and show no or little sign of metamorphism, such as (ultra)mafic intrusions in Shacun, zhujiapu, Banzhufan, qingshan, Xiaohekou, Jiaoziyan, Renjiawan and Daoshichong. The other one is ultrahigh pressure metamorphic (ultra)mafic rocks, some of them appeared as eelogites, such as complex in Bixiling and adjacent Maowu. Another one is intense deformed and metamorphic, termed as tectonic slice, alpine-type (ultra)mafic rocks. The most representative is Raobazhai and Dahuapin. However, there are many controversies about the formation of those (ultra)mafic rocks. Here, we select typical rocks of the three types. The PGE were determined by inductively coupled plasma mass spectrometry (ICP-MS) ater NiS fire-assay and tellurium co-precipitation.The PGE tracing shows that three components are needed in the source of the cretaceous (uitra)mafic intrusions. They could be old enriched sub-continental lithospheric mantle, lower crust and depleted asthenospheric mantle. The pattern of PGE also shows the primitive magma of these intrusions underwent S saturation. According to palladium, we can conclude that the mantle enrich in PGE. Distribution of PGE in Bixiiing and Maowu (ultra)mafic rocks display they are products of magmas fractional crystallization. The (ultra)mafic rocks in Bixiiing and Maowu are controlled by various magmatic processes and the source mantle is depleted in PGE. Of interest is that the mantle produced UHP (ultra)mafic rocks are PGE-depleted, whereas the mantle of cretaceous (ultra)mafic intrusions are enrich in PGE. This couldindicate that the mantle change from PGE-enriched to PGE-depleted during120-OOMa, which in accord with the time of tectonic system change in the East China. At the same time, (ultra)mafic intrusions in cretaceous took information of deep mantle, which means the processes in deep mantle arose structural movement in the crust The character of PGE in alpine-type (ultra)mafic rocks declared that the rocks had experienced two types of metasomatic processes - hydrous melt derived from slab and silicate melt. In addition, we analyze the platinum-group elements in volcanic rocks on the northern margin of the North China Craton, Fuxin. The volcanic rocks characterized by negative anomalies of platinum. This indicates that platinum alloys, which may host some Pt resided in the mantle. The PGE patterns also show that Jianguo alkali basalts derived from asthenospheric mantle source, but wulahada high-Mg andesites derived from lithospheric mantle.